US4587276A
Expired / Lapsed
US
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Polyphotoinitiators
Assignee: Henkel Loctite Corp
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Filing: 1983-08-31
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Granted: 1986-05-06
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Expires: 2003-08-31
Abstract
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)--R 8 --R 5 --H wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R 8 is selected from alkylene, alkenylene, alkylenoxy and oxy groups, and R 5 is selected from ##STR1## the R 6 groups are the same or different organo or halo groups and n is an integer.
Inventors
- 👤 Qcheng S. Lien
- 👤 Robert W. R. Humphreys
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 22:14
CPC Classifications
C; C08; C08G; C08G77/00; C08G77/04; C08G77/14; C08F; C08F2/00; C08F2/46; C08F2/48; C08F2/50; C08F299/00; C08F299/02; C08F299/08; C08G77/38; Y; Y10; Y10S; Y10S522/00; Y10S522/904
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
70 words
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 (hv)--R.sup.8 --R.sup.5 --H wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R 5 is selected from ##STR16## R 6 are the same or different organo or halo groups; n is an integer; and R 8 is selected from alkylene, alkenylene, alkyleneoxy and oxy groups.
Claim 2
Dependent Claim
70 words
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 (hv)--R.sup.8 --R.sup.5 --H wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R 5 is selected from ##STR16## R 6 are the same or different organo or halo groups; n is an integer; and R 8 is selected from alkylene, alkenylene, alkyleneoxy and oxy groups.
Claim 3
Dependent Claim
36 words
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.
Claim 4
Dependent Claim
38 words
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 R 8 is oxy.
Claim 5
Dependent Claim
71 words
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; (hv)--R.sup.8 --R.sup.5 -- wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R 5 is selected from ##STR17## R 6 are the same or different organo of halo groups; n is an integer; and R 8 is selected from alkylene, alkenylene, alkyleneoxy and oxy groups.
Claim 6
Dependent Claim
71 words
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; (hv)--R.sup.8 --R.sup.5 -- wherein (hv) is a photoinitiating aromatic-aliphatic ketone group, R 5 is selected from ##STR17## R 6 are the same or different organo of halo groups; n is an integer; and R 8 is selected from alkylene, alkenylene, alkyleneoxy and oxy groups.
Claim 7
Dependent Claim
74 words
A polyphotoinitiator as in claim 4 wherein (hv) is represented by one of formulas (a) (b) or (c): ##STR18## wherein R 1 is phenyl or substituted phenyl; R 2 is alkyl, substituted alkyl, aryl, substituted aryl or triorganosilyl; and R 3 and R 4 are H, alkyl, substituted alkyl, aryl or substituted aryl, or, R 3 and R 4 together with the carbon atom to which both are attached comprise a cyclic alkyl group.
Claim 8
Dependent Claim
26 words
A polyphotoinitiator as in claim 5 wherein (hv) is as defined by formula (a), R 2 is alkyl and R 3 is phenyl or substituted phenyl.
Claim 9
Dependent Claim
18 words
A polyphotoinitiator as defined in claim 4 further having a plurality of photocurable groups on the polymer backbone.
Claim 10
Dependent Claim
26 words
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.
Claim 11
Dependent Claim
21 words
A polyphotoinitiator as defined in claim 1 in a composition, said composition further comprising at least one free radical curable compound.
Claim 12
Dependent Claim
56 words
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.
Claim 13
Dependent Claim
48 words
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.
Claim 14
Independent Claim
85 words
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--R 5 --R 8 --(hv), wherein (hv) is a photoinitiating aromatic-aliphatic ketone group; R 5 is a group selected from ##STR19## R 6 are the same of different organo or halogroups; n is an integer; and R 8 is selected from alkylene, alkenylene, alkyleneoxy and oxy groups, said reaction conducted in the presence of a hydrosilation catalyst.
