Functionalized Q-T-siloxane-based polymeric materials with low siloxane ring content, specific degree of polymerization, and method for preparing same

A polymeric liquid polysiloxane material comprising:

• (i) non-organofunctional Q-type siloxane moieties selected from the group consisting of:
• (iv) mono-organofunctional T-type siloxane moieties selected from the group consisting of:
• wherein
• indicates a covalent siloxane bond to a silicon atom of another Q-, and/or T-type moiety as defined in (i) and/or (iv);
• R1 is selected from the group consisting of methyl, ethyl, propyl, —P(═O)(OR1′)(OH), —P(OR1′)2, and —P(═O)(OH)2;
• R1′ is selected from the group consisting of methyl, ethyl, propyl, and butyl;
• R2 is selected from the group consisting of methyl, vinyl, and phenyl;
• R3 is selected from the group consisting of methyl, vinyl, and phenyl;
• R5 is selected from the group consisting of R5N, R5U and R5S, wherein
• R5N is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear C5-16 alkyl residues, branched C5-16 alkyl residues, and cyclic C5-16 alkyl residues;
• R5U is selected from the group consisting of -L-Z1, -L-Z2 and —Z3, wherein
• L is an aliphatic linker selected from the group consisting of —CH2—, —CH2CH2—, —CH2CH2CH2—, —C6H4—, —C6H4—CH2—, and —CH2—CH2—C6H4—CH2—;
• z1 is a moiety selected from the group consisting of —SH, —NH2,
• Z2 is a moiety selected from the group consisting of
• wherein
• R7 is independently selected from the group consisting of methyl, ethyl and n-butyl, and o is an integer from 1 to 3, and
• Z3 is selected from the group consisting of vinyl, phenyl,
• wherein
• n is an integer selected from the group consisting of 1, 2, 3, 4, and 5, and
• R6 is selected from the group consisting of methyl, ethyl, n-butyl, linear C5-14 alkyl residues branched C5-14 alkyl residues;
• R5S is selected from the group consisting of -L′-Y1, -L′-Y2, and —Y3, wherein
• m is an integer selected from the group consisting of 1, 2, 3, and 4;
• R8 is selected from the group consisting of —Cl, —Br, —I, —F, —CN, —SCN, —N3, —NO2, —OH, —SO2OR1′, and —O—C(═O)R12;
• R9 is selected from the group consisting of —Cl, —Br, —I, —F, —CN, —COOH, —COOR1′, phenyl, o-vinylphenyl, m-vinylphenyl, and p-vinylphenyl;
• R9′ is selected from the group consisting of —COOH and —COOR1′;
• L′ is an aliphatic linker selected from the group consisting of —CH2—, —CH2CH2—, and —CH2CH2CH2—;
• and
• Y1 is a moiety selected from the group consisting of
• wherein o is an integer from 1 to 3;
• Y2 is a moiety selected from the group consisting of
• wherein SU indicates substituted or non-substituted;
• Y3 is a moiety selected from the group consisting of
• wherein
• X is absent, —(NH)— or —O—;
• R10 is selected from the group consisting of R10a, R10b, R10c, R10d, R12a, and
• R10a is selected from the group consisting of
• R10b is selected from the group consisting of:
• in monomeric, biuret and triisocyanurate form;
• R10c is selected from the group consisting of:
• wherein q is an integer from 1 to 25,
• wherein each of q1 to q4 are integers from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, wherein each of q5 to q7 are integers from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24, wherein each of q8 and q9 are integers from 0 to 6 and the sum of (q8+q9) is from 2 to 6;
• R10d is selected from the group consisting of:
• 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;
• R11 is selected from the group consisting of R8, —X—R1′, and R12c, and
• R12 is selected from the group consisting of R12a, R12b, and R12c, wherein
• R12a is selected from the group consisting of linear C1-18 alkyl, linear C2-18 alkenyl linear C2-18 alkynyl, branched C1-18 alkyl, branched C2-18 alkenyl, branched C2-18 alkynyl, substituted C1-18 alkyl, substituted C2-18 alkenyl, substituted C2-18 alkynyl, non-substituted C1-18 alkyl, non-substituted C2-18 alkenyl, non-substituted C2-18 alkynyl, cyclic C3-18 alkyl, cyclic C5-18 alkenyl, cyclic C8-18 alkynyl, substituted C3-18 alkyl, substituted C5-18 alkenyl, substituted C8-18 alkynyl, non-substituted C3-18 alkyl, non-substituted C5-18 alkenyl and non-substituted C8-18 alkynyl;
