Hydrosilation reaction utilizing a (cyclopentadiene)(sigma-aliphatic) platinum complex and a free radical photoinitiator

• US 6,376,569 B1
• Filed: 12/13/1990
• Issued: 04/23/2002
• Est. Priority Date: 12/13/1990
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Boardman, Larry D., Oxman, Joel D.
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US07/627,009
• Time in Patent Office: 4,149 Days
• Field of Search: 522/8, 522/12, 522/27, 522/29, 522/99, 522/16, 522/148, 528/15, 528/25, 528/31, 428/345, 428/343
• US Class Current: 522/29
• CPC Class Codes: C07F 7/0801 General processes
• CPC Class Codes: C07F 7/0879 Hydrosilylation reactions
• CPC Class Codes: C07F 7/1876 by reactions involving the formation of Si-C linkages
• 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: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08K 5/00 Use of organic ingredients
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08K 5/56 Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• 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 428/28 Web or sheet containing structurally defined element or component and having an adhesive outermost layer
• CPC Class Codes: Y10T 428/2809 including irradiated or wave energy treated component

Abstract

A process for the addition of compounds containing silicon-bonded hydrogen to compounds containing aliphatic unsaturation and compositions suitable for said process. The process is activated by actinic radiation and is conducted in the presence of a platinum complex having one cyclopentadienyl group that is eta-bonded to the platinum atom and three aliphatic groups that are sigma-bonded to the platinum atom and a free-radical photoinitiator that is capable of absorbing actinic radiation such that the hydrosilation reaction is initiated upon exposure to actinic radiation. The invention also provides compositions for use in the aforementioned process.

Claims

1. Radiation-curable composition comprising:

(a) a polyorganohydrosiloxane having the general formula;

wherein

each R¹⁶ can be the same or different and represents an alkyl group, an cycloalkyl group, a phenyl group, or hydrogen, at least two but no more than one-half of all the R¹⁶ groups in the siloxane being hydrogen,

m represents 0, 1, 2, 3, and

n represents a number having an average value from one to about 3000,

(b) a polyorganosiloxane having the general formula;

wherein

each R¹⁴ can be the same or different and represents a non-halogenated or halogenated ethylenically unsaturated group, a non-halogenated or halogenated alkyl group or cycloalkyl group, or the phenyl group, at least 70% of all R¹⁴ group being methyl groups, but no more than 10% of all R¹⁴ groups being vinyl or other alkenyl,

h represents a number having a value from 1 to about 3000, and

g represents 0, 1, 2, 3,

(c) a platinum complex represented by the formula;

wherein

Cp represents a cyclopentadienyl group that is eta-bonded to the platinum atom, the cyclopentadienyl group being unsubstituted or substituted with one or more groups that do not interfere in a hydrosilation reaction, and

each of R¹, R², and R³ represents an aliphatic group having from one to eighteen carbon atoms, said R¹, R², and R³ groups being sigma-bonded to the platinum atom,

(d) a free-radical photoinitiator that is capable of absorbing actinic radiation and has the general formula;

wherein R⁴ represents an unsubstituted aryl group or an aryl group substituted with one or more groups that do not interfere with the hydrosilation reaction, R⁵, R⁶, and R⁷ each independently represents a member selected from the group consisting of unsubstituted aryl groups and aryl groups substituted with one or more groups that do not interfere with the hydrosilation reaction, aliphatic groups having one to eighteen carbon atoms, and hydrogen.

2. The composition of claim 1, further including a sensitizer.

3. Radiation-curable composition comprising

(a) a polyorganohydrosiloxane having the general formula:

wherein

each R¹⁶ can be the same or different and represents an alkyl group, a cycloalkyl group, a phenyl group, or hydrogen, at least two but no more than one-half of all the R¹⁶ groups in the siloxane being hydrogen,

m represents 0, 1, 2 or 3, and

n represents a number having an average value from one to about 3000,

(b) a polyorganosiloxane having the general formula;

wherein

each R¹⁴ can be the same or different and represents a non-halogenated or halogenated ethylenically unsaturated group, a non-halogenated or halogenated alkyl group or cycloalkyl group, or the phenyl group, at least 70% of all R¹⁴ group being methyl groups, but no more than 10% of all R¹⁴ groups being vinyl or other alkenyl, and at least two of the R¹⁴ groups being vinyl or other alkenyl,

h represents a number having a value from 1 to about 3000, and

g represents 0, 1, 2, or 3,

(c) a platinum complex represented by the formula;

wherein

Cp represents a cyclopentadienyl group that is eta-bonded to the platinum atom, the cyclopentadienyl group being unsubstituted or substituted with one or more groups that do not interfere in a hydrosilation reaction, and

each of R¹, R², and R³ represents an aliphatic group having from one to eighteen carbon atoms, said R¹, R², and R³ groups being sigma-bonded to the platinum atom,

(d) a free-radical photoinitiator that is capable of absorbing actinic radiation and has the general formula;

wherein R⁸ represents an unsubstituted aryl group or an aryl group substituted with one or more groups that do not interfere with the hydrosilation reaction, and R⁹, R¹⁰, and R¹¹ each independently represents a member selected from the group consisting of unsubstituted aryl groups or an aryl group substituted with one or more groups that do not interfere with the hydrosilation reaction, an aliphatic group having from one to eighteen carbon atoms, and hydrogen.

4. The composition of claim 3, further including a sensitizer.