Polysiloxane polymer composition and preparation method thereof

Abstract

The invention relates to a polysiloxane polymer composition and a preparation method thereof. The polysiloxane polymer compositions of the present invention advantageously have a low content of cyclic siloxane small molecules, such as octamethylcyclotetrasiloxane (D4).

Description

Technical Field

[0001] The present invention relates to the field of polysiloxane polymers and compositions containing the polysiloxane polymers, in particular polysiloxane polymers containing quaternary ammonium groups, and also to a method for preparing the compositions containing the polysiloxane polymers. Background Art

[0002] Polysiloxane polymers have a wide range of uses in various fields. For example, such polymers are often used in fabric finishing agents or softeners. Such polysiloxane polymers generally contain a hydrophobic polysiloxane portion, a quaternary ammonium portion, and a hydrophilic portion, and the properties of these three portions give the polysiloxane polymer desired properties. In the prior art, the preparation of polysiloxane polymers involves the steps of reacting the polysiloxane portion, the quaternary ammonium portion, and the hydrophilic portion in the presence of a protonating agent and quaternizing. The protonating agent is added in a stoichiometric amount during the quaternization reaction.

[0003] Due to the wide application of polysiloxane polymers, it also brings corresponding environmental problems. During the storage and preparation of polysiloxane polymers, especially in the preparation process of the prior art, a large amount of environmentally unfriendly substances are generated, such as octamethylcyclotetrasiloxane, called D4, decamethylcyclopentasiloxane, called D5, and dodecamethylcyclohexasiloxane, called D6.

[0004] In view of the adverse effects of substances such as D4 on the environment, the European Chemicals Agency (ECHA) has listed D4 as a substance of very high concern (SVHC) and has set content requirements for it, with the goal of reducing D4, D5 or D6 in polysiloxane polymers or compositions containing them to a low level, for example, below 1000 ppm. The quaternized polysiloxane polymer products synthesized according to the prior art solutions cannot meet the requirements set by the European Chemicals Agency. For example, commercially available polysiloxane polymers containing quaternary ammonium moieties contain more than 1000 ppm of D4, D5 and D6 content, respectively.

[0005] No reliable solution is described in the prior art for reducing D4, D5 and D6 levels to below 1000 ppm on a long-term basis.

[0006] Therefore, there is a long-standing need for polysiloxane polymer compositions having low D4, D5 and / or D6 levels so that the public's increasing environmental concerns can be met. Summary of the invention

[0007] In view of the above technical problems, the present invention provides a polysiloxane polymer composition that meets the requirements of the European Chemicals Agency on the content of D4, D5 and D6, and provides a preparation method for obtaining such a polysiloxane polymer composition. The inventors found that by carrying out the reaction of synthesizing a polysiloxane polymer in the presence of a strong acid with a pKa of not more than 3.0, the resulting polysiloxane polymer composition has low D4, D5, and D6 contents (hereinafter collectively referred to as Dn). In addition, the inventors found that, regardless of whether a strong acid with a pKa of not more than 3.0 is used during the reaction of synthesizing the polysiloxane polymer, adding a strong acid with a pKa of not more than 3.0 after the synthesis reaction can reduce the Dn content in the resulting polysiloxane polymer composition, as well as reduce the Dn content generated during storage. Obviously, using a strong acid with a pKa of not more than 3.0 during and after the synthesis reaction can best reduce the Dn content. Therefore, the present invention solves the technical problems related to high Dn content in the prior art.

[0008] The present invention includes the following embodiments.

[0009] According to one embodiment of the present invention, the present invention provides a polysiloxane polymer composition, wherein the polysiloxane polymer composition is a product obtained by a method comprising the following steps:

[0010] reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p);

[0011] wherein the protonated component (p) comprises at least one protonated compound (c) having a pKa greater than 3.0 and at least one protonated compound (d) having a pKa no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0, and wherein the molar ratio (∑ molar 质子化化合物(c) / ∑ mole 质子化化合物(d) ) ranges from 9:1 to 0.1:1, preferably from 9:1 to 0.2:1, more preferably from 5:1 to 0.2:1, even more preferably from 2:1 to 0.2:1, most preferably from 2:1 to 0.4:1, still more preferably from 2:1 to 1:1;

[0012] The polysiloxane polymer comprises the following repeating units:

[0013] [-L 1 -(SiOR 1 R 2 ) n -L 2 -N + R 3 R 4 -ZN+ R 5 R 6 -] u Formula I,

[0014] Where u is 2 to 100; L 1 and L 2 are the same or different and are selected from a covalent bond and a hydrocarbon chain having 1 to 20 carbon atoms, which is optionally substituted by O, N or S atoms, or by a group containing O, N or S atoms; R 1 and R 2 are identical or different and are selected from optionally substituted hydrocarbon chains containing 1 to 20 carbon atoms, preferably methyl, n is 1 to 1000, preferably 20 to 500, preferably 40 to 450, more preferably 50 to 200, even more preferably 50 to 150; and

[0015] Z is a hydrocarbon chain containing 2 to 20 carbon atoms and is optionally substituted by O, N, S atoms, or by groups containing O, N or S atoms, preferably substituted by OH groups; R 3 , R 4 , R 5 and R 6 are the same or different and are selected from hydrocarbon chains containing 1 to 20 carbon atoms,

[0016] Alternatively, the polysiloxane polymer comprises repeating units having formula I':

[0017] [-L 3 '-Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4 '-N + (R 3 )(R 4 )-ZN + (R 5 )(R 6 )-] u Formula I'

[0018] Where n, u, L 1 , L 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Z is defined as above,

[0019] Y 3 and Y 4 are the same or different and are each independently selected from O, N(R 7 ) or S, R 7 =H or C1-C3 hydrocarbon group, such as C1-C3 alkyl;

[0020] L 3’ and L 4’ are the same or different and are selected from a covalent bond and a hydrocarbon chain substituted with a group containing O, N or S atoms, preferably OH, NH2 or SH and having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 3 to 4 carbon atoms; in particular, the OH, NH2 or SH is obtained from a ring-opening reaction of an oxygen-containing heterocycle having a single oxygen atom, a nitrogen-containing heterocycle having a single nitrogen atom or a sulfur-containing heterocycle having a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group) at the end of the corresponding alkylene group of the hydrophobic component (a);

[0021] Preferably, L 1 and L 2 are identical or different and are each independently selected from an alkylene group having 1 to 6 carbon atoms, in particular having 2, 3, 4 or 5 carbon atoms;

[0022] Preferably, R 3 , R 4 , R 5 and R 6 are each independently an alkyl group and Z is an alkylene group, more preferably Z is a straight chain alkylene group containing 2 to 8 carbon atoms such as butylene or hexylene, and R 3 , R 4 , R 5 and R 6 are the same or different and are each independently selected from an alkyl group containing 1 to 4 carbon atoms, for example, R 3 , R 4 , R 5 and R 6 All are methyl;

[0023] The polysiloxane polymer composition also includes a counter ion.

[0024] In the context of the present invention, aziridinyl groups and thioepoxy groups are epoxy equivalents in which the oxygen atom in the epoxy group is replaced by a nitrogen atom (or an amine group) and a sulfur atom, respectively.

[0025] According to one embodiment of the present invention, the polysiloxane polymer composition is a product obtained by a method comprising the following steps:

[0026] reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p); the protonated component (p) comprising at least one protonated compound (c) having a pKa greater than 3.0, and

[0027] using a protonated compound (d) during said reaction,

[0028] adding the protonated compound (d) after the reaction, or

[0029] using a protonated compound (d) during the reaction and adding the protonated compound (d) after the reaction;

[0030] The protonated compound (d) has a pKa of no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, and most preferably no greater than 1.0;

[0031] The polysiloxane polymer comprises the following repeating units:

[0032] [-L 1 -(SiOR 1 R 2 ) n -L 2 -N + R 3 R 4 -ZN + R 5 R 6 -] u Formula I,

[0033] Where u is 2 to 100; L 1 and L 2 are the same or different and are selected from a covalent bond and a hydrocarbon chain having 1 to 20 carbon atoms, which is optionally substituted by O, N or S atoms, or by a group containing O, N or S atoms; R 1 and R 2 are identical or different and are selected from optionally substituted hydrocarbon chains containing 1 to 20 carbon atoms, preferably methyl, n is 1 to 1000, preferably 20 to 500, preferably 40 to 450, more preferably 50 to 200, even more preferably 50 to 150; and

[0034] Z is a hydrocarbon chain containing 2 to 20 carbon atoms and is optionally substituted by O, N, S atoms, or by groups containing O, N or S atoms, preferably substituted by OH groups; R 3 , R 4 , R 5 and R 6 are the same or different and are selected from hydrocarbon chains containing 1 to 20 carbon atoms,

[0035] Alternatively, the polysiloxane polymer comprises repeating units having formula I':

[0036] [-L 3 '-Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4 '-N + (R 3 )(R 4 )-ZN + (R 5 )(R 6 )-] u Formula I'

[0037] Where n, u, L 1 , L 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Z is defined as above,

[0038] Y 3 and Y 4 are the same or different and are each independently selected from O, N(R 7 ) or S, R 7 =H or C1-C3 hydrocarbon group, such as C1-C3 alkyl;

[0039] L 3’ and L 4’ are the same or different and are selected from a covalent bond and a hydrocarbon chain substituted with a group containing O, N or S atoms, preferably OH, NH2 or SH and having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 3 to 4 carbon atoms; in particular, the OH, NH2 or SH is obtained from a ring-opening reaction of an oxygen-containing heterocycle having a single oxygen atom, a nitrogen-containing heterocycle having a single nitrogen atom or a sulfur-containing heterocycle having a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group) at the end of the corresponding alkylene group of the hydrophobic component (a);

[0040] Preferably, L 1 and L 2are identical or different and are each independently selected from an alkylene group having 1 to 6 carbon atoms, in particular having 2, 3, 4 or 5 carbon atoms;

[0041] Preferably, R 3 , R 4 , R 5 and R 6 are each independently an alkyl group and Z is an alkylene group, more preferably Z is a straight chain alkylene group containing 2 to 8 carbon atoms such as butylene or hexylene, and R 3 , R 4 , R 5 and R 6 are the same or different and are each independently selected from an alkyl group containing 1 to 4 carbon atoms, for example, R 3 , R 4 , R 5 and R 6 All are methyl;

[0042] The polysiloxane polymer composition also includes a counter ion.

[0043] According to one embodiment of the present invention, the polysiloxane polymer further comprises a 1 -(SiOR 1 R 2 ) n -L 2 -Y 1’ -EY 2’ -] v The repeating unit,

[0044] Wherein: v is 1 to 100, E is a covalent bond or a polyether moiety comprising one or more of the following repeating units: -(ethylene oxide) x -,-(propylene oxide) y -or-(butylene oxide) z -, x, y and z are the same or different and

[0045] x=0 or 1-100, preferably 1-20, more preferably 1-10, even more preferably 1-5, most preferably 1, 2 and 3,

[0046] y=0 or 1-100, preferably 1-20, more preferably 1-10, even more preferably 1-5, most preferably 1, 2 and 3,

[0047] z=0 or 1-100, preferably 1-20, more preferably 1-10, even more preferably 1-5, most preferably 1, 2 and 3,

[0048] x+y+z=0-100, preferably 0 and 1-100, more preferably 1-20, even more preferably 1-10, most preferably 0, 1, 2, 3;

[0049] Y 1’ and Y 2’ containing a functional group independently selected from the following: a nitrogen-containing group, an oxygen-containing group or a sulfur-containing group, preferably an amine-containing group, a hydroxyl-containing group or a thiol-containing group, more preferably an amine-containing group, most preferably a secondary amine-containing group, a tertiary amine-containing group, an amine salt derived from a secondary amine-containing group or a tertiary amine-containing group, or a quaternary ammonium-containing group, Y 1’ and Y 2’ At least one of the optionally contains a functional group connected to E or to Y 1’ and Y 2’ The other of and a hydrocarbon group containing 1 to 20 carbon atoms,

[0050] Alternatively, the polysiloxane polymer further comprises a repeating unit having the formula II':

[0051] [-L 3’ -Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4’ -Y 1’ -EY 2’ -] v Formula II'

[0052] Where n, v, L 1 , L 2 , R 1 , R 2 , E, Y 1’ , Y 2’ , L 3’ , Y 3 , Y 4 and L 4’ As defined above,

[0053] Preferably, Y 1’ and Y 2’ At least one of the above functional groups optionally contains a functional group connected to E or to Y 1’ and Y 2’ and another of the functional groups and containing 1-20 carbon atoms, in particular alkylene, such as linear or branched alkylene containing 1-6 or 1-3 carbon atoms, and at least one of the above functional groups is optionally directly connected to E by a covalent bond.

