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 allyl chloride, 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 glycerol, 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, glycidol 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 acetic acid 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.