Free radical polymerizable compositions comprising ionic silicones

A composition comprising an actinic radiation curable or thermally curable polyorganosiloxane ionomer having the general formula:

• M1aM2bM3cD1dD2eDefT1gT2hT3iQj. (I)
• wherein:
• M1=R1R2R3SiO1/2
• M2=R4R5R6SiO1/2
• M3=R7R8R9SiO1/2
• D1=R10R11SiO2/2
• D2=R12R13SiO2/2
• D3=R14R15SiO2/2
• T1=R16SiO3/2
• T2=R17SiO3/2
• T3=R18SiO3/2
• Q=SiO4/2
• wherein R1, R2, R5, R6, R8, R9, R11, R13, R15 are aliphatic, aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms. Example of useful hydrocarbon groups includes methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl and tert-pentyl;
• hexyl, such as the n-hexyl group;
• heptyl, such as the n- heptyl group;
• octyl, such as the n-octyl and isooctyl groups and the 2,2,4-trimethylpentyl group;
• nonyl, such as the n-nonyl group;
• decyl, such as the n-decyl group;
• cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals. Examples of aryl groups include phenyl, naphthyl;
• o-, m- and p-tolyl, xylyl, ethylphenyl, and benzyl.
• wherein R3, R10, R16 are independently selected from —CH2CH(R′)(CnH2n)—O—(C2H4O)o—(C3H6O)p—(C4H8O)q—R′, wherein subscript n is zero or positive and has a value in the range of 0 to 6, subscripts o, p and q are zero or positive and independently selected from a value in the range of 0 to 100, subject to the limitation of o +p +q greater than or equal to 1. R′ can be hydrogen or an aliphatic, aromatic or fluoro hydrocarbon having from 1 to 60 carbon atoms, or R′ can be independently chosen from glycolide {—C(O)CH2O—}, lactide {—C(O)CH(CH3)O—}, butyrolactide {—C(O)CH2CH2CH2O—} and caprolactide {—C(O)CH2CH2CH2CH2CH2O—} radicals or hydrocarbon radical defined by R1, wherein (i) or (ii)
• (i) R4, R12, R17 are monovalent radical-bearing ion-pairs, substantially free of free radical polymerizable moieties, and having the formula (II)
• A-Ix−Mny+ (II);
• where A is a spacing group having at least one spacing atom selected from a divalent hydrocarbon or hydrocarbonoxy group, where I is ionic groups such as sulfonate —SO3—, sulfate —OSO3−, carboxylate —COO−, phosphonate —PO32−, or phosphate —OPO32− groups, more specifically sulfonate —SO3−, where M is hydrogen or a cation independently selected from alkali metals, alkaline earth metals, transition metals, metals, metal complexes, quaternary ammonium and phosphonium groups, hydrocarbon cations, alkyl cations, organic cations, and cationic polymers,
• (ii) R4, R12, R17 can be zwitterions having the formula (III):
• —R′—NR″2+—R′″—I (III)
• where R′ is a divalent hydrocarbon radical containing from 1 to about 60 carbon atoms, specifically from 1 to about 20 carbon atoms, and more specifically from 1 to about 8 carbon atoms,
• R″ is monovalent hydrocarbon radical containing from 1 to about 60 carbon atoms, specifically from 1 to about 20 carbon atoms and more specifically from 1 to about 8 carbon atoms, and where
• R′″ is divalent hydrocarbon radical containing from 2 to about 20 carbon atoms, specifically from 2 to about 8 carbon atoms and more specifically from 2 to about 4 carbon atoms;
• and,
• I is an ionic group such as sulfonate —SO3−, sulfate —OSO3−, carboxylate —COO−, phosphonate —PO32−, or phosphate —OPO32− groups;
• and
• wherein R7, R14R18 are independently selected from unsaturated monovalent radicals or epoxy group containing radicals and are substantially free from ionic moieties;
• and
• where subscript n and superscript y are independently from 1 to 6 and x is the product of n times y, where the subscript a, b, c, d, e, f, g, h, i, j are zero or positive subject to the following limitations:
• to the sum a+b+c+d+e+f+g+h+i+j is greater than or equal to 2 and less than or equal to 6000, the sum b+e+h greater than 0 and the sum c+f+i greater than 0.