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

20230097589 · 2023-03-30

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention pertains to a branched polymeric liquid poly siloxane 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 significant amount of four-membered Q2-type and/or Q3-type siloxane ring species relative to the total Q-type siloxane species, and is optionally 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: ##STR00026## (ii) optionally tri-organofunctional M.sup.1-type siloxane moieties selected from the group consisting of: ##STR00027## (iii) optionally di-organofunctional D-type siloxane moieties selected from the group consisting of: ##STR00028## and (iv) mono-organofunctional T-type siloxane moieties selected from the group consisting of: ##STR00029## wherein custom-characterindicates 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, —CH.sub.2—CH.sub.2—Cl, 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, ##STR00030## 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, ##STR00031## wherein R.sup.7 is selected from the group consisting of methyl, ethyl, and n-butyl; R.sup.5S is selected from the group consisting of ##STR00032## ##STR00033## 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.1′, 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 ##STR00034## ##STR00035## wherein X is absent, —(NH)—, or —O—; R.sup.10 is selected from the group consisting of ##STR00036## ##STR00037## 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, 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 ##STR00038## 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 0.9 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 more than 0.25 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; 0 mol-% or at least 1 mol % of all R.sup.5 moieties in the material are R.sup.5S moieties; wherein the polysiloxane material comprises more than 25 mol-% four-membered combined Q.sup.2r-type and Q.sup.3s,d-type siloxane ring species relative to the total Q-type siloxane species; and/or the polysiloxane material comprises more than 50 mol-% four-membered combined Q.sup.3s,3d-type siloxane ring species relative to all Q.sup.3-type siloxane species; and/or the polysiloxane material comprises more than 3.0 mol-% double four-membered Q.sup.3d-type siloxane ring species relative to the total Q-type siloxane species; and/or the polysiloxane material comprises more than 14 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 at least 1 mol % of all R.sup.5 moieties in the material are R.sup.5S moieties; 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 ##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), 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 2, 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 groan consisting of ##STR00042## ##STR00043## R.sup.10 is selected from the group consisting of ##STR00044## 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 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 n-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 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 (iii) the degree of polymerization of the T-type siloxane moieties DP.sub.T-type is in the range of 1.2 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 mono-organofunctional T-type siloxane moieties comprise (i) a first population of mono-organofunctional T-type siloxane moieties, wherein R.sup.5 is selected from the group consisting of methyl, ethyl, 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, and either (a) a second population of mono-organofunctional T-type siloxane moieties, wherein R.sup.5 is selected from the group consisting of methyl, ethyl, 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, wherein the R.sup.5 groups of the first and second populations are not identical, (b) mono-organofunctional T-type siloxane moieties, wherein R.sup.5 is L-Z, vinyl, ##STR00045## or (c) mono-organofunctional T-type siloxane moieties, wherein R.sup.5 is R.sup.5S.

    8. 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.

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

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

    11. The method according to claim 22, wherein at least 1 mol %, of all R.sup.5 moieties in the material are R.sup.5S moieties, the method 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.

    12. The method according to claim 22, 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 condensation catalyst; wherein degree of polymerization of the Q-type poly siloxane DP.sub.Q-type is in the range of 1.5 to 2.7; and wherein the Q-type polysiloxane comprises more than 3 mol-% silanol groups (Si—OH); (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 condensation 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 condensation catalyst is present in at least one of steps (a) or (c).

    13. The method according to claim 22, 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 condensation catalyst; wherein degree of polymerization of the Q-type polysiloxane DP.sub.Q-type is in the range of 1.0 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); and/or (b2) di-organofunctional D-type silane Si(OR.sup.1).sub.2(R.sup.2)(R.sup.3); and/or (b3) mono-organofunctional T-type silane Si(OR.sup.1).sub.3(R.sup.5), wherein R.sup.5 is selected from R.sup.5U and R.sup.5S; in mono- or oligomeric form to the polysiloxane of (a); (c) optionally adding a condensation catalyst to the mixture of step (b); (d) heating the mixture of (c) in the presence 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 condensation catalyst is present in at least one of steps (a) or (c).

    14. The method according to claim 12, 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.

    15. The method according to claim 12, 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).

    16. The method according to claim 12, 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.

    17. The method according to claim 12, wherein the reaction temperature for steps (c) through (e) is in the range from 30 to 170, and the pressure during steps (c) through (e) is in the range of 0.1 bar to 2 bar.

