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FUNCTIONALIZED Q-T-SILOXANE-BASED POLYMERIC MATERIALS WITH LOW SILOXANE RING CONTENT AND METHOD FOR PREPARING SAME

20230037620 · 2023-02-09

    Inventors

    Cpc classification

    International classification

    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, as well as optionally tri-organofunctional M-type siloxane moieties and/or di-organofunctional D-type siloxane moieties characterized in that the polysiloxane material has a specified degree of polymerization, comprises a limited low amount of four-membered Q2-type and/or Q3-type siloxane ring species relative to the total Q-type siloxane species, and is functionalized at specific moieties. 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: ##STR00025## (ii) optionally tri-organofunctional M.sup.1-type siloxane moieties selected from the group consisting of: ##STR00026## (iii) optionally di-organofunctional D-type siloxane moieties selected from the group consisting of: ##STR00027##  and (iv) mono-organofunctional T-type siloxane moieties selected from the group consisting of: ##STR00028## wherein custom-character indicates a covalent siloxane bond to a silicon atom of another Q-, M-, D- and/or T-type moiety as defined in (i), (ii), (iii), 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, —P(═O)(OH).sub.2, methyl, and ethyl; R.sup.1′is selected from methyl, ethyl, propyl, and butyl; R.sup.2, R.sup.3 and R.sup.4 are each independently selected from the group consisting of methyl, ethyl, phenyl, cyclohexyl, vinyl, and cyclopentadienyl; R.sup.5 is selected from the group consisting of R.sup.5U and R.sup.5S, wherein R.sup.5U is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, branched or cyclic C.sub.5-16 alkyl residues, linear or branched hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, (1H,1H,2H,2H-perfluoro)hexadecyl, vinyl, phenyl, cyclohexyl, cyclopentadienyl, cyclopentyl, ##STR00029##  and -L-Z, wherein R.sup.6 is selected from the group consisting of methyl, ethyl, n-butyl, linear or branched C.sub.5-14 alkyl residues, (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; n is an integer selected from the group consisting of 1, 2, 3, 4, and 5; 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.4—CH.sub.2—, and —CH.sub.2—CH.sub.2—C.sub.6H.sub.4—CH.sub.2—; and Z is a moiety selected from the group consisting of Cl, Br, I, —OH, —SH, ##STR00030## wherein R.sup.7 is independently selected from the group consisting of methyl, ethyl, and n-butyl; R.sup.5S is selected from the group consisting of ##STR00031## ##STR00032## and -L′-Y, 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 —O—C(═O)R.sup.12; R.sup.9 is selected from the group consisting of —Cl, —Br, —I, —F, —CN, —COOH, —COOR.sup.r, phenyl, o-, m-, 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 is a moiety selected from the group consisting of ##STR00033## ##STR00034## wherein X is absent, —(NH)—, or —O—; R.sup.10 is selected from the group consisting of ##STR00035## ##STR00036## R.sup.11 is selected from the group consisting of R.sup.8, —X—R.sup.1′, and R.sup.12c; 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; R.sup.12b is selected from the group consisting of linear or branched, substituted or non-substituted alkyl ether, alkenyl ether, or alkynyl ether up to a molecular weight of 5000 g/mol; or substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) or polytetrahydrofuran up to a molecular weight of 5000 g/mol; unsubstituted polydimethylsiloxane or polydivinylsiloxane; and poly- and oligosaccharides up to a molecular weight of 5000 g/mol; or 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, or oligo-galactose with a molecular weight up to 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; or oligo- and poly-peptides made of naturally occurring amino acids up to a molecular weight of 5000 g/mol; and C.sub.12-24 fatty acids, naturally occurring C.sub.12-24 fatty acids, naturally occurring unsaturated fatty acids, optionally C.sub.12-24 naturally occurring unsaturated fatty acids with 1 to 3 double bonds, optionally epoxidized fatty acids, optionally epoxidized castor oil, soybean oil, sunflower oil, optionally ring opened epoxidized fatty acid based polyols, natural oil based polyols (NOPs), castor oil, soybean oil, or sunflower oil triglycerides. with the proviso that R.sup.5S is not ##STR00037## wherein the degree of polymerization of the Q-type moieties DP.sub.Q-type is in the range of 1.3 to 2.7; the degree of polymerization of the D-type siloxane moieties DP.sub.D-type is in the range of 1.0 to 1.9; the degree of polymerization of the T-type 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 (iii) in the polysiloxane material does not exceed 10 mol-%; the total content of di-organofunctional D-type siloxane moieties (iii) in the polysiloxane material does not exceed 50 mol-%; the material has a viscosity in the range of 10 to 100′000 cP; the material comprises less than 5 mol-% silanol groups (Si—OH); the atomic ratio of T- to Q-species in the material is in the range of 0.01:1 to 1:1; at least 1 mol-% of all R.sup.5 moieties in the material are R.sup.5S moieties; wherein the polysiloxane material comprises less than 45 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 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 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 mol-% double four-membered Q.sup.3d-type siloxane ring species relative to all Q.sup.3-type siloxane species.

    2. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.8 is selected from the group consisting of —Cl, —Br, —I, —CN, —SCN, —N.sub.3, —NO.sub.2, —SO.sub.2OR.sup.1′, and —O—C(═O)R.sup.1′; Y is selected from the group consisting of ##STR00038## ##STR00039## R.sup.10 is selected from the group consisting of ##STR00040## ##STR00041## R.sup.11 is selected from R.sup.8 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 and linear or branched, substituted or non-substituted C.sub.2-18 alkenyl; R.sup.12b is selected from the group consisting of linear or branched, non-substituted or terminally amino- or thiol-substituted alkyl or alkenyl ethers up to a molecular weight of 3000 g/mol, terminally amino- or thiol-substituted or unsubstituted poly(ethylene oxide), terminally amino- or thiol-substituted or unsubstituted poly(propylene oxide), or terminally amino- or thiol-substituted or unsubstituted polytetrahydrofuran; poly- or oligosaccharides up to a molecular weight of 3000 g/mol; or 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, or oligo-galactose with a molecular weight up to 3000 g/mol; and optionally unsubstituted polydimethylsiloxane or polydivinylsiloxane; and R.sup.12c is selected from the group consisting of amino acids and oligo- or poly-peptides up to a molecular weight of 3000 g/mol; or oligo- and poly-peptides made of naturally occurring amino acids up to a molecular weight of 3000 g/mol; and C.sub.12-24 fatty acids, 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, optionally epoxidized fatty acids, optionally epoxidized castor oil, soybean oil, sunflower oil, optionally ring opened epoxidized fatty acid based polyols, natural oil based polyols (NOPs), castor oil, soybean oil, or sunflower oil triglycerides.

    3. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R.sup.8 is selected from the group consisting of —Cl, —Br, —I, —CN, —SCN, —N.sub.3, —NO.sub.2, —SO.sub.2OR.sup.1′, and —O—C(═O)R.sup.1′; Y is selected from the group consisting of ##STR00042## R.sup.10 is selected from the group consisting of ##STR00043## R.sup.11 is selected from R.sup.8 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.1-12 alkyl and linear or branched, substituted or non-substituted C.sub.2-12 alkenyl; R.sup.12b is selected from the group consisting of linear, non-substituted or terminally amino-substituted alkyl ethers up to a molecular weight of 2000 g/mol, non-substituted or terminally amino-substituted poly(ethylene oxide), or non-substituted or terminally amino-substituted poly(propylene oxide); and poly- or oligosaccharides up to a molecular weight of 2000 g/mol; or poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligo-chitin, or oligo-beta-D-galactopyranuronic acid up to a molecular weight of 2000 g/mol; and 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/made of naturally occurring amino acids; castor oil, soybean oil, or sunflower oil triglycerides; and naturally occurring C.sub.12-24 fatty acids, or naturally occurring C.sub.12-24 unsaturated fatty acids with 1 to 3 double bonds.

    4. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein the material comprises (i) 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 siloxane moieties in the material; and/or (ii) chiral mono-organofunctional T.sup.1-type siloxane moieties in an amount of at least 3 mol-% relative to all mono-organofunctional T-type siloxane moieties in the material.

    5. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein (i) the degree of polymerization of the Q-type moieties DP.sub.Q-type is in the range of 1.5 to 2.5; (ii) the degree of polymerization of the D-type siloxane moieties DP.sub.D-type is in the range of 1.25 to 1.75; and/or (ii) the degree of polymerization of the T-type 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 the relative atomic ratio of T- to Q-species is in the range of 0.02:1 to 0.75:1.

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

    9. An emulsion obtainable by emulsifying a polymeric liquid material according to claim 1, comprising a predetermined amount of water, optionally in the presence of at least one surfactant.

    10. The method of claim 20, comprising the following steps: providing the polymeric liquid material, wherein at least 1 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-% R.sup.5S residues relative to all R.sup.5 residues; retrieving, optionally isolating and optionally purifying the polymeric liquid material.

    11. The method of claim 20, comprising the following steps: (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy/ethoxy/propoxy) polysiloxane precursor, optionally comprising (a1) di-organofunctional D-type siloxane moieties; and/or (a2) mono-organofunctional T-type siloxane moieties, wherein R.sup.5 is selected from R.sup.5U and R.sup.5S; optionally comprising less than 12 mol-% of (a1) and (a2) combined relative to the total amount of all Q-type species; optionally further comprising a rearrangement catalyst; wherein the precursor comprises at least 28, optionally at least 35, optionally 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% 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 2.7; (b) adding at least one of a (b1) tri-organofunctional M-type silane Si(OR.sup.1)(R.sup.2)(R.sup.3)(R.sup.4); (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.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) in the absence of water: (e) optionally repeating steps (b) to (d) at least once; (f) optionally functionalizing the R.sup.5U residues of the polymeric liquid material to obtain at least 1 mol-% R.sup.5S residues relative to all R.sup.5 residues; (g) retrieving, optionally isolating and optionally 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).

    12. The method according to claim 11, 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 the T-type silane is 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-% R.sup.5S residues relative to all R.sup.5 residues.

    13. The method according to claim 11, 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; wherein in optional step (e) the R.sup.5 of the T-type silane is selected from R.sup.5U and R.sup.5S, and the method optionally does not comprise the step (f).

    14. The method according to claim 11, wherein after step (d) or (e), the method further comprises the step of adding a tri-organofunctional M-type silane) Si(OR.sup.1)(R.sup.2)(R.sup.3)(R.sup.4), or M-type siloxane (R.sup.2)(R.sup.3)(R.sup.4)Si—O—Si(R.sup.2)(R.sup.3)(R.sup.4) and optionally a di-organofunctional D-type silane in mono- or oligomeric form as described in step (b2) in the presence of water and a suitable co-solvent and an acid catalyst, followed by heating the mixture, optionally to reflux.

