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SILOXANE-BASED POLYMERIC MATERIALS FOR EFFICIENT REARRANGEMENT AND CURING REACTIONS AND WITH SPECIFIC DEGREE OF POLYMERIZATION

20240294759 ยท 2024-09-05

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention pertains to a polymeric liquid polysiloxane material comprising non-organofunctional Q-type siloxane moieties and optionally mono-organofunctional T-type siloxane moieties, for efficient rearrangement and curing reactions. The present invention further pertains to associated uses of the material.

    Claims

    1.-16. (canceled)

    17. A polymeric liquid polysiloxane material comprising: (i) non-organofunctional Q-type siloxane moieties selected from the group consisting of: ##STR00064## wherein custom-character indicates a covalent siloxane bond to a silicon atom of another siloxane moiety; R.sup.1 is selected from the group consisting of MC, methyl, ethyl, propyl, and R.sup.1; R.sup.1 is selected from the group consisting of ##STR00065## wherein p is an integer from 1 to 4; R.sup.4 is absent, R.sup.4, or ##STR00066## wherein the carbonyl is attached to the L.sup.Q moiety; R.sup.4 is absent or selected from the grope consisting of ##STR00067## in monomeric, uretdione, biuret or tri-isocyanurate form; R.sup.14 is methyl, ethyl, propyl, or a covalent bond to the silicon atom of another siloxane moiety; L.sup.Q is selected from the group consisting of ##STR00068## and L.sup.Q; R.sup.Q1 is a polyol; L.sup.Q is selected from the group consisting of
    -(L.sup.Q1).sub.m1[(L.sup.Q1).sub.m2-R.sup.4].sub.m3-co-[(L.sup.Q2).sub.m2-R.sup.4].sub.m4-co-[(L.sup.Q1).sub.m2-R.sup.4-].sub.m5-(L.sup.Q1).sub.m1-, and
    -(L.sup.Q2).sub.m1[(L.sup.Q1).sub.m2-R.sup.4].sub.m3-co-[(L.sup.Q2).sub.m2-R.sup.4].sub.m4-co-[(L.sup.Q3).sub.m2-R.sup.4].sub.m5-(L.sup.Q1).sub.m1-, wherein L.sup.Q is about or less than 40'000 g/mol, and m1 is an integer from 0 to 15, m2 is an integer from 3 to 200, and m3, m4 and m5 are each independently integers from 0 to 10, with the proviso that at least one of m3 to m5 is not 0; MC is an alkali or earth alkali metal ion; and wherein the polysiloxane material comprises MC from 0.005 to 20 mol MC/mol Si in the polysiloxane material (mol-%); the polysiloxane material has a viscosity in the range of 2 to 100'000 cP; the polysiloxane material comprises less than 5 0.5 mol-% silanol groups (SiOH); and the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.3 to 2.7.

    18. The polymeric liquid polysiloxane material according to claim 17, further comprising (iv) mono-organofunctional T-type siloxane moieties selected from the group consisting of: ##STR00069## wherein R.sup.5 is selected from the group consisting of R.sup.5N, R.sup.5U and R.sup.5S, wherein R.sup.5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and linear, branched or cyclic C.sub.5-16 alkyl residues; R.sup.5U is selected from -L-Z.sup.1, -L-Z.sup.2, and Z.sup.3, wherein L is an aliphatic linker selected from the group consisting of CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, C.sub.6H.sub.4, C.sub.6H.sub.4CH.sub.2, and CH.sub.2CH.sub.2C.sub.6H.sub.4CH.sub.2; Z.sup.1 is a moiety selected from the group consisting of SH, NH.sub.2, ##STR00070## Z.sup.2 is a moiety selected from the group consisting of ##STR00071## wherein R.sup.7 is independently selected from the group consisting of methyl, ethyl, n-propyl and n-butyl and o is an integer from 1 to 3, and Z.sup.3 is selected from vinyl, phenyl, ##STR00072## wherein n is an integer selected from the group consisting of 1, 2, 3, 4, and 5, and R.sup.6 is selected from the group consisting of methyl, ethyl, n-butyl, and linear or branched C.sub.5-14 alkyl residues; R.sup.5S is selected from the group consisting of -L-Y.sup.1, -L-Y.sup.2, and Y.sup.3, wherein 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.7, and OC(?O)R.sup.12; R.sup.9 is selected from the group consisting of Cl, Br, I, F, CN, COOH, COOR.sup.7, phenyl, o-vinylphenyl, m-vinylphenyl, and p-vinylphenyl; R.sup.9 is selected from the group consisting of COOH and COOR.sup.7; L is an aliphatic linker selected from the group consisting of CH.sub.2, CH.sub.2CH.sub.2, and CH.sub.2CH.sub.2CH.sub.2; and Y.sup.1 is a moiety selected from the group consisting of ##STR00073## and wherein o is an integer from 1 to 3; X is absent, (NH) or O; Y.sup.2 is a moiety selected from the group consisting of ##STR00074## wherein SU indicates substituted or non-substituted; Y.sup.3 is a moiety selected from the group consisting of ##STR00075## m is an integer selected from the group consisting of 1, 2, 3, and 4; R.sup.10 is selected from the group consisting of R.sup.10a, R.sup.10b, R.sup.10c, R.sup.10d, R.sup.12a, and ##STR00076## R.sup.10a is selected from the group consisting of ##STR00077## ##STR00078## R.sup.10b is selected from the group consisting of: ##STR00079## in monomeric, uretdione, biuret and triisocyanurate form; R.sup.10c is selected from the group consisting of: ##STR00080## wherein q is an integer from 1 to 25, ##STR00081## ##STR00082## wherein ny is an integer from 0 to 4, q is an integer from 1 to 10, each of q1 to q4 are integers independently from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, each of q5 to q7 are integers independently from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24, each of q8 and q9 are integers independently from 0 to 6 and the sum of (q8+q9) is from 2 to 6, and R.sup.15 is selected from the group consisting of ##STR00083## R.sup.10d is selected from the group consisting of: ##STR00084## wherein r is an integer from 1 to 100, s is an integer from 1 to 15, and t is an integer from 1 to 10; R.sup.11 is selected from the group consisting of R.sup.8, XR.sup.7, R.sup.12c, and for Y.sup.2, R.sup.11 is further selected from ##STR00085## 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, linear or branched, substituted or non-substituted C.sub.2-18 alkenyl, and linear or branched, substituted or non-substituted C.sub.2-18 alkynyl, cyclic, substituted or non-substituted C.sub.3-18 alkyl, cyclic, substituted or non-substituted C.sub.5-18 alkenyl, and cyclic, substituted or non-substituted C.sub.8-18 alkynyl; R.sup.12b is selected from the group consisting of linear or branched, substituted or non-substituted alkyl ether, linear or branched, substituted or non-substituted alkenyl ether, linear or branched, substituted or non-substituted alkynyl ether, cyclic, substituted or non-substituted alkyl ether and cyclic, substituted or non-substituted alkenyl ether, each up to a molecular weight of 5000 g/mol; unsubstituted polydimethylsiloxane and unsubstituted polydivinylsiloxane; and polysaccharides and oligosaccharides up to a molecular weight of 5000 g/mol; and R.sup.12c is selected from the group consisting of amino acids, oligo-peptides, and poly-peptides up to a molecular weight of 5000 g/mol; and C.sub.12-24 fatty acids, with the proviso that R.sup.5S is not ##STR00086## wherein the degree of polymerization of the T-type alkoxy-terminated siloxane moieties DP.sub.T-type is in the range of 1.1 to 2.7; and the degree of polymerization of the Q-type alkoxy-terminated siloxane moieties DP.sub.Q-type is in the range of 1.1 to 2.7.

