FUNCTIONALIZED Q-T-SILOXANE-BASED POLYMERIC MATERIALS WITH LOW SILOXANE RING CONTENT, SPECIFIC DEGREE OF POLYMERIZATION, AND METHOD FOR PREPARING SAME

Abstract

The present invention pertains to a functionalized polymeric liquid polysiloxane material comprising non-organofunctional Q-type siloxane moieties and mono-organofunctional T-type siloxane moieties, wherein the material comprises a limited low amount of four-membered Q.sup.2-type and/or Q.sup.3-type siloxane ring species relative to the total Q-type siloxane species, and has a functionalization-specific degree of polymerization as well as T- to Q-type ratio. The present invention further pertains to methods for producing the polymeric liquid polysiloxane material as well as associated uses of the material.

Claims

1. A polymeric liquid polysiloxane material comprising: (i) non-organofunctional Q-type siloxane moieties selected from the group consisting of: ##STR00057## and (iv) mono-organofunctional T-type siloxane moieties selected from the group consisting of: ##STR00058## wherein indicates a covalent siloxane bond to a silicon atom of another Q-, M-, D-, and/or T-type moiety as defined in (i) and/or (iv); R.sup.1 is selected from the group consisting of methyl, ethyl, propyl, P(O)(OR.sup.1)(OH), P(OR.sup.1).sub.2, and P(O)(OH).sub.2; R.sup.1 is selected from methyl, ethyl, propyl, and butyl; R.sup.2 is selected from methyl, vinyl, and phenyl; R.sup.3 is selected from methyl, vinyl, and phenyl; R.sup.5 is selected from the group consisting of R.sup.5N, R.sup.5U and R.sup.5S, wherein R.sup.5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, and branched or cyclic C.sub.5-16 alkyl residues; R.sup.5U is selected from -L-Z.sup.1, -L-Z.sup.2 and Z.sup.3, wherein L is an aliphatic linker selected from the group consisting of CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, C.sub.6H.sub.4, C.sub.6H.sub.4CH.sub.2, and CH.sub.2CH.sub.2C.sub.6H.sub.4CH.sub.2; Z.sup.1 is a moiety selected from the group consisting of SH, NH.sub.2, ##STR00059## Z.sup.2 is a moiety selected from the group consisting of ##STR00060## wherein R.sup.7 is independently selected from the group consisting of methyl, ethyln and n-butyl and o is an integer from 1 to 3, and Z.sup.3 is selected from vinyl, phenyl, ##STR00061## wherein n is an integer selected from the group consisting of 1, 2, 3, 4, and 5, and R.sup.6 is selected from the group consisting of methyl, ethyl, n-butyl, and linear or branched C.sub.5-14 alkyl residues; R.sup.5S is selected from the group consisting of -L-Y.sup.1, -L-Y.sup.2, and Y.sup.3, wherein m is an integer selected from the group consisting of 1, 2, 3, and 4; R.sup.8 is selected from the group consisting of Cl, Br, I, F, CN, SCN, N.sub.3, NO.sub.2, OH, SO.sub.2OR.sup.1, and OC(O)R.sup.12; R.sup.9 is selected from the group consisting of Cl, Br, I, F, CN, COOH, COOR.sup.1, phenyl, o-vinylphenyl, m-vinylphenyl, and p-vinylphenyl; R.sup.9 is selected from the group consisting of COOH and COOR.sup.1; L is an aliphatic linker selected from the group consisting of CH.sub.2, CH.sub.2CH.sub.2, and CH.sub.2CH.sub.2CH.sub.2; and Y.sup.1 is a moiety selected from the group consisting of ##STR00062## wherein o is an integer from 1 to 3; Y.sup.2 is a moiety selected from the group consisting of ##STR00063## wherein SU indicates substituted or non-substituted; Y.sup.3 is a moiety selected from the group consisting of ##STR00064## wherein X is absent, (NH) or O; R.sup.10 is selected from the group consisting of R.sup.10a, R.sup.10b, R.sup.10c, R.sup.10d, R.sup.12a, and R.sup.10a is selected from the group consisting of ##STR00065## ##STR00066## ##STR00067## R.sup.10b is selected from the group consisting of: ##STR00068## in monomeric, biuret and triisocyanurate form; R.sup.10c is selected from the group consisting of: ##STR00069## wherein q is an integer from 1 to 25, ##STR00070## ##STR00071## wherein each of q1 to q4 are integers from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, wherein each of q5 to q7 are integers from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24, wherein each of q8 and q9 are integers from 0 to 6 and the sum of (q8+q9) is from 2 to 6; R.sup.10d is selected from the group consisting of: ##STR00072## wherein r is an integer from 1 to 100, s is an integer from 1 to 15, and t is an integer from 1 to 10; R.sup.11 is selected from the group consisting of R.sup.8, XR.sup.1, and R.sup.12c; and R.sup.12 is selected from the group consisting of R.sup.12a, R.sup.12b, and R.sup.12c, wherein R.sup.12a is selected from the group consisting of linear or branched, substituted or non-substituted C.sub.1-18 alkyl, C.sub.2-18 alkenyl and C.sub.2-18 alkynyl, and cyclic, substituted or non-substituted C.sub.3-18 alkyl, C.sub.5-18 alkenyl and C.sub.8-18 alkynyl; R.sup.12b is selected from the group consisting of linear or branched, substituted or non-substituted alkyl ether, alkenyl ether, alkynyl ether up to a molecular weight of 5000 g/mol, and cyclic, substituted or non-substituted alkyl ether and alkenyl ether up to a molecular weight of 5000 g/mol; unsubstituted polydimethylsiloxane and polydivinylsiloxane; and poly- and oligosaccharides up to a molecular weight of 5000 g/mol; and R.sup.12c is selected from the group consisting of amino acids, oligo- and poly-peptides up to a molecular weight of 5000 g/mol; and C.sub.12-24 fatty acids, with the proviso that R.sup.5S is not ##STR00073## wherein the degree of polymerization of the D-type alkoxy-terminated siloxane moieties DP.sub.D-type is in the range of 1.0 to 1.9; the degree of polymerization of the T-type alkoxy-terminated siloxane moieties DP.sub.T-type is in the range of 1.1 to 2.7; the total content of tri-organofunctional M-type siloxane moieties (ii) in the polysiloxane material does not exceed 20 mol-%, 10 mol-% or 5 mol-%; the total content of di-organofunctional D-type siloxane moieties (iii) in the polysiloxane material does not exceed 5, 10, or 15 mol-%; the material has a viscosity in the range of 2 to 100000 cP, about 5 to 50000 cP, or 5 to 1000 cP; the material comprises less than 5, 2.5, 2, 1.5, 1 or 0.5 mol-% silanol groups (SiOH); and further wherein the polysiloxane material comprises less than 45, less than 37, less than 30 or less than 25 mol-% four-membered combined Q.sup.2r-type and Q.sup.3s,d-type siloxane ring species relative to the total Q-type siloxane species; and/or the polysiloxane material comprises less than 70, less than 63, less than 56 or less than 50 mol-% four-membered combined Q.sup.3s,3d-type siloxane ring species relative to all Q.sup.3-type siloxane species; and/or the polysiloxane material comprises less than 4.5, less than 4.0, less than 3.5 or less than 3.0 mol-% double four-membered Q.sup.3d-type siloxane ring species relative to the total Q-type siloxane species; and/or the polysiloxane material comprises less than 25, less than 20, less than 17 or less than 14 mol-% double four-membered Q.sup.3d-type siloxane ring species relative to all Q.sup.3-type siloxane species, characterized in that when at least 65 mol-%, 75 mol-% or 85 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material are R.sup.5N, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.65 to 2.35, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.45:1; when the sum of all -L-Z.sup.1 and -L-Y.sup.1 residues amounts to at least 80 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.75 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1; when the sum of all Z.sup.3 and Y.sup.3 and/or the sum of all -L-Z.sup.2 and -L-Y.sup.2 amounts to at least 50 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.85 to 2.2, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1; when the sum of all -L-Z.sup.1, -L-Y.sup.1 and R.sup.5N amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.8 to 2.4, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.4:1; and when the sum of all R.sup.5N, Z.sup.3, Y.sup.3, -L-Y.sup.2 and -L-Z.sup.2 amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.7 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.25:1.

2. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and linear, branched or cyclic C.sub.5-16 alkyl residues; ##STR00074## Z.sup.1 is a moiety selected from the group consisting of SH, R.sup.8 is selected from the group consisting of Cl, Br, I, CN, SCN, and N.sub.3; Y.sup.1 is selected from the group consisting of ##STR00075## wherein o is an integer from 1 to 3; Y.sup.2 is a moiety selected from the group consisting of ##STR00076## Y.sup.3 is a moiety selected from the group consisting of ##STR00077## wherein X is absent, (NH) or O; R.sup.10 is selected from the group consisting of R.sup.10a, R.sup.10b, R.sup.10c, R.sup.10d, and R.sup.12a; R.sup.10a is selected from the group consisting of ##STR00078## R.sup.10b is selected from the group consisting of ##STR00079## and X is N; R.sup.10c is selected from the group consisting of ##STR00080## wherein q is an integer from 1 to 10, ##STR00081## ##STR00082## wherein each of q1 to q4 are integers from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, wherein each of q5 to q7 are integers from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24, wherein each of q8 and q9 are integers from 0 to 6 and the sum of (q8+q9) is from 2 to 6; R.sup.10d is selected from the group consisting of ##STR00083## wherein r is an integer from 1 to 25, s is an integer from 1 to 10 and t is an integer from 1 to 10; R.sup.11 is selected from R.sup.8 and/or R.sup.12c; and R.sup.12 is selected from the group consisting of R.sup.12a, R.sup.12b and R.sup.12c, wherein R.sup.12a is selected from the group consisting of linear or branched, substituted or non-substituted C.sub.1-18 alkyl and C.sub.2-18 alkenyl; R.sup.12c is selected from the group consisting of amino acids and oligo- or poly-peptides up to a molecular weight of 2000 g/mol; and C.sub.12-24 fatty acids or, ring opened epoxidized fatty acid based polyols.

3. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.1 is selected from the group consisting of methyl, ethyl, and propyl; R.sup.5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, and branched or cyclic C.sub.5-16 alkyl residues; L is an aliphatic linker selected from the group consisting of CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, and C.sub.6H.sub.4; Z.sup.1 is a moiety selected from the group consisting of SH, ##STR00084## Z.sup.2 is a moiety selected from the group consisting of ##STR00085## wherein R.sup.7 is independently selected from the group consisting of methyl, ethyl; Z.sup.3 is selected from vinyl, and phenyl; R.sup.8 is selected from the group consisting of Cl, Br, I, CN, and N.sub.3; R.sup.9 is selected from the group consisting of Cl, CN, COOH, COOR.sup.1, and phenyl; Y.sup.1 is selected from the group consisting of ##STR00086## wherein o is an integer from 2 to 3; Y.sup.2 is a moiety selected from the group consisting of ##STR00087## Y.sup.3 is a moiety selected from the group consisting of ##STR00088## wherein X is absent, (NH), or O; R.sup.10 is selected from the group consisting of R.sup.10a, R.sup.10b, R.sup.10c, and R.sup.10d; R.sup.10a is selected from the group consisting of ##STR00089## R.sup.10b is selected from the group consisting of ##STR00090## and X is N; R.sup.10c is selected from the group consisting of ##STR00091## wherein q is an integer from 1 to 6, ##STR00092## ##STR00093## wherein each of q1 to q4 are integers from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, wherein each of q5 to q7 are integers from 0 to 8 and the sum of (q5+q6+q7) is from 3 to 12, wherein each of q8 and q9 are integers from 0 to 4 and the sum of (q8+q9) is from 2 to 4; and R.sup.10d is selected from the group consisting of ##STR00094## wherein r is an integer from 1 to 20, s is an integer from 1 to 8 and t is an integer from 1 to 10; R.sup.11 is selected from R.sup.8 and/or R.sup.12c; and R.sup.12c is selected from the group consisting of amino acids and oligo- or poly-peptides up to a molecular weight of 1000 g/mol; and C.sub.12-24 fatty acids or ring opened epoxidized fatty acid based polyols.

4. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein the material comprises (v) at least two non-identically R.sup.5-substituted mono-organofunctional T-type alkoxy-terminated siloxane populations, each population making up at least 3 mol-% of all mono-organofunctional T-type moieties in the material; and/or (vi) chiral mono-organofunctional T.sup.1-type moieties in an amount of at least 3 mol-% relative to all mono-organofunctional T-type moieties in the material.

5. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein (vii) the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.6 to 2.4 and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.4:1 in all other cases than those defined in claim 1; (viii) if the material comprises about or more than 5 mol-% M-type moieties, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.7 to 2.5 and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.4:1; (ix) the degree of polymerization of the D-type alkoxy-terminated siloxane moieties DP.sub.D-type is in the range of 1.25 to 1.75; and/or (x) the degree of polymerization of the T-type alkoxy-terminated siloxane moieties DP.sub.T-type is in the range of 1.3 to 2.2.

6. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein the total content of di-organofunctional D-type siloxane and/or the total content tri-organofunctional M-type siloxane moieties is zero.

7. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein if at least 5 mol-% of the R.sup.5 residues of the material are -L-Z.sup.1 and/or L-Y.sup.1, excluding SH, ##STR00095## then the polysiloxane material comprises less than 750, 500 or 300 mol-ppm of a rearrangement catalyst; the polysiloxane material comprises 0 to 1500 mol-ppm of a rearrangement catalyst based on the total molar silicon content present in the material; and/or at least 1 mol-%, at least 3 mol-%, at least 5 mol % or at least 7 mol-% of the sum of all R.sup.5U and R.sup.5S moieties in the material are R.sup.5S moieties.

8. A hydrolysis or emulsion product obtainable by reacting at least one polymeric liquid material according to claim 1 with a predetermined amount of water or with a predetermined amount of a water-solvent mixture, a predetermined amount of water or with a predetermined amount of a water-solvent mixture in the presence of at least one surfactant for the hydrolysis product, or a predetermined amount of water in the presence of at least one surfactant for the emulsion product.

9. A method for preparing a polymeric liquid material according to claim 1, comprising the following steps: providing a polymeric liquid material according to claim 1, wherein at least 1 mol-%, at least 3 mol-%, at least 5 mol-%, at least 10 mol-% or at least 20 mol-% of all R.sup.5 moieties in the material are R.sup.5U moieties; functionalizing the R.sup.5U residues of the polymeric liquid material to obtain at least 1 mol-%, at least 3 mol-%, at least 5 mol-% or at least 7 mol-% R.sup.5S residues relative to the sum of all R.sup.5U and R.sup.5S residues; retrieving, isolating and/or purifying the polymeric liquid material.

10. A method for preparing a polymeric liquid material according to claim 1, comprising the following steps: (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy/ethoxy/propoxy) polysiloxane precursor, wherein the precursor comprises at least 28, at least 35, or at least 42 mol-% four-membered combined Q.sup.2r-type and Q.sup.3s,d-type siloxane ring species relative to the total Q-type siloxane species; and/or wherein the precursor comprises at least 60%, at least 67%, or at least 75% four-membered combined Q.sup.3s,3d-type siloxane ring species relative to all Q.sup.3-type siloxane species; and wherein degree of polymerization of the Q-type polysiloxane DP.sub.Q-type is in the range of 1.5 to 2.5, 1.6 to 2.4, or 1.65 to 2.35; (b) adding at least one of a (b1) tri-organofunctional M-type silane Si(OR.sup.1)(Me).sub.3; and/or (b2) di-organofunctional D-type silane Si(OR.sup.1).sub.2 (R.sup.2)(R.sup.3); and/or (b3) mono-organofunctional T-type silane Si(OR.sup.1).sub.3 (R.sup.5), wherein R.sup.5 is selected from R.sup.5N, R.sup.5U and R.sup.5S; in mono- or oligomeric form to the polysiloxane of (a); (c) optionally adding a rearrangement catalyst to the mixture of step (b); (d) heating the mixture of (c); (g) retrieving, isolating and/or purifying the polymeric liquid material; with the proviso that at least one of steps (a2) or (b3) is carried out, and with the proviso that a rearrangement catalyst is present in at least one of steps (a) or (c).

11. The method according to claim 10, wherein in step (a), the R.sup.5 of the T-type siloxane moiety is R.sup.5N and/or R.sup.5U; in step (b), the R.sup.5 of the T-type silane is R.sup.5N and/or R.sup.5U; and the method comprises the step (f) of functionalizing the R.sup.5U residues of the polymeric liquid material to obtain at least 1 mol-%, at least 3 mol-%, at least 5 mol-% or at least 7 mol-% R.sup.5S residues relative to the sum of all R.sup.5U and R.sup.5S residues.

12. The method according to claim 10, wherein in step (a), the R.sup.5 of the T-type siloxane moiety is R.sup.5U; in step (b), the R.sup.5 of at least one T-type silane is R.sup.5S; and wherein in optional step (e) the R.sup.5 of the T-type silane is selected from R.sup.5U and R.sup.5S.

13. The method according to claim 10, wherein after step (d) or (e), the method further comprises the step of adding a tri-organofunctional M-type silane or M-type siloxane and/or a di-organofunctional D-type silane in mono- or oligomeric form as described in step (b2) in the presence of water, a suitable co-solvent and an acid catalyst, followed by heating the mixture or refluxing the mixture.

14. The method according to claim 10, wherein the rearrangement catalyst is selected from the group consisting of Ti(IV)(OR.sup.13).sub.4 and Zr(IV)(OR.sup.13).sub.4; Ti(IV)X.sub.4 and Zr(IV)X.sub.4; OTi(IV)X.sub.2 and OZr(IV)X.sub.2); Ti(IV)X.sub.2(OR.sup.13).sub.2 and Zr(IV)X.sub.2 (OR.sup.13).sub.2; Ti(IV)X.sub.2(OAcAc).sub.2 and Zr(IV)X.sub.2 (OAcAc).sub.2; Ti(IV)(OSi(CH.sub.3).sub.3).sub.4 and Zr(IV)(OSi(CH.sub.3).sub.3).sub.4; (R.sup.13O).sub.2Ti(IV)(OAcAc).sub.2 and (R.sup.13O).sub.2Zr(IV)(OAcAc).sub.2; OTi(IV)(OAcAc).sub.2 and OZr(IV)(OAcAc).sub.2; Ti(IV)(OAc).sub.4 and Zr(IV)(OAc).sub.4; Ti(IV)(OAc).sub.2(OR.sup.13).sub.2 and Zr(IV)(OAc).sub.2 (OR.sup.13).sub.2; and OTi(IV)(OAc).sub.2 and OZr(IV)(OAc).sub.2; wherein R.sup.13 is selected from the group consisting of CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, CH.sub.2CH.sub.2CH.sub.3, C(CH.sub.3).sub.3, CH.sub.2CH.sub.2CH.sub.2CH.sub.3 and CH.sub.2CH.sub.2CH(CH.sub.3).sub.2 and wherein X is a halide, a pseudohalide, nitrate, chlorate or perchlorate.

