US 5,728,917 A · Polymer depolymerization using ruthenium and osmium carbene complexes

Abstract

Disclosed are ruthenium and osmium carbene compounds which are stable in the presence of a variety of functional groups and which can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins. Specifically, the present invention relates to carbene compounds of the formula ##STR1## wherein: M is Os or Ru; R and R.sup.1 are independently selected from hydrogen and functional groups C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.2 -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 or C.sub.1 -C.sub.20 alkylsulfinyl; each optionally substituted with C.sub.1 -C.sub.5 alkyl, a halogen, C.sub.1 -C.sub.5 alkoxy or with a phenyl group optionally substituted with a halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are each trialkyl phosphine ligands where at least one of the alkyl groups on the phosphine is a secondary alkyl or a cycloalkyl. A broad array of metathesis reactions are enabled including ring-opening metathesis polymerization of cyclic olefins, ring closing metathesis of acyclic dienes, cross metathesis involving at least one acyclic or unstrained cyclic olefin, and depolymerization of unsaturated polymers.

Claims17

Dependent claims

A process for depolymerizing an unsaturated polymer, the process comprising contacting an unsaturated polymer with a compound of the formula ##STR33## in the presence of an acyclic olefin or a modified acyclic olefin-containing a functional group selected from the group consisting of alcohol, thiol, ketone, aldehyde, ester, ether, amine, amide, imine, nitro acid, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen, wherein:

M is selected from the group consisting of Os and Ru;
R and R.sup.1 are independently selected from the group consisting of hydrogen and a substituent group 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, C.sub.2 -C.sub.20 alkoxycarbonyl, 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 and aryloxy;
X and X.sup.1 are anionic ligands;
and
L and L.sup.1 are independently selected from PR.sup.3 R.sup.4 R.sup.5, wherein R.sup.3 is selected from the group consisting of secondary alkyl, cycloalkyl, isobutyl, neopentyl, and neophyl and wherein R.sup.4 and R.sup.5 are independently selected from aryl, C.sub.1 -C.sub.10 primary alkyl, secondary alkyl, cycloalkyl, isobutyl, neopentyl, and neophyl.

2 more elements

A process for depolymerizing an unsaturated polymer, the process comprising contacting an unsaturated polymer with a compound of the formula ##STR34## in the presence of an acyclic olefin or a modified acyclic olefin containing a functional group selected from the group consisting of alcohol, thiol, ketone, aldehyde, ester, ether, amine, amide, imine, nitro acid, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen, wherein:

M is selected from the group consisting of Os and Ru;
R and R.sup.1 are independently selected from the group consisting of hydrogen and a first substituent group selected from the group consisting of vinyl, C.sub.1 -C.sub.10 alkyl, aryl, C.sub.1 -C.sub.10 carboxylate, C.sub.2 -C.sub.10 alkoxycarbonyl, C.sub.1 -C.sub.10 alkoxy, and aryloxy;
the first substituent group optionally substituted with a group selected from the group consisting of C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, and phenyl;
the phenyl optionally substituted with a group selected from the group consisting of halogen, C.sub.1 -C.sub.5 alkyl, and C.sub.1 -C.sub.5 alkoxy;
X and X.sup.1 are independently selected from the group consisting of halogen, hydrogen, diketonates, and a second substituent group selected from the group consisting of C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 alkoxide, aryloxide, C.sub.2 -C.sub.20 alkoxycarbonyl, arylcarboxylate, C.sub.1 -C.sub.20 carboxylate, aryl or C.sub.1 -C.sub.20 alkylsulfonate, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl, C.sub.1 -C.sub.20 alkylsulfinyl;
the second substituent group optionally substituted with a group selected from the group consisting of C.sub.1 -C.sub.5 alkyl, halogen, C.sub.1 -C.sub.5 alkoxy, and phenyl;
the phenyl optionally substituted with a group selected from the group consisting of halogen, C.sub.1 -C.sub.5 alkyl, and C.sub.1 -C.sub.5 alkoxy;
and
L and L.sup.1 are trialkyl phosphine ligands, wherein at least one of the alkyl groups is selected from the group consisting of secondary alkyl, cycloalkyl, isobutyl, neopentyl, and neophyl.

6 more elements

Dependencies are inferred from the claim text.

Polymer depolymerization using ruthenium and osmium carbene complexes

Life of this patent

Polymer depolymerization using ruthenium and osmium carbene complexes

Life of this patent

Abstract

Claims17