US 20020045707A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2002/0045707 A1 BOriak et al. (43) Pub. Date: Apr. 18, 2002

(54) PROCESS FOR MANUFACTURING A Related U.S. Application Data HYDROXYESTER DERVATIVE INTERMEDIATE AND EPOXY RESINS (63) Non-provisional of provisional application No. PREPARED THEREFROM 60/205,366, filed on May 18, 2000. (76) Inventors: Clinton J. Boriak, Jones Creek, TX Publication Classification (US); Zeng K. Liao, Lake Jackson, TX (51) Int. Cl...... C08F 8/00 (US) (52) U.S. Cl...... 525/107 Correspondence Address: THE DOW CHEMICAL COMPANY (57) ABSTRACT INTELLECTUAL PROPERTY SECTION A process for manufacturing an O-halohydrin intermediate P. O. BOX 1967 and an epoxy resin prepared therefrom including epoxidiz MIDLAND, MI 48641-1967 (US) ing an O-halohydrin intermediate produced from an in Situ halide Substitution-deesterification of an O-hydroxy ester (21) Appl. No.: 09/852,355 derivative which has been obtained by the coupling reaction of a phenol or a mixture of phenols and a glycidyl ester (22) Filed: May 9, 2001 optionally in the presence of a catalyst. US 2002/0045707 A1 Apr. 18, 2002

PROCESS FOR MANUFACTURING A HYDROXYESTER DERVATIVE INTERMEDIATE -continued AND EPOXY RESINS PREPARED THEREFROM HC-CHCH O BACKGROUND OF THE INVENTION propyleneoxide 0001. The present invention relates to a process for manufacturing an O-halohydrin ester derivative of at least one or more phenols and converting Such C-halohydrin ester Reaction Sequence (II) derivative to an epoxy resin. CH2=CHCH2Cl + Cl2 + H2O - - 0002 More specifically, the present invention relates to a proceSS for manufacturing an O-halohydrin derivative at at least one or more phenols, converting Such C-halohydrin ester derivative to an O-halohydrin intermediate of at least CH-CHCHCl + CH-CHCHCI one or more phenols and utilizing Such C-halohydrin inter mediate of the at least one or more phenols to make an epoxy C OH OH Cl resin. For example, the present invention is useful for C-chlorohydrins manufacturing bisphenol A (bis A) epoxy resin. 0.003 C.-Halohydrins are made, as reactive intermediates, CH-CHCHCl + CH-CHCHCl + Ca(OH)2 -- Via Several processes which are well known to those skilled in the art. Generally, the intermediate C-halohydrins are C OH OH Cl Subsequently converted into epoxides. In one widely prac HC CHCHCI ticed process, C.-halohydrins are made by reacting low O molecular weight olefin-containing compounds Such as pro epichlorohydrin pylene, butylene and , with halogens, Such as chlorine or bromine, in water. The C-halohydrins, more Specifically the C-chlorohydrins, from propylene, butylene and allyl chloride are Subsequently used for manufacturing 0004. In a well-known industrial process for producing propylene oxide, butylene oxide and epichlorohydrin (ECH) epoxy resins on a large commercial Scale, in a first Step, an respectively, in large Scale. The proceSS chemistries for the C-halohydrin, as a reactive intermediate, is made by reacting industrial processes of propylene oxide and ECH are out an active hydrogen-containing compound Such as an alco lined in the following reaction Sequences, Reaction hol, a phenol, a carboxylic acid or an amine with an Sequence (I) and Reaction Sequence (II). More specifically, epihalohydrin, such as epichlorohydrin (ECH) or epibromo Reaction Sequence (I) shows a process chemistry Scheme hydrin. Then, in a Second step, the C-halohydrin intermedi for industrial production of propylene oxide from chloro ate is converted into a glycidyl ether, glycidyl ester, or hydrins made Via chlorine in water route, and Reaction Sequence (II) shows a process chemistry Scheme for indus glycidyl amine under basic reaction conditions. trial production of epichlorohydrin from chlorohydrins 0005 The most widely made and particularly useful made via chlorine in water route. epoxy resin is bisphenol A (bis A) epoxy resin which is made by the coupling reaction of bis A and ECH to form the bis(O-chlorohydrin) intermediate in a first step. Then, in an Reaction Sequence (I) epoxide ring-forming dehydrochlorination reaction with CH2=CHCH + Cl2 + H2O - - base, as a Second step, the bis Abis(C-chlorohydrin) inter mediate is converted to the bis A diglycidyl ether epoxy resin. Such a two-step process for making an epoxy resin is CH-CHCH + CH-CHCH described by H. Lee and K. Neville in “Handbook of Epoxy Cl OH OH Cl Resins”, McGraw-Hill Book Co., New York, New York, C-chlorohydrins 1982, Reissue, 2-3 to 2-4. This process is shown in the following reaction sequence, Reaction Sequence (III). More Specifically, Reaction Sequence (III) shows a process chem CH-CHCH + CH-CHCH + Ca(OH)2 -- istry Scheme for a two-step, industrial manufacture of bis A C OH OH Cl epoxy resin via the reaction of bis A and ECH to make a chlorohydrin intermediate.

step 1 to-O) OH + epichlorohydrin -coupling catalyst - bisphenol A US 2002/0045707 A1 Apr. 18, 2002

-continued step 2 He CICH fictio (O) (O) out- CHCI base OH OH

bis-C-chlorohydrin intermediate of bisphenol A

CH-CHCHO OCHCH-CHN / 7 co-O-HO) O bisdiglycidyl ether of bisphenol A (bis A epoxy resin)

0006 The above two-step process of coupling bis A and Therefore, from an environmental Standpoint, there is a ECH followed by epoxide ring forming dehydrochlorination desire to reduce the consumption of chlorine and to reduce has also been combined into a Single-step reaction, wherein the generation of chlorinated by-products and waste water in the bis(C-chlorohydrin) intermediate of bis A is generated in the production of epoxy resin. Situ and converted into an epoxy simultaneously. Such a 0010. In addition, epoxy resins made from ECH by either Single-step process for making bis Aepoxy resin is described of the previously described two-step or Single-step pro in U.S. Pat. Nos. 4,499,255; 4,778,863; and 5,028,686. cesses, may have a high organic chloride content which may 0007 Another method to generate C-chlorohydrins, as be deemed as undesirable in Some applications, for example, reactive intermeditates, is described in U.S. Pat. No. 2,144, in electronic applications. 612 in which , which is an O-glycol, is converted into an O-chlorohydrin by reaction with anhydrous hydrogen 0011. It is therefore desired to provide a non-epichloro chloride (HCl) in the presence of a catalytic amount of acetic hydrin process for making epoxy resins Such as bis A epoxy acid (AcOH). U.S. Pat. No. 2,144.612 describes a process resin. That is, it is desired to provide an alternative epoxy that is shown in the following reaction sequence, Reaction resin route, i.e., an alternative process Without using ECH Sequence (IV), for making glycerol dichlorohydrin, a pre for manufacturing epoxy resins. cursor for epichlorohydrin from the C-glycol glycerol. More 0012 One non-epichlorohydrin process for manufactur Specifically, Reaction Sequence (IV) shows chemistry for ing epoxy resins is described in U.S. Pat. No. 6,001,945. In epichlorohydrin Synthesis via the reaction of glycerol with the process of U.S. Pat. No. 6,001,945, is used as HCl and AcOH to make glycerol dichlorohydrin. a reactant to produce an O-glycol derivative, which is Subsequently converted to an O-chlorohydrin via reaction with hydrogen chloride and a catalytic amount of Reaction Sequence (IV) via the process described in U.S. Pat. No. 2,144.612. Gly cidol is known to be a highly toxic and thermally unstable catalytic AcOH material tending to explosively Self-polymerize. At low CH-CH-CH + HC --> temperatures, Such as 70° C., glycidol is unstable and the OH OH OH loSS of epoxide content of glycidol is significant. Glycidol glycerol Self-polymerization diminishes glycidol Selectivity and product yield in its reactions, and the glycidol Self-polymer CH-CH-CH + Ca(OH)2 - - epichlorohydrin ization products complicate Separation and purification of C OH Cl the desired reaction product. These undesirable properties of glycidol are described in detail by A. Kleemann and R. glycerol chlorohydrin Wagner in “Glycidol Properties, Reactions, Applications”, Dr. Alfred Huthig Verlag, New York, New York, 1981, pp. 48-52. Thus, it is desirable to develop processes that can 0008 Although epichlorohydrin (ECH) is an important manufacture C-halohydrin intermediates as precursors for commercial product for making C-chlorohydrin intermedi manufacturing epoxy resins that do not require glycidol as a ates, and particularly for making the bis Abis C-chlorohy reactant. drin intermediate precursors of bis A epoxy resin, ECH provides a chlorine-intensive route to producing epoxy SUMMARY OF THE INVENTION resins. In the predominate commercial process for making ECH, ECH is made from allyl chloride, which in turn, is 0013. One aspect of the present invention is directed to a made from thermal chlorination of propylene using chlorine process for making an epoxy resin by converting an O.-ha gas, a process that produces chlorinated by-products. Gen lohydrin ester derivative of a phenol or mixture of phenols erally, chlorinated by-products are treated as waste material. to an epoxy resin. 0009 Additionally, a large amount of water is used when 0014) Another aspect of the present invention is directed converting allyl chloride into an O-chlorohydrin intermedi to a process for manufacturing an O-halohydrin intermediate ate, and this water must eventually also be treated as waste. of at least one or more phenols using an in Situ halide US 2002/0045707 A1 Apr. 18, 2002

Substitution-deesterification process to convert an O-hy drimerS. Ar may also be a moiety containing multinuclear droxy ester derivative of at least one or more phenols to the fused aromatic ringS Such as naphthalene, anthracene and C-halohydrin intermediate. The process is preferably carried naphthalene-formaldehyde novolac. Ar may also be a moi out under anhydrous conditions with an anhydrous hydrogen ety containing multinuclear fused aromatic rings with one or halide Such as hydrogen chloride, hydrogen bromide, or more heteroatoms such as O, N, S, Si, B or P, or any hydrogen iodide, as a reactant; and optionally, the proceSS is combination of these heteroatoms, for example, quinoxaline, carried out in the presence of a Solvent. thiophene and quinoline. Ar may also be a moiety containing mononuclear or multinuclear aromatic ring(s) fused with a 0.015 Yet another aspect of the present invention is cycloaliphatic ring(s) Such as indane, 1,2,3,4-tetrahy directed to an alternative, non-epichlorohydrin process for dronaphthalene and fluorene. Ar may also be a moiety manufacturing an epoxy resin of at least one or more phenols containing mononuclear or multinuclear aromatic ring(s) utilizing, as an intermediate product, the C-halohydrin inter fused with a cycloaliphatic ring(s) containing one or more mediate of at least one or more phenols as described above. heteroatoms such as O, N, S, Si, B or P, or any combination 0016 Still another aspect of the present invention is of these heteroatoms, for example, chroman, indoline and directed to the C-hydroxy ester derivative of at least one or thioindane. more phenols used in the above process for making the 0022. In Formula I, Ar can also be a moiety containing C-halohydrin intermediateS preferably prepared by reacting aryl groups in which each aryl group is connected to at least one phenol or a mixture of two or more phenols with oligomeric (for example, polymers with less than about a glycidyl ester, preferably glycidyl . The process for 5000 molecular weight average) or high molecular weight manufacturing the C-hydroxy ester derivative of at least one (for example, greater than about 5000 molecular weight or more phenols is preferably carried out in the presence of average) organosiloxane units. The aryl groups are attached a Solvent and a catalyst. directly to the Silicon atoms of the organosiloxane units, or the aryl groups are indirectly attached to the Silicon atoms of DETAILED DESCRIPTION OF THE the organosiloxane units via an organic aliphatic moiety, PREFERRED EMBODIMENT(S) organic cycloaliphatic moiety, organic aromatic moiety or 0.017. The present invention involves a novel process for any combination thereof. The organic aliphatic, manufacturing a phenolic-based C-halohydrin intermediate, cycloaliphatic or aromatic moiety should contain no more i.e., an O.-halohydrin intermediate made from one phenol or than about 20 carbon atoms. When the Armoiety contains a mixture of C-halohydrin intermediates made from a mix Such oligomeric or high molecular weight organosiloxane ture of two or more different phenols from a phenolic based units, then Z is preferably from 1 to 150. C.-halohydrin ester derivative. The O.-halohydrin intermedi 0023. In Formula I, O is an oxygen atom Substituted for ates are then used to make epoxy resins. a hydrogen atom on the aromatic ring(s) of the Ar moiety, and R' is an O-halohydrin propyl-containing moiety prefer C-Halohydrin Intermediates ably selected from: 0.018 Generally, the process of the present invention for manufacturing the C-halohydrin intermediates includes con Verting an O-hydroxy ester derivative of at least one or more 3 phenols to the C-halohydrin intermediate by an in Situ halide R Substitution-deesterification proceSS using a hydrogen -CRCR3-cR3 and s halide. Then, the C-halohydrin intermediates can be used to make epoxy resins by well-known techniques in the indus try, Such as, for example, by a ring-closing epoxidation reaction of the C-halohydrin intermediates with a base. More preferably, the epoxy resins which can be prepared by the 0024 where X is a halogen atom such as chlorine, process of the present invention include, for example, bromine or iodine, and Y is a hydroxyl group. The positions bisphenol A (bis A) diglycidyl ether epoxy resin. of X and Y may be interchanged. R in Formula I is preferably hydrogen; an alkyl group having from 1 to 20 0019. The C-halohydrin intermediates prepared in accor carbon atoms Such as methyl, ethyl and propyl; a dance with the process of the present invention are repre cycloaliphatic group having from 3 to 20 carbon atoms Such Sented for example by, but not limited to, the Structures of as cyclopentyl and cyclohexyl, an aromatic group having the following Formulas I-V. A preferred class of C-halohy from 6 to 20 carbon atoms Such as phenyl and naphthyl, or drin intermediates in the present invention is generically any combination thereof. Each individual R may be the same represented for example by the following Formula I: group or may be a different group from each other. (R), Ar(OR"), Formula I 0025) In one embodiment, when R' in Formula I above is 0020. In Formula I, y is from 0 to 750, and Z is from 1 to the following structure: 150. 0021. In Formula I, Ar is a moiety containing a mono nuclear aromatic ring Such as phenyl. Ar may also be a Y X moiety containing multinuclear aromatic rings, Such as -CHCH-CH biphenyl, 2,2-diphenyl propane, bisphenylene oxide, 1,1,2, 2-tetrakisphenylethane, Stilbene, phenol-formaldehyde novolac, creSol-formaldehyde novolac, phenol-dicyclopen 0026 the C-halohydrin is a 3-halo-2-hydroxy-1-propyl tadiene novolac and hyper-branched aromatic phenol den moiety-containing derivative or in Such derivative, the US 2002/0045707 A1 Apr. 18, 2002 hydroxy and halo groups may be interchanged to form a 2-halo-3-hydroxy-1-propyl moiety-containing derivative. 0027. In another embodiment, when R' in Formula I Formula II above is the following structure: (R), O (OR), Y X -CHC(CH)-CH 0034). In Formula II, y is from 0 to 5 and Z is from 1 to 4. In Formula II, O, R' and R have the same meaning as described above with reference to Formula I. C.-Halohydrin 0028 the C-halohydrin is a 3-halo-2-hydroxy-2-methyl intermediates of Formula II can be prepared from aromatic 1-propyl moiety-containing derivative or in Such derivative, hydroxyl group-containing precursors, Such as, for example, the hydroxy and halo groups may be interchanged to form a 2-methylphenol, 4-methylphenol, 4-methoxyphenol; 2,6- 2-halo-3-hydroxy-2-methyl-1-propyl moiety-containing dimethylphenol; 2,6-diisopropylphenol; 2,6-dibromophe derivative. nol; 1,2-dihydroxybenzene, 1,3-dihyroxybenzene, 1,4-dihy 0029. In yet another embodiment, when R' in Formula I droxybenzene, and mixtures thereof. above is the following structure: 0035) Other examples of C-halohydrin intermediates use ful in the present invention are binuclear aromatic C-halo hydrin intermediates which are represented, for example, by the following Formula III:

Formula III

Z. (RO)2 O- -O.(OR), 0030) the C-halohydrin is a 3-halo-2-hydroxy-1-cyclo hexyl moiety-containing derivative, or in Such derivative, 0036). In Formula III, each y is from 0 to 4, and each y can the hydroxy and halo groups may be interchanged to form a be the Same or different, and each Z is from 1 to 3, and each 2-halo-3-hydroxy-1-cyclohexyl moiety-containing deriva Z can be the same or different. In Formula III, O, R' and R' tive. In both derivatives, the propyl moiety is contained in have the same meaning as described above with reference to the cyclohexyl ring structure. Formula I. 0031) In Formula I, R is a group substituted for a 0037. In Formula III, Z may be nil; or Z can be a hydrogen atom on the aromatic ring(s) of the Armoiety. R heteroatom with or without substituents thereon to complete may be a halogen Such as chlorine, bromine, iodine or its necessary bonding Valence. The heteroatom is Selected fluorine, or a hydrocarbon radical Such as an alkyl group, a from O, N, S, Si, B or P, or any combination of two or more cycloaliphatic group or an aromatic group. R is preferably of the above heteroatoms. Z can also be, for example, an alkyl group having from 1 to 20 carbon atoms Such as C(O)-; -S(O)-, -C(O)NH-, -P(O)Ar-; an methyl, ethyl and propyl; a cycloaliphatic group having organic aliphatic moiety, Saturated or unsaturated, with or from 3 to 20 carbon atoms Such as cyclopentyl and cyclo without heteroatoms, Such as, for example, Oxydimethylene, hexyl, an aromatic group having from 6 to 20 carbon atoms methylene, 2.2-isopropylidene, isobutylene and Such as phenyl and naphthyl, or any combination thereof. -CR=CH-, where R is as defined with reference to The hydrocarbon radicals above may also contain one or Formula I above, a cycloaliphatic group, Saturated or unsat more heteroatoms such as O, N, S, Si, B or P, or any urated, with or without heteroatoms, Such as, for example, a combination of these heteroatoms. An example of a hydro cycloaliphatic ring with greater than 3 carbon atoms, an carbon radical containing an oxygen heteroatom is a meth aromatic group, with or without heteroatoms, or any com oxy group, an ethoxy group or a polyalkylene oxide group bination thereof. Zas described above in Formula III can be derived from alkylene oxides Such as oxide, pro partially or fully fluorinated, Such as, for example, 2,2- pylene oxide, butylene oxide and cyclohexene oxide. R as perfluoroiso-propylidene. described above in Formula I can be partially or fully 0038 Precursors useful for making the C-halohydrin fluorinated. intermediates of Formula III include, for example, 4,4'- dihydroxybiphenyl; 3,3',5,5'-tetramethyl-4,4'-dihydroxybi 0.032 More specific and preferred examples of C-halo phenyl; 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihy hydrin intermediates useful in the present invention are droxybiphenyl; bis(4-hydroxyphenyl)methane; bis(4- represented by Formulas II-V separately or as mixtures of hydroxyphenyl)sulfone, 2,2-bis(3,5-dibromo-4- two or more O.-halohydrin intermediates of Formulas II-V hydroxyphenyl)isopropylidene; 2,2-bis(4- which follow. hydroxyphenyl)isopropylidene; bisphenol K; 9.9-bis(4- 0.033 Examples of mononuclear aromatic C-halohydrin hydroxyphenyl)fluorene; 4,4'-dihydroxy-C.-methylstilbene; intermediates useful in the present invention are represented 1,3-bis(4-hydroxylphenyl)adamantane; and mixtures for example by the following Formula II: thereof. US 2002/0045707 A1 Apr. 18, 2002

