IIIHIII||||| USOO51361.10A United States Patent (19) 11) Patent Number: 5,136,110 Walters et al. 45) Date of Patent: Aug. 4, 1992 54 PROCESS FOR THE PREPARATION OF BSPHENOLS OTHER PUBLICATIONS (75 Inventors: Marlin E. Walters, West Columbia; 5. Liebig's Annalen der chemie 363: pp. 275-276 W.Fr. Richey, Emmett Tasset, Chical Abstract 29.855(7) (1935). both of Lake Jackson, all of Tex. Chemical Abstract 65:3795c (1966). (73, Assignee: The Dow Chemical Company, J. Amer. Chem. Soc. 37, pp. 2575-2591 (1915). Midland, Mich. Chemical Abstract 85:192405k (Japan Kokai 76 86,434). J. Amer. Chem. Soc. 61, pp. 345-348 (1939). 21 Appl. No.: 626,597 J. Amer. Chem. Soc. 76, pp. 4547-4550 (1954). (22 Filed: Dec. 12, 1990 Primary Examiner-Werren B. Lone Related U.S. Application Data 57 ABSTRACT (63) abandoned.Continuation-in-part of Ser. No. 472,508, Jan. 29, 1990, Thematic invention bisphenols is a reactingprocess fora phenolic the preparation compound, of triaro e.g. phenol, with a suitable halo-compound, for instance 51 Int, C. ....................... C07C37/18; CO7C39/12 1,1-dichloroethylbenzene, 1-chlorostyrene, or mixtures 52 U.S. Cl. .................................... 568/722; 568/717; thereof. The reaction may be conducted in the presence 568/723; 568/726 or absence of a solvent; an excess of the phenolic com 58 Field of Search ............... 568/722,727, 723, 718, pound can serve as the solvent. The product is conve 568/717, 726 niently recovered by removing the by-product HCl, (56) References Cited excess phenolic compound, excess solvent and cooling. Yields of bis-1,1-(4-hydroxyphenyl)-1-phenylethane U.S. PATENT DOCUMENTS which are greater than 90% of theoretical have been 2,634,297 4/1953 Moyle ................................. 568/78 obtained by the reaction of phenol and 1,1-dichloroeth 2,858,342 10/1958 Bender et al. ....................... 568/718 ylbenzene and a large portion of the yield is para iso 3,001,972 9/1961 Christenson et al. ............... 568/78 ner. Suitable halo-compounds include aromatic dihalo 3,378,518 4/1968 Doyle .................................. 568/718 compounds having at least one aliphatic substituent 4,467,122 8/1984 Szabolcs .............................. 568/78 having two alpha-halogen atoms and at least one beta FOREIGN PATENT DOCUMENTS halogen atom, halo-styrenes having structures corre 0259746 8/1987 European Pat. Off. sponding to such aromatic dihalo-compounds except 1092027 3/1958 Fed. Rep. of Germany ...... 568/718 that an alpha-halogen atom and a beta hydrogen atom 299757 5/1979 Fed. Rep. of Germany . are removed and there is a double bond between the 1296024 2/1986 Japan ................................... 568/78 alpha and beta carbon atoms, trihalotoluenes, and 885005 12/1961 United Kingdom. dihalocyanotoluenes. 894.620 4/1962 United Kingdom. 935061 3/1963 United Kingdom ................ 568/718 28 Claims, No Drawings 5,136,110 1. 2 ydroxyphenyl compounds, including triaromatic bis PROCESS FOR THE PREPARATION OF phenols, are preferably in the para isomer form (having BSPHENOLS the hydroxy group on the phenyl ring para to the at tachment of the phenyl ring to the carbon atom to CROSS-REFERENCE TO RELATED 5 which the other phenyl group(s) are attached) because - APPLICATION such isomers result in high polymers with desirable This application is a continuation-in-part of applica properties of high molecular weight, impact strength, tion serial number 472,508, filed Jan. 29, 1990, now modulus and the like. abandoned. 10 SUMMARY OF THE INVENTION BACKGROUND OF THE INVENTION Bisphenols are made by reacting a halo-compound This invention relates to preparation of bisphenols, which is (1) a trihalotoluene, (2) a dihalocyanotoluene, particularly bisphenols having a carbon atom having (3) an aromatic dihalo-compound having at least one bonded thereto an aliphatic group and at least three aliphatic substituent having two alpha-halogen substitu aromatic groups, at least two of which aromatic groups 15 ents and at least one beta hydrogen atom, (4) a corre each have at least one phenolic group, hereinafter re sponding halo-styrene or (5) mixtures thereof with a ferred to as triaromatic bisphenols. Bisphenols are the phenolic compound. At least two moles of the phenolic building block molecules for such materials as polycar compound per mole of halo-compound are preferably bonates, epoxy resins, polysulfones, polyarylates and employed. The reaction may be conducted with or the like. Bisphenols in which the phenolic rings are 20 without a solvent. The bisphenol is conveniently recov joined together through a single bridging carbon are ered by removing by-product HCl, excess phenolic usually manufactured by condensing two moles of phe compound and solvent (if any) and cooling to obtain the nol with an aldehyde or a ketone in the presence of an product. Alternatively, a