    15. The method according to claim 11, wherein the reaction temperature for steps (c) through (e) is in the range from 30 to 170° C., and the pressure during steps (c) through (e) is in the range of 0.1 bar to 2 bar.

    16. The method according to claim 11, 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; O═Ti(IV)X.sub.2 and O═Zr(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; O═Ti(IV)(OAcAc).sub.2 and O═Zr(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 O═Ti(IV)(OAc).sub.2 and O═Zr(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 anion, and wherein the catalyst amount in each of steps (a) or (c) is optionally between 0.01 and 5 mol-% based on the total molar silicon content present in said step.

    17. (canceled)

    18. The polymeric liquid material according to claim 1, comprising at least one population of mono-organofunctional T-type siloxane moieties with R.sup.5 selected from the group consisting of vinyl, methacrylate, butacrylate, acrylate, ##STR00044## as a crosslinker within a formulation, with a content of the polymeric liquid material in the range of 0.2% to 25% by weight with respect to the formulation.

    19. The polymeric liquid material according to claim 1, comprising at least one population of mono-organofunctional T-type siloxane moieties with R.sup.5 selected from methyl, ethyl, vinyl, methacrylate, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, and (1H,1H,2H,2H-perfluoro)hexadecyl, in a hydrophobic formulation, wherein the loading of the polymeric liquid, hydrolysis product or emulsion in the formulation is 0.5% to 25% by weight.

    20. A method for preparing a polymeric liquid material according to claim 1.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0270] FIGS. 1a, 1b, 1c, and 1d show exemplary 2D molecular structure representations of a typical pure Q-type precursor material or core in a general case (FIG. 1a) (all combinations of methoxy, ethoxy, propoxy for IV possible), and in three more specific cases with primarily ethoxy and less methoxy for R.sup.1 (FIG. 1b), roughly equal ethoxy and methoxy (FIG. 1c) as well as ethoxy R.sup.1 groups only but with a small amount of silanol groups also present (FIG. 1d).

    [0271] FIGS. 2a, 2b, 2c, and 2d show exemplary 2D molecular structure representations of typical materials described herein based on a pure Q-type precursor material only. In the general case (FIG. 2a), all combinations of M, D and T functionalizations are possible and indicated by the presence of selected T.sup.1, T.sup.2, D.sup.1, D.sup.2 and M.sup.1 moieties. Although T.sup.3 moieties are also possible in the general description, they are not included in this simplified 2D structural representation. Furthermore, the three specialized cases are limited to idealized compounds featuring (FIG. 2b) aminopropyl functional with partial —R.sup.10 functionalization of the amine groups, featuring both R.sup.5U and R.sup.5S, (FIG. 2c) R.sup.11-glycidoxypropyl-adduct functional with complete functionalization featuring only R.sup.5S as well as (FIG. 2d) phenyl-functional with partial —R.sup.11 functionalization of the phenyl (Ph) groups, featuring both R.sup.5U and R.sup.5S T-type siloxane moieties to illustrate aspects of diversity in terms of Q-type precursor/single T-type grafted siloxane combinations. The representations are for illustration purposes only and do not represent any limitation in further T (R.sup.5S and R.sup.5U), D, M-Type grafting combinations.

    [0272] FIG. 3 shows a .sup.29Si NMR spectrum of a material prepared from an ethoxy-based Q-type and a methoxy-based T-type precursor, illustrating the ethoxy/methoxy ligand exchange in both Q-type and T-type spectral domains in the final material. By example on T.sup.0 and Q.sup.0 monomers, the ethoxy/methoxy exchange is shown in the form of each moiety signature splitting into various subpeaks. For T.sup.0, a subset of three peaks, T.sup.0a, T.sup.0b is observed originating from T.sup.0 moieties comprising 3 ethoxy, as well as 2 ethoxy and 1 methoxy substituents. As this particular material is very rich in ethoxy, further peaks T.sup.0c (1 ethoxy and 2 methoxy) and also T.sup.0d (3 methoxy) cannot be resolved (too small signal). Analogously, for the Q.sup.0 spectral range a subset of 5 peaks Q.sup.0a, Q.sup.0b, Q.sup.0c can be seen, originating from Q.sup.0 moieties comprising 4 ethoxy, 3 ethoxy and 1 methoxy, 2 ethoxy and 2 methoxy with the Q.sup.0d (1 ethoxy and 3 methoxy substituents) and Q.sup.0e (4 methoxy) signals again not visible.

    [0273] FIG. 4 shows a .sup.29Si NMR spectrum of a material prepared from an ethoxy-based Q-type precursor featuring grafted M-type (from trimethylethoxysilane TMES), D-Type (from Dimethyldiethoxysilane DMDES) and both non-functionalized R.sup.5U and functionalized R.sup.5S T-type moieties (from partially —R.sup.11 functionalized mercaptopropyltriethoxysilane MPTES) in one material with labelling of individual moiety spectral peak signatures.

    [0274] FIG. 5 shows a .sup.29Si NMR spectrum of a material made from a TEOS oligomer Q-type precursor and two different triethoxysilane monomer T-type precursors, namely vinyltriethoxysilane (VTES) and aminopropyltriethoxysilane (APTES), where the aminopropyl-functional T-type was partially R.sup.5S-functionalized with organic R.sup.10 groups, meaning that vinyl T-type moieties contained only non-functionalized R.sup.5U and aminopropyl T-type moieties contained both non-functionalized R.sup.5U and functionalized R.sup.5S. Individual moieties belonging to the vinyl (V) and aminopropyl (AP, both R.sup.5U and R.sup.5S) R.sup.5-functional T-type subpopulations can be clearly spectrally resolved and are labelled for clarity.

    [0275] FIG. 6 shows the effect of the rearrangement grafting on the terasiloxane 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.

    [0276] FIG. 7 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. 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.

    [0277] FIGS. 8a, 8b, and 8c show the R.sup.5S-functionalization reaction monitoring by means of .sup.1H NMR spectra of the various intermediates used in the preparation of an R.sup.5S-functionalized Q-T polysiloxane material via the functionalization “on polysiloxane”. The various spectra show a reference spectrum of the organic substrate used for R.sup.5S-functionalization α,ω amino-terminated polypropylene glycol (Jeffamine D400, FIG. 8a), the R.sup.5U non-functionalized (R.sup.5U=glycidoxyporopyl (Gly)) T-type moiety bearing polysiloxane (FIG. 8b), and the R.sup.5S-functionalized polysiloxane polymeric liquid material obtained by epoxide ring opening functionalization with the organic substrate (FIG. 8c).

    [0278] FIGS. 9a, 9b, and 9c show the R.sup.5S-functionalization reaction monitoring by means of .sup.13C NMR spectra of the various intermediates used in the preparation of an R.sup.5S-functionalized Q-T polysiloxane material via the functionalization “on polysiloxane”. The various spectra show a reference spectrum of the organic substrate used for R.sup.5S-functionalization α,ω amino-terminated polypropylene Glycol (Jeffamine D400, FIG. 9a), the R.sup.5U non-functionalized (R.sup.5U=glycidoxyporopyl (Gly)) T-type moiety bearing polysiloxane (FIG. 9b), and the R.sup.5S-functionalized polysiloxane polymeric liquid material obtained by epoxide ring opening functionalization with the organic substrate (FIG. 9c).

    [0279] FIG. 10 shows .sup.29Si NMR spectra of an R.sup.5U=glycidoxyporopyl (Gly) T-type moiety bearing polysiloxane (top) and the same material after R.sup.5S-functionalization by epoxide ring opening with an α,ω amino-terminated polypropylene Glycol (Jeffamine D400, bottom).

    [0280] FIGS. 11a, 11b, 11c, and 11d show the R.sup.5S-functionalization reaction monitoring by means of .sup.1H NMR spectra of the materials used in the preparation of a non-R.sup.5S-functionalized Q-T polysiloxane material using the “T.sup.0 grafting” approach. The various spectra show the non-R.sup.5S-functionalized (R.sup.5U=—CH.sub.2CH.sub.2CH.sub.2—NH.sub.2) monomeric T-type silane APTES (FIG. 11a), a reference spectrum of the organic substrate used for R.sup.5S-functionalization diethylyeneglycol-diacrylate (DEGDA, FIG. 11b), the DEGDA-R.sup.5S-functionalization product with APTES constituting a functionalized R.sup.5S-bearing T.sup.0 monomer used later for condensation grafting (FIG. 11c) and finally the polysiloxane material featuring said grafted R.sup.5S-bearing T-type moieties (FIG. 11d).

    [0281] FIGS. 12a, 12b, 12c, and 12d show the R.sup.5S-functionalization reaction monitoring by means of .sup.13C NMR spectra of the materials used in the preparation of a R.sup.5S-functionalized Q-T polysiloxane material. The various spectra show the non-R.sup.5S-functionalized (R.sup.5U=—CH.sub.2CH.sub.2CH.sub.2—NH.sub.2) monomeric T-type silane APTES (FIG. 12a), a reference spectrum of the organic substrate used for R.sup.5S-functionalization diethylyeneglycol-diacrylate (DEGDA, FIG. 12b), the DEGDA-R.sup.5S-functionalization product with APTES constituting a functionalized R.sup.5S-bearing T.sup.0 monomer used later for condensation grafting (FIG. 12c) and finally the polysiloxane material featuring said grafted R.sup.5S-bearing T-type moieties (FIG. 12d).

    [0282] FIGS. 13a, 13b, and 13c show the R.sup.5S-functionalization reaction monitoring by means of .sup.1H NMR spectra of the materials used in the preparation of an R.sup.5S-functionalized Q-T polysiloxane material via the R.sup.5S-functionalization “on polysiloxane”. The various spectra show a reference spectrum of the organic substrate used for R.sup.5S-functionalization phthalic anhydride (PhA, FIG. 13a), the non-R.sup.5S-functionalized (R.sup.5U=aminopropyl (AP)) T-type moiety bearing polysiloxane (FIG. 13b), and the R.sup.5S-functionalized polysiloxane polymeric liquid material obtained by amid coupling with the organic substrate (FIG. 13c).