    19. The polymeric liquid polysiloxane material according to claim 18, wherein when the sum of all R.sup.1 residues in the material being MC, R.sup.1, or both, is ?0.5 mol-%, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.25 to 2.45.

    20. The polymeric liquid polysiloxane material according to claim 18, wherein when at least 65 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material are R.sup.5N, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.65 to 2.35, and the atomic ratio of T-species to Q-species in the material is in the range of 0.05:1 to 0.45:1; when the sum of all -L-Z.sup.1 and -L-Y.sup.1 residues amounts to at least 80 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.75 to 2.25, and the atomic ratio of T-species to Q-species in the material is in the range of 0.02:1 to 0.3:1; when the sum of all (i) Z.sup.3 and Y.sup.3, (ii) the sum of all -L-Z.sup.2 and -L-Y.sup.2, or (iii) a combination thereof, amounts to at least 50 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.85 to 2.2, and the atomic ratio of T-species to Q-species in the material is in the range of 0.02:1 to 0.3:1; when the sum of all -L-Z.sup.1, -L-Y.sup.1, and R.sup.5N amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.8 to 2.4, and the atomic ratio of T-species to Q-species in the material is in the range of 0.05:1 to 0.4:1; and when the sum of all R.sup.5N, Z.sup.3, Y.sup.3, -L-Y.sup.2, and -L-Z.sup.2 amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.7 to 2.25, and the atomic ratio of T-species to Q-species in the material is in the range of 0.05:1 to 0.25:1.

    21. The polymeric liquid polysiloxane material according to claim 18, wherein R.sup.5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and linear, branched or cyclic C.sub.5-16 alkyl residues; Z.sup.1 is a moiety selected from the group consisting of SH, ##STR00087## R.sup.8 is selected from the group consisting of Cl, Br, I, CN, SCN, and N.sub.3; Y.sup.1 is selected from the group consisting of ##STR00088## wherein o is an integer from 1 to 3; Y.sup.2 is a moiety selected from the group consisting of ##STR00089## Y.sup.3 is a moiety selected from the group consisting of ##STR00090## X is absent, (NH), or O; R.sup.10 is selected from the group consisting of R.sup.10a, R.sup.10b, R.sup.10c, R.sup.10d, and R.sup.12a; R.sup.10a is selected from the group consisting of ##STR00091## R.sup.10b is selected from the group consisting of ##STR00092## and in monomeric, uretdione, biuret and triisocyanurate form; R.sup.10c is selected from the group consisting of ##STR00093## wherein q is an integer from 1 to 10, ##STR00094## ##STR00095## wherein ny is an integer from 0 to 4, q is as defined above, each of q1 to q4 are integers from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, each of q5 to q7 are integers from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24, each of q8 and q9 are integers from 0 to 6 and the sum of (q8+q9) is from 2 to 6, and R.sup.15 is selected from the group consisting of ##STR00096## R.sup.10d is selected from the group consisting of ##STR00097## wherein r is an integer from 1 to 25, s is an integer from 1 to 10, and t is an integer from 1 to 10; R.sup.11 is selected from R.sup.8 and optionally R.sup.12c, and for Y.sup.2, R.sup.11 is further selected from ##STR00098## 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.12c is selected from the group consisting of amino acids or oligopeptides up to a molecular weight of 2000 g/mol, or polypeptides up to a molecular weight of 2000 g/mol; and C.sub.12-24 fatty acids.

