Patent GB-980988-A (GB)
Title: Improvements relating to polymethylene polymers
IPC: C08F8/06
Filed: 1963-03-04
Abstract: Normally solid modified polymethylene polymers containing for each 100 chain carbon atoms (A) monocarboxyl substituted side-chain hydrocarbon groups having the structure -CH2-COOH or -CH2-R-COOH where R is C1-C16 alkylene and/or halogen substituted C1-C16 alkylene, with the proviso that the alpha carbon to the carboxyl group shall be halogen-free and (B) unsubstituted side-chain C1-C16 alkyl groups or halogen substituted C1-C16 alkyl groups where A = 0.01 to 25, B = 0.0 to 49.99 and A + B does not exceed 50, may be prepared by ozonizing a chain-saturated polyhydrocarbon or halo-hydrocarbon polymer containing for each 100 chain carbon atoms (A) side-chain groups having the structure -CH2-CH = CR2R3 or -CH2-R-CH = CR2R3 where R is as above, R2 is an alkyl group and R3 is an alkyl group or hydrogen atom and (B) unsubstituted side-chain C1-C16 alkyl groups or halogen substituted C1 to C16 alkyl groups where A, B and A + B are as above. The preferred polyhydrocarbon polymers for ozonolysis are the sulphur-vulcanizable unsaturated rubber-like copolymers of at least one terminally unsaturated straight chain monoolefine containing 2 to 18 carbon atoms, and an aliphatic open chain structure <FORM:0980988/C3/1> where R1 is a C1 to C17 alkylene radical, R2 and R3 are as above, the diolefine making up 1 to 40 mole per cent of the copolymer, the copolymer having an iodine number 3 to 50 and an intrinsic viscosity in benzene at 25 DEG C. of 0.5 to 5.0.  Such copolymers are described in Specification 819,279, and the halohydrocarbon polymers are made by adding halogen or a hydrocarbon halide to such polymers.  Preferred halohydrocarbon polymers are made by copolymerizing (a) ethylene; (b) at least one compound CH2 = CH-CH2-Q where Q is a monovalent aliphatic hydrocarbon radical substituted by at least one halogen atom; (c) at least one diene <FORM:0980988/C3/2> as above and optionally (d) at least one compound R-CH = CH2 where R is an alkyl radical having 1 to 16 carbon atoms, in methylene chloride using a co-ordination catalyst, preferably diisobutyl aluminium monochloride with vanadium tris-(acetylacetonate).  The ozonolysis is preferably carried out in carbon tetrachloride at 20 to 30 DEG  C., in the presence of an acidic reagent bearing hydroxyl groups, e.g. methanol or acetic acid. After ozonization the ozonized solution is treated with an organic per-acid or other active-oxygen containing reagent for further oxidation.  The modified polymethylene polymers having at most 0.35 carboxyl groups per 100 chain carbon atoms, can be made directly without ozonizing, by copolymerizing at least one a -monoolefine CH2 = CH-Z where Z is hydrogen or a C1 to C16 alkyl, with a metal salt, preferably magnesium or zinc, of an a -monoolefine omega carboxylic acid in the presence of a co-ordination catalyst, in a hydrocarbon or halogenated hydrocarbon solvent, the said salt being at least slightly soluble under the polymerization conditions. In the examples:-(a) ethylene or ethylene + propylene are copolymerized with magnesium or zinc 10-hendecenoate, in tetrachloroethylene or methylene chloride using as catalyst diisobutylaluminium monochloride and vanadium tris - (acetylacetonate) or vanadium oxytrichloride; and (b) the following copolymers are ozonized:-ethylene/1-butene/1,4-hexadiene; ethylene/propylene/1,4-hexadiene; propylene/1 - butene/11 - ethyl - 1,11 - tridecadiene and ethylene/1,4-hexadiene.  Specifications 778,639 and 819,279 are referred to.