US 6,107,420 A · Thermally initiated polymerization of olefins using Ruthenium or osmium vinylidene complexes

Abstract

The present invention generally relates to the use of certain ruthenium and osmium complexes that are substantially inactive at a first temperature (preferably about room temperature) but become progressively more active at a higher second temperature. This difference in reactivities allows the reaction mixture to be formed and manipulated at the first temperature until polymerization is desired. When appropriate, the reaction mixture is heated to a suitable temperature (preferably greater than 50.degree. C.) to activate the catalyst and to initiate polymerization. Because both the initiation and the rate of polymerization may be controlled with temperature, the inventive methods are especially suitable for ring opening metathesis polymerization ("ROMP") reactions and for molding polymer articles that require extended pot-lives.

Claims22

Dependent claims

A method for controlling the initiation of metathesis polymerization comprising:

contacting a metathesis catalyst with an olefin in a reaction mixture at a first temperature and
heating the reaction mixture to a second temperature
wherein the metathesis catalyst is of the formula:
##STR7## wherein:
M is ruthenium or osmium;
X and X.sup.1 are each independently any anionic ligand;
L and L.sup.1 are each independently any neutral electron donor ligand;
and,
R and R.sup.1 are each independently hydrogen or substituent selected from the group consisting of C.sub.1 -C.sub.20 alkyl, C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl and C.sub.1 -C.sub.20 alkylsulfinyl, the substituent optionally substituted with one or moieties selected from the group consisting of C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.10 alkoxy, and aryl.

6 more elements

A method for controlling the initiation of ROMP polymerization comprising:

contacting a metathesis catalyst with a cyclic olefin in a reaction mixture at a first temperature and
heating the reaction mixture to a second temperature
wherein the metathesis catalyst is of the formula:
##STR10## wherein:
M is ruthenium;
R is hydrogen;
R.sup.1 is selected from the group consisting of C.sub.1 -C.sub.10 alkyl, C.sub.2 -C.sub.10 alkenyl, and aryl;
X and X.sup.1 are each independently selected from the group consisting of halide, CF.sub.3 CO.sub.2, CH.sub.3 CO.sub.2, CFH.sub.2 CO.sub.2, (CH.sub.3).sub.3 CO, (CF.sub.3).sub.2 (CH.sub.3)CO, (CF.sub.3)(CH.sub.3).sub.2 CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate;
and
L and L.sup.1 are each independently either (i) a phosphine of the formula PR.sup.3 R.sup.4 R.sup.5, wherein R.sup.3, R.sup.4, and R.sup.5 are each independently aryl or C.sub.1 -C.sub.10 alkyl, particularly primary alkyl, secondary alkyl or cycloalkyl or (ii) a heterocyclic carbene of the formula:
##STR11## wherein R.sup.6 and R.sup.7 are each independently selected from the group consisting of C.sub.1 -C.sub.20 alkyl, C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, cycloalkyl, and aryl, each optionally substituted with one or more moieties selected from the group consisting of C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.10 alkoxy, and aryl.

8 more elements

Dependencies are inferred from the claim text.

Thermally initiated polymerization of olefins using Ruthenium or osmium vinylidene complexes

Life of this patent

Thermally initiated polymerization of olefins using Ruthenium or osmium vinylidene complexes

Life of this patent

Abstract

Claims22