    22. The polymeric liquid hyperbranched polysiloxane material according to claim 18, wherein R.sup.1 is selected from the group consisting of MC, methyl, ethyl, and propyl; R.sup.5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and linear, branched or cyclic C.sub.5-16 alkyl residues; L is an aliphatic linker selected from the group consisting of CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, and C.sub.6H.sub.4; Z.sup.1 is a moiety selected from the group consisting of SH, ##STR00099## Z.sup.2 is a moiety selected from the group consisting of ##STR00100## wherein R.sup.7 is independently selected from the group consisting of methyl and ethyl; Z.sup.3 is selected from vinyl and phenyl; R.sup.8 is selected from the group consisting of Cl, Br, I, CN, and N.sub.3; R.sup.9 is selected from the group consisting of Cl, CN, COOH, COOR.sup.7, and phenyl; Y.sup.1 is selected from the group consisting of ##STR00101## wherein o is an integer from 2 to 3; Y.sup.2 is a moiety selected from the group consisting of ##STR00102## Y.sup.3 is a moiety selected from the group consisting of ##STR00103## wherein X is absent, (NH), or O; R.sup.10 is selected from the group consisting of R.sup.10a, R.sup.10b, R.sup.10c, and R.sup.10d; R.sup.10a is selected from the group consisting of ##STR00104## R.sup.10b is selected from the group consisting of ##STR00105## in monomeric, uretdione, biuret and triisocyanurate form; R.sup.10c is selected from the group consisting of ##STR00106## wherein q is an integer from 1 to 6, ##STR00107## ##STR00108## wherein each of q1 to q4 are integers independently from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, each of q5 to q7 are integers independently from 0 to 8 and the sum of (q5+q6+q7) is from 3 to 12, and each of q8 and q9 are integers independently from 0 to 4 and the sum of (q8+q9) is from 2 to 4; and R.sup.10d is selected from the group consisting of ##STR00109## wherein r is an integer from 1 to 20, s is an integer from 1 to 8 and t is an integer from 1 to 10; R.sup.11 is selected from R.sup.8 and R.sup.12c, and for Y.sup.2, R.sup.11 is further selected from ##STR00110## and R.sup.12c is selected from the group consisting of amino acids, oligopeptides up to a molecular weight of 1000 g/mol, or polypeptides up to a molecular weight of 1000 g/mol; and C.sub.12-24 fatty acids.

    23. The polymeric liquid polysiloxane material according to claim 18, wherein the material comprises at least one of at least two non-identically R.sup.5-substituted mono-organofunctional T-type alkoxy-terminated siloxane populations, each population making up at least 3 mol-% of all mono-organofunctional T-type moieties in the material; chiral mono-organofunctional T.sup.1-type moieties in an amount of at least 3 mol-% relative to all mono-organofunctional T-type moieties in the material; or a combination thereof.

    24. The polymeric liquid polysiloxane material according to claim 18, wherein at least one of the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.6 to 2.4 and the atomic ratio of T-species to Q-species in the material is in the range of 0.02:1 to 0.4:1; if the material comprises about or more than 5 mol-% M-type moieties, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.7 to 2.5 and the atomic ratio of T-species to Q-species in the material is in the range of 0.02:1 to 0.4:1; the degree of polymerization of the T-type alkoxy-terminated siloxane moieties DP.sub.T-type is in the range of 1.3 to 2.2; and a combination thereof; or a combination thereof.

    25. The polymeric liquid polysiloxane material according to claim 17, wherein at least one of: L.sup.Q is selected from the group consisting of ##STR00111## wherein I is an integer from 4 to 600; R.sup.Q1 is selected from the group consisting of low molecular linear or branched polyol, low molecular linear or branched polyether polyol, low molecular linear or branched polyester polyol, low molecular linear or branched acrylic polyol, low molecular linear or branched polycarbonate polyol, and low molecular linear or branched natural oil based polyol; MC is selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba; or a combination thereof.

    26. The polymeric liquid polysiloxane material according to claim 17, wherein at least one of: 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; 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; 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; 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; or a combination thereof.

    27. The polymeric liquid polysiloxane material according to claim 18, wherein at least one of: R.sup.5N is selected from the group consisting of linear or branched hexyl, linear or branched octyl, 2,4,4-trimethylpentyl, linear or branched dodecyl, linear or branched hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H, 2H, 2H-perfluoro)octyl, cyclohexyl, cyclopentadienyl, cyclopentyl, (1H,1H, 2H, 2H-perfluoro)dodecyl, and (1H,1H, 2H, 2H-perfluoro)hexadecyl; R.sup.6 is selected from the group consisting of (CH.sub.2).sub.5CH.sub.3, (CH.sub.2).sub.6CH.sub.3, (CH.sub.2).sub.7CH.sub.3, (CH.sub.2).sub.8CH.sub.3, (CH.sub.2).sub.9CH.sub.3, (CH.sub.2).sub.11CH.sub.3, and (CH.sub.2).sub.13CH.sub.3; R.sup.12b is selected from the group consisting of substituted or unsubstituted poly(ethylene oxide), substituted or unsubstituted poly(propylene oxide) polytetrahydrofuran, substituted or unsubstituted poly D-glucose, substituted or unsubstituted oligo-D-glucose, substituted or unsubstituted chitosan, substituted or unsubstituted deacetylated oligo-chitin, substituted or unsubstituted oligo-beta-D-galactopyranuronic acid, substituted or unsubstituted poly alginic acid, substituted or unsubstituted oligo-alginic acid, substituted or unsubstituted poly amylose, substituted or unsubstituted oligo amylose, substituted or unsubstituted poly-galactose, and substituted or unsubstituted oligo-galactose, each with a molecular weight up to 5000 g/mol; R.sup.12c is selected from the group consisting of oligopeptides and polypeptides, each made of naturally occurring amino acids up to a molecular weight of 5000 g/mol, naturally occurring unsaturated fatty acids, C.sub.12-24 naturally occurring unsaturated fatty acids with 1 to 3 double bonds, epoxidized fatty acids, epoxidized castor oil, soybean oil, sunflower oil, ring opened epoxidized fatty acid based polyols, natural oil based polyols (NOPs), castor oil, soybean oil, and sunflower oil triglycerides; R.sup.12c is selected from the group consisting of oligopeptides and polypeptides, each made of naturally occurring amino acids up to a molecular weight of 2000 g/mol or up to a molecular weight of 1000 g/mol; or a combination thereof.

