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US 5,665,850 AGranted
Polymeric organometallic photoinitiators and the cationically crosslinkable polyorganosiloxane compositions which comprise them
AssigneeRhone-Poulenc Chimie
InventorChristian Priou
Life of this patent
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Abstract
Processes of preparing polymeric photoinitiators are disclosed. The polymers are prepared by either a hydrosilation reaction of a SiH containing siloxane or a ring opening reaction of an epoxy functional siloxane. The resulting polymeric photoinitiators are cationic polymers consisting of organometallic complex salts which are grafted onto a polyorganosiloxane backbone.
Claims6
A process for preparing a photoinitiator of formula (I) ##STR9## wherein:
- m is an integer or fractional number ranging from 0.5 to 50;
- n is an integer or fractional number ranging from 0 to 500;
- p equal to 0;
- the sum m+n is greater than or equal to 2;
- the R.sup.1 symbols are identical or different and each represents a linear or branched alkyl radical having from 1 to 6 carbon atoms or a phenyl radical;
- the A symbol represents an organometallic salt of formula (II):
- (L.sup.1 L.sup.2 M).sup.q+ X.sup.-.sub.q (II)
- in which formula:
- M represents a metal selected from the group consisting of Mn, Cr, Mo, W, Fe, Re and Co;
- L.sup.1 represents one ligand or 2 ligands, which are identical or different, bonded to the metal M by .pi. bonds, which ligand(s) are selected from the group consisting of .eta..sup.3 -allylalkyl, .eta..sup.5 -cyclopentadienyl, .eta..sup.7 -cycloheptatrienyl and .eta..sup.6 -aromatic compounds selected from the group consisting of .eta..sup.6 -benzene ligands and compounds having from 2 to 4 aromatic rings, each ring being capable of contributing 3 to 8 .pi. electrons to the valency layer of the metal M;
- L.sup.2 represents 0 to 3 identical or different ligand(s) bonded to the metal M by .sigma. electrons, and is selected from the group consisting of CO and NO.sub.2.sup.+ ;
- X.sup.- is a halogenated complex anion selected from the group consisting of BF.sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-, and SbF.sub.6.sup.- and mixtures thereof;
- q is a positive integer equal to 1 or 2;
- the valency bond uniting the monovalent symbol A to Z being carried by a carbon atom of the ligand L.sup.1 or one of the two ligands L.sup.1 ;
- R.sup.2 represents a divalent organic radical selected from the group consisting of:
- (1) linear or branched alkylene radicals having from 2 to 6 carbon atoms;
- and
- (2) radicals of formula:
- --R.sup.3 --O--R.sup.4 -- (III)
- in which the R.sup.3 and R.sup.4 radicals, which are identical or different, represent linear or branched alkylene radicals having from 1 to 6 carbon atoms;
- and
- Z is a group of the formula:
- (5)--Si(R.sup.7).sub.2 -- (V)
- in which the R.sup.4 radicals are identical or different and each represent a linear or branched alkyl radical having from 1 to 6 carbon atoms when R.sup.2 is represented by (1) or (2);
- said process comprising the steps of reacting a compound of formula (VIII) ##STR10## wherein:
- R.sup.1, m and n have the same meaning indicated above for formula (I),
- with a precursor of the A--Z--R.sup.2 -- substituent carrying an ethylenic unsaturation at the free end of the hydrocarbon group bonded to the A--Z-- assembly by a hydrosilation reaction in the presence of a catalyst to yield a compound of formula (I).
24 more elements
A process for preparing a photoinitiator of formula (I) ##STR11## wherein:
- m is an integer or fractional number ranging from 0.5 to 50;
- n is an integer or fractional number ranging from 0 to 500;
- p is an integral or fractional number ranging from 0 to 50;
- the sum m+n is greater than or equal to 2;
- the R.sup.1 symbols are identical or different and each represents a linear or branched alkyl radical having from 1 to 6 carbon atoms or a phenyl radical;
- the A symbol represents an organometallic salt of formula (II):
- (L.sup.1 L.sup.2 M).sup.q+ X.sup.-.sub.q (II)
- in which formula:
- M represents a metal selected from the group consisting of Mn, Cr, Mo, W, Fe, Re and Co;
- L.sup.1 represents one ligand or 2 ligands, which are identical or different, bonded to the metal M by .pi. bonds, which ligand(s) are selected from the group consisting of .eta..sup.3 -allylalkyl, .eta..sup.5 -cyclopentadienyl, .eta..sup.7 -cycloheptatrienyl and .eta..sup.6 -aromatic compounds selected from the group consisting of .eta..sup.6 -benzene ligands and compounds having from 2 to 4 aromatic rings, each ring being capable of contributing 3 to 8 .pi. electrons to the valency layer of the metal M;
- L.sup.2 represents 0 to 3 identical or different ligand(s) bonded to the metal M by .sigma. electrons, and is selected from the group consisting of CO and NO.sub.2.sup.+ ;
- X.sup.- is a halogenated complex anion selected from the group consisting of BF.sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-, and SbF.sub.6.sup.- and mixtures thereof;
- q is a positive integer equal to 1 or 2;
- the valency bond uniting the monovalent symbol A to Z being carried by a carbon atom of the ligand L.sup.1 or one of the two ligands L.sup.1 ;
- R.sup.2 represents a divalent organic radical selected from the group consisting of:
- (3) alkylenecyclohexylene radicals in which the alkylene portion of the radical, which is linear or branched, contains from 2 to 4 carbon atoms and the cyclohexylene portion of the radical, which is connected to the Z group, contains an OH group;
- and
- (4) radicals of formula:
- --R.sup.5 --O--R.sup.6 -- (IV)
- in which the R.sup.5 and R.sup.6 radicals, which are identical or different, represent linear or branched alkylene radicals having from 1 to 6 carbon atoms and wherein the R.sup.6 radical is substituted by one or two OH groups;
- --Z is --O--CO--
- B represents the precusor radical of the R.sup.2 radical containing at its end which is opposite to that bonded to the silicon atom, an epoxy group resulting from the union of
- an oxygen atom with two carbon atoms belonging to an alkyl chain or to a cyclohexyl radical;
- said process comprising the steps of converting all or part of the B radicals of a compound of formula (x) ##STR12## wherein:
- R.sup.1, B, m, P and n have the same meaning indicated above for formula (I),
- into A--Z--R-- substituents, by an opening reaction of the epoxy group by a free COOH functional group carried by the L.sup.1 ligand or one of the two L.sup.1 ligands of the organometallic salt which will be therefore the precursor of the A--Z-assembly, to yield a compound of formula (I).
23 more elements
Dependencies are inferred from the claim text.