Polyphotoinitiators

• US 4,587,276 A
• Filed: 08/31/1983
• Issued: 05/06/1986
• Est. Priority Date: 06/20/1983
• Status: Expired due to Fees

• Current Assignee: Samuel Q.S. Lin
• Original Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Inventors: Humphreys, Robert W. R., Lien, Qcheng S.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/528,287
• Time in Patent Office: 979 Days
• Field of Search: 204/159.13, 204/159.15, 556/436, 525/105, 525/479
• US Class Current: 522/34
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: Y10S 522/904 Monomer or polymer contains initiating group

Abstract

Novel polymeric photocleavable photoinitiators are prepared by the hydrosilation reaction of an organosilicon hydride grafting agent which has a photoinitiating aromatic-aliphatic ketone derivative of at least one organo group, with a polymer having a plurality of unsaturated olefinic or acetylenic sites in the presence of a hydrosilation catalyst. Preferred polymers are butadiene or alkyl substituted butadiene polymers and copolymers and vinyl functional polyorganosiloxanes. The grafting agents have the formula (hv)--R⁸ --R⁵ --H wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R⁸ is selected from alkylene, alkenylene, alkylenoxy and oxy groups, and R⁵ is selected from ##STR1## the R⁶ groups are the same or different organo or halo groups and n is an integer.

Claims

1. A polyphotoinitiator comprising the hydrosilation reaction product of a host polymer having olefinic or acetylenic unsaturation with at least one grafting agent represented by the formula

View Dependent Claims (2, 3, 9, 10, 11, 22, 23, 24, 25, 27)

2. A polyphotoinitiator as in claim 1 wherein the host polymer is selected from the group consisting of homopolymers and copolymers of butadiene or alkyl substituted butadienes;

polyorganosiloxanes having pendant vinyl or allyl groups and unsaturated polyesters.

3. A polyphotoinitiator as in claim 1 comprising the said reaction product of a said host polymer and a mixture of said grafting agent compounds, said mixture comprising at least one grafting agent in which R⁸ is oxy.

9. A polyphotoinitiator as defined in claim 1 in a composition, said composition further comprising at least one free radical curable compound.

10. A composition as in claim 9 wherein said curable compound is selected from the group consisting of esters of acrylic and methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-subsituted acrylamides and methacrylamides;

vinyl esters, styrene, alkylstyrenes, halostyrenes, divinylbenzene, vinylnaphthalene, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, diallyl phthalate, diallyl maleate, triallyl isocyanurate, triallyl phosphate and ethylene glycol diallyl ether.

11. A composition as in claim 9 wherein said curable compound is selected from methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n- or tert-butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate and mixtures thereof.

22. A polyphotoinitiator as in claim 2 wherein the host polymer is selected from homopolymers and copolymers of butadiene or alkyl substituted butadienes.

23. A polyphotoinitiator as in claim 22 wherein the host polymer is polybutadiene.

24. A composition comprising a photoinitiator as n claim 22 and a free radically cureable compound.

25. A composition as in claim 24 wherein the cureable compound is an ester of acrylic or methacrylic acid.

27. A composition as in claim 9 wherein R⁵ of the polyphotoinitiator is ##STR25## and n is 1.

4. A polyphotoinitiator comprising a polymeric backbone with a plurality of photoinitiating groups pendently attached thereto through intermediate alkylene or alkenylene groups, the photoinitiating groups having the structure;

space="preserve" listing-type="equation">(hv)--R.sup.8 --R.sup.5 --

wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R⁵ is selected from ##STR17## R⁶ are the same or different organo of halo groups;

n is an integer; and

R⁸ is selected from alkylene, alkenylene, alkyleneoxy and oxy groups.

5. A polyphotoinitiator as in claim 4 wherein (hv) is represented by one of formulas (a) (b) or (c):

##STR18## wherein R¹ is phenyl or substituted phenyl;

R² is alkyl, substituted alkyl, aryl, substituted aryl or triorganosilyl; and

R³ and R⁴ are H, alkyl, substituted alkyl, aryl or substituted aryl, or, R³ and R⁴ together with the carbon atom to which both are attached comprise a cyclic alkyl group.