[0054] The above expression “(ethylene oxide) x” refers to the units obtained after polymerization of ethylene oxide.

[0055] According to one embodiment of the present invention, the hydrophobic component (a) comprises a structure having formula III:

[0056] X 1 -L 1 -(SiOR 1 R 2 ) n -L 2 -X 2 Formula III

[0057] Where: L 1 and L 2 are identical or different and are selected from a covalent bond and a hydrocarbon chain having 1 to 20 carbon atoms, which is optionally substituted by O, N or S atoms, or by a group containing O, N or S atoms; X 1 and X 2 The groups are identical or different and are selected from H, epoxy or hydroxyl, or derived from ethylene oxide, propylene oxide or butylene oxide, and when L 1 and L 2 When it is a covalent bond, X 1 and X 2 The group is H; R 1 and R 2 are the same or different and are selected from optionally substituted hydrocarbon chains containing 1 to 20 carbon atoms, preferably methyl, n is 1 to 1000, preferably 20 to 500, preferably 40 to 450, more preferably 50 to 200, even more preferably 50 to 150,

[0058] Alternatively, the hydrophobic component (a) comprises a structure having the formula III':

[0059] L 3 -Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4 Formula III'

[0060] Among them, n, L 1 , L 2 , R 1 , R 2 , Y 3 and Y 4 As defined above, L 3 and L 4The same or different and are a hydrocarbon chain containing an oxygen-containing heterocycle with a single oxygen atom, a nitrogen-containing heterocycle with a single nitrogen atom, or a sulfur-containing heterocycle with a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group), preferably a 3-5-membered ring, and having 2-20 carbon atoms, preferably an alkylene group with 2-6 carbon atoms, more preferably an alkylene group with 3-4 carbon atoms; in particular, the oxygen-containing heterocycle with a single oxygen atom, the nitrogen-containing heterocycle with a single nitrogen atom, or the sulfur-containing heterocycle with a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group) is located at the end of the alkylene group.

[0061] According to one embodiment of the present invention, the quaternized component (b) comprises the structure of the following formula IV:

[0062] NR 3 R 4 -Z-NR 5 R 6 Formula IV

[0063] Wherein: Z is a straight chain, branched or cyclic hydrocarbon moiety containing 2 to 20 carbon atoms, and is optionally substituted by O, N, S atoms, or by a group containing O, N or S atoms, preferably substituted by an OH group; R 3 , R 4 , R 5 and R 6 are the same or different and are selected from hydrocarbon groups containing 1 to 20 carbon atoms,

[0064] Alternatively, the quaternized component (b) comprises the structure of Formula IV':

[0065] N(R 3 )(R 4 )-ZN(R 5 )(R 6 ) Formula IV'

[0066] Among them, R 3 , R 4 , R 5 , R 6 and Z is as defined above;

[0067] Preferably, R 3 , R 4 , R 5 and R 6 are each independently an alkyl group and Z is an alkylene group, more preferably Z is a straight chain alkylene group containing 2 to 8 carbon atoms such as butylene or hexylene, and R 3 , R 4 , R 5and R 6 are the same or different and are each independently selected from an alkyl group containing 1 to 4 carbon atoms, for example, R 3 , R 4 , R 5 and R 6 All are methyl.

[0068] According to one embodiment of the present invention, a hydrophilic component (e) is also present in the reaction, and the hydrophilic component (e) contains a structure having Formula V:

[0069] Y 1 -EY 2 Formula V

[0070] Where: E has the same meaning as defined above; Y 1 and Y 2 contains a functional group independently selected from the following: a nitrogen-containing group, an oxygen-containing group or a sulfur-containing group, preferably an amine-containing group, a hydroxyl-containing group or a thiol-containing group, more preferably an amine-containing group, most preferably a primary amine-containing group or a secondary amine-containing group, Y 1 and Y 2 At least one of the optionally contains a functional group connected to E or to Y 1 and Y 2 The other of and a hydrocarbon group containing 1 to 20 carbon atoms,

[0071] Alternatively, the hydrophilic component (e) comprises a structure having the formula V':

[0072] Y 1 -EY 2 Formula V'

[0073] where Y 1 , Y 2 and E is defined as above,

[0074] Preferably, Y 1 and Y 2 At least one of the above functional groups optionally contains a functional group connected to E or to Y 1 and Y 2 and another of the functional groups and containing 1-20 carbon atoms, in particular alkylene, such as linear or branched alkylene containing 1-6 or 1-3 carbon atoms, and at least one of the above functional groups is optionally directly connected to E by a covalent bond.

[0075] According to one embodiment of the present invention, the protonated compound (c) comprises one or more of the following:

[0076] ○ Straight-chain or branched, saturated or unsaturated, optionally containing -O- or substituted by -OH C2-C 30Carboxylic acid, preferably a carboxylic acid containing an ether group, having R e -O-(EO) p -CH2COOH structure, where p = 1-100 and R e is an optionally substituted hydrocarbon group containing 1 to 20 carbon atoms, preferably an alkyl group;

[0077] ○ Straight chain or branched C 18 -C 200 Polymerized fatty carboxylic acids,

[0078] ■Preferred are the following types of polymerized fatty carboxylic acids:

[0079] R p1 [(-C(O)-XR p6 ) m -C(O)-XR p7 ] x or

[0080] R p1 [(XC(O)-R p6 ) m -XC(O)-R p7 ] x ,

[0081] Where R p1 or R p7 At least one of, or R p1 and R p7 At least one of them carries one or more carboxyl groups,

[0082] In particular,

[0083] -Linear polymerized fatty carboxylic acids of the following types

[0084] HO-C(O)-R p6 (-XC(O)-R p6 ) m-1 -XC(O)-R p7 ,

[0085] More specifically HO-C(O)-R p6 -(OC(O)-R p6 ) m -OC(O)-R p7 ,

[0086] - branched linear polymeric fatty carboxylic acids, in particular derived from partial esters of polyfunctional carboxylic acids, in particular derived from the dicarboxylic acids succinic and maleic acid with castor oil or lesquerella oil, for example

[0087]

[0088] One R in the above formula is And the remaining two R are

[0089]

[0090] -Branched polymer fatty carboxylic acid

[0091] ■ Or preferably the following types of polymerized fatty carboxylic acids:

[0092] XR p6 (-C(O)-XR p6 ) m-1 -C(O)-XR p7 or

[0093] R p6 (-C(O)-XR p6 ) m-1 -C(O)-XR p7 ,

[0094] In the latter two types, R p7 The group carries at least one carboxylic acid group,

[0095] ■ Or preferably the following types of polymerized fatty carboxylic acids:

[0096] R p1 [(-C(O)-XR p6 ) m -C(O)OH] x ,

[0097] In the above polymerized fatty carboxylic acid formula, each independently,

[0098] x=1-50,m=1-20,X=O or NR p11 , preferably X=O,

[0099] R p1 is selected from x-valent, optionally substituted hydrocarbon groups having up to 1000 carbon atoms, preferably 2-300 carbon atoms, more preferably 3-200 carbon atoms, even more preferably 3-150 carbon atoms, in particular 3-50 carbon atoms, more in particular 3-20 carbon atoms, and containing optionally one or more groups selected from: -O-, -NH-, -C(O)-, -C(S)-, tertiary amine groups and is optionally substituted by one or more groups selected from OH groups and halogen groups;

[0100] R p6independently selected from optionally substituted linear, cyclic or branched, saturated or unsaturated hydrocarbon groups having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 8 to 18 carbon atoms;

[0101] R p7 independently selected from optionally substituted linear, cyclic or branched, saturated or unsaturated hydrocarbon groups having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 8 to 18 carbon atoms, which optionally contain one or more groups selected from the following: -O-, -NH-, -C(O)-, -C(S)-, tertiary amine groups Quaternary ammonium group and which is optionally substituted by an OH group or a halogen group, wherein R p7 The group does not contain a combination of -C(O)- and -(O)- groups, or a combination of -C(O)- and -NH- or tertiary amine groups, that form an internal carboxylate group or an internal amide group; provided that at least one R p6 Having more than 6 carbon atoms;

[0102] R p11 independently selected from hydrogen, optionally substituted linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 100 carbon atoms, which optionally contain one or more radicals selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amine radicals and is optionally substituted with one or more hydroxyl or halogen groups;

[0103] ■ Or preferably the following types of polymerized fatty carboxylic acids:

[0104]

[0105] In this formula, R is

[0106]

[0107] Preferably, the protonated compound (c) comprises one or more selected from the group consisting of acidic amino acids, such as aspartic acid and glutamic acid, lactic acid, 2-ethylhexanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, ricinoleic acid, 12-hydroxy-octadecanoic acid, succinic acid, maleic acid, tartaric acid, polyether carboxylic acids, citric acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid and lauric acid.

[0108] According to one embodiment of the present invention, the protonated compound (d) comprises one or more selected from the following: an acid containing a sulfonate group, preferably an alkyl or aryl substituted sulfonic acid, a hydrohalic acid, an oxygen-containing acid from an element of main group V to VI, an acid containing a sulfate group, an acid containing a phosphate group or a phosphonate group, a carboxylic acid containing 2 to 20 carbon atoms;

[0109] Preferably, the protonated compound (d) comprises one or more selected from the group consisting of phosphoric acid, optionally substituted aminosulfonic acid, methylaminosulfonic acid, HCl, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, hydrogen sulfate, phosphonic acid, aminophosphonic acid or aminocarboxylic acid.

[0110] According to one embodiment of the present invention, the weight content of the components in the reaction relative to the sum of the weight contents of the components is:

[0111] Hydrophobic component (a), 50-95%, preferably 60%-90%, more preferably 70-90%,

[0112] Quaternized component (b), 0.1-10%, preferably 0.3-7%, more preferably 0.5-5%,

[0113] Optional hydrophilic component (e), 0%, or 0.1-10%, preferably 0.3-7%, more preferably 0.5-5%, protonated component (p), 0.1%-20%, preferably 0.5-15%, more preferably 1-10%, and

[0114] Optional reaction medium (f), 0%, or 1-60%, preferably 5-50%, more preferably 10-40%, most preferably reaction medium (f) consists of 5-20% of dipropylene glycol n-butyl ether and 5-20% of water,

[0115] Provided that the sum of the weight contents of the above components does not exceed 100%.