0039) Other examples of C-halohydrin intermediates use molecular weight average) organosiloxane unit; in which ful in the present invention are multinuclear aromatic C-ha case, the aryl groups are attached to the Silicon atoms of the lohydrin intermediates which are represented, for example, organosiloxane unit directly or through an organic aliphatic, by the following Formula IV: cycloaliphatic or aromatic group; or any combination thereof, with no more than about 20 carbon atoms. When Z. is an oligomeric or high molecular weight organosiloxane Formula IV unit, m' in Formula V is preferably from 1 to 150. 0046 Precursors useful for making the C-halohydrin (R), intermediates of Formula V include, for example, tris(4- (R), (R), hydroxyphenyl)methane; 1,1,1-tris(3,5-dimethyl-4-hydrox yphenyl)methane; 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; (RO)2iO-(O-)-O. i. (OR), and mixtures thereof. (OR), 0047 Preferably, the O.-halohydrin intermediates of the present invention, include for example, the phenolic C-chlo rohydrin intermediates made from phenols, Such as 1,3- 0040. In Formula IV, each y, each Z and Z are the same dihydroxybenzene, 1,4-dihydroxybenzene, 1,5-dihydrox as has been previously described above in Formula III. In ynaphthalene; 2,6-dihydroxynaphthalene; 4,4'- Formula IV, m is from 0.001 to 10. In Formula IV, O, R and dihydroxybiphenyl; 3,3',5,5'-tetramethyl-4,4'- Rhave the same meaning as described above with reference dihydroxybiphenyl; 3,3',5,5'-tetramethyl-2,2',6,6'- to Formula I. tetrabromo-4,4'-dihydroxybiphenyl; bis(4- 0041) Precursors useful for making the C-halohydrin hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) intermediates of Formula IV include, for example, phenol isopropylidene, phenol-formaldehyde novolac (functional formaldehyde novolac (functionality greater than 2); ity >2); o-cresol-formaldehyde novolac (functionality >2); o-cresol-formaldehyde novolac (functionality greater than phenol-dicyclopentadienyl novolac (functionality >2); 2); phenol-dicyclopentadienyl novolac (functionality greater naphthol-formaldehyde novolac (functionality >2); 1,1,1- than 2), naphthol-formaldehyde novolac (functionality tris(4-hydroxyphenyl)methane; 1,1,2,2-tetrakis(4-hydrox greater than 2); and mixtures thereof. yphenyl)ethane; and mixtures thereof. 0048 Preferably, the O.-halohydrin intermediates of the 0042. Other examples of C-halohydrin intermediates use present invention, include for example, phenolic C-chloro ful in the present invention are multi-nuclear aromatic hydrin intermediates, Such as, 1,3-dihydroxybenzene bis(3- C-halohydrin intermediates which are represented, for chloro-2-hydroxypropyl) ether; 1,4-dihydroxybenzene example, by the following Formula V: bis(3-chloro-2-hydroxypropyl) ether; 1,5-dihydroxynaph thalene-bis(3-chloro-2-hydroxypropyl) ether; 2,6-dihydrox ynaphthalene bis(3-chloro-2-hydroxypropyl) ether; 4,4'-di Formula V hydroxybiphenyl bis(3-chloro-2-hydroxypropyl) ether; 3,3', (R), 5,5'-tetramethyl-4,4'-dihydroxybiphenyl bis(3-chloro-2- hydroxypropyl) ether; 3,3',5,5'-tetramethyl-2,2',6,6'- (RO), O)}-z tetrabromo-4,4'-dihydroxybiphenyl bis(3-chloro-2- hydroxypropyl) ether; bis(4-hydroxyphenyl)methane bis(3- chloro-2-hydroxypropyl) ether; 2,2-bis(4- hydroxyphenyl)isopropylidene bis(3-chloro-2- 0043. In Formula V, each y and each Z are the same as has hydroxypropyl) ether, phenol-formaldehyde novolac been previously described above in Formula III. In Formula (3-chloro-2-hydroxypropyl) ether (functionality >2); V, O, R and R have the same meaning as described o-cresol-formaldehyde novolac (3-chloro-2-hydroxypropyl) previously with reference to Formula I. ether (functionality >2); phenol-dicyclopentadienyl novolac 0044) In Formula V, Z is an organic aliphatic moiety, (3-chloro-2-hydroxypropyl) ether (functionality >2), naph Saturated or unsaturated, with or without heteroatoms Such thol-formaldehyde novolac (3-chloro-2-hydroxypropyl) as O, N, S, Si, B or P, or any combination of two or more ether (functionality >2); of the above heteroatoms, wherein the aliphatic moiety has 1,1,1-tris(4-hydroxyphenyl)methane tris(3-chloro-2-hy from 1 to 20 carbon atoms, Such as, for example, methine; droxypropyl) ether; 1,1,2,2-tetrakis(4-hydroxyphenyl)e- a cycloaliphatic moiety, Saturated or unsaturated, with or thane tetrakis(3-chloro-2-hydroxypropyl) ether; and mix without heteroatoms, having from 3 to 20 carbon atoms, tures thereof. Such as, for example, cyclohexane tri-yl; an aromatic moiety, 0049. In addition, the chloro and hydroxyl groups in the with or without heteroatoms, Such as, for example, benzen above 3-chloro-2-hydroxyl-1-propyl moiety-containing etriyl, naphthylenetriyl and fluorenetriyl.; or any combina derivatives may be interchanged to form 3-hydroxy-2- tion thereof. Z. preferably contains no more than about 20 chloro-1-propyl moiety-containing derivatives. carbon atoms. Z as described above in Formula V can be partially or fully fluorinated, Such as, fluoromethine. 0050. The C-halohydrin intermediates of the present invention comprise from about 10 to about 100 percent, 0045. In Formula V, m' is generally 3 or 4. However, Z. more preferably from about 25 to about 100 percent, most may also be an oligomeric (for example, less than about preferably from about 50 to about 100 percent, of the total 5000 molecular weight average) organosiloxane unit or high weight of one or more than one component as illustrated in molecular weight (for example, greater than about 5000 the above Formulas I-V. US 2002/0045707 A1 Apr. 18, 2002

0051. The C-halohydrin intermediates of the present droxypropane, partially or fully fluorinated derivatives invention, for example as illustrated in the above Formulas thereof; and any combination thereof. I-V, are prepared by first obtaining an O-hydroxy ester 0057. In general, the amount of the solvent, optional derivative of at least one or more phenols and then convert Component (C), used in the present invention may be a ratio ing the C-hydroxy ester derivative to the C-halohydrin of from about 0 to about 50 parts (on a weight basis) of a intermediate using an in Situ halide Substitution-deesterifi Single Solvent or a mixture of two or more Solvents to 1 part cation process. More particularly, the C-halohydrin interme C-hydroxy ester derivative. A more preferred Solvent to diates of the present invention are prepared by reacting (A) O-hydroxy ester derivative ratio is from about 0 to about 10 an O-hydroxy ester derivative of at least one or more phenols parts Solvent per 1 part C.-hydroxy ester derivative. The most with (B) a hydrogen halide and optionally in the presence of preferred solvent to C-hydroxy ester derivative ratio is from (C) a solvent. about 0 to about 5 parts solvent per 1 part C.-hydroxy ester 0.052 The halogen halide, Component (B), useful in the derivative. manufacturing the C-halohydrin intermediates of the present 0058. The temperature in the above reaction for in situ invention may include, for example, hydrogen chloride, halide substitution-deesterification of the C-hydroxy ester hydrogen bromide and hydrogen iodide. derivative is generally from about 0° C. to about 150 C.; preferably from about 20° C. to about 130 C.; and more 0053. The amount of hydrogen halide, Component (B), preferably from about 40 C. to about 110° C. At a tem useful in manufacturing the C-halohydrin intermediates of perature below 0° C., the reaction is not complete. At a the present invention should be Sufficient to ensure Substan tially complete conversion of the C-hydroxy ester derivative temperature above about 150 C., undesirable chlorination to the C-halohydrin intermediate. The amount of hydrogen reactions may take place. halide used is generally from about 0.50 mole to about 20 0059. The pressure used in the above reaction process for moles of hydrogen halide relative to the equivalents of in situ halide Substitution-deesterification of the C-hydroxy C-hydroxy ester moieties being reacted in the C-hydroxy ester derivative for manufacturing the C-chlorohydrin inter ester derivative; preferably from about 0.75 mole to about 10 mediate may be atmospheric, Subatmospheric or Superatmo moles of hydrogen halide relative to the equivalents of Spheric. The pressure is not critical and may be determined C-hydroxy ester moieties being reacted in the C-hydroxy by parameterS Such as type of hydrogen halide used, reaction ester derivative; and more preferably from about 0.95 mole temperature, type of Solvent used or the Solvent azeotrope to about 5 moles of hydrogen halide relative to the equiva boiling points. lents of C-hydroxy ester moieties being reacted in the O-hydroxy ester derivative. 0060. The in situ halide substitution-deesterifiction of O-hydroxy ester derivative to make the C-halohydrin inter 0.054 The hydrogen halide may be added neat to the mediate can be carried out in a batch or in a continuous reaction as a liquid or as a gas. When added to the reaction reaction mode. In a batch reaction, the C-hydroxy ester as a gas, the hydrogen halide may be added as a continuous derivative is optionally dissolved in the solvent and the Stream of gas. The hydrogen halide may also be dissolved in hydrogen halide is added to the reactor as previously a Solvent, Such as those described in reference to Component described above. In a batch process, it is highly desirable to (C) below, and added to the reactor as a solution. When an run the reaction under pressure to maintain the hydrogen amount of halogen halide in excess of the Stoichiometric halide in the Solution phase. When the batch reaction using amount necessary to ensure complete conversion of the of hydrogen halide in Solution phase is completed, the exceSS C-hydroxy ester derivative is used, the exceSS amount may hydrogen halide and the carboxylic acid produced by dees be removed from the reaction mixture by washing with terification may be removed from the reaction mixture by water or careful neutralization with base. It is preferred to Washing with water or by careful neutralization with base. recover and recycle the exceSS hydrogen halide by distilling Or, the exceSS hydrogen halide and the carboxylic acid may the hydrogen halide from the reaction mixture. be recovered and recycled as described below. 0055 The solvent, optional Component (C), which may 0061. In some instances, for example when using hydro be used in the above process for making the C-halohydrin gen chloride gas, it may be beneficial to purge the gas intermediate may be, but is not limited to, aliphatic and continuously through a reactor while efficiently mixing or cyclic hydrocarbons Such as pentane, hexane, octane, iso agitating the reaction mixture in the reactor. In this process, octane, cyclohexane and cyclooctane; aromatic hydrocar the hydrogen chloride gas exiting the reactor is collected and bons Such as benzene, toluene and Xylene; chlorinated recycled to the reactor. Solvents Such as methylene dichloride, tetrachloroethane and chlorobenzene, aprotic Solvents Such as acetone, methyl 0062. In a continuous halide substitution-deesterification iso-butyl ketone, acetonitrile, dimethoxyethane, 2,2'- process, the C-hydroxy ester derivative can optionally be dimethoxy diethyl ether, dioxane, dimethyl sulfoxide and mixed with a solvent and then intimately mixed with hydro 1-methoxy-2-acetoxypropane; protic Solvents Such as etha gen halide as the C-hydroxy ester derivative and optionally nol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, Solvent is fed into a reactor. The reactors which may be used tert-butanol, 1-pentanol, tert-amyl alcohol, 1-hexanol, are well known in the art, for example, the reactor may be cyclohexanol and 1-methoxy-2-hydroxypropane; partially of a tubular design. After the reaction product leaves the or fully fluorinated derivatives thereof; and any combination reactor, the reaction product may pass through a Series of thereof. Optionally, the solvent may be used with or without purification Steps. For example, in one embodiment when a the presence of water. Solvent is used that boils at a lower temperature than the carboxylic acid produced, the reaction product may be: first, 0056. When protic alcohol solvents are optionally used, it distilled to remove excess hydrogen halide where the hydro is preferred that the alcohol Solvents are Secondary or gen halide may then be recycled to the halide Substitution tertiary alcoholic Solvents, Such as isopropyl alcohol, 2-bu deesterification reactor; Second, distilled to remove the Sol tanol, tert-butanol, tert-amyl alcohol and 1-methoxy-2-hy vent, wherein the solvent may then be recycled to a halide US 2002/0045707 A1 Apr. 18, 2002

Substitution-deesterification unit; and third, distilled to remove the carboxylic acid product of the deesterification wherein the carboxylic acid product may then be recycled to Yi X an allyl ester process. R3 0.063. In another second embodiment, when a solvent is -CRCR3-cR3 and used that boils at a higher temperature than the carboxylic acid produced, the reaction product may be: first, distilled to remove the hydrogen halide wherein the hydrogen halide may then be recycled to the halide substitution-deesterifi cation reactor; and Second, distilled to remove the carboxy lic acid product of the deesterification. In the Second 0070 wherein R is as defined previously for Formula I, embodiment above, the solvent may optionally be removed Y' is a hydroxyl group and X is a carboxy or carboxylic acid for example by distillation, or the solvent need not be ester moiety having the following general Structure: removed, wherein the Solvent is carried forward as a Solvent for Subsequent epoxidation Step. The distillation Steps described above may be carried out at atmospheric pressure, under Subatmosphoric pressure or under Superatmospheric preSSure as is well known in the art. RCO 0064. It is highly desirable and preferred to carry out the above processes whereby the C-halohydrin intermediate can be converted to the epoxy resin without additional purifica 0071) wherein R" is hydrogen; an alkyl group having tion. from 1 to 20 carbon atoms Such as methyl, ethyl and propyl; 0065. The halide substitution-deesterification of the an alkenyl group having from 2 to 20 carbon atoms Such as C-hydroxy ester derivative to make the C-halohydrin inter ethenyl, propenyl and methyl propenyl; a cycloaliphatic mediate of this invention is illustrated by the following group having from 3 to 20 carbon atoms Such as cyclopentyl reaction Sequence, Reaction Sequence (V) which shows the and cyclohexyl, or an aromatic group having from 6 to 20 chloride Substitution-deacetyloxylation of an O-hydroxy carbon atoms Such as phenyl and naphthyl. R" is preferably acetate derivative. More specifically, Reaction Sequence (V) a methyl group. shows the chloride Substitution-deacetyloxylation of an C-hydroxy acetate derivative to Synthesize an O-chlorohy 0072 The positions of X" and Y may be interchanged. drin intermediate of the present invention. 0073. In one embodiment, when R' in Formula VI above is for example: Reaction Sequence (V)

HCIAsolvent Yi X -CHCH-CH (O-o-c-f-A. B

0074 the O.-hydroxy ester derivative is a 3-carboxy-2- (O-o-c-f-p - AcOH hydroxy-1-propyl moiety-containing component or in Such A. B component, the hydroxy and ester (i.e., carboxy) groups may be interchanged to form a 2-carboxy-3-hydroxy-1-propyl moiety-containing component. 0.066. In the above Reaction Sequence V. A may be OH and B may be OAc; or A may be OAc and B may be OH. 0075). In another embodiment, when R' is for example: C.-Hydroxy Ester Derivatives 0067. The C-hydroxy ester derivatives, Component (A), Yi X useful the present invention are represented for example by, but not limited to, the structures of the following Formulas -CHC(CH3) o CH2 VI-X. A preferred class of C-hydroxy ester derivatives used in the present invention to make C-halohydrin intermediates is generically represented for example by the following 0076 in Formula VI above, the C-hydroxy ester deriva Formula VI: tive is a 3-carboxy-2-hydroxy-2-methyl-1-propyl moiety (R), Ar(OR"), Formula VI containing component or in Such component, the hydroxy 0068. In Formula VI, y, z Ar, O and R are as defined and ester groups may be interchanged to form a 2-carboxy previously for Formula I. 3-hydroxy-2-methyl-1-propyl-containing component. 0069. In Formula VI, R' is an O-hydroxy ester propyl 0077. In yet another embodiment, when R' in Formula containing moiety preferably Selected from: VI above is for example: US 2002/0045707 A1 Apr. 18, 2002