    18. The method according to claim 1, wherein the condensation catalyst is an acid selected from the group consisting of Bronsted acids and Lewis acids; inorganic mineral acids; organic acids; acidic metal ion salts, optionally transition metal ions salts; acids with a pKa value below 4 or with a negative pKa value; and acid-releasing compounds, chlorosilanes, monochloro-, dichloro- or trichlorosilanes; wherein the catalyst amount in each of steps (a) or (c) is optionally between 0.005 and 5 mol % with respect to the total molar silicon content present in said step.

    19. (canceled)

    20. 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, ##STR00046## 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.

    21. The polymeric liquid material according to claim 8, 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.

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

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0248] The following Figures and Examples serve to illustrate the invention and are not intended to limit the scope of the invention as described in the appended claims. If not mentioned otherwise, the term “tetrasiloxane ring species” in these examples refers to the sum of all Q.sup.2 and Q.sup.3 tetrasiloxane ring species with respect to the total amount of Q species in the material.

    [0249] FIGS. 1a and 1b. FIG. 1a shows exemplary 2D molecular structure representations of a typical pure Q-type precursor material or core in a general case (FIG. 1a) (DP.sub.Q-type=2.15, OH/Si=0.1) with roughly 5.5% silanol groups, and in one more specific case with primarily ethoxy also silanol groups (approximately 11%) present (FIG. 1b) (DP.sub.Q-type=2.15, OH/Si=0.2).

    [0250] FIGS. 2a, 2b, and 2c 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. Note that the R.sup.5 ligands on the T-type moieties may comprise both unsubstituted R.sup.5U and substituted R.sup.5S functionalities. Furthermore, the two specialized cases are illustrated with idealized compounds featuring only unsubstituted vinyl: —CH═CH.sub.2 (FIG. 2b) and in the case of two T-type grafts containing a first R.sup.5U=Me and a second partially substituted Mercaptopropyl T-type population with R.sup.5U=Mp and R.sup.5S=—CH.sub.2CH.sub.2CH.sub.2—S—R.sup.1° functionalities. The representations are for illustration purposes only and do not represent any limitation in further D, M-Type or T-type (R.sup.5U, R.sup.5S) substitution and grafting combination options.

    [0251] FIG. 3 shows a .sup.29Si NMR spectrum of a material prepared from an ethoxy-based Q-type and an ethoxy-based T-type precursor featuring still significant amounts of silanol groups e.g. (Q.sup.1.sub.(1,2), Q.sup.2.sub.(1,1), Q.sup.3.sub.(1,0) peaks) in the amount >5% and >51% Q-type tetrasiloxane ring species.

    [0252] FIG. 4 shows an a .sup.29Si NMR spectrum of a material obtained by grafting a precursor material with a spectrum given in FIG. 3 above and >5% silanol groups with 15% mol of methyltriethoxy-silane (MTES) measured by the total amount of Q-type moieties in said precursor with 1000 ppm nitric acid. The corresponding material has a silanol content of >3% and >52% Q-type tetrasiloxane ring species, illustrating that the condensation grafting effectively lowers the silanol content.

    [0253] FIG. 5 shows a .sup.29Si NMR spectrum of a material prepared from an ethoxy-based Q-type precursor a higher initial silanol content of >8% essentially and grafting 15% mol of methyltriethoxy-silane (MTES) measured by the total amount of Q-type moieties in said precursor with 1000 ppm nitric acid. The corresponding material has a silanol content of >4% and >51% Q-type tetrasiloxane ring species. The corresponding silanol species Q.sup.1(1,2) Q.sup.2(1 1) Q.sup.2(1,0) are marked in the spectra for clarity.

    [0254] FIG. 6 shows a .sup.29Si NMR spectrum of a material prepared from an ethoxy-based Q-type precursor which was essentially free of silanol groups and 15% mol of methyltriethoxy-silane (MTES) measured by the total amount of Q-type moieties in said precursor with 1000 ppm nitric acid was grafted with additional water addition. The corresponding material has a silanol content of >2% and >51% Q-type tetrasiloxane ring species

    [0255] FIG. 7 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 methyltriethoxysilane (MTES) and vinyltriethoxysilane (VTES). Individual moieties belonging to the methyl (Me) and isobutyl (iB) R.sup.5-functional T-type subpopulations can be clearly spectrally resolved and are labelled for clarity.

    [0256] FIG. 8 shows a .sup.29Si NMR spectrum of a material made from a TEOS Q-type and featuring T-type and D-type moieties with their respective signatures labelled for clarity.

