SILOXANE POLYMERS WITH A CENTRAL POLYSILOXANE POLYMER BLOCK WITH TERMINAL ORGANOFUNCTIONAL RADICALS COMPRISING UREA AND/OR CARBAMATE GROUPS AND AMINO ACID RADICALS

1 . A siloxane polymer of the general formula I comprising a central polysiloxane polymer block B,

(i) which is substituted with organofunctional radicals,

(ii) the polymer block B has linear and/or branched structures with at least two difunctional siloxane units,

(iii) the polymer block B has on at least two terminal silicon atoms or at least one terminal and at least one lateral silicon atom on the siloxane units of polymer block B, the organofunctional radicals -Q1 and -Q2, where the radicals are identical or different,

Q2-B-Q1  (I)

where -Q1 corresponds to the general formula IIa and -Q2 corresponds to the formula IIb,

-Q1=-Q1′-A-(C═O)-D-Q1″-A′-(C═O)-D′-Q1*  (IIa)

-Q2=-Q2′-A-(C═O)-D-Q2″-A′-(C═O)-D′-Q2*  (IIb)

where A is —NH—, —O— or —S— and D is —NH—, in each case independently in formulae IIa and IIb,

where A′ is —NH— and D′ is —NH—, —O— or —S—, in each case independently in formulae IIa and IIb, where each radical Q1 and Q2 of the formulae IIa or IIb has at least one bivalent urea group and one further bivalent urea or carbamate group

with Q1′ and Q2′ in each case independently comprising a bivalent hydrocarbon radical with 6 to 200 carbon atoms optionally comprising at least one heteroatom selected from O, N and S, a bivalent radical comprising aryl, arylalkyl groups optionally comprising at least one heteroatom O, N or S or polyether radicals containing alkyl, aryl or alkyl and aryl groups,

with Q1″ and Q2″ in each case independently comprising a bivalent linear, branched and/or cyclic alkyl radical having 4 to 200 carbon atoms or a bivalent radical comprising an aryl and/or arylalkyl radical with 6 to 200 carbon atoms, and

with -D′-Q1* and -D′-Q2* with D′, as defined above, and where -D′-Q1* and -D′-Q2* in each case independently comprise radicals which are derived from an amino acid, an amino acid derivative or salts thereof.

2 . The siloxane polymer according to claim 1 , wherein

in the siloxane polymer of the general formulae I, IIa and IIb -D′-Q1* and -D′-Q2* in each case independently form radicals which are derived from an amino acid, an amino acid derivative or salts thereof and D′ is —NH in each case independently in -D′-Q1* and -D′-Q2* is in the alpha position relative to an ester or a carboxyl group of the amino acid, of the amino acid derivative or salt, where the ester includes alkyl esters with 1 to 25 carbon atoms or aryl esters.

3 . The siloxane polymer according to claim 1 , wherein

in the siloxane polymer of the general formula I, the polymer block B corresponds to the general formula IIIa or IIIb, where B is

where a, b, c, d and e in formulae IIIa and IIIb are in each case independently an integer

where a is from 1 to 200,

where b is from 0 to 200,

where c is from 0 to 200,

where d is from 0 to 200,

where e is from 0 to 200 and

where R 1 in formulae IIIa or IIIb are in each case independently identical or different, where R 1 comprises alkyl radicals with 1 to 22 carbon atoms, or phenyl radicals,

where R 2 in formulae IIIa or IIIb is an alkyl radical with 1 to 22 carbon atoms, an alkyl radical with at least one heteroatom selected from N, O, S or a phenyl radical.

4 . The siloxane polymer according to claim 1 , wherein

b, c, d and e are 0 and a is 20 to 100.

5 . The siloxane polymer according to claim 1 , wherein

R 1 and R 2 are selected from alkyl groups with 1, 2, 3 or 4 carbon atoms.