15. A product obtainable by the method of claim 9.

16. A product obtainable by the method of claim 10.

17. The polymeric liquid hyperbranched polysiloxane material according to claim 1, further comprising at least one of: (ii) tri-organofunctional M-type siloxane moieties selected from the group consisting of: ##STR00096## (iii) di-organofunctional D-type siloxane moieties selected from the group consisting of: ##STR00097## and.

18. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.5N is selected from the group consisting of linear or branched hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H, 2H, 2H-perfluoro)octyl, cyclohexyl, cyclopentadienyl, cyclopentyl, (1H,1H, 2H, 2H-perfluoro)dodecyl and (1H,1H, 2H, 2H-perfluoro)hexadecyl.

19. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.6 is selected from the group consisting of (CH.sub.2).sub.5CH.sub.3, (CH.sub.2).sub.6CH.sub.3, (CH.sub.2).sub.7CH.sub.3, (CH.sub.2).sub.8CH.sub.3, (CH.sub.2).sub.9CH.sub.3, (CH.sub.2).sub.11CH.sub.3 and (CH.sub.2).sub.13CH.sub.3.

20. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.12b is selected from the group consisting of substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) and polytetrahydrofuran; and poly D-glucose, Oligo-D-glucose, chitosan, deacetylated oligo-chitin, oligo-beta-D-galactopyranuronic acid, poly alginic acid, oligo-alginic acid, poly amylose, oligo amylose, poly-galactose, and oligo-galactose with a molecular weight up to 5000 g/mol.

21. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.12c is selected from the group consisting of oligo- and poly-peptides made of naturally occurring amino acids up to a molecular weight of 5000 g/mol; naturally occurring C.sub.12-24 fatty acids; naturally occurring unsaturated fatty acids; C.sub.12-24 naturally occurring unsaturated fatty acids with 1 to 3 double bonds; epoxidized fatty acids; epoxidized castor oil, soybean oil, sunflower oil; ring opened epoxidized fatty acid based polyols; natural oil based polyols (NOPs); and castor oil, soybean oil, or sunflower oil triglycerides.

22. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein when the sum of all Z.sup.3 and Y.sup.3 and/or the sum of all -L-Z.sup.2 and -L-Y.sup.2 amounts to at least 50 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, and the material further comprises R.sup.5 residues being -L-Z.sup.1, the sum of R.sup.5 residues being -L-Y.sup.1 and -L-Z.sup.1 being less than 20 mol-%, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.85 to 2.2, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1.

23. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein when the sum of all -L-Z.sup.1, -L-Y.sup.1 and R.sup.5N amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, at least 30 mol-% of the R.sup.5 residues of the material being -L-Z.sup.1 and/or -L-Y.sup.1 and at least 10 mol-% of the R.sup.5 residues of the material being R.sup.5N, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.8 to 2.4, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.4:1.

24. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein when the sum of all R.sup.5N, Z.sup.3, Y.sup.3, -L-Y.sup.2 and -L-Z.sup.2 amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the sum of all Z.sup.3, Y.sup.3, -L-Y.sup.2 and -L-Z.sup.2 amounts to at least 20 mol-% of the R.sup.5 residues of the material, at least 20 mol-% of the R.sup.5 residues of the material being R.sup.5N, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.7 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.25:1

25. The method according to claim 10, wherein the Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy/ethoxy/propoxy) polysiloxane precursor comprises (a1) di-organofunctional D-type siloxane moieties; (a2) mono-organofunctional T-type siloxane moieties, wherein R.sup.5 is selected from R.sup.5N, R.sup.5U and R.sup.5S; and/or further comprises a rearrangement catalyst and/or tri-organofunctional M-type siloxane moieties.

26. The method according to claim 24, wherein the Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy/ethoxy/propoxy) polysiloxane precursor comprises less than 12 mol-% of (a1) and (a2) combined relative to the total amount of all Q-type species.

27. The method according to claim 18, further comprising at least one of: (c) adding a rearrangement catalyst to the mixture of step (b); (d) heating the mixture of (c) is performed in the absence of water; (e) repeating steps (b) to (d) at least once; or (f) functionalizing the R.sup.5U residues of the polymeric liquid material to obtain at least 1 mol-%, at least 3 mol-%, at least 5 mol-% or at least 7 mol-% R.sup.5S residues relative to the sum of all R.sup.5U and R.sup.5S residues.

28. The method of claim 12, wherein the method does not comprise the step (f).

29. The method of claim 14, wherein the catalyst amount in each of steps (a) or (c) is between 0.01 and 5 mol-%, or between 0.05 or 0.1 to 3 mol-%, based on the total molar silicon content present in said step.

Description

FIGURES

[0341] FIG. 1 shows exemplary 2D molecular structure representations of a typical pure Q-type polyalkoxysilane material described herein with generalized R.sup.1 substituents for two different DP.sub.Qtype values to illustrate the surface to volume dependence on the size or more specifically on the DP.sub.Qtype values: In FIG. 1a, an exemplary Q-type precursor featuring ring species with 20 Silicon atoms and a DP.sub.Qtype value of 2.25 and 1.5 accessible alkoxy groups (circled) per Si atom onto which T-type silane moieties can be grafted is shown. In FIG. 1b, a Q-type polycondensate with 7 Silicon atoms and a DP.sub.Qtype value of 1.57 and 2.14 accessible alkoxy groups (circled) per Si atom onto which T-type silane moieties could be grafted is shown. This goes to illustrate that the surface to volume ratio for the structure in FIG. 1b. is much higher and sufficient functionalization would require a substantially higher T:Q molar ratio, hence it does not qualify as a direct precursor to prepare materials described herein. Furthermore, the dendritic macromonomer aspect (number of graftable sites per molecule) is significantly smaller in the case shown in FIG. 1b.