    [0257] FIG. 9 shows a .sup.29Si NMR spectrum of a material made from a TEOS Q-type and featuring T-type D-type and M-type moieties with their respective signatures labelled for clarity.

    [0258] FIGS. 10a, 10b, 10c, and 10d show the substitution reaction monitoring by means of .sup.1H NMR spectra of the various intermediates used in the preparation of a substituted Q-T polysiloxane material. The various spectra show the unsubstituted (R.sup.5U=—CH.sub.2CH.sub.2CH.sub.2—NH.sub.2) T.sup.0T-type silane APTES (top), a reference spectrum of the organic substrate used for R.sup.5S-functionalization hexanediol-diacrylate (HDDA, FIGS. 10a and 10b), the HDDA-substitution product with APTES constituting a functionalized R.sup.5S bearing T.sup.0 monomer used later for condensation grafting (FIG. 10c) and finally the polysiloxane material featuring said grafted R.sup.5S-bearing T-type moieties (FIG. 10d).

    [0259] FIGS. 11a, 11b, 11c, and 11d show the substitution reaction monitoring by means of .sup.13C NMR spectra of the various intermediates used in the preparation of a substituted Q-T polysiloxane material. The various spectra show the unsubstituted (R.sup.5U=—CH.sub.2CH.sub.2CH.sub.2—NH.sub.2) T.sup.0T-type silane APTES (FIG. 11a), a reference spectrum of the organic substrate used for R.sup.5S-functionalization hexanediol-diacrylate (HDDA, FIG. 11b), the HDDA-substitution 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).

    DETAILED DESCRIPTION OF THE INVENTION

    EXAMPLES

    [0260] 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.

    Example 1

    [0261] 666.5 g/5.22 mol Si equivalent of a commercial ethylsilicate Q-type precursor “Dynasylan Silbond 50” (Evonik Industries) was placed inside a 1000 ml round bottom and heated via electric heating mantle to a temperature of 85° C. Next, 63.2 g/0.385 mol of a monomeric T-type precursor Propylrimethoxysilane (PTMS) was added followed by 0.88 ml of a 1M nitric acid condensation catalyst solution. The mixture was then kept stirring for 24 hours, at which point the heating source was turned off and the mixture allowed to cool to room temperature. .sup.29Si NMR analysis confirmed that the product contained less than 14% T.sup.0-monomer measured by the total amount of T-type moieties and more than 45% of Q-type tetrasiloxane ring species and >1.1% of Q-type silanol species right after the synthesis.

    Example 1b

    [0262] A material identical to the one described in Example 1 was prepared with the difference that the catalyst used was sulfuric acid and 0.15 ml of a 1M solution was added and that the reaction time was 65 hours. The product contained less than 8% T.sup.0-monomer measured by the total amount of T-type moieties and more than 47% of Q-type tetrasiloxane ring species and more than 77% of combined Q.sup.30d-type siloxane ring species relative to all Q.sup.3-type siloxane species in the material. The total Q-type silanol species concentration right after the synthesis was >0.8%.

    Example 1c

    [0263] A material identical to the one described in Example 1 was prepared with the sole difference that in addition to the Propyltrimethoxysilane, also a D-type silane Divinyldimethoxysilane (DVDMS 27.4 g/0.19 mol) was added to the Q-type precursor. The product contained less than 11% T.sup.0-monomer measured by the total amount of T-type moieties and more than 48% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >1.2%.

    Example 1d

    [0264] A material identical to the one described in Example 1c was prepared with the sole difference that the D-type silane used was Divinylchlorosilane (DVDMS 27.4 g/0.19 mol) which is a hydrochloric acid releasing silane. Consequently, no additional condensation catalyst (Nitric acid 1M) was added was added together with the T- and D-type silanes. The product contained less than 6% T.sup.0-monomer measured by the total amount of T-type moieties and more than 48% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >0.6%.

    Example 2

    [0265] 1150 g/7.86 mol Si equivalent of a commercial ethylsilicate Q-type precursor “Wacker Silicate TES 40 WN” (Wacker) was placed inside a 21 round bottom flask. Next, 210.2 g/1.18 mol of a monomeric T-type precursor Methyltriethoxysilane (MTES) was added followed by a sulfuric acid condensation catalyst in an amount to make up a concentration of 1000 ppm in the total mixture. During heating of the mixture to 75° C., 36.0 g/2.0 mol of water diluted into 150 ml ethanol were added to the reaction mixture slowly. The mixture was then kept stirring for 48 hours, at which point residual alcohol was removed by vacuum distillation and the mixture allowed to cool to room temperature. .sup.29Si NMR analysis confirmed that the product contained less than 2% T.sup.0-monomer measured by the total amount of T-type moieties and more than 51% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >3.7%.

