Visible radiation activated hydrosilation reaction

• US 4,916,169 A
• Filed: 09/09/1988
• Issued: 04/10/1990
• Est. Priority Date: 09/09/1988
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Boardman, Larry D., Oxman, Joel D.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US07/242,478
• Time in Patent Office: 578 Days
• Field of Search: 522/26, 522/27, 522/29, 522/48, 522/49, 522/53, 522/67, 522/69, 522/99, 522/104, 522/110, 522/172, 528/15
• US Class Current: 522/27
• CPC Class Codes: A61K 6/90 Compositions for taking dental impressions
• 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 77/70 Siloxanes defined by use of the MDTQ nomenclature
• 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 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

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 visible 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 sensitizer that is capable of absorbing visible light and is capable of transferring energy to said platinum complex such that the hydrosilation reaction is initiated upon exposure to visible light. The invention also provides for use in the aforementioned process.

Claims

1. A hydrosilation process which comprises reacting a composition comprising a compound having aliphatic unsaturation and a compound containing at least one silicon-bonded hydrogen atom and not having more than three hydrogen atoms attached to any one silicon atom, in the presence of both a (η

⁵ -cyclopentadienyl)tri(σ

-aliphatic)platinum complex and a sensitizer that is capable of absorbing visible light and that is capable of transferring energy to said platinum complex such that the hydrosilation reaction is initiated upon exposure to visible light.

2. The process of claim 1 wherein said reaction is carried out by means of exposing said composition to visible radiation.

3. The process of claim 1 wherein said sensitizer has a triplet energy of at least 31 Kcal/mole.

4. The process of claim 1 wherein said sensitizer is a polycyclic aromatic compound.

5. The process of claim 4 wherein said polycyclic aromatic compound has from two to five rings, inclusive.

6. The process of claim 5 wherein said polycyclic aromatic compound is selected from the group consisting of 9,10-dimethylanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethylanthracene, and azulene.

7. The process of claim 1 wherein said sensitizer is an aromatic compound containing a ketone chromophore.

8. The process of claim 7 wherein said aromatic compound is a thioxanthone.

9. The process of claim 8 wherein said thioxanthone is selected from the group consisting of thioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

10. The process of claim 1 wherein the platinum complex has the formula ##STR12## wherein Cp represents a cyclopentadienyl group that is eta-bonded to the platinum atom, the cyclopentadienyl group being unsubstituted or substituted by 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.

11. The process of claim 10 wherein the platinum complex is selected from the group consisting of:

(η

⁵ -cyclopentadienyl)trimethylplatinum,

(η

⁵ -methylcyclopentadienyl)trimethylplatinum,

(η

⁵ -trimethylsilylcyclopentadienyl)trimethylplatinum, and

(η

⁵ -dimethylphenylsilylcyclopentadienyl)trimethylplatinum.

12. The process of claim 1 wherein the composition comprises from about 0.1 to about 10.0 equivalent weights of the compound having silicon-bonded hydrogen per equivalent weight of the compound having aliphatic unsaturation, and, per 1,000,000 parts by weight of the total composition, from about 5 to about 1000 parts by weight of the platinum catalyst, and from about 50 to about 50,000 parts by weight of the sensitizer.

13. The process of claim 1 wherein the compound containing aliphatic unsaturation is a polyorganosiloxane having the general formula:

##STR13## wherein each R⁶ independently represents a member selected from the group consisting of non-halogenated or halogenated ethylenically-unsaturated groups, non-halogenated or halogenated alkyl groups, non-halogenated or halogenated cycloalkyl groups, and the phenyl group, provided that at least 70% of all R⁶ groups are methyl groups, but no more than 10% of all R⁶ groups are vinyl groups or other alkenyl groups, further provided that at least two of the R⁶ groups are vinyl groups or other alkenyl groups,

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

g is 0, 1, 2, or 3.