    [0283] FIGS. 14a, 14b, and 14c show the R.sup.5S-functionalization reaction monitoring by means of .sup.13C NMR spectra of the various materials used in the preparation of an R.sup.5S-functionalized Q-T polysiloxane material via the R.sup.5S-functionalization “on polysiloxane”. The various spectra show a reference spectrum of the organic substrate used for R.sup.5S-functionalization phthalic anhydride (PhA, FIG. 14a), the non-R.sup.5S-functionalized (R.sup.5U=aminopropyl (AP)) T-type moiety bearing polysiloxane (FIG. 14b), and the R.sup.5S-functionalized polysiloxane polymeric liquid material obtained by amid coupling with the organic substrate (FIG. 14c).

    DETAILED DESCRIPTION OF THE INVENTION

    Examples

    [0284] 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.

    [0285] 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:

    [0286] Example 1 describes various preparation protocols of non-R.sup.5S-functionalized (i.e. R.sup.5U-bearing) liquid materials.

    [0287] Example 2 describes a general protocol with examples for the R.sup.5S-functionalization of R.sup.5U-bearing T-type monomers with various organic substrates resulting in complete or partial conversion of R.sup.5U into R.sup.5S substituents.

    [0288] Example 3 describes various functionalization protocols employing different functionalization protocols (specifically, organic functionalizations “on polysiloxane” meaning that the organic functionalization reaction is carried out on R.sup.5U-bearing T-type moieties on a Q-T(D,M) polysiloxane or alternatively “T.sup.0 grafting”, where a previously prepared non-R.sup.5S-functionalized (i.e. R.sup.5U-bearing) T-type monomer (or oligomer) is being grafted by rearrangement grafting mechanism.

    [0289] Example 4 then describes combinations of organic R.sup.5S-functionalizations employing both, functionalization “on polysiloxane” and “T.sup.0 grafting” combining at least on of each of those types of R.sup.5S-functionalizations in one material.

    Example 1: Synthesis of an Non-R.SUP.5S.-Functionalized D-50/(APTMS:TMCS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.M-type.)=1:(0.20:0.05:0.05)

    [0290] 483 g/3.78 mol Si equivalent of a commercial ethylsilicate Q-type precursor “Dynasylan Silbond 50” (Evonik Industries) or equivalent was placed inside a 1 L round bottom flask with refluxing column in an oil bath together with 134.2 g/0.75 mol of a monomeric T-type precursor Methyltriethoxysilane (MTES) and with 28.0 g/0.19 mol of a monomeric D-type precursor Dimethyldiethoxysilane (DMDES). The mixture was heated to a temperature of 100° C. at which point a rearrangement catalyst Tetrakis(trimethylsiloxy)titanium(IV) was added to the hot mixture. The mixture was kept stirring for a period of 40 hours, at which point 20.5 g/0.19 mol of a monomeric M-type precursor Trimethylchlorosilane (TMCS) was added and kept stirring for half an hour. Next, a solution containing 120 g of absolute ethanol and 5.5 g/0.31 mol of water was added to the hot reaction mixture, which was then left to reflux for 2 hours. Finally, the residual solvent was removed by replacing the reflux condenser by a distillation bridge and distilling it off. Approximately 125 g of condensate and 669.8 g of crude reaction product were isolated. .sup.29Si NMR analysis confirmed that the product contained less than 8% T.sup.0-monomer measured by the total amount of T-type and moieties, respectively as well as less than 19% of Q-type tetrasiloxane ring species.

    Example 1b: Alternative Synthesis of D-50/(APTMS:DVDMS:TMCS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.:n.SUB.M-type.)=1:(0.20:0.05:0.05)

    [0291] The procedure shown in the above Example 1 was modified in terms of the mode of addition of the TMCS M-type precursor, which was added together with 50 ml of Ethanol but no additional water in the very beginning together with the Q-type precursors. Furthermore, during R.sup.5U-T-type grafting, also a D-type monomer (Diphenyldimethoxysilane, DPhDMS, 46.2 g/0.19 mol) precursor was added. M and Q-type precursor were first refluxed at 100° C. for 7 h before T-type and D-type precursors and rearrangement catalyst were added (same quantities). Following a 37 h reaction time, excess volatiles were removed by distillation, first at ambient pressure and then at 200 mbar vacuum.

    Example 1c: Synthesis of a TEOS Polycondensate/(PTES+N3-PTES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.05+0.08)

    [0292] 334 g of a Q-type precursor with a DP_Q.sub.type 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 were placed inside a 1 L round bottom flask together where after 27.4 g/0.13 mol of a monomeric T-type precursor Propyltriethoxysilane (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 118° 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 6.5% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 27% of Q-type tetrasiloxane ring species.

    Example 1d: Synthesis of a Non-R.SUP.5S.-Functionalized Ethylsilicate Polycondensate/(PTES+APTMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.05+0.15)

    [0293] Again, the exact same synthesis procedure as in Example 1c above was used to prepare the material, with the sole difference that O═Zr(IV)(OAcAc).sub.2 was added as a catalyst instead of Titanium(IV)isopropoxide for the rearrangement grafting of T-type precursors and that the amount and type of the second T-type precursor (APTMS instead of N3-PTES) was varied.

    Example 1e: Alternative Synthesis of a Non-e-Functionalized TEOS Polycondensate/(PTES+N3-PTES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.05+0.08)

    [0294] The exact same synthesis procedure as in Example 1c above was used to prepare the material, with the main difference that the first T-type precursor PTES was already added together with TEOS during the Q-type precursor preparation step, resulting in a mixed Q-T precursor with a molar n.sub.Q-type:n.sub.T-type ratio of =1:0.05. During the second condensation step, an additional aliquot of a second rearrangement catalyst, Hf(NO.sub.3).sub.4 was added while the remaining parameters and preparation steps were left unchanged. .sup.29Si NMR analysis confirmed that the product contained less than 4.5% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 25% of Q-type tetrasiloxane ring species and less than 49% of % (Q.sup.3s,d)/Q.sup.3 ring species.

    Example 1f: Synthesis of a Non-e-Functionalized TEOS Polycondensate/(Alkinyl Functional T Type) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.03)

    [0295] 0.46 mol equivalent of a Q-type precursor with a DP_Q.sub.type of 1.84 and 41.2% ring species which had previously been prepared by controlled hydrolysis of commercial Ethylsilicate-40 was placed inside a 100 ml round bottom flask. Next, 4.2 g/13.8 mmol of an alkenyl terminated T-type precursor (O-(propargyl)-N-(triethoxysilylpropyl)carbamate, Gelest Inc.) and 250 ppm of a Titanium(IV) t-butoxide rearrangement catalyst were added. The mixture was heated to a temperature of 109° C. with stirring. The reaction solution was kept at temperature for 14 hours hours under nitrogen gas atmosphere, at which point the mixture was allowed to cool to room temperature. .sup.29Si NMR analysis confirmed that the product contained less than 8% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 31% of Q-type tetrasiloxane ring species.

    Example 1g: Synthesis of a Non-e-Functionalized Ethylsilicate Polycondensate/(PTES+APTMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.05+0.15)

    [0296] Again, the exact same synthesis procedure as in Example 1c above was used to prepare the material, with the difference that O═Zr(IV)(OAcAc).sub.2 was added as a catalyst instead of Titanium(IV)isopropoxide for the rearrangement grafting of T-type precursors and that the amount and type of the second T-type precursor (APTMS instead of N3-PTES) was varied. .sup.29Si NMR analysis confirmed that the product contained less than 5% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 24% of Q-type tetrasiloxane ring species.

    Example 1h: Synthesis of a Non-e-Functionalized Methylsilicate Polycondensate/(oligoPTES+APTMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.05+0.15)

    [0297] 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 1.63 and that the first T-type precursor PTES was added in oligomeric form (oligoPTES). .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 21% of Q-type tetrasiloxane ring species.

    Example 1i: Synthesis of a Non-e-Functionalized TMOS/TEOS/TPOS Polycondensate/(Cl-PTES:DMDES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.20:0.05)

    [0298] 1.33 mol equivalent of a Q-type precursor was prepared by controlled hydrolysis of a TMOS, TEOS and TPOS mixture in a molar ratio of 0.3:0.4:0.3. A first rearrangement grafting step was carried out by mixing said precursor with 48.0 g/0.20 mol of 3-chloropropyltriethoxysilane (Cl-PTES) in a microwave autoclave reactor for 19 minutes. Bis-acetylacetonato-titanium(IV)-diisopropoxide was used as the rearrangement catalyst. For the second grafting, an additional 16.0 g/0.067 mol Cl-PTES T-Type precursor and 9.9 g/0.067 mol DMDES D-Type precursor were added and the reaction was again carried out for an additional 67 minutes in the same microwave autoclave reactor. The finished reaction product was isolated and residual volatiles removed on a laboratory rotary evaporator. .sup.29Si NMR analysis confirmed that the product contained less than 9% of combined T.sup.0-monomers and less than 11% D.sup.0-monomers measured by the total amount of T-type and D-type moieties, respectively, and less than 22% of Q-type tetrasiloxane ring species.

    Example 1j Synthesis of a Non-e-Functionalized Ethylsilicate 40/GPTMS Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.10)

    [0299] 380 g/2.6 mol ethylsilicate with 40% SiO.sub.2 solids content from Wacker (Wacker Silicate TES 40 WN) was poured into a pressure-tight autoclave with lid was added together with 62.4 g/0.26 mol of a T-type precursor (3-Glycidyloxypropyl)trimethoxysilane and O═Zr(IV)(NO.sub.3).sub.2 as a catalyst. The autoclave was then hermetically sealed and heated to a temperature of 108° C. resulting in pressure buildup. The mixture was allowed to react for a period of 14 h, after which the autoclave was cooled to room temperature and the crude reaction product was isolated. .sup.29Si NMR analysis confirmed that the product contained less than 9.5% of total T.sup.0-monomer measured by the total amount of T-type moieties and less than 22% of Q-type tetrasiloxane ring species.

    Example 1k: Synthesis of a Non-R.SUP.5S.-Functionalized TMOS+TPOS:DMDES Polycondensate Precursor/(MTES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.05:0.05)

    [0300] 2.2 mol Si equivalent of a Q-type precursor with a DP_Q.sub.type of 2.03 and 44.7% ring species prepared by nonhydrolytic condensation of a 50:50 molar ratio mixture of TMOS and TPOS with acetic anhydride in the presence of a Titanium(IV) methoxide rearrangement catalyst, containing also a D-type silane co-precursor DMDES constituting a molar ratio of n.sub.Q-type:n.sub.D-type of =1:0.05 were placed inside a 1 L round bottom flask. Grafting of the T-type precursor MTES was then carried out using additional Ti(IV) ethoxide as a rearrangement catalyst. .sup.29Si NMR analysis confirmed that the product contained less than 7.0% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 25% of Q-type tetrasiloxane ring species.

