Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments

A process for making a reactive silsesquioxane oligomer comprising the steps of:

• a) providing a trifunctional polyhedral oligomeric silsesquioxane of the formula Si.sub.7 R.sub.7 O.sub.9 (OA).sub.3, where OA is --OH, --OSb(CH.sub.3).sub.4, --OSn(CH.sub.3).sub.3, or --OTl, and R is an alkyl, alkenyl, aryl, or alkoxy group;
• and
• b) corner capping said trifunctional polyhedral silsesquoxane by sequentially reacting said trifunctional silsesquioxane with tetrachlorosilane, phosphinimine and an aldehyde to form a polyhedral silsesquioxane oligomer having the formula Si.sub.7 R.sub.7 O.sub.12 M(A) wherein M is a silane and Z contains a vinylic group.

A process for the synthesis of polymers containing silsesquioxanes, comprising the steps of:

• a) providing a polyhedral oligomeric silsesquioxane of the formula Si.sub.7 R.sub.7 O.sub.12 M(Z), where R is an alkyl, alkenyl, aryl, or alkoxy group, M is a silane, siloxane or organometallic group, and Z is a reactive group selected form the group consisting of hydrides, esters, acids, acrylates, alcohols, amines, alkoxides, aldehydes, halides, halogen-substituted alkyl groups, halogen-substituted alkenyl groups, halogen-substituted aryl groups, alpha-epoxides, and cylic compounds which can undergo a ring opening polymerization or ring opening metathesis polymerization;
• and
• b) reacting said polyhedral oligomeric silsesquioxane at the site of said reactive Z group with an oligomer, polymer, reactive co-monomer, or catalyst to form a homopolymer or copolymer containing silsesquioxane groups.

A process for the synthesis of polymers containing silsesquioxanes, comprising the steps of:

• a) providing a trifunctional polyhedral oligomeric silsesquioxane of the formula Si.sub.7 R.sub.7 O.sub.9 (OA).sub.3, where OA is --OH, --OSb(CH.sub.3).sub.4, --OSn(CH.sub.3).sub.3, or --OTl, and R is an alkyl, alkenyl, aryl, or alkoxy group;
• and
• b) reacting said trifunctional silsesquioxane with an oligomer, polymer or monomeric reagent by a corner capping reaction to form a block or graft copolymer containing silsesquioxane groups.

A compound of the formula Si.sub.7 R.sub.7 O.sub.12 M(Z), where R is an alkyl, alkenyl, aryl or alkoxy group, M is a silane, siloxane, or organometallic group, and Z is a reactive group selected from the group consisting of (CH.sub.2).sub.3 OC(O)CHCH.sub.2, (CH.sub.2).sub.3 OC(O)CCH.sub.3 CH.sub.2, (CH.sub.2).sub.2 C.sub.6 H.sub.4 CH.sub.2 OC(O)CCH.sub.3 CH.sub.2, (CH.sub.2).sub.2 C.sub.6 H.sub.4 CH.sub.2 OC(O)CHCH.sub.2, CHCH.sub.2, CH.sub.2 CHCH.sub.2, (CH.sub.2).sub.6 CHCH.sub.2, CH.sub.2 (CH.sub.2).sub.8 (CHCH.sub.2), (CH.sub.2).sub.2 C.sub.6 H.sub.4 CH.sub.2 OH, and CH.sub.2 C.sub.6 H.sub.4 OH.

A compound of the formula Si.sub.7 R.sub.7 O.sub.12 M(Z), where R is an alkyl, alkenyl, aryl or alkoxy group, M is a silane, siloxane, or organometallic group, and Z is a reactive group selected from the group consisting of C.sub.5 Me.sub.4 (CHCH.sub.2), OSi(CH.sub.3).sub.2 (CH.sub.2).sub.3 OC(O)CHCH.sub.2, and OSi(CH.sub.3).sub.2 (CH.sub.2).sub.3 OC(O)CCH.sub.3 CH.sub.2.

A compound of the formula ##STR7## where R.sub.8 is a reacted olefin group, and MSi.sub.7 R.sub.7 O.sub.12 is a silsesquioxane, where M is a silane, siloxane, or organometallic group, R is an alkyl, alkenyl, aryl or alkoxy group and n is a number which provides a weight average molecular weight for the compound of from about 5,000 to 250,000.

A compound of the formula ##STR8## where R.sub.8 is a reacted olefin group and R.sub.9 is formed from a reacted co-monomer containing acrylic or olefin groups, and MSi.sub.7 R.sub.7 O.sub.12 is a silsesquioxane, where M is a silane, siloxane, or organometallic group, R is an alkyl, alkenyl, aryl or alkoxy group and n is a number equal to or greater than 1 which provides a weight average molecular weight for said compound of from about 5,000 to 250,000.

A compound of the formula ##STR9## where is a polymer backbone, R.sub.10 is formed form a reacted vinyl or olefinic group, and MSi.sub.7 R.sub.7 O.sub.12 is a silsesquioxane, where M is a silane, siloxane, or organometallic group, R is an alkyl, alkenyl, aryl or alkoxy group, and n is a number equal to or greater than 1 which provides a weight average molecular weight for the compound of from about 5,000 to 500,000.

A compound of the formula (O.sub.12 R.sub.7 Si.sub.7 M).sub.n --(R.sub.11).sub.m --(MSi.sub.7 R.sub.7 O.sub.12).sub.n where R.sub.11 is a reacted oligomer or polymer, and MSi.sub.7 R.sub.7 O.sub.12 is a silsesquioxane, where M is a silane, siloxane, or organometallic group, R is an alkyl, alkenyl, aryl or alkoxy group, and m and n are numbers which provide a weight average molecular weight for said compound of from about 2,500 to 500,000.