A kind of water-washable amino-polyether co-modified polysiloxane and preparation method thereof

Abstract

The present invention provides a water-washable amino and polyether co-modified polysiloxane, which introduces a polyether group on the side chain through a balanced reaction of polysiloxane, and on the basis of improving the hydrophilicity of silicone oil, does not destroy the main chain structure of polysiloxane, and maintains the compliant performance of the main chain of polysiloxane. The present invention utilizes the Michael addition reaction of α, β unsaturated carbonyl compounds, and introduces a trialkoxysilane structure through an amino group and a compound formula V having both a trialkoxysilyl group and an acryloxy group; the trialkoxy structure can react with the carbon hydroxyl group on the fiber substrate to form a chemical bond. In an aqueous emulsion, the amino polyether-modified polysiloxane can not only form a hydrogen bond with the fiber substrate, but also form a silicon-oxygen-carbon chemical bond, which greatly improves the water-washing resistance. At the same time, since the amino group of the amino polyether co-modified polysiloxane is a secondary amine or a tertiary amine, its yellowing resistance effect is significantly improved.

Description

Technical Field

[0001] The invention relates to the technical field of textile softeners, and in particular to a water-washable amino-polyether co-modified polysiloxane and a preparation method thereof. Background Art

[0002] Amino-modified polysiloxane is an important component of fabric softening finishing. Fabrics finished with amino-modified polysiloxane emulsion are soft, smooth, elastic, wrinkle-resistant, and have good antistatic properties and certain washability. However, in order to improve the hydrophilicity of amino-modified polysiloxane, polyvinyl alcohol needs to be introduced as a hydrophilic group. Currently, polyvinyl alcohol is mainly introduced into the main chain. With the introduction of polyvinyl alcohol groups, the hydrophilicity of the fabric is improved, but at the same time, the washability of the finished fabric becomes worse. In addition, the introduction of polyvinyl alcohol structure into the main chain destroys the flexibility of the siloxane chain, making the softening finishing effect of amino-modified polysiloxane worse.

[0003] Chinese patent document CN101874059A (CN200880117697.3) discloses an organopolysiloxane containing quaternary ammonium groups. The patent prepares polydimethylsiloxane modified with quaternary ammonium groups by reacting terminal epoxy silicone oil with tertiary amine under acid catalysis. The fabrics finished by the polysiloxane have good hydrophilic effect and soft finishing effect. The quaternary amine structure provides a good yellowing resistance effect, but it is not very helpful for water resistance performance. Therefore, the patent is superior to the properties of silicone softeners containing polyglycols in terms of softness and washing resistance durability, but its water washing resistance is still poor. And its water washing resistance is achieved by the reaction of excess epoxy groups in the system with hydroxyl groups on the fabric. The copolymer synthesized in the patent is an epoxy-terminated polymer. First, the introduction of polyether breaks the siloxane chain structure; secondly, the epoxy groups are at both ends of the molecular chain, so the regulation of the epoxy group content can only be regulated by changing the molecular weight of the polymer, and the hydrophilic property cannot be conveniently adjusted. Chinese patent document CN1965015A (CN200580019120.5) discloses a method for modifying a fiber substrate with a siloxane copolymer. The patent first reacts a hydrogen-terminated polydimethylsiloxane with an allyl polyether, and then reacts an organic amine with the polyether-modified polysiloxane through an isocyanate to obtain a polyurethane-modified polysiloxane with both hydrophilicity and soft finishing. The patent uses polyurethane-modified polydimethylsiloxane for fabric finishing, and uses hydroxyl-terminated allyl polyether to connect polysiloxane segments and urethane segments. The method has the following characteristics: ① The polyurethane segments and polyether segments are on the main chain, which breaks the flexibility of polysiloxane, and ② the improvement of its water resistance is achieved by the polyurethane segments being able to form hydrogen bonds with the surface of the fabric fibers. The force of the hydrogen bonds is much smaller than the force of the chemical bonds, so the water-washing resistance of the modified material in the patent is poor. Chinese patent document CN106146856A (CN201610632480.2) discloses a method for preparing a ternary copolymerized block hydrophilic amino silicone oil, wherein hydrogen-terminated polydimethylsiloxane reacts with allyl epoxy polyether under a catalyst to obtain epoxy polyether silicone oil, and then the obtained epoxy polyether silicone oil reacts with amino-terminated polyether under a solvent to obtain a ternary copolymerized silicone oil, and the obtained silicone oil can give the fabric good hydrophilic properties. This patent adopts the traditional synthesis method of ternary copolymerized silicone oil, and its characteristics are: ① The polyether hydrophilic chain segment is introduced into the main chain, breaking the flexibility of the siloxane chain, and ② The hydrophilicity is good, but the water washing resistance is poor.