    Example 1l: Synthesis of a Non-R.SUP.5S.-Functionalized TEOS &TMOS/SH-PTMS Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.15)

    [0301] 511 g/2.66 mol Si of tetramethoxysilane (TMOS) and 277 g/1.33 mol Si of tetramethoxysilane (TEOS) and Zirconium(IV)-isobutoxide catalyst were placed inside a 1 L round bottom flask with distillation bridge resulting in a relative molar ratio of TMOS to TEOS monomer for the Q-type precursor preparation of 2:1. The flask was purged with nitrogen, sealed, and left under nitrogen pressure (balloon) and immersed into a hot oil bath, which was kept at 130° C. The Q-Type monomer/catalyst mixture was brought to temperature with stirring at 500 rpm. Once the temperature has been reached, a selected amount (465.3 g/4.56 mol) acetic anhydride was added in portions. Soon thereafter, refluxing of the reaction byproduct ethyl acetate occurred. After approximately 8 minutes, a continuous stream of methyl acetate and ethyl acetate was distilling over through the distillation bridge and collected in the capture vessel. The reaction continued for a total time of about 75 more minutes, at which point it stopped, coinciding with the ceasing of the methyl/ethyl acetate distilling over. The collection vessel was removed after a total reaction time of 1 h and 40 minutes and emptied, yielding a total mass of 725 g of collected condensate and 465 g of Q-type precursor. .sup.29Si NMR analysis confirmed that the precursor had a DP_Q.sub.type of 2.22 and 51.0% Q-type tetrasiloxane ring species before the grafting step. This precursor was then mixed with 117.8 g/0.6 mol Mercaptopropyltrimethoxysilane (SH-PTMS) as a T-type precursor. The mixture was then again heated up to temperature of 115° C. with stirring in the same reaction vessel and was kept for 5 hours, at which point the heating source was removed and the product allowed to cool to room temperature. .sup.29Si NMR analysis confirmed that the product contained less than 8.3% of total T.sup.0-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 43.2% of % (Q.sup.3s,d)/Q.sup.3 ring species.

    Example 1m: Synthesis of a Non-R.SUP.5S.-Functionalized TEOS/(PhTES+PTMS:DPhDES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type .n.SUB.D-type.)=1:(0.10+0.05:0.05)

    [0302] 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 (Buchi versoclave, 11) 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 propyltrimethoxysilane (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 13 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 26.9% of Q-type tetrasiloxane ring species.

    Example 1n: Synthesis of a Non-R.SUP.5S.-Functionalized TEOS/(PhTES+PTMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.10+0.05)

    [0303] The exact same synthesis procedure as in Example 1m above was used to prepare the material with the sole difference that the D-type precursor was omitted during the synthesis. .sup.29Si NMR analysis confirmed that the product contained less than 13% T.sup.0-monomer measured by the total amount of T-type and D-type moieties as well as less than 26.9% of Q-type tetrasiloxane ring species.

    Example 1o: Synthesis of a Non-R.SUP.5S.-Functionalized TEOS (Oligomer)/(TESPT+VTES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:(0.17+0.06)

    [0304] 2.66 mol Si equivalent of a Q-type precursor made by the “silanol route” (preparation of triethoxysilanol from TEOS with sodium hydroxide, followed by workup and condensation of the triethoxysilanol) were placed inside a 500 ml glass cylinder with cap. Next, 185.8 g/0.44 mol of a first T-type precursor Bis(triethoxysilylpropyl)tetrasulfide (TESPT) and 23.1 g/0.16 mol of a second T-type precursor vinyltriethoxysilane (VTES) was added together with a bis-acetylacetonato-titanium(IV)-diisopropoxide rearrangement catalyst. The mixture was heated to 80° C. and was kept stirring for a period of 6 days. Residual solvent was removed by pulling a 100 mbar vacuum for 30 minutes. .sup.29Si NMR analysis confirmed that the product contained less than 42% T.sup.0 species measured by the total amount of T-type moieties as well as less than 29.2% of Q-type tetrasiloxane ring species.

    Example 1p: Synthesis of a Non-e-Functionalized TEOS (Oligomer)/MaPTMS Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type.=1:0.10

    [0305] A procedure identical to the one described in Example 1j was used to prepare this material, with the key differences that the T-type precursor was 3-Methacryloxypropyltrimethoxysilane (MaPTMS) dissolved in a cosolvent (Methyl ethyl ketone) and that the autoclave was heated by means of a microwave source and a reduced reaction time of 3.5 hours was used. .sup.29Si NMR analysis confirmed that the product contained less than 11% of total T.sup.0-monomer measured by the total amount of T-type moieties and less than 24% of Q-type tetrasiloxane ring species.

    Example 2 a-l: General Synthetic Protocol for the Preparation of R.SUP.5S.-Functionalized Graftable T.SUP.0 .Monomers (or Oligomers) to be Used in Rearrangement Grafting

    [0306] In a typical experiment, an non-R.sup.5S-functionalized “R.sup.5U monomer” (or oligomer) is functionalized using the following protocol: The “R.sup.5U monomer” is used neat or dissolved in a solvent (SO). It is then reacted with a suitable organic substrate (SU) exemplified by the specific examples a to l in Table 1 below by slow dosing of the latter. The reaction stoichiometry is selected according to the ability of the multifunctionality of the individual SU compounds. The mode of addition can also be inversed, meaning that the organic substrate can be placed in the vessel first (with solvent SO) and then the “R.sup.5U monomer” T-type silane dosed slowly. As a general rule of thumb, the material which is the stoichiometrically limiting component is the one being dosed to the component which is present in excess. The reaction is then kept at a desired reaction temperature with stirring for a desired reaction time (TR), if needed in the presence of a suitable catalyst. Depending on the type of reaction, a workup and purification step may be necessary. The resulting R.sup.5S-functionalized T.sup.0 monomer can the be used for rearrangement grafting onto a suitable Q(T,D) precursor material as exemplified in Example 3 below.

    TABLE-US-00001 TABLE 1 Silane substrate Organic Reaction Example [R.sup.5U- substrate Solvent time # Monomer] [SU] Stoichiometry [SO] [TR] Temperature Catalyst Reference Lit. 2a Aminopropyl Epoxide 1:8 4 h 80 J. Vinyl Add. DGEBA Technol., 2016, 22(1), 80-87 2b Mercaptopropyl Epoxide 1:1 THF/DMSO/ 2 h r.t. Base J. Polym. Sci. Bisphenol F DGE DMF (e.g. TBAF) Part A: Polym. Chem., 54, 3057-3070 2c Aminopropyl Aldehyde 2.5% (v/v) 0.5 h.sup.  r.t. Applied Surface Glutaraldehyde in PBS Science, 2014, 305, 522-530 2d Chloropropyl Friedel-crafts 1 h 45 AlCl.sub.3 alkylation nitrobenzene 2e Phenyl Chlorination FeCl.sub.3 Cl.sub.2, FeCI.sub.3 2f Phenyl Friedel-crafts 1 h 45 AlCl.sub.3 alkylation (e- rich aromatic?) RX 2g Azidopropyl via iodide to 1) 1:3 .sup.  1) DCM; 18 h;  r.t.; Tetrahedron, ether (2step) 2) conjugate 1-8 h.sup.  reflux 2012, 68, 1) t-Bul, aq. acid of 9606-9611 Na.sub.2S.sub.2O.sub.3; 2) KOR alkoxide 2h Glycidoxypropyl Jeffamine 1:1 1 h 120 Poly(propylene glycol) bis(2-aminopropyl ether) 2i Aminopropyl Fatty acid DMF 24 h  60 J.Oleo Sci., 2017, 66(7), 771-784 2j Cylcloepoxypropyl Chitosan/hydrolysed 8:1 2% w/v 0.5 h.sup.  r.t. Polymers, 2020, chitin CS 12, 2723 Chitosan solution in aq. acetic acid 2k Vinyl Acrylonitrile oligomer 1:2 DCM 2 h 40/reflux [Ru] Green Chem., (cross-metathesis?) 2011, 13, (meth)acrylonitrile 2258-227 2l Mercaptopropyl Alkylation to 2 eq. CH.sub.3CN 20 h  80 Zn, L- RSC Adv., 2015, alkyl- base Proline 5, 32675- thioether 32678 NaOBu; RX (aromatic)

    TABLE-US-00002 TABLE 2 Siloxane Organic Example substrate Organic substrate # [R.sup.5U] DP_Q.sub.type DP_T.sub.type functionalization [SU] Stoichimetry 3a Aminopropyl 2.15 1.88 On Diepoxide 1:8 Polysiloxane 3b Azidopropyl 1.65 1.35 T.sup.0 Alkyne grafting 3c Alkyne 1.88 1.56 T.sup.0 Azide grafting 3d Aminoethyl 2.24 2.14 On HDDA  >1:1.5 Polysiloxane (Diacrylate) 3e Aminopropyl 2.35 2.21 On HDI Polysiloxane 3f Aminopropyl 1.94 1.77 On Triisocyanate Polysiloxane (IPDI trimer) 3g Mercaptopropyl 2.04 1.88 T.sup.0 4, 4-MDI grafting 3h Hydroxypropyl 1.46 1.33 On TDI Polysiloxane 3i Chloropropyl 1.77 1.38 On Ethylenediame Polysiloxane 3j Glycidoxypropyl 1.91 1.68 T.sup.0 amino-PDMS grafting 3k Aminopropyl 1.64 1.58 On Maleic 1:1 Polysiloxane anhydride 3l Mercaptopropyl 1.84 On Phthalic 1:1 Polysiloxane anhydride 3m Propyl-methacrylate 1.55 1.37 On MMA Polysiloxane 3n TESPT 1.92 1.48 On Styrene Polysiloxane 3o Aminopropyl 2.11 2.05 T.sup.0 Acid grafting chloride, TEA 3p Aminopropyl 1.81 1.46 On 4-bromobenzaldehyde, 1:1:1 Polysiloxane B(OCH.sub.2CF.sub.3).sub.3 3q Mercaptopropyl 2.06 1.99 On Bromo- Polysiloxane isopentane 3r Mercaptopropyl 2.44 2.26 T.sup.0 1-hexene grafting 3s Phenyl 1.87 1.72 T.sup.0 Ethyl grafting oxalate chloride 3t Aminopropyl 2.1 1.67 T.sup.0 Oligopeptide grafting Reference Lit. Reaction J. Non Cryst Example Solvent time Temperature solids, # [SO] [TR] [° C.] Catalyst 2008, 143(5), 188 3a 4 h 80 Macromol. Rapid Comm. 2020, 41, 1900359 3b Large r.t. Cu(l), range [Ru] 3c 3d 1 h 40 3e Toluene 3 h 70 J. Org. Chem, 2013, 9, 2378-2386 3f 3g THF 0.5 h.sup.  r.t. Base Polym. (DBU) Chem., 2011, 2, 88-90 3h Toluene DBTDL Wood Sci. Technol., 2020, 54, 1091-111 3i DMF 9 h r.t. Et3N RSCAdv., 2014, 4, 18229-18233 3j 3k 55 3l 80 3m 3n 3o DCM r.t. 3p THF 2 h r.t. Org. Lett. 2015, 17, 10, 2442-2445 3q DMPA 3r 3s DCM 1 h r.t. AlCl.sub.3 Synthesis, 13, 2006, 2103-2112 3t Amyl acohol/water

