Patent GB-1049963-A (GB)
Title: Process for forming polyphenylene ether resins
IPC: C09D5/44
Filed: 1965-07-23
Abstract: The invention comprises a process for forming polyphenylene ether resins of formula <FORM:1049963/C6-C7/1> where n is from 10 to 1500, Q is a hydrogen or halogen atom or a monovalent hydrocarbon radical without a tertiary alpha-carbon atom or a halohydrocarbon radical having at least two carbon atoms between the halogen atom and the phenol nucleus and without a tertiary alpha-carbon atom; Q1 and Q11 are the same as Q but, in addition, may be hydrocarbonoxy radicals without tertiary alphacarbon atoms, or halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and the phenol nucleus and without tertiary alpha-carbon atoms; and Q1 11 is the same as Q1 and Q11 but, in addition, may be one of the radicals <FORM:1049963/C6-C7/2> where <FORM:1049963/C6-C7/3> is a single ringed heterocyclic radical, Z being O or S,J is a monovalent substituted or unsubstituted hydrocarbon substituent and R1 is the same as J but, in addition, may be hydrogen; wherein an electric current is conducted through a solution or emulsion comprising up to 50% by weight of a monomer of formula <FORM:1049963/C6-C7/4> where Q,Q1,Q11 and Q111 are as above, and is hydrogen, chlorine, bromine or iodine, a copper salt as a catalyst, ammonia or a secondary or tertiary amine as a complexing agent, and an ionic conductor.  The solution or emulsion containing the monomer, copper salt and ammonia or amine, may form an anolyte separated from a catholyte by an ion exchange membrane or unglazed porcelain.  For continuous polymerization the catholyte may flow through a series of cells alternating with a series of cells through which anolyte flows in the opposite direction, there being porous diaphragms or ion exchange membranes between the cells.  In Examples polymers are obtained from 2, 6-demethylphenol and from tetrahydropyran -2-ol 3-methylcatechol-1 ether in solutions prepared from pyridine, methanol, N, N, N1, N1-tetra-methyl-1, 3-butanediamine and aqueous hydrochloric acid, and from benzene, acetone, dimethylformamide methylpropylamine and methylpropylamine hydrochloride, and in emulsions prepared from oleic acid, benzene, sodium chloride, potassium ferricyanide, triethanolamine, aqueous ammonia, N, N, N1, N1-tetramethyl-1, 3-butanediamine, an addition product of ethylene oxide and propylene glycol, potassium chloride, potassium manganate, dimethylamine, sodium hydroxide and water; the catalysts are cuprous chloride, copper sulphate and cuprous acetate.  Other materials are mentioned.ALSO:The invention comprises a process for forming polyphenylene ether resins of formula <FORM:1049963/C3/1> where n is from 10 to 1500, Q is a hydrogen or halogen atom or a monovalent hydrocarbon radical without a tertiary alpha-carbon atom or a halohydrocarbon radical having at least two carbon atoms between the halogen atom and the phenol nucleus and without a tertiary alpha-carbon atom; Q1 and Q11 are the same as Q but, in addition, may be hydrocarbonoxy radicals without tertiary alphacarbon atoms, or halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and the phenol nucleus and without tertiary alpha-carbon atoms; and Q111 is the same as Q1 and Q11 but, in addition, may be one of the radicals <FORM:1049963/C3/2> or <FORM:1049963/C3/3> where <FORM:1049963/C3/4> is a single ringed heterocyclic radical Z being O or S, J is a monovalent substituted or unsubstituted hydrocarbon substituent and R1 is the same as J but, in addition, may be hydrogen; wherein an electric current is conducted through a solution or emulsion comprising up to 50% by weight of a monomer of formula <FORM:1049963/C3/5> where Q, Q1, Q11 and Q111 are as above, an X is hydrogen, chlorine, bromine or iodine, a copper salt as a catalyst, ammonia or a secondary or tertiary amine as a complexing agent, and an ionic conductor.  The solution or emulsion containing the monomer, copper salt and ammonia or amine, may form an anolyte separated from a catholyte by an ion exchange membrane or unglazed porcelain.  For continuous polymerization the catholyte may flow through a series of cells alternating with a series of cells through which anolyte flows in the opposite direction, there being porous diaphragms or ion exchange membranes between the cells.  In examples polymers are obtained from 2,6-dimethylphenol and from tetrahydropyran-2-ol 3-methylcatechol-1 ether in solutions prepared from pyridine, methanol, N,N,N1,N1-tetra-methyl-1,3-butanediamine and aqueous hydrochloric acid, and from benzene, acetone, dimethylformamide methylpropylamine and methylpropylamine hydrochloride, and in emulsions prepared from oleic acid, benzene, sodium chloride, potassium ferricyanide, triethanolamine, aqueous ammonia, N,N,N1,N1-tetramethyl-1,3-butanediamine, an addition product of ethylene oxide and propylene glycol, potassium chloride, potassium manganate, dimethylamine, sodium hydroxide and water; the catalysts are cuprous chloride, copper sulphate and cuprous acetate.  Other materials are mentioned.