    Example 2b

    [0266] A material identical to the one described in Example 2 was prepared, however after the reaction was complete and before vacuum distillation, a second T-type silane precursor bis-[3-(triethoxysilyl)propyl]tetrasulfide (64.7 g/0.12 mol) were added to the mixture and kept stirring at temperature for an additional 20 hours. The product contained less than 9% T.sup.0-monomer measured by the total amount of T-type moieties and more than 49% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >2.0%.

    Example 2c

    [0267] A material identical to the one described in Example 2b was prepared, however instead of a second T-type silane (TESPT), an M-type silane precursor hexamethyldisiloxane (HMDSO, 152.7 g/0.94 mol) was added during the second condensation step. The product contained less than 19% T.sup.0-monomer measured by the total amount of T-type moieties and more than 44% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >1.4%.

    Example 2d

    [0268] A material identical to the one described in Example 2b was prepared, however 33.7 g/0.15 mol of isobutyltriethoxysilane was added as the second silane (instead of TESPT) together with 16.1 g/0.13 mol of a D-type silane precursor dimethyldimethoxysilane (DMDMS). The product contained less than 16% T.sup.0-monomer measured by the total amount of T-type moieties and more than 46% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >1.4%.

    Example 2e

    [0269] A material identical to the one described in Example 2d was prepared, with the sole difference that during the second condensation step in addition to T-type and D-type silane precursor, also 15.8 g/0.13 mol of an M-type silane precursor trimethylethoxysilane (TMES) were added. The reaction time for the second condensation step was increased from 20 h (example 2b) to 32 hours. The product contained less than 18% T.sup.0-monomer measured by the total amount of T-type moieties and more than 48% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >1.5%.

    Example 3

    [0270] 225 g/2.33 mol Si equivalent of an ethylsilicate Q-type precursor prepared by hydrolysis and condensation of TEOS with a degree of polymerization DP Q-type of 2.27 and 10.5% of Q-type silanol content was placed inside a 500 ml Pyrex glass bottle with tight sealing cap. Next, 63.2 g/0.44 mol of a monomeric T-type precursor Phenyltriethoxysilane (PhTES) was added followed by 3 ml of a 0.2M ethanolic trifluoroacetic acid condensation catalyst solution. The mixture was homogenized and the flask with tightly sealed cap was placed inside a heating cabinet at 100° C. for 28 hours. Residual volatiles were then removed on a standard laboratory rotary evaporator. .sup.29Si NMR analysis confirmed that the product contained less than 7% T.sup.0-monomer measured by the total amount of T-type moieties and more than 51% of Q-type tetrasiloxane ring species and >2.6% of Q-type silanol species right after the synthesis.

    Example 3b

    [0271] A material identical to the one described in Example 3 was prepared, yet, additionally an M-type silane precursor trimethylethoxysilane (TMES, 22.1 g/0.19 mol) was added together with the T-type silane and the homogenized mixture was split up into 8 teflon microwave tubes. The reaction was then carried out in a microwave reactor at a set temperature of 125° C. in a series of 12 repeating microwave heating cycles of 30 minutes each followed by a cooldown period. After removal of volatiles on a rotary evaporator, the final product contained less than 12% T.sup.0-monomer measured by the total amount of T-type moieties and more than 41% of Q-type tetrasiloxane ring species. The total Q-type silanol species concentration right after the synthesis was >1.8%.

    Example 3c

    [0272] A material identical to the one described in Example 3 was prepared with the differences that the Q-type precursor material was derived from Tetramethoxysilane (TMOS) and had a DP-value of 2.03 and that it also contained an amount of 0.13 mol of co-condensated T-type precursor 3-azidopropyl-trimethoxysilane. .sup.29Si NMR analysis confirmed that the product contained less than 8% T.sup.0-monomer measured by the total amount of T-type moieties and more than 43% of Q-type tetrasiloxane ring species and >2.0% of Q-type silanol species right after the synthesis.