14. The process of claim 1 wherein the compound containing silicon-bonded hydrogen is a polyorganohydrosiloxane having the general formula:

##STR14## wherein each R⁸ independently represents a member selected from the group consisting of alkyl groups, cycloalkyl groups, phenyl group, and hydrogen, provided that at least two but no more than one-half of all the R⁸ groups in the siloxane are hydrogen,

m is 0, 1, 2 or 3, and

n is a number having an average value from one to about 3000.

15. The process of claim 1 wherein the compound having aliphatic unsaturation is one having olefinic unsaturation.

16. A radiation-curable composition comprising:

(a) a silicon compound containing at least one hydrogen atom attached to silicon per molecule, there being not more than three hydrogen atoms attached to any one silicon atom,

(b) a compound containing aliphatic unsaturation,

(c) a (η

⁵ -cyclopentadienyl)tri(σ

-aliphatic)platinum complex, and

(d) a sensitizer that is capable of absorbing visible light and that is capable of transferring energy to said platinum complex when said composition is exposed to visible light.

17. The composition of claim 16 wherein said sensitizer has a triplet energy of at least 31 Kcal/mole.

18. The composition of claim 16 wherein said sensitizer is a polycyclic aromatic compound.

19. The composition of claim 18 wherein said polycyclic aromatic compound has from two to five rings, inclusive.

20. The composition of claim 19 wherein said polycyclic aromatic compound is selected from the group consisting of 9,10-dimethylanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethylanthracene, and azulene.

21. The composition of claim 16 wherein said sensitizer is an aromatic compound containing a ketone chromophore.

22. The composition of claim 21 wherein said aromatic compound is a thioxanthone.

23. The composition of claim 22 wherein said thioxanthone is selected from the group consisting of thioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

24. The composition of claim 16 wherein the platinum complex is represented by the formula:

##STR15## wherein Cp represents a cyclopentadienyl group that is eta-bonded to the platinum atom, the cyclopentadienyl group being unsubstituted or substituted by 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.

25. The composition of claim 24 wherein the platinum complex is selected from the group consisting of:

(η

⁵ -cyclopentadienyl)trimethylplatinum,

(η

⁵ -methylcyclopentadienyl)trimethylplatinum,

(η

⁵ -trimethylsilylcyclopentadienyl)trimethylplatinum, and

(η

⁵ -dimethylphenylsilycyclopentadienyl)trimethylplatinum.

26. The composition of claim 16, said composition comprising from about 0.1 to about 10.0 equivalent weights of the compound having silicon-bonded hydrogen per equivalent weight of the compound having aliphatic unsaturation, and per 1,000,000 parts by weight of the total composition, from about 5 to about 1000 parts by weight of the platinum complex and from about 50 to about 50,000 parts by weight of the sensitizer.

27. Radiation-curable composition comprising

(a) a polyorganohydrosiloxane having the general formula:

##STR16## wherein each R⁸ independently represents a member selected from the group consisting of alkyl groups, cycloalkyl groups, phenyl group, and hydrogen, provided that at least two but no more than one-half of all the R⁸ groups in the siloxane are hydrogen;

m is 0, 1, 2 or 3, and

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

(b) a polyorganosiloxane having the general formula;

##STR17## wherein each R⁶ independently represents a member selected from the group consisting of non-halogenated or halogenated ethylenically unsaturated groups, non-halogenated or halogenated alkyl groups, non-halogenated or halogenated cycloalkyl groups, and the phenyl group, provided that at least 70% of all R⁶ groups are methyl groups, but no more than 10% of all R⁶ groups are vinyl groups or other alkenyl groups, further provided that at least two of the R⁶ groups are vinyl groups or other alkenyl groups,

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

g is 0, 1, 2, or 3,

(c) a platinum complex represented by the formula;

##STR18## wherein Cp represents a cyclopentadienyl group that is eta-bonded to the platinum atom, the cyclopentadienyl group being unsubstituted or substituted by one of more groups that are inert 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, and

(d) a sensitizer that is capable of absorbing visible light and that is capable of transferring energy to said platinum complex when said composition is exposed to visible light.