droxybiphenyl; bis(4-hydroxyphenyl)methane; bis(4- hydroxyphenyl)sulfone, 2,2-bis(3,5-dibromo-4- hydroxyphenyl)isopropylidene; 2,2-bis(4- R3 y-(R's hydroxyphenyl)isopropylidene; bisphenol K; 9.9-bis(4- hydroxyphenyl)fluorene; 4,4'-dihydroxy-C.-methylstilbene; R3 R3 1,3-bis(4-hydroxylphenyl)adamantane; and mixtures Yi Xi thereof. 0085. Other examples of C-hydroxy ester derivatives useful in the present invention are multi-nuclear aromatic 0078 the O.-hydroxy ester derivative is a 3-carboxy-2- C-hydroxy ester derivatives which are represented by the hydroxy-1-cyclohexyl moiety-containing component or, in following Formula IX: Such component, the hydroxy and ester groups may be interchanged to form a 2-carboxy-3-hydroxy-1-cyclohexyl moiety-containing component. In both derivatives, the pro Formula IX pyl moiety is contained in the cyclohexyl ring Structure. 0079 More specific and preferred examples of C-hy (R), droxy ester derivatives useful in the present invention are (R), (R), represented by Formulas VII-X separately or as mixtures of two or more C.-hydroxy ester derivatives of Formulas VII-X (RO); i. (OR), which follow. 3O-(O-)-O. (OR), 0080 Examples of mononuclear aromatic C-hydroxy ester derivatives useful in the present invention are repre sented by the following Formula VII: 0086) In Formula IX, y, z, Z, m, O and Rare as described above for Formula IV. In Formula IX, R has the same meaning as described above with reference to Formula VI. Formula VII 0087 Precursors useful for making the C-hydroxy ester (R), derivatives of Formula IX include, for example, phenol formaldehyde novolac (functionality greater than 2); O (OR), o-cresol-formaldehyde novolac (functionality greater than 2); phenol-dicyclopentadienyl novolac (functionality greater than 2), naphthol-formaldehyde novolac (functionality 0081. In Formula VII, y, z, O and R have the same greater than 2); and mixtures thereof. meaning as described above with reference to Formula II. In 0088. Other examples of C-hydroxy ester derivatives Formula VII, R' has the same meaning as described above useful in the present invention are multi-nuclear aromatic with reference to Formula VI. C.-Hydroxy ester derivatives C-hydroxy ester derivatives which are represented by the of Formula VII compound, can be prepared from aromatic following Formula X: hydroxyl group-containing precursors, Such as, for example, 2-methylphenol, 4-methylphenol, 4-methoxyphenol; 2,6- dimethylphenol; 2,6-diisopropylphenol; 2,6-dibromophe nol; 1,2-dihydroxybenzene, 1,3-dihyroxybenzene, 1,4-dihy Formula X droxybenzene, and mixtures thereof. (R), 0082) Other examples of C-hydroxy ester derivatives (RO)2RO)--z useful in the present invention are binuclear aromatic C-hy m droxy ester derivatives which are represented by the follow ing Formula VIII: 0089. In Formula X, y, z, Z'm', O and Rare the same as previously described above for Formula V. In Formula X, Formula VIII R" has the same meaning as described previously with reference to Formula VI. Z. 0090 Precursors useful for making the C-hydroxy ester (RO), O)--O.(OR), derivatives of Formula V include, for example, tris(4-hy droxyphenyl)methane; 1,1,1-tris(3,5-dimethyl-4-hydrox yphenyl)methane; 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; 0083) In Formula VIII, y, z, Z, O and R have the same and mixtures thereof. meaning as described above with reference to Formula III. 0091. The preferred C-hydroxy ester derivatives useful in In Formula VIII, R' has the same meaning as described the present invention include, more specifically, the phenolic above with reference to Formula VI. C-hydroxy ester derivatives made from phenols, Such as 0084 Precursors useful for making the C-hydroxy ester 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,5-dihy derivatives of Formula VIII include, for example, 4,4'- droxynaphthalene; 2,6-dihydroxynaphthalene; 4,4'-dihy dihydroxybiphenyl; 3,3',5,5'-tetramethyl-4,4'-dihydroxybi droxybiphenyl; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphe phenyl; 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihy nyl, 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'- US 2002/0045707 A1 Apr. 18, 2002 dihydroxybiphenyl; bis(4-hydroxyphenyl) methane; 2.2- 11a alkaline earth metals, such as Mg" or Ca"; or of Group bis(4-hydroxyphenyl)isopropylidene; phenol-formaldehyde 11b metals, such as Zn, or Group IIIa metals, such as Al". novolac (functionality >2); o-cresol-formaldehyde novolac The inorganic or organic acids include, for example, but are (functionality >2); phenol-dicyclopentadienyl novolac not limited to, acetic acid; trifluoro acetic acid; phosphoric (functionality >2); naphthol-formaldehyde novolac (func acid; Silicic acid; or their derivatives, and the like. Examples tionality >2); 1,1,1-tris(4-hydroxyphenyl)methane; 1,1,2,2- of the catalysts include Sodium acetate, Sodium phosphate tetrakis(4-hydroxyphenyl) ethane; and mixtures thereof. and Sodium Silicate. Optionally, co-catalysts Such as linear 0092. The C-hydroxy ester derivatives of phenols or polyalkylene oxide ethers or macrocyclic ethers, for mixtures of phenols of the present invention, include more example, but not limited to, crown ethers, can be used in Specifically, the phenolic C-hydroxy ester derivatives, Such combination with the above-mentioned catalysts in order to as, 1,3-dihydroxybenzene bis(3-acetoxy-2-hydroxypropyl) enhance the catalytic reactivity. ether; 1,4-dihydroxybenzene bis(3-acetoxy-2-hydroxypro 0098. The catalysts, Component (F), useful for coupling pyl) ether; 1,5-dihydroxynaphthalene bis(3-acetoxy-2-hy in the present invention may be the compounds containing droxypropyl) ether; 2,6-dihydroxynaphthalene bis(3-ac organopnicogen cations. The organopnicogen cation is com etoxy-2-hydroxypropyl) ether; 4,4'-dihydroxybiphenyl prised of at least one pnicogen, that is an element of Group bis(3-acetoxy-2-hydroxypropyl) ether; 3,3',5,5'-tetramethyl IVa and at least one organic Substituent bonded to the 4,4'-dihydroxybiphenyl bis(3-acetoxy-2-hydroxypropyl) pnicogen atom. The anionic counter ions of Such organop ether; 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihy nicogen cations may be for example, hydroxides, halides, droxybiphenyl bis(3-acetoxy-2-hydroxypropyl) ether; bis(4- Such as chloride and bromide, bisulfates, carbonates, hydroxyphenyl)methane bis(3-acetoxy-2-hydroxypropyl) , phosphonates, and Silanolates. ether; 2,2-bis(4-hydroxyphenyl) isopropylidene bis(3-ac etoxy-2-hydroxypropyl) ether; phenol-formaldehyde 0099 More specifically, the organopnicogen-containing novolac (3-acetoxy-2-hydroxypropyl) ether catalysts useful for coupling in the present invention are (functionality >2); o-cresol-formaldehyde novolac (3-ac comprised of at least one or more quaternary cationic etoxy-2-hydroxypropyl) ether (functionality >2); phenol centers, consisting of nitrogen, phosphorous, arsenic, anti dicyclopentadienyl novolac (3-acetoxy-2-hydroxypropyl) mony or bismuth, with one or more organic Substituents ether (functionality >2); naphthol-formaldehyde novolac bound to each quaternary cationic center. The organic Sub (3-acetoxy-2-hydroxypropyl) ether (functionality >2); 1,1, Stituents may be hydrocarbons containing from 1 to 20 1-tris(4-hydroxyphenyl)methane tris(3-acetoxy-2-hydrox carbon atoms Selected from linear, branched or cyclic ali ypropyl) ether; 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane tet phatic hydrocarbons or aromatic hydrocarbons, with or rakis (3-acetoxy-2-hydroxypropyl) ether; and mixtures without heteroatoms, such as N, P, S, O and Si; or halide thereof. atoms, Such as F, Cl, Brand I; or a combination thereof. 0100 Examples of nitrogen-containing quaternary cat 0.093 Moreover, in the above-preferred structures, the ionic centers having a Single cationic center useful for acetoxy and hydroxy groups in the above 3-acetoxy-2- homogenous coupling catalysts of the present invention are hydroxyl-1-propyl moiety-containing derivatives may be tetramethylammonium, tetraethylammonium, tetraiSopropy interchanged to form 3-hydroxy-2-acetoxy-1-propyl moi lammonium, tetrabutylammmonium, tetraisobutylammo ety-containing derivatives. nium, tetrahexylammonium, tetraoctylammonium, tetrai 0094. In one preferred embodiment, the C-hydroxy ester Sooctylammonium, tetraphenylammonium, derivative, Component (A) above, useful in the present benzyltrimethylammonium, benzyltriethylammonium, ben invention may be obtained by reacting a glycidyl ester (D) Zyltrihexylammonium, benzyltrioctylammonium, methylt with at least one or more phenolic compounds (E) in the rioctylammonium, decyltrimetylammonium, tetradodecy lammonium, hexadecyltrimethylammonium, presence of a catalyst (F) and optionally in the presence of ethanoltrimethylammonium, ethanoltriethylammonium, tri a solvent (G). methoxysilylpropyltributylammonium, triethoxysilylpropy 0.095 The catalyst, Component (F), may be used in the ltributylammonium, trimethoxysilylpropyltrim above process to cause the coupling reaction of the glycidyl ethylammonium, trimethoxysilylpropyltriethylammonium, ester Component (D) and the at least one or more phenolic octadecyldimethyltrimethoxysilylpropylammonium, tet compounds Component (E). The catalyst, Component (F), radecyldimethyl(3-trimethoxysilylpropyl)ammonium and may be Selected from any of the catalysts generally known the like. as phase transfer catalysts. The phase transfer catalysts may be homogenous or heterogeneous. 0101 Examples of nitrogen-containing quaternary cat ionic centers having more than one cationic center useful for 0096. The catalysts useful for the coupling reaction of homogenous coupling catalysts of the present invention are, glycidyl esters and phenols of the present invention may be for example, hexamethylethylenediammonium, hexaethyl for example, the hydroxides of Group Ia (new IUPAC ethylenedia monium, hexamethylpropylenediammonium, periodic table notation) alkali metals, such as Na', K" or hexaethylpropylenediammonium and the like. Cs"; or of Group 11a alkaline earth metals, Such as Mg or 0102) Examples of phosphorous-containing quaternary Ca"; or of Group 11b metals, such as Zn", or of Group IIIa cationic centerS having only a single cationic center useful metals, such as Al". Examples of the catalyst include for homogenous coupling catalysts of the present invention Sodium hydroxide and potassium hydroxide. are tetramethylphosphonium, tetraethylphosphonium, tetra 0097 Also, the catalysts useful in the present invention propylphosphonium, tetraiSopropylphosphonium, tetrabu may be, for example, the inorganic or organic acid Salts of tylphosphonium, tetraisobutylphosphonium, tetrahep Group Ia alkali metals, such as Na', K" or Cs"; or of Group tylphosphonium, tetraphenylphosphonium, US 2002/0045707 A1 Apr. 18, 2002 benzyltrimethylphosphonium, benzyltriethylphosphonium, Zeolite, having hydroxyl or hydroxyl-equivalent functional ethyltriphenylphosphonium, ethyltritolylphosphonium, groups, Such as methoxy, ethoxy, isopropoxy and tert cyclohexyltriphenylphosphonium, 2-chloroethyltriph butoxy, then a Sol-gel, Silicate or Zeolite having multi enylphosphonium, butyltriphenylphosphonium, tetraben quaternary ammonium or quaternary phosphonium cationic Zylphosphonium, allyltrimethylphosphonium, allyltriph centerS is formed. In Such instances, the quaternary cationic enylphosphonium, centers are anchored or tethered to the Sol-gel, Silicate or trimethylsilylethoxyethyltriphenylphosphonium and the Zeolite. like. Examples of Such phosphonium phenolic-epoxy cou 0107 The silicate and zeolite solid support materials pling catalysts are disclosed in U.S. Pat. Nos. 4,808,692; useful in the present invention are, for example, those with 4,755,542 and 4,632,971; and in European Patent Applica micro-crystalline Structure having high Surface area or those tion 360195 A2, all of which are incorporated herein by having a pore Structure with pore size larger than Standard reference. molecular Sieves Such as a 4A type. The Silicates and Zeolites 0103) The homogenous catalysts useful for the coupling having large pore size are for example, TS-1, TS-2, ZSM-5, reaction of the present invention may include any combi ZSM-11, ZSM-12, ZSM-22, AZM-48, AIPO4-5, AIPO4-11, nation of the nitrogen-containing quaternary cationic cen Zeolite X, Zeolite Y, Linde type L, VPI-5, NCL-1, MCM-41 ters, any combination of the phosphorous-containing qua and MCM-48. ternary cationic centers or any combination of the nitrogen 0108. The amount of catalyst, Component (F), useful in containing quaternary cationic centers and the phosphorous the above process for making the C-hydroxy ester deriva containing quaternary cationic centerS described above. tives of the present invention is from about 0.001% to about 0104. The active moiety of coupling catalysts may be part 1000% by weight based on the amount of the phenol or of an organic, inorganic or hybrid organic-inorganic oligo mixture of phenols used in the reaction. When the catalyst is meric or polymeric Structure. a homogeneous catalyst, the amount of catalyst useful in the above process for making the C-hydroxy ester derivatives of 0105. When an organic, inorganic or hybrid organic the present invention is preferably from about 0.001% to inorganic oligomeric or polymeric Structure contains more about 10% by weight based on the amount of the phenol or than one hydrocarbon Substituent containing 1-20 carbon mixture of phenols used in the reaction, more preferably atoms Selected from linear, branched or cyclic aliphatic or from about 0.001% to about 5% by weight based on the aromatic Substituents, with or without heteroatoms, Such as amount of the phenol or mixture of phenols used in the N, P, S, O and Si; or halide atoms, Such as F, Cl, Br and I, reaction and most preferably from about 0.001% to about or the combination thereof, and such hydrocarbon substitu 2% by weight based on the amount of the phenol or mixture ents are pendant to the oligomeric or polymeric backbone of phenols used in the reaction. and bound to a quaternary cationic center, the organic, inorganic or hybrid organic-inorganic oligomeric or poly 0109 When the catalyst is a heterogeneous catalyst, the meric Structure may be linked with more than one anionic amount of catalyst used in the above proceSS for making the counter ion. In this instance, the coupling catalysts are C-hydroxy ester derivatives of the present invention is anchored to the organic, inorganic, or hybrid organic-inor preferably from about 1% to about 50% by weight based on ganic polymeric Support to form a heterogeneous coupling the amount of the phenol or mixture of phenols used in the catalyst. An example of Such a quaternary, cationic center reaction, more preferably from about 1% to about 200% by containing hydrocarbon Substituent on a polymeric Support weight based on the amount of the phenol or mixture of phenols used in the reaction and most preferably from about is the benzyltrimethylammonium group formed when croSS 1% to about 1000% by weight based on the amount of the linked polystyrene is chloromethylated and then aminated phenol or mixture of phenols used in the reaction. Larger with trimethyl amine. Another example of a hydrocarbon amounts of heterogeneous catalyst than amounts of homo Substituent bound to a quaternary cationic center and pen geneous catalyst can be used because the Solid-phase het dant to a polymeric backbone is the benzyltrimethylammo erogeneous catalysts are easily recovered by decantation or nium group formed when croSS-linked polyvinylbenzylchlo filtration; or the heterogeneous catalyst is contained in a ride is aminated with trimethyl amine. reactor while reactants and Solvent flow over the catalyst. 0106 When trimethoxysilyl- or triethoxysilyl-containing 0110. In general, the amount of reactant glycidyl ester, cationic centerS Such as for example trimethoxysilylpropy Component (D), useful in the present invention may be in a ltributylammonium, triethoxysilylpropyltributylammonium, ratio of from about 0.5 equivalents to about 50 equivalents trimethoxysilylpropyltrimethylammonium, trimethoxysilyl of glycidyl ester per one equivalent of phenolic hydroxyl. A propyltriethylammonium, trimethoxysilylpropyloctade more preferred ratio of glycidyl ester to phenolic hydroxyl cyldimethylammonium, tetradecyldimethyltrimethoxy useful in the present invention is from about 0.75 equiva Sillylpropylammonium, lents to about 20 equivalents of glycidyl ester per one trimethylsilylethoxyethyltriphenylphosphonium, and the equivalent of phenolic hydroxyl. The most preferred ratio of like and any mixture thereof are condensed with a monosi glycidyl ester to phenolic hydroxyl useful in the present lane, Such as dimethyldiethoxysilane, diethydiethoxysilane, invention is from about 0.9 equivalents to about 10 equiva methyltriethoxysilane, ethyltriethoxysilane, tetraiSopropoxy lents of glycidyl ester per one equivalent phenolic hydroxyl. Silane, tetraethoxy Silane and the like, and any mixture thereof, or condensed with a linear, cyclic, branched or 0111 The solvent, Component (G), useful in the present ladder-type Siloxane having hydroxyl or hydroxyl-equiva invention may be the same as the Solvent, Component (C), lent functional groups, Such as methoxy, ethoxy, isopropoxy in addition, the Solvent may include water and the glycidyl and tert-butoxy, or condensed with a three-dimensional ester, Component (D). When the amount of glycidyl ester Silsesquioxane, precondensed siloxane Sol-gel, a Silicate or a reacted with the phenolic compound(s) in a coupling reac US 2002/0045707 A1 Apr. 18, 2002

tion is in excess, for example, when the amount of reactant 85%. The overall conversion of phenolic hydroxyl to C-hy glycidyl ester used in the present invention is about 1.25 or droxy ester derivative can be controlled by the reaction greater equivalents per equivalent of phenolic hydroxyl, temperature, reaction time, the amount of glycidyl ester used then the amount of excess glycidyl ester may act as a as reactant and by the type and amount of the catalyst used. Solvent. 0119 When unreacted phenolic hydroxyl groups remain 0112 Preferably, solvent, Component (G), useful in the after the coupling reaction between glycidyl ester and a present invention includes, for example, protic Solvents that phenol or a mixture of phenols, the phenolic hydroxyl are Secondary or tertiary alcoholic Solvents Such as isopropyl groups may further react via two different reactions during alcohol, 2-butanol, tert-butanol, tert-amyl alcohol and the overall process of the present invention. In a first 1-methoxy-2-hydroxypropane; partially or fully fluorinated reaction, the unreacted phenolic hydroxyl groups may con derivatives thereof, and any combination thereof. tinue to react with glycidyl ester to make C-hydroxy ester during the recovery of the glycidyl ester. This first reaction 0113. The above preferred solvents, Component (G), may may occur after the coupling reaction in the Overall process be used in combination with water, aliphatic and cyclic of the present invention when the coupling reaction product hydrocarbons, aromatic hydrocarbons, chlorinated Solvents, is Subjected to elevated temperatures required to recover non-polar aprotic Solvents or any combination thereof. excess glycidyl ester as described below. 0114. When water is used in combination with other 0120 Additionally, in a second reaction, the unreacted Solvents, the ratio of Solvent or mixture of Solvents to water phenolic hydroxyl groups may react with epoxy resins is generally about 1 part (on a weight basis) Solvent to 1 part during the epoxidation Stage of the overall process of the water. Preferably, the ratio of solvent to water is from about present invention to make epoxy resins. When the unreacted 1 to about 100 parts solvent per 1 part water. Most prefer phenolic hydroxyl groups react with the epoxy resins in this ably, the ratio of solvent to water is from about 1 to about manner, the molecular weight of the epoxy resin increases, 500 parts solvent per 1 part water. and therefore, the epoxy equivalent weight (EEW) of the 0115) In general, the amount of solvent, Component (G), epoxy resin decreases. In Some instances, it may be desirable used in the present invention may be a ratio of from about to control the EEW of the epoxy resin by the above reaction 0 to about 50 parts (on a weight basis) of a single solvent or of unreacted phenolic hydroxyl groups and epoxy resins. a mixture of two or more Solvents per 1 part phenol or 0121. In the coupling reaction, it is additionally desired mixture of phenols used in the reaction. A more preferred that the Self-polymerization of the glycidyl ester, Compo ratio of solvent to phenol or mixture of phenols is from about nent (D), Such as glycidyl acetate, is limited to a minimum 0 to about 10 parts solvent per 1 part phenol or mixture of amount So yields of the C-hydroxy ester derivative may be phenols used in the reaction. The most preferred ratio of maximized. The Self-polymerization of glycidyl esters solvent to phenol or mixture of phenols is from about 0 to occurs when the epoxide groups on different molecules of about 5 parts Solvent per 1 part phenol or mixture of phenols the glycidyl ester react with one another to form a polyol used in the reaction. having carboxylic acid ester moieties pendant to the polyol 0116. The temperature useful in the above process for backbone. making the C-hydroxy ester derivatives by reacting a phe nolic compound or a mixture of two or more phenolic 0122) When the catalyst used in the above process for compounds with a glycidyl ester is generally from about 10 making the C-hydroxy ester derivative of the present inven C. to about 160° C., preferably from about 25° C. to about tion is a homogeneous catalyst, the reaction may be carried 135° C. and most preferably from about 50° C. to about 110° out using equipment well known in the art Such as a batch C. At a temperature lower than 10 C., the coupling reaction reactor, a continuous Stirred tank reactor or a continuous of the phenolic compound with the glycidyl ester is not reactOr. complete. At a temperature greater than 160 C., the cou 0123. When the catalyst used in the above process for pling reaction of phenolic compound and glycidyl ester is making the C-hydroxy ester derivatives of the present inven not selective for the C-hydroxy ester derivative, and the tion is a heterogeneous catalyst, the reaction may be carried decomposition of glycidyl ester can occur through Several out using equipment well known in the art Such as a batch pathways leading to lower yields of desired C-hydroxy ester reactor, a continuous Stirred tank reactor or a fixed-bed or derivative. fluidized-bed continuous reactor. 0117 The pressure useful in the above process for mak 0.124. In the above process for making the C-hydroxy ing the C-hydroxy ester derivative may be atmospheric, ester derivatives of the present invention, the reaction prod Subatmospheric or Superatmospheric. The pressure is not uct from the reactors described above may be further pro critical and may be determined by various parameterS Such cessed by techniques well know to those skilled in the art. as reaction temperature, type of Solvent used or the Solvent azeotrope boiling points. 0.125. In one preferred embodiment of the present inven tion, the Solvent if optionally used has a boiling point either 0118. In the coupling reaction, it is desired that the lower or higher than the boiling point of the glycidyl ester. conversion of phenolic hydroxyl of a phenol or mixture of In this preferred embodiment, the C-hydroxy ester reaction phenols to the C-hydroxy ester derivative is greater than product may be washed with water to remove homogeneous 50%. It is more preferred that the conversion of phenolic coupling catalyst(s). The washed C-hydroxy ester reaction hydroxyl of a phenol or mixture of phenols to the C-hydroxy product may be distilled under atmospheric, Subatmospheric ester derivative is greater than 65%. It is most preferred that or Superatmospheric conditions to recover Solvent(s) if the conversion of phenolic hydroxyl of a phenol or mixture optionally used and to recover unreacted, excess glycidyl of phenols to the C-hydroxy ester derivative is greater than ester. The Solvent(s) and glycidyl ester recovered may be US 2002/0045707 A1 Apr. 18, 2002 recycled directly to the coupling reactor; or the Solvent(s) when the C-hydroxy ester derivative is a Single component, and glycidyl ester recovered may be additionally purified the Single component is a compound containing an O-hy before being recycled to the coupling reactor. The C-hy droxy ester moiety. For example, when the C-hydroxy ester droxy ester derivative isolated by this proceSS may be used derivative is two or more components, one of the compo with or without additional purification. The processing Steps nents which make up the C-hydroxy ester derivative must be described above may be carried out in any order to effi a compound which contains at least one O-hydroxy ester ciently separate the coupling catalyst(s), Solvent and gly moiety, with or without other moieties, and the other com cidyl ester from each other. ponent(s) may be selected from a compound containing at 0126. In a second preferred embodiment of the present least one C-diester moiety and a compound containing at invention, the Solvent, if optionally used, is Selected to have least one O-glycol moiety. It is contemplated that one of the a higher boiling point than the boiling point of the glycidyl components that make up the C-hydroxy ester derivative ester. In this embodiment, the C-hydroxy ester reaction may include a compound which contains a mixture of two or product may be washed with water to remove homogeneous more moieties Selected from an O-hydroxy ester moiety, an coupling catalyst. The washed C-hydroxy ester reaction C-diester moiety and an O-glycol moiety. product may be distilled under atmospheric, Subatmospheric 0129. As one embodiment of the present invention, phe or Superatmospheric conditions to recover excess, unreacted nol is reacted with glycidyl acetate, to form an O-hydroxy glycidyl ester which may be recycled directly to the cou ester derivative which is a mixture comprising an O-hydroxy pling reactor or which may be additionally purified before acetate compound as the major component; and an O-diac being recycled to the coupling reactor. In this embodiment, etate compound and an O-glycol compound as the minor the Solvent which has a higher boiling point than the glycidyl components of the C-hydroxy ester derivative. It is theorized ester is not removed by distillation and the mixture of that during the coupling reaction a Series of transesterifica solvent and C-hydroxy ester is directly carried forward to the tion reactions may occur in which the C-hydroxy acetate halide Substitution-deesterification Step of the present inven compound is converted into a mixture including an O-diac tion. etate and an O-glycol compound. 0127. In the process of the present invention, the cou 0.130. As described above, the O.-hydroxy ester derivative pling of an active hydrogen-containing compound, Such as of the present invention may comprise a single component a phenol, and a glycidyl ester, Such as glycidyl acetate, easily or a mixture of two or more components. Generally, the takes place to make the C-hydroxy ester derivative. The C-hydroxy ester derivative of the present invention contains reaction Selectivity to the desired C-hydroxy ester derivative C-hydroxy ester moieties, C-diester moieties and O-glycol is maximized under the set of conditions that optimize moieties in a ratio of 5-100 percent:0-95 percent:0-95 per catalyst, Solvent and temperature. Maximum Selectivity to cent, respectively; preferably in a ratio of 15-100 percent:0- the desired C-hydroxy ester derivative is obtained when the 85 percent:0-85 percent, respectively; and more preferably phenolic reactant attacks the glycidyl ester at the terminal in a ratio of 30-100 percent:0-70 percent:0-70 percent, methylene (-CH-) group of the epoxide moiety. When respectively. the phenolic reactant attacks the glycidyl ester at the internal 0131 The following reaction sequence, Reaction methine (-CH=) group of the epoxide moiety, a C-hy Sequence (VI), generally illustrates the reaction of coupling droxy ester derivative is formed. Such a C-hydroxy ester phenol and glycidyl acetate and the Sequential transesteri derivative can not be converted to the desired C-chlorohy fication reactions. More Specifically, Reaction Sequence drin intermediate of the present invention. (VI) shows the coupling reaction between phenol and gly 0128 Under the conditions of the coupling reaction, the cidyl acetate yielding the C-hydroxy ester derivative of the C-hydroxy ester derivative may comprise a Single compo present invention comprising an O-hydroxyacetate, an O-di nent or a mixture of two or more components. For example, acetate and an O-glycol.

Reaction Sequence (VI)

catalyst OH -- D1NoA. He O solvent glycidyl OH phenol acetate C-hydroxyacetate

ester exchange reactions

(O)-irraOH (O)-rro.OH (O)-rro.OAc C-glycol C-hydroxyacetate C-diacetate US 2002/0045707 A1 Apr. 18, 2002

0132) The C-hydroxy ester derivative of the present 0136 wherein w may be 1 to 6. invention formed when the phenolic reactant reacts with a glycidyl ester may be a reactant in Sequential reactions other Phenolic Compounds than transesterification reactions. In two other of the Sequen tial reactions of the C-hydroxy ester derivative, the C-hy 0137 The phenolic compounds, Component (E), useful droxy ester component of the derivative reacts with more in the above process for making the C-hydroxy ester deriva glycidyl ester. In one of the two other reactions, the hydroxy tives, are represented by, but not limited to, the Structures of group of the C-hydroxy ester component reacts with the the following Formulas XI-XV. A preferred class of phenolic epoxide moiety of a glycidyl ester forming a product con compounds useful in the present invention to react with taining two glycidyl ester molecules. This reaction between the hydroxy group of the C-hydroxy ester component and glycidyl esters to make C-hydroxy ester derivatives is the glycidyl ester may be repeated forming a Second product generically represented by the following Formula XI: containing three glycidyl ester molecules. This reaction may (R), Ar(OH), Formula XI be repeated more than two times. 0133. The second of the other reactions is an ester 0138). In Formula XI, y, z, Ar and R, are as defined eXchange reaction of the glycidyl ester with the hydroxy previously for Formula I, and OH is a hydroxyl group group of the C-hydroxy ester component of the derivative Substituted for hydrogen atom on the aromatic ring(s) of the forming an O-diester and a glycidol derivative. Ar moiety. 0134. When the above sequential reactions of the C-hy 0.139 More specific and preferred examples of phenolic droxy ester derivative are minimized by optimizing catalyst, compounds useful in the present invention are represented Solvent and temperature, the glycidyl ester Selectivity to by Formulas XII-XV, separately or as mixtures of two or O-hydroxy ester derivative is greater than 65%. More pre more phenolic compounds of Formulas XII-XV which fol ferred, the glycidyl ester Selectivity to the desired C-hydroxy low. ester derivative is greater than 80%. Most preferred, the glycidyl ester Selectivity to the desired C-hydroxy ester 0140) Examples of mononuclear phenolic compounds derivative is greater than 95%. useful in the present invention are represented by the fol 0135 The following reaction sequence, Reaction lowing Formula XII: Sequence (VII), generally illustrates the two Sequential reactions described above of an O-hydroxy ester derivative and the glycidyl ester. The two Sequential reactions shown Formula XII are for the reaction of phenol and glycidyl acetate coupling product with glycidyl acetate. More Specifically, Reaction (R), Sequence (VII) shows Sequential reactions of the C-hydroxy acetate derivative of phenol and glycidyl acetate showing O (OH), Sequential hydroxy-epoxy coupling reaction and Sequential ester eXchange reaction.

