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

1 . A polymeric liquid polysiloxane material comprising:

(i) non-organofunctional Q-type siloxane moieties selected from the group consisting of:

(ii) optionally tri-organofunctional M 1 -type siloxane moieties selected from the group consisting of:

(iii) optionally di-organofunctional D-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-, M-, D-and/or T-type moiety as defined in (i), (ii), (iii) and/or (iv);

R 1 is selected from the group consisting of methyl, ethyl, propyl, —P(═O)(OR 1 ′) (OH), —P(OR 1 ′) 2 , and —P(═O)(OH) 2 ;

R 1 ′ is selected from the group consisting of methyl, ethyl, propyl and butyl;

R 2 , R 3 and R 4 are each independently selected from the group consisting of methyl, ethyl, phenyl, cyclohexyl, vinyl and cyclopentadienyl;

R 5 is selected from the group consisting of R 5U and R 5S , wherein

R 5U is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, branched or cyclic C 5-16 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

R 6 is selected from the group consisting of methyl, ethyl, n-butyl, and linear or branched C 5 -14 alkyl residues;

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 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —C 6 H 4 —, —C 6 H 4 —CH 2 —, and —CH 2 —CH 2 —C 6 H 4 —CH 2 —; and

Z is a moiety selected from the group consisting of Cl, Br, I, —OH, —SH,

wherein R 7 is independently selected from the group consisting of methyl, ethyl, and n-butyl;

R 5S 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;

R 8 is selected from the group consisting of —Cl, —Br, —I, —F, —CN, —SCN, —N 3 , —NO 2 , —OH, —SO 2 OR 1′ , and —O—C(═O)R 12 ;

R 9 is selected from the group consisting of —Cl, —Br, —I, —F, —CN, —COOH, —COOR r , phenyl, o-, m-, and p-vinylphenyl;

R 9′ is selected from the group consisting of —COOH and —COOR 1′ ;

L′ is an aliphatic linker selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, and —CH 2 CH 2 CH 2 —; and

Y is a moiety selected from the group consisting of

wherein

X is absent, —(NH)—, or —O—;

R 10 is selected from the group consisting of

R 11 is selected from the group consisting of R 8 , —X—R 1′ , and R 12c ;

R 12 is selected from the group consisting of R 12a , R 12b , and R 12c , wherein

R 12a is selected from the group consisting of linear or branched, substituted or non-substituted C 1-18 alkyl, linear or branched, substituted or non-substituted C 2-18 alkenyl, and linear or branched, substituted or non-substituted C 2-18 alkynyl;

R 12b 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

polyaccharides up to a molecular weight of 5000 g/mol, and oligosaccharides up to a molecular weight of 5000 g/mol; and

R 12c 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

C 12-24 fatty acids;

with the proviso that R 5S is not

wherein

the degree of polymerization of the Q-type siloxane moieties DP Q-type is in the range of 1.3 to 2.7;

the degree of polymerization of the D-type siloxane moieties DP D-type is in the range of 1.0 to 1.9;

the degree of polymerization of the T-type siloxane moieties DP T-type is in the range of 1.1 to 2.7;

the total content of tri-organofunctional M-type siloxane moieties (iii) in the polysiloxane material does not exceed 10 mol-%;

the total content of di-organofunctional D-type siloxane moieties (iii) in the polysiloxane material does not exceed 50 mol-%;

the material has a viscosity in the range of 10 to 100′000 cP, as measured by a cylindrical rotation viscometer according to standard ASTM E2975-15;

the material comprises less than 5 mol-% silanol groups (Si—OH);

the atomic ratio of T- to Q-species in the material is in the range of 0.01:1 to 1:1;

at least 1 mol-% of all R 5 moieties in the material are R 5S moieties;

wherein

the polysiloxane material comprises less than 45 mol-% four-membered combined Q 2r -type and Q 3s,d -type siloxane ring species relative to the total Q-type siloxane species; and/or

the polysiloxane material comprises less than 70 mol-% four-membered combined Q 3s,3d -type siloxane ring species relative to all Q 3 -type siloxane species; and/or

the polysiloxane material comprises less than 4.5 mol-% double four-membered Q 3d -type siloxane ring species relative to the total Q-type siloxane species; and/or

the polysiloxane material comprises less than 25 mol-% double four-membered Q 3d -type siloxane ring species relative to all Q 3 -type siloxane species.