    Example 3 a-t: General Synthetic Protocol for the Preparation of R.SUP.5S.-Functionalized Polymeric Liquid Materials According to this Invention Using Either One of Two Distinct Preparative Approaches

    [0307] In a typical experiment, an polymeric liquid material exhibiting at least one T-type silane can be R.sup.5S-functionalized using either of two approaches, namely, i) by rearrangement grafting of an R.sup.5S-functionalized graftable T.sup.0 monomer or oligomer or ii) by direct organic functionalization of already grafted, suitable R.sup.5U-T-type moieties on the material using specific organic functionalization reactions. Either one of these protocols can be used interchangeably if chemically meaningful and applicable and also multiple times, however for clarity, in this example only single R.sup.5S-functionalizations were selected on any given polymeric liquid material. A list of typical examples a to t is presented above in Table 2. Please note that for each specific R.sup.5S-functionalization, a matching specific “organic functionalization” protocol is assigned. The choice of protocol is not compulsory for the given Siloxane (R.sup.5)/organic (SU) substrate combination.

    [0308] Methodology for “T.sup.0 Grafting” R.sup.5S-Functionalization:

    [0309] A R.sup.5S-functionalized T.sup.0 monomer or oligomer bearing organofunctional groups, which can be one selected from the list of examples in Table 1, is grafted to a non-R.sup.5S-functionalized (i.e. R.sup.5U-bearing) polymeric liquid material as for example the ones described in Example 1. The rearrangement reaction grafting is carried out by reacting said R.sup.5S-functionalized T-type monomer or oligomer with a polymeric liquid material in the presence of a rearrangement catalyst. Temperature, catalyst and duration of the reaction are chosen such that satisfactory grafting efficacy is reached. Optionally, different grafting conditions can be tested out and the grating efficacy analyzed by means of .sup.29Si NMR spectroscopy in order to find the optimal grafting conditions.

    [0310] Methodology for “on Polysiloxane” R.sup.5S-Functionalization:

    [0311] In this case, the organic R.sup.5S-functionalization is carried out directly on suitable R.sup.5U-bearing T-type moieties, which have already previously been grafted. In analogy to Example 2, the T-type grafted polysiloxane featuring suitable R.sup.5U-moieties for functionalization (all descriptions in Example 1 with exception of Example 1k qualify in general, while there are many other possible combinations) is used neat or dissolved in a solvent (SO). It is then reacted with a suitable organic substrate (SU) exemplified by the specific examples in Table 2 above by slow dosing of the latter. Again, the reaction stoichiometry is selected according to the ability of the multifunctionality of the individual SU compounds. The mode of addition can also be inversed, meaning that the organic substrate can be placed in the vessel first (with solvent SO) and then the organic substrate (SU) slowly. As a general rule of thumb, the material which is the stoichiometrically limiting component is the one being dosed to the component which is present in excess. The reaction is then kept at a desired reaction temperature with stirring for a desired reaction time (TR), if needed in the presence of a suitable catalyst. Depending on the type of reaction, a workup and purification step may be necessary.

    Example 4a

    [0312] A non-R.sup.5S-functionalized TMOS+TPOS:MTES:DMDES polycondensate material according to Example 1k was prepared. Next, an R.sup.5S-functionalized T.sup.0 monomer according to Example 2c was prepared and grafted using a standard rearrangement grafting protocol (90° C., 32 h, Ti(IV)isopropoxide rearrangement catalyst). .sup.29Si NMR analysis confirmed that the product contained less than 10.5% of total T.sup.0-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 41.1% of % (Q.sup.3s,d)/Q.sup.3 ring species.

    Example 4b

    [0313] A non-R.sup.5S-functionalized Q-T polycondensate according to a simplified protocol given in Example 3q was prepared from a starting material according to Example 11. Next, a second R.sup.5S-functionalized T.sup.0 monomer according to Example 2i was grafted using a standard rearrangement grafting protocol (100° C., 24 h, Ti(IV)isopropoxide rearrangement catalyst). .sup.29Si NMR analysis confirmed that the product contained less than 7.2% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 25% of Q-type tetrasiloxane ring species.

    Example 4c

    [0314] A material identical to the one described in Example 4b was prepared but with the difference that during the Example 2i T.sup.0 monomer grafting, an additional M-type precursor ethoxytrimethyl-silane (ETMS) was added. .sup.29Si NMR analysis confirmed that the product contained less than 8.5% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 24% of Q-type tetrasiloxane ring species.

    Example 4d

    [0315] A non-R.sup.5S-functionalized Q-T polymeric liquid material featuring -propyl and azidopropyl R.sup.5U-substituents was prepared according to Example 1c. Next, an R.sup.5S-functionalized T.sup.0 monomer according to Example 2b was separately prepared and grafted using a standard rearrangement grafting protocol (100° C., 24 h, Ti(IV)isopropoxide rearrangement catalyst). Next, the azidopropyl substituents were partially functionalized by means of Cu(s) catalyzed Click chemistry with a 4-chlorohexine with a targeted degree of R.sup.5S functionalization of 40%. .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 26% of Q-type tetrasiloxane ring species.

    Example 4e

    [0316] A material identical to the one prepared in Example 4d, wherein at the end of the synthesis a second T.sup.0 monomer according to Example 2e was grafted onto the polysiloxane liquid material using a standard rearrangement grafting protocol (100° C., 24 h, no additional rearrangement catalyst addition). .sup.29Si NMR analysis confirmed that the product contained less than 7.1% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 30% of Q-type tetrasiloxane ring species.

    Example 4f

    [0317] A non-R.sup.5S-functionalized Q-T polymeric liquid material featuring -propyl and aminopropyl R.sup.5U-substituents was prepared according to Example 1h. Next, an R.sup.5S-functionalized T.sup.0 monomer according to Example 2i was separately prepared and grafted using a standard rearrangement grafting protocol (100° C., 24 h, Ti(IV)isopropoxide rearrangement catalyst). Next, residual R.sup.5U-aminopropyl substituents were completely functionalized by reaction with an excess of hexamethylene diisocyanate (HDI) in toluene according to Example 3e. .sup.29Si NMR analysis confirmed that the product contained less than 9.7% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 22% of Q-type tetrasiloxane ring species.

    Example 4g

    [0318] A material identical to Example 4f was prepared with the sole difference that during the grafting of the second T.sup.0 monomer also a D-type silane dimethyldiethoxysilane and additional rearrangement catalyst were added to the grafting solution. .sup.29Si NMR analysis confirmed that the product contained less than 5.9% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 26% of Q-type tetrasiloxane ring species.

    Example 4 h

    [0319] A non-R.sup.5S-functionalized Q-T polymeric liquid material featuring -propyl and -phenyl R.sup.5U-substituents was prepared according to Example 1n. Next, an R.sup.5S-functionalized T.sup.0 monomer according to Example 2i (only partial conversion with aminosilane monomer excess) was separately prepared and grafted using a standard rearrangement grafting protocol (100° C., 24 h, Ti(IV)isopropoxide rearrangement catalyst). Next, residual R.sup.5U-aminopropyl substituents were completely functionalized by reaction with an excess of bisphenol A diglycidyl ether (DGEBA). .sup.29Si NMR analysis confirmed that the product contained less than 11% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 22% of Q-type tetrasiloxane ring species.

    Example 4i

    [0320] A material identical to Example 4 h was prepared with the sole difference that after the end of the reaction, R.sup.5U-phenyl groups were partially functionalized by means of a Friedel-Crafts acylation. .sup.29Si NMR analysis confirmed that the product contained less than 9.7% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 29% of Q-type tetrasiloxane ring species.

    Example 4j

    [0321] A material identical to Example 4i was prepared with the difference that during the grafting of the R.sup.5S-functionalized T.sup.0 monomer according to Example 2i also a D-type monomer diphenyl-dimethoxysilane (DPhDMS) and additional rearrangement catalyst were added to the grafting solution. Furthermore, during the Friedel Crafts acylation, a partial reaction also took place on the phenyl groups (R.sup.2, R.sup.3 in this case are also reactive) of the D-type moieties. .sup.29Si NMR analysis confirmed that the product contained less than 7.4% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 23% of Q-type tetrasiloxane ring species.

    Example 4k

    [0322] A Q-type precursor prepared by controlled hydrolysis of TEOS was used as precursor, onto which two R.sup.5S-functionalized T.sup.0 monomers which had been independently prepared to Examples 21 and 2c were grafted using a standard rearrangement grafting protocol (100° C., 24 h, Ti(IV)isopropoxide rearrangement catalyst). .sup.29Si NMR analysis confirmed that the product contained less than 4.2% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 27% of Q-type tetrasiloxane ring species.

    Example 4l

    [0323] A material prepared according to Example 4k was first mixed with an M-type precursor HMDSO in 98% ethanol and reacted in the presence of catalytic amounts of hydrochloric acid for 1 h at 85° C. Next, an aliquot of hexamethyldisilazane was added to the mixture and stirring continued for another 45 minutes. Residual volatiles were then removed by means of vacuum distillation. Then, a third R.sup.5S-functionalized T.sup.0 monomer was added which had been independently prepared according to Examples 2j was grafted using a standard rearrangement grafting protocol (100° C., 24 h, Ti(IV)isopropoxide rearrangement catalyst). .sup.29Si NMR analysis confirmed that the product contained less than 6.7% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 28% of Q-type tetrasiloxane ring species.

    Example 4m

    [0324] A non-R.sup.5S-functionalized TEOS: TESPT+VTES polycondensate material according to Example 1o was prepared. Next, an R.sup.5S-functionalized T.sup.0 monomer according to Example 2i was prepared and grafted using a standard rearrangement grafting protocol (90° C., 32 h, Ti(IV)isopropoxide rearrangement catalyst). Next, functionalization of radical polymerizable R.sup.5U-groups was achieved by reacting the mixture with acrylonitrile in a controlled radical polymerization protocol. .sup.29Si NMR analysis confirmed that the product contained less than 7.7% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 44.2% of % (Q.sup.3s,d)/Q.sup.3 ring species.