    28. The polymeric liquid polysiloxane material according to claim 18, wherein at least one of: when (i) the sum of all Z.sup.3 and Y.sup.3, (ii) the sum of all -L-Z.sup.2 and -L-Y.sup.2, or (iii) a combination thereof, amounts to at least 50 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, and the material further comprises R.sup.5 residues being -L-Z.sup.1, the sum of R.sup.5 residues being -L-Y.sup.1 and -L-Z.sup.1 being less than 20 mol-%, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.85 to 2.2, and the atomic ratio of T-species to Q-species in the material is in the range of 0.02:1 to 0.3:1; when the sum of all -L-Z.sup.1, -L-Y.sup.1, and R.sup.5N amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, at least 30 mol-% of the R.sup.5 residues of the material being -L-Z.sup.1, -L-Y.sup.1, or a combination thereof, and at least 10 mol-% of the R.sup.5 residues of the material being R.sup.5N, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.8 to 2.4, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.4:1; when the sum of all R.sup.5N, Z.sup.3, Y.sup.3, -L-Y.sup.2, and -L-Z.sup.2 amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the sum of all Z.sup.3, Y.sup.3, -L-Y.sup.2, and -L-Z.sup.2 amounts to at least 20 mol-% of the R.sup.5 residues of the material, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-type is in the range of 1.7 to 2.25, and the atomic ratio of T-species to Q-species in the material is in the range of 0.05:1 to 0.25:1; when the sum of all R.sup.5N, Z.sup.3, Y.sup.3, -L-Y.sup.2, and -L-Z.sup.2 amounts to at least 90 mol-% of all R.sup.5 residues of the T-type siloxane moieties in the polysiloxane material, the sum of all Z.sup.3, Y.sup.3, -L-Y.sup.2, and -L-Z.sup.2 amounts to at least 20 mol-% of the R.sup.5 residues of the material, at least 20 mol-% of the R.sup.5 residues of the material being R.sup.5N, the degree of polymerization of the Q-type alkoxy-terminated moieties DP.sub.Q-t.sub.ype is in the range of 1.7 to 2.25, and the atomic ratio of T-species to Q-species in the material is in the range of 0.05:1 to 0.25:1; or a combination thereof.

    29. A hydrolysate or emulsion precursor comprising at least one polymeric liquid material according to claim 1.

    30. A hydrolysate or emulsion precursor according to claim 29, further comprising at least one of an acid, a base, a buffer an oil, a co-emulsifier, or a combination thereof.

    31. A hydrolysis or emulsion product produced by reacting the at least one polymeric liquid material of claim 29 with a predetermined amount of water or with a predetermined amount of a water-solvent mixture.

    32. A glass fiber sizing formulation comprising the polymeric liquid polysiloxane material according to claim 18, and at least one of a silane hydrolysate, a lubricant, a polymer resin, a biopolymer, a film former, an emulsifier, or a combination thereof.

    33. The glass fiber sizing formulation according to claim 32, wherein the polymeric liquid polysiloxane material is in the form of a hydrolysate or emulsion precursor comprising at least one polymeric liquid material or in the form of a hydrolysis or emulsion obtainable by reacting the at least one polymeric liquid material of claim 30 with a predetermined amount of water or with a predetermined amount of a water-solvent mixture.

    34. The glass fiber sizing formulation according to claim 32, wherein the material comprises at least one of: T-type siloxane moieties, with R.sup.5 being R.sup.5U, .sup.R5N, or a combination thereof; T-type siloxane moieties, with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof, wherein at least 10 mol %, or at least an amount between 10 to 75 mol-%, of all R.sup.5 in the material are R.sup.5U, R.sup.5N, or a combination thereof; T-type siloxane moieties, with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof, wherein at least 10 mol %, or at least an amount between 10 to 75 mol-%, of all R.sup.5 in the material are R.sup.5U, R.sup.5N, or a combination thereof, and, wherein the material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1; or T-siloxane moieties with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof, wherein at least 10 mol %, or at least an amount between 10 to 75 mol-%, of all R.sup.5 in the material are R.sup.5U, R.sup.5N, or a combination thereof, and, wherein the material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1, wherein at least 0.1 mol %, or at least an amount between 0.1 to 3.0 mol-%, of all R.sup.1 of the material are R.sup.1.

    35. A 2K curable epoxy resin formulation comprising at least one resin, one hardener and at least one polymeric liquid polysiloxanes material of claim 18, as defined in (I.), (II.), (IV.) and (V.) below, wherein the hardener is selected from: (I.) the polymeric liquid polysiloxane material, (II.) the polymeric liquid polysiloxane material, wherein at least 1 mol-% of all R.sup.5 of the material are R.sup.5S with R.sup.5S=L-Y.sup.1; and (III.) an amine hardener, a mercapto hardener, an amide hardener, and amidoamine hardener, a carboxylic hardener, or an anhydride hardener. wherein the resin comprises: (IV.) the polymeric liquid polysiloxane material, wherein at least 1 mol-% of all R.sup.5 of the material are R.sup.5U being ##STR00112## or a combination thereof, (V.) the polymeric liquid polysiloxane material, wherein at least 50 or 80 mol-% of all R.sup.5 of the material are R.sup.5S being L-Y.sup.1, wherein Y.sup.1 comprises R.sup.10d functionalization, wherein R.sup.10d is bonded through a nitrogen or a sulfur atom to Y, or (VI.) an epoxy resin.