Reaction Sequence (VII)

OAc

O O).wH

O OAc + glycidyl acetate

OH C-hydroxyacetate CS + glycidyl acetate-- (O)-rro. + glycidol ester exchange OAc C-diacetate US 2002/0045707 A1 Apr. 18, 2002

0141). In Formula XII, y, z and R have the same meaning as described above with reference to Formula II, and OH has the same meaning as described above with reference to Formula XV Formula XI. (R), 0142 Included among the compounds represented by Formula XII are, for example, 4-methylphenol, 4-methox O)--z yphenol; 2,6-dimethylphenol; 2,6-diisopropylphenol; 2,6- (HO), dibromophenol; 1,2-dihydroxybenzene; 1,3-dihydroxyben Zene, 1,4-dihydroxybenzene, and mixtures thereof. 0143. Other examples of phenolic compounds useful in 0150. In Formula XV, y, z, R, Z and m' have the same the present invention are binuclear phenolic compounds meaning as described above with reference to Formula V. which are represented by the following Formula XIII: and OH has the same meaning as described above with reference to Formula XI 0151. Included among the phenolic compounds repre Formula XIII sented by Formula XV are, for example, tris(4-hydroxyphe nyl)methane; Z. 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)methane; 1,1,2,2- (HO)(R),RO)- 2. -O.(OH), tetrakis(4-hydroxyphenyl)ethane; and mixtures thereof. 0152 The preferred phenolic compounds of the present 0144) In Formula XIII, y, z, R and Z have the same invention include more specifically, the phenols, Such as meaning as described above with reference to Formula III, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,5-dihy and OH has the same meaning as described above with droxynaphthalene; 2,6-dihydroxynaphthalene; 4,4'-dihy reference to Formula XI. droxybiphenyl; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphe 0145 Included among the phenolic compounds repre nyl, 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'- sented by Formula XIII are, for example, 4,4'-dihydroxybi dihydroxybiphenyl; bis(4-hydroxyphenyl)methane; 4,4'- phenyl; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl; 3,3',5, bis(2,6-dibromophenol)isopropylidene; 2,2-bis(4- 5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl; hydroxyphenyl)isopropylidene; phenol-formaldehyde bis(4-hydroxyphenyl)methane; bis(4-hydroxyphenyl)sul novolac (functionality >2); o-cresol-formaldehyde novolac fone, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)isopropy (functionality >2); phenol-dicyclopentadienyl novolac lidene, 2,2-bis(4-hydroxyphenyl)isopropylidene, bisphenol (functionality >2); naphthol-formaldehyde novolac (func K; 9.9-bis(4-hydroxyphenyl)fluorene; 4,4'-dihydroxy-O-me tionality >2); 1,1,1-tris(4-hydroxyphenyl)methane; 1,1,2,2- thylstilbene; 1,3-bis(4-hydroxylphenyl)adamantane; and tetrakis(4-hydroxyphenyl)ethane; and mixtures thereof. mixtures thereof. 0146). Other examples of phenolic compounds useful in Glycidyl Ester the present invention are multinuclear phenolic compounds 0153. The glycidyl ester, Component (D), useful in the which are represented by the following Formula XIV: above process for making the C-hydroxy ester derivatives, is a material known to those skilled in the art and is represented by the following Formula XVI: Formula XIV

(R), Formula XVI (R), (R), RCORS (HO), i. (OH), iO-(O-)-O.(OH), 0154) In Formula XVI, R is as defined previously for 0147 In Formula XIV, y, z, R, Z and m have the same Formula VI. meaning as described above with reference to Formula IV, O155 In F Ol la XVI., R is a glycidylglvcidvl moimoiety preferablyferabl and OH has the same meaning as described above with Selected from: reference to Formula XI. 0148 Included among the phenolic compounds repre sented by Formula XIV are, for example, phenol-formalde hyde novolac (functionality greater than 2); o-cresol-form /V R3 y-(R)s aldehyde novolac (functionality greater than 2); phenol -CRC-CR and dicyclopentadienyl novolac (functionality greater than 2); k naphthol-formaldehyde novolac (functionality greater than R3 OS R3 2); and mixtures thereof. 0149 Other examples of phenolic compounds useful in the present invention are multi-nuclear phenolic compounds 0156 where O is oxygen, and R is as defined previously which are represented by the following Formula XV: for Formula VI. US 2002/0045707 A1 Apr. 18, 2002

O157. In one embodiment, when R in Formula XVI Such process, carboxylic acids are esterified through reaction above is with epichlorohydrin (ECH) in the presence of base. Such a process for making glycidyl esters is described by R. Nair, et al., in Synth. Commun., 29, (15), pp. 2559-2566, (1999), O which is incorporated herein by reference. / M -CHC-CH 0.168. In another well-known process for making glycidyl H esters, carboxylic acid esters are transesterified with glycidol in the presence of catalysts. Such a transesterification pro cess is described by H. Zondler, et al., in Helv. Chim. Acta, 0158 the glycidyl ester is a “glycidyl ester.” 60, (6), pp. 1845-1860, (1977), which is incorporated herein by reference. 0159. Examples of glycidyl esters useful in the present invention are glycidyl formate, glycidyl acetate, glycidyl 0169. In yet another well-known process for making propionate, glycidylbutyrate, glycidyl cyclopentanoate, gly glycidyl esters, carboxylic acid halides are esterified through cidyl cyclohexanoate, glycidyl benzoate, glycidyl naphtha reaction with glycidol and a tertiary amine. Such general noate and mixtures thereof. esterification process is discussed by J. March, Advanced Organic Chemistry, Third Edition, pp. 346-347, John Wiley 0160. In another embodiment, when R in Formula XVI & Sons, New York, (1985), which is incorporated herein by above is reference. 0170 In one preferred embodiment, glycidyl esters are O prepared by epoxidizing (H) an allyl ester by any of Several / V well-know epoxidation reaction processes, Such as for -CHC-CH example by reacting the allyl ester, Component (H), with (I) CH an oxidant material. 0171 Glycidyl esters, in general, and glycidyl acetate, in particular, can be prepared by epoxidizing the corresponding 0.161 the glycidyl ester is a “methylglycidyl ester.” allyl ester using a number of oxidants. The oxidant, Com 0162 Examples of methylglycidyl esters useful in the ponent (I), useful in the above process may be, for example, present invention are methylglycidyl formate, methylgly aromatic and aliphatic organic peracids, organic peroxyim cidyl acetate, methylglycidyl propionate, methylglycidyl idic acids, dioxiranes and hypochlorous acid. Glycidyl butyrate, methylglycidyl cyclopentanoate, methylglycidyl esters, in general, and glycidyl acetate, in particular, can also cyclohexanoate, methylglycidyl benzoate, methylglycidyl be prepared by epoxidizing the corresponding allyl ester by naphthanoate and mixtures thereof. catalytic epoxidation using air (oxygen), 0163) In yet another embodiment, when R in Formula and organic hydroperoxides as oxidants. XVI above is 0172 In one embodiment of the present invention, pro ceSSes which use aromatic peracids Such as, for example, m-chloroperbenzoic acid, described by A. Garcia Martinez, HH M. Oliver Ruiz, and J. L. M. Contelles in Synthesis, 1, pp. 125-128, (1986), which is incorporated herein by reference; peroxybenzoic acid, described by Moffett and Slomp in J. Amer: Chem. Soc., 76, pp. 3678-3681, (1954), which is incorporated herein by reference; and monoperoxyphthalic acid, described by Bohlmann and Sinn in Chem. Ber, 88, pp. 1869-1876, (1955), which is incorporated herein by refer ence, may be used to effect epoxidation of allyl esters in excellent yields. 0164) the glycidyl ester is a “cyclohexylglycidyl ester.” 0.173) In another embodiment of the present invention, 01.65 Examples of cyclohexylglycidyl esters useful in processes which use aliphatic peracids, Such as, for example, the present invention are cyclohexylglycidyl formate, cyclo peracetic acid (also known as peroxyacetic acid) are also hexylglycidyl acetate, cyclohexylglycidyl propionate, very effective oxidants for Synthesizing glycidyl esters from cyclohexylglycidyl butyrate, cyclohexylglycidyl cyclopen allyl esters and are described, for example, in U.S. Pat. No. tanoate, cyclohexylglycidyl cyclohexanoate, cyclohexylgly 2,761,870, which is incorporated herein by reference. This cidyl benzoate, cyclohexylglycidyl naphthanoate and mix type of oxidant can also be generated in Situ by reaction of tures thereof. air (oxygen) with the corresponding aliphatic aldehyde, as 0166 The glycidyl esters most useful in the present described in U.S. Pat. No. 4,721,798, which is incorporated invention are glycidyl formate, glycidyl acetate, methylgly herein by reference. cidyl formate and methylglycidyl acetate. The most pre ferred glycidyl ester for use in the present invention is 0.174. In another embodiment of the present invention, glycidyl acetate. processes which use peroxyimidic acids, Such as the one described by R. Murry in J. Org. Chem, 63, pp. 1730-1731, 0167. The glycidyl esters of Formula XVI above can be (1998), which is incorporated herein by reference, are useful prepared by any of Several well-known processes. In one in the Synthesis of glycidyl esters from allyl esters. US 2002/0045707 A1 Apr. 18, 2002

0.175. In another embodiment of the present invention, titanium alkoxides, as described by H. Hoshi, T. Ohnuma, S. organic dioxiranes may also effect the epoxidation of allyl Aburaki, M. Konishi, and T. Oki in Tetrahedron Lett., 34, pp. esters to glycidyl esters. Dimethyldioxaranes are described, 1047-1050, (1993); and vanadium oxide complexes, as for example, by R. Murry in Chem. Rey, 89, pp. 1187-120, described by H. H. A. M. Hassan and C. Tamm in Helv. (1989), which is incorporated herein by reference. Perfluo rodimethyldioxaranes from a perfluoroketone and hydrogen Chim. Acta, 77, pp. 838-849, (1994); all of which are peroxide are described, for example, by R. Sheldon in Chem. incorporated herein by reference. Commun., pp. 263-264, (1999), which is incorporated herein 0181 Metal oxides known to epoxidize allyl esters by reference. include those based on ruthenium, as described by H. 0176). In still another embodiment of the present inven Ohtake, T. Higuchi, and M. Hirobe in Tetrahedron Lett., 33, tion, hypochlorous acid, optionally as its alkali metal Salt, pp. 2521-2524, (1992); chromium, as described by F. Bohl and an inorganic base, Such as Sodium hydroxide, Sodium mann, J. Jakupovic, H. Robinson, and R. M King in Phy carbonate, potassium hydroxide, potassium carbonate or tochemistry, pp. 109-112, (1981); and platinum, as described calcium hydroxide, may be used to give high yields of allyl ester epoxidation products, as described by A. Foucaud and by T. Nakashima, T. Ueno, and H. Fukami in Tetrahedron E. de Rouille in Synthesis, 9, pp. 787-789, (1990) which is Lett., 23, pp. 4469-4472, (1982); all of which are incorpo incorporated herein by reference. rated herein by reference. 0177. In yet another embodiment of the present inven 0182 The allyl ester, Component (H), used in the above tion, processes which use catalysts and air (oxygen) as process for making the glycidyl esters, is a common material oxidant can be used to make glycidyl esters from allyl esters. known to those skilled in the art and is represented by the Examples of Such catalysts include Silver or gold on titanium following Formula XVII: silicate supports, as described in WO 9952883, WO 9900188 and WO 9800415; and Pt(III) halide catalysts, as described in U.S. Pat. No. 5,670,674; all of which are Formula XVII incorporated herein by reference. 0178. In another embodiment of the present invention, RCOR6 processes which use catalysts and hydrogen peroxide or organic hydroperoxides as Oxidant may be reacted with allyl esters to form glycidyl esters as described in WO99/62894, which is incorporated herein by reference. More Specifically, 0183) In Formula XVII, R" is as defined previously for glycidyl esters may be made from allyl esters in the presence Formula VI. of titanium-containing Zeolites, as described, for example, in 0184. In Formula XVII, R is an allyl moiety preferably U.S. Pat. Nos. 5,684,170 and 5,466,835; in the presence Selected from: tungsten oxides, as described by Y. Fort, A. Olszewski-Ortar, and P. Caubere in Tetrahedron, 48, pp. 5099-5110, (1992); in the presence of rhenium salts as described in WO 9833786; and in the presence of manganese salts, as R3 31 (R), described by D. E. De Vos, B. F. Sels, M. Reynaers, Y. V. S. -CRC=CR and Rao, and P. A. Jacobs in Tetrahedron Lett., 39, pp. 3221 3224, (1998); all of which are incorporated herein by R3 R3 reference. 0179 Hydrogen peroxide can also be used in conjunction with organic and organometallic co-reagents, Such as 0185 where R is as defined previously for Formula VI. ketones, as described in EP 129,814 and DE 3,323,329; anhydrides, as described in U.S. Pat. No. 4,590,286; and aryl 0186. In one embodiment, when R in Formula XVII Selenium compounds, as described in JP 59,076.077 aryl above is the following Structures: diselenides in which the aryl groups are Substituted with electron withdrawing groupS. Such as, for example, perfluo romethyl, fluoro, chloro and nitro and described by R. A. Sheldon, et al., in J. Chem. Soc., Perkin Trans., 1, pp. 224-228, (2001); all of which are incorporated herein by reference. 0180. In another embodiment of the present invention, 0187 the allyl ester is an “allyl ester.” glycidyl esters may be made by processes which use cata lysts and organic hydroperoxides as oxidants to epoxidize 0188 The allyl esters useful in the present invention, allyl esters. Glycidyl esters may be made from allyl esters in include for example, but are not limited to, allyl formate, the presence of organic hydroperoxides and various cata allyl acetate, allyl propionate, allylbutyrate, allyl cyclopen lysts, Such as, for example, certain binary borides, as tanoate, allyl cyclohexanoate, allyl benzoate and allyl naph described in U.S. Pat. Nos. 4,215,061; 4,215,060; and 4,215, thanoate. 059; and British Patent GB 1517,908; titanium silicates, as described in U.S. Pat. No. 5,780,654; Vanadium-porphyrin 0189 In another embodiment, when R in Formula XVII complexes, as described in Japanese Patent JP 60,190,774; above is the following structure: US 2002/0045707 A1 Apr. 18, 2002

MO N R3 X ( R3)6 CH -CRC-CRk and 0.190 carboxylic acids or carboxylic acid anhydrides are R3 C. R3 esterified through reaction with or substituted allyl alcohols. Such esterification methods are described by G. Mallavarapu, et al., in Indian J. Chem., Sec. B, (16 B), pp. 0199 where R is as defined previously for Formula I. 725-726, (1978) and in German Patents DE 2,504.231 and 0200. In one embodiment, when R'" in Formula XVIII 2,504.230; all of which are incorporated herein by reference. above has the following structure: 0191 In another well-known process for making allyl esters, carboxylic acid esters are transesterified with allyl alcohol or Substituted allyl alcohols in the presence of O catalysts. Such a transesterification process is described in / M U.S. Pat. No. 4,112,235, which is incorporated herein by -CHC-CH reference. H 0.192 In yet another well-known process for making allyl esters, carboxylic acid Salts are reacted with allyl halides, for 0201 the glycidyl ether is a “glycidyl ether.” instance allyl chloride or allyl bromide, or substituted allyl halides. Such esterification processes are described in Japan 0202) In Formula XVIII, R" is a glycidyl-containing Patents.JP53108914 and 43027849; and by T. Kawaki, et al. moiety preferably selected from: in Bull. Chem. Soc. Jap., 45, (10), pp. 3130-3132, (1972); all of which are incorporated herein by reference. 0193 In yet another process for making allyl esters, allyl /V R3 y-(R)s alcohols or substituted allyl alcohols are reacted with alde -CRC-CR and hydes and oxygen in the presence of catalysts. Such an R3 esterification process is described by French Patent FR 1563259, which is incorporated herein by reference. R3 CS R3 0194 Allyl esters in general, and allyl acetate in particu lar, can be preferably prepared by the oxidative carboxyla 0203 where R is as defined previously for Formula I. tion of propylene or a propylene derivative. The allyl ester most useful in the present invention is allyl acetate and allyl 0204. In one embodiment, when R" in Formula XVIII acetate may be made, for example, by or other above has the following structure: transition metal catalyzed oxidative acetoxylation of pro pene with acetic acid, such as described in U.S. Pat. Nos. O 3,970,713; 4,647,690; and 5,011,980; all of which are incor / M porated herein by reference. o CHC o CH2

0.195 Another allyl ester useful in the present invention H is methallyl acetate which may be synthesized from isobu tylene using a process Similar to that for allyl acetate Such as described in German Patents DE 1,964,085 and DE 2,057, 087 and in Japanese patents JP 53,127,409 and JP 57,131, 0205) the glycidyl ether is a “glycidyl ether.” 741; all of which are incorporated herein by reference. 0206. In another embodiment, when R'" in Formula XVIII above has the following structure: Epoxy Compounds

0196. The aryl glycidyl ether epoxy compounds that are O made by the process of the present invention are represented / M by, but not limited to, the structures of the following -CHC-CH Formulas XVIII-XXII: CH (R), Ar(OR"), Formula XVIII 0197) In Formula XVIII, y, z, Ar., O and Rare as defined previously for Formula I. 0207 the glycidyl ether is a “methylglycidyl ether.” 0198 In Formula XVIII, R'" is a glycidyl-containing 0208. In yet another embodiment, when R'" in Formula moiety preferably selected from: XVIII above has the following structure: US 2002/0045707 A1 Apr. 18, 2002 18

invention include for example 1,3-dihydroxybenzene digly cidyl ether; 1,3-dihydroxybenzene dimethylglycidyl ether; HH 1,4-dihydroxybenzene diglycidyl ether; 1,4-dihydroxyben Zene dimethylglycidyl ether, 1.5-naphthalene diglycidyl ether; 1,5-naphthalene dimethylglycidyl ether; 2,6-naphtha lene diglycidyl ether; 2,6-naphthalene dimethylglycidyl ether; 4,4'-dihydroxybiphenyl diglycidyl ether; 4,4'-dihy droxybiphenyl dimethylglycidyl ether; 3,3',5,5'-tetramethyl 4,4'-dihydroxybiphenyl diglycidyl ether; 3,3',5,5'-tetram ethyl-4,4'-dihydroxybiphenyl dimethylglycidyl ether; 3,3',5, 5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl 0209) the glycidyl ether is a “cyclohexylglycidyl ether.” diglycidyl ether; 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4, 0210 More specific and preferred examples of epoxy 4'-dihydroxybiphenyl dimethylglycidyl ether; bis(4-hydrox resins that may be prepared according to the present inven yphenyl)methane diglycidyl ether; tion are represented by Formulas XIX-XXII which follow. bis(4-hydroxyphenyl)methane dimethylglycidyl ether; 2,2- bis(4-hydroxyphenyl) isopropylidene diglycidyl ether; 0211 Examples of mononuclear aryl glycidyl ether 2,2-bis(4-hydroxyphenyl)isopropylidene dimethylglycidyl epoxy resins that may be prepared according to the present ether; phenol-formaldehyde novolac glycidyl ether (func invention are represented by the following Formula XIX: tionality greater than 2); phenol-formaldehyde novolac methylglycidyl ether (functionality greater than 2); o-cresol formaldehyde novolac glycidyl ether (functionality greater Formula XIX than 2); o-cresol-formaldehyde novolac methylglycidyl (R), ether (functionality greater than 2); phenol-dicyclopentadi enyl novolac glycidyl ether (functionality greater than 2); (O. (OR), phenol-dicyclopentadienyl novolac methylglycidyl ether (functionality greater than 2), naphthol-formaldehyde novolac glycidyl ether (functionality greater than 2), naph 0212) In Formula XIX, y, z, O and R have the same thol-formaldehyde for example, Such as the same phase meaning as described above with reference to Formula II. In transfer catalysts described previously. The epoxidation pro Formula XIX, R" has the same meaning as described above cedures may be carried out as a batch reaction wherein the with reference to Formula XVIII. Mononuclear phenols base may be added in one part initially, added intermittently useful as precursors for preparing the above mononuclear or added continuously. The epoxidation procedure may also aryl glycidyl ether epoxy resins of the present invention are, be carried out as a continuous reaction wherein the C-halo for example, 2-methylphenol, 4-methylphenol, 4-methoX hydrin intermediate, the base, the Solvent and optionally the yphenol; 2,6-dimethylphenol; 2,6-diisopropylphenol; 2,6- phase transfer catalyst are added Simultaneously and con dibromophenol; 1,2-dihydroxybenzene; 1,3-dihyroxyben tinuously to a reactor. When the epoxidation procedure is Zene, 1,4-dihydroxybenzene, and mixtures thereof. carried out as a continuous reaction, the reactor may be a 0213 Other examples of aryl glycidyl ethers prepared by Single, one-stage reactor or the reactor may be a complex the process of the present invention are the dinuclear aryl reactor having multiple Stages. Such epoxidation proce glycidyl ether epoxy resins that are represented by the dures, including post-treatment procedures for achieving low chlorine epoxy resins for electronic applications, are following Formula XX: generally taught in U.S. Pat. Nos. 4,499.255; 4,778,863; 4,785,061; and 5,028,686; all of which are incorporated Formula XX herein by reference. (R), (R), 0217. With reference back to the C-hydroxy ester deriva tive of at least one or more phenols, Component (A) above, the C-hydroxy ester derivative is preferably prepared using (RO), O)--(O. (OR), a three-step process which includes: (1) manufacturing an allyl ester or a substituted allyl ester, Component (H); (2) manufacturing a glycidyl ester or a Substituted glycidyl 0214) In Formula XX, y, z, Z, O and R have the same ester, Component (D), from the allyl ester of Step (1); and meaning as described above with reference to Formula III. (3) coupling at least one or more phenols, Component (E), In Formula XX, R'" has the same meaning as described with the glycidyl ester or a Substituted glycidyl ester of Step above with reference to Formula XVIII. (2) to manufacture the O.-hydroxy ester derivative of at least 0215 Phenols useful for making the epoxy resins of one or more phenols, Component (A). Formula XX include, for example, 4,4'-dihydroxybiphenyl; 0218. When the C-hydroxy ester derivative, Component 3,3',5,5-tetramethyl-4,4'-dihydroxybiphenyl; 3.31.5,5'-tet (A), is prepared by the above three-step process and Such ramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl; three-Step proceSS is combined with the above-described bis(4-hydroxyphenyl)methane; bis(4-hydroxyphenyl)sul process for preparing an O-halohydrin intermediate from the fone, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)isopropy C-hydroxy ester derivative and with a proceSS for making an lidene, 2,2-bis(4-hydroxyphenyl)isopropylidene, bisphenol epoxy resin from the C-halohydrin, generally, the process of K; 9.9-bis(4-hydroxyphenyl)fluorene; 4,4'-dihydroxy-C.- the present invention for making phenol-based epoxy resins 0216 Examples of preferred aryl glycidyl ethers and aryl may be illustrated by the following five-step process which methylglycidyl ethers made by the process of the present is one embodiment of the present invention: US 2002/0045707 A1 Apr. 18, 2002 19

0219 Step 1: Oxidatively carboxylating a propylene or a 0223 Step 5: Epoxidizing the C-halohydrin intermediate propylene derivative to manufacture an allyl ester or a of Step 4 by a ring-closure proceSS using a base to convert substituted allyl ester; the C-halohydrin intermediate of Step 4 to a phenol-based epoxy resin. 0220 Step 2: Epoxidizing the allyl ester or a substituted allyl ester of Step 1 to manufacture a glycidyl ester or a 0224. In one embodiment of the present invention, the Substituted glycidyl ester; above five-step process may be more specifically illustrated by the following general reaction Sequence, Reaction 0221) Step 3: Reacting at least one or more phenols with Sequence (VIII), showing the manufacture of bisphenol A a glycidyl ester or a Substituted glycidyl ester of Step 2 in the epoxy resin from propylene. More specifically, Reaction presence of Selected catalysts where the reaction is the Sequence (VIII) shows the conversion of propylene to coupling reaction of at least one or more phenols with the bisphenol A epoxy resin via the conversion of a bis(O- epoxide functionality of the glycidyl group of a glycidyl hydroxy acetate) derivative to a bis(O-chlorohydrin) inter ester or a Substituted glycidyl ester to manufacture an mediate.