2 . The polymeric liquid polysiloxane material according to claim 1 , wherein

R 8 is selected from the group consisting of —Cl, —Br, —I, —CN, —SCN, —N 3 , —NO 2 , —SO 2 OR 1′ , and —O—C(═O)R 1′ ;

Y is selected from the group consisting of

R 10 is selected from the group consisting of

R 11 is selected from the group consisting of R 8 and R 12c ; and

R 12 is selected from the group consisting of R 12a , R 12b , and R 12c , wherein

R 12a is selected from the group consisting of linear or branched, substituted or non-substituted C 1-18 alkyl and linear or branched, substituted or non-substituted C 2-18 alkenyl;

R 12b is selected from the group consisting of

linear or branched, non-substituted or terminally amino- or thiol-substituted alkyl ethers up to a molecular weight of 3000 g/mol, and linear or branched, non-substituted or terminally amino- or thiol-substituted alkenyl ethers up to a molecular weight of 3000 g/mol;

poly-saccharides up to a molecular weight of 3000 g/mol, and oligosaccharides up to a molecular weight of 3000 g/mol; and

unsubstituted polydimethylsiloxane and polydivinylsiloxane; and

R 12c is selected from the group consisting of

amino acids, oligo-peptides up to a molecular weight of 3000 g/mol, and poly-peptides up to a molecular weight of 3000 g/mol.

3 . The polymeric liquid polysiloxane material according to claim 1 , wherein

R 8 is selected from the group consisting of —Cl, —Br, —I, —CN, —SCN, —N 3 , —NO 2 , —SO 2 OR 1′ , and —O—C(═O)R 1′ ;

Y is selected from the group consisting of

R 10 is selected from the group consisting of

R 11 is selected from the group consisting of R 8 and R 12c ; and

R 12 is selected from the group consisting of R 12a , R 12b , and R 12c , wherein

R 12a is selected from the group consisting of linear or branched, substituted or non-substituted C 1-12 alkyl and linear or branched, substituted or non-substituted C 2-12 alkenyl;

R 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; and

poly-saccarides up to a molecular weight of 2000 g/mol, and oligosaccharides up to a molecular weight of 2000 g/mol; and

R 12c is selected from the group consisting of

amino acids, oligo-peptide up to a molecular weight of 2000 g/mol made of naturally occuring amino acids, and poly-peptides up to a molecular weight of 2000 g/made of naturally occurring amino acids;

castor oil, soybean oil, sunflower oil triglycerides; and

naturally occurring C 12-24 fatty acids.

4 . The polymeric liquid polysiloxane material according to claim 1 , wherein the material comprises

(i) at least two non-identically R 5 -substituted mono-organofunctional T-type alkoxy-terminated siloxane populations, each population making up at least 3 mol-% of all mono-organofunctional T-type siloxane moieties in the material; and/or

(ii) chiral mono-organofunctional T 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 polysiloxane material according to claim 1 , wherein

(i) the degree of polymerization of the Q-type siloxane moieties DP Q-type is in the range of 1.5 to 2.5;

(ii) the degree of polymerization of the D-type siloxane moieties DP D-type is in the range of 1.25 to 1.75; and/or

(ii) the degree of polymerization of the T-type siloxane moieties DP T-type is in the range of 1.3 to 2.2.

6 . The polymeric liquid 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 polysiloxane material according to claim 1 , wherein the relative atomic ratio of T- to Q-species is in the range of 0.02:1 to 0.75:1.

8 . A hydrolysis product obtained 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.

9 . An emulsion obtained by emulsifying a polymeric liquid material according to claim 1 , with a predetermined amount of water.

10 . A method for preparing a polymeric liquid material according to claim 1 , the method comprising the following steps:

providing the polymeric liquid material, wherein at least 1 mol-% of all R 5 moieties in the material are R 5U moieties;

functionalizing the R 5U residues of the polymeric liquid material to obtain at least 1 mol-% R 5S residues relative to all R 5 residues;

retrieving, the polymeric liquid material.

11 . A method for preparing a polymeric liquid material according to claim 1 , the method 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 5 is selected from the group consisting of R 5U and R 5S ;

optionally further comprising a rearrangement catalyst;

wherein the precursor comprises at least 28 mol-% four-membered combined Q 2r -type and Q 3s,d -type siloxane ring species relative to the total Q-type siloxane species; and/or

wherein the precursor comprises at least 60% four-membered combined Q 3s,3d -type siloxane ring species relative to all Q 3 -type siloxane species; and

wherein degree of polymerization of the Q-type polysiloxane DP Q-type is in the range of 1.5 to 2.7;

(b) adding at least one of a

(b1) tri-organofunctional M-type silane Si(OR 1 )(R 2 )(R 3 )(R 4 ) in mono- or oligomeric form;

(b2) di-organofunctional D-type silane Si(OR 1 ) 2 (R 2 )(R 3 ) in mono- or oligomeric form; and/or