6 . The siloxane polymer according to claim 1 , wherein

the radicals -Q1 and -Q2 in the general formula I are independently selected from

-Q1=-Q1′-A-(C═O)-D-Q1″-A′-(C═O)-D′-Q1*  (IIa)

-Q2=-Q2′-A-(C═O)-D-Q2″-A′-(C═O)-D′-Q2*  (IIb)

a) where A is —O—, D is —NH—, A′ is —NH— and D′ is —NH—,

b) where A is —NH—, D is —NH—, A′ is —NH— and D′ is —NH—,

c) where A is —, D is —NH—, where A′ is —NH— and D′ is —NH—,

d) where A is —O—, D is —NH—, A′ is —NH— and D′ is —O—,

e) where A is —NH—, D is —NH—, A′ is —NH— and D′ is —O—,

f) where A is —S—, D is —NH—, A′ is —NH— and D′ is —O—,

g) where A is —O—, D is —NH—, A′ is —NH— and D′ is —S—,

h) where A is —NH—, D is —NH—, A′ is —NH— and D′ is —S— or

i) where A is —S—, D is —NH—, A′ is —NH— and D′ is —S—.

7 . The siloxane polymer according to claim 1 , wherein

in the radicals -Q1 and -Q2 of the formula I, the radicals -D′-Q1* and -D′-Q2* are in each case independently derived from amino acids, amino acid derivatives or salts thereof, comprising

nonpolar amino acids comprising alanine, valine, methionine, leucine, isoleucine, proline, tryptophan, phenylalanine,

basic amino acids comprising lysine, arginine, histidine,

polar and neutral amino acids tyrosine, threonine, glutamine, glycine, serine, cysteine, asparagine and/or

acidic amino acids selected from glutamic acid and aspartic acid,

and their mono-, dicarboxylic acid esters, amides with primary amino groups of the amino acids, amides of the carboxylic acid groups of the amino acids and/or esters with the primary hydroxyl groups, thioesters of the HS groups or amides with secondary amino groups of the amino acids.

8 . The siloxane polymer according to claim 1 , wherein

in the radicals -Q1 and -Q2 of the formula I,

A is —O—, D is —NH—, A′ is —NH— and D′ is —NH—, —O— or —S— and the radicals -D′-Q1* and -D′-Q2* are in each case independently derived from amino acids, amino acid derivatives or salts thereof, amides with primary amino groups of the amino acids, amides of the carboxylic acid groups of the amino acids and/or esters with the primary hydroxyl groups or thioesters of the HS group, and salts thereof.

9 . The siloxane polymer according to claim 1 , wherein

in the radicals -Q1 and -Q2 of the formula I, the bivalent radicals -Q1″- and -Q2″- are independently selected from bivalent, linear, branched or cyclic alkylene radicals with 4 to 25 carbon atoms.

10 . The siloxane polymer according to claim 1 , wherein

in the radicals -Q1 and -Q2 of the formula I, the bivalent radicals -Q1′- and -Q2′- are selected from alkylene radicals with 3 to 22 carbon atoms optionally with at least one heteroatom comprising N, O or S, or from polyether radicals containing alkyl, aryl or alkyl and aryl groups of the formulae IVa or IVb

where Q1′ and Q2′ are in each case independently

-T-O—(CH 2 —CH 2 —O—) x —(CH 2 —CH(R#)O—) y (SO)—R″  (IVa)

-T-O—(CH 2 —CH 2 —O—) x —(CH 2 —CH(R#)O—)—R″  (IVb),

where T=bivalent hydrocarbon radical with 2 to 4 carbon atoms,

where x=0 to 200, y=0 to 200, where x and y are integers, with the proviso that x or y is at least 1,

where R# is hydrogen or methyl, and

R″ is linear or branched alkylene.