[0116] According to one embodiment of the present invention, the polysiloxane polymer composition is acidic, preferably having a pH of 2 to less than 7, more preferably a pH of 2 to 6, even more preferably a pH of 3 to 6, still more preferably a pH of 4 to 6, and most preferably a pH of 4 to 5.5, wherein the pH is measured as follows: the polysiloxane polymer composition is diluted with a mixed solvent to a concentration of 10% in a weight ratio of 1:10, and the pH value is measured, wherein the mixed solvent is a mixed solvent of isopropanol and water in a volume ratio of 5:3,

[0117] In particular, in the case where a protonated compound (d) is used after the reaction is completed, the pH value is the result of the added protonated compound (d); more particularly, the pH of the polysiloxane polymer composition is 4.2 to 6, 4.4 to 6 or 4.6 to 6, or the pH of the polysiloxane polymer composition is 4.2 to 5.5, 4.4 to 5.5 or 4.6 to 5.5 or 4.6 to 5.7.

[0118] According to one embodiment of the present invention, the molar ratio of the protonated component (p) relative to the tertiary amine groups in the quaternized component (b) is lower than the stoichiometric ratio, the stoichiometric ratio or higher, preferably the molar ratio of the protonated component (p) relative to the tertiary amine groups in the quaternized component (b) is no more than 0.5 times, 0.7 times, 0.9 times, 1.0 times, 1.2 times, 1.4 times, 1.5 times, 2 times, 3 times or 4 times the stoichiometric ratio, preferably the molar ratio of the protonated component (p) relative to the tertiary amine groups in the quaternized component (b) is 0.5 to 4:1, more preferably 0.5 to 2:1, 0.7 to 2:1 or 0.9 to 2:1, even more preferably 0.5 to <1:1, 1:1, >1 to 2:1, most preferably >1 to 1.5:1, >1 to 1.4:1 or >1 to 1.2:1.

[0119] According to one embodiment of the present invention, the reaction is carried out in the presence of a reaction medium (f), and the reaction medium (f) preferably comprises a polar solvent and a non-polar solvent. The polar solvent is preferably selected from water, alcohols, ethers, esters and glycols, and the non-polar solvent is preferably selected from saturated, unsaturated or aromatic hydrocarbons, such as toluene and xylene. Preferably, the reaction medium (f) comprises a mixture of water and alcohol or a mixture of water and ether, in particular a mixture of water and 2-propanol or a mixture of water and dipropylene glycol n-butyl ether. Preferably, the mass ratio of dipropylene glycol n-butyl ether to water is 0.5:1 to 10:1, or 0.7:1 to 7:1, or 1:1 to 5:1.

[0120] According to one embodiment of the present invention, the molar ratio between the repeating unit of formula I and the repeating unit of formula II is 0.1 to 4, or 1 to 4, or 2 to 3.

[0121] According to one embodiment of the present invention, the molar ratio between the hydrophobic component (a) and the quaternized component (b) is 1 to 10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6.

[0122] According to one embodiment of the present invention, the molar ratio between the hydrophilic component (e) and the quaternized component (b) is from 0.05 to 0.9, or from 0.1 to 0.8, or from 0.2 to 0.7, or from 0.3 to 0.6, or from 0.4 to 0.5.

[0123] According to one embodiment of the present invention, in the case where a protonated compound (d) is used during the reaction, in order to obtain the polysiloxane polymer composition, there is a step of adding the protonated compound (d) after the reaction.

[0124] According to one embodiment of the present invention, in the case where a protonated compound (d) is used during the reaction, in order to obtain the polysiloxane polymer composition, the protonated compound (d) is not added after the reaction.

[0125] According to one embodiment of the present invention, in the case where a protonated compound (d) is used after the reaction is completed, the reaction for obtaining the polysiloxane polymer composition is carried out in the presence of the protonated compound (d).

[0126] According to one embodiment of the present invention, in the case where a protonated compound (d) is used after the reaction is completed, the reaction to obtain the polysiloxane polymer composition is carried out without the protonated compound (d).

[0127] According to one embodiment of the present invention, in the case where a protonated compound (d) is used after the reaction is completed, during the reaction the protonated component (p) comprises at least one protonated compound (c) having a pKa greater than 3.0 and at least one protonated compound (d) having a pKa of not greater than 3.0, preferably not greater than 2.5, preferably not greater than 2.0, more preferably not greater than 1.5, most preferably not greater than 1.0, and wherein the molar ratio (∑ molar) of all protonated compounds (c) to all protonated compounds (d) during the reaction is 质子化化合物(c) / ∑ mole 质子化化合物(d) ) ranges from 9:1 to 0.1:1, preferably 9:1 to 0.2:1, more preferably 5:1 to 0.2:1, even more preferably 2:1 to 0.2:1, most preferably 2:1 to 0.4:1, still more preferably 2:1 to 1:1.

[0128] According to one embodiment of the present invention, in the case of using a protonated compound (d) after the reaction is completed, the reaction to obtain the polysiloxane polymer composition is carried out in the absence of a protonated compound (d), wherein the molar ratio of all protonated compounds (c) to all protonated compounds (d) is 1:0.2 to 1:1.

[0129] According to one embodiment of the present invention, in the case where a protonated compound (d) is used during the reaction and after the reaction, the molar ratio between the sum of the protonated compound (c) and the protonated compound (d) used during the reaction and the protonated compound (d) added after the reaction is 1:0.1 to 1:1, preferably 1:0.2 to 1:1, more preferably 1:0.2 to 1:0.8, even more preferably 1:0.2 to 1:0.6, and most preferably 1:02 to 1:0.4.

[0130] In one embodiment, the pKa of the protonated compound (d) is no greater than 2.5 and the pKa of the protonated compound (c) is greater than 2.5, or the pKa of the protonated compound (d) is no greater than 2.0 and the pKa of the protonated compound (c) is greater than 2.0.

[0131] The present invention also provides a method for preparing a polysiloxane polymer composition, wherein the method comprises:

[0132] reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p);

[0133] wherein the protonated component (p) comprises at least one protonated compound (c) having a pKa greater than 3.0 and at least one protonated compound (d) having a pKa no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0, and wherein the molar ratio of the protonated compound (c) to the protonated compound (d) ranges from 9:1 to 0.1:1, preferably from 9:1 to 0.2:1, more preferably from 5:1 to 0.2:1, even more preferably from 2:1 to 0.2:1, most preferably from 2:1 to 0.4:1, still more preferably from 2:1 to 1:1.

[0134] According to one embodiment of the present invention, in the case where a protonated compound (d) is used during the reaction, in order to obtain the polysiloxane polymer composition, there is a step of adding the protonated compound (d) after the reaction.

[0135] According to one embodiment of the present invention, in the case where a protonated compound (d) is used during the reaction, in order to obtain the polysiloxane polymer composition, the protonated compound (d) is not added after the reaction.

[0136] The present invention also provides another method for preparing a polysiloxane polymer composition, wherein the method comprises:

[0137] reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p); the protonated component (p) comprising at least one protonated compound (c) having a pKa greater than 3.0;

[0138] A protonated compound (d) having a pKa of no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0 is added after the reaction.

[0139] According to one embodiment of the present invention, in the case where a protonated compound (d) is used after the reaction is completed, the reaction for obtaining the polysiloxane polymer composition is carried out in the presence of the protonated compound (d).

[0140] According to one embodiment of the present invention, in the case where a protonated compound (d) is used after the reaction is completed, the reaction to obtain the polysiloxane polymer composition is carried out without the protonated compound (d).

[0141] The polysiloxane polymer composition according to the present invention or the polysiloxane polymer composition prepared by the method according to the present invention can be used in the fields of fibers, fabrics, cosmetics or personal care.

[0142] The polysiloxane polymer composition according to the present invention has a Dn content of less than 1000 ppm, which makes the polysiloxane polymer composition of the present invention more environmentally friendly than the polysiloxane polymer composition of the prior art and meets the Dn content requirements of the European Chemicals Agency (ECHA). DETAILED DESCRIPTION

[0143] Polysiloxane polymer composition and preparation method thereof

[0144] The polysiloxane polymer composition according to the present invention is a composition containing a polysiloxane polymer, wherein the polysiloxane polymer contains at least a polysiloxane portion (hydrophobic portion) and a quaternary ammonium portion, and optionally other portions such as a hydrophilic portion.

[0145] In the context of the present invention, unless otherwise stated, expressions such as "hydrocarbon group", "hydrocarbon chain", "alkyl" or "alkylene" used in the various components are intended to cover any form of molecular moiety, such as optionally substituted, saturated or unsaturated (for hydrocarbon group or hydrocarbon chain), straight-chain, branched or cyclic forms of molecular moieties.

[0146] The current method for preparing the above-mentioned polysiloxane polymers relies on the reaction of a hydrophobic component (a) containing a polysiloxane backbone and a quaternized component (b) containing tertiary amine groups and optionally other components (such as a hydrophilic component (e)) in the presence of a protonated component (p), wherein the protonated component (p) is an acid, and its amount is approximately equal to the stoichiometric ratio relative to the tertiary amine groups in the quaternized component (b). After the reaction is completed (after the reaction), a polysiloxane polymer composition is obtained, which is generally alkaline and contains a high Dn content, for example, a D4 content of more than 1000 ppm.

[0147] Without wishing to be bound by theory, the inventors have found based on experiments and studies that polymers containing positively charged quaternary ammonium moieties and polysiloxane moieties tend to produce high levels of Dn under alkaline conditions. Therefore, adjusting the reaction product mixture to be acidic helps to reduce the content of Dn.

[0148] The inventors have found based on experiments that if a certain amount of strong acid (corresponding to the protonated compound (d), herein refers to an acid with a pKa of no more than 3.0, preferably no more than 2.5, preferably no more than 2.0, more preferably no more than 1.5, and most preferably no more than 1.0) is used during the above reaction, the polysiloxane polymer composition obtained after the reaction has a lower Dn content. It was found that the Dn content is reduced when the molar ratio of the protonated component (p) relative to the tertiary amine groups in the quaternized component (b) is substoichiometric, stoichiometric or higher, preferably the molar ratio of the protonated component (p) relative to the tertiary amine groups in the quaternized component (b) is no more than 0.5 times, 0.7 times, 0.9 times, 1.0 times, 1.2 times, 1.4 times, 1.5 times, 2 times, 3 times or 4 times the stoichiometric ratio, preferably the molar ratio of the protonated component (p) relative to the tertiary amine groups in the quaternized component (b) is 0.5 to 4:1, more preferably 0.5 to 2:1, 0.7 to 2:1 or 0.9 to 2:1, even more preferably 0.5 to <1:1, 1:1, >1 to 2:1, most preferably >1 to 1.5:1, >1 to 1.4:1 or >1 to 1.2:1.

[0149] In addition, in the case of using a strong acid during the reaction, it was found that when the molar ratio of the protonated compound (c) to the protonated compound (d) during the reaction is in the range of 9:1 to 0.1:1, preferably 9:1 to 0.2:1, more preferably 5:1 to 0.2:1, even more preferably 2:1 to 0.2:1, most preferably 2:1 to 0.4:1, still more preferably 2:1 to 1:1, it is advantageous to reduce the Dn content.

[0150] On the other hand, the inventors have experimentally found that, regardless of whether a strong acid is used during the reaction, when a strong acid (corresponding to the protonated compound (d)) is added to the reaction product mixture after the above reaction process, the obtained polysiloxane polymer composition has a lower Dn content. Therefore, in the case where a strong acid is used after the reaction, it is preferred to make the polysiloxane polymer composition acidic, and the polysiloxane polymer composition preferably has a pH of 2 to less than 7, more preferably a pH of 2 to 6, even more preferably a pH of 3 to 6, still more preferably a pH of 4 to 6, and most preferably a pH of 4 to 5.5, wherein the pH is measured as follows: the pH value is measured after the polysiloxane polymer composition is diluted with a mixed solvent to a concentration of 10% in a weight ratio of 1:10, and the mixed solvent is a mixed solvent of isopropanol and water in a volume ratio of 5:3, in particular, in the case where a protonated compound (d) is used after the reaction is completed, the pH value is the result of the added protonated compound (d); more particularly, the pH of the polysiloxane polymer composition is 4.2 to 6, 4.4 to 6 or 4.6 to 6, or the pH of the polysiloxane polymer composition is 4.2 to 5.5, 4.4 to 5.5 or 4.6 to 5.5 or 4.6 to 5.7.