• R12b is selected from the group consisting of
• linear alkyl ether, branched alkyl ether, substituted alkyl ether, non-substituted alkyl ether, linear alkenyl ether, branched alkenyl ether, substituted alkenyl ether, non-substituted alkenyl ether, linear alkynyl ether, branched alkynyl ether, substituted alkynyl ether, non-substituted alkynyl ether, cyclic alkyl ether, substituted alkyl ether, non-substituted alkyl ether, cyclic alkenyl ether, substituted alkenyl ether, and non-substituted alkenyl ether, wherein the alkyl ether, alkenyl ether, and alkynyl ether have a molecular weight of up to 5000 g/mol;
• unsubstituted polydimethylsiloxane and unsubstituted polydivinylsiloxane;
• and
• poly- and oligosaccharides up to a molecular weight of 5000 g/mol;
• and
• R12c is selected from the group consisting of
• amino acids up to a molecular weight of 5000 g/mol, oligo-peptides up to a molecular weight of 5000 g/mol and poly-peptides up to a molecular weight of 5000 g/mol;
• and
• C12-24 fatty acids,
• with the proviso that R55 is not
• wherein
• the degree of polymerization of the T-type siloxane moieties DPT-type is in the range of 1.1 to 2.7;
• the material has a viscosity in the range of 2 to 100′000 cP, about 5 to 50′000 cP, or 5 to 1′000 cP, as measured by a cylindrical rotation viscometer according to standard ASTM E2975-15;
• the material comprises less than 5, 2.5, 2, 1.5, 1 or 0.5 mol-% silanol groups (Si—OH);
• and
• further wherein
• the polysiloxane material comprises less than 45, less than 37, less than 30 or less than 25 mol-% four-membered combined Q2r-type and Q3s,d-type siloxane ring species relative to the total Q-type siloxane species;
• and/or
• the polysiloxane material comprises less than 70, less than 63, less than 56 or less than 50 mol-% four-membered combined Q3s,3d-type siloxane ring species relative to all Q3-type siloxane species;
• and/or
• the polysiloxane material comprises less than 4.5, less than 4.0, less than 3.5 or less than 3.0 mol-% double four-membered Q3d-type siloxane ring species relative to the total Q-type siloxane species;
• and/or
• the polysiloxane material comprises less than 25, less than 20, less than 17 or less than 14 mol-% double four-membered Q3d-type siloxane ring species relative to all Q3-type siloxane species,
• characterized in that
• when at least 65 mol-%, 75 mol-% or 85 mol-% of all R5 residues of the T-type siloxane moieties in the polysiloxane material are R5N, the degree of polymerization of the Q-type siloxane moieties DPQ-type is in the range of 1.65 to 2.35, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.45:1;
• when the sum of all -L-Z1 and -L′-Y1 residues amounts to at least 80 mol-% of all R5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type siloxane moieties DPQ-type is in the range of 1.75 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1;
• when the sum of all Z3 and Y3 and/or the sum of all -L-Z2 and -L′-Y2 amounts to at least 50 mol-% of all R5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type siloxane moieties DPQ-type is in the range of 1.85 to 2.2, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1;
• when the sum of all -L-Z1, -L′-Y1 and R5N amounts to at least 90 mol-% of all R5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type siloxane moieties DPQ-type is in the range of 1.8 to 2.4, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.4:1;
• and
• when the sum of all R5N, z3, Y3, -L′-Y2 and -L-Z2 amounts to at least 90 mol-% of all R5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization of the Q-type siloxane moieties DPQ-type is in the range of 1.7 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.25:1.