11 . The siloxane polymer according to claim 1 , wherein

in the radicals -Q1 and -Q2 of the formula (I), at least one of the bivalent radicals -Q1″- and -Q2″- is independently a bivalent cyclohexane-containing radical selected from the formulae Va and Vb (Va) (Vb)

12 . The siloxane polymer according to claim 1 , wherein

the siloxane of the general formula I corresponds to the siloxane polymer of the general formula XI where

M a1 M A a2 M B a3 D b1 D A b2 D B b3 T c1 T A c 2T B c3 Q d1   (XI)

where M=[R 16 3 SiO 1/2 ], M A =[R 17 R 16 2 SiO 1/2 ], M B =[R 18 R 16 2 SiO 1/2 ],

where D=[R 16 2 SiO 2/2 ], D A =[R 17 1 R 16 1 SiO 2/2 ], D B =[R 18 1R 16 1SiO 2/2 ],

where T=[R 16 SiO 3/2 ], T A =[R 17 SiO 3/2 ], T B =[R 18 SiO 3/2 ], Q=[SiO 4/2 ],

where R 16 , independently of one another, are identical or different linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 30 carbon atoms or else aromatic hydrocarbon radicals having 6 to 30 carbon atoms, where R 17 is in each case independently -Q1 or -Q2,

where R 18 independently of one another are identical or different linear or branched, saturated or olefinically unsaturated hydrocarbon radicals with 8 to 30 carbon atoms, aromatic hydrocarbon radical with 6 to 40 carbon atoms, alkylaryl radical with 7 to 40 carbon atoms, a linear or branched optionally double-bond-containing aliphatic hydrocarbon radical with 2 to 30 carbon atoms that is interrupted by one or more heteroatoms, such as oxygen, NH, NR′ where R′ is an optionally double-bond-containing C1 to C30-alkyl radical, a linear or branched optionally double-bond-containing aliphatic hydrocarbon radical with 2 to 30 carbon atoms interrupted by one or more functionalities selected from the group —OH, —O—C(O)—, —(O)C—O—, —NH—C(O)—, —(O)C—NH, —(CH 3 )N—C(O)—, —(O)C—N(CH 3 )—, —S(O 2 )—O—, —O—S(O 2 )—, —S(O 2 )—NH—,

—NH—S(O 2 )—, —S(O 2 )—N(CH 3 )—, —N(CH 3 )—S(O 2 )—, a linear or branched optionally double-bond-containing aliphatic or cycloaliphatic hydrocarbon radical with 1 to 30 carbon atoms terminally functionalized with OH, OR′, NH 2 , N(H)R′, N(R′) 2 where R′ is an optionally double-bond-containing C1 to C30-alkyl radical, or a blockwise or randomly constructed polyether according to (R 5 —O) n —R 6 , where R 5 is a linear or branched hydrocarbon radical containing 2 to 4 carbon atoms, n is 1 to 100, and R 6 is hydrogen, a linear or branched optionally double-bond-containing aliphatic hydrocarbon radical with 1 to 30 carbon atoms, an optionally double-bond-containing cycloaliphatic hydrocarbon radical with 5 to 40 carbon atoms, an aromatic hydrocarbon radical with 6 to 40 carbon atoms, an alkylaryl radical with 7 to 40 carbon atoms, or a radical —C(O)—R 7 where R 7 is a linear or branched optionally double-bond-containing aliphatic hydrocarbon radical with 1 to 30 carbon atoms, an optionally double-bond-containing cycloaliphatic hydrocarbon radical with 5 to 40 carbon atoms, an aromatic hydrocarbon radical with 6 to 40 carbon atoms, an alkylaryl radical with 7 to 40 carbon atoms with the indices

a1=0-200,

a2=0-30,

a3=0-30, b1=2 to 5000, b2=0 to 100,

b3=0 to 100, c1=0 to 30,

c2=0 to 30,

c3=0 to 30,

d1=0 to 30,

with the proviso that at least one of the indices selected from a2 and a3 is not equal to 0.

