Platinum/alkenylcyclohexene complexes useful for hydrosilylation catalysis

• US 4,699,813 A
• Filed: 12/20/1985
• Issued: 10/13/1987
• Est. Priority Date: 12/20/1984
• Status: Expired due to Fees

• Current Assignee: Rhone-Poulenc Specialites Chimiques "Les Miroirs"
• Original Assignee: Rhone-Poulenc Specialites Chimiques (Sanofi )
• Inventors: Cavezzan, Jacques
• Primary Examiner(s): MARQUIS, MELVYN I
• Application Number:
  US06/811,350
• Time in Patent Office: 662 Days
• Field of Search: 528/15, 528/31, 528/32, 427/387, 525/478, 524/861, 524/862, 428/447
• US Class Current: 427/387
• CPC Class Codes: B01J 2231/323 Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• CPC Class Codes: B01J 2531/828 Platinum
• CPC Class Codes: B01J 31/2291 Olefins
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 31/26 containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• CPC Class Codes: B01J 31/30 Halides
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08K 5/56 Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• CPC Class Codes: C08L 2666/52 Metal-containing compounds
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Novel platinum/olefin complexes, useful for the hydrosilylation curing catalysis of hardenable organopolysiloxane compositions, are facilely prepared by reacting a platinum halide with at least one alkali or alkaline earth metal carbonate or bicarbonate in the presence of an alkenylcyclohexene ligand having the general formula: ##STR1## wherein R₁ is an alkenyl radical having from 2 to 6 carbon atoms, and R₂ is a hydrogen atom or an inert organic radical, and said complex having a ratio, in gram-atoms of halogen to gram-atoms of platinum, ranging from virtually 0 to 4.

Claims

1. A composition of matter comprising an organopolysiloxane curable by hydrosilylation with an organohydropolysiloxane, and a catalytically effective amount of a hydrosilylation catalyst which comprises a platinum/olefin complex, the olefin moiety thereof which comprises an alkenylcyclohexene having the ganeral formula:

##STR4## wherein R₁ is an alkenyl radical having from 2 to 6 carbon atoms, and R₂ is a hydrogen atom or an inert organic radical, and said complex having a ratio, in gram-atoms of halogen to gram-atoms of platinum, ranging from virtually 0 to 4.

2. The organopolysiloxane composition as defined by claim 1, comprising:

(1) at least one organopolysiloxane having, per molecule, at least two alkylenically unsaturated groups bonded to a silicon atom; and

(2) at least one organohydropolysiloxane having, per molecule, at least three .tbd.SiH groups.

3. The organopolysiloxane composition as defined by claim 2, comprising:

(1) at least one organopolysiloxane containing silyloxy units of the formula;

##EQU5## in which Y is an alkylenically unsaturated hydrocarbon group having from 2 to 4 carbon atoms, Z is an inert monovalent hydrocarbon, a ranges from 1 to 3;

b ranges from 0 to 2 and the sum a +b ranges from 1 to 3, with any remaining units comprising units of the formula;

##EQU6## in which Z is as defined above and c ranges from 0 to 3; and

(2) at least one organohydropolysiloxane containing silyloxy units of the formula;

##EQU7## in which W is Z, d ranges from 1 to 3, c ranges from 0 to 2, and d+e ranges from 1 to 3, with any remaining units comprising units of the formula;

##EQU8## in which W is as defined above and g ranges from 0 to 3.

4. The organopolysiloxane composition as defined by claim 3, diluted in an organic solvent compatible therewith.

5. The organopolysiloxane composition as defined by claim 3, solvent-free, and having a viscosity no greater than 5000 mPa.s at 25°

C.

6. A process for the addition of at least one organopolysiloxane having alkylenically unsaturated groups to at least one organohydropolysiloxane having .tbd.SiH groups comprising mixing at least one organopolysiloxane having, per molecule, at least two alkylenically unsaturated groups bonded to a silicon atom with at least one organohydropolysiloxane having, per molecule, at least three .tbd.SiH groups and a catalytically effect amount of a hydrosilylation catalyst which comprises a platinum/olefin complex the olefin moiety thereof which comprises an alkenylcyclohexene having the general formula:

##STR5## wherein R₁ is an alkenyl radical having from 2 to 6 carbon atoms, and R₂ is a hydrogen atom or an inert organic radical, and said complex having a ratio, in gram-atoms of halogen to gram-atoms of platinum, ranging from virtually 0 to 4.

7. The process of claim 6 further comprising coating the admixture toa substrate.

8. The process of claim 6 further comprising reacting the admixture at a temperature of from about room temperature ot 200°

C.

9. The process of claim 6 wherein the process forms an elastomer.

10. The process of claim 6 wherein the admixture further comprises a filler material.

11. The process of claim 8 wherein the process forms a shaped article.