Preparation of unsaturated copolymers

Claim 2

A PROCESS FOR PREPARING SULFUR VULCANIZABLE COPOLYMERS BY BRINGING AT LEAST ONE A-OLEFIN AND AT LEAST ONE CYCLOMONOOLEFIN AND/OR A NONCONJUGATED CYCLOPOLYOLEFIN INTO CONTACT WITH A CATALYST CAPABLE OF PROMOTING OLEFIN CROSSMETATHESIS BETWEEN AN A-OLEFIN AND A CYCLOMONOOLEFIN OR A NONCONJUGATED CYCLOPOLYOLEFIN, THEN REACTING SAID OLEFIN CROSS-METATHESIS PRODUCT MIXTURE WITHOUT CATALYST REMOVAL WITH AT LEAST ONE A-OLEFIN USNG A COORDINATION CATALYST COMPRISING AT LEAST ONE METAL COMPOUND, THE METAL PORTION OF WHICH IS SELECTED FROM THE TRANSITION METALS OF GROUPS IVB AND VB OF THE PERIODIC TABLE IN CONJUNCTION WITH AT LEAST ONE ORGANOMETALLIC COMPOUND, THE METAL PORTION OF WHICH IS SELECTED FROM METALS OF GROUPS IA, IIA, IIB AND IIIA OF THE PERIODIC TABLE.

Claim 3

A process according to claim 1 wherein the cyclomonoolefin is at least one selected from the group of cyclobutene, cyclopentene, cyclooctene, cyclononene, cyclodecene, cycloundecene and cyclododecene.

Claim 4

A process according to claim 1 wherein the Alpha -olefins contain from 2 carbon atoms through 20 carbon atoms.

Claim 5

The process according to claim 1 wherein the reaction temperature is from about -20*C. to about 100*C.

Claim 6

The process according to claim 1 wherein the olefin cross-metathesis catalyst comprises A. at least one organometallic compound wherein the metal portion is selected from the group consisting of Ia, IIa, IIb, IIIa and IVa Groups of the Periodic Table of Elements, B. at least one metal derivative wherein the metal portion is selected from the group consisting of molybdenum and tungsten, and C. at least one compound selected from a group consisting of oxygen and compounds of the general formula R-Y-R'' wherein Y is selected from the group of oxygen and sulfur and wherein R and R'' are radicals selected from the group consisting of (1) hydrogen, (2) alkyl, (3) aryl, (4) arylalkyl, (5) alkaryl, (6) alkenyl, (7) when Y is S and R'' is H, then R can be thioalkyl, thioarylalkyl, and thioalkaryl, (8) when Y is O and R'' is H, then R can be alkoxy, arylalkoxy and alkaryloxy, and (9) radicals of (2) through (8) wherein at least one hydrogen is substitutEd by a group selected from hydroxyl (OH) and thiol (SH).

Claim 7

The process according to claim 5 wherein the three catalyst components, (A), (B) and (C) as previously defined are within a molar ratio of (B)/(C) ranging from about 0.2/1 to at least about 20/1 and the molar ratio of (A)/(B) is within the range of about 0.5/1 to at least 15/1; more preferred ratios are (B)/(C) of 0.5/1 to 5/1 and (A)/(B) of 0.5/1 to 8/1; still more preferred ratios are (B)/(C) of 1/1 to 2/1 and (A)/(B) of 0.75/1 to 5/1.

Claim 8

The process according to claim 1 wherein the coordination catalyst comprises one or more salts of a transition metal such as titanium, zirconium, hafnium, vanadium, niobium or tantalum and the salts are halides, oxyhalides, alcoholates, sulfates, nitrates, phosphates, acetates, propionates, benzoates, acetylacetonates and the like; in conjunction with one or more organometallic compounds of metals of Groups Ia, IIa, IIb and IIIa of the Periodic Table where the organic groups are preferably alkyl groups containing 1-10 carbon atoms or aryl groups such as phenyl, tolyl or napththyl and when the metal compound is multivalent, any valence not satisfied by an organic group may be satisfied by hydride, chloride, bromide, iodide or fluoride.

Claim 9

The process according to claim 7 wherein the molar ratio of the organometallic compound/transition metal salt is from about 0.5 to 15, preferably about 0.75 to 5, most preferably about 2 to 3.

Claim 10

A process according to claim 1 wherein the olefin cross-metathesis catalyst consists of (A) tetralkyltin, (B) tungsten halide and (C) dialkyl ether and the molar ratio of (A)/(B) ranges from about 0.5/1 to 15/1 and the molar ratio of (B)/(C) ranges from 0.2/1 to 20/1.

Claim 11

A process according to claim 1 wherein the olefin cross-metathesis catalyst consists of (A) alkylaluminum halide, (B) tungsten halide and (C) an alcohol and the molar ratio of (A)/(B) ranges from 0.5/1 to about 15/1 and the molar ratio of (B)/(C) ranges from about 0.2/1 to about 20/1.

Claim 12

Sulfur vulcanizable unsaturated rubber-like copolymers produced by the process according to claim 1.

Claim 13

Sulfur vulcanizable unsaturated rubber-like copolymers produced by the process according to claim 11 wherein the cross-metathesis reaction is between at least one Alpha -olefin containing 3 carbon atoms through 6 carbon atoms and at least one cyclomonoolefin and/or nonconjugated cyclopolyolefin containing 5 carbon atoms through 12 carbon atoms, and the Alpha -olefin for copolymerization is at least one selected from the group consisting of ethylene, propylene, butene, pentene and hexene.