Claim 15
Independent Claim
85 words
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--R 5 --R 8 --(hv), wherein (hv) is a photoinitiating aromatic-aliphatic ketone group; R 5 is a group selected from ##STR19## R 6 are the same of different organo or halogroups; n is an integer; and R 8 is selected from alkylene, alkenylene, alkyleneoxy and oxy groups, said reaction conducted in the presence of a hydrosilation catalyst.
Claim 16
Dependent Claim
15 words
A method as in claim 12 wherein the hydrosilation catalyst is a Platinium based catalyst.
Claim 17
Dependent Claim
12 words
A method as in claim 13 wherein the catalyst is chloroplatinic acid.
Claim 18
Dependent Claim
36 words
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.
Claim 19
Dependent Claim
48 words
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.
Claim 20
Dependent Claim
76 words
A method as in claim 12 wherein (hv) is selected from the groups represented by formulas (a) (b) or (c): ##STR20## wherein R 1 is phenyl or substituted phenyl; R 2 is alkyl, substituted alkyl, aryl, substituted aryl or trimethylsilyl; and R 3 and R 4 are H, alkyl, substituted alkyl, aryl or substituted aryl, or R 3 and R 4 together with the carbon atom to which both are attached comprise a cyclic alkyl group.
Claim 21
Dependent Claim
32 words
A method as in claim 12 in which said grafting agent is prepared by the hydrosilation of a compound having the formula: CH.sub.2 ═CH--CH.sub.2 --(hv) with a dihydrosilicon compound selected from: ##STR21##
Claim 22
Dependent Claim
18 words
A method as in claim 13 wherein the said hydrosilation reaction is conducted in a methacrylate ester diluent.
Claim 23
Independent Claim
91 words
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: (hv)--R.sup.8 --R.sup.5 -- wherein (hv) is a photoinitiating aromatic-aliphatic ketone group; R 5 is selected from ##STR22## n is an integer; R 6 are the same or different organo or halo groups; and R 8 is alkylene, alkenylene, alkyleneoxy or oxy.
Claim 24
Independent Claim
91 words
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: (hv)--R.sup.8 --R.sup.5 -- wherein (hv) is a photoinitiating aromatic-aliphatic ketone group; R 5 is selected from ##STR22## n is an integer; R 6 are the same or different organo or halo groups; and R 8 is alkylene, alkenylene, alkyleneoxy or oxy.
Claim 25
Dependent Claim
61 words
A method as in claim 12 wherein said grafting agent is prepared by the hydrosilation of a compound having the formula: (hv)--CH.sub.2 CH═CH.sub.2 (A) with a compound of the formula: ##STR23## where R 7 is a hydrolyzable group, hydrolysis of the R 7 group to give the corresponding silanol and condensation of the resulting product with another compound of formula (B).
Claim 26
Dependent Claim
22 words
A polyphotoinitiator as in claim 2 wherein the host polymer is selected from homopolymers and copolymers of butadiene or alkyl substituted butadienes.
Claim 27
Dependent Claim
12 words
A polyphotoinitiator as in claim 22 wherein the host polymer is polybutadiene.
Claim 28
Dependent Claim
15 words
A composition comprising a photoinitiator as n claim 22 and a free radically cureable compound.
Claim 29
Dependent Claim
18 words
A composition as in claim 24 wherein the cureable compound is an ester of acrylic or methacrylic acid.
Claim 30
Dependent Claim
15 words
A polyphotointiator as in claim 4 wherein R 5 is ##STR24## and n is 1.
Claim 31
Dependent Claim
18 words
A composition as in claim 9 wherein R 5 of the polyphotoinitiator is ##STR25## and n is 1.
Claim 32
Dependent Claim
15 words
A method as in claim 12 wherein R 5 is ##STR26## and n is 1.
Claim 33
Dependent Claim
15 words
A method as in claim 20 wherein R 5 is ##STR27## and n is 1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1989-05-05 | 1989-11-04 | 1990-05-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-05-05 | 1993-11-04 | 1994-05-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-05-05 | 1997-11-04 | 1998-05-06 | $7700.00 | Window Closed / Lapsed |