    36. The 2K curable epoxy resin formulation according to claim 35, wherein at least one of: at least 1 mol-% of all R.sup.5 of the material are R.sup.5U with R.sup.5U=L-Z.sup.1; Y.sup.1 is functionalized by R.sup.10a; at least 30 mol-% R.sup.10d functionalization; the formulation further comprises a catalyst, a filler, or a combination thereof; or a combination thereof.

    37. A humidity curing formulation comprising the polymeric liquid polysiloxane material according to claim 17.

    38. A humidity curing formulation comprising the polymeric liquid polysiloxane material according to claim 18, wherein at least one of: the polymeric liquid polysiloxane material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1; the polymeric liquid polysiloxane material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1, wherein at least 0.1 mol %, or at least an amount between 0.1 to 3.0 mol-%, of all R.sup.1 of the material are R.sup.1; the humidity curing formulation further comprises at least one of an aminosilane curing catalyst, an organometallic curing catalyst, an amine-based curing catalyst, a water scavenger, a plasticizer or softener, a filler, a stabilizer, a silane terminated polymer (STP) resin, or a combination thereof; or a combination thereof.

    39. A binder, adhesive, sealant, elastomer, or coating comprising the polymeric liquid polysiloxane material according to claim 17.

    40. A binder, adhesive, sealant, elastomer, or coating comprising the polymeric liquid polysiloxane material according to claim 17, and at least one type of R.sup.5N-functionality, R.sup.5U-functionality, R.sup.5S-functionality, R.sup.1-functionality, or a combination thereof.

    41. A cosmetics, personal care, or (protective) coating formulation comprising the polymeric liquid polysiloxane material according to claim 17.

    42. A cosmetics, personal care, or (protective) coating formulation comprising the polymeric liquid polysiloxane material according to claim 18, and at least one type of R.sup.5N-functionality, R.sup.5U-functionality, R.sup.5S-functionality, R.sup.1-functionality, or a combination thereof, wherein at least one of: the polymeric liquid polysiloxane material is in the form of a hydrolysis or emulsion product produced by reacting the at least one polymeric liquid material with a predetermined amount of water or with a predetermined amount of a water-solvent mixture; the cosmetics, personal care, or (protective) coating formulation comprises the polymeric liquid polysiloxane material in the form of a hydrolysis or emulsion product produced by reacting the at least one polymeric liquid material with a predetermined amount of water or with a predetermined amount of a water-solvent mixture, wherein the material comprises T-type siloxane moieties with R.sup.5 being R.sup.5U and/or .sup.R5N; or the cosmetics, personal care, or (protective) coating formulation comprises the polymeric liquid polysiloxane material in the form of a hydrolysis or emulsion product produced by reacting the at least one polymeric liquid material with a predetermined amount of water or with a predetermined amount of a water-solvent mixture, wherein the material comprises T-type siloxane moieties with R.sup.5 being R.sup.5U and/or .sup.R5N and wherein the material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1.

    43. A silicone elastomer formulation comprising the polymeric liquid polysiloxane material according to claim 17, and a silicone OH fluid, a silicone vinyl fluid a silicone hydrido fluid, or a combination thereof.

    44. A silicone elastomer formulation comprising the polymeric liquid polysiloxane material according to claim 18, and a silicone OH fluid, a silicone vinyl fluid a silicone hydrido fluid, or a combination thereof, wherein at least one of: the material comprises T-type siloxane moieties with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof; the material comprises T-type siloxane moieties with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof, wherein at least 10 mol %, or an amount between 10 to 75 mol-%, of all R.sup.5 in the material are R.sup.5U, R.sup.5N, or a combination thereof; the material comprises T-type siloxane moieties with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof, wherein at least 10 mol %, or an amount between 10 to 75 mol-%, of all R.sup.5 in the material are R.sup.5U, R.sup.5N, or a combination thereof, and, wherein the material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1; the material comprises T-type siloxane moieties with R.sup.5 being R.sup.5U, R.sup.5N, or a combination thereof, wherein at least 10 mol %, or an amount between 10 to 75 mol-%, of all R.sup.5 in the material are R.sup.5U, R.sup.5N, or a combination thereof, and, wherein the material comprises Q-type siloxane moieties, T-type siloxane moieties, or a combination thereof, with R.sup.1 being R.sup.1, wherein at least 0.1 mol %, or at least an amount between 0.1 to 3.0 mol-%, of all R.sup.1 of the material are R.sup.1; or a combination thereof.

    Description

    FIGURES

    [0389] FIG. 1 shows exemplary 2D molecular structure representations of exemplary Q-type polysiloxane materials as described herein (e.g. according to appended claim 1) comprising R.sub.1=MC units. In FIG. 1a, an exemplary Q-type precursor is shown featuring representative R.sup.1 substituents ethyl and MC only. In FIG. 1b, an exemplary Q-type polysiloxane material is shown featuring ethyl and Na as exemplary R.sup.1 substituents, where the MC=Na is drawn in its ion pair (SiO.sup.? Na.sup.+) form.