13 . The siloxane polymer according to claim 1 , wherein

the siloxane polymer is selected from siloxane polymers of the formulae Ia and Ib or mixtures of these

where n or n′ is in each case independently selected from an integer from 3 to 22,

where a is from 1 to 200,

where b is from 0 to 200,

where c is from 0 to 200,

where d is from 0 to 200,

where e is from 0 to 200 and

where R′ in formulae Ia and Ib are in each case independently identical or different,

where R 1 comprises alkyl radicals with 1 to 4 carbon atoms or phenyl radicals,

where R 2 is alkyl radical with 1 to 22 carbon atoms, an alkyl radical with at least one heteroatom selected from N, O, S or phenyl radical and

where -D′-Q1* and -D′-Q2* are in each case independently derived from amino acids, amino acid derivatives or salts thereof, and

where Q1′ and Q2′ in formula Ib are in each case independently alkylene with 2 to 40 carbon atoms or a polyether of the formulae IVa or IVb

-T-O—(CH 2 —CH 2 —O—)—(CH 2 —CH(R)O—)—(SO)—R″  (IVa)

-T-O—(CH 2 —CH 2 —O—)—(CH 2 —CH(R)O—)—R″  (IVb)

where T=bivalent hydrocarbon radical with 2 to 4 carbon atoms,

where x=0 to 200 and y=0 to 200, where x and y are integers, with the proviso that x or y is at least 1,

where R# is hydrogen or methyl, and

where R″ is hydrogen or linear or branched alkylene.

14 . The siloxane polymer according to claim 1 , wherein

the siloxane polymer is selected from siloxane polymers of the formula Ia* and Ib*

where n or n′ in each case independently is selected from an integer from 3 to 22,

where a is from 1 to 200,

where b is from 0 to 200,

where c is from 0 to 200,

where d is from 0 to 200,

where e is from 0 to 200 and

where R′ in formulae Ia* and Ib* is in each case independently identical or different, where R 1 comprises alkyl radicals with 1 to 4 carbon atoms or phenyl radicals,

where R 2 is alkyl radical with 1 to 22 carbon atoms,

an alkyl radical with at least one heteroatom comprising N, O, S or phenyl radical and where Q1* and Q2* are in each case independently selected from amino acids, amino acid derivatives or salts thereof, where the fragment —NH-Q1* and —NH-Q2*, as a result of reaction of the secondary alpha-amino groups of the aminoacids, derivatives thereof or the salts with the isocyanate, forms a urea group, and where the amino acids comprising nonpolar amino acids comprising alanine, valine, methionine, leucine, isoleucine, proline, tryptophan, phenylalanine, basic amino acids comprising lysine, arginine, histidine, polar and neutral amino acids comprising tyrosine, threonine, glutamine, glycine, serine, cysteine, asparagine and/or the acidic amino acids selected from glutamic acid and aspartic acid, and their mono-, dicarboxylic acid esters, amides with primary amino groups of the amino acids, amides of the carboxylic acid groups of the amino acids and/or esters with the primary hydroxyl groups or thioesters of the HS group or salts thereof, and in formula Ib* where Q1′ and Q2′ are in each case independently

-T-O—(CH 2 —CH 2 —O—)—(CH 2 —CH(R#)O—) y (SO)—R″  (IVa)

-T-O—(CH 2 —CH 2 —O—)—(CH 2 —CH(R#)O—) y —R″  (IVb),

where T=bivalent hydrocarbon radical with 2 to 4 carbon atoms,

where x=0 to 200, y=0 to 200, where x and y are integers with the proviso that x or y is at least 1,

where R# is hydrogen or methyl, and

where R″ is hydrogen or linear or branched alkylene.

15 . A process for the preparation of a siloxane polymer and of compositions comprising these siloxane polymers or mixtures of the siloxane polymers with a central polysiloxane polymer block B, by reacting

a) a polysiloxane diisocyanate of the formula VII, with at least one amino acid, an amino acid derivative, salt thereof or mixtures thereof, giving a siloxane polymer of the general formula I

OCN-Q2″-D-(O═C)-A-Q2′-B-Q1′-A-(C═O)-D-Q1″-NCO  (VII)

Q2-B-Q1  (I)

where -Q1 corresponds to the general formula IIa and -Q2 corresponds to the formula IIb,

-Q1=-Q1′-A-(C═O)-D-Q1″-A′-(C═O)-D′-Q1*  (IIa)

