Catalysts and methods for ring opening metathesis polymerization

Patent metadata

Field	Value
Publication number	US-9932440-B2
Application number	US-201715452505-A
Country	US
Kind code	B2
Filing date	Mar 7, 2017
Priority date	Feb 21, 2014
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.

First claim

The invention claimed is:

1. A poly(dicyclopentadiene) polymer, wherein the polymer is greater than 95% syndiotactic as determined by 13 C NMR.

2. The polymer of claim 1 , wherein double bonds in the polymer backbone is greater than 90% cis as determined by 13 C NMR.

3. The polymer of claim 1 , wherein double bonds in the polymer backbone is greater than 95% cis as determined by 13 C NMR.

4. The polymer of claim 1 , wherein M n of the polymer is greater than about 5,000.

5. A composition comprising:
the polymer of claim 1 , and a tungsten-containing compound.

6. The composition of claim 5 , wherein the tungsten-containing compound is a compound of formula I:

wherein:
R 1 is —C(R 1a ) 3 ;
each R 1a is independently an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic or polycyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:
two R 1a groups are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:
three R 1a groups are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 4-10 membered, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

each of R 2 and R 3 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; or:
R 2 and R 3 are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:
two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

R 4 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen;
R 5 is —OAr a ; and
Ar a is optionally substituted

7. The composition of claim 6 , wherein each R 1a is optionally substituted C 1-6 aliphatic or phenyl.

8. The composition of claim 6 , wherein R 1 is

9. The composition of claim 5 , wherein the tungsten-containing compound is a compound of formula II:

wherein:
each of R 2 and R 3 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; or:
R 2 and R 3 are optionally taken together with the carbon atom to which they are attached to form an optionally substituted 3-10 membered, monocyclic, bicyclic or polycyclic, saturated or partially unsaturated ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:
two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

R 4 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen;
R 5 is —OAr a ;
Ar a is optionally substituted

n is 0-2; and
each R8 is independently a phosphorus-containing ligand, wherein the phosphorus-containing ligand is bonded to W through a phosphorus atom.

10. The composition of claim 9 , wherein the compound of formula II has the structure of formula II-a:

wherein:
R 4 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen;
R 5 is —OAr a ;
Ar a is optionally substituted

each R 6 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NR

Assignees

• Massachusetts Inst Technology

Inventors

• Schrock Richard Royce
• Autenrieth Benjamin

Classifications

• B01J31/2265

  Carbenes or carbynes, i.e.(image) · CPC title

• C07F11/00

  Compounds containing elements of Groups 6 or 16 of the Periodic Table · CPC title

• C08G2261/3325

  derived from other polycyclic systems · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title