[0151] As a non-limiting example, the above-mentioned favorable pH range may be applicable to a reaction system in which the weight content of the components in the reaction relative to the sum of the weight contents of the components is:

[0152] Hydrophobic component (a), 50-95%, preferably 60%-90%, more preferably 70-90%,

[0153] Quaternized component (b), 0.1-10%, preferably 0.3-7%, more preferably 0.5-5%,

[0154] Optional hydrophilic component (e), 0%, or 0.1-10%, preferably 0.3-7%, more preferably 0.5-5%, protonated component (p), 0.1%-20%, preferably 0.5-15%, more preferably 1-10%, and

[0155] Optional reaction medium (f), 0%, or 1-60%, preferably 5-50%, more preferably 10-40%, most preferably reaction medium (f) consists of 5-20% of dipropylene glycol n-butyl ether and 5-20% of water,

[0156] Provided that the sum of the weight contents of the above components does not exceed 100%.

[0157] If the protonated compound (d) in the protonated component (p) is added in the form of an aqueous solution, the protonated compound (d) is expressed in the weight content of the protonated component (p) as the weight of the aqueous solution.

[0158] In the case where a protonated compound (d) is used after the reaction is completed, the reaction to obtain the polysiloxane polymer composition can be carried out in the absence of a protonated compound (d), in which case the molar ratio of all protonated compounds (c) to all protonated compounds (d) is 1:0.2 to 1:1, which can obtain a reduced Dn content.

[0159] In addition, in the case where the protonated compound (d) is used after the reaction is completed, the protonated component (p) may also contain the protonated compound (d) during the reaction, and wherein the molar ratio (∑ molar) of all protonated compounds (c) and all protonated compounds (d) during the reaction is 质子化化合物(c) / ∑ mole 质子化化合物(d) ) ranges from 9:1 to 0.1:1, preferably from 9:1 to 0.2:1, more preferably from 5:1 to 0.2:1, even more preferably from 2:1 to 0.2:1, most preferably from 2:1 to 0.4:1, still more preferably from 2:1 to 1:1. In the case where a protonated compound (d) is used during the reaction and after the reaction is completed, the molar ratio between the sum of the protonated compound (c) and the protonated compound (d) used during the reaction and the protonated compound (d) added after the reaction is from 1:0.1 to 1:1, preferably from 1:0.2 to 1:1, more preferably from 1:0.2 to 1:0.8, even more preferably from 1:0.2 to 1:0.6, most preferably from 1:02 to 1:0.4. It has been found that the use of the above amounts of protonated compounds is advantageous in obtaining a reduced Dn content.

[0160] Unless otherwise specified, the pH values ​​mentioned in the present invention refer to the pH values ​​measured after the test object (e.g., polysiloxane polymer composition or reactant mixture) is diluted to a concentration of 10% (diluted at a weight ratio of 1:10) with a mixed solvent. The mixed solvent used for dilution is a mixed solvent of isopropanol and water in a volume ratio of 5:3. After the test object and the mixed solvent are fully mixed and dissolved, the S20 SevenEasy TM The pH value is measured with a pH meter. The 1:10 dilution refers to diluting 1 part by weight of the test substance with 9 parts by weight of a mixed solvent. Based on the above research, the inventors found that the best results can be obtained by using a strong acid both during the reaction and after the reaction. Specifically, the use of a strong acid during the reaction can reduce the content of Dn produced during the reaction. Subsequently, the use of a strong acid after the reaction is completed can reduce the content of Dn produced during storage. The overall result is that the content of Dn (such as D4) in the main process involving the production and storage of polysiloxane polymers is reduced. Obviously, the present invention is not limited to this optimal mode of implementation. The use of a strong acid during the reaction process and after the reaction is completed can be implemented separately or together.

[0161] Furthermore, in the case where a strong acid is used both during the reaction and after the reaction, the strong acids used during the reaction and after the reaction may be the same or different, although the same word "strong acid" is used. In the present invention, the expression "protonated compound (d)" is intended to include one or more strong acids that meet the definition of the present invention. This principle also applies to other components / ingredients. When the "protonated compound (d)" is used both during the reaction and after the reaction, the "protonated compound (d)" used during the reaction and after the reaction may be the same or different.

[0162] In view of the above, a number of preferred methods for obtaining the polysiloxane polymer composition can be summarized as follows.

[0163] To obtain the polysiloxane polymer composition, the protonated compound (d) is used only during the above-mentioned reaction.

[0164] To obtain the polysiloxane polymer composition, the protonated compound (d) is used or added only after the above reaction.

[0165] To obtain the polysiloxane polymer composition, the protonated compound (d) is used during the above reaction and added after the above reaction.

[0166] Thus, the inventors have discovered a method for effectively reducing the Dn content. Since the positively charged quaternary ammonium moiety and polysiloxane moiety and alkaline conditions are factors that cause high Dn content, the present invention is not limited to reducing the Dn content that occurs during the preparation and storage of polymers containing only quaternary ammonium moieties and polysiloxane moieties. When the polymer contains moieties other than quaternary ammonium moieties and polysiloxane moieties, it is believed that the scheme of the present invention can reduce the Dn generated when synthesizing and / or storing such polymers.

[0167] For example, the inventors used a hydrophobic component (a) containing a polysiloxane backbone, a quaternized component (b) containing a tertiary amine group, and a hydrophilic component (e) (optional component, preferably containing an amine group) to react in the presence of a protonated component (p) containing a protonated compound (d), and found that the resulting polysiloxane polymer composition had a low Dn content. On the other hand, if a strong acid is added after the above reaction (no strong acid is present during the reaction), it is found that the resulting polysiloxane polymer composition also has a low Dn content.

[0168] In the above exemplary system, the hydrophilic component (e) is used together with the hydrophobic component (a) to adjust the hydrophilicity-hydrophobicity of the polysiloxane polymer, and those skilled in the art can determine the amount of the hydrophilic component (e) according to the specific application of the polysiloxane polymer. Similarly, the ratio between the quaternized component (b) and the other components can also be determined according to the specific application of the polysiloxane polymer. Therefore, there is no special limitation on the content of each repeating unit in the polysiloxane polymer involved in the present invention, and the content can be adjusted as needed. The same principle applies to the size or length of the hydrophilic component (e) and the hydrophobic component (a).

[0169] Therefore, there is no particular limitation on the composition of the polysiloxane polymer, except that the polymer contains a polysiloxane moiety and a quaternary ammonium moiety, and the ratio between the moieties is not particularly limited.

[0170] As a non-limiting example of the composition of repeating units in the polymer, the molar ratio between the repeating units of formula I defined above and the repeating units of formula II defined above is 0.1 to 4, or 1 to 4, or 2 to 3. As a non-limiting example of the content of each component in the reaction of the preparation method, the molar ratio between the hydrophobic component (a) and the quaternary ammonium component (b) is 1 to 10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6; the molar ratio between the hydrophilic component (e) (if present) and the quaternary ammonium component (b) is 0.05 to 0.9, or 0.1 to 0.8, or 0.2 to 0.7, or 0.3 to 0.6, or 0.4 to 0.5.

[0171] In addition, the length of the repeating unit in the polymer can also be adjusted according to actual needs and is not particularly limited.

[0172] In order to reduce the Dn content, the inventors found that it is necessary to use a strong acid with a pKa of no more than 3.0 during and / or after the reaction. If only a weak acid is used for the reaction or only a weak acid is added after the reaction, the Dn content cannot be effectively reduced. For example, the inventors found in an experiment that lauric acid (pKa = 6.92) and acetic acid (pKa = 4.76) (both protonated compounds (c)) are used as protonated components (p) during the reaction without adding any strong acid with a pKa of no more than 3.0, and the D4 content in the obtained reaction product mixture exceeds 1000ppm. After the reaction, citric acid (pKa = 3.13, protonated compound (c)) is added to the product mixture, and the resulting mixture is aged at 85°C for 24 hours, and it is found that the D4 content exceeds 1000ppm.

[0173] In contrast, when methanesulfonic acid (pKa=2, strong acid, protonated compound (d)) was added during the reaction, the D4 content in the resulting reaction product mixture was less than 1000 ppm. When methanesulfonic acid was added to the product mixture after the reaction, the resulting mixture was aged at 50°C for 4 weeks and the D4 content was still less than 1000 ppm.

[0174] Dn in the present invention can be measured using the following method, 0.5g (for example, accurate to 0.1mg) sample is weighed and placed in a 20mL glass bottle, 10mL of a mixed solvent of methanol and toluene (the volume ratio of methanol to toluene is 1:2) is accurately added thereto, and the mixed solvent contains 0.05mg / mL of n-dodecane as an internal standard. After fully mixing, the mixture is placed on a shaking table and shaken for 4h. After filtering the supernatant with a needle filter head for organic phase, an Agilent 6890 gas chromatograph is used, and a DB-5 (60m x 0.25mm x 0.25um) chromatographic column is used to test D4, D5, and D6 content.

[0175] Non-limiting examples of protonating compounds (d) as strong acids include: acids containing sulfonate groups, preferably alkyl or aryl substituted sulfonic acids, hydrohalic acids, oxo acids from elements of main groups V to VI, acids containing sulfate groups, acids containing phosphate groups or phosphonate groups, or carboxylic acids containing 2 to 20 carbon atoms;

[0176] Preferably, the protonated compound (d) comprises one or more selected from the group consisting of phosphoric acid, optionally substituted aminosulfonic acid, methylaminosulfonic acid, HCl, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, hydrogen sulfate, phosphonic acid, aminophosphonic acid or aminocarboxylic acid.

[0177] The above exemplary protonated compounds (d) are those having a pKa of no more than 3.0, preferably no more than 2.5, preferably no more than 2.0, more preferably no more than 1.5, and most preferably no more than 1.0. For example, for carboxylic acids containing 2 to 20 carbon atoms, the protonated compounds (d) according to the present invention are carboxylic acids with strong acid properties, such as trifluoroacetic acid. In other words, carboxylic acids containing 2 to 20 carbon atoms whose pKa does not meet the definition of the present invention are not within the scope of the protonated compounds (d) of the present invention.

[0178] There are no particular requirements for the protonated compound (c) of the present invention. Examples of the protonated compound (c) of the present invention are defined in the Summary of the Invention section. As a protonated compound (c), its role in such reactions is generally to provide a proton. Therefore, in one embodiment, the pKa of the protonated compound (d) is not more than 2.5 and the pKa of the protonated compound (c) is greater than 2.5, or the pKa of the protonated compound (d) is not more than 2.0 and the pKa of the protonated compound (c) is greater than 2.0.

[0179] The polysiloxane polymers to which the present invention relates exist commercially available products, which means that the preparation methods of such polysiloxane polymers are known, but the methods of the prior art result in high Dn contents. The methods for preparing polysiloxane polymers containing quaternary ammonium moieties, except for the use of strong acids, are within the ordinary technical capabilities of those skilled in the art. That is, those skilled in the art are capable of implementing the preparation methods (except for the use of strong acids) using appropriate reaction conditions, including temperature, reaction time, reaction medium, etc. For example, this type of reaction can be carried out at 30-180° C. until the reaction is complete.