-Q2=-Q2′-A-(C═O)-D-Q2″-A′-(C═O)-D′-Q2*  (IIb)

where A is —NH—, —O— or —S— and D is —NH— in each case independently in formulae IIa and IIb,

where A′ is —NH— and D′ is —NH—, —O— or —S— in each case independently in formulae IIa and IIb, where each radical Q1 and Q2 of the formula IIa or IIb in each case independently has at least one bivalent urea group and one further bivalent urea or a carbamate group, or

b) a polysiloxane of the formula VI, with an amino acid isocyanate selected from the formulae IXa, IXb, IXc, IXd or mixtures thereof

HA-Q2′-B-Q1′-AH  (VI)

Q2*—NH(CO)NH-″2Q-NCO  (IXa)

Q1*—NH(CO)NH-″1-NCO  (IXb)

Q2*—NH(CO)NH-Q2″-NCO  (IXc)

Q1*—NH(CO)NH-Q1″-NCO  (IXd)

where A is —NH—, —O— or —S— and D is —NH— in each case independently in formulae VII, I and VI,

where Q1′ and Q2′ in each case independently comprising a bivalent hydrocarbon radical with 6 to 200 carbon atoms optionally comprising at least one heteroatom O, N or S, a bivalent radical comprising aryl, arylalkylgroups or a bivalent radical comprising aryl, arylalkyl groups optionally comprising at least one heteroatom O, N or S or polyether radicals containing alkyl, aryl or alkyl and aryl groups, in each case independently in formulae VII, I and VI,

where Q1″ and Q2″ in each case independently comprises a bivalent linear, branched and/or cyclic alkyl radical with 4 to 200 carbon atoms, or a bivalent radical comprising an aryl and/or arylalkyl radical with 6 to 200 carbon atoms, in each case independently in formulae VII, I, IXa, IXb, IXc and IXd

where —NH-Q1* and —NH-Q2* comprises in each case independent radicals which are derived from an amino acid, amino acid derivative or salt thereof.

16 . The process according to claim 15 , wherein

formulae IXa, IXb, IXc and/or IXd and I—NH-Q1* and —NH-Q2* in each case independently comprise radicals which are derived from an amino acid, amino acid derivative or salt thereof and —NH in —NH-Q1* and —NH-Q2* in each case is in the alpha position relative to an ester or a carboxyl group of the amino acid, the amino acid derivative or salt thereof, where the ester comprises alkyl ester with 1 to 25 carbon atoms or aryl ester.

17 . The process according to claim 15 , wherein

the polysiloxane of the formula VI is reacted with a diisocyanate to give a polysiloxane diisocyanate of the formula VII,

HA-Q2′-B-Q1′-AH  (VI)

OCN-Q2″-D-(O═C)-A-Q2′-B-Q1′-A-(C═O)-D-Q1″-NCO  (VII)

where A is selected from —O, —NH, —S—

where -AH is selected from —OH, —NH 2 , and —SH and

where -Q2″- and/or -Q1″- independently selected from a bivalent, linear, branched and/or cyclic alkyl radical with 4 to 200 carbon atoms, or a bivalent radical comprising an aryl and/or arylalkyl radical with 6 to 200 carbon atoms, where the molar ratio of HA groups in the polysiloxane to isocyanate groups in formula VII is at least 1:1.

18 . The process according to claim 15 , which comprises

reacting

(i) a) a polysiloxane-group-containing linear and/or branched polymer block B, with at least two terminal Si—H groups or at least one terminal Si—H group and at least one lateral Si—H group, or b) a polysiloxane group of the formula XI with at least one

R 17 is hydrogen,

with (ii) an olefinic compound comprising alkylene and optionally comprising at least one heteroatom N and/or O,

where the olefinic compound has in each case independently an allyl or vinyl group and corresponds to the formulae VIIIa and/or VIIIb

Q1′-AH  (VIIIa)

Q2′-AH  (VIIIb)

in the presence of

(iii) a catalyst to give a polysiloxane of the formula VI

HA-Q2′-B-Q1′-AH  (VI)

where in each case independently in formulae VIIIa, VIIIb and VI with AH independently selected from —OH and —NH 2 and with -Q2′- and -Q1′- in each case independently in formulae VIIIa, VIIIb and VI comprising a bivalent hydrocarbon radical with 6 to 200 carbon atoms optionally comprising at least one heteroatom O or N a bivalent radical comprising aryl, arylalkyl groups optionally comprising at least one heteroatom O or N olefinic polyether.

