Patent GB-1095931-A (GB)
Title: Dispersions of synthetic polymers
Inventor: DUELL ENID GILLIAN
IPC: C08G85/00
Filed: 1963-05-16
Abstract: A process for producing a dispersion in organic liquid of a polymer in which the link between monomers or comers forming the polymeric chain involves an atom other than carbon is characterized in that the monomer or comers dissolved in the organic liquid are polymerized to form the polymer which is insoluble in the organic liquid and forms dispersed particles therein, the polymerization being carried out in the presence of a compound comprising a polymeric chain solvated by the organic liquid and a group or groups which will copolymerize with the monomer or comer, at least a minor proportion of the monomer or comer being copolymerized with the group(s) of the compound to attach non-solvated polymeric chain(s) thereto and form a block or graft copolymer in which the solvated polymeric chain is linked to non-solvated polymeric chain(s) at on average not more than two points along the solvated polymeric chain.  The nature of the solvated polymeric constituent of the block or graft copolymer (i.e. the precursor) depends upon the nature of the organic liquid used, where it is an aliphatic hydrocarbon suitable solvatable polymeric constituents are polymers of long chain esters of acrylic or methacrylic acids polymeric vinyl esters of long chain acids, polymeric vinyl alkyl ethers and polymers of ethylene, propylene, butadiene and isoprene, where it is an aromatic hydrocarbon suitable constituents are the above, shorter chain analogues, aromatic polyesters, alkyds, aromatic polyethers, aromatic polycarbonates, and polymers of styrene and vinyl toluene, and where the liquid is polar, e.g. methyl or ethyl alcohol, the constituents include polymers of acrylic or methacrylic acid, carboxymethyl celluloses, polyethylene or polypropylene glycols, hydroxylated polymers, e.g. polyvinyl alcohol or polymers of glycol mono-methacrylates.  The nature of the copolymerizable group of the precursor depends on the nature of the monomers or comers from which the polymer is to be formed. Many examples of such systems are given and include the following: (1) diacid halide and aliphatic diol as monomer (A), an aliphatic hydroxy group as precursor copolymerizable group (B) and hydrochloric acid acceptor, e.g. tertiary base as initiator or catalyst (C), (2) diacid halide and aromatic diol (A), acid chloride or aromatic hydroxy compound as (B), (C) unchanged, (3) diamine and trichloroformate (or disulphonyl chloride) as (A), amine or acid chloride as (B), (C) unchanged. (4) Diisocyanate and diol as (A) hydroxyl as (B) and organo-tin compounds as (C). (5) Diisocyanates or monoisocyanates as (A), a copolymerizing isocyanate group, e.g. formed by reaction of diisocyanate with hydroxyethyl-methacrylate copolymer as (B) and cyclic phosphalene oxide or n-butyl lithium as (C).  (6) Aldehydes as (A) copolymerizing aldehyde group as (B) and irradiation at low temperature as (C).  (7) Formaldehyde or beta-proprolactone as (A), dialkyl aminomethacrylate, the reaction product of amines or ammonia with a glycidyl methacrylate copolymer or H-vinyl pyrrolidone as (B) and with or without additional amine as (C). (8) Cyclic ethers or esters as (A), copolymerizing epoxy, hydroxyl or carboxyl as (B) and aluminium triisobutyl or boron trifluoride as (C) and (9) lactams and pyrrolidone as (A), N-acyl lactams as (B) and sodium hydride, ethoxide or lactam as (C).  It is preferred that the copolymerizable groups of the precursor and those of the main monomer or comers should have a reactivity ratio of between 0.1 to 10 and most preferably about unity.  In examples the following systems are disclosed: (1) (A) m-octyl methacrylate/ethylene ethylene glycol monomethacrylate (B) isophthaloyl dichloride - terephthaloyl dichloride-bis - (4 - hydroxyphenyl) - 2,2 - propane (C) 2,6-butadine.  (2) (A) N-phenyl methacrylate/n-octyl methacrylate (B) isophthaloyl dichloride/bis - (4 - hydroxyphenyl -2,2 - propane (C) 2,6-butidine, (3) (A) lauryl methacrylate/glycidyl methacrylate / p - hydroxy - benzoic acid (B) isophthaloyl dichloride and bis-(4-hydroxyphenyl) - 2,2 - propane and (C) 2,6-butidine, (4) (A) lauryl methacrylate/glycidyl methacrylate/4,41 - bis - (4 - hydroxyphenyl) pentanoic acid (B) isophthaloyl dichloride and bis - (4 - hydroxyphenyl - 2,2 - propane (C) 2,6-butidine, (5) (A) methyl methacrylate/methacryloyl chloride (B) terephthaloyl chloride, bis-(4 - hydroxyphenyl) - 2,2 - propane and (C) 2,6 - butidine, (6) (A) glycidyl methacrylate/laurylmethacrylate (B) ethylene oxide (C) boron trifluoride etherate, (7) (A) as for (6) (A), (B) trionane (C) as for (6) (C), (8) (A) as above, (B) beta-propiolactene (C) as above, (9) (A) lauryl methacrylate/glycidyl methacrylate (B) glycidyl acetate (C) as above, (10 (A) as above (B) phenyl glycidyl ether (C) as above, (11) (A) as above, (B) epichlorhydrin, (C) as above, (12) (A) as above, (B) the copolymer of phenyl glycidyl ether and bis-chloromethyl oxacyclobutane, (C) as above, (13) (A) as above, (B) phenyl glycidyl ether, (C) aluminium triisobutyl, (14) n-octyl methacrylate/ethylene glycol monomethacrylate, (B) phenyl glycidyl ether, (C) boron trifluoride etherate, (15) (A) vinyl stearate, maleic anhydride, (B) trioxane, (C) as above, (16) (A) as in (6) (A), (B) trioxane, (C) as above, (17) lauryl methacrylate, (18) (A) beta - diethylaminoethyl methacrylate/lauryl methacrylate, (B) formaldehyde, (C) - 70 DEG  C., (19) (A) lauryl methacrylate/laurylmethacrylate black, (B) and (C) as above, (20) (A) as above, (B) beta-propiolactone, (C) heat, (21) (A) laurylmethacrylate / N - vinyl pyrrolidone, (B) formaldehyde, (C) - 70 DEG  C., (22) laurylmethacrylate/methyl methacrylate/N-methacrylol caprolactam, (B) e -caprolactam, (C) sodium lactam, (23) (A) as above, (B) 3,3-dimethylazetidinone, (C) potassium pyrrolidone, (24) lauryl methacrylate / glycidyl methacrylate / methacrylic acid, (B) trioxane, (C) borontrifluoride ethereate, (25) (A) as in (14) (A), (B) phenylisocyanate, (C) n-butyl lithium and (26) (A) as above, (B) diisocyanatodiphenyl methane, (C) di-n-butyltin laurate and 1-ethyl-3-methyl-3-phopholine-1-oxide.