    Example 4n

    [0325] A material identical to Example 4m was prepared with the difference that after the last step (controlled radical polymerization) residual vinyl groups were functionalized in a separate reaction step by means of a thiol-ene reaction with an excess of 1-hexene according to Example 3r. .sup.29Si NMR analysis confirmed that the product contained less than 7.4% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 26% of Q-type tetrasiloxane and less than 42.5% of % (Q.sup.3s, d)/Q.sup.3 ring species ring species.

    Example 5: Synthesis of TEOS/(iBTES:TMES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.20:0.05)

    [0326] 311 g of crude precursor from Example 4 were placed inside a 1 L round bottom flask together with 146.0 g/0.53 mol of a monomeric T-type precursor Octyltriethoxysilane (OTES) and 27.2 g/0.13 mol of a monomeric D-type precursor Dimethyldiethoxysilane (DMDES). The mixture was heated to a temperature of 100° C. at which point a rearrangement catalyst bis-acetylacetonato-titanium(IV)-diacetate was added to the hot mixture. The mixture was kept stirring for a period of 48 hours, at which point any residual solvent was removed by pulling a 250 mbar vacuum for 5 minutes. .sup.29Si NMR analysis confirmed that the product contained less than 11% T.sup.0-monomer and less than 5% of D.sup.0-monomer measured by the total amount of T-type and D-type moieties, respectively as well as less than 23% of Q-type tetrasiloxane ring species.

    Example 5b: Alterative Synthesis of TEOS/(OTES:DVDMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.25:0.05)

    [0327] Instead of adding both T-type and D-type monomers together with a premade Q-type precursor from Example 4, here a premade precursor already containing the D-type moieties introduced during the precursor condensation step according to Example 4d was used. Accordingly, the premade crude precursor batch from Example 4d was further premixed with 182.4 g/0.66 mol of a monomeric T-type precursor Octyltriethoxysilane (OTES) and the same type and amount of rearrangement catalyst. The remaining protocol was identical to the one described in Example 5. .sup.29Si NMR analysis confirmed that the product contained less than 15% T.sup.0-monomer and less than 5% of D.sup.0-monomer measured by the total amount of T-type and D-type moieties as well as less than 29.5% of Q-type tetrasiloxane ring species and 45.8% Q.sup.3s,d/Q.sup.3 ring species.

    Example 6: Synthesis of TEOS/(APTMS+PTES) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.20+0.05)

    [0328] 334 g of crude precursor from Example 4b were placed inside a 1 L round bottom flask together where after 27.4 g/0.13 mol of a monomeric T-type precursor Propyltriethoxysilane (PTES) and 95.0 g/0.53 mol of a second T-type precursor 3-aminopropyltremethoxysilane (APTMS) were added together with a rearrangement catalyst Zirconium(IV)-chloride. The mixture was heated to a temperature of 125° C. and was kept stirring for a period of 5.5 hours, at which point any residual solvent was removed by pulling a 250 mbar vacuum for 5 minutes. .sup.29Si NMR analysis confirmed that the product contained less than 7% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 27% of Q-type tetrasiloxane ring species.

    Example 6b: Alterative Synthesis of TEOS/(APTMS+PTES) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.20+0.05)

    [0329] In analogy to example 5b, also here the entire premade crude precursor batch from Example 4e containing already the PTES T-type functional silane in Q-T oligomeric form was mixed with 95.0 g/0.53 mol of the second T-type precursor 3-aminopropyltremethoxysilane (APTMS) and the same type and amount of rearrangement catalyst. The remaining protocol was identical to the one described in Example 6. .sup.29Si NMR analysis confirmed that the product contained less than 6% of total T.sup.0-monomer measured by the total amount of T-type moieties and less than 24% of Q-type tetrasiloxane ring species.

    Example 7: Synthesis of an Ethylsilicate-40/(iBTES:TMES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.+n.SUB.M-type.)=1:0.15:0.05

    [0330] The precursor material batch prepared in Example 4f was poured into a 1 L sealable glass bottle and additional catalyst, Ti(IV)bromide, was added together with 87.8 g/0.40 mol of a T-type precursor isobutyl-triethoxysilane (iBTES) and 31.1 g/0.26 mol of an M-type precursor trimethylethoxysilane (TMES). The bottle was then lightly sealed and placed inside a heating cabinet which was set to a constant temperature of 100° C. The mixture was allowed to react for a period of 100 h at this temperature, after which the crude reaction product was isolated. .sup.29Si NMR analysis confirmed that the product contained less than 10% of total T.sup.0-monomer measured by the total amount of T-type moieties and less than 21% of Q-type tetrasiloxane ring species.

    Example 8: Synthesis of TMOS/GPTMS Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type.=1:0.10

    [0331] The precursor material batch prepared in Example 4c was poured into a pressure-tight autoclave with lid and additional catalyst was added together with 62.4 g/0.26 mol of a T-type precursor (3-Glycidyloxypropyl)trimethoxysilane. The autoclave was then hermetically sealed and heated to a temperature of temperature of 110° C. resulting in pressure buildup. The mixture was allowed to react for a period of 14 h, after which the autoclave was cooled to room temperature and the crude reaction product was isolated. .sup.29Si NMR analysis confirmed that the product contained less than 8% of total T.sup.0-monomer measured by the total amount of T-type moieties and less than 23% of Q-type tetrasiloxane ring species.

    Example 9: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.44 from Tetraethoxysilane or its Oligomers

    [0332] Tetraethoxysilane (TEOS) in monomeric or oligomeric form was hydrolyzed in the presence of a cosolvent according to the state of the art with a water stoichiometry amount required to achieve a desired degree of polymerization of the precursor material DP_Q.sub.type=2.44 using a standard hydrolysis/condensation catalyst. Once the hydrolysis was completed, excess cosolvent and alcohol released during the hydrolysis were removed by vacuum distillation. .sup.29Si NMR analysis revealed 54.9% of Q-type tetrasiloxane ring species in the precursor material.

    Example 9b: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.0 from Tetrapropoxysilane or its Oligomers

    [0333] A material identical to the one in Example 9 was prepared, with the exception that tetrapropoxysilane (TPOS) was used as a starting Q-type monomer or oligomer and that the stoichiometric amount of water added was adjusted to yield a degree of polymerization DP_Q.sub.type=2.0. .sup.29Si NMR analysis of the precursor material revealed 44.5% of Q-type tetrasiloxane ring species.

    Example 9c: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=1.72 from Tetraethoxysilane or its Oligomers

    [0334] A material identical to the one in Example 9 was prepared, with the exception that the stoichiometric amount of water added was adjusted to yield a degree of polymerization DP_Q.sub.type=1.72. .sup.29Si NMR analysis of the precursor material revealed 33.7% of Q-type tetrasiloxane ring species.

    Example 9d: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.2 from Tetraethoxysilane or its Oligomers

    [0335] A material identical to the one in Example 9 was prepared, with the exception that the stoichiometric amount of water added was adjusted to yield a degree of polymerization DP_Q.sub.type=2.2. .sup.29Si NMR analysis of the precursor material revealed 47.0% of Q-type tetrasiloxane ring species.

    Example 9e: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.56 from Tetraethoxysilane or its Oligomers

    [0336] A material identical to the one in Example 9 was prepared, with the exception that the stoichiometric amount of water added was adjusted to yield a degree of polymerization DP_Q.sub.type=2.56. .sup.29Si NMR analysis of the precursor material revealed 57.0% of Q-type tetrasiloxane ring species.

    Example 9f: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.0 from Tetraethoxysilane or its Oligomers with Addition of a Rearrangement Catalyst

    [0337] A material identical to the one in Example 9b was prepared, with the exception that in addition to a standard hydrolysis/condensation catalyst, also an amount of Hf(IV)ethoxide was added as a rearrangement catalyst towards the end of the hydrolysis process. .sup.29Si NMR analysis of the precursor material revealed 46.8% of Q-type tetrasiloxane ring species.

    Example 9g: Preparation of a Mixed Q-Type/D-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.2 and DP_D.SUB.type.=1.5 from Ethylsilicate-40 and DMDMS with n.SUB.Q-type.:n.SUB.D-type.=1:0.05

    [0338] A material identical to the one in Example 9d was prepared, with the exception that in addition to the oligomeric ethylsilicate-40 Q-type source an amount of a D-type source DMDMS of 5% measured by the respective molar amounts of Si was used for its preparation. Furthermore, the stoichiometric amount of water added was adjusted to further account for the targeted DP_D.sub.type=1.5 value. .sup.29Si NMR analysis of the precursor material revealed 45.2% of Q-type tetrasiloxane ring species.

    Example 9h: Alternative Preparation of a Mixed Q-Type/D-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.2 and DP_D.SUB.type.=1.5 from Ethylsilicate-40 and DMDCS with n.SUB.Q-type.:n.SUB.D-type.=1:0.05

    [0339] A material identical to the one in Example 9g was prepared, with the exception that Dimethyldichlorosilane (DMDCS) was used as a D-type source instead of DMDMS. Residual hydrochloric acid was removed at the end of the reaction by bubbling with nitrogen as a purge gas. .sup.29Si NMR analysis of the precursor material revealed 43.6% of Q-type tetrasiloxane ring species.

    Example 10: Synthesis of a TPOS (Oligomer)/(Cl-PTMS: HMDSO) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.+n.SUB.M-type.)=1:0.15:0.09

    [0340] 5.87 mol Si equivalent of a Q-type precursor prepared according to Example 9b was placed inside a 2 L round bottom flask with refluxing column and a resistive heating mantle together with 146.1 g/0.90 mol of a dimer M-type precursor Hexamethyldisiloxane (HMDSO). To this mixture a solution consisting of 25 ml Ethanol and 0.3 ml trifluoroacetic acid (TFA) were added. The setup was then heated to 110° C. mantle temperature with stirring and allowed to react for 2 h in a first reaction step a), at which point the refluxing column was replaced by a distillation bridge and residual volatiles distilled off first at ambient pressure and towards then end with a vacuum reaching 180 mbar at the point where distillate collection had stopped completely.

