Patent GB-887609-A (GB)
Title: Improvements in high molecular weight resins
IPC: C08G59/06
Filed: 1959-10-19
Abstract: High molecular weight resins are made by subjecting monochlorohydrin ethers of hydroxyalkyl or hydroxyaliphatic ethers of a dihydric phenol to dehydrohalogenation with an alkaline dehydrohalogenating agent.  In modifications of the process, the dehydrohalogenation is effected in the presence of epichlorohydrin which may or may not be present in excess and/or a dihydric phenol or a chlorohydrin or glycidyl-chlorohydrin ether thereof.  The monochlorohydrin ethers are made by reacting 1 mol of an hydroxyalkyl or hydroxyaliphatic ether of a dihydric phenol with 1 mol of epichlorohydrin in the presence of a condensation catalyst, e.g. boron trifluoride etherate, the hydroxyalkyl or hydroxyaliphatic ethers being made by reacting dihydric phenols, e.g. bis-phenol-A, resorcinol or hydroquinone with:- (a) ethylene chlorohydrin in the presence of caustic soda, or (b) monoepoxides, e.g. glycidol, ethylene oxide, butyl glycidyl ether, isopropyl glycidyl ether or styrene oxide or (c) a monochlorohydrin ether of a mono-, di- or trihydric alcohol or (d) monoglycidyl ethers of trihydric alcohols.  Specified alkaline dehydrohalogenating agents are sodium silicate, sodium aluminate and sodium zincate.  Examples (5) to (9) describe the dehydrohalogenation of the monochlorohydrin ethers of:-(5) and (6) the hydroxyethyl ether of bis-phenol-A; (7) the hydroxyethyl ether of resorcinol; (8) the isopropyl glycidyl ether adduct of bis-phenol-A and (9) the glycerine ether of resorcinol, in the presence of excess epichlorohydrin to produce monomeric diglycidyl ethers which may be used in the preparation of epoxy resins. Examples (10) to (13) describe the dehydrohalogenation in the presence of excess epichlorohydrin and (10) to (12) bis-phenol-A; (13) resorcinol, of the monochlorohydrin ethers of:- (10) the isopropyl glycidyl ether adduct of bis-phenol-A; (11) the hydroxyethyl ether of bis-phenol-A; (12) the hydroxyethyl ether of resorcinol and (13) the glycerine ether of resorcinol. Examples (16) to (19) describe the dehydrohalogenation in the presence of excess epichlorohydrin and (16) the mixed chlorohydrin-glycidyl ethers of bis-phenol-A; (17) and (19) the dichlorohydrin ether of bis-phenol-A and (18) the mixed chlorohydrin-glycidyl ethers of resorcinol, of the monochlorohydrin ethers of:- (16) and (17) the hydroxyethyl ether of bis-phenol-A and (18) and (19) the isopropyl glycidyl ether adduct of bis-phenol-A. Examples (20) and (21) describe the preparation of high molecular weight polyhydric alcohols by the dehydrohalogenation of the monochlorohydrin ethers of:-(20) the hydroxyethyl ether of bis-phenol-A and (21) the hydroxypropyl ether of resorcinol. Examples (22) and (23) describe the preparation of epoxy resins by dehydrohalogenating the monochlorohydrin ether of the hydroxyethyl ether of bis-phenol-A in the presence of less than a molar equivalent of epichlorohydrin.  Examples (24) to (28) describe the preparation of polymeric dihydric phenols by dehydrohalogenating in the presence of:-(24) to (26) and (28) bis-phenol-A and (27) resorcinol, the monochlorohydrin ethers of:-(24) to (27) the hydroxyethyl ether of bis-phenol-A and (28) the hydroxyethyl ether of resorcinol; the products of Examples (26) to (28) being converted to epoxy resins by reaction with epi-chlorohydrin. Examples (29) and (30) describe the preparation of epoxy resins by dehydrohalogenating in the presence of epichlorohydrin and bis-phenol-A the monochlorohydrin ether of the hydroxyethyl ether of:-(29) bis-phenol-A and (30) resorcinol.ALSO:Aliphatic-aromatic diglycidyl ethers, largely or mainly monomeric in nature are made by the dehydrohalogenation with an alkaline dehydrohalogenating agent of a monochlorohydrin ether of an hydroxyalkyl or hydroxyaliphatic ether of a dihydric phenol in the presence of excess epichlorohydrin and optionally a dihydric phenol of a chlorohydrin or glycidyl-chlorohydrin ether thereof. The monochlorohydrin ethers are made by reacting 1 mol of an hydroxyalkyl or hydroxyaliphatic ether of a dihydric phenol with 1 mol of epichlorohydrin in the presence of a condensation catalyst, e.g. boron trifluoride etherate, the hydroxyl alkyl or hydroxyaliphatic ethers being made by reacting dihydric phenols, e.g. bis-phenol-A, resorcinol or hydroquinone with: (a) ethylene monochlorohydrin in the presence of caustic soda, or (b) monoepoxides, e.g. glycidol, ethylene oxide, butyl glycidyl ether, isopropyl glycidyl ether or styrene oxide, or (c) a monochlorohydrin ether of a mono-, di- or trihydric alcohol or (d) monoglycidyl ethers of polyhydric alcohols. Specified alkaline dehydrohalogenating agents are sodium silicate, sodium aluminate and sodium zincate.  Examples (1) to (4) describe the preparation of monohydroxy alkyl ethers from: (1) bis-phenol-A and epichlorohydrin; (2) bis-phenol-A and ethylene carbonate; (3) bis-phenol-A and iso-propyl glycidyl ether and (4) resorcinol and glycerine carbonate.  Examples (5) to (9) describe the reaction of epichlorohydrin with: (5) and (6) the hydroxyethyl ether of bis-phenol-A; (7) the hydroxy ethyl ether of resorcinol; (8) the iso-propyl glycidyl ether adduct of bis-phenol-A and (9) the glycerine ether of resorcinol to form the monochlorohydrin ethers which are then dehydrohalogenated in the presence of excess epichlorohydrin to form diglycidyl ethers.  Ex-amples (10) to (13) describe the preparation of composite aliphatic-aromatic glycidyl ethers and glycidyl ethers of dihydric phenols by dehydrohalogenating in the presence of a dihydric phenol and excess epichlorohydrin, the monochlorohydrin ethers of: (10) the iso-propyl glycidyl ether adduct of bis-phenol-A; (11) the hydroxyethyl ether of bis-phenol-A; (12) the hydroxyethyl ether of resorcinol and (13) the glycerine ether of resorcinol, the dihydric phenols used being: (10), (11) and (12) bis-phenol-A; (13) resorcinol.  Example (14) describes the preparation of a glycidyl chlorohydrin ether of bis-phenol-A. Examples (16) to (19) describe the dehydrohalogenation in the presence of excess epichlorohydrin of the monochlorohydrin ethers of: (16) and (17) the hydroxyethyl ether of bis-phenol-A; (18) and (19) the isopropyl glycidyl ether adduct of bis-phenol-A in the presence of: (16) mixed chlorohydrin-glycidyl ethers of bis-phenol-A; (17) and (19) the dichlorohydrin ether of bis-phenol-A and (18) the mixed-glycidyl-chlorohydrin ether of resorcinol.