Reaction Sequence (VIII) Step 1 catalyst n-CH3 - HOAc --- S1\ OAc allyl ester

Step 2 epoxidation S-1No. He OAc O allyl ester glycidyl ester Step 3 CH coupling O OAc + bis A - He- i-y-cu-o o-cu-ti-ji, glycidyl ester AcO OH CH OH OAC bis-(C-hydroxy ester) Step 4 CH bis-(o-hydroxy ester) + HCI halide substitution

tie-i-in-ch-o-O-H-O-o-c-Cl OH CH OH Cl bis-(o-chlorohydrin) Step 5

O CH epoxidation / V bis-(o-chlorohydrin) + base --> HC-HC-CH-O -(O)--O-o-o-o/AO-CH-CH-CH CH bisglycidyl ether (bis A epoxy resin)

C-hydroxy ester derivative comprised predominately of an 0225. The above Reaction Sequence (VIII) shows only C-hydroxy ester component of at least one or more phenols, the major component, the bisphenol A bis(O-hydroxy 0222 Step 4: In situ halide substituting-deesterifying the acetate), of the bis(O-hydroxy ester) derivative, that is made C-hydroxy ester derivative comprised predominately of an in Step 3. Other minor components may be prepared during C-hydroxy ester component of at least one or more phenols the Reaction Sequence (VIII). Included among the minor of Step 3 to manufacture an O.-halohydrin intermediate of the components which comprise the bis(O-hydroxy acetate) present invention; and derivative reaction product of Step 3 may be, for example, US 2002/0045707 A1 Apr. 18, 2002 20 phenolic compounds having C-diacetate and C-glycol moi a short path distillation apparatus, and 10g of pure glycidyl eties, Such as bisphenol A bis(C-diacetate) and bisphenol A acetate was collected upon distillation at 90° C. to 100° C. bis(O-glycol), respectively. Also included among the minor at less than 15 mmHg. components comprising the bis(O-hydroxy acetate) deriva 0232 Experiment A2 tive reaction product of Step 3 may be, for example, bisphe 0233. In this part of Example 1, a 250-mL, four-necked, nol A compounds having two groups, in any combination, glass reactor equipped with a cooling condenser, a thermom Selected from the group of moieties comprising O-hydroxy eter, a magnetic Stirrer, a nitrogen inlet and an ice-water acetate, C-diacetate and O-glycol. cooling bath was employed. To the reactor were added 50 cc of acetonitrile and a mixture containing 0.08 g (0.45 mmole) 0226. In addition, the above Reaction Sequence (VIII) of MnSOHO and 2 g of water. The resultant reaction does not show all the possible positional isomers of the mixture was thoroughly mixed and 0.12 g of N,N',N'- bis(O-hydroxy acetate) and bis(O-chlorohydrin) bis A trimethyl-1,3,9-triazacyclononane (TMTACN, 0.69 mmole derivatives shown in Steps 3 and 4, respectively. For mole) was added to the reaction mixture, followed by the example, different positional isomers of the bis(O-hydroxy addition of a mixture containing 0.042 g (0.45 mmole) of acetate) bisphenol A derivative shown in Step 3 may be oxalic acid, 0.060 g (0.45 mmole) of sodium oxalate and 2 created by Switching the positions of the hydroxy and g of water. acetate groups on one or on both of the C-hydroxy acetate 0234. After thoroughly mixing the resultant reaction mix moieties. ture, 15 g of allyl acetate (0.15 mole) was added into the 0227. The epoxy resins prepared in the present invention reaction mixture. The reactor contents were cooled to 10 C., may be used in various applications including for example, and 28.5 g (0.3 mole) of aqueous 35 percent hydrogen coatings, Such as water-borne and Solvent-borne coatings, peroxide Solution was added to the reaction mixture over can and coil coatings, powder coatings, industrial and about 30 minutes. Upon addition of the first portion of marine protective coatings; adhesives, Sealants, composites, hydrogen peroxide, the reaction mixture immediately turned and electrical applications, Such as electrical laminates and pink, and then the color quickly disappeared. An exothermic electronic encapsulation. reaction was observed, and the temperature of the reaction mixture increased to 15 to 20 C. The reactor was periodi cally cooled with the ice-water bath to maintain the reaction EXAMPLE 1. temperature at 15 C. The reaction was stopped after 4 0228 A. Epoxidation of Allyl Acetate to Glycidyl hours. The reaction mixture was analyzed by gas chroma Acetate Experiment A1 tography (GC)/mass spectrometry (MS) for unreacted allyl acetate, for glycidyl acetate and for hydrolyzed epoxy, 0229. In this part of Example 1, a 100-mL, four-necked, which is present as a glycol impurity. The conversion of allyl glass reactor equipped with a cooling condenser, a thermom acetate was 75 percent, and the Selectivity to glycidyl acetate eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp was greater than 95 percent. with a thermocontroller was employed. To the reactor were added 20 g (0.2 mole) of allyl acetate (commercially avail 0235. The reaction mixture was extracted with two 100 able from Aldrich Chemical Co.), 20 mL of methylene mL portions of methylene chloride. The methylene chloride chloride, 0.50 g (1.0 mole percent based on the amount of extracts were combined and washed with one 50-mL portion allyl acetate) of methyltrioxorhenium (MTO) and 0.76 g (15 of water. The methylene chloride-acetonitrile solution of mole percent based on the amount of allyl acetate) of reaction product was concentrated using rotary evaporation pyrazole. The resultant reaction mixture was stirred at at 90° C. and 100 mmHg. The crude glycidyl acetate was ambient temperature under a nitrogen atmosphere for 5 transferred to a 100-mL, round-bottom flask equipped with minutes. Then 38 g (2 molar equivalents based on the a short path distillation apparatus, and 9.5g of pure glycidyl amount of allyl acetate) of aqueous 35 percent hydrogen acetate was collected upon distillation at 90° C. to 100° C. peroxide Solution as an oxidant was added into the reactor at at less than 15 mmHg. ambient temperature. A slight eXothermic reaction occurred, 0236. The above procedure in this Experiment A2 was and the temperature of the reaction mixture reached 30° C. repeated five additional times, and the products from the The reaction was carried out at 25 C. for about 12 hours and total of six experiments were combined to yield a total of 50 then at 30° C. for 2 additional hours. g of glycidyl acetate. 0230. The reaction mixture was analyzed by gas chro 0237 Experiment A3 matography (GC)/mass spectrometry (MS) for unreacted allyl acetate, for glycidyl acetate and for hydrolyzed epoxy, 0238. In this part of Example 1, a 100-mL, four-necked, which is present as a glycol impurity. The conversion of allyl glass reactor equipped with a cooling condenser, a thermom acetate was greater than 80 percent, and the Selectivity to eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp glycidyl acetate was greater than 95 percent. with thermo-controller was employed. To the reactor were added 20 g (0.2 mole) of allyl acetate (commercially avail 0231. The crude reaction mixture was extracted with two able from Aldrich Chemical Co.), 20 mL of methylene 100-mL portions of methylene chloride. The methylene chloride, 1.00 g (2.0 mole percent based on the amount of chloride extracts were combined and washed with one allyl acetate) of methyltrioxorhenium (MTO) and 1.51 g (15 50-mL portion of water. The methylene chloride solution mole percent based on the amount of allyl acetate) of was concentrated by rotary evaporation at 90° C. and under pyrazole. The resultant reaction mixture was stirred at a vacuum of 100 mmHg. The crude glycidyl acetate was ambient temperature under a nitrogen atmosphere for 5 transferred to a 100-mL, round-bottom flask equipped with minutes. Then 38 g (2 equivalents based on the amount of US 2002/0045707 A1 Apr. 18, 2002 allyl acetate) of aqueous 35 percent hydrogen peroxide alcohol Solvent of the organic phase were removed by rotary Solution as an oxidant was added into the reactor at ambient evaporation at 90° C. and 15 mmHg yielding 2.6 g of crude temperature. A slight exothermic reaction occurred, and the C-hydroxy acetate derivative of phenol. temperature of the reaction mixture reached 27 C. The reaction was carried out at 25 C. for about 12 hours. The 0247 The above procedure in this Experiment B2 was reaction mixture was analyzed by gas chromatography repeated two additional times at a scale of 0.075 moles of (GC)/mass spectrometry (MS) for unreacted allyl acetate, phenol. The products from the above three experiments were for glycidyl acetate and for hydrolyzed epoxy, which is combined to form a total of 17.9 g of C-hydroxy acetate present as a glycol impurity. The conversion of allyl acetate derivative of phenol. was greater than 85 percent, and the Selectivity to glycidyl 0248 C. In Situ Chloride Substitution-Deesterification of acetate was greater than 95 percent. C.-Hydroxy Acetate Derivative of Phenol 0239). The crude reaction mixture was extracted with two 0249. In this part of Example 1, a 100-mL four-necked, 100-mL portions of methylene chloride, and the two meth glass reactor equipped with a cooling condenser connected ylene chloride extracts were combined. The extract was to a gas Scrubber containing 40 percent KOH, a thermom washed once with 50 mL of water. The methylene chloride eter, a magnetic Stirrer, a fritted glass gas dispersion tube and Solution was concentrated using rotary evaporation at 90° C. a heating lamp with thermo-controller was employed. To the and 100 mmHg. The crude glycidyl acetate was transferred reactor were added 15.7 g of the crude C-hydroxy acetate to a 100-mL, round-bottom flask equipped with a short path derivative of phenol as prepared in Experiment B2 above distillation apparatus, and 11 g of pure glycidyl acetate and 50 g of 1-methoxy-2-hydroxypropane as Solvent. The collected upon distillation at 90° C. to 100° C. at less than mixture was heated to 90° C. HCl gas was slowly bubbled 15 mmHg. into the mixture for about 2 hours after which time the 0240 The above procedure in this Experiment A3 was C-hydroxy acetate derivative of phenol was converted into repeated three additional times, and the glycidyl acetate C-chlorohydrin intermediate of phenol. Gas chromatogra obtained from these three experiments was combined with phy (GC) coupled with mass spectrometry (MS) analysis the glycidyl acetate from Experiment A3 above to yield 45 indicated that the C-chlorohydrin intermediate formed was 1-chloro-2-hydroxy-3-phenoxypropane in greater than 95 g of pure glycidyl acetate. percent yield. 0241 B. Coupling of Glycidyl Acetate with Phenol 0250) The reaction product was washed from the reactor 0242 Experiment B1 with two 100-mL portions of methylene chloride. The two 0243 In this part of Example 1, a 100-mL, four-necked, 100-mL portions of methylene chloride containing the crude glass reactor equipped with a cooling condenser, a thermom reaction product were combined and washed once with 50 eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp mL of water. The methylene chloride Solution was concen with thermo-controller was employed. To the reactor were trated under vacuum using rotary evaporation at 90° C. and added 11.6 g (0.1 mole) of glycidyl acetate from Experiment less than 10 mmHg to yield about 10 g of crude C.-chloro A3 above, 20 g of tert-amyl alcohol, 0.075 g (1.5 mole hydrin intermediate of phenol. GC analysis indicates the percent based on phenol) benzyltrimethylammonium chlo product contains a minor amount of 1-methoxy-2-acetoxy ride, and 2.35 g (0.025 mole) of phenol. The resultant propane, which is formed through transesterification of the reaction mixture was stirred at 85 C. for 7 hours. The crude 1-methoxy-2-hydroxypropane Solvent with the C-hydroxy reaction mixture was analyzed by GC, and the elution times acetate derivative of phenol. of the products were identical to the products in Example 1 0251 D. Epoxidation of C.-Chlorohydrin Intermediate of Part C below which were identified by GC/MS analysis. The Phenol conversion of phenol was greater than 95 percent and the ratio of 2-hydroxy-3-acetoxy-1-phenoxypropane to 2,3-di 0252) In this part of Example 1, a 100-mL, four-necked, acetoxy-1-phenoxypropane was 1.8 (based on GC peak area glass reactor equipped with a cooling condenser, a thermom percent). eter, a magnetic Stirrer, an addition funnel for liquids and a heating lamp with a thermo-controller was employed. To the 0244 Experiment B2 reactor were added 10 g of crude C-chlorohydrin interme 0245. In this part of Example 1, a 50-mL, four-necked, diate of phenol prepared in Part C above. The crude C.-chlo glass reactor equipped with a cooling condenser, a thermom rohydrin intermediate contains about 8.5 g of 1-chloro-2- eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp hydroxy-3-phenoxypropane and 1.5 g of 1-methoxy-2- with thermo-controller was employed. To the reactor were acetoxypropane (the amounts are based on GC area percent added 11.6 g (0.1 mole) of glycidyl acetate from Experiment data). To the reactor was also added 20 g of 1-methoxy-2- A2 above, 20 g of tert-amyl alcohol, 0.075 g (1.5 mole hydroxypropane as Solvent. The resultant reaction mixture percent based on phenol) benzyltrimethylammonium chlo was heated to 55° C. Using the addition funnel, 5.12 g of 50 ride and 2.35 g (0.025 mole) of phenol. The resultant percent aqueous NaOH solution (0.065 mole of NaOH) was reaction mixture was stirred at 85 C. for 6 hours. The added slowly to the heated mixture over a period of 15 reaction mixture was analyzed by GC/MS. The conversion minutes after which the mixture was allowed to react for of phenol was greater than 95 percent. about an additional 20 minutes. GC analysis of the resultant product indicated that greater than 95 percent of the C-chlo 0246 To the crude reaction mixture was added 50 mL of rohydrin intermediate was converted into phenyl glycidyl methylene chloride, and the Solution was washed once with ether as identified by GC elution time comparison with an 20 mL of water. The aqueous and organic phases were authentic Sample of phenyl glycidyl ether. This reaction Separated. The excess glycidyl acetate and the tert-amyl mixture of epoxy product was not further purified. US 2002/0045707 A1 Apr. 18, 2002 22

EXAMPLE 2 mL, round-bottom flask equipped with a short path distilla tion apparatus, and 12 g of pure glycidyl acetate was 0253 A. Epoxidation of Allyl Acetate to Glycidyl collected upon distillation at 90° C. to 100° C. at less than Acetate 15 mmHg. Analysis by GC/MS confirmed the material to be 0254. In this part of Example 2, a 100-mL, four-necked, glycidyl acetate. glass reactor equipped with a cooling condenser, a thermom eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp 0256 The procedure of Part A above was repeated three with thermo-controller was employed. To the reactor were additional times at a Scale of 80 gallyl acetate (0.8 mole), added 20 g (0.2 mole) of allyl acetate (commercially avail and the quantities of glycidyl acetate produced in the four able from Aldrich Chemical Co.), 40 mL of acetonitrile, 1.28 experiments were combined to yield a total of 180 g. g (2.5 mole percent based on the amount of allyl acetate) of methyltrioxorhenium (MTO) and 2.04 g (15 mole percent 0257 B. Coupling of Glycidyl Acetate with Bisphenol A based on the amount of allyl acetate) of pyrazole. The 0258 Experiment B1 resultant reaction mixture was Stirred at ambient temperature under a nitrogen atmosphere for 5 minutes. Then 38 g (2 0259. In this part of Example 2, a 50-mL, four-necked, molar equivalents based on the amount of allyl acetate) of glass reactor equipped with a cooling condenser, a thermom aqueous 35 percent hydrogen peroxide Solution as an oxi eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp dant was added into the reactor at ambient temperature. An with thermo-controller was employed. To the reactor were exothermic reaction occurred, and the temperature reached added 5.8 g (0.05 mole) of glycidyl acetate from Part A 45 C. Cooling with an ice-water bath was necessary to above, 20g of tert-amyl alcohol, 0.038 g (1.5 mole percent lower the temperature to 30 to 35° C. The reaction was based on bisphenol A) benzyltrimethylammonium chloride carried out at 35 C. for about 5 hours. The reaction mixture and 1.42 g (0.006 mole) of bisphenol A. The reactor contents was analyzed by gas chromatography (GC)/mass spectrom were stirred at 85°C. for 8 hours. The crude reaction mixture etry (MS) for unreacted allyl acetate, for glycidyl acetate and was analyzed by gas chromatography (GC)/mass spectrom for hydrolyzed epoxy, which is present as a glycol impurity. etry (MS). The conversion of bisphenol A was greater than The conversion of allyl acetate was greater than 75 percent, 95 percent. and the Selectivity to glycidyl acetate was greater than 95 0260 The tert-amyl alcohol and excess glycidyl acetate percent. were removed from the reaction mixture using rotary evapo 0255 The reaction mixture was extracted with two 100 ration at 90° C. and 10 to 15 mmHg yielding a crude mL portions of methylene chloride. The methylene chloride bis(O-hydroxyacetate) derivative of bisphenol A. This reac extracts were combined and washed with one 50-mL portion tion product was not carried forward in the reaction Scheme, of water. The methylene chloride was removed from the but was additionally analyzed by high pressure liquid chro reaction mixture using rotary evaporation at 95 C. and 100 matography (HPLC)/mass spectrometry (MS) and the result mmHg. The crude glycidyl acetate was transferred to a 100 of the analysis is shown in Table I below.

TABLE I HPLC/MS Analysis of Coupling Product from Bisphenol A and Glycidyl Acetate

Structure Reference No. by Mass Structure() Area 26 376 st st th st st 9 Ji-in-a--()–: O-CH-CH-CH CH 492a stin-li-c-o-( st )--(th )-o-c-b-c-o-c-b-h.OH st t CH

492b Isomer of 492a 418 it pi th it 34 Ji-in-a--()–: O-CH-CH-CH CH

460a Isomer of 460b and 460c US 2002/0045707 A1 Apr. 18, 2002 23

TABLE I-continued HPLC/MS Analysis of Coupling Product from Bisphenol A and Glycidyl Acetate

Structure Reference No. by Mass Structure() Area 26 534 OH Ac CH Ac OH Ac Ji-in-at-o-( )--(hi, )-o-c-b-c-o-c-b- 576a Isomer of 576b and 576c

460b Ac OH CH OH Ac 3O --al-O-()--()-o-c-b-hi, SO2a Isomer of 502b, 502c, and 502d

46Oc OH, OH CH Ac Ac 5 in-l-al-o-( )--()--in-li-li,hi, 5O2b Isomer of 502a, 502c, and 502d

576b OH Ac CH Ac OH Ac --al-O-( )--(hi, )-o-c-b-c-e-a-ki

576c OH Ac CH OH Ac Ac in-li-ul-O-()--()--in-l-al-o-c-b-hi, SO2c Ac OH CH Ac Ac --al-O-()--()-----,hi, SO2d Isomer of 502c 9 544a Isomer of 544b 544b Ac -i-o-o-()--()-----,Ac CH Ac Ac CH (“Ac” in Table I = “OAc”

0261) Experiment B2 was analyzed by gas chromatography, and the conversion of 0262. In this part of Example 2, a 50-mL, four-necked, bisphenol A was greater than 95 percent. glass reactor equipped with a cooling condenser, a thermom 0263. The tert-amyl alcohol and excess glycidyl acetate eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp were removed from the reaction mixture using rotary evapo with thermo-controller was employed. To the reactor were ration at 90° C. and 10 to 15 mmHg yielding 3.1 g of crude added 11.6 g (0.1 mole) of glycidyl acetate from Part A bis(O-hydroxyacetate) derivative of bisphenol A. above, 20g of tert-amyl alcohol, 0.076 g (1.5 mole percent 0264. The procedure of Experiment B2 above reaction based on bisphenol A) benzyltrimethylammonium chloride was repeated one additional time. The combined crude and 2.82 g (0.012 mole) of bisphenol A. The reactor contents bis(O-hydroxy acetate) derivative of bisphenol A from the were stirred at 85°C. for 5 hours. The crude reaction mixture two experiments weighed 6.5 g. US 2002/0045707 A1 Apr. 18, 2002 24

0265 Experiment B3 reaction mixture was analyzed by gas chromatography, and 0266. In this part of Example 2, a 250-mL, four-necked, the conversion of bisphenol A was greater than 95 percent. glass reactor equipped with a cooling condenser, a thermom eter, a magnetic Stirrer, a nitrogen inlet and a heating lamp 0267 The tert-amyl alcohol and excess glycidyl acetate with thermo-controller was employed. To the reactor were were removed from the reaction mixture using rotary evapo added 45 g (0.4 mole) of glycidyl acetate from Part Aabove, ration at 90° C. and 10 to 15 mmHg yielding crude bis(O- 100 g of tert-amyl alcohol, 0.304 g (1.5 mole percent based hydroxy acetate) derivative of bisphenol A. This reaction on bisphenol A) benzyltrimethylammonium chloride and product was analyzed by high pressure liquid chromatogra 11.28 g (0.05 mole) of bisphenol A. The reactor contents phy (HPLC)/mass spectrometry (MS) and the analysis of the were stirred at 90° C. to 95 C. for 3.5 hours. The crude major components is shown in Table II below.

