Acrylate- or methacrylate-functional organopolysiloxanes

• US 5,091,440 A
• Filed: 12/08/1989
• Issued: 02/25/1992
• Est. Priority Date: 12/08/1989
• Status: Expired due to Term

• Current Assignee: Wacker Silicones Corporation
• Original Assignee: Wacker Silicones Corporation
• Inventors: Griswold, Roy M.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US07/447,758
• Time in Patent Office: 809 Days
• Field of Search: 528/25, 528/26, 528/29, 528/32, 528/24, 528/21, 522/99, 522/172
• US Class Current: 522/99
• CPC Class Codes: C07F 7/0838 Compounds with one or more Si-O-Si sequences compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/392 containing sulfur
• CPC Class Codes: C09D 11/101 Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Abstract

Radiation polymerizable acrylate- or methacrylate-functional organo-polysiloxanes having the structural formula ##STR1## wherein R is a radical selected from the group consisting of monovalent hydrocarbon radicals having from 1 to 20 carbon atoms, substituted monovalent hydrocarbon radicals having from 1 to 20 carbon atoms, monovalent hydrocarbonoxy radicals having from 1 to 20 carbon atoms and a radical of the formula: ##STR2## in which at least one R is a radical of formula (I), R¹ is hydrogen or a methyl radical, R² is selected from the group consisting of a multivalent hydrocarbonoxy radical and a multivalent hydrocarbonoxy radical containing non-terminal atoms selected from the group consisting of oxygen, sulphur and nitrogen atoms, R³ is a divalent hydrocarbon radical or a divalent hydrocarbonoxy radical, a is a number having an average value of from 0.7 to 2.6, b is a number of from 1 to 5, and x is a number from 2 to 1000.

The acrylate- or methacrylate-functional organopolysiloxanes are combined with a photosensitizer and/or a peroxide and cured by radiation and/or heat. High energy electrons may be used in lieu of a photosensitizer or peroxide to cure these compositions.

Claims

1. Acrylate- or methacrylate-functional organopolysiloxane compositions containing an organopolysiloxane of the formula ##STR13## wherein R is a radical selected from the group consisting of monovalent hydrocarbon radicals having from 1 to 20 carbon atoms, substituted monovalent hydrocarbon radicals having from 1 to 20 carbon atoms, monovalent hydrocarbonoxy radicals having from 1 to 20 carbon atoms and a radical of the formula ##STR14## wherein at least one R is a radical of formula (I), R¹ is selected from the group consisting of hydrogen and a methyl radical, R² is selected from the group consisting of a multivalent hydrocarbonoxy radical and a multivalent hydrocarbonoxy radical containing non-terminal atoms selected from the group consisting of oxygen, and nitrogen atoms, R³ is selected from the group consisting of a divalent hydrocarbon radical and a divalent hydrocarbonoxy radical, a is a number having an average value of from 0.7 to 2.6, b is a number of from 1 to 5, and x is a number of from 2 to 200;

said acrylate- or methacrylate-functional organopolysiloxane compositions are obtained by reacting a mercapto-functional compound selected from the group consisting of mercaptofunctional monohydric alcohols, mercapto-functional polyhydric alcohols, mercapto-functional monohydric alcohols containing non-terminal atoms selected from the group consisting of oxygen and nitrogen atoms and mercapto-functional polyhydric alcohols containing non-terminal atoms selected from the group consisting of oxygen and nitrogen atoms with organopolysiloxanes containing vinyl or allyl groups and thereafter the result product is reacted with an acid or ester thereof selected from the group consisting of an acrylic and methacrylic acid in the presence of a free radical initiator.

2. The composition of claim 1, wherein the R² radical is a multivalent hydrocarbonoxy radical.

3. The composition of claim 1, wherein the R² radical is a multivalent hydrocarbonoxy radical containing non-terminal atoms selected from the group consisting of oxygen and nitrogen atoms.

4. The composition of claim 1, wherein the R³ radical is a divalent hydrocarbonoxy radical having from 2 to 20 carbon atoms.

5. The composition of claim 1, wherein the R³ radical is a divalent hydrocarbonoxy radical having from 2 to 20 carbon atoms.

6. The composition of claim 1, wherein the R¹ radical is hydrogen.

7. The composition of claim 1, wherein the R radical is a substituted monovalent hydrocarbon raical in which substituted groups are selected from the group consisting of a cyano radical, acryloxy radical, methacryloxy radical, hydroxyl radical and a radical of the formula

8. The composition of claim 1, wherein the R radical is a vinyl radical.

9. The composition of claim 1, wherein the R radical is an allryl radical.

10. The composition of claim 1, wherein the composition contains a photosensitizer.

11. The composition of claim 1, wherein the composition contains an organic peroxide.

12. The composition of claim 10, wherein the composition also contains an organic peroxide.

13. The composition of claim 10, wherein the photosensitizer is present in an amount of from about 0.5 to about 20 percent by weight based on the weight of the acrylate- or methacrylate-functional organopolysiloxane.

14. The composition of claim 11, wherein the organic peroxide is present in an amount of from about 0.1 to about 10 percent by weight based on the weight of the acrylate- or methacrylate-functional organopolysiloxane.

15. A process for preparing acrylate- or methacrylate-functional organopolysiloxane compositions which comprises reacting (1) a sulfide selected from the group consisting of an alkylene sulfide and hydrogen sulfide with a polyhydric alcohol in the presence of an alumina catalyst to form a mercapto-functional polyhydric alcohol, (2) reacting the resultant mercapto-functional polyhydric alcohol with an organopolysiloxane having aliphatic unsaturation to form a carbinol-functional organopolysiloxane and thereafter (3) reacting the resultant carbinol-functional organopolysiloxane with a compound selected from the group consisting of acrylic acid, methacrylic acid and esters thereof.

16. The process of claim 15, wherein the mercaptofunctional polyhydric alcohol is prepared by reacting a metal sulfide with an epoxy-functional polyhydric alcohol.

17. The process of claim 15, wherein the mercaptofunctional polyhydric alcohol is prepared by reacting a fluoropyridinum salt and sodium N,N-dimethylthiocarbamate with a polyhydric alcohol.