Single component inorganic/organic network materials and precursors thereof

Claim 2

An inorganic/organic composition of the idealized empirical formula (II): X(SiO.sub.1.5).sub.n (II) wherein n is an integer greater than or equal to 2; and X is at least one flexible organic link selected from the group consisting of: (a) R 1 m SiY 4-m ; (b) ring structures ##STR29## (c) R 1 m Si(OSi(CH 3 ) 2 Y) 4-m ; (d) R 1 m Si(OY) 4-m ; (e) CH 3 SiY 2 --O--SiY 2 CH 3 ; (f) Y(CH 3 ) 2 Si--C 6 H 4 --Si(CH 3 ) 2 Y; (g) O[--C 6 H 4 --Si(CH 3 ) 2 Y] 2 ; (h) O[Si(CH 3 ) 2 Y] 2 ; (i) Y(CH 3 ) 2 SiCH 2 --CH 2 Si(CH 3 ) 2 Y; (j) Y 3 SiOSiY 3 ; (k) Y 3 Si(CH 2 ) b SiY 3 ; (l) Y 3 SiC 6 H 4 SiY 3 ; (m) substituted benzene selected from the group consisting of: (i) C 6 H 3 (SiZ 3-a Y a ) 3 ; (ii) C 6 H 2 (SiZ 3-a Y a ) 4 ; (iii) C 6 H(SiZ 3-a Y a ) 5 ; and (iv) C 6 (SiZ 3-a Y a ) 6 ; and (n) substituted cyclohexane selected from the group consisting of: (i) 1,2-C 6 H 10 (Y) 2 ; 1,3-C 6 H 10 (Y) 2 ; 1,4-C 6 H 10 (Y) 2 ; (ii) 1,2,4-C 6 H 9 (Y) 3 ; 1,2,3-C 6 H 9 (Y) 3 ; 1,3,5-C 6 H 9 (Y) 3 ; (iii) 1,2,3,4-C 6 H 8 (Y) 4 ; 1,2,4,5-C 6 H 8 (Y) 4 ; 1,2,3,5-C 6 H 8 (Y) 4 ; (iv) 1,2,3,4,5-C 6 H 7 (Y) 5 ; and (v) C 6 H 6 (Y) 6 ; wherein: Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl; Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 1 is alkyl of 1 to about 8 carbon atoms or aryl; R 2 to R 9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is 1, 2 or 3; p is an even integer from 4 to 10; and b is an integer from 1 to 10.

