Claims
- 1. 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.sup.1.sub.m SiY.sub.4-m ;
- (b) ring structures ##STR29## (c) R.sup.1.sub.m Si(OSi(CH.sub.3).sub.2 Y).sub.4-m ; (d) R.sup.1.sub.m Si(OY).sub.4-m ;
- (e) CH.sub.3 SiY.sub.2 --O--SiY.sub.2 CH.sub.3 ;
- (f) Y(CH.sub.3).sub.2 Si--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y;
- (g) O[--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y].sub.2 ;
- (h) O[Si(CH.sub.3).sub.2 Y].sub.2 ;
- (i) Y(CH.sub.3).sub.2 SiCH.sub.2 --CH.sub.2 Si(CH.sub.3).sub.2 Y;
- (j) Y.sub.3 SiOSiY.sub.3 ;
- (k) Y.sub.3 Si(CH.sub.2).sub.b SiY.sub.3 ;
- (l) Y.sub.3 SiC.sub.6 H.sub.4 SiY.sub.3 ;
- (m) substituted benzene selected from the group consisting of:
- (i) C.sub.6 H.sub.3 (SiZ.sub.3-a Y.sub.a).sub.3 ;
- (ii) C.sub.6 H.sub.2 (SiZ.sub.3-a Y.sub.a).sub.4 ;
- (iii) C.sub.6 H(SiZ.sub.3-a Y.sub.a).sub.5 ; and
- (iv) C.sub.6 (SiZ.sub.3-a Y.sub.a).sub.6 ; and
- (n) substituted cyclohexane selected from the group consisting of:
- (i) 1,2-C.sub.6 H.sub.10 (Y).sub.2 ; 1,3-C.sub.6 H.sub.10 (Y).sub.2 ; 1,4-C.sub.6 H.sub.10 (Y).sub.2 ;
- (ii) 1,2,4-C.sub.6 H.sub.9 (Y).sub.3 ; 1,2,3-C.sub.6 H.sub.9 (Y).sub.3 ; 1,3,5-C.sub.6 H.sub.9 (Y).sub.3 ;
- (iii) 1,2,3,4-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,4,5-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,3,5-C.sub.6 H.sub.8 (Y).sub.4 ;
- (iv) 1,2,3,4,5-C.sub.6 H.sub.7 (Y).sub.5 ; and
- (v) C.sub.6 H.sub.6 (Y).sub.6 ;
- wherein:
- Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl;
- Y is (CR.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.1 is alkyl of 1 to about 8 carbon atoms or aryl;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R.sup.4 to R.sup.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.
- 2. 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.sup.1.sub.m SiY.sub.4-m ;
- (b) ring structures ##STR30## (c) R.sup.1.sub.m Si(OSi(CH.sub.3).sub.2 Y).sub.4-m ; (d) R.sup.1.sub.m Si(OY).sub.4-m ;
- (e) CH.sub.3 SiY.sub.2 --O--SiY.sub.2 CH.sub.3 ;
- (f) Y(CH.sub.3).sub.2 Si--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y;
- (g) O[--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y].sub.2 ;
- (h) O[Si(CH.sub.3).sub.2 Y].sub.2 ;
- (i) Y(CH.sub.3).sub.2 SiCH.sub.2 --CH.sub.2 Si(CH.sub.3).sub.2 Y;
- (j) Y(CF.sub.2).sub.p Y, provided that when p is 6, Y is other than ethylene;
- (k) Y.sub.3 SiOSiY.sub.3 ;
- (l) Y.sub.3 Si(CH.sub.2).sub.b SiY.sub.3 ;
- (m) Y.sub.3 SiC.sub.6 H.sub.4 SiY.sub.3 ;
- (n) substituted benzene selected from the group consisting of:
- (i) C.sub.6 H.sub.3 (SiZ.sub.3-a Y.sub.a).sub.3 ;
- (ii) C.sub.6 H.sub.2 (SiZ.sub.3-a Y.sub.a).sub.4 ;
- (iii) C.sub.6 H(SiZ.sub.3-a Y.sub.a).sub.5 ; and
- (iv) C.sub.6 (SiZ.sub.3-a Y.sub.a).sub.6 ; and