19 . The process according to claim 15 , wherein

a polysiloxane diisocyanate of the formula VII is reacted with an amino acid, amino acid derivative, salts thereof or mixtures thereof,

OCN-Q2″-D-(O═C)-A-Q2′-B-Q1′-A-(C═O)-D-Q1″-NCO  (VII)

where B is a linear and/or branched polysiloxane polymer block B, with -Q2′- and -Q1′- in each case independently comprising a bivalent hydrocarbon radical with 6 to 200 carbon atoms optionally comprising at least one heteroatom O, N, or S, a bivalent radical comprising aryl, arylalkyl groups optionally comprising at least one heteroatom O, N or S, or polyether radicals containing alkyl, aryl or alkyl and aryl groups, where A is in each case independently —NH—, —O— or —S— and D is —NH— in each case independently in formula VII, and where -Q2″- and/or -Q1″- are independently selected from a bivalent, linear, branched and/or cyclic alkyl radical with 4 to 200 carbon atoms, or a bivalent radical comprising an aryl and/or arylalkyl radical with 6 to 200 carbon atoms,

20 . The process according to claim 15 , wherein

the amino acid, the amino acid derivative or the salt has a secondary amino group, where the amino acid, the amino acid derivative or salts thereof are selected from nonpolar amino acids selected from alanine, valine, methionine, leucine, isoleucine, proline, tryptophan, phenylalanine, basic amino acids comprising arginine, histidine, polar and neutral amino acids comprising tyrosine, threonine, glutamine, glycine, serine, cysteine, asparagine and/or acid amino acids selected from glutamic acid and aspartic acid, where the derivatives of the amino acids comprise the mono-, dicarboxylic acid esters, amides of the primary amino groups of the amino acids, amides of the carboxylic acid groups of the amino acids and/or esters with the primary hydroxyl groups or thioesters of the HS group of the amino acids.

21 . The process according to claim 15 , wherein

a diisocyanate is reacted with an amino acid derivative or salt thereof to give an amino acid isocyanate.

22 . A composition obtainable by the process according to claim 15 .

23 . A compositions comprising the siloxane polymers according to claim 12 , and mixtures thereof comprising

a) siloxane polymers of the general formula XI, and mixtures thereof or

b) siloxane polymers with a central polysiloxane polymer block B selected from

(i) at least one siloxane polymer of the general formula I, and mixtures comprising this polymer,

(ii) at least one siloxane polymer of the general formula Ia, and mixtures comprising this polymer or

(iii) at least one siloxane polymer of the general formula Ib, and mixtures comprising this polymer.

24 . An intermediate for preparing siloxane polymers of the formula I according to claim 1 , selected from amino acid isocyanates or salts or mixtures thereof, of formulae IXa, IXb, IXc and IXd

Q2*—NH(CO)NH-″2Q-NCO  (IXa)

and/or

Q1*—NH(CO)NH-″1Q-NCO  (IXb)

Q2*—NH(CO)NH-Q2″-NCO  (IXc)

and/or

Q1*—NH(CO)NH-Q1″-NCO  (IXd)

in particular with amino acid isocyanates of the formulae IXa*, IXb*, IXc*, IXd* or salts thereof

25 . A formulation comprising at least one siloxane polymer according to claim 1 .

26 . A method of utilizing the siloxane polymers according to claim 1 as additives in cosmetic formulations, as additives in pharmaceutical formulations, in coatings, pastes, as foam stabilizers or foam additives for polyurethane foams, as hand improvers or impregnation compositions during the during the production of fibres, textiles, in cosmetic formulations for the treatment, post-treatment and protection of keratin fibres, and also skin and skin appendages, as additives in detergents, fabric softener formulations, in cosmetic formulations including creams, rinses, hair washing compositions, washing compositions, setting compositions, care rinses, care pastes, sprays, hair sprays, for improving the combability of keratin or textile fibres of natural or synthetic origin.