(b3) mono-organofunctional T-type silane Si(OR 1 ) 3 (R 5 ) in mono- or oligomeric form, wherein R 5 is selected from the group consisting of R 5U and R 5S ;

to the polysiloxane of (a);

(c) optionally adding a rearrangement catalyst to the mixture of step (b);

(d) heating the mixture of (c) in the absence of water:

(e) optionally repeating steps (b) to (d) at least once;

(f) optionally functionalizing the R 5U residues of the polymeric liquid material to obtain at least 1 mol-% R 5S resides relative to all R 5 residues;

(g) retrieving, the polymeric liquid material;

with the proviso that at least one of steps

(a) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly (methoxy/ethoxy/propoxy) polysiloxane precursor comprising mono-organofunctional T-type siloxane moieties, wherein R 5 is selected from R 5U and R 5S or

(b) adding mono-organofunctional T-type silane Si(OR 1 ) 3 (R 5 ) in mono-or oligomeric form, wherein R 5 is selected from R 5U and R 5S

is carried out, and

with the proviso that a rearrangement catalyst is present in at least one of steps (a) or (c).

12 . The method according to claim 11 , wherein

in step (a), the R 5 of the T-type siloxane moiety is R 5U ;

in step (b), the R 5 of the T-type silane is R 5U ; and

the method comprises the step (f) of functionalizing the R 5U residues of the polymeric liquid material to obtain at least 1 mol-% R 5S residues relative to all R 5 residues.

13 . The method according to claim 11 , wherein

in step (a), the R 5 of the T-type siloxane moiety is R 5U ;

in step (b), the R 5 of at least one T-type silane is R 5S ; wherein in optional step (e) the R 5 of the T-type silane is selected from the group consisting of R 5U and R 5S , and

the method comprises or does not comprise the step (f).

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

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

16 . The method according to claim 11 , wherein the rearrangement catalyst is selected from the group consisting of

Ti(IV)(OR 13 ) 4 and Zr(IV)(OR 13 ) 4 ;

Ti(IV)X 4 and Zr(IV)X 4 ;

O═Ti(IV)X 2 and O═Zr(IV)X 2 );

Ti(IV)X 2 (OR 13 ) 2 and Zr(IV)X 2 (OR 13 ) 2 ;

Ti(IV)X 2 (OCOCH 3 COCH 3 ) 2 and Zr(IV)X 2 (OCOCH 3 COCH) 2 ;

Ti(IV)(OSi(CH 3 ) 3 ) 4 and Zr(IV)(OSi(CH 3 ) 3 ) 4 ;

(R 13 O) 2 Ti(IV)(OCOCH 3 COCH 3 ) 2 and (R 13 O) 2 Zr(IV)(OCOCH 2 COCH 3 ) 2 ;

O═Ti(IV)(OCOCH 3 COCH 3 ) 2 and O═Zr(IV)(OCOCH 3 COCH 3 ) 2 ;

Ti(IV)(OCOCH 3 ) 4 and Zr(IV)(OCOCH 3 ) 4 ;

Ti(IV)(OCOCH 3 ) 2 (OR 13 ) 2 and Zr(IV)(OCOCH 3 ) 2 (OR 13 ) 2 ; and

O═Ti(IV)(OCOCH 3 ) 2 and O═Zr(IV)(OCOCH 3 ) 2 ;

wherein R 13 is selected from the group consisting of —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —CH 2 CH 2 CH 3 , —C(CH 3 ) 3 , —CH 2 CH 2 CH 2 CH 3 , and CH 2 CH 2 CH(CH 3 ) 2 , and wherein X is a halide, a pseudohalide, nitrate, chlorate, or perchlorate anion.

17 . The polymeric liquid material according to claim 1 , comprising at least one population of mono-organofunctional T-type siloxane moieties with R 5 selected from the group consisting of vinyl, methacrylate, butacrylate, acrylate,

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.

18 . The polymeric liquid material according to claim 1 comprising at least one population of mono-organofunctional T-type siloxane moieties with R 5 selected from the group consisting of 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 in the formulation is 0.5% to 25% by weight.

19 . The method according to claim 10 , further comprising isolating the polymeric liquid material, purifying the polymeric liquid material, or isolating and purifying the polymeric liquid material.

20 . The method according to claim 11 , wherein at least one of:

the Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly (methoxy/ethoxy/propoxy) polysiloxane precursor, comprises less than 12 mol-% of (a1) and (a2) combined relative to the total amount of all Q-type species;

the method further comprises isolating the polymeric liquid material, purifying the polymeric liquid material, or isolating and purifying the polymeric liquid material; or a combination thereof.

21 . The method according to claim 16 , wherein the catalyst amount in each of steps (a) or (c) is between 0.01 and 5 mol-% based on the total molar silicon content present in said step.