[0342] FIG. 2 shows exemplary 2D molecular structure representations of typical materials described herein based on a pure Q-type precursor material only. In FIG. 2a, a grafted material comprising M, D and T moieties is shown with R.sup.5U, R.sup.5S but no R.sup.5N functionality. In FIG. 2b, a grafted polymeric liquid material comprising only R.sup.11-functionalized R.sup.5S glycidoxypropyl T-type moieties is shown and the R.sup.1 residues are comprised of ethoxy and methoxy. In FIG. 2c, a grafted polymeric liquid material comprising two kinds of T-type is shown, namely R.sup.10-functionalized R.sup.5S aminopropyl, as well as non-functionalizable R.sup.5N propyl moieties and the R.sup.1 residues are comprised of ethoxy and methoxy. The representations are for illustration purposes only and do not represent any limitation in further T (R.sup.5N, R.sup.5S and R.sup.5U), D, M-Type grafting and functionalization combinations.

[0343] FIG. 3 shows the effect of the rearrangement grafting on the tetrasiloxane ring species content. The upper .sup.29Si NMR spectrum of a polyethylsilicate Q-type precursor material displays an abundance of Q.sup.2r and Q.sup.3s,d tetrasiloxane ring species. The lower .sup.29Si NMR spectrum shows a material made from that exact polyethylsilicate Q-type precursor by means of Ti(IV)-catalyzed rearrangement grafting with a single triethoxysilane monomer T-type precursor with peak assignment of the corresponding Q-type and T-type moieties. One can clearly see that the product contains much fewer Q.sup.2r and Q.sup.3s,d tetrasiloxane ring species than the Q-type precursor material which it was made from. Specifically, a large fraction of Q.sup.2r species have been converted to Q.sup.2l and also most Q.sup.3d and some Q.sup.3s tetrasiloxane ring species have disappeared and are replaced by linear Q.sup.3l species presumably as a result of the rearrangement grafting reaction.

[0344] FIG. 4 shows the disappearance of ring species exemplified by the % (Q.sup.2r&Q.sup.3s,d) ring species indicator during a model grafting reaction of MTES on a Q-type model precursor compound with increasing reaction time based on analysis of time dependent .sup.29Si NMR data. The disappearance of ring species during thermal treatment in the presence of a rearrangement catalyst is concurrent with the grafting of the monomeric T-type model silane compound onto the Q-type precursor.

EXAMPLES

[0345] In all examples, the mol-percentage of (tetrasiloxane) ring species refers to the sum of all Q.sup.2 and Q.sup.3 ring species relative to the total number of Q species also referred herein as % (Q.sup.2r&Q.sup.3s,d) ring species unless specifically mentioned otherwise.

[0346] In all examples, the mol-percentage of (tetrasiloxane) ring species refers to the sum of all Q.sup.2 and Q.sup.3 ring species relative to the total number of Q species also referred herein as % (Q.sup.2r&Q.sup.3s,d) ring species unless specifically mentioned otherwise. Examples are structured as follows:

[0347] Example 1 describes selected preparation protocols of non-R.sup.5S-functionalized (i.e. R.sup.5N and R.sup.5U-bearing) liquid materials.

[0348] Example 2 describes selected examples for preparing R.sup.5S-functionalized materials. R.sup.5S modification was confirmed by means of .sup.1H and .sup.13C NMR spectroscopy.

[0349] Example 3 illustrates the effect of DP.sub.Qtype and atomic T:Q ratios on application relevant properties illustrated by simple tests

Example 1a: Synthesis of a TEOS Polycondensate/(PTES+N3-PTES) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.05+0.08)

[0350] 334 g of a Q-type precursor with a DP.sub.Qtype of 2.17 and 44.7% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium(IV) isopropoxide rearrangement catalyst (1250 ppm, present in the Q-type precursor) were placed inside a 1 L round bottom flask with reflux condenser together where after 27.4 g/0.13 mol of a monomeric T-type precursor Propylriethoxysilane (PTES) and 52.2 g/0.21 mol of a second T-type precursor 3-azidopropyltrimethoxysilane (N3-PTES) without further rearrangement catalyst addition. The mixture was heated to a temperature of 124 C. and was kept stirring for a period of 9 hours, at which point any residual volatiles were removed by pulling a 250 mbar vacuum for 5 minutes. .sup.29Si NMR analysis confirmed that the product contained less than 8.2% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 29.2% of Q-type tetrasiloxane ring species.

Example 1b: Synthesis of a Non-R.SUP.5S.-Functionalized Ethylsilicate Polycondensate/(PTES+OTES) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.08+0.11)

[0351] The same synthesis procedure as in Example 1a above was used to prepare the material, with the differences that the i) Q-type precursor was prepared from hydrolysis of a commercial ethylsilicate oligomer (Wacker silicate TES 40 WN), ii) 1100 ppm OZr(IV)(OAcAc).sub.2, was added as a catalyst instead of Titanium(IV)isopropoxide for the rearrangement grafting of T-type precursors and that iii) the amount and type of the second T-type precursor two non-functionalisable R.sup.5N T-type silanes (PTESPropyltriethoxysilane and OTESn-Octyltriethoxysilane) used during rearrangement were changed and the reaction time was 12 h. .sup.29Si NMR analysis confirmed that the product contained less than 13.5% of total T0-monomer measured by the total amount of T-type moieties, respectively as well as less than 24.8% of Q-type tetrasiloxane ring species.

Example 1c: Synthesis of a Non-R.SUP.5S.-Functionalized Ethylsilicate Polycondensate/(PTES+APTMS) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.03+0.15)

[0352] The exact same synthesis procedure as in Example 1b above was used to prepare the material, with the sole difference that 250 ppm Ti(OEt).sub.4 was added as a catalyst for the rearrangement grafting of T-type precursors and that the amount and the second T-type precursor (APTMSaminopropyltrimethoxysilane instead of OTES) was changed to a functionalizable R.sup.5U type. .sup.29Si NMR analysis confirmed that the product contained less than 6.1% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 23.8% of Q-type tetrasiloxane ring species.