TABLE II HPLC/MS Analysis of Coupling Product from Bisphenol A and Glycidyl Acetate Structure Reference No. by Mass ID (MW)* Structure Area 26 376 &for 384 Unknown 418 & for 460a OH OH CH OH Ac 10.7 b-?i-al-O-()--(y-o-c-f-hi, &for OAC OH CH OAC OH bi-li-o-o-()--(y-o-c-b-hi, 46Ob OAC OH CH OH OAc 31.4 bi-n-at-o-( )--(hi, )--a-h-r

576 OH OAC 6.6 ch-hi-li, OAc h CH OH OAC lu-l-al-o-( )--()--in-li-khi, SO2a OAc OAc CH OAC OH 1.2 bi-li-ul-O-()--(y-o-c-b-h.hi, 502b OAc OAc CH OH OAc 32.9 k-ki-a-o-( )--()--in-li-khi, 66Oa OAc OAc 0.4 ch-hi-li, lu-l-al-O-()--()--a-lih OAc CH OAc OAc CH US 2002/0045707 A1 Apr. 18, 2002 25

TABLE II-continued HPLC/MS Analysis of Coupling Product from Bisphenol A and Glycidyl Acetate

Structure Reference No. by Mass ID (MW)* Structure Area 26

66Ob OAc OAc 8.93

CH-CH-CH OAC O CH OAc OAc CH-CH- al-o-()–: O-CH-CH-CH CH * Identification by molecular weight.

0268 C. In Situ Chloride Substitution-Deesterification of obtained from the conventional coupling of bisphenol A and Bis(C-Hydroxy Acetate) Derivative of Bisphenol A epichlorohydrin and by GC/MS analysis. 0269 Experiment C1 0271 Experiment C2 0272. In this part of Example 2, a 250-mL, four-necked, 0270. In this part of Example 2, a 100-mL, four-necked, glass reactor equipped with a cooling condenser connected glass reactor equipped with a cooling condenser connected to a gas Scrubber containing 40 percent KOH, a thermom to a gas Scrubber containing 40 percent KOH, a thermom eter, a magnetic Stirrer, a fritted glass gas inlet tube and a eter, a magnetic Stirrer, a fritted glass gas inlet tube and a heating lamp with thermo-controller was employed. To the heating lamp with thermo-controller was employed. To the reactor were added the crude C-hydroxy acetate derivative reactor were added 5 g of crude bis(O-hydroxy acetate) of bisphenol A from Part B3 above and 100 g 1-methoxy derivative of bisphenol A from Experiment B2 above and 50 2-hydroxypropane. The mixture was heated to 90° C. to 95 g of 1-methoxy 2-hydroxy propane Solvent. The mixture was C. HCl gas was slowly bubbled into the mixture for about 3 heated to 90° C. to 95°C. HCl gas was slowly bubbled into hours after which time GC analysis showed greater than 95 the mixture for about 3 hours after which time GC analysis percent of the bis(O-hydroxy acetate) derivative of bisphe showed greater than 95 percent of the bis(O-hydroxy nol A was converted into the bis(O-chlorohydrin) derivative acetate) derivative of bisphenol A was converted into the of bisphenol A. This reaction product was analyzed by high bis(O-chlorohydrin) intermediate of bisphenol A, the struc pressure liquid chromatography (HPLC)/mass spectrometry ture of which was confirmed by GC comparison with (MS) and the analysis of the major components is shown in standard bis(O-chlorohydrin) intermediate of bisphenol A Table III below.

TABLE III

HPLC/MS Analysis of Chloride Substitution Deesterification Product of Bisphenol A and Glycidyl Acetate Coupling Product.

Structure Reference by Mass Structure Area 26 394 hi--at-o-O--O-o-c-b-st th st st 28.4 CH 486 fk-n-at-o-O--O-o-c-b-al-o-c-b-h. st th OH st f 1.5 CH

52O Unknown 4.8 US 2002/0045707 A1 Apr. 18, 2002 26

TABLE III-continued HPLC/MS Analysis of Chloride Substitution Deesterification Product of Bisphenol A and Glycidyl Acetate Coupling Product. Structure Reference by Mass Structure Area 26 412 C OH CH pi 47.O lu-ri—cil-o l O-CH-CH-CH l, 454 C OAc CH OH Cl 1.3 lu-ri—cil-o l O-CH-CH-CH hi, * Identification by molecular weight. D. Epoxidation of bis(C-chlorohydrin) derivative of bisphenol A

0273. In this part of Example 2, a 250-mL, four-necked, addition funnel, 12 g of 50 percent acqueous NaOH solution glass reactor equipped with a cooling condenser, a thermom (0.15 mole of NaOH) was added slowly to the heated eter, a magnetic Stirrer, an addition funnel for liquids and a mixture over a period of 60 minutes at 50° C. to 52 C., after heating lamp with a thermo-controller was employed. Into which time the mixture was allowed to react for about an the reactor was transferred the crude bis(O-chlorohydrin) additional 60 minutes at 50 C. to 52 C. GC analysis of the derivative of bisphenol A prepared in Experiment C2 above. resultant product indicated that greater than 90 percent of the To the reactor was also added 100 g of 1-methoxy-2- bis(O-chlorohydrin) derivative was converted into bisphenol hydroxypropane as Solvent. At ambient temperature, 12 g of A diglycidyl ether as identified by GC elution time com 50 percent aqueous NaOH solution (0.15 mole of NaOH) parison with an authentic commercial sample. The epoxy was added slowly to the mixture over a period of 30 minutes, product was dissolved into 150 mL methyl ethyl ketone/ after which the mixture was allowed to react for about an toluene (50/50 volume) and was washed twice with 50 mL additional 30 minutes in order to neutralize unreacted HCl portions of water. The organic phase was separated and dissolved in the mixture. concentrated by rotary evaporation at 90° C. to 95 C. and 0274. After removing the precipitated salt by filtration, less than 15 mmHg, yielding 13 g of epoxy resin having an the resultant Solution was transferred into another 250-mL, epoxy content of 20.55 percent and an epoxy equivalent four-necked, glass reactor equipped with a cooling con weight of 209. This reaction product was analyzed by high denser, a thermometer, a magnetic Stirrer, an addition funnel pressure liquid chromatography (HPLC)/mass spectrometry for liquids and a heating lamp with a thermo-controller. The (MS) and the analysis of the major components is shown in reaction mixture was heated to 50 to 52 C. Using the Table IV below.

TABLE IV HPLC/MS Analysis of Epoxidation Product of Chloride Substitution-Deesterification Product of Bisphenol A and Glycidyl Acetate Coupling Product

Structure Reference No. by Mass ID (MW)* Structure Area 26 394 st t OH, OH 1.94% CH-CH-CH-O O-CH-CH-CH CH 358 /\ th OH, OH 9.32% CH-CH-CH-O O-CH-CH-CH CH US 2002/0045707 A1 Apr. 18, 2002 27

TABLE IV-continued HPLC/MS Analysis of Epoxidation Product of Chloride Substitution-Deesterification Product of Bisphenol A and Glycidyl Acetate Coupling Product

Structure Reference No. by Mass ID (MW)* Structure Area 26

414a or 414b 2.06%

/\ CH OH OH, OH (An-at-o-O--O-o-c-b-al-o-c-b-rl, CH OH CH al-o-li-al-o-c-b-al-o-O-l, O-CH-CH=CH

400 2.20% y \ CH OH OAC (An-a-o-O--O-o-c-b-hi, 412 unknown 2.67%

376a 3.60%

y \ CH C OH (An-cr-0-( )--(hi, )-o-c-b-h. 376b 3.70%

/\ CH OH Cl (An-co-o-O--O-o-c-b-h.hi, 340 67.90% y \ CH y \ (An-co-o-O--O-o-c-Anhi,

374 unknown O.21%

418 O.51% lu-l-al-O-(C OAc )--(CH )-o-c-Any \ CH * Identification by molecular weight. US 2002/0045707 A1 Apr. 18, 2002 28

0275 HPLC analysis shows the major component is to complete its necessary bonding Valence, (iii) -C(O)-, diglycidyl ether of bisphenol A. (iv)-S(O) , (v)-C(O)NH-, (vi) -P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic moiety, Saturated or What is claimed is: unsaturated, with or without heteroatoms, or (viii) a partially 1. A process for making an epoxy resin comprising or fully fluorinated organic aliphatic or cycloaliphatic moi converting an O-hydroxy ester derivative of at least one or ety, more phenols to an epoxy resin. 2. A process for making an epoxy resin comprising (a) converting at least one or more phenols to an O-hydroxy ester derivative by reacting the at least one or more phenols Formula IV with a glycidyl ester or Substituted glycidyl ester and (b) (R), converting the C-hydroxy ester derivative of the at least one or more phenols to an epoxy resin. 3. A process of making an epoxy resin comprising (a) (R), O)-)-Z )-z-H( (R), converting an O-hydroxy ester derivative of at least one or (RO), i. (OR), more phenols to an O.-halohydrin intermediate of at least one (OR), or more phenols and (b) converting the C-halohydrin inter mediate of at least one or more phenols to an epoxy resin. 4. A process of making an epoxy resin comprising (a) wherein y is 0 to 4, and each y can be the same or different; reaction of the C-hydroxy ester derivative of at least one or Z is 1 to 3, and each Z can be the same or different; R' is an more phenols with a hydrogen halide to form an O-halohy C-halohydrin propyl-containing moiety; R is a group Sub drin intermediate of at least one or more phenols and (b) Stituted for a hydrogen atom on the aromatic ring; Zis (i) nil, epoxidizing the C-halohydrin intermediate of at least one or (ii) a heteroatom with or without substituents thereon to more phenols to form an epoxy resin. complete its necessary bonding Valence, (iii) -C(O)-, (iv) 5. A process for making a C-halohydrin intermediate of at S(O) , (v) -C(O)NH-, (vi) -P(O)Ar-, (vii) an least one or more phenols comprising reacting (a) an O-hy organic aliphatic or cycloaliphatic moiety, Saturated or droxy ester derivative of at least one or more phenols with unsaturated, with or without heteroatoms, or (viii) a partially (b) a hydrogen halide. or fully fluorinated organic aliphatic or cycloaliphatic moi 6. The process of claim 3, 4 or 5 wherein the O.-halohydrin ety; and m is from 0.001 to 10; or intermediate of at least one or more phenols comprises a Structure having the following Formula I: Formula V (R), Ar(OR"), Formula I (R), wherein y is from 0 to 750, Z is from 1 to 150, Ar is an aromatic-containing moiety, R is an O-halohydrin pro pyl-containing moiety and R is a group Substituted for (RO)2 O)}-z a hydrogen atom on the Ar moiety. 7. The process of claim 6 wherein the O.-halohydrin intermediate of at least one or more phenols comprises a wherein y is 0 to 4, and each y can be the same or different; Structure represented by any one or more of the following Z is 1 to 3, and each Z can be the same or different; R' is an Formulas II-V: C-halohydrin propyl-containing moiety; R is a group Sub Stituted for a hydrogen atom on the aromatic ring; Z is (i) an organic aliphatic moiety, Saturated or unsaturated, with or Formula II without heteroatoms, wherein the aliphatic moiety has from 1 to 20 carbon atoms, (ii) a cycloaliphatic moiety, Saturated or unsaturated, with or without heteroatoms, having from 3 to 20 carbon atoms, (iii) an aromatic moiety, with or without (C."(OR), heteroatoms, having 6 to 20 carbon atoms, (iv) a partially or fully fluorinated organic aliphatic, cycloaliphatic or aro wherein y is 0 to 5; Z is 1 to 4; R is an O-halohydrin matic moiety, (v) or any combination thereof, and m' is 3 or propyl-containing moiety; and R is a group Substituted for 4. a hydrogen atom on the Ar moiety; 8. The process of claim 7 wherein R' is selected from:

Formula III Y X R3 x1 (R), -C(R)CR3-c(R) and Z. (RO), RO-O.(OR), wherein y is 0 to 4, and each y can be the same or different; Z is 1 to 3, and each Z can be the same or different; R' is an wherein X and Y may be a halogen atom or hydroxyl group C-halohydrin propyl-containing moiety; R is a group Sub with the proviso that when X is a halogen Y must be a Stituted for a hydrogen atom on the aromatic ring, and Z is hydroxyl and when Y is a halogen X must be a hydroxyl; and (i) nil, (ii) a heteroatom with or without substituents thereon R is hydrogen, an alkyl group having from 1 to 20 carbon US 2002/0045707 A1 Apr. 18, 2002 29 atoms, a cycloaliphatic group having from 3 to 20 carbon 11. The process of claim 10 wherein the C-chlorohydrin atoms, an aromatic group having from 6 to 20 carbon atoms intermediate of at least one or more phenols is Selected from or any combination thereof. the group comprising 2,2-bis(4-hydroxyphenyl)isopropy 9. The process of claim 8 wherein R' is selected from: lidene bis(3-chloro-2-hydroxypropyl) ether; 2.2-bis(4-hy droxyphenyl)isopropylidene bis(2-chloro-3-hydroxypropyl) ether; and mixtures thereof. 12. The process of claims 1-5 wherein the O.-hydroxy ester derivative of at least one or more phenols, comprises a -CHCH-CH and -CHC-CH structure represented by the following Formula VI: CH (R), Ar(OR"), Formula VI wherein X and Y may be a halogen atom or hydroxyl group wherein y is from 0 to 750; Z is from 1 to 150; Ar is an with the proviso that when X is a halogen Y must be a aromatic-containing moiety; R is an O-hydroxy ester hydroxyl and when Y is a halogen X must be a hydroxyl. propyl-containing moiety; and R is a group Substituted 10. The process of claim 7 wherein the O.-halohydrin for a hydrogen atom on the Ar moiety. intermediate of at least one or more phenols is an O-chlo 13. The process of claim 12 wherein the C-hydroxy ester rohydrin intermediate Selected from the group comprising derivative of at least one or more phenols, comprises a 1,3-dihydroxybenzene bis(3-chloro-2-hydroxypropyl)ether; structure represented by any one or more of Formulas VII-X 1,4-dihydroxybenzene bis(3-chloro-2-hydroxypropyl)ether; as follows: 1,5-dihydroxynaphthalene bis(3-chloro-2-hydroxypropyl) ether; 2,6-dihydroxy-naphthalene bis(3-chloro-2-hydrox ypropyl) ether; 4,4'-dihydroxybiphenyl bis(3-chloro-2-hy Formula VII droxypropyl) ether; 3,3',5,5'-tetramethyl-4,4'-dihydroxybi phenyl bis(3-chloro-2-hydroxypropyl) ether; 3,3',5,5'- (C. tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl (OR), bis(3-chloro-2-hydroxypropyl) ether; bis(4-hydroxyphenyl)methane bis(3-chloro-2-hydroxypro wherein y is 0 to 5; Z is 1 to 4; R is an O-hydroxy ester pyl) ether; 2,2-bis(4-hydroxyphenyl)isopropylidene-bis(3- propyl-containing moiety; and R is a group Substituted for chloro-2-hydroxypropyl) ether, phenol-formaldehyde a hydrogen atom on the aromatic ring; novolac (3-chloro-2-hydroxypropyl) ether(functionality greater than 2); o-cresol-formaldehyde novolac (3-chloro 2-hydroxypropyl) ether (functionality greater than 2); phe Formula VIII nol-dicyclopentadienyl novolac (3-chloro-2-hydroxypropyl) ether (functionality greater than 2), naphthol-formaldehyde (R),O ) (R), novolac (3-chloro-2-hydroxypropyl) ether (functionality (RO), O)--O (OR), greater than 2); 1,1,1-tris(4-hydroxyphenyl)methane tris(3- chloro-2-hydroxypropyl) ether; 1,1,2,2-tetrakis(4-hydrox wherein y is 0 to 4, and each y can be the same or different; yphenyl)ethane tetrakis(3-chloro-2-hydroxypropyl) ether; Z is 1 to 3, and each Z can be the same or different; R' is an 1,3-dihydroxybenzene bis(2-chloro-3-hydroxypropyl)ether; C-hydroxy ester propyl-containing moiety; R is a group 1,4-dihydroxybenzene bis(2-chloro-3-hydroxypropyl)ether; Substituted for a hydrogen atom on the aromatic ring, and Z 1,5-dihydroxynaphthalene bis(2-chloro-3-hydroxypropyl) is (i) nil, (ii) a heteroatom with or without substituents ether; 2,6-dihydroxy-naphthalene bis(2-chloro-3-hydrox thereon to complete its necessary bonding Valence, (iii) -C(O) , (iv) -S(O) , (v) -C(O)NH-, (vi) ypropyl) ether; 4,4'-dihydroxybiphenyl bis(2-chloro-3-hy -P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic droxypropyl) ether; 3,3',5,5'-tetramethyl-4,4'-dihydroxybi moiety, Saturated or unsaturated, with or without heteroat phenyl bis(2-chloro-3-hydroxypropyl) ether; 3,3',5,5'- oms, or (viii) a partially or fully fluorinated organicaliphatic tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl or cycloaliphatic moiety; bis(2-chloro-3-hydroxypropyl) ether; bis(4-hydroxyphenyl)methane bis(2-chloro-3-hydroxypro pyl) ether, 2.2-bis(4-hydroxyphenyl)isopropylidene bis(2- Formula DX chloro-3-hydroxypropyl) ether; phenol-formaldehyde novolac (2-chloro-3-hydroxypropyl) ether (functionality (R), greater than 2); o-cresol-formaldehyde novolac (2-chloro 3-hydroxypropyl) ether (functionality greater than 2); phe Z. Z. nol-dicyclopentadienyl novolac (2-chloro-3-hydroxypropyl) ether (functionality greater than 2), naphthol-formaldehyde (RO), O)-(O-)-O.i. (OR), novolac (2-chloro-3-hydroxypropyl) ether (functionality (OR), greater than 2); 1,1,1-tris(4-hydroxyphenyl)methane tris(2- chloro-3-hydroxypropyl) ether; 1,1,2,2-tetrakis(4-hydrox wherein y is 0 to 4, and each y can be the same or different; yphenyl)ethane tetrakis(2-chloro-3-hydroxypropyl) ether; z is 1 to 3, and each Z can be the same or different; R is an and mixtures thereof. O-hydroxy ester propyl-containing moiety; R is a group US 2002/0045707 A1 Apr. 18, 2002 30