[0180] The preparation method of the present invention can be carried out in the presence of reaction medium (f) as required. Reaction medium (f) preferably includes polar solvent and non-polar solvent, polar solvent is preferably selected from water, alcohols, ethers, esters and glycols, non-polar solvent is preferably selected from saturated, unsaturated or aromatic hydrocarbons, such as toluene and xylene, preferably, reaction medium (f) comprises a mixture of water and alcohol or a mixture of water and ether, particularly a mixture of water and 2-propanol or a mixture of water and dipropylene glycol n-butyl ether. The selection and proportioning of solvent can be adjusted as required. Preferably, the mass ratio of dipropylene glycol n-butyl ether to water is 0.5:1 to 10:1, or 0.7:1 to 7:1, or 1:1 to 5:1.

[0181] The polysiloxane polymer composition according to the present invention or the polysiloxane polymer composition prepared according to the method of the present invention can be used in the field of fiber, fabric, cosmetics or personal care. It is known to those skilled in the art that polysiloxane polymers containing quaternary ammonium moieties can be used to treat fibers or fabrics, for example as part of a composition for this purpose, and can be used in cosmetics or personal care. It is a known practice to use polysiloxane polymer compositions in these fields. In view of the low Dn content of the polysiloxane polymer combination of the present invention, compared with conventional polysiloxane polymer compositions, the use of the polysiloxane polymer composition of the present invention in the field of fiber, fabric, cosmetics or personal care will be more friendly to the environment.

[0182] The present invention can be beneficially applied to any silicone bearing a quaternary ammonium moiety.

[0183] This includes, i.e., monofunctional quaternized silicone organic compounds, ABA type - diquaternized organosilicon compounds, centrally quaternized organosilicon compounds of the BAB type, ABA type with more than one quaternary ammonium moiety at both chain ends - polyquaternized organosilicon compounds, T or Q branched organosilicon compounds with terminal quaternary ammonium moieties, polyquaternized polycyclic organosilicon compounds of the (AB)n type, polyquaternized polycyclic organosilicon compounds of the (AB)n type partially containing terminal ester groups, organosilicon compounds with quaternized moieties in the pending side chains.

[0184] Optionally, these quaternized silicon organic compounds contain alkylene oxide moieties, which are preferably derived from ethylene oxide, propylene oxide, butylene oxide or glycidol. The incorporation of these alkylene oxide moieties can be achieved by using the corresponding amino derivatives, chloroacetic acid derivatives or glycidyl derivatives.

[0185] Preferred precursors for incorporating the silicon organic compound moiety are, namely, tertiary amino derivatives, chloroacetic acid derivatives, haloalkyl derivatives, and glycidyl derivatives.

[0186] Example

[0187] The present invention is described hereinafter in an illustrative manner, and the present invention is not limited to the following examples.

[0188] Materials used:

[0189]

[0190]

[0191] *Jeffamin is a type of polyetheramine, i.e., a compound having an amine group at the end and containing polyether repeating units, which is commercially available.

[0192] Test Method

[0193] pH measurement: The test substance is diluted with the mixed solvent (1:10 dilution). After the test substance and the mixed solvent are fully mixed and dissolved, the S20 SevenEasy TM The pH value is measured by a pH meter. The mixed solvent for dilution is a mixed solvent of isopropanol and water in a volume ratio of 5:3. The 1:10 dilution refers to diluting 1 part by weight of the test object with 9 parts by weight of the mixed solvent.

[0194] Measurement of Dn (D4, D5, D6): Weigh 0.5g of sample and place it in a 20mL glass bottle, accurately add 10mL of a mixed solvent of methanol and toluene (the volume ratio of methanol to toluene is 1:2), and the mixed solvent contains 0.05mg / mL n-dodecane as an internal standard. After thorough mixing, place the mixture on a shaker and shake for 4h. Take the supernatant and filter it with a needle filter for the organic phase, and use an Agilent 6890 gas chromatograph, DB-5 (60m x 0.25mm x 0.25um) chromatographic column to test the content of D4, D5, and D6.

[0195] Experiment 1 - Study of Dn content when strong acid is not used during and after the reaction

[0196] 1-1 In order to examine the Dn level in the product mixture obtained from the reaction when no strong acid was used both during and after the reaction, the following experiment was conducted.

[0197] Comparative Example 1

[0198] 8.98 g of Jeffamin (0.0150 mol), 9.71 g of TMHDA (0.0564 mol), 16.94 g of lauric acid (0.0847 mol), 9.28 g of acetic acid (0.0564 mol), 67.12 g of DPnB and 31.19 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 600 g of epoxy-terminated polysiloxane (0.0706 mol) was added. The reaction was carried out at 95° C. for 12 hours under mixing to obtain a product.

[0199] The product contained 1183 ppm of D4, 409 ppm of D5 and 611 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 9.2.

[0200] It can be seen that when no strong acid is used during and after the reaction (the protonated component consists of only weak acid), the product mixture obtained by the reaction has more than 1000 ppm of D4, and the pH shows alkaline characteristics.

[0201] 1-2 In order to examine the level of Dn produced by the product mixture after aging when no strong acid is used during and after the reaction, the following experiment was conducted.

[0202] Comparative Example 2

[0203] 17.73 g of Jeffamin (0.014 mol), 11.64 g of TMHDA (0.032 mol), 29.54 g of lauric acid (0.07 mol), 4.73 g of acetic acid (0.0373 mol), 47.2 g of DPnB and 18.36 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 400 g of epoxy-terminated polysiloxane (0.0466 mol) was added. The reaction was carried out at 85 ° C for 10 hours under mixing to obtain a product. The product was aged at 85 ° C for 24 hours. After the product was diluted to a concentration of 10% with a mixed solvent, the measured pH was 8.9. The inventors found that aging does not significantly change the pH value of the composition.

[0204] The product contained 1226 ppm of D4, 277 ppm of D5 and 40 ppm of D6.

[0205] It can be seen that when no strong acid is used during and after the reaction (the protonated component consists only of weak acid), the composition has more than 1000 ppm of D4 after aging, and the pH exhibits alkaline characteristics.

[0206] 1-3 In order to examine the Dn level produced by the product mixture after aging when a weak acid was added after the reaction, the following experiment was performed.

[0207] Comparative Example 3

[0208] 5.6 g of Jeffamin (0.0093 mol), 6.31 g of TMHDA (0.0367 mol), 9.33 g of lauric acid (0.0466 mol), 2.24 g of acetic acid (0.0373 mol), 43.79 g of DPnB and 19.46 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 400 g of epoxy-terminated polysiloxane (0.0466 mol) was added. The reaction was carried out at 85° C. for 10 hours under mixing to obtain a product. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 9.2.

[0209] To 100 g of the reaction product, 0.79 g of acetic acid and 8 g of DPnB were added, followed by aging at 85° C. for 24 hours.

[0210] The product contained 1588 ppm of D4, 393 ppm of D5 and 147 ppm of D6. The pH of the product was measured to be 6 after it was diluted with a mixed solvent to a concentration of 10%.

[0211] Comparative Example 4

[0212] Comparative Example 2 was repeated, except that after the reaction was completed, 2 g of citric acid and 5 g of DPnB were added to 100 g of the reaction product. Subsequently, the same aging step was performed. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 5.7.

[0213] The product contained 1534 ppm of D4, 265 ppm of D5 and 41 ppm of D6.

[0214] It can be seen that when a weak acid is added after the reaction is completed, the product mixture obtained by the reaction has more than 1000 ppm of D4 after aging. It is worth noting that even if the pH value of the product mixture is reduced, a large amount of D4 is still produced in Comparative Examples 3 and 4 because a strong acid is not used.

[0215] Experiment 2 - Study of Dn content when strong acid is used during the reaction

[0216] Example 1

[0217] 8.4 g of Jeffamin (0.014 mol), 9.23 g of TMHDA (0.054 mol), 16.79 g of lauric acid (0.084 mol), 7 g of 36.5% HCl aqueous solution (0.07 mol), 65.97 g of DPnB and 21.21 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 600 g of epoxy-terminated polysiloxane (0.0706 mol) was added. The reaction was carried out at 85° C. for 8 hours under mixing to obtain a product.

[0218] The product contained 349 ppm of D4, 972 ppm of D5 and 218 ppm of D6. The pH of the product was measured to be 9 after it was diluted with a mixed solvent to a concentration of 10%.

[0219] It can be seen that when a strong acid is used in the reaction, a lower pH of the reactant mixture is conducive to obtaining a lower D4 content; and the D4 content is also reduced after aging.

[0220] Example 2

[0221] 5.6 g of Jeffamin (0.0093 mol), 6.31 g of TMHDA (0.0367 mol), 10.26 g of lauric acid (0.0513 mol), 1.96 g of acetic acid (0.0326 mol), 2.26 g of aminosulfonic acid (0.0233 mol), 46.11 g of DPnB and 46.11 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 400 g of epoxy-terminated polysiloxane (0.0466 mol) was added. The reaction was carried out at 85° C. for 16 hours under mixing to obtain a product.

[0222] The product contained 133 ppm of D4, 313 ppm of D5 and 548 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 7.8.

[0223] Example 3

[0224] 5.6 g of Jeffamin (0.0093 mol), 6.31 g of TMHDA (0.0367 mol), 9.33 g of lauric acid (0.0466 mol), 1.96 g of acetic acid (0.0326 mol), 1.95 g of ethanesulfonic acid (0.0186 mol), 42.36 g of DPnB and 9.31 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 400 g of epoxy-terminated polysiloxane (0.0466 mol) was added. The reaction was carried out at 85° C. for 10 hours under mixing to obtain a product.

[0225] The product contained 499 ppm of D4, 552 ppm of D5 and 689 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 8.4.

[0226] Example 4

[0227] 4.2 g of Jeffamin (0.007 mol), 4.74 g of TMHDA (0.0275 mol), 7 g of lauric acid (0.035 mol), 3.36 g of methanesulfonic acid (0.035 mol), 32.47 g of DPnB and 9.02 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 300 g of epoxy-terminated polysiloxane (0.035 mol) was added. The reaction was carried out at 85° C. for 12 hours under mixing to obtain a product.

[0228] The product contained 226 ppm of D4, 50 ppm of D5 and 52 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 8.2.

[0229] Example 5

[0230] 5.6 g of Jeffamin (0.0093 mol), 6.15 g of TMHDA (0.0357 mol), 9.33 g of lauric acid (0.0466 mol), 11.43 g of 20% H2SO4 aqueous solution (0.0233 mol), 36.57 g of DPnB and 10.74 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 400 g of epoxy-terminated polysiloxane (0.0466 mol) was added. The reaction was carried out at 85° C. for 8 hours under mixing to obtain a product.

[0231] The product contained 414 ppm of D4, 412 ppm of D5 and 42 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 7.8.

[0232] It can be seen that adding a strong acid during the reaction can reduce the Dn content in the product mixture.

[0233] Experiment 3 - Study on Dn content when strong acid is not added during the reaction but added after the reaction

[0234] Example 6

[0235] Comparative Example 3 was repeated except that 1 g of methanesulfonic acid and 8 g of DPnB were added to 100 g of the reaction product, followed by aging at 85° C. for 24 hours.

[0236] The product contained 780 ppm of D4, 203 ppm of D5 and 96 ppm of D6. The pH of the product was measured to be 6 after it was diluted with a mixed solvent to a concentration of 10%.

[0237] Example 7

[0238] Comparative Example 3 was repeated except that 4.8 g of a 20% aqueous solution of aminosulfonic acid and 8 g of DPnB were added to 100 g of the reaction product, followed by aging at 85° C. for 24 hours.

