Patent GB-984310-A (GB)
Title: Halogen-containing acrylic esters and polymers thereof
IPC: C08F220/22
Filed: 1962-12-18
Abstract: Polymerizable vicinal acryloyloxy-halo compounds are prepared by reacting an ethylenically unsaturated compound with an alkyl hypohalite and an acid acrylic compound (defined as an a ,b -ethylenically unsaturated monocarboxylic acid or a half-ester of an a ,b -ethylenically unsaturated dicarboxylic acid.  Long chain vicinal acryloyloxy-halo compounds of formula <FORM:0984310/C2/1> are claimed per se where <FORM:0984310/C2/2> is an aliphatic open chain of from 10 to 24 carbon atoms; R is hydrogen or a monovalent aliphatic group; X is halogen; R1 is hydrogen or -COOY; when R1 is hydrogen, R2 is hydrogen, C1- 4 alkyl, C1- 4 alkoxy, halogen, phenyl, benzoyl or -CH2COOY; when R1 is -COOY, R2 is hydrogen, halogen or C1- 4 alkyl; and Y is a C1- 18 monovalent aliphatic group, a C6- 18 monovalent alicyclic group or a C6- 18 monovalent aromatic group.  R may contain substituents such as hydroxy, carboxy, carboxylate, carbamyl, amino, nitrilo, carbamato, halogen, acyloxy, mercapto, alkoxy or aryloxy groups. The preferred long chain ethylenic starting materials are glyceride oils.  Tertiary alkyl hypohalites are preferred. Suitable acid acrylic compounds include acrylic acid and substituted acrylic acids and half-esters of a ,b -ethylenically unsaturated dicarboxylic acids. Many are specified.  An important class of products are those based on fumaric acid half-esters. Fumaric acid half-esters may be prepared by isomerising the corresponding maleic half-esters before the halocylation reaction or isomerisation may be effected on the acryloyloxy-halo products from maleic half-esters.  The haloacylation reaction may be effected at temperatures from - 50 to + 150 DEG  C.  A catalyst may be used, e.g. a tetraalkylammonium salt or a tetraalkylphosphonium salt.  The reaction product may contain by products of types R-CH2-CHX-CH(OR3)-CH2-R and R-CH2-CHX-CH = CH-R where R3 is the alkyl group from the hypohalite. These need not be separated before polymerization. Examples describe the preparation of products from: (a) as ethylenic compound: various glyceride oils, soybean monoglyceride and a series of esters of tall oil fatty acids; heptene, methacrylic acid, allyl chloride, octadecene-1, cyclooctene, styrene, dicyclopentadiene, ethylene and propylene; (b) as acid acrylic compound:  acrylic acid, methacrylic acid, methyl, ethyl and isopropyl hydrogen maleates and methyl, ethyl, isopropyl, isobutyl, secondary butyl, allyl, 4-methyl-2-pentyl, 2-ethylhexyl and tridecyl hydrogen fumarates; and (c) as hypohalite:  tertiary butyl and tertiary amyl hypochlorites.  Many other suitable starting materials are specified.  The compounds of formula II may also be prepared by reacting an ethylenically unsaturated long chain compound with an acrylic acid R1CH = CR2-COOH and free halogen in the presence of an alkaline catalyst or by reaction of a vicinal epoxy long chain compound with an acrylyl halide.  In examples a mixture of soybean oil, acrylic acid, calcium acrylate and tetramethylammonium chloride is treated with chlorine, and epoxidized soybean oil is reacted with acrylyl chloride or methacrylyl bromide.  The above-named hydrogen fumarates are prepared in examples by isomerization, using PCl3, SOCl2 or AlCl3 as catalyst, of the corresponding hydrogen maleates, themselves obtained by the reaction of maleic anhydride and the appropriate alcohol. Many other isomerization catalysts are specified.  Methacrylyl bromide by the reaction of methacrylic acid and PBr3.ALSO:Polymers are prepared from vicinal haloacryloyloxy compounds containing the moity <FORM:0984310/C3/1> where R1 is hydrogen or an esterified carboxylic group (for preparation see Division C2). The monomeric starting materials may also contain substantial amounts of compounds with the <FORM:0984310/C3/2> moities. An important class of monomers has the formula <FORM:0984310/C3/3> where C-CH2-CH-CH-CH2-R is an aliphatic open chain of from 10 to 24 carbon atoms; R is hydrogen or a monovalent aliphatic group, X is halogen, R1 is hydrogen or -COOY, when R1 is hydrogen, R2 is hydrogen, C1-4 alkyl, C1-4 alkoxy, halogen, phenyl, benzyl or -CH2COOY; when R1 is -COOY, R2 is hydrogen, halogen or C1-4 alkyl; and Y is a C1-18 monovalent aliphatic group or a C6-18 monovalent alicyclic or aromatic group.  R may contain substituents such as hydroxy, carboxy, carboxylate, carbamyl, amino, nitrilo, carbamate, halogen, acyloxy, mercapto, alkoxy or aryloxy groups.  The preferred compounds are derived from glyceride oils. The acryloyloxy group may be derived from unsubstituted or substituted acrylic acids or from half-esters of a ,b -ethylenically unsaturated dicarboxylic acids, particularly maleic and fumaric.  Many examples are given. Polymerization may be effected with ionic or free radical catalysts, benzoyl peroxide being used in examples. Homopolymers may be made or copolymers with other vinylidene monomers of which many are specified including acrylic and methacrylic acids and esters, styrene, a -methylstyrene, allyl alcohol, vinyl toluene, vinyl esters, vinyl and vinylidene chlorides, acrylamide, acrylonitrile, butadiene, dibutyl fumarate, isoprene, diallyl phthalate, vinyl crotonate.  A large number of polymers are prepared in examples.