- (o) substituted cyclohexane selected from the group consisting of:
- (i) 1,2-C.sub.6 H.sub.10 (Y).sub.2 ; 1,3-C.sub.6 H.sub.10 (Y).sub.2 ; 1,4-C.sub.6 H.sub.10 (Y).sub.2 ;
- (ii) 1,2,4-C.sub.6 H.sub.9 (Y).sub.3 ; 1,2,3-C.sub.6 H.sub.9 (Y).sub.3 ; 1,3,5-C.sub.6 H.sub.9 (Y).sub.3 ;
- (iii) 1,2,3,4-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,4,5-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,3,5-C.sub.6 H.sub.8 (Y).sub.4 ;
- (iv) 1,2,3,4,5-C.sub.6 H.sub.7 (Y).sub.5 ; and
- (v) C.sub.6 H.sub.6 (Y).sub.6 ;
- wherein:
- Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl;
- Y is (CR.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.1 is alkyl of 1 to about 8 carbon atoms or aryl;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R.sup.4 to R.sup.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.sup.1.sub.m SiY.sub.4-m ;
- (b) ring structures ##STR31## (c) R.sup.1.sub.m Si(OSi(CH.sub.3).sub.2 Y).sub.4-m ; (d) R.sup.1.sub.m Si(OY).sub.4-m ;
- (e) CH.sub.3 SiY.sub.2 --O--SiY.sub.2 CH.sub.3 ;
- (f) Y(CH.sub.3).sub.2 Si--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y;
- (g) O[--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y].sub.2 ;
- (h) O[Si(CH.sub.3).sub.2 Y].sub.2 ;
- (i) Y(CH.sub.3).sub.2 SiCH.sub.2 --CH.sub.2 Si(CH.sub.3).sub.2 Y;
- (j) Y(CF.sub.2).sub.p Y, provided that when p is 6, Y is other than ethylene;
- (k) Y.sub.3 SiOSiY.sub.3 ;
- (l) Y.sub.3 Si(CH.sub.2).sub.b SiY.sub.3 ;
- (m) Y.sub.3 SiC.sub.6 H.sub.4 SiY.sub.3 ;
- (n) substituted benzene selected from the group consisting of:
- (i) C.sub.6 H.sub.3 (SiZ.sub.3-a Y.sub.a).sub.3 ;
- (ii) C.sub.6 H.sub.2 (SiZ.sub.3-a Y.sub.a).sub.4 ;
- (iii) C.sub.6 H (SiZ.sub.3-a Y.sub.a).sub.5 ; and
- (iv) C.sub.6 (SiZ.sub.3-a Y.sub.a).sub.6 ; and
- (o) substituted cyclohexane selected from the group consisting of:
- (i) 1,2-C.sub.6 H.sub.10 (Y).sub.2 ; 1,3-C.sub.6 H.sub.10 (Y).sub.2 ; 1,4-C.sub.6 H.sub.10 (Y).sub.2
- (ii) 1,2,4-C.sub.6 H.sub.9 (Y).sub.3 ; 1,2,3-C.sub.6 H.sub.9 (Y).sub.3 ; 1,3,5-C.sub.6 H.sub.9 (Y).sub.3 ;
- (iii) 1,2,3,4-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,4,5-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,3,5-C.sub.6 H.sub.8 (Y).sub.4 ;
- (iv) 1,2,3,4,5-C.sub.6 H.sub.7 (Y).sub.5 ; and
- (v) C.sub.6 H.sub.6 (Y).sub.6 ;
- wherein:
- Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl;
- Y is (CR.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.1 is alkyl of 1 to about 8 carbon atoms or aryl;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R.sup.4 to R.sup.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.degree.-100.degree. C.; and
- (C) isolating the resulting inorganic/organic composition of formula (II).