6. A polyphotoinitiator as in claim 5 wherein (hv) is as defined by formula (a), R² is alkyl and R³ is phenyl or substituted phenyl.

7. A polyphotoinitiator as defined in claim 4 further having a plurality of photocurable groups on the polymer backbone.

8. A polyphotoinitiator as defined in claim 7 wherein the photocurable groups are selected from acrylate, methacrylate, vinyl, silicon hydride, alkylthiol, styryl, acrylamido, methacrylamido, maleate and itaconate.

26. A polyphotointiator as in claim 4 wherein R⁵ is ##STR24## and n is 1.

12. A method of preparing a polyphotoinitiator comprising the reacting of a host polymer having olefinic or acetylenic unsaturation with at least one grafting agent represented by the formula H--R⁵ --R⁸ --(hv), wherein (hv) is a photoinitiating aromatic-aliphatic ketone group;

R⁵ is a group selected from ##STR19## R⁶ are the same of different organo or halogroups;

n is an integer; and

R⁸ is selected from alkylene, alkenylene, alkyleneoxy and oxy groups, said reaction conducted in the presence of a hydrosilation catalyst.

13. A method as in claim 12 wherein the hydrosilation catalyst is a Platinium based catalyst.

14. A method as in claim 13 wherein the catalyst is chloroplatinic acid.

15. A method as in claim 12 wherein the host polymer is selected from the group consisting of homopolymers and copolymers of butadiene or alkyl substituted butadienes;

polyorganosiloxanes having pendant vinyl or allyl groups; and

unsaturated polyesters.

16. A method as in claim 15 wherein the host polymer is a homopolymer or copolymer of butadiene or an alkyl substituted butadiene and said grafting agent is reacted therewith in amount which does not exceed the number of equivalents of pendant vinyl groups present in the host polymer.

17. A method as in claim 12 wherein (hv) is selected from the groups represented by formulas (a) (b) or (c):

##STR20## wherein R¹ is phenyl or substituted phenyl;

R² is alkyl, substituted alkyl, aryl, substituted aryl or trimethylsilyl; and

R³ and R⁴ are H, alkyl, substituted alkyl, aryl or substituted aryl, or R³ and R⁴ together with the carbon atom to which both are attached comprise a cyclic alkyl group.

18. A method as in claim 12 in which said grafting agent is prepared by the hydrosilation of a compound having the formula:

space="preserve" listing-type="equation">CH.sub.2 ═

CH--CH.sub.2 --(hv)

with a dihydrosilicon compound selected from;

##STR21##

19. A method as in claim 13 wherein the said hydrosilation reaction is conducted in a methacrylate ester diluent.

21. A method as in claim 12 wherein said grafting agent is prepared by the hydrosilation of a compound having the formula:

space="preserve" listing-type="equation">(hv)--CH.sub.2 CH═

CH.sub.2 (A)

with a compound of the formula;

##STR23## where R⁷ is a hydrolyzable group, hydrolysis of the R⁷ group to give the corresponding silanol and condensation of the resulting product with another compound of formula (B).

28. A method as in claim 12 wherein R⁵ is ##STR26## and n is 1.

20. A method of preparing a graft copolymer comprising irradiating a polyphotoinitiator composition with UV light, the polyphotoinitiator composition comprising a mixture of an ethylenically unsaturated monomer and a polyphotoinitiator, the polyphotoinitiator comprising a polymeric backbone with a plurality of photoinitiating groups pendently attached thereto, the photoinitiating group having the structure:

space="preserve" listing-type="equation">(hv)--R.sup.8 --R.sup.5 --

wherein (hv) is a photoinitiating aromatic-aliphatic ketone group;

R⁵ is selected from ##STR22## n is an integer;

R⁶ are the same or different organo or halo groups; and

R⁸ is alkylene, alkenylene, alkyleneoxy or oxy.

29. A method as in claim 20 wherein R⁵ is ##STR27## and n is 1.