Substituted for a hydrogen atom on the aromatic ring; Z is (i) nil, (ii) a heteroatom with or without substituents thereon to complete its necessary bonding Valence, (iii) -C(O(iv) S(O) , (v) -C(O)NH-, (vi) -P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic moiety, Saturated or unsaturated with or without heteroatoms, or (viii) a partially or fully fluorinated organic aliphatic or cycloaliphatic moi wherein R" is hydrogen, an alkyl group having from 1 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon ety; and m is from 0.001 to 10; or atoms, a cycloaliphatic group having from 3 to 20 carbon atoms, or an aromatic group having from 6 to 20 carbon Formula X atOmS. (R), 17. The process of claim 16 wherein the R" is a methyl grOup. (RO),RO)}-z 18. The process of claim 13 wherein the C-hydroxy ester derivative of phenols or mixtures of phenols is Selected from the group comprising 1,3-dihydroxybenzene bis(3-acetoxy 2-hydroxypropyl) ether; 1,4-dihydroxybenzene bis(3-ac wherein y is 0 to 4, and each y can be the same or different; etoxy-2-hydroxypropyl) ether; 1,5-dihydroxynaphthalene z is 1 to 3, and each Z can be the same or different; R is an bis(3-acetoxy-2-hydroxypropyl) ether; 2,6-dihydroxynaph O-hydroxy ester propyl-containing moiety; R is a group thalene bis(3-acetoxy-2-hydroxypropyl) ether; 4,4'-dihy Substituted for a hydrogen atom on the aromatic ring, Z is droxybiphenyl bis(3-acetoxy-2-hydroxypropyl) ether; 3,3', (i) an organic aliphatic moiety, Saturated or unsaturated, with 5.5-tetramethyl-4,4'-dihydroxybiphenyl bis(3-acetoxy-2- or without heteroatoms, wherein the aliphatic moiety has hydroxypropyl) ether; 3,3',5,5'-tetramethyl-2,2',6,6'- from 1 to 20 carbon atoms, (ii) a cycloaliphatic moiety, tetrabromo-4,4'-dihydroxybiphenyl bis(3-acetoxy-2- Saturated or unsaturated, with or without heteroatoms, hav hydroxypropyl) ether; bis(4-hydroxyphenyl)methane bis(3- ing from 3 to 20 carbon atoms, (iii) an aromatic moiety, with acetoxy-2-hydroxypropyl) ether; 2,2-bis(4- or without heteroatoms, having 6 to 20 carbon atoms, (iv) a hydroxyphenyl)isopropylidene di(3-acetoxy-2- partially or fully fluorinated organic aliphatic, cycloaliphatic hydroxypropyl) ether, phenol-formaldehyde novolac or aromatic moiety, or (v) any combination thereof, and m' (3-acetoxy-2-hydroxypropyl) ether (functionality greater is 3 or 4. than 2); o-cresol-formaldehyde novolac (3-acetoxy-2-hy 14. The process of claim 13 wherein R is selected from: droxypropyl) ether (functionality greater than 2); phenol dicyclopentadienyl novolac (3-acetoxy-2-hydroxypropyl) ether (functionality greater than 2), naphthol-formaldehyde Yi X novolac (3-acetoxy-2-hydroxypropyl) ether (functionality R3 31 (R), greater than 2); 1,1,1-tris(4-hydroxyphenyl)methane tris(3- acetoxy-2-hydroxypropyl) ether; 1,1,2,2-tetrakis(4-hydrox yphenyl)ethane tetrakis (3-acetoxy-2-hydroxypropyl) ether; R3 R3 1,3-dihydroxybenzene bis(2-acetoxy-3-hydroxypropyl) Yi Xi ether; 1,4-dihydroxybenzene bis(2-acetoxy-3-hydroxypro pyl) ether; 1,5-dihydroxynaphthalene bis(2-acetoxy-3-hy wherein X" and Y may be a hydroxyl group or a carboxylic droxypropyl) ether; 2,6-dihydroxynaphthalene bis(2-ac acid ester moiety, with the proviso that when X is a hydroxyl etoxy-3-hydroxypropyl) ether; 4,4'-dihydroxybiphenyl group Y must be a carboxylic acid ester moiety and when bis(2-acetoxy-3-hydroxypropyl) ether; 3,3',5,5'-tetramethyl Y is a hydroxyl group X must be a carboxylic acid ester 4,4'-dihydroxybiphenyl bis(2-acetoxy-3-hydroxypropyl) moiety; and R is hydrogen, an alkyl group having from 1 to ether; 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihy 20 carbon atoms, a cycloaliphatic group having from 3 to 20 droxybiphenyl bis(2-acetoxy-3-hydroxypropyl) ether; bis(4- carbon atoms, an aromatic group having from 6 to 20 carbon hydroxyphenyl)methane bis(2-acetoxy-3-hydroxypropyl) atoms or any combination thereof. ether; 2,2-bis(4-hydroxyphenyl)isopropylidene bis(2-ac 15. The process of claim 14 wherein R' is selected from: etoxy-3-hydroxypropyl) ether; phenol-formaldehyde novolac (2-acetoxy-3-hydroxypropyl) ether (functionality greater than 2); o-cresol-formaldehyde novolac (2-acetoxy Yi Xi Yi Xi 3-hydroxypropyl) ether (functionality greater than 2); phe nol-dicyclopentadienyl novolac (2-acetoxy-3-hydroxypro —culti-li, and -a-lu, pyl) ether (functionality greater than 2), naphthol formaldehyde novolac (2-acetoxy-3-hydroxypropyl) ether CH (functionality greater than 2); 1,1,1-tris(4-hydroxyphenyl)methane tris(2-acetoxy-3-hy wherein X" and Y may be a hydroxyl group or a carboxylic droxypropyl) ether; 1,1,2,2-tetrakis(4-hydroxyphenyl)e- acid ester moiety, with the proviso that when X is a hydroxyl thane tetrakis(2-acetoxy-3-hydroxypropyl) ether; and mix group Y must be a carboxylic acid ester moiety and when tures thereof. Y is a hydroxyl group X must be a carboxylic acid ester 19. The process of claim 18 wherein the C-hydroxy ester moiety. derivative of phenols or mixtures of phenols is Selected from 16. The process of claim 15 wherein the carboxylic acid the group comprising 2,2-bis(4-hydroxyphenyl)isopropy ester moiety has the following general Structure: lidene bis(3-acetoxy-2-hydroxypropyl) ether; 2.2-bis(4-hy US 2002/0045707 A1 Apr. 18, 2002 droxyphenyl)isopropylidene bis(2-acetoxy-3-hydroxypro Solvents, aprotic Solvents, protic Solvents, partially or fully pyl) ether; and mixtures thereof. fluorinated Solvents and mixtures thereof. 20. The process of claim 12 wherein the C-hydroxy ester 31. The process of claim 30 wherein the solvent is an derivative of at least one or more phenols, (Component (A)), alcohol, a chlorinated Solvent or mixtures thereof. is a single component represented by any one of Formulas 32. The process of claims 1-5 wherein the C-hydroxy ester VI-X or a mixture of two or more components wherein at derivative of at least one or more phenols, is prepared by least one of the components in the mixture comprises a reacting (1) at least one or more phenols with (2) a glycidyl structure represented by any one of Formulas VI-X. ester or a Substituted glycidyl ester. 21. The process of claim 20 wherein the C-hydroxy ester 33. The process of claim 32 wherein Component (1), the propyl-containing moiety is Selected from: one or more phenols, comprises a structure represented by the following Formula XI:

Yi Xi (R), Ar(OH), Formula XI R3 y-(R)6 wherein y is 0 to 750; Z is 1 to 150; Ar is an aromatic -C(R)?R3-c(R3) and containing moiety; and R is a group Substituted for a hydrogen atom on the Ar moiety. R3 R3 34. The process of claim 33 wherein Component (1), the Yi Xi one or more phenols, comprises a structure represented by any one or more of Formulas XII-XV as follows: wherein X" and Y may be a hydroxyl group or a carboxylic acid ester moiety, with the proviso that when X is a hydroxyl group Y must be a carboxylic acid ester moiety and when Formula XII Y is a hydroxyl group X must be a carboxylic acid ester (R), moiety; and R is hydrogen, an alkyl group having from 1 to 20 carbon atoms, a cycloaliphatic group having from 3 to 20 O carbon atoms, an aromatic group having from 6 to 20 carbon (OH), atoms or any combination thereof. 22. The process of claim 20 wherein Component (A), the whereiny is 0 to 5; Z is 1 to 4; and R is a group substituted C-hydroxy ester derivative of at least one or more phenols, for a hydrogen atom on the aromatic ring; is a mixture comprising (i) a component having an O-hy droxy ester moiety wherein X and Y may be a hydroxyl group or a carboxylic acid ester moiety, with the proviso that Formula XIII when X is a hydroxyl group Y must be a carboxylic acid (R), (R), ester moiety and when Y" is a hydroxyl group X must be a carboxylic acid ester moiety, (ii) a component having an O)--O C.-diester moiety wherein X and Y are both carboxylic acid (HO), (OH), ester moieties, and (iii) a component having an O-glycol moiety wherein X" and Y are both hydroxyl. wherein y is 0 to 4, and each Y can be the same or different; 23. The process of claim 22 wherein the percentages of Z is 1 to 3, and each Z can be the same or different; R is a C-hydroxy ester moieties, C-diester moieties and O-glycol group Substituted for a hydrogen atom on the aromatic ring; moieties in Component (A) are 5 to 100 percent, 0 to 95 and Z is (i) nil, (ii) a heteroatom with or without substituents percent and 0 to 95 percent, respectively. thereon to complete its necessary bonding Valence, (iii) 24. The process of claim 23 wherein the percentages of -C(O) , (iv) -S(O) , (v) -C(O)NH-, (vi) C-hydroxy ester moieties, C-diester moieties and O-glycol -P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic moieties in Component (A) are 15 to 100 percent, 0 to 85 moiety, Saturated or unsaturated, with or without heteroat percent and 0 to 85 percent, respectively. oms, or (viii) a partially or fully fluorinated organic, ali 25. The process of claim 24 wherein the percentages of phatic or cycloaliphatic moiety; C-hydroxy ester moieties, C-diester moieties and O-glycol moieties in Component (A) are 30 to 100 percent, 0 to 70 percent and 0 to 70 percent, respectively. Formula XIV 26. The process of claim 4 or 5 wherein the hydrogen halide is hydrogen chloride. (R), 27. The process of claims 26 wherein the amount of the (R), (R), hydrogen halide is from about 0.5 mole to about 20 moles of hydrogen halide relative to the equivalents of C-hydroxy (HO),RO)--(KO)-)-O. i. (OH), ester moieties being reacted in the C-hydroxy ester deriva tive. (OH), 28. The process of claim 4 or 5 wherein step (a) is carried out at a temperature of from about 0° C. to about 150 C. wherein y is 0 to 4, and each y can be the same or different; 29. The process of claim 4 or 5 wherein step (a) is carried Z is 1 to 3, and each Z can be the same or different; R is a out in the presence of a Solvent. group Substituted for a hydrogen atom on the aromatic ring; 30. The process of claim 29 wherein the solvent is Z is (i) nil, (ii) a heteroatom with or without substituents Selected from aliphatic hydrocarbon Solvents, cyclic hydro thereon to complete its necessary bonding Valence, (iii) carbon Solvents, aromatic hydrocarbon Solvents, chlorinated -C(O) , (iv) -S(O) , (v) -C(O)NH-, (vi) US 2002/0045707 A1 Apr. 18, 2002 32

-P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic 38. The process of claim 37 wherein Component (2), the moiety, Saturated or unsaturated, with or without heteroat glycidyl ester, is glycidyl acetate. oms, or (viii) a partially or fully fluorinated organic aliphatic 39. The process of claim 32 wherein the amount of or cycloaliphatic moiety; and m is from 0.001 to 10; or glycidyl ester reacted with at least one or more phenols is from about 0.5 equivalents to about 50 equivalents of glycidyl ester per one equivalent of phenolic hydroxyl. Formula XV 40. The process of claim 32 wherein the reaction of (R), preparing the C-hydroxy ester derivative of at least one or more phenols, is carried out in the presence of a Solvent. RO)}-z 41. The process of claim 32 wherein the reaction of (HO), preparing the C-hydroxy ester derivative of at least one or more phenols, is carried out in the presence of a catalyst. 42. The process of claim 41 wherein the catalyst is a phase wherein y is 0 to 4, and each Y can be the same or different; transfer catalyst. z is 1 to 3, and each z can be the same or different; R is a 43. The process of claim 42 wherein the catalyst is an group Substituted for a hydrogen atom on the aromatic ring; organopnicogen-containing catalyst. Z is (i) an organic aliphatic moiety, Saturated or unsaturated, 44. The process of claim 42 wherein the catalyst is with or without heteroatoms, wherein the aliphatic moiety homogeneous or heterogeneous. has from 1 to 20 carbon atoms, (ii) a cycloaliphatic moiety, Saturated or unsaturated, with or without heteroatoms, hav 45. The process of claim 44 wherein the catalyst is from ing from 3 to 20 carbon atoms, (iii) an aromatic moiety, with about 0.001 percent to about 1000 percent by weight based or without heteroatoms, having 6 to 20 carbon atoms, (iv) a on the amount of the phenol or mixture of phenols used in partially or fully fluorinated organic aliphatic, cycloaliphatic the reaction. or aromatic moiety, (v) or any combination thereof, and m' 46. The process of claim 32 wherein the reaction of is 3 or 4. preparing the C-hydroxy ester derivative of at least one or 35. The process of claim 32 wherein Component (2), the more phenols, is carried out at a temperature of from about glycidyl ester, is represented by the following Formula XVI: 10° C. to about 16O C. 47. A proceSS for making an O.-halohydrin intermediate comprising the Steps of; Formula XVI O (a) preparing an O-hydroxy ester derivative of at least one | or more phenols by reacting at least one or more RCORS phenols with a glycidyl ester or Substituted glycidyl ester, and wherein R" is hydrogen, an alkyl group having from 1 to 20 (b) reacting the C-hydroxy ester derivative of at least one carbon atoms, an alkenyl group having from 2 to 20 carbon or more phenols with a hydrogen halide to form the atoms, a cycloaliphatic group having from 3 to 20 carbon C-halohydrin intermediate. atoms, or an aromatic group having from 6 to 20 carbon 48. A process for manufacturing an epoxy resin compris atoms; and R is a glycidyl moiety preferably selected from: ing epoxidizing an O.-halohydrin intermediate prepared according to the process of claim 47. 49. A process for manufacturing an epoxy resin compris O R3 31 (R), ing the Steps of:

3 (a) preparing an O-hydroxy ester derivative of at least one R R3 R3 or more phenols by reacting at least one or more phenols with a glycidyl ester or Substituted glycidyl ester, wherein R is hydrogen, an alkyl group having from 1 to 20 (b) preparing an O.-halohydrin intermediate as in claim 47; carbon atoms, a cycloaliphatic group having from 3 to 20 and carbon atoms, an aromatic group having from 6 to 20 carbon atoms, or any combination thereof. (c) epoxidizing the C-halohydrin intermediate of Step (b). 50. The process of claim 49 wherein the glycidyl ester or 36. The process of claim 35 wherein R is selected from: Substituted glycidyl ester is prepared by esterifying glycidol or a Substituted glycidol with a carboxylic acid or a car O O boxylic acid halide. / / 51. The process of claim 49 wherein the glycidyl ester or -CHC-CH and -cis-cl. Substituted glycidyl ester is prepared by epoxidation of an H CH allyl ester or a Substituted allyl ester of a carboxylic acid. 52. A process for manufacturing an epoxy resin compris ing the Steps of: 37. The process of claim 36 wherein Component (2), the glycidyl ester, is Selected from glycidyl formate, glycidyl (a) providing a glycidyl ester or Substituted glycidyl ester acetate, methylglycidyl formate and methylglycidyl acetate. of a carboxylic acid; US 2002/0045707 A1 Apr. 18, 2002

(b) preparing an O-hydroxy ester derivative of at least one where R is hydrogen, an alkyl group having from 1 to 20 or more phenols by reacting at least one or more carbon atoms, a cycloaliphatic group having from 3 to 20 phenols with the glycidyl ester or Substituted glycidyl carbon atoms, an aromatic group having from 6 to 20 carbon ester of Step (a); atoms, or any combination thereof. (c) preparing an O-halohydrin intermediate as in claim 3, 58. The epoxy resin of claim 57 wherein R" is selected 4 or 5; and from: (d) epoxidizing the C-halohydrin intermediate of Step (c). 53. A proceSS for manufacturing an epoxy resin compris O O ing the Steps of /N / M -CHC-CH and -CHC-CH. (a) providing an allyl ester or a Substituted allyl ester of a carboxylic acid; H CH (b) preparing a glycidyl ester or a Substituted glycidyl ester by epoxidizing the allyl ester or a Substituted allyl 59. The epoxy resin of claim 56 represented by any one ester of Step (a) with an oxidant; of the following Formulas XIX-XXII: (c) preparing an O-hydroxy ester derivative of at least one or more phenols by reacting at least one or more Formula XIX phenols with the glycidyl ester or a Substituted glycidyl ester of Step (b); (d) preparing an O-halohydrin intermediate as in claim 47; (C. (OR), and (e) epoxidizing the C-halohydrin intermediate of Step (d) whereiny is 0 to 5; Z is 1 to 4; R" is a glycidyl-containing to form an epoxy resin product. moiety; and R is a group Substituted for a hydrogen atom on 54. A proceSS for manufacturing an epoxy resin compris the Ar moiety; ing the Steps of (a) providing allyl acetate; Formula XX (b) preparing glycidyl acetate by epoxidizing the allyl (R), (R), acetate of Step (a) with an oxidant; (c) preparing a bis(O-hydroxy acetoxy) derivative of (RO), O)--O (OR), bisphenol A by reacting bisphenol A with the glycidyl acetate of Step (b); wherein y is 0 to 4, and each y can be the same or different; (d) preparing a bis(O-chlorohydrin) intermediate of Z is 1 to 3, and each Z can be the same or different; R" is bisphenol A by reacting the bis(O-hydroxy acetoxy) a glycidyl-containing moiety; R is a group Substituted for a derivative of bisphenol A of Step (c) with hydrogen hydrogen atom on the aromatic ring; and Z is (i) nil, (ii) a chloride; and heteroatom with or without substituents thereon to complete (e) epoxidizing the bis(O-chlorohydrin) intermediate of its necessary bonding Valence, (iii) -C(O)-, (iv) bisphenol A of Step (d) to form an epoxy resin product. S(O) , (v) -C(O)NH-, (vi) -P(O)Ar-, (vii) an 55. An epoxy resin product made by any one of the organic aliphatic or cycloaliphatic moiety, Saturated or processes of claims 48 to 54. unsaturated, with or without heteroatoms, or (viii) a partially 56. An epoxy resin product made by any one of the or fully fluorinated organic aliphatic or cycloaliphatic moi processes of claims 48 to 54 comprising a structure repre ety, sented by the following Formula XVIII: (R), Ar(OR"), Formula XVIII Formula XXI wherein y is from 0 to 750; Z is from 1 to 150; Ar is an aromatic-containing moiety; R" is a glycidyl-contain (R), ing moiety; and R is a group Substituted for a hydrogen atom on the Ar moiety. Z. Z. 57. The epoxy resin of claim 56 wherein R'" is a (RO), O)-(O-)-O.i. (OR), glycidyl-containing moiety Selected from: (OR),

O R3 31 (R), wherein y is 0 to 4, and each y can be the same or different; z is 1 to 3, and each Z, can be the same or different; R'" is -C(R3)2C-C(R) and a glycidyl-containing moiety; R is a group Substituted for a 3 R R3 R3 hydrogen atom on the aromatic ring; Z is (i) nil, (ii) a heteroatom with or without substituents thereon to complete its necessary bonding Valence (iii), -C(O)-, (iv) S(O) , (v) -C(O)NH-, (vi) -P(O)Ar-, (vii) an US 2002/0045707 A1 Apr. 18, 2002 34 organic aliphatic or cycloaliphatic moiety, Saturated or 63. A composition comprising an O-hydroxy ester deriva unsaturated, with or without heteroatoms, or (viii) a partially tive of at least one or more phenols represented by the or fully fluorinated organic aliphatic or cycloaliphatic moi following Formula VI: ety; and m is from 0.001 to 10; or (R), Ar(OR"), Formula VI wherein y is from 0 to 750; Z is from 1 to 150; Ar is an aromatic-containing moiety; R is an O-hydroxy ester Formula XXII propyl-containing moiety; and R is a group Substituted for a hydrogen atom on the Ar moiety. Z 64. The composition of claim 63 wherein the C-hydroxy O ester derivative of at least one or more phenols, comprises (RO), m a structure represented by any one or more of Formulas VII-X as follows: wherein y is 0 to 4, and each y can be the same or different; Z is 1 to 3, and each Z can be the same or different; R" is a glycidyl-containing moiety; R is a group Substituted for a Formula VII hydrogen atom on the aromatic ring; Z is (i) an organic aliphatic moiety, Saturated or unsaturated, with or without heteroatoms, wherein the aliphatic moiety has from 1 to 20 (C. (OR), carbon atoms, (ii) a cycloaliphatic moiety, Saturated or unsaturated, with or without heteroatoms, having from 3 to 20 carbon atoms, (iii) an aromatic moiety, with or without wherein y is 0 to 5; Z is 1 to 4; R' is an O-hydroxy ester heteroatoms, having 6 to 20 carbon atoms, a partially or fully propyl-containing moiety; and R is a group Substituted for fluorinated organic aliphatic, cycloaliphatic or aromatic a hydrogen atom on the aromatic ring, moiety, (v) or any combination thereof, and m' is 3 or 4. 60. The epoxy resin of claim 59 selected from the group Formula VIII comprising aryl glycidyl ethers and aryl methylglycidyl ethers. (R), (R), 61. The epoxy resin of claim 59 selected from the group comprising 1,3-dihydroxybenzene diglycidyl ether; 1,3-di (RO), RO)--O (OR), hydroxybenzene dimethylglycidyl ether; 1,4-dihydroxyben Zene diglycidyl ether, 1,4-dihydroxybenzene dimethylgly wherein y is 0 to 4, and each y can be the same or different; cidyl ether, 1.5-naphthalene diglycidyl ether, 1,5- z is 1 to 3, and each Z can be the same or different; R is an naphthalene dimethylglycidyl ether; 2,6-naphthalene O-hydroxy ester propyl-containing moiety; R is a group diglycidyl ether; 2,6-naphthalene dimethylglycidyl ether; Substituted for a hydrogen atom on the aromatic ring, and Z 4,4'-dihydroxybiphenyl diglycidyl ether; 4,4'-dihydroxybi is (i) nil, (ii) a heteroatom with or without substituents phenyl dimethylglycidyl ether; 3,3',5,5'-tetramethyl-4,4'-di thereon to complete its necessary bonding Valence, (iii) hydroxybiphenyl diglycidyl ether; 3,3',5,5'-tetramethyl-4,4'- -C(O) , (iv) -S(O) , (v) -C(O)NH-, (vi) dihydroxybiphenyl dimethylglycidyl ether; 3,3',5,5'- -P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl moiety, Saturated or unsaturated, with or without heteroat diglycidyl ether; 3,3',5,5'-tetramethyl-2,2',6,6'-tetrabromo-4, oms, or (viii) a partially or fully fluorinated organicaliphatic 4'-dihydroxybiphenyl dimethylglycidyl ether; bis(4-hydrox or cycloaliphatic moiety; yphenyl)methane diglycidyl ether; bis(4-hydroxyphenyl)methane dimethylglycidyl ether; 2,2- bis(4-hydroxyphenyl)isopropylidene diglycidyl ether; 2,2- Formula IX bis(4-hydroxyphenyl)isopropylidene dimethylglycidyl ether; phenol-formaldehyde novolac glycidyl ether (func (R), tionality greater than 2); phenol-formaldehyde novolac (R), (R), methylglycidyl ether (functionality greater than 2); o-cresol formaldehyde novolac glycidyl ether (functionality greater than 2); o-cresol-formaldehyde novolac methylglycidyl (RO), RO)—z z}(O.i. (OR), ether (functionality greater than 2); phenol-dicyclopentadi (OR), enyl novolac glycidyl ether (functionality greater than 2); phenol-dicyclopentadienyl novolac methylglycidyl ether wherein y is 0 to 4, and each y can be the same or different; (functionality greater than 2), naphthol-formaldehyde Z is 1 to 3, and each Z can be the same or different; R' is an novolac glycidyl ether (functionality greater than 2), naph C-hydroxy ester propyl-containing moiety; R is a group thol-formaldehyde novolac methylglycidyl ether (function Substituted for a hydrogen atom on the aromatic ring; Z is (i) ality greater than 2); 1,1,1-tris(4-hydroxyphenyl)methane nil, (ii) a heteroatom with or without substituents thereon to triglycidyl ether, 1,1,1-tris(4-hydroxyphenyl)methane trim complete its necessary bonding Valence, (iii) -C(O)-, (iv) ethylglycidyl ether; 1,1,2,2-tetrakis(4-hydroxyphenyl)e- S(O) , (v) -C(O)NH-, (vi) -P(O)Ar-, (vii) an thane tetraglycidyl ether; 1,1,2,2-tetrakis(4-hydroxyphe organic aliphatic or cycloaliphatic moiety, Saturated or nyl)ethane tetramethylglycidyl ether; and mixtures thereof. unsaturated, with or without heteroatoms, or (viii) a partially 62. The epoxy resin of claim 61 wherein the epoxy resin or fully fluorinated organic aliphatic or cycloaliphatic moi is 2,2-bis(4-hydroxyphenyl)isopropylidene diglycidyl ether. ety; and m is from 0.001 to 10; or US 2002/0045707 A1 Apr. 18, 2002 35