    [0341] With the vacuum pump turned off, the reaction vessel was then brought to ambient pressure with nitrogen and 140.0 g/0.70 mol of a monomer T-type precursor (3-Chloropropyl)-trimethoxysilane (Cl-PTMS) and Ti(IV)-methoxide as a catalyst were added. The mixture kept at 120° C. with stirring for an additional 6 hours for a second reaction step b) and then removed from the heating source and allowed to cool to room temperature. 975.4 g of crude reaction product were isolated. .sup.29Si NMR analysis confirmed that the product contained less than 5% T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 26% of Q-type tetrasiloxane ring species.

    Example 11: Synthesis of TEOS (Oligomer)/(GPTMS+VTMS) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.10+0.05)

    [0342] 18.4 g/137 mmol of Q-type precursor as prepared in Example 9f together with a first ((3-Glycidyloxypropyl)trimethoxysilane (GPTMS), 3.3 g/14 mmol) and a second (Vinyltrimethoxysilane (VTMS), 1.0 g/7 mmol T-type precursor) were placed inside a 50 ml Teflon vessel and installed inside a matching organic synthesis microwave reactor (flexiWAVE, Milestone Inc.). A preinstalled synthesis protocol with a synthesis temperature of up to 190° C. was run which lasted 6 minutes. Upon cooldown, 22.6 g of crude reaction product were isolated. NMR analysis confirmed that the product contained less than 4% T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 21% of Q-type tetrasiloxane ring species.

    Example 12: Synthesis of TEOS (Oligomer)/MaPTMS Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type.=1:0.10

    [0343] A procedure identical to the one described in Example 8 was used to prepare this material, with the key differences that a Q-type precursor material prepared according to Example 9c and 3-Methacryloxypropyltrimethoxysilane (MaPTMS) were used as starting materials together with a cosolvent (ethyl acetate) and that the autoclave was heated by means of a microwave source and a reduced reaction time of 3 hours 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 and less than 24% of Q-type tetrasiloxane ring species.

    Example 13: Synthesis of Ethylsilicate-40/(HS-PTMS:DMDMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.15:0.05)

    [0344] A procedure identical to the one described in Example 8 was used to prepare this material, with the key differences that a Q-type precursor material prepared according to Example 9g and 3-Mercaptopropyltrimethoxysilane (HS-PTMS) were used as starting materials. .sup.29Si NMR analysis confirmed that the product contained less than 4% of total T.sup.0-monomer and 4% of total D.sup.0-monomer measured by the total amount of T-type and D-type moieties, respectively and less than 24% of Q-type tetrasiloxane ring species.

    Example 13b: Synthesis of Ethylsilicate-40/(HS-PTMS:DMDCS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.15:0.05)

    [0345] A procedure identical to the one described in Example 13 was used to prepare this material, with the key differences that a precursor material prepared according to Example 9 h was used as starting material. .sup.29Si NMR analysis confirmed that the product contained less than 6% of total T.sup.0-monomer and 3% of total D.sup.0-monomer measured by the total amount of T-type and D-type moieties, respectively and less than 26% of Q-type tetrasiloxane ring species.

    Example 14: Synthesis of TEOS (Oligomer)/(VTES:HMDSO) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.M-type.)=1:(0.25:0.26)

    [0346] A procedure identical to the one described in Example 10 was used to prepare this material, with the key differences that a Q-type precursor material prepared according to Example 9d and 3-Mercaptopropyltrimethoxysilane (HS-PTMS) was used as starting materials and in a higher molar amount (1:0.25 targeted Q-type to T-type molar Si ratio) during the second reaction step b). During the first reaction step a), a 5-fold molar excess of HMDSO with respect to the desired Q-type to M-type molar Si ratio was used and the first reaction step was carried out at 105° C. for 4 h. .sup.29Si NMR analysis confirmed that the product contained less than 19% of total T.sup.0-monomer measured by the total amount of T-type moieties and less than 17% of Q-type tetrasiloxane ring species.

    Example 15: Synthesis of TEOS (Oligomer)/(VTES:MTMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.30:0.12)

    [0347] A procedure identical to the one described in Example 6 was used to prepare this material, with the key differences that a precursor material prepared according to Example 9e and Vinyltriethoxysilane (VTES) as well as Methyltrimethoxysilane (MTMS) were used as Q-type and T-type starting materials, respectively. Oxo-titanium(IV)diacetylacetonate was used as the rearrangement catalyst. .sup.29Si NMR analysis confirmed that the product contained less than 9% of combined T.sup.0-monomers measured by the total amount of T-type moieties and less than 22% of Q-type tetrasiloxane ring species.

    Example 16: Synthesis of TEOS/(APTES+MTMS+PTES) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.20+0.05+0.05)

    [0348] A procedure identical to the one described in Example 6 was used to prepare this material, with the key differences that a precursor material prepared according to Example 9d made from TEOS and 3-Aminopropyltriethoxysilane (APTES), Methyltrimethoxysilane (MTMS) as well as Propyltriethoxysilane (PTES) were used as Q-type and first, second and third T-type starting materials, respectively. A mixture of Zr(IV)ethoxide and Ti(IV)n-propoxide was used as the rearrangement catalyst. .sup.29Si NMR analysis confirmed that the product contained less than 7% of combined T.sup.0-monomers measured by the total amount of T-type moieties and less than 16% of Q-type tetrasiloxane ring species.

    Example 16b: Alternative Synthesis of TEOS/(APTES+MTMS+PTES) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.20+0.05+0.05)

    [0349] A procedure identical to the one described in Example 16 was used to prepare this material, with the key differences that some amount/s of at least one of the three T-type precursors was/were already included during the preparation of the precursor material according to Example 9d, analogous to the acetic anhydride, non-hydrolytic precursor co-condensation route described in Example 6c. A O═Ti(IV)(SCN).sub.2 and O═Zr(IV)(OAc).sub.2 mixture was used as rearrangement catalyst. .sup.29Si NMR analysis confirmed that the product contained less than 5% of combined T.sup.0-monomers measured by the total amount of T-type moieties and less than 20% of Q-type tetrasiloxane ring species.

    Example 16c: Alternative Synthesis of TEOS/(APTES+MTMS+PTES) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.20+0.05+0.05)

    [0350] A procedure identical to the one described in Example 16b was used to prepare this material, with the key differences that some amount/s of at least one of the three T-type trialkoxysilane precursors that have been included in the preparation of the precursor material according to the described modified process inspired by Example 9d, had been replaced by Trichlorosilane counterparts. .sup.29Si NMR analysis confirmed that the product contained less than 9% of combined T.sup.0-monomers measured by the total amount of T-type moieties and less than 23% of Q-type tetrasiloxane ring species.

    Example 16d: Alternative Synthesis of TEOS/(APTES+MTMS+PTES) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:(0.20+0.05+0.05)

    [0351] A procedure identical to the one described in Example 16 was used to prepare this material, with the key differences that APTES was first grafted onto the Q-type precursor material prepared according to Example 9d in a first rearrangement protocol. For this, the equivalent amounts of the Q-type and first T-type precursor, respectively, was heated to 125° C. and reacted for 4 hours in the presence of (EtO).sub.2Zr(IV)(OAcAc).sub.2 as a catalyst. The reaction mixture was then allowed to cool to a temperature of 90° C. at which point, Methyltrimethoxysilane (MTMS) as well as Propyltriethoxysilane (PTES) were then added as second and third T-type precursor. The mixture was then allowed to react for an additional 26 h at that temperature. .sup.29Si NMR analysis confirmed that the product contained less than 14% of combined T.sup.0-monomers measured by the total amount of T-type moieties and less than 22% of Q-type tetrasiloxane ring species.

    Example 17: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.4 from Tetramethoxysilane or its Oligomers

    [0352] Analogous to Example 9, Tetraethoxysilane (TMOS) in monomeric or oligomeric form was hydrolyzed in the presence of a cosolvent according to the state of the art with a water stoichiometry amount required to achieve a desired degree of polymerization of the precursor material DP_Q.sub.type=2.4 using a standard hydrolysis/condensation catalyst. Once the hydrolysis was completed, excess cosolvent and alcohol released during the hydrolysis were removed by vacuum distillation. .sup.29Si NMR analysis revealed 53.0% of Q-type tetrasiloxane ring species in the precursor material.

    Example 18: Synthesis of TEOS (Oligomer)/(TESPT:VTES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.M-type.)=1:(0.17:0.06)

    [0353] 242.6 g of crude precursor from Example 17 were placed inside a 500 ml glass cylinder with cap. Next, 185.8 g/0.44 mol of a first T-type precursor Bis(triethoxysilylpropyl)tetrasulfide (TESPT) and 23.1 g/0.16 mol of a second T-type precursor vinyltriethoxysilane (VTES) was added together with a bis-acetylacetonato-titanium(IV)-diisopropoxide rearrangement catalyst. The mixture was heated to 75° C. and was kept stirring for a period of 6 days. Residual solvent was removed by pulling a 100 mbar vacuum for 30 minutes. .sup.29Si NMR analysis confirmed that the product contained less than 44% T.sup.0-monomer measured by the total amount of T-type moieties as well as less than 29.2% of Q-type tetrasiloxane ring species.

    Example 19: Preparation of a Mixed Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.28 from Tetramethoxysilane (TMOS) and Tetraethoxysilane (TEOS)

    [0354] 511 g/2.66 mol Si of tetramethoxysilane (TMOS) and 277 g/1.33 mol Si of tetramethoxysilane (TEOS) and Zirconium(IV)-isobutoxide catalyst were placed inside a 1 L round bottom flask with distillation bridge. In other words, the relative molar ratio of TMOS to TEOS monomer used was 2:1. The flask was purged with nitrogen, sealed, and left under nitrogen pressure (balloon) and immersed into a hot oil bath which was kept at 130° C. The Q-Type monomer/catalyst mixture was brought to temperature with stirring at 500 rpm. Once the temperature has been reached, a selected amount (465.3 g/4.56 mol) acetic anhydride was added in portions. Refluxing of the reaction byproduct ethyl acetate occurred rather quickly. After approximately 8 minutes, a continuous stream of methyl acetate and ethyl acetate was distilling over through the distillation bridge and collected in the capture vessel. The reaction continued for a total time of about 70 more minutes, at which point it stopped, commensurate with the ceasing of the methyl/ethyl acetate distilling over. The collection vessel was removed after a total reaction time of 1 h and 25 minutes and emptied, yielding a total mass of 725 g of collected condensate and 465 g of Q-type precursor. .sup.29Si NMR analysis confirmed that the precursor had a DP_Q.sub.type of 2.22 and 51.0% Q-type tetrasiloxane ring species.