- 3. A method for modifying a sol-gel glass to generate a sol-gel glass that can tolerate increased drying rates and shows lower brittleness comprising:
- (A) combining a star gel precursor 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, of halogen;
- n is an integer greater than or equal to 2; and
- X is at least one flexible organic link selected from the group consisting
- (a) R.sup.1.sub.m SiY.sub.4-m ;
- (b) ring structures ##STR32## (c) R.sup.1.sub.m Si(OSi(CH.sub.3).sub.2).sub.4-m, (d) R.sup.1.sub.m Si(OY).sub.4-m ;
- (e) CH.sub.3 SiY.sub.2 --O--SiY.sub.2 CH.sub.3 ;
- (f) Y(CH.sub.3).sub.2 Si--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y;
- (g) O[--C.sub.6 H.sub.4 --Si(CH.sub.5).sub.2 Y].sub.2 ;
- (h) O[Si(CH.sub.3).sub.2 Y].sub.2 ;
- (i) Y(CH.sub.3).sub.2 SiCH.sub.2 --CH.sub.2 Si(CH.sub.3).sub.2 Y;
- (j) Y(CF.sub.2).sub.p Y;
- (k) Y.sub.3 SiOSiY.sub.3 ;
- (l) Y.sub.3 Si(CH.sub.2).sub.b SiY.sub.3 ;
- (m) Y.sub.3 SiC.sub.6 H.sub.4 SiY.sub.3 ;
- (n) substituted benzene selected from the group consisting of:
- (i) C.sub.6 H.sub.3 (SiZ.sub.3-a Y.sub.a).sub.3 ;
- (ii) C.sub.6 H.sub.2 (SiZ.sub.3-a Y.sub.a).sub.4 ;
- (iii) C.sub.6 H(SiZ.sub.3-a Y.sub.a).sub.5 ; and
- (iv) C.sub.6 (SiZ.sub.3-a Y.sub.a).sub.6 ; and
- (o) substituted cyclohexane selected from the group consisting of:
- (i) 1,2-C.sub.6 H.sub.10 (Y).sub.2 ; 1,3-C.sub.6 H.sub.10 (Y).sub.2 ; 1,4-C.sub.6 H.sub.10 (Y).sub.2
- (ii) 1,2,4-C.sub.6 H.sub.9 (Y).sub.3 ; 1,1,3-C.sub.6 H.sub.9 (Y).sub.3 ; 1,3,5-C.sub.6 H.sub.9 (Y).sub.3 ;
- (iii).sub.1,2,3,4 -C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,4,5-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,3,5-C.sub.6 H.sub.8 (Y).sub.4 ;
- (iv).sub.1,2,3,4,5 -C.sub.6 H.sub.7 (Y).sub.5 ; and
- (v) C.sub.6 H.sub.6 (Y).sub.6 ;
- wherein:
- Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl;
- Y is (CR.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.1 is alkyl of 1 to about 8 carbon atoms or aryl;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R.sup.4 to R.sup.7 is hydrogen;
- m is 0, I or 2;
- k and h are each independently an integer from 0 to 10, provided that 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 i to 10;
- with an inorganic alkoxide sol-gel precursor;
- (B) mixing in water with a solvent and a catalyst, or mixing a carboxylic acid having a maximum pk.sub.a value of about 4 optionally in the presence of a solvent; and
- (C) drying.
- 4. A method for coating a substrate comprising reacting the star gel precursor 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, or halogen;
- 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.sup.1.sub.m Si(Y).sub.4-m ;
- (b) ring structures ##STR33## (c) R.sup.1.sub.m Si(OSi(CH.sub.3).sub.2 Y).sub.4-m, (d) R.sup.1.sub.m Si(OY).sub.4-m,
- (e) CH.sub.3 SiY.sub.2 --O--SiY.sub.2 CH.sub.3 ;
- (f) Y(CH.sub.3).sub.2 Si--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y;
- (g) O[--C.sub.5 H.sub.4 --Si(CH.sub.3).sub.2 Y].sub.2 ;
- (h) O[Si(CH.sub.3).sub.2 Y].sub.2 ;
- (i) Y(CH.sub.3).sub.2 SiCH.sub.2 --CH.sub.2 Si(CH.sub.3).sub.2 Y;
- (j) Y(CF.sub.2).sub.p Y;
- (k) Y.sub.3 SiOSiY.sub.3 ;
- (l) Y.sub.3 Si(CH.sub.2).sub.b SiY.sub.3 ;
- (m) Y.sub.3 SiC.sub.6 H.sub.4 SiY.sub.3 ;
- (n) substituted benzene selected from the group consisting of:
- (i) C.sub.6 H.sub.3 (SiZ.sub.3-a Y.sub.a).sub.3 ;
- (ii) C.sub.6 H.sub.2 (SiZ.sub.3-a Y.sub.a).sub.4 ;
- (iii) C.sub.6 H(SiZ.sub.3-a Y.sub.a).sub.5 ; and
- (iv) C.sub.6 (SiZ.sub.3-a Y.sub.a).sub.6 ; and
- (o) substituted cyclohexane selected from the group consisting of:
- (i) 1,2-C.sub.6 H.sub.10 (Y).sub.2 ; 1,3-C.sub.6 H.sub.10 (Y).sub.2 ; 1,4-C.sub.6 H.sub.10 (Y).sub.2