[0239] The product contained 361 ppm of D4, 81 ppm of D5 and 45 ppm of D6. The pH of the product was measured to be 6 after it was diluted with a mixed solvent to a concentration of 10%.

[0240] It can be seen from Examples 6 and 7 that even if no strong acid is used during the reaction, a low Dn content, especially a D4 content, can still be obtained by adding a strong acid after the reaction.

[0241] From the comparison between Example 6 and Example 7 and Comparative Example 3, it can be seen that the additional addition of weak acid after the reaction is completed, even if the pH is adjusted to acidic, still cannot effectively reduce the content of D4.

[0242] Experiment 4 - Study of Dn content when strong acid is added during and after the reaction

[0243] Example 8

[0244] Example 1 was repeated except that 36.5% aqueous HCl was added after the reaction to give a product mixture pH of 4.6 (measured after diluting it to a concentration of 10%), and then the product mixture was aged at 85°C for 40 hours.

[0245] The product contained 311 ppm of D4, 263 ppm of D5 and 632 ppm of D6.

[0246] Next, aging was carried out for 3 months at 50° C. The product contained 806 ppm of D4, 405 ppm of D5 and 686 ppm of D6.

[0247] Example 9

[0248] Example 1 was repeated except that 36.5% aqueous HCl was added after the reaction to make the pH of the product mixture 6 (measured after diluting it to a concentration of 10%), and then the product mixture was aged at 85°C for 40 hours.

[0249] The product contained 443 ppm of D4, 296 ppm of D5 and 664 ppm of D6.

[0250] Example 10

[0251] Example 1 was repeated except that 36.5% aqueous HCl was added after the reaction to make the pH of the product mixture 6.7 (measured after diluting it to a concentration of 10%), and then the product mixture was aged at 85°C for 40 hours.

[0252] The product contained 550 ppm of D4, 316 ppm of D5 and 548 ppm of D6.

[0253] Embodiment 11

[0254] 5.59 g of Jeffamin (0.0466 mol), 6.31 g of TMHDA (0.0367 mol), 9.33 g of lauric acid (0.0466 mol), 3.58 g of methanesulfonic acid (0.0373 mol), 48.27 g of DPnB and 9.65 g of water were charged into a reactor and mixed to obtain a solution. Subsequently, 400 g of epoxy-terminated polysiloxane (0.0466 mol) was added. The reaction was carried out at 85° C. for 20 hours under mixing to obtain a product.

[0255] Subsequently, 10 g of a 14% aqueous solution of aminosulfonic acid and 8 g of DPnB were added to 130 g of the obtained product, and the mixture was aged at 50°C for 4 weeks.

[0256] The product contained 667 ppm of D4, 218 ppm of D5 and 59 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 4.8.

[0257] Example 12

[0258] Example 11 was repeated except that 1 g of methanesulfonic acid and 5 g of DPnB were added to 80 g of the obtained product and aged at 50°C for 4 weeks.

[0259] The product contained 358 ppm of D4, 159 ppm of D5 and 93 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 5.4.

[0260] Example 13

[0261] Example 11 was repeated except that 6 g of a 14% aqueous solution of aminosulfonic acid and 5 g of DPnB were added to 80 g of the obtained product and aged at 50°C for 4 weeks.

[0262] The product contained 324 ppm of D4, 93 ppm of D5 and 33 ppm of D6. After the product was diluted with a mixed solvent to a concentration of 10%, the measured pH was 5.3.

[0263] Since strong acid was used during and after the reaction, the Dn content did not exceed 1000 ppm after aging for 4 weeks.

[0264] The above examples of the present invention partially show that low cyclic (Dn) content can be achieved by

[0265] - using a protonated compound (d) in combination with a protonated compound (c) during the reaction (quaternization);

[0266] - after quaternization with the protonated compound (c), adding the protonated compound (d);

[0267] - using the protonated compound (d) in combination with the protonated compound (c) during the quaternization and subsequently adding the protonated compound (d) after the quaternization.

[0268] Experiment 5 - Supplementary study of Dn content when strong acid is added after the reaction: Effect of pH range

[0269] The following examples are not intended to limit the invention to specific embodiments, but rather to illustrate preferred embodiments of the invention.

[0270] Comparative Example 5

[0271] 5.60 g of Jeffamin (0.0093 mol), 6.31 g of TMHDA (0.0367 mol), 9.33 g of lauric acid (0.0466 mol), 2.24 g of acetic acid (0.0373 mol), 39.27 g of DPnB and 19.47 g of water were charged into a reactor and mixed to obtain a solution, and then 400 g of epoxy-terminated polysiloxane (0.0706 mol) was added, and the reaction was carried out at 85° C. for 10 hours under mixing to obtain a product.

[0272] The pH of the obtained product (measured after diluting it to a concentration of 10%) was measured to be 9.5.

[0273] After the product was stored at room temperature for 7 days, the test results showed that the product contained 1052 ppm of D4, 214 ppm of D5 and 377 ppm of D6.

[0274] After aging at 50°C for 2 weeks, the product contained 1823 ppm of D4, 346 ppm of D5, and 409 ppm of D6.

[0275] This comparative example shows that when no strong acid is added after the reaction, the D4 content is already very high after 7 days of storage at room temperature, and the D4 content increases sharply after aging.

[0276] Embodiment 14

[0277] Comparative Example 5 was repeated except that 1 g of a 20% aqueous solution of aminosulfonic acid and 3 g of DPnB were added to 57 g of the obtained product. The pH of the obtained product (measured after diluting it to a concentration of 10%) was measured to be 7.4.

[0278] After the product was stored at room temperature for 7 days, the test results showed that the product contained 588 ppm of D4, 137 ppm of D5, and 306 ppm of D6.

[0279] After aging at 50°C for 2 weeks, the product contained 1074 ppm of D4, 260 ppm of D5, and 343 ppm of D6.

[0280] Embodiment 15

[0281] Comparative Example 5 was repeated except that 1.5 g of a 20% aqueous solution of aminosulfonic acid and 2.5 g of DPnB were added to 53.8 g of the obtained product. The pH of the obtained product (measured after diluting it to a concentration of 10%) was measured to be 6.6.

[0282] After the product was stored at room temperature for 7 days, the test results showed that the product contained 509 ppm of D4, 134 ppm of D5, and 303 ppm of D6.

[0283] After aging at 50°C for 2 weeks, the product contained 1015 ppm of D4, 267 ppm of D5, and 372 ppm of D6.

[0284] Example 16

[0285] Comparative Example 5 was repeated except that 6 g of a 20% aqueous solution of aminosulfonic acid and 4 g of DPnB were added to 64.5 g of the obtained product. The pH of the obtained product (measured after diluting it to a concentration of 10%) was measured to be 3.5.

[0286] After the product was stored at room temperature for 7 days, the test results showed that the product contained 593 ppm of D4, 160 ppm of D5, and 324 ppm of D6.

[0287] After aging at 50°C for 2 weeks, the product contained 1033 ppm of D4, 275 ppm of D5, and 313 ppm of D6.

[0288] Embodiment 17

[0289] Comparative Example 5 was repeated except that 3 g of a 20% aqueous solution of aminosulfonic acid and 2.5 g of DPnB were added to 50.2 g of the obtained product. The pH of the obtained product (measured after diluting it to a concentration of 10%) was measured to be 5.7.

[0290] After the product was stored at room temperature for 7 days, the test results showed that the product contained 429 ppm of D4, 121 ppm of D5, and 284 ppm of D6.

[0291] After aging at 50°C for 2 weeks, the product contained 854 ppm of D4, 246 ppm of D5, and 337 ppm of D6.

[0292] Embodiment 18

[0293] Comparative Example 5 was repeated except that 4.5 g of a 20% aqueous solution of aminosulfonic acid and 3 g of DPnB were added to 53.5 g of the obtained product. The pH of the obtained product (measured after diluting it to a concentration of 10%) was measured to be 4.6.

[0294] After the product was stored at room temperature for 7 days, the test results showed that the product contained 400 ppm of D4, 91 ppm of D5, and 272 ppm of D6.

[0295] After aging at 50°C for 2 weeks, the product contained 584 ppm of D4, 154 ppm of D5, and 295 ppm of D6.

[0296] Compared with Comparative Example 5, Examples 14 to 16 show that adding a strong acid after the reaction to reduce the pH to near neutrality or a certain degree of acidity (eg pH = 3.5) can achieve better results than not adding a strong acid, i.e., a lower Dn content.

[0297] Compared with Examples 14 to 16, Examples 17 and 18 show that the lower the pH value, the better. A pH greater than or equal to 4 can achieve better effects, i.e., lower Dn content, than a lower pH. Therefore, it is believed that a pH greater than or equal to 4 is a preferred pH range when a strong acid is added after the reaction is completed, and a more preferred pH range is 4 to 6.

Claims

1. A polysiloxane polymer composition, wherein the polysiloxane polymer composition is a product obtained by a process comprising the steps of: reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p); wherein the protonated component (p) comprises at least one protonated compound (c) having a pKa greater than 3.0 and at least one protonated compound (d) having a pKa no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0, and wherein the molar ratio (∑ molar 质子化化合物(c) / ∑ mole 质子化化合物(d) ) ranges from 9:1 to 0.1:1, preferably from 9:1 to 0.2:1, more preferably from 5:1 to 0.2:1, even more preferably from 2:1 to 0.2:1, most preferably from 2:1 to 0.4:1, still more preferably from 2:1 to 1:1; The polysiloxane polymer comprises the following repeating units: [-L 1 -(SiOR 1 R 2 ) n -L 2 -N + R 3 R 4 -Z-N + R 5 R 6 -] u Formula I, Where u is 2 to 100; L 1 and L 2 are the same or different and are selected from a covalent bond and a hydrocarbon chain having 1 to 20 carbon atoms, which is optionally substituted by O, N or S atoms, or by a group containing O, N or S atoms; R 1 and R 2 are identical or different and are selected from optionally substituted hydrocarbon chains containing 1 to 20 carbon atoms, preferably methyl, n is 1 to 1000, preferably 20 to 500, preferably 40 to 450, more preferably 50 to 200, even more preferably 50 to 150; and Z is a hydrocarbon chain containing 2 to 20 carbon atoms and is optionally substituted by O, N, S atoms, or by groups containing O, N or S atoms, preferably substituted by OH groups; R 3 , R 4 , R 5 and R 6 are the same or different and are selected from hydrocarbon chains containing 1 to 20 carbon atoms, Alternatively, the polysiloxane polymer comprises repeating units having formula I': [-L 3 ’-Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4 ’-N + (R 3 )(R 4 )-Z-N + (R 5 )(R 6 )-] u Formula I’ Where n, u, L 1 , L 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Z is defined as above, Y 3 and Y 4 are the same or different and are each independently selected from O, N(R 7 ) or S, R 7 =H or C1-C3 hydrocarbon group, such as C1-C3 alkyl; L 3’ and L 4’ are the same or different and are selected from a covalent bond and a hydrocarbon chain substituted with a group containing O, N or S atoms, preferably OH, NH2 or SH and having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 3 to 4 carbon atoms; in particular, the OH, NH2 or SH is obtained from a ring-opening reaction of an oxygen-containing heterocycle having a single oxygen atom, a nitrogen-containing heterocycle having a single nitrogen atom or a sulfur-containing heterocycle having a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group) at the end of the corresponding alkylene group of the hydrophobic component (a); Preferably, L 1 and L 2 are identical or different and are each independently selected from an alkylene group having 1 to 6 carbon atoms, in particular having 2, 3, 4 or 5 carbon atoms; Preferably, R 3 , R 4 , R 5 and R 6 are each independently an alkyl group and Z is an alkylene group, more preferably Z is a straight chain alkylene group containing 2 to 8 carbon atoms such as butylene or hexylene, and R 3 , R 4 , R 5 and R 6 are the same or different and are each independently selected from an alkyl group containing 1 to 4 carbon atoms, for example, R 3 , R 4 , R 5 and R 6 All are methyl; The polysiloxane polymer composition also includes a counter ion.

