Q-T-siloxane-based polymeric materials with high siloxane ring content and method for preparing same

A polymeric liquid polysiloxane material comprising:

• (i) non-organofunctional Q-type siloxane moieties selected from the group consisting of:
• and
• (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, R3 and R4 are each independently selected from the group consisting of methyl, ethyl, phenyl, cyclohexyl, vinyl, —CH2—CH2—Cl and cyclopentadienyl;
• R6 is selected from the group consisting of methyl, ethyl, n-butyl, linear C5-14 alkyl residues and branched C5-14 alkyl residues;
• n is an integer selected from the group consisting of 1, 2, 3, 4 and 5;
• 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-, m-, and p-vinylphenyl;
• R9′ is selected from the group consisting of —COOH and —COOR1′;
• R5 is selected from the group consisting of R5U and R5S,
• wherein
• R5U is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, branched or cyclic C5-16 alkyl residues, (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, cyclopentadienyl,
• and -L-Z, wherein
• L is an aliphatic linker selected from the group consisting of —CH2—, —CH2CH2—, —CH2CH2CH2—, —C6H4—, —C6H4—CH2—, and —CH2—CH2—C6H4—CH2;
• and
• Z is a moiety selected from the group consisting of CI, Br, I, —OH, —SH,
• wherein R7 is selected from the group consisting of methyl, ethyl, and n-butyl;
• R5S is selected from the group consisting of
• and -L′-Y, wherein
• m is an integer selected from the group consisting of 1, 2, 3 and 4;
• L′ is an aliphatic linker selected from the group consisting of —CH2—, —CH2CH2—, and —CH2CH2CH2—;
• and
• Y is a moiety selected from the group consisting of
• wherein
• X is absent, —(NH)—, or —O—;
• R10 is selected from the group consisting of
• R11 is selected from the group consisting of R8, -X-R1′ and R12c,
• R12 is selected from the group consisting of R12a, R12b and R12c, wherein
• R12a is selected from the group consisting of linear or branched, substituted or non-substituted C1-18 alkyl, linear or branched, substituted or non-substituted C2-18 alkenyl and linear or branched, substituted or non-substituted C2-18 alkynyl;
• R12b is selected from the group consisting of
• linear or branched, substituted or non-substituted alkyl ether up to a molecular weight of 5000 g/mol, linear or branched, substituted or non-substituted alkenyl ether up to a molecular weight of 5000 g/mol, and linear or branched, substituted or non-substituted alkynyl ether up to a molecular weight of 5000 g/mol;
• unsubstituted polydimethylsiloxane and unsubstituted polydivinylsiloxane;
• and
• polysaccharides up to a molecular weight of 5000 g/mol and oligosaccharides up to a molecular weight of 5000 g/mol;
• and
• R12c is selected from the group consisting of
• amino acids, 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 R5S is not
• wherein
• the degree of polymerization of the Q-type siloxane moieties according to DPQ-type=Σ(n AQn)/Σ(AQn)=(AQ1+2 AQ2+3 AQ3+4 AQ4)/(AQ0+AQ1+AQ2+AQ3+AQ4) is in the range of 1.3 to 2.7, wherein Qn is a Si atom coordinated by n siloxane bonds through bridging oxygen atoms;
• the degree of polymerization of the T-type siloxane moieties according to DPT-type=Σ(n ATn)/Σ(ATn)=(AT1+2 AT2+3 AT3)/(AT0+AT1+AT2+AT3) is in the range of 0.9 to 2.7, wherein Tn is a Si atom coordinated by n siloxane bonds through bridging oxygen atoms;
• 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 R5 moieties in the material are R5S moieties;
• wherein
• the polysiloxane material comprises more than 25 mol-% four-membered combined Q2r-type and Q3,sd-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 Q3s,3d-type siloxane ring species relative to all Q3-type siloxane species;
• and/or
• the polysiloxane material comprises more 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 more than 14 mol-% double four-membered Q3d-type siloxane ring species relative to all Q3-type siloxane species.