    [0390] FIG. 2 shows exemplary 2D molecular structure representations of typical Q-T core-shell type polysiloxane materials described herein (e.g. according to appended claim 2) comprising R.sup.1=MC units. In FIG. 2a, material comprising grafted T-type moieties is shown with R.sup.5U and exemplary R.sup.5S (-L-Y.sup.1R.sup.10d) functionality. In FIG. 2b, a polymeric liquid material comprising grafted T-type moieties with R.sup.5U functionality and STP functionalities as well as MC=K residues drawn in the ion pair (SiO.sup.? K.sup.+) form is shown. The representations are for illustration purposes only and do not represent any limitation in further T (R.sup.5N, R.sup.5S and R.sup.5U), D, M-Type grafting and functionalization combinations.

    [0391] FIG. 3 shows .sup.29Si NMR spectra comparing MC=Na (FIG. 3b 0.05 mol-%, FIG. 3c 0.7 mol %) against a standard titanium(IV)-isopropoxide (TIP) rearrangement catalyst (FIG. 3e 0.54 mol-% TIP, FIG. 3d 0.27 mol-%). All percentages are mol-%. One can clearly see the lack of any grafting reaction in the absence of catalysts (FIG. 3a) and the high activity of the MC=Na catalyst system even at low concentrations. The data is based on Example 2e shown below.

    EXAMPLES

    [0392] 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.

    [0393] 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:

    [0394] Example 1 describes selected preparation protocols of MC containing Q-type polysiloxane materials using various MC combinations.

    [0395] Example 2 describes the preparation of R.sup.5N, R.sup.5U and R.sup.5S-functionalized materials comprising both Q-type and T-type moieties by rearrangement grafting using MC type catalyst systems.

    [0396] Example 3 illustrates the effect of MC in various applications and formulations (emulsions, hybrid STPs, silicone elastomer) involving both MC catalyzed rearrangement and curing reactions.

    Example 1a: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=2.12 and an MC=Na Content of 0.3% Mol (MC)/Mol (Si)

    [0397] A Q-type precursor was prepared from a commercial ethylsilicate oligomer (Evonik Dynasylan 40) by controlled hydrolysis adding a mixture comprising ethanol and water and a catalytic amount of oxalic acid at 65? C. for 8 hours in a round bottom flask with distillation bridge. Next, the heater temperature was set to 95? C. and residual solvent was distilled off over the course of 90 minutes. Next, an amount of sodium hydroxide (MC) catalyst corresponding to the desired final concentration in the material was added and residual solvent removed by vacuum (140 mbar/25 minutes). .sup.29Si NMR analysis confirmed that the product contained less than 1.0% of total Q.sup.0-monomer (Tetraethoxysilane) measured by the total amount of Q-type moieties, respectively as well as less than 24.8% of Q-type tetrasiloxane ring species and a DP.sub.Qtype value of 2.12.

    Example 1b: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=1.92 and an MC=Na Content of 1.8% Mol (MC)/Mol (Si)

    [0398] A similar synthesis procedure as in Example 1 above was used to prepare the material, with the key difference that tetramethoxysilane (TMOS) was used as a raw material and the condensation was carried out using the silanol route (Macromol. Chem. Phys, 2003, 204(7), 1014-1026). Following an initial purification of the material, a desired amount of NaOH was added and mixture distilled under vacuum at 75? C. .sup.29Si NMR analysis confirmed that the product contained less than 1.6% of total Q.sup.0-monomer (Tetramethoxysilane) measured by the total amount of Q-type moieties, respectively as well as less than 21.2% of Q-type tetrasiloxane ring species and a DP.sub.Qtype value of 2.12 and a MC=Na content of 1.8% mol (MC)/mol (Si).

    Example 1c: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=1.85 and an MC=Li Content of 0.6% Mol (MC)/Mol (Si)

    [0399] A material was produced exactly like in example 1a, with the main difference, that instead of Sodium Hydroxide, Lithium oxide (Li.sub.2O) was used as a MC source and a different DP value was targeted. Comparable results regarding ring species were obtained.

    Example 1d: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=1.85 and an MC=Li Content of 0.08% Mol (MC)/Mol (Si)

    [0400] A material was produced exactly like in example 1a, with the main difference, that instead of Sodium Hydroxide, Lithium amide (LiNH.sub.2) was used as a MC source and a different DP value was targeted. Comparable results regarding ring species were obtained.

    Example 1e: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=2.33 and an MC=K Content of 18% Mol (MC)/Mol (Si)

    [0401] A material was produced exactly like in example 1a, with the main difference, that instead of Sodium Hydroxide, Potassium hydroxide (KOH) was used as a MC source and a different DP value was targeted. Comparable results regarding ring species were obtained.

    Example 1f: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=1.58 and an MC=Mg Content of 0.06% Mol (MC)/Mol (Si)

    [0402] A material was produced exactly like in example 1a, with the main difference, that Tetraemethoxysilane (TMOS) was used as a precursor and instead of Sodium Hydroxide, Magnesium hydroxide Mg(OH).sub.2 was used as a MC source and a different DP value was targeted. Comparable results regarding ring species were obtained.

    Example 1g: Synthesis of a MC-Qtype Polysiloxane Material with a DP.SUB.Qtype.=1.75 and an MC=K Content of 0.022% Mol (MC)/Mol (Si)

    [0403] A material was produced exactly like in example 1a, with the main difference, that instead of Sodium Hydroxide, Sodium Superoxide (NaO.sub.2) was used as a MC source and a different DP value was targeted. Comparable results regarding ring species were obtained.

    2a: Synthesis of a R.sup.5U Non-Functionalized Ethylsilicate Q-Type/(PTMS+APTMS) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.08+0.11)

    [0404] First a Q-type precursor according to example 1a with MC=Li was prepared and heated to 90? C. in a stirred glass reactor. Next, a mixture of two T-type precursors PTMS (propyltrimethoxysilane) and APTMS (3-aminopropyltrimethoxysilane) was added and the mixture stirred for 16 h. .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 25.7% of Q-type tetrasiloxane ring species. The final MC=Li content was 0.25% mol (MC)/mol (Si).