Example 1d: Synthesis of a Non-R.SUP.5S.-Functionalized Methylsilicate Polycondensate/(oligoVTES+APTMS) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.05+0.15)

[0353] The exact same synthesis procedure as in Example 1g above was used to prepare the material, with the difference that the Q-type precursor was a methylsilicate precursor prepared from tetramethoxysilane (TMOS) with a DP.sub.Qtype value of 1.94 and that the first T-type precursor VTES was added in oligomeric form (oligoVTES). .sup.29Si NMR analysis confirmed that the product contained less than 13% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 25.7% of Q-type tetrasiloxane ring species.

Example 1e: synthesis of a non-R.SUP.5S.-functionalized methylsilicate polycondensate/(VTES) polycondensate material with nQ-type:(nT-type)=1:(0.22)

[0354] A material was prepared in exactly the same way as in Example 1c above, with the difference that the VTES T-type precursor was added in monomeric form and that no APTMS was used. .sup.29Si NMR analysis confirmed that the product contained less than 13% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 25.3% of Q-type tetrasiloxane ring species.

Example 1f: Synthesis of a Non-R.SUP.5S.-Functionalized TEOS &TMOS/SH-PTMS Polycondensate Material with nQ-Type:(nT-Type)=1:(0.15)

[0355] 4 mol of a mixed (TMOS 66%/TEOS33%) Q-type precursor prepared by hydrolytic condensation with a DP.sub.Qtype of 2.19 and 51.0% Q-type tetrasiloxane was mixed with 117.8 g/0.6 mol mercaptopropyltrimethoxysilane (SH-PTMS) as a T-type precursor. The mixture was then again heated up with 670 ppm of Ti(IV) isopropoxide to a temperature of 115 C. with stirring in a glass reactor and kept for 17 hours, at which point the heating source was removed and the product was isolated. .sup.29Si NMR analysis confirmed that the product contained less than 8.3% of total TO-monomer measured by the total amount of T-type moieties, respectively as well as less than 22% of Q-type tetrasiloxane ring species and less than 44.8% of % (Q.sup.3s,d)/Q.sup.3 ring species.

Example 1g: Synthesis of a Non-R.SUP.5S.-Functionalized TEOS/(PhTES+APTMS:DPhDES) Polycondensate Material with nQ-Type:(nT-Type:nD-Type)=1:(0.03+0.15:0.05)

[0356] An amount containing 4.5 mol Si equivalent of a Q-type precursor prepared by controlled hydrolysis of TEOS was injected into a hermetically sealed stirred glass reactor (Bchi versoclave, 1 l) set to a temperature of 105 C. Next, 108.2 g/0.45 mol and 37.0 g/0.23 mol of a first and second T-type monomer precursor phenyltriethoxysilane (PhTES) and aminopropyltrimethoxysilane (PTMS) were also injected into the hot autoclave together with 56.2 g/0.23 mol of a D-type precursor diphenyldimethoxysilane (DPhDMS) and Titanium(IV)-methoxide as a catalyst. The mixture was kept at temperature with stirring for 29 hours and then removed from the heating source and allowed to cool to room temperature. .sup.29Si NMR analysis confirmed that the product contained less than 16% T.sup.0-monomer and less than 11% of D.sup.0-monomer measured by the total amount of T-type and D-type moieties, respectively, as well as less than 22.7% of Q-type tetrasiloxane ring species.

Example 2a: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1a

[0357] A material prepared according to Example 1a was R.sup.5S functionalized on its azide (L-N.sub.3) groups by direct on polysiloxane reaction with a mixture of an alkynylated poly-propylene glcol (A-PPG) and a cyclic substituted alkyne Difluorocyclooctyne (DIFO) leading to partial -L-Y.sup.2 functionalization. The A-PPG material was first prepared by reacting a 450 g/mol PPG with an alkyne in the presence of SO.sub.2F.sub.2 in DMSO as a solvent/activator system. An equimolar amount of A-PPG and DIFO was used in the presence of a Cu-catalyst with a total alkyne to azide ratio of 0.82:1 and the reaction was carried out at room temperature in ethanol leading to a partial substitution with 58% yield as confirmed by NMR analysis.

Example 2b: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1b

[0358] A material prepared according to Example 1b containing only R.sup.5N and no functionalizable R.sup.5U groups was functionalized T.sup.0 grafting of a previously prepared functionalized T.sup.0 monomer. Said functionalized monomer was prepared by reacting 2-hydroxyacetophenone in methanol under reflux with aminopropyltriethoxysilane (APTES) for 3 h and removing the MeOH solvent by distillation. The functionalized T.sup.0 monomer was then rearrangement grafted to a material prepared according to example 1b at 100 C. for 32 h.

Example 2c: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1c

[0359] A material prepared according to Example 1c was R.sup.5S functionalized on its amino (L-NH.sub.2) groups by direct on polysiloxane reaction with a triacrylate (trimethylolpropane triacrylateTMPTA) leading to complete -L-Y.sup.1 functionalization. A 2:1 molar ratio (50% molar excess of TMPTA) was used based on the effective aminic proton to acrylate group ratio. The reaction was carried neat at room temperature for 24 hours and the product confirmed by NMR analysis.

Example 2d: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1d

[0360] A material prepared according to Example 1d was R.sup.5S functionalized on its vinyl (CHCH.sub.2) groups by direct on polysiloxane radical polymerization in a gel emulsion containing a low concentration of a polymer precursor methyl-methacrylate (MMA) leading to Y.sup.3 functionalization with oligo-hybrid PMMA. A 6:1 molar ratio of vinyl groups to MMA precursor was used and the reaction triggered by a photoinitiator and a 365 nm UV light source. The reaction product was identified and confirmed by NMR analysis.

Example 2e: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1f

[0361] A material prepared according to Example 1f was R.sup.5S functionalized on its mercapto (-L-SH) groups by direct on polysiloxane modification with an isocyanate (Methylene diphenyl diisocyanateMDI) leading to L-Y.sup.1 isocyanate (R.sup.10b, XN) functionalization with grafted MDI units. A 1:2.38 molar ratio of mercapto groups to MDI reagent was used and the reaction was carried out neat at 0 C. with stirring overnight. The reaction product was identified and confirmed by NMR analysis.

Example 2f: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1g

[0362] A material prepared according to Example 1g was R.sup.5S functionalized on its amino (-L-NH.sub.2) groups by direct on polysiloxane modification with an epoxide precursor (Bisphenol F diglycidyl etherBFDGE) leading to L-Y.sup.1 epoxy (R.sup.10d) functionalization with grafted BFDGE units. A 1:2 molar ratio based on the effective aminic proton to BFDGE molar ratio was used and the reaction was carried out neat overnight at 80 C. with 1% of a dimethylbenzylamine catalyst. The reaction product was identified and confirmed by NMR analysis.