    Example 3d

    [0273] A material identical to the one described in Example 3 was prepared with the differences that the Q-type precursor material was derived from a mixture of Ethylsilicate 40 and tetrapropoxysilane (TPOS) with a molar ratio of Si from ethoxy-terminated to propoxy-terminated of 6.3:1 and had a DP-value of 1.97 and that it also contained an amount of 0.41 mol of co-condensated T-type precursor 3-glycidoxypropyl-trimethoxysilane. .sup.29Si NMR analysis confirmed that the product contained less than 11% T.sup.0-monomer measured by the total amount of T-type moieties and more than 45% of Q-type tetrasiloxane ring species and >2.0% of Q-type silanol species right after the synthesis.

    Example 3e

    [0274] A material identical to the one described in Example 3 was prepared with the difference that after the first T-type silane (PhTES) condensation, an M-type silane Hexamethyldisiloxane (HMDSO, 58.2 g/0.36 mol) was also grafted in a second step, over the course of 22 hours at 100° C. in the same heating cabinet. .sup.29Si NMR analysis confirmed that the product contained less than 8% T.sup.0-monomer measured by the total amount of T-type moieties and more than 43% of Q-type tetrasiloxane ring species and >1.9% of Q-type silanol species right after the synthesis.

    Example 3f

    [0275] A material identical to the one described in Example 3e was prepared with the differences that during the second HMDSO condensation grafting step, a D-type precursor (diphenyldimethoxy-silane, DPhDMS, 57.6 g/0.24 mol) was also cocondensated together with the HMDSO. The process conditions for the second condensation were otherwise left unchanged. .sup.29Si NMR analysis confirmed that the product contained less than 10% T.sup.0-monomer measured by the total amount of T-type moieties and more than 44% of Q-type tetrasiloxane ring species and >1.7% of Q-type silanol species right after the synthesis.

    Example 3g

    [0276] A material identical to the one described in Example 3f was prepared with the differences that during the second HMDSO/DPhDMS condensation grafting step, a mixture of 3.8 g of water in 45 ml of absolute methanol was added and the resulting mixture briefly homogenized. The process conditions for the second condensation were otherwise left unchanged. .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 and more than 46% of Q-type tetrasiloxane ring species and >3.2% of Q-type silanol species right after the synthesis.

    Example 3h

    [0277] A material identical to the one described in Example 3 was prepared with the difference in a condensation grafting step, a prehydrolysate of dimethyldiethoxysilane (DMDES, 0.11 mol total Si), which had been previously been prepared by controlled hydrolysis of the monomer in ethanolic solution with a DP D-type=0.94 was used. The process conditions for the second condensation were otherwise left unchanged. .sup.29Si NMR analysis confirmed that the product contained less than 8% T.sup.0-monomer measured by the total amount of T-type moieties and more than 50% of Q-type tetrasiloxane ring species and >1.5% of Q-type silanol species right after the synthesis.

    Example 3i

    [0278] A material identical to the one described in Example 3 was prepared with the difference that the T-type precursor used was 3-mercaptopropyl-trimethoxysilane (MPTMS) in oligomercic form with a DP-T.sub.type of 1.06 (before the condensation reaction) which had previously been prepared by controlled hydrolysis of the T-type monomer MPTMS in ethanolic solution. .sup.29Si NMR analysis confirmed that the product contained less than 4% T.sup.0-monomer measured by the total amount of T-type moieties and more than 48% of Q-type tetrasiloxane ring species and >1.5% of Q-type silanol species right after the synthesis.

    Example 3j

    [0279] A material identical to the one described in Example 3 was prepared with the sole difference that a different Q-type precursor was used which had previously been prepared by controlled hydrolysis of tetrapropoxysilane (TPOS) which had a DP-Q.sub.type value of 1.79 (before the condensation grafting reaction). with a NMR analysis confirmed that the product contained less than 18% T.sup.0-monomer measured by the total amount of T-type moieties and more than 39% of Q-type tetrasiloxane ring species and >1.5% of Q-type silanol species right after the synthesis.

    Example 3k

    [0280] A material identical to the one described in Example 3 was prepared with the difference that the Q-type precursor had been prepared by condensation of tetraethoxysilane using the silanol route (preparation of trimethoxysilanol using first a strong base to prepare sodium treithoxysilanloate and second the subsequent protonation with acetic acid to create tiethoxysilanol and third condensation of the triethoxysilanol obtained in this way) and that 0.13 mol of water in 5 ml Ethanol were added during the condensation grafting step of the T-type silane. NMR analysis confirmed that the product contained less than 9% T.sup.0-monomer measured by the total amount of T-type moieties and more than 47% of Q-type tetrasiloxane ring species and >2.2% of Q-type silanol species right after the synthesis.

