Process for the direct polymerization of allyl ethers, crotyl ethers and allyl alcohols

• US 5,886,115 A
• Filed: 02/18/1997
• Issued: 03/23/1999
• Est. Priority Date: 02/18/1997
• Status: Expired due to Term

• Current Assignee: Rensselaer Polytechnic Institute
• Original Assignee: Rensselaer Polytechnic Institute
• Inventors: Crivello, James V.
• Primary Examiner(s): KRASS, FREDERICK F
• Application Number:
  US08/801,952
• Time in Patent Office: 763 Days
• Field of Search: 526/194, 526/128, 526/126
• US Class Current: 526/126
• CPC Class Codes: C08F 16/08 Allyl alcohol
• CPC Class Codes: C08F 16/20 Monomers containing three or more carbon atoms in the unsaturated aliphatic radical
• CPC Class Codes: C08F 4/26 of manganese, iron group metals or platinum group metals

Abstract

A process for the direct polymerization of allyl ethers, crotyl ethers and allyl alcohols is disclosed. The process comprises bringing into reactive proximity an allyl ether, crotyl ether or allyl alcohol compound; a transition metal carbonyl complex catalyst; and a cocatalyst bearing at least one silicon-hydrogen bond. Preferably, the catalyst is a cobalt carbonyl complex, and most preferably, the catalyst is dicobalt octacarbonyl. While virtually any compound bearing at least one silicon-hydrogen bond can be used as cocatalyst, phenylsilane is the most preferred. The process promotes the polymerization of allyl alcohols, mono-, di-, tri-, tetra- and multifunctional allyl and crotyl ether monomers, as well as terminal and pendent allyl and crotyl ether functional groups within oligomers and polymers.

Claims

1. A process for polymerizing an allyl ether, crotyl ether or allyl alcohol comprising bringing into reactive proximity:

(a) a compound having at least one allyl ether, crotyl ether or allyl alcohol functional group;

(b) a transition metal carbonyl complex catalyst; and

(c) a cocatalyst having at least one silicon-hydrogen bond.

2. The process of claim 1 wherein said compound having at least one allyl ether, crotyl ether or allyl alcohol functional group;

said transition metal carbonyl complex catalyst; and

said cocatalyst having at least one silicon-hydrogen bond are mixed at a temperature sufficient to induce polymerization of said compound having at least one allyl ether, crotyl ether or allyl alcohol functional group.

3. The process of claim 1 wherein said transition metal carbonyl complex catalyst is chosen from the group consisting of carbonyl complexes of the Group VIII elements Rh, Ir, Ni, Fe, Ru, Os and Co.

4. The process of claim 3 wherein the transition metal carbonyl complex is chosen from the group consisting of Co₂ (CO)₈ and Co₄ (CO)₁₂.

5. The process of claim 4 wherein the transition metal carbonyl complex is Co₂ (CO)₈.

6. The process of claim 1 wherein the cocatalyst is chosen from the group consisting of monoalkyl silanes, monoaryl silanes, dialkyl silanes, alkylaryl silanes, diaryl silanes, trialkyl silanes, dialkylaryl silanes, alkyldiaryl silanes, triaryl silanes, cyclic silanes, polymeric silanes, dichlorochlormethylsilane, 1,1,3,3-tetramethyldisiloxane, tetramethyldisilane, trichlorosilane and triethoxysilane.

7. The process of claim 6 wherein the cocatalyst is phenylsilane.

8. The process of claim 1 wherein bringing the elements (a), (b) and (c) into reactive proximity comprises mixing the transition metal carbonyl complex catalyst and the cocatalyst having at least one silicon-hydrogen bond prior to adding the compound having at least one allyl ether, crotyl ether or allyl alcohol functional group.

9. The process of claim 1 wherein bringing the elements (a), (b) and (c) into reactive proximity comprises mixing the transition metal carbonyl complex catalyst and the compound having at least one allyl ether, crotyl ether or allyl alcohol functional group prior to adding the cocatalyst having at least one silicon-hydrogen bond.

10. A curable composition kit comprising:

(a) a compound having at least one allyl ether, crotyl ether or allyl alcohol functional group;

(b) a transition metal carbonyl complex catalyst; and

(c) a cocatalyst bearing at least one silicon-hydrogen bond.

11. The curable composition kit of claim 10 wherein the transition metal carbonyl complex catalyst is chosen from the group consisting of carbonyl complexes of the Group VIII elements Rh, Ir, Ni, Fe, Ru, Os and Co.

12. The curable composition kit of claim 11 wherein the transition metal carbonyl complex is chosen from the group consisting of Co₂ (CO)₈ and Co₄ (CO)₁₂.

13. The curable composition kit of claim 12 wherein the transition metal carbonyl complex is Co₂ (CO)₈.

14. The curable composition kit of claim 10 wherein the cocatalyst is chosen from the group consisting of monoalkyl silanes, monoaryl silanes, dialkyl silanes, alkylaryl silanes, diaryl silanes, trialkyl silanes, dialkylaryl silanes, alkyldiaryl silanes, triaryl silanes, cyclic silanes, polymeric silanes, dichlorochlormethylsilane, 1,1,3,3-tetramethyldisiloxane, tetramethyldisilane, trichlorosilane and triethoxysilane.

15. The curable composition kit of claim 14 wherein the cocatalyst is phenylsilane.