Example 2g: Preparation of an R.SUP.5S .Functionalized Material Based on an R.SUP.5U .Polysiloxane Material Prepared Using a Preparation Protocol Described in Example 1g

[0363] A material was first prepared using the same protocol as in Example 1g but using 3-(2-aminoethylamino)propyltrimethoxysilane (AEAPTMS)a mixed secondary and primary amine bearing T.sup.0 precursor instead of APTMS and using a T:Q molar ratio of said aminotrimethoxysilane of 0.11:1 instead of the previously used 0.15:1 during grafting. This material was then R.sup.5S functionalized on its amino (-L-NH(CH.sub.2).sub.2NH.sub.2) groups by direct on polysiloxane modification with the same epoxide precursor (Bisphenol F diglycidyl etherBFDGE) leading to epoxy (R.sup.10d) functionalization with grafted BFDGE units. A 1:1.5 molar ratio based on the effective aminic proton to BFDGE molar ratio was used and the reaction was carried out neat overnight at 80 C. with 1% of a dimethylbenzylamine catalyst. The reaction product was identified and confirmed by NMR analysis.

Example 2h: Alternative Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1g

[0364] A material prepared according to Example 1g was R.sup.5S functionalized on its Phenyl (Y.sup.3R.sup.8) groups by direct on polysiloxane modification with Chlorine (aromatic halogenation) in the presence of an AlCl.sub.3 catalyst to yield a Y.sup.3 (R.sup.8 on phenyl) functionalization.

Example 2i: Improved Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1g

[0365] A material identical to the one described above was prepared by first chlorinating trichlorophenylsilane with Cl.sub.2 and an AlCl.sub.3 catalyst to yield (p-chlorophenyl-trichlorosilane) which was then purified by distillation but this time using the better suited T.sup.0 grafting approach. The (p-chlorophenyl)trichlorosilane was then converted to (p-chlorophenyl)trimethoxysilane by quenching it in methanol and isolation. The resulting (p-chlorophenyl)trichlorosilane was then grafted in a desired quantity together with phenyltrimethoxysilane (PhTMS) in a protocol identical to the one described in Example 1g to yield the desired degree of Y.sup.3 (R.sup.8 on phenyl) functionalization.

Example 2j: Alternative Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1f

[0366] A material prepared according to Example 1f was R.sup.5S functionalized on its on its mercapto (-L-SH) groups by direct on polysiloxane modification with an epoxide precursor (Bisphenol A diglycidyl etherBADGE) leading to L-Y.sup.1 epoxy (R.sup.10d) functionalization with grafted BADGE units. A 1:4 molar ratio of mercapto (SH) to BADGE was used and the reaction was carried out neat overnight at 90 C. with 0.5% of a dimethylbenzylamine catalyst. The reaction product was identified and confirmed by NMR analysis.

Example 2k: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1e

[0367] A material prepared according to Example 1e was R.sup.5S functionalized by T.sup.0 grafting of a functionalized T-monomer which was obtained by reacting aminorpopyltriethoxysilane (APTES) pyromellitic dianhydride (PDA) in a 1:0.62 (aminic protons to PDA) molar ratio. The reaction mixture was T.sup.0 grafted in a second step (90 C., 35 hours) without additional rearrangement catalyst in a T:Q ratio of 0.06:1 on top of the already existing VTES T-type moieties. The reaction product was identified and confirmed by NMR analysis.

Example 2l: Alternative Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1e

[0368] On a material prepared according to Example 1e, first a second T-type monomer was grafted onto, namely Bis[3-(triethoxysilyl)propyl] Tetrasulfide (TESPT) in a T:Q molar ratio of 0.04:1 with additional rearrangement catalyst (600 ppm Ti(IV)-isopropoxide). The reaction product was then modified in dilute organic solution with a small amount of styrene monomer using an organic peroxide as radical initiator. The viscous, modified (vinyl & TESPT units) radical reaction product was identified and confirmed by NMR analysis.

Example 2m: Preparation of an R.SUP.5S .Functionalized Material Based on a Material Prepared According to Example 1f

[0369] A material prepared according to Example 1f was R.sup.5S functionalized on its mercapto (-L-SH) groups by direct on polysiloxane modification with an epoxidized fatty acid (epoxidized soybean oil) leading to a direct SR.sup.12c functionalization. A 1:1.42 molar ratio of mercapto groups to epoxidized soybean oil reagent was used and the reaction was carried out at 65 C. in toluene. The reaction product was identified and confirmed by NMR analysis.

Example 3a: Effect of DP.SUB.Q-type .and T:Q Molar Ratio on the Reactivity of Vinyl Functional Polymeric Liquid Materials

[0370] A series of compounds according to example 1e were prepare but starting from ethoxy-polysiloxane Q-type precursors. 10 ml aliquots of the resulting materials were then placed in an oil bath at 140 C. with stirring and once they had reached temperature, 50 mg of dicumylperoxide (DCP) was added as a radical initiator. All materials had a DP.sub.Qtype value above 1.8 and they self-polymerized, presumably because of their macro-monomer character. The time to polymerization at 140 C. was recorded showing the dependence of the radical polymerization/crosslinking reactivity on both DP Qtype and T:Q molar ratios.

[0371] In the table below, we can see the time to polymerization as a function of DP.sub.Qtype and T:Q ratio at 140 C. (after DCP addition).

TABLE-US-00001 DP Q-type 1.82 1.97 2.15 T:Q ratio = 0.15:1 4 minutes 3 minutes 2 minutes T:Q ratio = 0.26:1 1 minutes 1 minutes <1 minute

Example 3b: Comparative Example Demonstrating the Lack of Reactivity of Vinyl Functional Polymeric Liquid Materials with Low DP.SUB.Qtype .Value

[0372] Materials identical to the ones above were prepared and tested but this time starting from an Ethylsilicate (DYNASYLAN 40, Evonik Industries) precursor onto which VTMS was grafted to yield T:Q ratios of 0.16:1 and 0.26:1, in analogy to the above example. When tested for self-polymerization with DCP at 140 C. in the same manner as described in Example 3a, no polymerization was observed even after one hour at temperature, indicating insufficient reactivity, which can be attributed as a lack of macro-monomer or resinous character and is a direct consequence of the lower DP.sub.Qtype.