2. A polysiloxane polymer composition, wherein the polysiloxane polymer composition is a product obtained by a process comprising the steps of: reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p); the protonated component (p) comprising at least one protonated compound (c) having a pKa greater than 3.0, and using a protonated compound (d) during said reaction, adding the protonated compound (d) after the reaction, or using a protonated compound (d) during the reaction and adding the protonated compound (d) after the reaction; The protonated compound (d) has a pKa of no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, and most preferably no greater than 1.0; The polysiloxane polymer comprises the following repeating units: [-L 1 -(SiOR 1 R 2 ) n -L 2 -N + R 3 R 4 -Z-N + R 5 R 6 -] u Formula I Where u is 2 to 100; L 1 and L 2 are the same or different and are selected from a covalent bond and a hydrocarbon chain having 1 to 20 carbon atoms, which is optionally substituted by O, N or S atoms, or by a group containing O, N or S atoms; R 1 and R 2 are identical or different and are selected from optionally substituted hydrocarbon chains containing 1 to 20 carbon atoms, preferably methyl, n is 1 to 1000, preferably 20 to 500, preferably 40 to 450, more preferably 50 to 200, even more preferably 50 to 150; and Z is a hydrocarbon chain containing 2 to 20 carbon atoms and is optionally substituted by O, N, S atoms, or by groups containing O, N or S atoms, preferably substituted by OH groups; R 3 , R 4 , R 5 and R 6 are the same or different and are selected from hydrocarbon chains containing 1 to 20 carbon atoms, Alternatively, the polysiloxane polymer comprises repeating units having formula I': [-L 3 ’-Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4 ’-N + (R 3 )(R 4 )-Z-N + (R 5 )(R 6 )-] u Formula I’ Where n, u, L 1 , L 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Z is defined as above, Y 3 and Y 4 are the same or different and are each independently selected from O, N(R 7 ) or S, R 7 =H or C1-C3 hydrocarbon group, such as C1-C3 alkyl; L 3’ and L 4’ are the same or different and are selected from a covalent bond and a hydrocarbon chain substituted with a group containing O, N or S atoms, preferably OH, NH2 or SH and having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 3 to 4 carbon atoms; in particular, the OH, NH2 or SH is obtained from a ring-opening reaction of an oxygen-containing heterocycle having a single oxygen atom, a nitrogen-containing heterocycle having a single nitrogen atom or a sulfur-containing heterocycle having a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group) at the end of the corresponding alkylene group of the hydrophobic component (a); Preferably, L 1 and L 2 are identical or different and are each independently selected from an alkylene group having 1 to 6 carbon atoms, in particular having 2, 3, 4 or 5 carbon atoms; Preferably, R 3 , R 4 , R 5 and R 6 are each independently an alkyl group and Z is an alkylene group, more preferably Z is a straight chain alkylene group containing 2 to 8 carbon atoms such as butylene or hexylene, and R 3 , R 4 , R 5 and R 6 are the same or different and are each independently selected from an alkyl group containing 1 to 4 carbon atoms, for example, R 3 , R 4 , R 5 and R 6 All are methyl; The polysiloxane polymer composition also includes a counter ion.

3. The polysiloxane polymer composition according to claim 1 or 2, wherein the polysiloxane polymer further comprises a polysiloxane having the formula II[-L 1 -(SiOR 1 R 2 ) n -L 2 -Y 1’ -EY 2’ -] v The repeating unit, in: v is 1 to 100, E is a covalent bond or a polyether moiety comprising one or more of the following repeating units: -(ethylene oxide) x -,-(propylene oxide) y -or-(butylene oxide) z -, x, y and z are the same or different and x=0 or 1-100, preferably 1-20, more preferably 1-10, even more preferably 1-5, most preferably 1, 2 and 3, y=0 or 1-100, preferably 1-20, more preferably 1-10, even more preferably 1-5, most preferably 1, 2 and 3, z=0 or 1-100, preferably 1-20, more preferably 1-10, even more preferably 1-5, most preferably 1, 2 and 3, x+y+z=0-100, preferably 0 and 1-100, more preferably 1-20, even more preferably 1-10, most preferably 0, 1, 2, 3; Y 1’ and Y 2’ containing a functional group independently selected from the following: a nitrogen-containing group, an oxygen-containing group or a sulfur-containing group, preferably an amine-containing group, a hydroxyl-containing group or a thiol-containing group, more preferably an amine-containing group, most preferably a secondary amine-containing group, a tertiary amine-containing group, an amine salt derived from a secondary amine-containing group or a tertiary amine-containing group, or a quaternary ammonium-containing group, Y 1’ and Y 2’ At least one of the optionally contains a functional group connected to E or to Y 1’ and Y 2’ The other of and a hydrocarbon group containing 1 to 20 carbon atoms, Alternatively, the polysiloxane polymer further comprises a repeating unit having the formula II': [-L 3’ -Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4’ -Y 1’ -E-Y 2’ -] v Formula II' Where n, v, L 1 , L 2 , R 1 , R 2 , E, Y 1’ , Y 2’ , L 3’ , Y 3 , Y 4 and L 4’ As defined above, Preferably, Y 1’ and Y 2’ At least one of the Above Functional group attached to E or to Y 1’ and Y 2’ and another of the functional groups and containing 1-20 carbon atoms, in particular alkylene, such as linear or branched alkylene containing 1-6 or 1-3 carbon atoms, and at least one of the above functional groups is optionally directly connected to E by a covalent bond.

4. The polysiloxane polymer composition of any one of claims 1 to 3, wherein the hydrophobic component (a) comprises a structure having formula III: X 1 -L 1 -(SiOR 1 R 2 ) n -L 2 -X 2 Formula III in: L 1 and L 2 are identical or different and are selected from a covalent bond and a hydrocarbon chain having 1 to 20 carbon atoms, which is optionally substituted by O, N or S atoms, or by a group containing O, N or S atoms; X 1 and X 2 The groups are identical or different and are selected from H, epoxy or hydroxyl, or derived from ethylene oxide, propylene oxide or butylene oxide, and when L 1 and L 2 When it is a covalent bond, X 1 and X 2 The group is H; R 1 and R 2 are the same or different and are selected from optionally substituted hydrocarbon chains containing 1 to 20 carbon atoms, preferably methyl, n is 1 to 1000, preferably 20 to 500, preferably 40 to 450, more preferably 50 to 200, even more preferably 50 to 150, Alternatively, the hydrophobic component (a) comprises a structure having the formula III': L 3 -Y 3 -L 1 -(Si(R 1 )(R 2 )O) n -Si(R 1 )(R 2 )-L 2 -Y 4 -L 4 Formula III' Among them, n, L 1 , L 2 , R 1 , R 2 , Y 3 and Y 4 As defined above, L 3 and L 4 The same or different and are a hydrocarbon chain containing an oxygen-containing heterocycle with a single oxygen atom, a nitrogen-containing heterocycle with a single nitrogen atom, or a sulfur-containing heterocycle with a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group), preferably a 3-5-membered ring, and having 2-20 carbon atoms, preferably an alkylene group with 2-6 carbon atoms, more preferably an alkylene group with 3-4 carbon atoms; in particular, the oxygen-containing heterocycle with a single oxygen atom, the nitrogen-containing heterocycle with a single nitrogen atom, or the sulfur-containing heterocycle with a single sulfur atom (e.g., an epoxy, aziridine or thioepoxy group) is located at the end of the alkylene group.

5. The polysiloxane polymer composition of any one of claims 1 to 4, wherein the quaternized component (b) comprises the structure of Formula IV: NR 3 R 4 -Z-NR 5 R 6 Formula IV in: Z is a linear, branched or cyclic hydrocarbon moiety containing 2 to 20 carbon atoms, and is optionally substituted by O, N, S atoms, or by groups containing O, N or S atoms, preferably substituted by OH groups; R 3 , R 4 , R 5 and R 6 are the same or different and are selected from hydrocarbon groups containing 1 to 20 carbon atoms, Alternatively, the quaternized component (b) comprises the structure of Formula IV': N(R 3 )(R 4 )-Z-N(R 5 )(R 6 ) Formula IV’ Among them, R 3 , R 4 , R 5 , R 6 and Z is as defined above; Preferably, R 3 , R 4 , R 5 and R 6 are each independently an alkyl group and Z is an alkylene group, more preferably Z is a straight chain alkylene group containing 2 to 8 carbon atoms such as butylene or hexylene, and R 3 , R 4 , R 5 and R 6 are the same or different and are each independently selected from an alkyl group containing 1 to 4 carbon atoms, for example, R 3 , R 4 , R 5 and R 6 All are methyl.

6. The polysiloxane polymer composition according to any one of claims 1 to 5, wherein a hydrophilic component (e) is also present in the reaction, and the hydrophilic component (e) comprises a structure having Formula V: Y 1 -E-Y 2 Formula V in: E has the meaning as defined in claim 3; Y 1 and Y 2 contains a functional group independently selected from the following: a nitrogen-containing group, an oxygen-containing group or a sulfur-containing group, preferably an amine-containing group, a hydroxyl-containing group or a thiol-containing group, more preferably an amine-containing group, most preferably a primary amine-containing group or a secondary amine-containing group, Y 1 and Y 2 At least one of the optionally contains a functional group connected to E or to Y 1 and Y 2 The other of and a hydrocarbon group containing 1 to 20 carbon atoms, Alternatively, the hydrophilic component (e) comprises a structure having the formula V': Y 1 -E-Y 2 Formula V' where Y 1 , Y 2 and E is defined as above, Preferably, Y 1 and Y 2 At least one of the Above Functional group attached to E or to Y 1 and Y 2 and another of the functional groups and containing 1-20 carbon atoms, in particular alkylene, such as linear or branched alkylene containing 1-6 or 1-3 carbon atoms, and at least one of the above functional groups is optionally directly connected to E by a covalent bond.