    Example 20: Synthesis of TEOS/(APTMS:DMDMS) Polycondensate Material with n.SUB.Q-type.:n.SUB.T-type .1:n.SUB.D-type .1:(0.20:0.10)

    [0355] 310 g of crude precursor from Example 19 were placed inside a 1 L round bottom flask together where after 0.27 mol (Si basis) of a T-type precursor 3-aminopropyltrimethoxysilane in oligomer form (oligo-APTMS) and 16.0 g/0.13 mol of a D-type precursor dimethyldimethoxysilane (DMDMS) were added together without additional rearrangement catalyst other than the amount already present in the Q-type precursor from Example 19. The mixture was heated to a temperature of 110° C. and was kept stirring for a period of 29 hours, at which point any residual solvent was removed by pulling a 250 mbar vacuum for 5 minutes and nitrogen was bubbled through the reaction mixture for a period of 15 minutes to remove additional VOC. .sup.29Si NMR analysis confirmed that the product contained less than 7% of total T.sup.0-monomer and 22% of total D.sup.0-monomer measured by the total amount of T-type and D-type moieties, respectively as well as less than 25% of Q-type tetrasiloxane ring species.

    Example 21: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=1.52 from a Mixture of Tetramethoxysilane (TMOS) and Tetraethoxysilane (TEOS)

    [0356] A mixture consisting of Tetramethoxysilane (TMOS) and Tetraethoxysilane (TEOS) in a 20% to 80% molar ratio were hydrolyzed in the presence of a cosolvent according to the state of the art with a water stoichiometry amount required to achieve a desired degree of polymerization of the precursor material DP_Q.sub.type=1.52 using a standard hydrolysis/condensation catalyst. Once the hydrolysis was completed, excess cosolvent and alcohol released during the hydrolysis were removed by vacuum distillation. .sup.29Si NMR analysis revealed 35.7% of Q-type tetrasiloxane ring species in the precursor material.

    Example 22: Synthesis of a TMOS+TEOS/(tFPTMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.)=1:0.07

    [0357] An amount containing 1.92 mol Si equivalent of a mixed Methoxy/Ethoxy terminated Q-type precursor prepared according to Example 21 was filled into a 500 ml round bottom which in turn was placed inside a resistive heating mantle and set to a temperature of 95° C. Next, 29.3 g/0.13 mol of a monomer T-type precursor (3,3,3 trifluoropropyl)-trimethoxysilane (tFPTMS) and Ti(IV)-tetraethoxide (TEOT) catalyst were added. The mixture kept at 95° C. with stirring for an additional 19 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 18% T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 24% of Q-type tetrasiloxane ring species.

    Example 23: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.0 from Tetraethoxysilane (TEOS) by Means of the Silanol Method

    [0358] Sodium triethoxysilanolate was first prepared by mixing 1 g (3.5 mol) pulverized sodium hydroxide with a solution of 728 g (3.5 mol) tetraethoxysilane in 1.3 l of toluene at 5° C. with stirring. After 2 h at temperature, the solvent phase consisting of toluene and ethanol produced during the reaction were distilled under vacuum. The oily residue was dried overnight in a vacuum drying chamber at 50 mbar and 40° C., yielding 628 g of crude product.

    [0359] A solution of sodium triethoxysilanolate from the above step in toluene was prepared from 322 g of the crude product by filling it up with toluene to a total volume of 1800 ml in a 31 round bottom flask. This solution was added dropwise to a solution of a stoichiometric amount of acetic acid in 1 l of toluene at 0° C., again with vigorous stirring. The amount of acetic acid for stoichiometric consumption was calculated based on the theoretical formula of the sodium triethoxysilanolate and assuming 100% purity of the crude product. After filtering off the precipitated sodium acetate and washing with toluene, residual solvent (primarily toluene) was again removed by distillation from the combined reaction mixture and sodium acetate washing liquids at 45° C. and <15 mbar absolute pressure. The product yield was 133.9 g of a yellowish liquid which was identified as triethoxysilanol. The final polyethoxysiloxane Q-type precursor was then synthesized by adding the obtained triethoxysilanol (133.9 g) to a water free solution of 22.5 g ammonia (dried over sodium hydroxide pellets) dissolved in 100 ml absolute ethanol over a period of 90 minutes at −30° C. After allowing the mixture to warm to room temperature, the reaction mixture was left standing over night where after residual ammonia and ethanol were again removed by vacuum distillation followed by 10 minutes of nitrogen purge gas bubbling distilled off to give 102.7 g of a yellow polyethoxysiloxane Q-type precursor material. .sup.29Si NMR analysis of the precursor material revealed 45% of Q-type tetrasiloxane ring species.

    Example 24: Synthesis of a TEOS/(VTES+MTMS:TMMS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.M-type.)=1:(0.1+0.05:0.1)

    [0360] An amount containing 1.92 mol Si equivalent of a mixed Methoxy/Ethoxy terminated Q-type precursor prepared according to Example 21 was filled into a 500 ml round bottom which in turn was placed inside a resistive heating mantle and set to a temperature of 90° C. Next, 36.5 g/0.19 mol of a first monomer T-type precursor vinyltriethoxysilane (VTES) and 13.1 g/0.1 mol of a second monomer T-type precursor methyltrimethoxysilane (MTMS) as well as Ti(IV)-bromide rearrangement catalyst were added. The mixture was heated to and kept at 110° C. with stirring for 8 hours, whereafter the temperature was again lowered to 90° C. and 20.0 g/0.19 mol of an M-type precursor trimethyl-methoxysilane (TMMS) was dosed over the course of half an hour to the reaction mixture. The mixture was then kept stirring for an additional 12 hours at 90° C. and removed from the heating source. .sup.29Si NMR analysis confirmed that the product contained less than 14% of T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 24% of Q-type tetrasiloxane ring species.

    Example 25: Preparation of a Q-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.1 from a Mixture of Tetraethoxysilane (TEOS) and Silicon Tetrachloride (SiCl.SUB.4.) by Means of the “Chloride Route”

    [0361] A mixture containing Tetraethoxysilane (TEOS) and silicon tetrachloride in 2:1 molar ratio were heated up inside a closed autoclave vessel to a temperature of 145° C., at which point, 0.75% of zirconium tetrachloride (ZrCl.sub.4) was added as a condensation catalyst. The mixture was kept stirring under inert gas atmosphere. After 21 h, the reaction was stopped and the mixture was brought to room temperature, whereafter ethyl chloride as a side product and residual volatiles were removed by distillation. The Q-type polycondensate material was a slightly yellowish liquid which was collected following the workup and analyzed. .sup.29Si NMR analysis revealed 51.5% of Q-type tetrasiloxane ring species in the precursor material.

    Example 25b: Alternative Preparation of a Q-Type/D-Type Polycondensate Precursor Material with a Targeted DP_Q.SUB.type.=2.0 and DP_D.SUB.type.=1.75 from a Mixture of Tetraethoxysilane (TEOS), Silicon Tetrachloride (SiCl.SUB.4.) and Diphenyldichlorosilane (DPhDCS) by Means of the “Chloride Route” with n.SUB.Q-type.:n.SUB.D-type.=1:0.05

    [0362] A procedure comparable to Example 25 was used to prepare the mixed Q-Type/D-type precursor material. Alternatively, Tetramethoxysilane (TMOS), Silicon Tetrachloride and Diphenyldichlorosilane (DPhDCS) in a 1.95:0.94:0.05 molar ratio were used as starting materials. The reaction was carried out at 135° C. for 25 h with 0.9% Zirconium(IV) tetraacetate as a condensation catalyst. The mixed Q-type/D-type polycondensate material was a slightly yellowish liquid which was collected upon cooling, depressurization of the autoclave as well as workup and analyzed. .sup.29Si NMR analysis revealed 48.6% of Q-type tetrasiloxane ring species in the precursor material.

    Example 26: Synthesis of a TEOS/(PhTES+PTMS:DPhDES) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.10+0.05:0.05)

    [0363] An amount containing 4.5 mol Si equivalent of a Q-type precursor prepared according to Example 25 was placed inside a stirred glass reactor (Buchi versoclave, 11) 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 propyltrimethoxysilane (PTMS) were charged into the reactor 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 13 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 26% T.sup.0-monomer and less than 16% of D.sup.0-monomer measured by the total amount of T-type and D-type moieties respectively as well as less than 26.9% of Q-type tetrasiloxane ring species.

    Example 26b: Alternative Synthesis of a TEOS/(PhTES+PTMS: DPhDCS) Polycondensate Material with n.SUB.Q-type.:(n.SUB.T-type.:n.SUB.D-type.)=1:(0.10+0.05:0.05)

    [0364] A procedure comparable to Example 26 was used to prepare the material, with the difference, that an alternatively prepared mixed Q-type/D-type precursor material was used. Consequently, during the preparation, no additional D-type monomer needed to be added, but only PhTES and PTMS were added to the precursor material. All other steps and reagents were left unchanged. .sup.29Si NMR analysis confirmed that the product contained less than 23% 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 27.2% of Q-type tetrasiloxane ring species.

    Example 27: Efficiency Testing for Potential Rearrangement Catalysts

    [0365] 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 n.sub.Q-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)-chloride 2.18 1.41 5.6 33.8 0.65 Yes Ti(IV)- 2.08 1.65 5.8 24.6 52.0 Yes isopropoxide Zn(II)-chloride 2.19 0.64 41.2 50.9 81.3 No 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 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.

    Example 28: Hydrolysis of a Polymeric Liquid Material

    [0366] 40 g of Ethanol and 29.3 g of a crude reaction product from Example 3j were mixed and heated to 40° C. in an Erlenmeyer flask with stirring. Once the temperature had equilibrated, 4 ml of a 0.1 M methanesulfonic acid solution was added followed by 3 ml of distilled water. After a brief mixing step (magnetic stirrer), the solution was transferred into a glass bottles with hermetically sealing cap and kept in an oven at 40° C. for 16 hours. The final hydrolysis product was then filtered and stored in the refrigerator.

    Example 29: Preparation of a Water in Oil Emulsion

    [0367] 228 g of a sample of a material sample of Example 3k was mixed with 600 ml of distilled water and 50 g of a surfactant (Tween20) were added. The two-phase system was then vigorously stirred using a mechanical impeller stirrer at 35° C. for 1 h. The resulting emulsion was a low-viscous stable emulsion with a shelf life of several weeks without noticeable settling effects.

    Example 30: Preparation of an Oil in Water Emulsion

    [0368] 90 g of a sample of a material sample of Example 4k was mixed with 34.5 ml distilled water and 2.2 g of sodium dodecyl sulfate (SDS). The two-phase system was then homogenized using a high-rpm mechanical homogenizer. The resulting emulsion was a creamy paste, which had a shelf life of several weeks when kept in a tightly sealed container.