Claim 3

A process for the preparation of the composition of formula (II) X(SiO.sub.1.5).sub.n (II) wherein n is an integer greater than or equal to 2; and X is at least one flexible organic link selected from the group consisting of: (a) R 1 m SiY 4-m ; (b) ring structures ##STR30## (c) R 1 m Si(OSi(CH 3 ) 2 Y) 4-m ; (d) R 1 m Si(OY) 4-m ; (e) CH 3 SiY 2 --O--SiY 2 CH 3 ; (f) Y(CH 3 ) 2 Si--C 6 H 4 --Si(CH 3 ) 2 Y; (g) O[--C 6 H 4 --Si(CH 3 ) 2 Y] 2 ; (h) O[Si(CH 3 ) 2 Y] 2 ; (i) Y(CH 3 ) 2 SiCH 2 --CH 2 Si(CH 3 ) 2 Y; (j) Y(CF 2 ) p Y, provided that when p is 6, Y is other than ethylene; (k) Y 3 SiOSiY 3 ; (l) Y 3 Si(CH 2 ) b SiY 3 ; (m) Y 3 SiC 6 H 4 SiY 3 ; (n) substituted benzene selected from the group consisting of: (i) C 6 H 3 (SiZ 3-a Y a ) 3 ; (ii) C 6 H 2 (SiZ 3-a Y a ) 4 ; (iii) C 6 H(SiZ 3-a Y a ) 5 ; and (iv) C 6 (SiZ 3-a Y a ) 6 ; and (o) substituted cyclohexane selected from the group consisting of: (i) 1,2-C 6 H 10 (Y) 2 ; 1,3-C 6 H 10 (Y) 2 ; 1,4-C 6 H 10 (Y) 2 ; (ii) 1,2,4-C 6 H 9 (Y) 3 ; 1,2,3-C 6 H 9 (Y) 3 ; 1,3,5-C 6 H 9 (Y) 3 ; (iii) 1,2,3,4-C 6 H 8 (Y) 4 ; 1,2,4,5-C 6 H 8 (Y) 4 ; 1,2,3,5-C 6 H 8 (Y) 4 ; (iv) 1,2,3,4,5-C 6 H 7 (Y) 5 ; and (v) C 6 H 6 (Y) 6 ; wherein: Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl; Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 1 is alkyl of 1 to about 8 carbon atoms or aryl; R 2 to R 9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is 1, 2 or 3; p is an even integer from 4 to 10; and b is an integer from 1 to 10 comprising: (A) mixing at least one compound of formula (III): X(SiQ.sub.3).sub.n (III) wherein: Q is alkoxy of 1 to about 8 carbon atoms, acyloxy of 1 to about 8 carbon atoms; n is an integer greater than or equal to 2; and X is at least one flexible organic link selected from the group consisting of: (a) R 1 m SiY 4-m ; (b) ring structures ##STR31## (c) R 1 m Si(OSi(CH 3 ) 2 Y) 4-m ; (d) R 1 m Si(OY) 4-m ; (e) CH 3 SiY 2 --O--SiY 2 CH 3 ; (f) Y(CH 3 ) 2 Si--C 6 H 4 --Si(CH 3 ) 2 Y; (g) O[--C 6 H 4 --Si(CH 3 ) 2 Y] 2 ; (h) O[Si(CH 3 ) 2 Y] 2 ; (i) Y(CH 3 ) 2 SiCH 2 --CH 2 Si(CH 3 ) 2 Y; (j) Y(CF 2 ) p Y, provided that when p is 6, Y is other than ethylene; (k) Y 3 SiOSiY 3 ; (l) Y 3 Si(CH 2 ) b SiY 3 ; (m) Y 3 SiC 6 H 4 SiY 3 ; (n) substituted benzene selected from the group consisting of: (i) C 6 H 3 (SiZ 3-a Y a ) 3 ; (ii) C 6 H 2 (SiZ 3-a Y a ) 4 ; (iii) C 6 H (SiZ 3-a Y a ) 5 ; and (iv) C 6 (SiZ 3-a Y a ) 6 ; and (o) substituted cyclohexane selected from the group consisting of: (i) 1,2-C 6 H 10 (Y) 2 ; 1,3-C 6 H 10 (Y) 2 ; 1,4-C 6 H 10 (Y) 2 (ii) 1,2,4-C 6 H 9 (Y) 3 ; 1,2,3-C 6 H 9 (Y) 3 ; 1,3,5-C 6 H 9 (Y) 3 ; (iii) 1,2,3,4-C 6 H 8 (Y) 4 ; 1,2,4,5-C 6 H 8 (Y) 4 ; 1,2,3,5-C 6 H 8 (Y) 4 ; (iv) 1,2,3,4,5-C 6 H 7 (Y) 5 ; and (v) C 6 H 6 (Y) 6 ; wherein: Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl; Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 1 is alkyl of 1 to about 8 carbon atoms or aryl; R 2 to R 9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is 1, 2 or 3; p is an even integer from 4 to 10; and b is an integer from 1 to 10, in the presence of water a solvent and a catalyst, or in the presence of at least one carboxylic acid having a maximum pKa value about 4.0 and containing from 0 to 20 mole % water and an optional solvent; (B) maintaining the mixture resulting from step (A) at a temperature within the range of about 0°-100° C.; and (C) isolating the resulting inorganic/organic composition of formula (II).