wherein R" is hydrogen; an alkyl group having from 1 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon Formula X atoms, a cycloaliphatic group having from 3 to 20 carbon (R), atoms, or an aromatic group having from 6 to 20 carbon atOmS. O)--z 68. The composition of claim 67 wherein R" is a methyl (RO), grOup. 69. The composition of claim 64 wherein the C-hydroxy ester derivative of phenols or mixtures of phenols is Selected wherein y is 0 to 4, and each y can be the same or different; from the group comprising 1,3-dihydroxybenzene bis(3- z is 1 to 3, and each Z can be the same or different; R is an acetoxy-2-hydroxypropyl) ether; 1,4-dihydroxybenzene O-hydroxy ester propyl-containing moiety; R is a group bis(3-acetoxy-2-hydroxypropyl) ether; 1,5-dihydroxynaph Substituted for a hydrogen atom on the aromatic ring, Z is thalene bis(3-acetoxy-2-hydroxypropyl) ether; 2,6-dihy (i) an organic aliphatic moiety, Saturated or unsaturated, with droxynaphthalene bis (3-acetoxy-2-hydroxypropyl) ether; or without heteroatoms, wherein the aliphatic moiety has 4,4'-dihydroxybiphenyl bis (3-acetoxy-2-hydroxypropyl) from 1 to 20 carbon atoms, (ii) a cycloaliphatic moiety, ether; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl bis(3-ac Saturated or unsaturated, with or without heteroatoms, hav etoxy-2-hydroxypropyl) ether; 3,3',5,5'-tetramethyl-2,2',6, ing from 3 to 20 carbon atoms, (iii) an aromatic moiety, with 6'-tetrabromo-4,4'-dihydroxybiphenyl bis(3-acetoxy-2-hy or without heteroatoms, having 6 to 20 carbon atoms, (iv) a droxypropyl) ether; bis (4-hydroxyphenyl)methane bis partially or fully fluorinated organic aliphatic, cycloaliphatic (3-acetoxy-2-hydroxypropyl) ether; 2,2-bis(4-hydroxyphe or aromatic moiety, or (v) any combination thereof, and m' nyl) isopropylidene bis(3-acetoxy-2-hydroxypropyl) ether; is 3 or 4. phenol-formaldehyde novolac (3-acetoxy-2-hydroxypropyl) 65. The composition of claim 64 wherein the C-hydroxy ether (functionality greater than 2); o-cresol-formaldehyde ester propyl-containing moiety is Selected from: novolac (3-acetoxy-2-hydroxypropyl) ether (functionality greater than 2); phenol-dicyclopentadienyl novolac (3-ac etoxy-2-hydroxypropyl) ether (functionality greater than 2); 31 (R), naphthol-formaldehyde novolac (3-acetoxy-2-hydroxypro Yi X pyl) ether (functionality greater than 2); 1,1,1-tris(4-hydrox -CRCR3-dR3 and yphenyl)methane tris(3-acetoxy-2-hydroxypropyl) ether; R3 R3 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane tetrakis(3-acetoxy Yi Xi 2-hydroxypropyl) ether; 1,3-dihydroxybenzene bis(2-ac etoxy-3-hydroxypropyl) ether; 1,4-dihydroxybenzene bis(2- acetoxy-3-hydroxypropyl) ether; 1,5-dihydroxynaphthalene wherein X" and Y may be a hydroxyl group or a carboxylic bis(2-acetoxy-3-hydroxypropyl) ether; 2,6-dihydroxynaph acid ester moiety, with the proviso that when X is a hydroxyl thalene bis(2-acetoxy-3-hydroxypropyl) ether; 4,4'-dihy group Y must be a carboxylic acid ester moiety and when droxybiphenyl bis(2-acetoxy-3-hydroxypropyl) ether; 3,3', Y is a hydroxyl group X must be a carboxylic acid ester 5.5-tetramethyl-4,4'-dihydroxybiphenyl bis(2-acetoxy-3- moiety; and R is hydrogen, an alkyl group having from 1 to hydroxypropyl) ether; 3,3',5,5'-tetramethyl-2,2',6,6'- 20 carbon atoms, a cycloaliphatic group having from 3 to 20 tetrabromo-4,4'-dihydroxybiphenyl bis(2-acetoxy-3- carbon atoms, an aromatic group having from 6 to 20 carbon hydroxypropyl) ether, bis(4-hydroxyphenyl)methane di(2- atoms or any combination thereof. acetoxy-3-hydroxypropyl) ether; 2,2-bis(4-hydroxyphenyl) 66. The composition of claim 65 wherein R' is selected isopropylidene di(2-acetoxy-3-hydroxypropyl) ether; phe from: nol-formaldehyde novolac (2-acetoxy-3-hydroxypropyl) ether (functionality greater than 2); o-cresol-formaldehyde novolac (2-acetoxy-3-hydroxypropyl) ether (functionality Yi X Yi Xi greater than 2); phenol-dicyclopentadienyl novolac (2-ac etoxy-3-hydroxypropyl) ether (functionality greater than 2); -CHCH-CH and -CH-C-CH naphthol-formaldehyde novolac (2-acetoxy-3-hydroxypro CH pyl) ether (functionality greater than 2); 1,1,1-tris(4-hydrox yphenyl)methane tris(2-acetoxy-3-hydroxypropyl) ether; 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane tetrakis (2-ac wherein X" and Y may be a hydroxyl group or a carboxylic etoxy-3-hydroxypropyl) ether; and mixtures thereof. acid ester moiety, with the proviso that when X is a hydroxyl 70. The composition of claim 69 wherein the C-hydroxy group Y must be a carboxylic acid ester moiety and when ester derivative of phenols or mixtures of phenols is Selected Y is a hydroxyl group X must be a carboxylic acid ester from the group comprising 2,2-bis(4-hydroxyphenyl)isopro moiety. pylidene bis(3-acetoxy-2-hydroxypropyl) ether; 2,2-bis(4- 67. The composition of claim 66 wherein the carboxylic hydroxyphenyl) isopropylidene bis(2-acetoxy-3-hydrox acid ester moiety has the following general Structure: ypropyl) ether; and mixtures thereof. 71. The composition of claim 64 wherein the C-hydroxy ester derivative of at least one or more phenols, (Component (A)), is a single component represented by any one of RCO Formulas VI-X or a mixture of two or more components wherein at least one of the components is represented by any one of Formulas VI to X. US 2002/0045707 A1 Apr. 18, 2002 36

72. The composition of claim 71 wherein Component (A), wherein y is 0 to 4, and each y can be he same or different; the C-hydroxy ester derivative of at least one or more z is 1 to 3, and each z can be the same or different; R is a phenols, is a mixture comprising (i) a component having an group Substituted for a hydrogen atom on the aromatic ring; O-hydroxy ester moiety wherein X" and Y may be a hydroxyl group or a carboxylic acid ester moiety, with the and Z is (i) nil, (ii) a heteroatom with or without substituents proviso that when X is a hydroxyl group Y' must be a thereon to complete its necessary bonding Valence, (iii) carboxylic acid ester moiety and when Y" is a hydroxyl -C(O) , (iv) -S(O) , (v) -C(O)NH-, (vi) group X must be a carboxylic acid ester moiety, (ii) a -P(O)Ar-, (vii) an organic aliphatic or cycloaliphatic component having an O-diester moiety wherein X" and Y are moiety, Saturated or unsaturated, with or without heteroat both carboxylic acid ester moieties, and (iii) a component oms, or (viii) a partially or fully fluorinated organicaliphatic having an O-glycol moiety wherein X" and Y are both hydroxyl. or cycloaliphatic moiety; 73. The composition of claim 72 wherein the percentages of C-hydroxy ester moieties, C.-diester moieties and O-glycol moieties in Component (A) are 5 to 100 percent, 0 to 95 Formula XIV percent and 0 to 95 percent, respectively. 74. The composition of claim 73 wherein the percentages (R), of C-hydroxy ester moieties, C.-diester moieties and O-glycol moieties in Component (A) are 15 to 100 percent, 0 to 85 (R), (R), percent and 0 to 85 percent, respectively. 75. The composition of claim 74 wherein the percentages O)—z z}(O. (HO), i. (OH), of C-hydroxy ester moieties, C.-diester moieties and O-glycol moieties in Component (A) are 30 to 100 percent, 0 to 70 (OH), percent and 0 to 70 percent, respectively. 76. A proceSS for producing an O-hydroxy ester derivative of at least one or more phenols having a structure repre sented by the following Formula VI: wherein y is 0 to 4, and each y can be the same or different; (R), Ar(OR"), Formula VI Z is 1 to 3, and each Z, can be the same or 2 different; R is wherein y is from 0 to 750; Z is from 1 to 150; Ar is an a group Substituted for a hydrogen atom on the aromatic aromatic-containing moiety; R is an O-hydroxy ester ring, Z is (i) nil, (ii) a heteroatom with or without Substitu propyl-containing moiety; and R is a group Substituted ents thereon to complete its necessary bonding Valence, (iii) for a hydrogen atom on the Ar moiety; the process -C(O), (iv)-S(O) , (v)-C(O)NH-, (vi) -P(O)Ar-, comprising reacting (1) at least one or more phenols (vii) an organic aliphatic or cycloaliphatic moiety, Saturated with (2) a glycidyl ester or a Substituted glycidyl ester. 77. The process of claim 76 wherein Component (1), the or unsaturated, with or without heteroatoms, or (viii) a one or more phenols, comprises a structure represented by partially or fully fluorinated organic aliphatic moiety; and m the following Formula XI: is from 0.001 to 10; or (R), Ar(OH), Formula XI wherein y is 0 to 750; Z is 1 to 150; Ar is an aromatic containing moiety; and R is a group Substituted for a hydrogen atom on the Ar moiety. Formula XV 78. The process of claim 77 wherein Component (1), the (R), one or more phenols, comprises a structure represented by any one or more of Formulas XII-XV as follows: (HO), O)}-z

Formula XII wherein y is 0 to 4, and each y can be the same or different; (C. (OH), Z is 1 to 3, and each Z can be the same or different; R is a group Substituted for a hydrogen atom on the aromatic ring; Z (i) is an organic aliphatic moiety, Saturated or unsaturated, wherein y is 0 to 5, and each y can be the same or different; with or without heteroatoms, wherein the aliphatic moiety Z is 1 to 4, and each Z can be the same or different; and R' has from 1 to 20 carbon atoms, (ii) a cycloaliphatic moiety, is a group Substituted for a hydrogen atom on the aromatic Saturated or unsaturated, with or without heteroatoms, hav ring, ing from 3 to 20 carbon atoms, (iii) an aromatic moiety, with or without heteroatoms, having 6 to 20 carbon atoms, (iv) a Formula XIII partially or fully fluorinated organic aliphatic, cycloaliphatic (R), (R), or aromatic moiety, or (V) any combination thereof, and m' is 3 or 4. (HO), O)--O (OH), 79. The process of claim 76 wherein Component (2), the glycidyl ester or Substituted glycidyl ester, comprises a structure represented by the following Formula XVI: US 2002/0045707 A1 Apr. 18, 2002 37

91. The process of claim 72 wherein the reaction of preparing the C-hydroxy ester derivative is carried out at a temperature of from about 10 C. to about 160° C. Formula XVI 92. A product made by the process of claim 76. 93. A composition comprising at least two or more components wherein at least one of the components is an RCORS O-hydroxy ester derivative of claim 63 and at least one of the components is a C-halohydrin intermediate of at least one or wherein R" is hydrogen, an alkyl group having from 1 to 20 more phenols comprising a structure represented by the carbon atoms, an alkenyl group having from 2 to 20 carbon following Formula I: atoms, a cycloaliphatic group having from 3 to 20 carbon (R), Ar(OR"), Formula I atoms, or an aromatic group having from 6 to 20 carbon wherein y is from 0 to 750; Z is from 1 to 150; Ar is an atoms; and R is a glycidyl moiety. aromatic-containing moiety; R is an O-halohydrin pro 80. The process of claim 79 wherein R is selected from: pyl-containing moiety; and R is a group Substituted for a hydrogen atom on the Ar moiety. 94. The composition of claim 93 wherein the C-halohy drin intermediate of at least one or more phenols comprises O 31 (R), a structure represented by any one or more of the following Formulas II-V: -C(R)2C-C(R) and R3 R3

Formula II wherein R is hydrogen, an alkyl group having from 1 to (R), 20carbon atoms, a cycloaliphatic group having from 3 to 20 carbon atoms, an aromatic group having from 6 to 20 carbon O (OR), atoms, or any combination thereof. 81. The process of claim 80 wherein R is selected from: wherein y is 0 to 5; Z is 1 to 4; R is an O-halohydrin propyl-containing moiety; and R is a group Substituted for a hydrogen atom on the Ar moiety; O O / M / M -CHC- CH2 and o CHC- CH2.

H CH Formula III (R), (R), 82. The process of claim 81 wherein Component (2), the glycidyl ester or Substituted glycidyl ester, is Selected from (RO),3)--O (OR), glycidyl formate, glycidyl acetate, methylglycidyl formate and methylglycidyl acetate. wherein y is 0 to 4, and each y can be the same or different; 83. The process of claim 82 wherein Component (2), the Z is 1 to 3, and each Z can be the same or different; R' is an glycidyl ester, is glycidyl acetate. C-halohydrin propyl-containing moiety; R is a group Sub 84. The process of claim 76 wherein the amount of Stituted for a hydrogen atom on the aromatic ring, and Z is glycidyl ester or Substituted glycidyl ester reacted with at (i) nil, (ii) a heteroatom with or without substituents thereon least one or more phenols is from about 0.5 equivalents to to complete its necessary bonding Valence, (iii) -C(O)-, about 50 equivalents of glycidyl ester or Substituted glycidyl (iv)-S(O) , (v)-C(O)NH-, (vi) -P(O)Ar-, (vii) an ester per one equivalent of phenolic hydroxyl. organic aliphatic or cycloaliphatic moiety, Saturated or 85. The process of claim 76 wherein the reaction of unsaturated, with or without heteroatoms, or (viii) a partially preparing the C-hydroxy ester derivative is carried out in the or fully fluorinated organic aliphatic or cycloaliphatic moi presence of a Solvent. ety, 86. The process of claim 76 wherein the reaction of preparing the C-hydroxy ester derivative is carried out in the presence of a catalyst. 87. The process of claim 86 wherein the catalyst is a phase transfer catalyst. Formula IV 88. The process of claim 87 wherein the catalyst is an organopnicogen-containing catalyst. (R), 89. The process of claim 88 wherein the catalyst is (R), (R), homogeneous or heterogeneous. 90. The process of claim 89 wherein the catalyst is from (RO),C-(O-)-O i. (OR), about 0.001 percent to about 1000 percent by weight based (OR), on the amount of the phenol or mixture of phenols used in the reaction. US 2002/0045707 A1 Apr. 18, 2002 38 wherein y is 0 to 4, and each y can be the same or different; 97. The composition of claim 94 wherein the C-chloro z is 1 to 3, and each Z, can be the same or different; R is an hydrin intermediate of at least one or more phenols is C-halohydrin propyl-containing moiety; R is a group Sub Selected from the group comprising 1,3-dihydroxybenzene Stituted for a hydrogen atom on the aromatic ring, Z is (i) nil, bis(3-chloro-2-hydroxypropyl)ether; 1,4-dihydroxybenzene (ii) a heteroatom with or without substituents thereon to bis(3-chloro-2-hydroxypropyl) ether; 1,5-dihydroxynaph complete its necessary bonding Valence, (iii) -C(O)-, (iv) thalene bis(3-chloro-2-hydroxypropyl) ether; 2,6-dihydrox -S(Ohd 2) , (v) -C(O)NH-, (vi) -P(O)Ar-, (vii) an ynaphthalene bis(3-chloro-2-hydroxypropyl) ether; 4,4'-di organic aliphatic or cycloaliphatic moiety, Saturated or hydroxybiphenyl-bis(3-chloro-2-hydroxypropyl) ether; 3,3', unsaturated, with or without heteroatoms, or (viii) a partially 5,5'-tetramethyl-4,4'-dihydroxybiphenyl bis(3-chloro-2- or fully fluorinated organic aliphatic or cycloaliphatic moi hydroxypropyl) ether; 3,3',5,5'-tetramethyl-2,2',6,6'- ety; and m is from 0.001 to 10; or tetrabromo-4,4'-dihydroxybiphenyl bis(3-chloro-2- Formula V hydroxypropyl) ether; bis(4-hydroxyphenyl)methane-bis(3- chloro-2-hydroxypropyl) ether; 2,2-bis(4- (R), hydroxyphenyl)isopropylidene bis(3-chloro-2- hydroxypropyl) ether, phenol-formaldehyde novolac (RO) (O)}z2. m (3-chloro-2-hydroxypropyl) ether (functionality greater than 2); o-cresol-formaldehyde novolac (3-chloro-2-hydroxypro pyl) ether (functionality greater than 2); phenol-dicyclopen wherein y is 0 to 4, and each y can be the same or different; Z is 1 to 3, and each Z can be the same or different; R' is an tadienyl novolac (3-chloro-2-hydroxypropyl) ether (func C-halohydrin propyl-containing moiety; R is a group Sub tionality greater than 2), naphthol-formaldehyde novolac Stituted for a hydrogen atom on the aromatic ring; Z is (i) an (3-chloro-2-hydroxypropyl) ether (functionality greater than organic aliphatic moiety, Saturated or unsaturated, with or 2); 1,1,1-tris(4-hydroxyphenyl)methane tris(3-chloro-2-hy without heteroatoms, wherein the aliphatic moiety has from droxypropyl) ether; 1,1,2,2-tetrakis(4-hydroxyphenyl)e- 1 to 20 carbon atoms, (ii) a cycloaliphatic moiety, Saturated thane tetrakis(3-chloro-2-hydroxypropyl) ether; 1,3-dihy or unsaturated, with or without heteroatoms, having from 3 droxybenzene bis(2-chloro-3-hydroxypropyl) ether; 1,4- to 20 carbon atoms, (iii) an aromatic moiety, with or without dihydroxybenzene bis(2-chloro-3-hydroxypropyl) ether; heteroatoms, having 6 to 20 carbon atoms, (iv) a partially or 1,5-dihydroxynaphthalene bis(2-chloro-3-hydroxypropyl) fully fluorinated organic aliphatic, cycloaliphatic or aro ether; 2,6-dihydroxynaphthalene bis(2-chloro-3-hydrox matic moiety, or (V) any combination thereof, and m' is 3 or ypropyl) ether; 4,4'-dihydroxybiphenyl bis(2-chloro-3-hy 4. droxypropyl) ether; 3,3',5,5'-tetramethyl-4,4'-dihydroxybi 95. The composition of claim 94 wherein R is selected phenyl bis(2-chloro-3-hydroxypropyl) ether; 3,3',5,5'- from: tetramethyl-2,2',6,6'-tetrabromo-4,4'-dihydroxybiphenyl bis(2-chloro-3-hydroxypropyl) ether; Y X R3 31 (R), bis(4-hydroxyphenyl)methane bis(2-chloro-3-hydroxypro -C(R)2CR-6(R) and pyl) ether, 2,2-bis(4-hydroxyphenyl)isopropylidene bis(2- chloro-3-hydroxypropyl) ether; phenol-formaldehyde novolac (2-chloro-3-hydroxypropyl) ether (functionality greater than 2); o-cresol-formaldehyde novolac (2-chloro 3-hydroxypropyl) ether (functionality greater than 2); phe wherein X and Y may be a halogen atom or hydroxyl group nol-dicyclopentadienyl novolac (2-chloro-3-hydroxypropyl) with the proviso that when X is a halogen Y must be a ether (functionality greater than 2), naphthol-formaldehyde hydroxyl and when Y is a halogen X must be a hydroxyl; and novolac (2-chloro-3-hydroxypropyl) ether (functionality R is hydrogen, an alkyl group having from 1 to 20 carbon greater than 2); 1,1,1-tris(4-hydroxyphenyl)methane tris(2- atoms, a cycloaliphatic group having from 3 to 20 carbon chloro-3-hydroxypropyl) ether; 1,1,2,2-tetrakis(4-hydrox atoms, an aromatic group having from 6 to 20 carbon atoms, yphenyl)ethane tetrakis(2-chloro-3-hydroxypropyl) ether; or any combination thereof. and mixtures thereof. 96. The composition of claim 95 wherein R' is selected 98. The composition of claim 97 wherein the C-chloro from: hydrin intermediate of at least one or more phenols is Selected from the group comprising 2,2-bis(4-hydroxyphe nyl)isopropylidene bis(3-chloro-2-hydroxypropyl) ether; 2,2-bis(4-hydroxyphenyl)isopropylidene bis(2-chloro-3-hy droxypropyl) ether; and mixtures thereof. 99. The composition of claim 93 wherein the C-halohy -CHCH-CH and —all-cit, drin intermediate of at least one or more phenols comprising CH a structure represented by Formula I is present in an amount of from about 10 to less than about 100 percent by weight. 100. The composition of claim 99 wherein the C-halohy wherein X and Y may be a halogen atom or hydroxyl group drin intermediate of at least one or more phenols comprising with the proviso that when X is a halogen Y must be a a structure represented by Formula I is present in an amount hydroxyl and when Y is a halogen X must be a hydroxyl. of from about 25 to less than about 100 percent by weight. US 2002/0045707 A1 Apr. 18, 2002 39

101. The composition of claim 100 wherein the C-halo 104. The composition of claim 103 wherein the epoxy hydrin intermediate of at least one or more phenols com resin product comprising a structure represented by Formula prising a Structure represented by Formula I is present in an XVIII is present in an amount of from about 25 to about 100 amount of from about 50 to about 100 percent by weight. percent by weight. 102. An epoxy resin composition comprising at least two or more components wherein at least one of the components 105. The composition of claim 104 wherein the epoxy is an epoxy resin product as claimed in claim 56. resin product comprising a structure represented by Formula 103. The composition of claim 102 wherein the epoxy XVIII is present in an amount of from about 50 to about 100 resin product comprising a structure represented by Formula percent by weight. XVIII is present in an amount of from about 10 to about 100 percent by weight.