    Example 4

    [0281] A material identical to the one described in Example 3 was prepared with the difference that two T-type precursors were used, namely Methlytriethoxysilane and Mercaptopropyl-trimethoxysilane (MPTMS). Following the successful preparation of the R.sup.5U (mercaptopropyl) functional polysiloxane material, a partial substitution of the R.sup.5U reactive thiopropyl groups using a thiol-ene reaction was carried out. To do so, the material was mixed with hexyl-acrylate in the presence of DMF as a solvent. 1% by weight of a phosphine catalyst (e.g. Dimethylphenylphosphine) was added and the reaction was left stirring for 12 hours. The reaction product was isolated and an R.sup.5S degree of substitution of groups of 50% confirmed by 1H NMR.

    Example 4b

    [0282] A substituted material was prepared based on an existing phenyl-functional material. Following the successful preparation of said R.sup.5U material according to example 3b, bromination on the aromatic phenyl rings was then carried out with elemental bromine in a 1:1 molar ration of—phenyl groups to Br.sub.2 in in a neat system with FeBr.sub.3 as a catalyst. The reaction product was isolated and a mixture of different Bromine ring substitutions was visible in the .sup.1H and .sup.13C NMR R.sup.5S, with a quantification yielding an average degree of substitution of 1.3 Br per phenyl (65% of the theoretical substitution yield).

    Example 4c

    [0283] A substituted material according to the preparation protocol used in Example 1 was prepared, however an R.sup.5S T-Type substituted monomer was used for grafting instead of PTES and a reaction time of 30 h was chosen. The substituted monomer had previously been prepared by reacting a 3:1 molar excess of hexanediol-diacrylate (HDDDA) with aminopropyltriethoxysilane (APTES) at room temperature. .sup.29Si NMR analysis confirmed that the product contained less than 11% T.sup.0-monomer measured by the total amount of T-type moieties and more than 42% of Q-type tetrasiloxane ring species and >0.8% of Q-type silanol species right after the synthesis

    Example 5

    Efficiency Testing for Potential Condensation Grafting Catalysts

    [0284] 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, a Q-type precursor made by hydrolysis of ethylsilicate-40 with a DP.sub.Q-type value of 2.08 and with 9% silanol content was used. A molar ratio .sub.nQ-type:n.sub.T-type of 1:0.15 was chosen 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, 1000 ppm of a model condensation 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-00001 % % Condensation % (Q.sup.2rQ.sub.3s, d)/ (Q.sup.3d)/ catalyst Catalyst: DP.sub.Q-Type DP.sub.Q-Type T.sup.0 Q.sub.tot Q.sup.3 performance Nitric acid 2.20 1.39 9.9 51.4 83.2 High Sulfuric acid 2.18 1.12 5.8 48.6 82.9 High Acetic acid 2.16 0.73 38.7 49.9 83.3 Medium

    [0285] Following the spectral NMR analysis, one can evaluate the performance and suitability of a catalyst in terms of its ability to graft T.sup.0 monomers (DP.sub.T-Type and % T.sup.0 indicators) as well as the percentage of residual tetrasiloxane ring species after the grafting step (%(Q.sup.2r&Q.sup.3s,d)/Q.sub.tot and %(Q.sup.3s,d)/Q.sup.3 indicators). Generally, the protocol gives a comparative indication, as poorly performing catalysts could also be used but would require higher reaction temperatures, longer reaction times or higher concentrations to achieve the same or a comparable grafting effect.

    Example 6

    Hydrolysis of a Polymeric Liquid Material

    [0286] 69 g of Ethanol and 55.3 g of a crude reaction product from Example 2b were mixed and heated to 40° C. in an Erlenmeyer flask with stirring. Once the temperature had equilibrated, 6 ml of a 0.3 M nitric acid solution was added followed by 4.5 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 50° C. for 12 hours. The final hydrolysis product was then filtered and stored in the refrigerator.

    Example 7

    Preparation of a Water in Oil Emulsion

    [0287] 149 g of a sample of a material sample of Example 3i was mixed with 400 ml of distilled water and 19 g of a surfactant (Sodium laurate) 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 good shelf life.

    Example 8

    Preparation of an Oil in Water Emulsion

    [0288] 90 g of a sample of a material sample of Example 2c was mixed with 34.5 ml distilled water and 0.4 g of a surfactant (Pluronic P123). 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.