crystallization solvent is used. acid catalyst. Bisphenol A is the most commonly used bisphenol and is made from the reaction of acetone with 25 In contrast with conventional technology, the new phenol. Because it must be performed under mild tem method is rapid and uses a simple purification to give perature conditions (50-70 C.) to minimize the forma the desired product. For instance, yields of bis-1,1-(4- tion of undesirable coproducts, it is a slow reaction. hydroxyphenyl)-1-phenylethane (Bisphenol AP) of up Other bisphenols are employed to impart specific prop to 95 percent of theoretical can be obtained using this erties to the above resins. Some of these properties are, 30 process. for example, toughness, strength, better thermal proper The reaction is broadly applicable with other aro ties and solvent resistance. Bisphenol AP, the bisphenol matic hydroxy compounds such as naphthols and substi of phenol and acetophenone (bis-1,1-(4-hydroxy tuted phenols which can be reacted with the halo-com phenyl)-1-phenylethane), is known to improve the ther pounds in place of phenol to prepare analogous bis mal properties of polycarbonates, polyarylates and 35 hydroxyaromatic derivatives. epoxy resins over similar materials made from bisphenol There is advantageously high selectivity for the para A. isomers. For instance, we have now discovered that The condensation of phenol with acetophenone, under mild conditions, the reaction of phenol with 1,1- however, is very slow. Even with zinc chloride as a dichloroethylbenzene (DCEB) will produce bisphenol catalyst, the reaction requires two days to complete AP rapidly with excellent selectivity to the pip' isomer, (U.S. Pat. No. 4,467,122). Then an extended work-up preferably with greater than 94% selectivity. This se must be performed to remove as much residual zinc lectivity is unexpected in view of the known art. salts as possible. With HCl as the catalyst, the reaction DETAILED DESCRIPTION OF THE requires 10-14 days. These process limitations, along INVENTION with the lack of commercially significant quantities of 45 acetophenone, have hindered the development of useful The process of the invention is represented by the applications for Bisphenol AP. A more facile process reaction: should allow wider use of this valuable monomer. In order to achieve the high molecular weights re CX-22 quired to produce the desired thermal and mechanical properties, the bisphenol starting materials for such thermoplastics as polycarbonates and polyarylates pref. (R) OH erably have the constituent phenol groups substituted in the para position in greater than 98% selectivity. Al o (R") though most of the ortho-substituted material can be 55 CX-CHR'. OH separated by crystallization, it is most desirable for good process economics to minimize the product containing gf. g5-> ar (R) p any ortho isomer. In one reference, J. American Chemi (R) (R") (R") cal Society, 76, 4547(1954), 1-chloroethylbenzene is o reported to react with phenol to give a mixture of iso OH mers of 1-(hydroxyphenyl)-1-phenylethane having the hydroxy group of the phenyl group in the ortho and para position in a mole ratio of 55 ortho to 45 para (R),9 c=CH position. It would be desirable to prepare triaromatic bisphe 65 wherein each R" is independently H or an aliphatic nols more quickly than is typical for condensations of group; each R, or R" is independently an inert substitu acetophenone with phenols and to prepare them such ent or an aliphatic or aromatic group wherein two or that there is a high selectivity for the para isomer. Bish more R's and/or 2 or more R's are optionally joined to 5,136,110 3 4. form cycloaliphatic or aromatic groups; R" is CN or a solvent and cool to effect the crystallization of the (R")p-phenyl-OH in the case of the -CX22 starting bisphenol. material, -CHR'2 in the case of the dihalo starting Although the reaction is autocatalytic because the material or -CH2R' in the case of the halostyrene start HCl produced by the reaction is an effective catalyst, ing material; X is a halogen, either chlorine or bromine, any strong acid catalyst, advantageously HC or any preferably chlorine; Z is a chlorine, bromine or a cyano other hydrogen halide, may be added to the phenol as a group (CN); y is an integer of from 0 to 5, preferably catalyst for the reaction, preferably before the addition from 0 to about 2, more preferably from 0 to 1; p is an of the halo-compound because addition of the acid cata integer of from 0 to 4, preferably from 0 to about 2, most lyst is more useful before the concentration of HCl preferably from 0 to 1. When R is an aliphatic group, 10 produced in the reaction has reached a desired catalytic each R" preferably has from 1 to about 15 carbon atoms, concentration. It is advantageous to conduct the reac more preferably from 1 to about 5 carbon atoms.