    2b: Synthesis of a R.sup.5S-Functionalized Q-Type Polycondensate/(3-MPTMS) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.17) and L-Y1-R.sup.10d Functionalization

    [0405] First a Q-type precursor according to example 1a but without any MC content (leave MC addition step out) was prepared and heated to 90? C. in a stirred glass reactor. Next, a T-type precursors 3-MPTMS (3-mercapto-propyltrimethoxy-silane) was added and the mixture stirred for 16 h for MC induced rearrangement grafting. Next a quantity of a material from example 1b to yield a final concentration of MC=Na of 0.41% mol (MC)/mol (Si) in the mixture was added. Rearrangement grafting in the presence of MC=Na was then carried out for a period of 12 h at 100? C. The resulting product was R's functionalized on its mercapto (-L-SH) groups by direct on polysiloxane modification with an epoxide precursor (Bisphenol A diglycidyl etherBADGE) leading to L-Y.sup.1 epoxy (R.sup.10d) functionalization with grafted BFDGE units. A 1:3.6 molar ratio based on SH to BADGE molar ratio was used and the reaction was carried out neat overnight at 90? C. with 0.3% of a dimethylbenzylamine catalyst. The reaction product was identified and confirmed by NMR analysis. .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 25.7% of Q-type tetrasiloxane ring species. The final MC=K content was 0.25% mol (MC)/mol (Si).

    2c: Synthesis of a R.sup.5N Non-Functional Ethylsilicate Q-Type/(OTES) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.14)

    [0406] A Q-type precursor according to example 1a was prepared, but simultaneously with the addition of the MC source (NaOH, molar amount=0.2% mol (MC)/mol (Si)) an amount of a T-type precursor OTES (octyltriethoxysilane)taken into account in the total Si mol amountwas added and the mixture stirred at 100? C. for 16 h. .sup.29Si NMR analysis confirmed that the product had a DP.sub.Qtype value of 1.92 and contained less than 21% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 25.7% of Q-type tetrasiloxane ring species. The final MC=Na content was 0.2% mol (MC)/mol (Si).

    Example 2d: Synthesis of a R.SUP.5U .Non-Functionalized Ethylsilicate Q-Type/(APTES) Polycondensate Material with nQ-Type:(nT-Type)=1:(0.10)

    [0407] A preparation protocol identical to the one described in Example 2a was used with the exception that only APTES was used as T-type precursor and a MC=Na content of 0.15% mol (MC)/mol (Si) was used for rearrangement grafting. The material had a DP.sub.Qtype value of 2.02 and contained less than 9% of total T.sup.0-monomer measured by the total amount of T-type moieties, respectively as well as less than 23.1% of Q-type tetrasiloxane ring species.

    Example 2e: Use of MC-Comprising Polysiloxane Materials as Rearrangement Catalyst for Q-T-Rearrangement Grafting

    [0408] A material according to example 2c was prepared Na from a pure Q-type core material (DP.sub.Q-type=2.24) using MC=Na as rearrangement catalyst and Ti(IV)-isopropoxide (TIP) as a comparative model rearrangement catalyst. Grafting was carried out at 100? C. for 8 h at two catalyst concentrations for each catalyst and the conversion (DP.sub.T-type) as well as residual ungrafted OTES monomer (% T?) characterized using standard protocols from .sup.29Si NMR data. Results are tabulated below and clearly show that MC=Na is a much more effective rearrangement catalyst than standard Ti systems. The corresponding .sup.29Si NMR Spectra are shown in FIG. 3, exemplifying the high activity of the MC type rearrangement catalyst.

    TABLE-US-00002 Rearrangement catalyst/ % concentration T.sup.0 DP.sub.T-type DP.sub.Q-type none/ 97.8 0.02 2.24 NaOH/0.05% 15.2 1.56 2.09 NaOH/0.1% 4.7 1.82 2.04 TIP/0.27% 77.2 0.29 2.24 TIP/0.54% 44.9 0.71 2.17

    Example 3a: Effect of DP.SUB.Q-type .and MC=Na Concentration on the Stabilization of Emulsions Made from Q.SUB.type .Polysiloxanes with Varying DP and Monomeric Octyltriethoxysilane T.SUB.type .Precursors

    [0409] The example aims to demonstrate the influence of MC content on the water-in-oil emulsion stability from Q-type precursors and monomeric octyltriethoxysilane. For each test sample, four aliquots of 20 g of a Q-type polyethoxysilanes with respective DP.sub.Qtype values of 0 (pure TEOS), 1.32, 1.68, 1.97 and 2.28) were combined with 6.55 g of monomeric octyltriethoxysilane and the desired amount of MC=Na added in the form of a material according to example 1b to reach 0 (no addition), 0.05, 0.1 and 0.15 mol % MC/total Si. Next, 10 mL of each mixture was combined with 5 mL distilled deionized water and briefly shaken. Each sample was then emulsified with a homogenizer for 20 seconds and then left undisturbed until phase separation occurred. The time at which two distinct phases became clearly identifiable was recorded as the phase separation time which is tabulated below.