- (ii) 1,2,4-C.sub.6 H.sub.9 (Y).sub.3 ; 1,2,3-C.sub.6 H.sub.9 (Y).sub.3 ; 1,3,5-C.sub.6 H9(Y).sub.3 ;
- (iii) 1,2,3,4-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,4,5-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,3,5-C.sub.6 H.sub.8 (Y).sub.4 ;
- (iv) 1,2,3,4,5-C.sub.6 H.sub.7 (Y).sub.5 ; and
- (v) C.sub.6 H.sub.6 (Y).sub.6 ;
- wherein,
- Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl or aryl;
- Y is (CR.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.1 is alkyl of 1 to about 8 carbon atoms or aryl;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that it least one of R.sup.4 to R.sup.7 is hydrogen;
- m is 0, 1 or 2;
- X and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; and
- 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 a strong carboxylic acid having a maximum pk.sub.a value of about 4, optionally in the presence of a solvent; dipping the substrate in the resulting mixture; removing the coated Substrate from the mixture and drying the coating to generate a substrate coated with a 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.sup.1.sub.m SiY.sub.4-m ;
- (b) ring structures ##STR34## (c) R.sup.1.sub.m Si(OSi(CH.sub.5).sub.2 Y).sub.4-m, (d) R.sup.1.sub.m Si(OY).sub.4-m,
- (e) CH.sub.3 SiY.sub.2 --O--SiY.sub.2 CH.sub.3 ;
- (f) Y(CH.sub.3).sub.2 Si--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y;
- (g) O[--C.sub.6 H.sub.4 --Si(CH.sub.3).sub.2 Y].sub.2 ;
- (h) O[Si(CH.sub.5).sub.2 Y].sub.2 ;
- (i) Y(CH.sub.3).sub.2 SiCH.sub.2 --CH.sub.2 Si(CH.sub.3).sub.2 Y;
- (j) Y(CF.sub.2).sub.p Y, provided that when p is 6, Y is other than ethylene;
- (k) Y.sub.3 SiOSiY.sub.3 ;
- (l) Y.sub.3 Si(CH.sub.2).sub.b SiY.sub.3 ;
- (m) Y.sub.3 SiC.sub.6 H.sub.4 SiY.sub.3 ;
- (n) substituted benzene selected from the group consisting of:
- (i) C.sub.6 H.sub.3 (SiZ.sub.3-a Y.sub.a).sub.3 ;
- (ii) C.sub.6 H.sub.2 (SiZ.sub.3-a Y.sub.a).sub.4 ;
- (iii) C.sub.6 H(SiZ.sub.3-a Y.sub.a); .sub.5 ; and
- (o) substituted cyclohexane selected from the group consisting of:
- (i) 1,2-C.sub.6 H.sub.10 (Y).sub.2 ; 1,3-C.sub.6 H.sub.10 (Y).sub.2 ; 1,4-C.sub.6 H.sub.10 (Y).sub.2 ;
- (ii) 1,2,4-C.sub.6 H.sub.9 (Y).sub.3 ; 1,2,3-C.sub.6 H.sub.9 (Y).sub.3 ; 1,3,5-C.sub.6 H.sub.9 (Y).sub.3 ;
- (iii) 1,2,3,4-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,4,5-C.sub.6 H.sub.8 (Y).sub.4 ; 1,2,3,5-C.sub.6 H.sub.8 (Y).sub.4 ;
- (iv) 1,2,3,4,5-C.sub.6 H.sub.7 (Y).sub.5 ; and
- (v) C.sub.6 H.sub.6 (Y).sub.6 ;
- wherein:
- Z is an alkyl group of 1 to 4 carbon atoms, 3,3,3-trifluoropropyl, aralkyl, or aryl;
- Y is (CR.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.1 is alkyl of 1 to about 8 carbon atoms or aryl;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl of 1 to about 8 carbon atoms or aryl, provided that at least one of R.sup.4 to R.sup.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.
- 5. 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.sup.2 R.sup.3).sub.k CR.sup.4 R.sup.5 CR.sup.6 R.sup.7 (CR.sup.8 R.sup.9).sub.h --;
- R.sup.2 to R.sup.9 are each independently hydrogen, alkyl or 1 to about 8 carbon atoms or aryl, provided that at least one of R.sup.4 to R.sup.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.
Parent Case Info
This is a continuation-in-part of application Ser. No. 07/945,777 filed Sep. 16, 1992, now abandoned.
US Referenced Citations (11)
Foreign Referenced Citations (1)
Number |
Date |
Country |
2067435 |
Oct 1992 |
CAX |
Continuation in Parts (1)
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Number |
Date |
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Parent |
945777 |
Sep 1992 |
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