7. The polysiloxane polymer composition of any one of claims 1 to 6, wherein the protonated compound (c) comprises one or more of the following: ° Straight-chain or branched, saturated or unsaturated, optionally containing -O- or substituted by -OH C2-C 30 Carboxylic acid, preferably a carboxylic acid containing an ether group, having R e -O-(EO) p -CH2COOH structure, where p = 1-100 and R e is an optionally substituted hydrocarbon group containing 1 to 20 carbon atoms, preferably an alkyl group; ○ Straight chain or branched C 18 -C 200 Polymerized fatty carboxylic acids, ■Preferred are the following types of polymerized fatty carboxylic acids: R p1 [(-C(O)-XR p6 ) m -C(O)-XR p7 ] x or R p1 [(X-C(O)-R p6 ) m -X-C(O)-R p7 ] x , Where R p1 or R p7 At least one of, or R p1 and R p7 At least one of them carries one or more carboxyl groups, In particular, -Linear polymerized fatty carboxylic acids of the following types HO-C(O)-R p6 (-X-C(O)-R p6 ) m-1 -X-C(O)-R p7 , More specifically HO-C(O)-R p6 -(OC(O)-R p6 ) m -OC(O)-R p7 , - branched linear polymeric fatty carboxylic acids, in particular from partial esters of polyfunctional carboxylic acids, in particular from partial esters of the dicarboxylic acids succinic and maleic acid with castor oil or leclera oil, for example One R in the above formula is And the remaining two R are -Branched polymer fatty carboxylic acid ■ Or preferably the following types of polymerized fatty carboxylic acids: XR p6 (-C(O)-XR p6 ) m-1 -C(O)-XR p7 or R p6 (-C(O)-X-R p6 ) m-1 -C(O)-X-R p7 , In the latter two types, R p7 The group carries at least one carboxylic acid group, ■ Or preferably the following types of polymerized fatty carboxylic acids: R p1 [(-C(O)-X-R p6 ) m -C(O)OH] x , In the above polymerized fatty carboxylic acid formula, each independently, x=1-50,m=1-20,X=O or NR p11 , preferably X=O, R p1 is selected from x-valent, optionally substituted hydrocarbon groups having up to 1000 carbon atoms, preferably 2-300 carbon atoms, more preferably 3-200 carbon atoms, even more preferably 3-150 carbon atoms, in particular 3-50 carbon atoms, more in particular 3-20 carbon atoms, and containing optionally one or more groups selected from: -O-, -NH-, -C(O)-, -C(S)-, tertiary amine groups and is optionally substituted by one or more groups selected from OH groups and halogen groups; R p6 independently selected from optionally substituted linear, cyclic or branched, saturated or unsaturated hydrocarbon groups having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 8 to 18 carbon atoms; R p7 independently selected from optionally substituted linear, cyclic or branched, saturated or unsaturated hydrocarbon groups having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 8 to 18 carbon atoms, which optionally contain one or more groups selected from the following: -O-, -NH-, -C(O)-, -C(S)-, tertiary amine groups Quaternary ammonium group and which is optionally substituted by an OH group or a halogen group, wherein R p7 The group does not contain a combination of -C(O)- and -(O)- groups, or a combination of -C(O)- and -NH- or tertiary amine groups, that form an internal carboxylate group or an internal amide group; provided that at least one R p6 Having more than 6 carbon atoms; R p11 independently selected from hydrogen, optionally substituted linear, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radicals having up to 100 carbon atoms, which optionally contain one or more radicals selected from -O-, -NH-, -C(O)-, -C(S)-, tertiary amine radicals and is optionally substituted with one or more hydroxyl or halogen groups; ■ Or preferably the following types of polymerized fatty carboxylic acids: In this formula, R is Preferably, the protonated compound (c) comprises one or more selected from the group consisting of acidic amino acids, such as aspartic acid and glutamic acid, lactic acid, 2-ethylhexanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, ricinoleic acid, 12-hydroxy-octadecanoic acid, succinic acid, maleic acid, tartaric acid, polyether carboxylic acids, citric acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid and lauric acid.

8. The polysiloxane polymer composition according to any one of claims 1 to 7, wherein the protonated compound (d) comprises one or more selected from the group consisting of: an acid containing a sulfonate group, preferably an alkyl or aryl substituted sulfonic acid, a hydrohalic acid, an oxo acid from elements of main groups V to VI, an acid containing a sulfate group, an acid containing a phosphate group or a phosphonate group, a carboxylic acid containing 2 to 20 carbon atoms; Preferably, the protonated compound (d) comprises one or more selected from the group consisting of phosphoric acid, optionally substituted aminosulfonic acid, methylaminosulfonic acid, HCl, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, hydrogen sulfate, phosphonic acid, aminophosphonic acid or aminocarboxylic acid.

9. The polysiloxane polymer composition according to any one of claims 1 to 8, wherein the weight content of the components in the reaction relative to the sum of the weight contents of the components is: Hydrophobic component (a), 50-95%, preferably 60%-90%, more preferably 70-90%, Quaternized component (b), 0.1-10%, preferably 0.3-7%, more preferably 0.5-5%, Optional hydrophilic component (e), 0%, or 0.1-10%, preferably 0.3-7%, more preferably 0.5-5%, Protonated component (p), 0.1% to 20%, preferably 0.5 to 15%, more preferably 1 to 10%, and Optional reaction medium (f), 0%, or 1-60%, preferably 5-50%, more preferably 10-40%, most preferably reaction medium (f) consists of 5-20% of dipropylene glycol n-butyl ether and 5-20% of water, Provided that the sum of the weight contents of the above components does not exceed 100%.

10. The polysiloxane polymer composition according to any one of claims 1 to 9, wherein the polysiloxane polymer composition is acidic, preferably has a pH of 2 to less than 7, more preferably a pH of 2 to 6, even more preferably a pH of 3 to 6, still more preferably a pH of 4 to 6, and most preferably a pH of 4 to 5.5, wherein the pH is measured as follows: the pH value is measured after the polysiloxane polymer composition is diluted with a mixed solvent to a concentration of 10% in a weight ratio of 1:10, the mixed solvent being a mixed solvent of isopropanol and water in a volume ratio of 5:3, In particular, in the case where a protonated compound (d) is used after the reaction is completed, the pH value is the result of the added protonated compound (d); more particularly, the pH of the polysiloxane polymer composition is 4.2 to 6, 4.4 to 6 or 4.6 to 6, or the pH of the polysiloxane polymer composition is 4.2 to 5.5, 4.4 to 5.5 or 4.6 to 5.5 or 4.6 to 5.

7.

11. The polysiloxane polymer composition of any one of claims 1 or 3 to 9, wherein the molar ratio of the protonated component (p) to the tertiary amine groups in the quaternized component (b) is less than the stoichiometric ratio, the stoichiometric ratio or higher, preferably the molar ratio of the protonated component (p) to the tertiary amine groups in the quaternized component (b) is no more than 0.5 times, 0.7 times, 0.9 times, 1.0 times, 1.2 times, 1.4 times, 1.5 times, 2 times, 3 times or 4 times the stoichiometric ratio, preferably the molar ratio of the protonated component (p) to the tertiary amine groups in the quaternized component (b) is 0.5 to 4:1, more preferably 0.5 to 2:1, 0.7 to 2:1 or 0.9 to 2:1, even more preferably 0.5 to <1:1, 1:1, >1 to 2:1, most preferably >1 to 1.5:1, >1 to 1.4:1 or >1 to 1.2:

1.

12. The polysiloxane polymer composition according to any one of claims 1 to 11, wherein the reaction is carried out in the presence of a reaction medium (f), the reaction medium (f) preferably comprising a polar solvent and a non-polar solvent, the polar solvent is preferably selected from water, alcohols, ethers, esters and glycols, the non-polar solvent is preferably selected from saturated, unsaturated or aromatic hydrocarbons, such as toluene and xylene, preferably, the reaction medium (f) comprises a mixture of water and an alcohol or a mixture of water and an ether, in particular a mixture of water and 2-propanol or a mixture of water and dipropylene glycol n-butyl ether, preferably, the mass ratio of dipropylene glycol n-butyl ether to water is 0.5:1 to 10:1, or 0.7:1 to 7:1, or 1:1 to 5:

1.

13. The polysiloxane polymer composition of any one of claims 1 to 12, wherein the molar ratio between the repeating units of formula I and the repeating units of formula II is 0.1 to 4, or 1 to 4, or 2 to 3.

14. The polysiloxane polymer composition of any one of claims 1-13, wherein the molar ratio between the hydrophobic component (a) and the quaternized component (b) is 1 to 10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6.

15. The polysiloxane polymer composition of any one of claims 1 to 14, wherein the molar ratio between the hydrophilic component (e) and the quaternized component (b) is from 0.05 to 0.9, or from 0.1 to 0.8, or from 0.2 to 0.7, or from 0.3 to 0.6, or from 0.4 to 0.

5.

16. The polysiloxane polymer composition according to any one of claims 1, 3 to 15, wherein in order to obtain the polysiloxane polymer composition, there is a step of adding a protonated compound (d) after the reaction.

17. The polysiloxane polymer composition according to any one of claims 1, 3 to 15, wherein no protonated compound (d) is added after the reaction in order to obtain the polysiloxane polymer composition.

18. The polysiloxane polymer composition according to any one of claims 2 to 15, wherein the reaction to obtain the polysiloxane polymer composition is carried out in the presence of a protonated compound (d).

19. The polysiloxane polymer composition according to any one of claims 2 to 15, wherein the reaction to obtain the polysiloxane polymer composition is carried out in the absence of a protonated compound (d).

20. The polysiloxane polymer composition of any one of claims 2-16 and 18-19, wherein during the reaction the protonated component (p) comprises at least one protonated compound (c) having a pKa greater than 3.0 and at least one protonated compound (d) having a pKa no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0, and wherein the molar ratio (∑ molar) of all protonated compounds (c) to all protonated compounds (d) during the reaction is 质子化化合物(c) / ∑ mole 质子化化合物(d) ) ranges from 9:1 to 0.1:1, preferably 9:1 to 0.2:1, more preferably 5:1 to 0.2:1, even more preferably 2:1 to 0.2:1, most preferably 2:1 to 0.4:1, still more preferably 2:1 to 1:

1.

21. The polysiloxane polymer composition of claim 19, wherein the molar ratio of all protonated compounds (c) to all protonated compounds (d) is from 1:0.2 to 1:

1.

22. The polysiloxane polymer composition of claim 16, 18 or 20, wherein the molar ratio between the sum of the protonated compound (c) and the protonated compound (d) used during the reaction and the protonated compound (d) added after the reaction is 1:0.1 to 1:1, preferably 1:0.2 to 1:1, more preferably 1:0.2 to 1:0.8, even more preferably 1:0.2 to 1:0.6, most preferably 1:02 to 1:0.

4.

23. The polysiloxane polymer composition of any one of claims 1-22, wherein the pKa of the protonated compound (d) is no greater than 2.5 and the pKa of the protonated compound (c) is greater than 2.5, or the pKa of the protonated compound (d) is no greater than 2.0 and the pKa of the protonated compound (c) is greater than 2.

0.

24. A method for preparing a polysiloxane polymer composition as described in any one of claims 1, 3-17, 20 and 22-23, wherein the method comprises: reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p); wherein the protonated component (p) comprises at least one protonated compound (c) having a pKa greater than 3.0 and at least one protonated compound (d) having a pKa no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0, and wherein the molar ratio of the protonated compound (c) to the protonated compound (d) ranges from 9:1 to 0.1:1, preferably from 9:1 to 0.2:1, more preferably from 5:1 to 0.2:1, even more preferably from 2:1 to 0.2:1, most preferably from 2:1 to 0.4:1, still more preferably from 2:1 to 1:

1.

25. The method according to claim 24, wherein there is a step of adding a protonated compound (d) after the reaction in order to obtain the polysiloxane polymer composition.

26. The method of claim 24, wherein no protonating compound (d) is added after the reaction in order to obtain the polysiloxane polymer composition.

27. A method for preparing a polysiloxane polymer composition as described in any one of claims 2-15 and 18-23, wherein the method comprises: reacting a hydrophobic component (a) comprising a polysiloxane backbone and a quaternized component (b) comprising a tertiary amine group in the presence of a protonated component (p); the protonated component (p) comprising at least one protonated compound (c) having a pKa greater than 3.0; A protonated compound (d) having a pKa of no greater than 3.0, preferably no greater than 2.5, preferably no greater than 2.0, more preferably no greater than 1.5, most preferably no greater than 1.0 is added after the reaction.

28. The method of claim 27, wherein the reaction to obtain the polysiloxane polymer composition is carried out in the presence of a protonated compound (d).

29. The method of claim 27, wherein the reaction to obtain the polysiloxane polymer composition is carried out in the absence of a protonated compound (d).

30. Use of the polysiloxane polymer composition according to any one of claims 1 to 23 or the polysiloxane polymer composition prepared by the method according to any one of claims 24 to 29 in the fields of fiber, fabric, cosmetics or personal care.

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