UV-active chromophore functionalized polysiloxanes and copolymers made therefrom

A copolymer comprising at least one polysiloxane having units of Formula VI represented by:

• wherein;
• R1 and R2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical;
• R3 is an organic UV absorbing group derived from an allyl substituted 2-hydroxybenzophenone, allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone, allyl substituted 2-(2′-hydroxy-5′-methylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-tert.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-methyl-5′-tert.-butyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-cyclohexyl-phenyl)-2H-benzotriazole, allyl substituted 2′-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-isooctylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-tert.-butyl-5′-sec.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole or allyl substituted dibenzoylresorcinol;
• R4 is a hydrocarbon radical optionally substituted with oxygen and nitrogen, or a group of Formula II(a) or Formula II(b)
• wherein A and B are a hydrocarbon radical;
• R5 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group;
• x is from 1 to 300;
• y is from 0 to 50 and z is from 1 to 50.

A method of preparing a polysiloxane copolymer, comprising polymerizing an organosiloxane represented by Formula I:

• wherein R1 and R2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical;
• R3 is an organic UV absorbing group derived from an allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone, allyl substituted 2-(2′-hydroxy-5′-methylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-tert.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-methyl-5′-tert.-butyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-cyclohexyl-phenyl)-2H-benzotriazole, allyl substituted 2′-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-isooctylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-tert.-butyl-5′-sec.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole or allyl substituted dibenzoylresorcinol;
• R4 is hydrocarbon radical optionally substituted with oxygen and nitrogen, a group of Formula II(a) or Formula II(b)
• wherein A and, B are a hydrocarbon radical;
• R5 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group;
• R6 is a hydroxyl group;
• x is from 1 to 300;
• y is from 0 to 50 and z is from 1 to 50, with a compound represented by Formula VIII:
• where R8 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group;
• and R9 is a hydroxyl group;
• and V is selected from the group consisting of:
• wherein R10 and R11 are independently a hydrogen, halogen, an alkyl group having from 1 to 18 carbon atoms, an aryl group having from 3 to 14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbon atoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, or a carboxyl group;
• in the presence of a carbonate precursor.