    TABLE-US-00003 mol % Q-type precursor effect on emulsion stability MC/ DP = 0 total Si (TEOS) DP = 1.32 DP = 1.68 DP =1.97 DP = 2.28 0 30 s 2 mmin 5 min 7 min 10 min 0.05% 2 m 15 min 2 h 10 h 10 h 0.10% 2 h 12 h 12 h 24 h 26 h 0.20% 4 h 20 h 20 h >8 d >12 d

    Example 3b: Comparative Example Water/Oil Emulsions Using Grafted R.SUP.5U .Materials

    [0410] A grafted OTES Q-T polysiloxane material according to example 2c was first prepared separately with a DP.sub.Qtype values of 1.92 and emulsified in the same way as described above in example 3a (20 ml with 10 ml water, no extra MC addition). The respective water in oil emulsion had a nearly unlimited shelf-life. No phase separation/change in viscosity were observed over the course of 4 months storage under ambient conditions. This clearly shows, that MC assisted rearrangement-grafted hydrophobic Q-T octyl-polysiloxanes offer far superior emulsion stability compared to the reference systems made from Q-polyethoxysiloxane/OTES monomer mixtures.

    Example 3c: MC Catalyzed Grafting and Reactivity of Q-T Polysiloxane/STP Hybrid Resins

    [0411] Various commercial PPG-polyol based STP resins and an aminopropyl-functionalised Q-T polysiloxane comprising up to 0.35% mol MC=Na based on total Si in the polysiloxane material were combined at 1:1 equivalent mass ratios to create Q-T polysiloxane/STP hybrid resins. The MC concentration was adjusted to the desired level by starting with a material according to example 2d and adding additional MC when needed. MC free samples (MC concentration=0) were prepared using a MC-free analogous Q-T polysiloxane precursor which had been prepared separately (DP.sub.Qtype=1.99, less than 11% of total T.sup.0-monomer, less than 21.2% of Q-type tetrasiloxane ring species.

    [0412] Mixtures comprising Q-T polysiloxanes and commercial STP resins A-G were shaken and left to react under ambient conditions in closed containers for two hours at room temperature. Directly after preparation and mixing, the mixture had a phase separated turbid emulsion like appearance. The ability to react at room temperature to form a stable homogeneous R.sup.1 functionalized hybrid STP reaction product was confirmed by the mixture turning translucent. Similarly, an identical set of samples was placed in a heating cabinet at 100? C. For all samples (with and without MC addition) until translucent, for a maximum of 24 hours.

    [0413] From the table it becomes evident, that MC-free hybrid resin STP mixtures do not react at room temperature at all (not a single hybrid resin mixture turns clear/forms a stable hybrid resin), whereas MC additions of up to 0.35% are leading for all of the above STPs to form clear transparent hybrid resins with the aminofunctional Q-T polysiloxane.

    [0414] Finally, 10 ml aliquots of 100? C. heating cabinet prepared hybrid STP resins (only the ones which gave a clear reaction product) were poured on a polyethylene foil substrate and a 1 mm thick film drawn using a doctor blade setup. The films were then allowed to cure simultaneously at room temperature and the skin formation time as well as full curing times (final, dry thickness approximately 650 m). We observe from the skin formation time (SFT) and full curing (peel-off) time (FCT), that there is also a noticeable increase in speed of the formulations, although the effect is less pronounced than for the resin preparation. For the curing times, the typical speed increase is between 10% and 30%, however there are large differences depending on the STP resin type. Clearly, these results shows the effect of the MC addition on hybrid STP resin formation (preparation) and reactivity (curing).

    TABLE-US-00004 Reac- 100? Reac- STP RT tion C. tion resin MC = Na reac- time at reac- time at SFT FCT type conc. tion RT tion 100? C. [min] [h] A 0 No n/a Yes 1440 3.3 3 h 50 B 0 No n/a No n/a C 0 No n/a Yes 1440 4.8 5 h 00 D 0 No n/a No n/a E 0 No n/a Yes 960 3.1 3 h 25 F 0 No n/a No n/a G 0 No n/a No n/a A 0.16 mol % Yes 20 Yes 5 3 2 h 50 B 0.16 mol % Yes 360 Yes 60 5.8 5 h 15 C 0.16 mol % Yes 25 Yes 6 4.3 4 h 35 D 0.35 mol % Yes 300 Yes 100 6.7 6 h 00 E 0.16 mol % Yes 15 Yes 3 2.8 3 h 20 F 0.2 mol % Yes 60 Yes 10 4.5 3 h 55 G 0.16 mol % Yes 120 Yes 20 7 4 h 55

    Example 3d: Tin-Free Curing of a Silicone Resin Elastomer Formulation

    [0415] A RTV 1K silicone formulation was prepared from a silicone oil (100'000 cSt, Wacker Chemie) and a low viscosity OH fluid (250 cSt, BRB silicones) was mixed together with a hydrophobic silica filler (Aerosil R8200, Evonik Industries) and 0.50 pHr (per hundred rubber) of a crosslinker (methyl tris(methylethylketo-xime)silane) as well as 0.50 pHr of a material from Example 2d were mixed together in a speedmixer.

    [0416] The formulation was spread onto a glass substrate as a 1 mm thick film and cured at 23? C./45% relative humidity. The material was fully cured in 13 minutes, while the skin formation time was 3-4 minutes. Shore A hardness of the fully cured formulation was 91. In comparison with the comparative Example 3e below, the curing time was greatly reduced and the formulation is free from organotin compounds. The silicone elastomer also shows significantly higher peel strength compared to Example 3e below.

    Example 3e: Curing of a Comparative Reference Silicone Resin Elastomer Formulation

    [0417] A RTV 1K silicone formulation was prepared in an identical manner as the above Example 3d, however without the use of a material from Example 2d. Instead, 0.5 pHr of an organotin based curing catalyst (TIB KAT 223, organotin compound) was used.

    [0418] The formulation was again spread onto a glass substrate as a 1 mm thick film and cured at 23? C./45% relative humidity. The material was fully cured in 42 minutes, while the skin formation time was 12-15 minutes. Shore A hardness of the fully cured formulation was 83.