Patent GB-997172-A (GB)
Title: Plasticized halogen-containing resins
IPC: C08L27/06
Filed: 1962-04-02
Abstract: Fumarate esters of formula <FORM:0997172/C2/1> where R is an aliphatic or alicyclic hydrocarbon radical of valence x, x is 2 to 6 and R1 is alkyl, cycloalkyl, alkenyl or aralkyl, and/or of formula R1 -(-OAOR)-)-n O -(-AOR2)m-Hy where A is the fumaryl radical, R is a divalent aliphatic or alicyclic hydrocarbon radical, R1 and R1 are each alkyl, cycloalkyl, alkenyl or aralkyl, n is 0, 1 or 2, m and y are unlike and each 0 or 1 and m + n is at least 1, may be prepared by reacting (a) a particle ester of maleic acid of formula <FORM:0997172/C2/2> with a compound of formula R1OH in the presence of a halogen-containing compound; (b) a fumarate ester of formula <FORM:0997172/C2/3> with a polyhydroxy compound containing 2 to 6 hydroxyl groups, the molar ratio of fumarate ester to polyhydroxy compound being 1 to 1.5x to 1 where x is the number of said hydroxyl groups; or (c) a fumaryl chloride of formula <FORM:0997172/C2/4> with a polyhydroxy compound containing 2 to 6 hydroxyl groups, the molar ratio of chloride to polyhydroxy compound being x to 1 where x is the number of said hydroxyl groups.  Extensive lists of suitable reactants are given and examples describe the preparation of fumarate esters by reacting 1,3-butanediol bis-(acid maleate) with (1) butanol, (5) 2-ethylhexanol, (6) methanol, (7) isopentanol, (8) isohexanol, (9) isooctanol, (15) ethoxyethoxyethanol, (16) butanol and allyl alcohol and (17) cyclohexanol; dipropylene glycol bis-(acid maleate) with (2) butanol; 1,2,6-hexanetriol tris-(acid maleate) with (3) butanol; diethylene glycol bis-(acid maleate) with (4) butanol; 1,2-propanediol bis-(acid maleate) with (10) 2-ethylhexanol; ethylene glycol bis-(acid maleate) with (11) 2-ethylhexanol; triethylene glycol bis-(acid maleate) with (12) propen-1-ol-3, and (13) propen-1-ol-3 and butanol; neopentyl glycol bis-(acid maleate) with (14) butanol; and pentaerythritol acid maleate with (18) butanol; by reacting 1,3-butanediol with (20) diisobutyl fumarate, (21) di-2-ethylhexyl fumarate, (22) dibenzyl fumarate, (33) diisohexyl fumarate, and (37) dicyclohexyl fumarate; dipropylene glycol with (23) dibutyl fumarate and (24) di-2-ethylhexyl fumatate; diethylene glycol with (25) dibutyl fumarate and (26) diisobutyl fumarate; triethylene glycol with (27) dibutyl fumarate, (28) diisobutyl fumarate and (29) di-2-ethylhexyl fumarate; and 1,2,6-hexanetriol with (30) dibutyl fumarate; and by reacting 1,3-butane-diol with (39) isohexyl, (40) 2-ethylhexyl and (41) isodecyl fumaryl chlorides; dipropylene glycol with (42) butyl, (43) isohexyl and (44) 2-ethylhexyl fumaryl chlorides; triethylene glycol with (45) butyl, (46) isohexyl and (47) 2-ethylhexyl fumaryl chlorides; 1,2,6-hexanetriol with (48) butyl and (49) isohexyl fumaryl chlorides; and pentaerythritol with (50) butyl fumaryl chloride. The maleic acid half-esters used in Examples 1-18 are prepared by reacting maleic anhydride with the appropriate alcohol.ALSO:Compositions comprise a polymer in which at least 50% by weight is formed from halogen-containing monomers having a terminal ethylenically unsaturated group and, as plasticizer therefor, a polymerizable fumarate ester which is (a) a product obtainable by reacting a partial ester of maleic acid of structure <FORM:0997172/C3/1> R is an aliphatic or alicyclic radical of valence x and x is an integer from 2 to 6, with a hydroxy compound of formula R1OH, where R1 is alkyl, cycloalkyl, alkenyl or aralkyl, in the presence of a halogen-containing compound, or (b) a product obtainable by reacting a fumarate ester of formula <FORM:0997172/C3/2> where R1 is alkyl, cycloalkyl, alkenyl or aralkyl with a polyhydroxy compound having 2 to 6 hydroxyl groups, the molar ratio of fumarate ester to polyhydroxy compound being 1 to 1.5x : 1, where x is also the number of said hydroxyl groups, or (c) a product obtainable by reacting a fumaryl chloride of formula <FORM:0997172/C3/3> where R1 is alkyl, cycloalkyl, alkenyl or aralkyl, with a polyhydroxy compound having 2 to 6 hydroxyl groups, the molar ratio of chloride to polyhydroxy compound being x : 1, where x is the number of said hydroxyl groups.  Specified polymers are polymers of vinyl chloride, vinylidene chloride, chlorostyrene, vinyl chloracetate and chloroprene, and copolymers thereof with vinylidene halides, vinyl esters, acrylic and methacrylic esters, vinyl aromatic compounds, conjugated dienes, maleic, fumaric, itaconic and crotonic esters, and unsaturated acid amides and nitriles.  Conventional plasticizers, e.g. phosphates, phthalates, adipates, sebacates and azelates and epoxidized oils; stabilizers and fillers may be present and the compositions may comprise a catalyst, e.g. benzoyl peroxide, acetyl peroxide or t-butyl perbenzoate, to facilitate polymerization of the fumarate ester plasticizer.  The compositions may be in the form of plastisols, and mouldings may be prepared by curing under pressure.  Examples describe compositions comprising polyvinyl chloride, dibasic lead phosphite, t-butyl perbenzoate and fumarate esters prepared by reacting (A and B) 1,3-butanediol bis-(acid maleate) and butanol, (C) dipropylene glycol bis-(acid maleate) and butanol, (D) 1,2,6-hexanetriol tris-(acid maleate) and butanol, and 1,3-butanediol bis-(acid maleate) with (E) 2-ethylhexanol, (F) isohexanol and (G) ethoxy-ethoxyethanol; by reacting 1,3-butanediol with (H) diisohexyl fumarate and (I) dibutyl fumarate; and by reacting (J) butyl fumaryl chloride with 1,3-butanediol.