Example 3c: Effect of DP.SUB.Qtype .on the Reactivity of BADGE-(Epoxy) R.SUP.5S .Functionalized Mercapto-Functional Polymeric Liquid Materials

[0373] Three BADGE modified mercapto-bearing polysiloxanes were prepared according to the preparation protocol described example 2f with DP.sub.Qtype values of 1.77, 1.92 and 2.18, respectively and a constant T:Q molar ratio of 0.15:1. The corresponding BADGE modified compounds were reacted with 10 weight % of a standard amine hardener for epoxy resins in a warm heating cabinet. The respective curing times of the epoxy resin systems decreased within the series of increasing DP.sub.Qtype value and were recorded as 95, 78 and 55 minutes respectively, again demonstrating the dependence of reactivity on the DP-value.

Example 3d: Effect of T:Q Molar Ratio on the Reactivity of MDI-(Isocyanate) R.SUP.5S .Functionalized Mercapto-Functional Polymeric Liquid Materials

[0374] Three MDI modified mercapto-bearing polysiloxanes were prepared according to the preparation protocol described in example 2e with a constant DP.sub.Qtype value of 2.19 but T:Q ratios (mercapto R.sup.5U of the polysiloxane prepared prior to MDI functionalization) were chosen as 0.07:1, 0.15:1 and 0.24:1, respectively and the weighed amount of MDI used to modify was taken from Example 2e and kept the same for all three T:Q ratio examples (constant amount of isocyanate in all cases). The corresponding MDI modified compounds were reacted with a 4000 MW PPG polyol in the presence of 1% DABCO as a catalyst. The respective curing times of the epoxy resin systems decreased within the series of increasing T:Q molar ratio. The corresponding measured curing times in the series (from lowest to highest T:Q ratio) were 71, 52 and 19 minutes, respectively, showing a pronounced effect on the system's reactivity.

Example 3e: Effect of DP.SUB.Qtype .and T:Q Molar Ratio on the Reactivity of DPGDA-(Diacrylate) R.SUP.5S .Functionalized Amino-Functional Polymeric Liquid Materials

[0375] A series of materials similar to the one shown in Example 1c were prepared from Q_type precursors with different DP values and then also different APTMS grafting degrees were chosen. In contrast to the material described in Example 1c, there was no R.sup.5N nonfunctionalizable T-type silane (propyltriethoxysilane, PTES) present in the prepared R.sup.5U analogues, meaning that the materials contained APTMS as the only grafted T-type silane. These R.sup.5U materials were then R.sup.5S functionalized with a given molar ratio of DPGDA (di-propylene glycol diacrylate) to amino protons to yield the corresponding diacrylate Michael adducts.

[0376] Next the stability of these compounds in the absence of any stabilizers was investigated which is a measure of their propensity to self-polymerize and thus their reactivity. To do so, DPGDA (-L-Y.sup.1) R.sup.5S functionalized polymeric liquid materials were stored at 45 C. and at room temperature, respectively. The table below shows the time to gelation/self polymerization as a function of DP.sub.Qtype and the T:Q molar ratio: The samples at 40 C. are at constant T:Q molar ratio and thus also constant DPGDA content in the material. They show that with increasing DP.sub.Qtype (precursor core size), the materials are more reactive and polymerize sooner.

[0377] The room temperature study below shows that samples prepared at a medium DP.sub.Qtype but with varying T:Q molar ratio are more stable at lower T:Q ratios which makes sense, as this translates into a lower total functionality/extent of R.sup.5S functionalization in the material as well. Interestingly, the lowest DP.sub.Qtype of 1.85 and intermediate T:Q ratio (0.15:1) leads to a material that is still reactive but that seems reasonably stable at room temperature.

TABLE-US-00002 Molar DP T:Q ratio DPGDA Q_type molar ratio Temperature DPGDA:amino Gel time [ ] [ ] [ C.] H [days] 1.85 0.15:1 40 0.75 11 2.03 0.15:1 40 0.75 3 2.18 0.15:1 40 0.75 2 1.85 0.15:1 22 1 no gelation 2.03 0.10:1 22 1 23 2.03 0.15:1 22 1 11 2.03 0.20:1 22 1 5

Example 4: Efficiency Testing for Potential Rearrangement Catalysts

[0378] A protocol was devised to test various model catalysts for their efficiency to catalyze grafting of a T-type monomeric model silane methyltriethoxysilane (MTES). Briefly, commercial Dynasylan Silbond 50 was used as Q-type precursor. A molar ratio.sub.nQ-type:n.sub.T-type of 1:0.15 was used and 30 ml aliquots of a premixed solution containing said Q-type and T-type silane precursor were filled into 50 ml glass bottles with lid. To each bottle, 1% by weight of model rearrangement catalyst was added and a blank sample was further included in the study. All glass bottles were simultaneously placed inside a heating cabinet which was kept at 100 C. and the samples were left there for a 24 h incubation period. After that, they were removed from the cabinet and allowed to cool to room temperature and analyzed by means of .sup.29Si NMR spectroscopy.

TABLE-US-00003 Catalyst: DP.sub.Q-Type DP.sub.T-Type % T.sup.0 %(Q.sup.2r&Q.sup.3s, d)/Q.sub.tot %(Q.sup.3s, d)/Q.sup.3 Rearrangement No cat. 2.12 0.56 51.6 48.9 80.8 Fe(II)- 2.18 1.41 5.6 33.8 0.65 Yes chloride Ti(IV)- 2.08 1.65 5.8 24.6 52.0 Yes isopropoxide Zn(II)- 2.19 0.64 41.2 50.9 81.3 No chloride Zr(IV)- 2.16 1.84 4.4 25.3 51.6 Yes oxynitrate
Following the spectral NMR analysis, one can evaluate the performance and suitability of a catalyst in terms of its ability to graft T.sup.0 monomers (DP.sub.T-Type and % T.sup.0 indicators) as well as the percentage of residual tetrasiloxane ring species after the grafting step (% (Q.sup.2r&Q.sup.3s,d)/Q.sub.tot and % (Q.sup.3s,d)/Q.sup.3 indicators.