Claim 4

A process for the preparation of the composition of formula (II) X(SiO.sub.1.5).sub.n (II) wherein n is an integer greater than or equal to 2; and X is at least one flexible organic link selected from the group consisting of: (a) R 1 m SiY 4-m ; (b) ring structures ##STR30## (c) R 1 m Si(OSi(CH 3 ) 2 Y) 4-m ; (d) R 1 m Si(OY) 4-m ; (e) CH 3 SiY 2 --O--SiY 2 CH 3 ; (f) Y(CH 3 ) 2 Si--C 6 H 4 --Si(CH 3 ) 2 Y; (g) O[--C 6 H 4 --Si(CH 3 ) 2 Y] 2 ; (h) O[Si(CH 3 ) 2 Y] 2 ; (i) Y(CH 3 ) 2 SiCH 2 --CH 2 Si(CH 3 ) 2 Y; (j) Y(CF 2 ) p Y, provided that when p is 6, Y is other than ethylene; (k) Y 3 SiOSiY 3 ; (l) Y 3 Si(CH 2 ) b SiY 3 ; (m) Y 3 SiC 6 H 4 SiY 3 ; (n) substituted benzene selected from the group consisting of: (i) C 6 H 3 (SiZ 3-a Y a ) 3 ; (ii) C 6 H 2 (SiZ 3-a Y a ) 4 ; (iii) C 6 H(SiZ 3-a Y a ) 5 ; and (iv) C 6 (SiZ 3-a Y a ) 6 ; and (o) substituted cyclohexane selected from the group consisting of: (i) 1,2-C 6 H 10 (Y) 2 ; 1,3-C 6 H 10 (Y) 2 ; 1,4-C 6 H 10 (Y) 2 ; (ii) 1,2,4-C 6 H 9 (Y) 3 ; 1,2,3-C 6 H 9 (Y) 3 ; 1,3,5-C 6 H 9 (Y) 3 ; (iii) 1,2,3,4-C 6 H 8 (Y) 4 ; 1,2,4,5-C 6 H 8 (Y) 4 ; 1,2,3,5-C 6 H 8 (Y) 4 ; (iv) 1,2,3,4,5-C 6 H 7 (Y) 5 ; and (v) C 6 H 6 (Y) 6 ; wherein: Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl; Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 1 is alkyl of 1 to about 8 carbon atoms or aryl; R 2 to R 9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is 1, 2 or 3; p is an even integer from 4 to 10; and b is an integer from 1 to 10 comprising: (A) mixing at least one compound of formula (III): X(SiQ.sub.3).sub.n (III) wherein: Q is alkoxy of 1 to about 8 carbon atoms, acyloxy of 1 to about 8 carbon atoms; n is an integer greater than or equal to 2; and X is at least one flexible organic link selected from the group consisting of: (a) R 1 m SiY 4-m ; (b) ring structures ##STR31## (c) R 1 m Si(OSi(CH 3 ) 2 Y) 4-m ; (d) R 1 m Si(OY) 4-m ; (e) CH 3 SiY 2 --O--SiY 2 CH 3 ; (f) Y(CH 3 ) 2 Si--C 6 H 4 --Si(CH 3 ) 2 Y; (g) O[--C 6 H 4 --Si(CH 3 ) 2 Y] 2 ; (h) O[Si(CH 3 ) 2 Y] 2 ; (i) Y(CH 3 ) 2 SiCH 2 --CH 2 Si(CH 3 ) 2 Y; (j) Y(CF 2 ) p Y, provided that when p is 6, Y is other than ethylene; (k) Y 3 SiOSiY 3 ; (l) Y 3 Si(CH 2 ) b SiY 3 ; (m) Y 3 SiC 6 H 4 SiY 3 ; (n) substituted benzene selected from the group consisting of: (i) C 6 H 3 (SiZ 3-a Y a ) 3 ; (ii) C 6 H 2 (SiZ 3-a Y a ) 4 ; (iii) C 6 H (SiZ 3-a Y a ) 5 ; and (iv) C 6 (SiZ 3-a Y a ) 6 ; and (o) substituted cyclohexane selected from the group consisting of: (i) 1,2-C 6 H 10 (Y) 2 ; 1,3-C 6 H 10 (Y) 2 ; 1,4-C 6 H 10 (Y) 2 (ii) 1,2,4-C 6 H 9 (Y) 3 ; 1,2,3-C 6 H 9 (Y) 3 ; 1,3,5-C 6 H 9 (Y) 3 ; (iii) 1,2,3,4-C 6 H 8 (Y) 4 ; 1,2,4,5-C 6 H 8 (Y) 4 ; 1,2,3,5-C 6 H 8 (Y) 4 ; (iv) 1,2,3,4,5-C 6 H 7 (Y) 5 ; and (v) C 6 H 6 (Y) 6 ; wherein: Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl; Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 1 is alkyl of 1 to about 8 carbon atoms or aryl; R 2 to R 9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is 1, 2 or 3; p is an even integer from 4 to 10; and b is an integer from 1 to 10, in the presence of water a solvent and a catalyst, or in the presence of at least one carboxylic acid having a maximum pKa value about 4.0 and containing from 0 to 20 mole % water and an optional solvent; (B) maintaining the mixture resulting from step (A) at a temperature within the range of about 0°-100° C.; and (C) isolating the resulting inorganic/organic composition of formula (II).

Claim 9

An inorganic/organic gel of the idealized empirical formula: X(SiO.sub.1.5).sub.n wherein: n is an integer greater than or equal to 2; and X is at least one flexible organic link of the formula: Y(CF.sub.2).sub.p Y, wherein: Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 2 to R 9 are each independently hydrogen, alkyl or 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; k and h are each independently an integer from 4 to 10, provided that at least one of k or h is zero; and p is an even integer from 4 to 10.

Claim 10

An inorganic/organic gel of the idealized empirical formula: X(SiO.sub.1.5).sub.n wherein: n is an integer greater than or equal to 2; and X is at least one flexible organic link of the formula: Y(CF.sub.2).sub.p Y, wherein: Y is (CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) h --; R 2 to R 9 are each independently hydrogen, alkyl or 1 to about 8 carbon atoms or aryl, provided that at least one of R 4 to R 7 is hydrogen; k and h are each independently an integer from 4 to 10, provided that at least one of k or h is zero; and p is an even integer from 4 to 10.