Q-T-siloxane-based polymeric materials with high 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:

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);

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, —CH 2 —CH 2 —Cl and cyclopentadienyl;

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

n is an integer selected from the group consisting of 1, 2, 3, 4 and 5;

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 1′ , phenyl, o-, m-, and p-vinylphenyl;

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

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

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 CI, Br, I, —OH, —SH,

wherein R 7 is 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;

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

polysaccharides 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 according to DP Q-type =Σ(n A Qn )/Σ(A Qn )=(A Q1 +2 A Q2 +3 A Q3 +4 A Q4 )/(A Q0 +A Q1 +A Q2 +A Q3 +A Q4 ) 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 DP T-type =Σ(n A Tn )/Σ(A Tn )=(A T1 +2 A T2 +3 A T3 )/(A T0 +A T1 +A T2 +A T3 ) 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 R 5 moieties in the material are R 5S moieties;

wherein

the polysiloxane material comprises more than 25 mol-% four-membered combined Q 2r -type and Q 3,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 Q 3s,3d -type siloxane ring species relative to all Q 3 -type siloxane species; and/or

the polysiloxane material comprises more than 3.0 mol-% double four-membered Q 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 3d -type siloxane ring species relative to all Q 3 -type siloxane species.

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

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

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-or-alkenyl ethers up to a molecular weight of 3000 g/mol;

polysaccharides up to a molecular weight of 3000 g/mol and oligosaccharides up to a molecular weight of 3000 g/mol; and

unsubstituted polydimethylsiloxane and unsubstituted 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; and

C 12-24 fatty acids.

3 . The polymeric liquid polysiloxane material according to claim 2 , 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

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

castor oil triglycerides, soybean oil triglycerides, and 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 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;

and/or

(iii) the degree of polymerization of the T-type siloxane moieties DP T-type is in the range of 1.2 to 2.2.

6 . The polymeric liquid polysiloxane material according to claim 1 , wherein the total content of di-organofunctional D-type siloxane moieties 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 mono-organofunctional T-type siloxane moieties comprise

(i) a first population of mono-organofunctional T-type siloxane moieties, wherein R 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 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 5 groups of the first and second populations are not identical,

(b) mono-organofunctional T-type siloxane moieties, wherein R 5 is L-Z, vinyl,

or

(c) mono-organofunctional T-type siloxane moieties, wherein R 5 is R 5S .

8 . 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.

9 . A hydrolysis product obtained by reacting at least one polymeric liquid polysiloxane 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 obtained by emulsifying a polymeric liquid polysiloxane material according to claim 1 with a predetermined amount of water, optionally in the presence of at least one surfactant.

11 . A method for preparing a polymeric liquid polysiloxane material according to claim 1 , wherein at least 1 mol-% of all R 5 moieties in the material are R 5S moieties, the method comprising the following steps:

providing the polymeric liquid polysiloxane 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 polysiloxane material to obtain at least 1 mol-% R 5S residues relative to all R 5 residues;

retrieving, optionally isolating and optionally purifying the polymeric liquid polysiloxane material.

12 . A method for preparing a polymeric liquid polysiloxane material according to claim 1 , 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 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 according to DP Q-type =Σ(n A Qn )/Σ(A Qn ) =(A Q1 +2 A Q2 +3 A Q3 +4 A Q4 )/(A Q0 +A Q1 +A Q2 +A Q3 +A Q4 ) is in the range of 1.5 to 2.7, wherein Dn is a Si atom coordinated by n siloxane bonds through bridging oxygen atoms; and

wherein the Q-type polysiloxane comprises more than 3, 5, 10, 15 or 20 mol-% silanol groups (Si—OH);

(b) adding at least one of a

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

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

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

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

(g) retrieving, optionally isolating and optionally purifying the polymeric liquid polysiloxane material;

with the proviso that at least one of:

the precursor of step (a) comprises mono-organofunctional T-type siloxane moieties, wherein R 5 is selected from the group consisting of R 5U and R 5S ,

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

a combination thereof, and

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

13 . A method for preparing a polymeric liquid polysiloxane material according to claim 1 , 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 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 according to DP Q-type =Σ(n A Qn )/Σ(A Qn ) =(A Q1 +2 A Q2 +3 A Q3 +4 A Q4 )/(A Q0 +A Q1 +A Q2 +A Q3 +A Q4 ) is in the range of 1.0 to 2.7, wherein Dn is a Si atom coordinated by n siloxane bonds through bridging oxygen atoms; and

wherein the Q-type polysiloxane comprises more than 3, 5, 10, 15 or 20 mol-% silanol groups (Si—OH);

(b) adding at least one of a

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

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

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

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

(g) retrieving, optionally isolating and optionally purifying the polymeric liquid polysiloxane material;

with the proviso that at least one of:

the precursor of step (a) comprises mono-organofunctional T-type siloxane moieties, wherein R 5 is selected from the group consisting of R 5U and R 5S ,

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

a combination thereof, 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 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 polysiloxane material to obtain at least 1 mol-% R 5S residues relative to all R 5 residues.

15 . The method according to claim 12 , 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 R 5U and R 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 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 in monomeric 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° C., 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 12 , 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 . A formulation comprising the polymeric liquid polysiloxane material according to claim 1 , the formulation comprising at least one population of mono-organofuncational T-type siloxane moieties with R 5 selected from the group consisting of vinyl, methacrylate, butacrylate, acrylate,

as a crosslinker within the formulation, with a content of the polymeric liquid polysiloxane material in the range of 0.2% to 25% by weight with respect to the formulation.

20 . A hydrophobic formulation comprising the polymeric liquid polysiloxane material according to claim 1 , the hydrophobic formulation 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, wherein the loading of the polymeric liquid polysiloxane material in the formulation is 0.5% to 25% by weight.

21 . The polymeric liquid polysiloxane material according to claim 1 , further comprising at least one of:

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

or

(iii) optionally di-organofunctional D-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);

the degree of polymerization of the D-type siloxane moieties according to DP D-type =Σ(n A Dn )/Σ(A Dn ) =(A D1 +2 A D2 )/(A D0 +A D1 +A D2 ) is in the range of 1.0 to 1.9, wherein Dn is a Si atom coordinated by n siloxane bonds through bridging oxygen atoms;

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

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