Patent GB-1230597-A (GB)
IPC: C08K3/00
Filed: 1968-06-26
Abstract: 1,230,597. Elastomeric compositions. CHARBONNAGES DE FRANCE. 26 June, 1968 [27 June, 1967; 16 May, 1968], No. 30495/68. Heading C3P. Compositions of an elastomeric material having a glass-transition temperature lower than - 10 C., comprises 100 parts by weight of a compound which is an amorphous polymer of bicyclo [2.2.1]-heptene-2 or a derivative thereof, having the Formula I (in which R is H, CH 3 , CO 2 CH 3  or OCOCH 3 , and R<SP>1</SP> is H or CO 2 CH 3 , with the condition that when R<SP>1</SP> is CO 2 CH 3 , R also represents CO 2 CH 3 ) or a copolymer thereof, 30 to 200 parts of a compound with a freezing point lower than - 30 C. such as an organic ester, aliphatic, aromatic or naphthenic hydrocarbon, and 0 to 300 parts of a filler. Suitable polymers are a homo-polymer of bicyclo [2.2.1] heptene-2, methyl - 5 bicyclo [2.2.1] heptene - 2, the methyl esters of bicyclo [2.2.1] heptene-2 oic-5 or dioic-5,6 acids or an acetate of bicyclo [2.2.1] heptene-2-ol-5 or copolymers thereof. The polymers may be prepared by adding to the monomer(s), dissolved in a suitable solvent, an initiator such as ruthenium chloride and a reducing agent such as an alcohol, and degasifying the solution and heating to between 30 and 120 C. for about 6 hours. The polymer may then be mixed with the compound having a freezing point lower than - 30 C., together with a filler if necessary, in an internal mixer or roller mixer, preferably at 80 C. to reduce the viscosity of the polymer. In the examples, the following polymers are prepared: polybicyclo [2.2.1] heptene - 2, (BCH), polymethyl - 5 bicyclo [2.2.1] heptene - 2, (MBCH), copolymers thereof, a polymer of an acetate of bicyclo [2.2.1] heptene-2 ol-5, a polymer of a methyl ester of bicyclo [2.2.1] heptene-2 oic-5 acid, or a copolymer of BCH or MBCH with an acetate of bicyclo [2.2.1] heptene-2 ol-5 or a methyl diester of exocis or trans bicyclo [2.2.1] heptene-2 dioic 5,6 acid, these polymers being prepared by dissolving the monomer(s) in a suitable solvent and adding an initiator such as hydrated ruthenium chloride, and a reducing agent. The polymers are washed with methanol and impregnated with a methanol solution of an anti-oxidizing agent [bis (2-hydroxy-3 tert. butyl 5 methyl-phenyl) methane]. In further examples, the above polymers are mixed with low freezing point compounds and fillers to form elastomeric composition. Exemplified compositions are: (1) poly BCH and a perhydrogenate of chrysene oil (this perhydrogenate contained predominantly naphthenic and aromatic hydrocarbons); (2) poly BCH and a naphthenic oil or an aromatic oil, with silica or carbon black; (3) poly BCH and diiso octyl phthalate with silica or carbon black; (4) poly MBCH, an aromatic oil, and silica or carbon black; (5) a polymer of the acetate of bicyclo [2.2.1] heptene-2 ol-5, diiso octyl phthalate and carbon black; (6) as (5) wherein the polymer is derived from the methyl ester of bicyclo [2.2.1] heptene-2 oic-5 acid; (7) a copolymer of the acetate of bicyclo [2.2.1] heptene-2 ol-5 and BCH, aromatic oil or diiso octyl phthalate and carbon black; (8) a copolymer of MBCH and the acetate of bicyclo [2.2.1.] heptene-2 ol-5, diiso octyl phthalate and carbon black; (9) a copolymer of BCH and the methyl ester of bicyclo [2.2.1] heptene-2 oic -5 acid, diiso octyl phthalate and carbon black; (10) a copolymer of MBCH or BCH and the methyl diester of exo-cis or trans bicyclo [2.2.1] heptene-2 dioic-5,6 acid. These compositions are mixed with vulcanizing ingredients and vulcanized.