Patent GB-649121-A (GB)
Title: Improvements in or relating to the preparation of haloaryl allyl carbonates and polymers and copolymers thereof
IPC: C08F18/20
Filed: 1948-02-07
Abstract: Halo-aryl allyl carbonates (see Group IV (b)) are polymerized optionally in admixture with other polymerizable materials by heating in the presence of a polymerization catalyst.  Products obtained range in characteristics from softviscous liquids to extremely hard rigid solids.  Polymerization catalysts specified are those conventional in the art and although polymerization may be effected in solution or aqueous emulsion it is preferred to heat the monomeric ester below about 150 DEG  C., preferably 60-100 DEG  C., in a closed vessel under vacuum or an inert atmosphere in the presence of 0.5-5.0 per cent by weight of catalyst.  For the production of copolymers compounds are instanced from the following classes: vinyl and vinylidene compounds, esters of acrylic and alpha-substituted acrylic acids, mono- and di-olefinic hydrocarbons and especially polyallyl esters.  Conventional compounding ingredients may be admixed with the polymers or copolymers.  It is stated that o-chloro-p-tertiary butyl phenyl-, 2-bromo-4-tertiary butyl phenyl-, and o-chloro-p-phenyl-phenyl-allyl carbonate may be polymerized with peroxide type catalysts and in examples: (1) p-chloro-, (2) m-chloro- and (3) o-chloro-phenyl allyl carbonates are polymerized at 60 DEG C. under nitrogen in the presence of o-chloro-benzoyl peroxide to give (1) and (2) viscous liquids and (3) a hard water-white solid, in (4) 2,4-dichlorophenyl allyl carbonate is heated at 60 DEG  C. under nitrogen with acetyl benzoyl peroxide to give a heavy syrupy liquid, (5) 2,6-dichlorophenyl allyl carbonate is heated at 60 DEG  C. and then 100 DEG  C. under carbon dioxide and with benzoyl peroxide to give a hard, glass-like solid, (6) o-chloro-p-phenylisopropyl-phenyl allyl carbonate heated at 60 DEG  C. in the presence of acetyl benzoyl peroxide to form a heavy syrup, (7) o-chloro-phenyl allyl carbonate and diallyl hydroquinone dicarbonate are heated together at 60 DEG  C. in the presence of o-chloro-benzoyl peroxide to give a hard thermoplastic resin and a similar result is obtained by the substitution of the above dicarbonate with diallyl 2,2-bis-(3,5-dichloro-4-hydroxy-phenyl) propane dicarbonate and in (8) o-chloro-p-phenylisopropyl-phenyl allyl carbonate is heated with diallyl-2,2-bis-(3-chloro-4-hydroxyphenyl) propane dicarbonate at 60 DEG  C. with o-chloro-benzoyl peroxide to give either a hard gloss-like substance or a tough non-thermoplastic material depending upon the quantities of reactants used.ALSO:Halo-aryl allyl carbonates are obtained by reacting an allyl halo-carbonate with a nuclear halogenated phenol in the presence of an alkali metal hydroxide. Esters containing condensed aromatic rings, e.g. halo-naphthyl allyl carbonates may be prepared but are not so useful as compounds containing the phenyl radical optionally substituted with hydrocarbon groups.  Chlorine is the preferred halogen and iodine, bromine and fluorine are also specified.  Preferably the chlorine is substituted in the ortho position in the benzene ring.  Esters instances are o-chloro-p-tertiary-butyl-phenyl-, 2-bromo-4 - tertiary butyl phenyl-, o - chloro - p - phenylphenyl, - trichlorophenyl-, pentachlorophenyl-, chlorotolyl-, chloroxylyl-, chlorocumyl- and chloronaphthyl-allyl carbonates.  The esters are used as plasticizers and may be polymerized to give synthetic resins (see Group IV (a)). In examples, allyl chlorocarbonate is reacted at below 10 DEG  C. in aqueous sodium hydroxide solution with (1) p-chlorophenol, (2) m-chlorophenol, (3) o-chlorophenol, (4) 2,4-dichloro phenol in acetone, (5) 2,6-dichlorophenol in ether and (6) o-chloro-p-(phenylisopropyl)-phenol to give the corresponding chlorophenyl allyl carbonate.