[0004] Chinese patent document CN 109880107 A (CN 109880107 A) discloses a polysiloxane compound modified with a polyether and a quaternary ammonium cation, and its preparation and application. However, the patent adopts a reaction of terminal aminopropyl polydimethylsiloxane with terminal epoxy polyether, and then reacts with epoxy quaternary ammonium salt to obtain a polyether-polysiloxane copolymer. The modified polymer obtained in the patent has the following characteristics: ① the polyether is on the main chain, which reduces the flexibility of the polysiloxane; ② the hydroxyl group in the structure reacts very slowly with the hydroxyl group and carboxyl group of the fabric; ③ each amino group may react with two epoxy groups. Therefore, the patent method is likely to cause cross-linking of the system, and the requirements for the reaction process may be strict. Chinese patent document CN 110776641 A (201911281321.2) provides a method for preparing amino polyether modified polysiloxane, which first introduces a polyether segment into the side chain and simultaneously introduces an epoxy group into the side chain; then the epoxy group of the side chain reacts with an organic amine to form the final amino modified polysiloxane. However, in general, the reactivity of the epoxy group is relatively low, so the reaction of the epoxy group with the hydroxyl group of the fabric is very slow and reversible, which will lead to a decrease in water washing resistance, and the water washing resistance effect it imparts to the fabric will be much lower than that of alkoxysilane. Summary of the invention

[0005] The purpose of the present invention is to solve the problem that the hydrophilicity, softness and water wash resistance of amino- and polyether-modified polysiloxanes existing in the prior art are difficult to improve at the same time, and to provide a water-resistant amino- and polyether-modified polysiloxane that can impart softness, hydrophilicity and yellowing resistance to fibers (e.g., natural or artificial substrates with fiber structures, especially fabric sheets) and a preparation method thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A water-washable amino-polyether co-modified polysiloxane, the structural formula of which is:

[0008]

[0009] Wherein, group A is a group containing one or more nitrogen atoms, B is a hydrocarbon group containing at least one carbon atom, and R 1 is hydrogen or methyl, R 2 is any group; x+y is 1 to 200, x is 1 to 200, y is 0 to 199; a is 1 to 50; b is 5 to 1500; c is 0.1-10; wherein R' is R 3 Or -OR 4 Group, R 3 is a hydrocarbon group having 1 to 18 carbon atoms, R 4 is a hydrocarbon group of 1 to 18 carbon atoms; R 5 is a hydrocarbon group of 1 to 18 carbon atoms; R6 A hydrogen atom or a methyl group.

[0010] Preferably, x+y is 2-98, x is 2-50, and y is 0-48; more preferably, x+y is 2-25, x is 2-25, and y is 0-18. More preferably, a is 1-21; b is 40-850. More preferably, c is 0.4-5. More preferably, x+y is 10-21, x is 5-21, and y is 0-15. Further preferably, a+b+c is 45-850.

[0011] Preferably, the A group is a group containing an amino group, and the amino group is at least one of a secondary amino group or a tertiary amino group; further preferably, the A group includes -CH2CH2CH2NH-, -CH2CH2CH2NHCH2CH2NH-, -CH2CH2CH2OCH2CH2NH-, -CH2CH2CH2NHCH2CH2CH2NH-, B is an alkane group consisting of 1 to 8 (-CH2-), preferably 1-3, such as one of methylene (-CH2-), dimethylene (-CH2CH2-), and trimethylene (-CH2CH2CH2-).

[0012] Preferably, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;

[0013] Preferably, the R 2 is one of alkyl, alkenyl and aryl. 2 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl (e.g., n-hexyl, cyclohexyl), heptyl (e.g., n-heptyl), octyl (e.g., n-octyl), dodecyl, hexadecyl, etc.; examples of alkenyl groups include allyl, etc.; examples of aryl groups include phenyl, benzyl, etc.

[0014] More preferably, R 2 It is -H or an alkyl group having 1 to 16 carbon atoms.

[0015] Preferably, R 3The group includes a chain alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl (e.g., n-hexyl), heptyl (e.g., n-heptyl), octyl (e.g., n-octyl), nonyl (e.g., n-nonyl), dodecyl (e.g., n-dodecyl), octadecyl (e.g., n-octadecyl); a cycloalkyl group, such as one of cyclopentyl, cyclohexyl and methylcyclohexyl; an aryl group, such as one of phenyl, naphthyl, o- / m- / p-methylphenyl, xylyl, ethylphenyl, benzyl, α-phenylethyl and β-phenylethyl.

[0016] Preferably, R 3 The group is a hydrocarbon group of 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group of 1 to 3 carbon atoms; examples of the hydrocarbon group of 1 to 3 carbon atoms include methyl, ethyl, and n-propyl.

[0017] R 4 , R 5 Same group type as R 3 .

[0018] More preferably, R 3 , R 4 The group is -CH3; R 5 It is -CH3, -CH3CH2, -CH(CH3)2.

[0019] Preferably, the amino content in the co-modified polysiloxane is 0.05 to 0.9 mmol / g (the amount of substance contained in nitrogen atoms per gram of sample), and preferably the amino content is 0.1 to 0.8 mmol / g (the amount of substance contained in nitrogen atoms per gram of sample);

[0020] The viscosity of the co-modified polymer is 100-200000 mPa.s, preferably 200-100000 mPa.s, more preferably 500-50000 mPa.s, and more preferably 700-40000 mPa.s.

[0021] The present invention also provides a method for preparing the water-washable amino-polyether co-modified polysiloxane, comprising the following steps:

[0022] (1) A trimethylsiloxy-terminated side chain hydrogen polydimethylsiloxane (Formula I) and a polyethylene oxide propylene oxide (Formula II) react in the presence of a catalyst to obtain a polyethylene oxide propylene oxide-modified polydimethylsiloxane. The reaction equation is as follows:

[0023]

[0024] (CH3)3SiO-[Si(CH3)2O] z -[SiH(CH3)O]n -Si(CH3)3(I)

[0025] wherein z+n is 2 to 200; z is 1 to 199, and n is 1 to 199;

[0026] Preferably z+n is 2 to 150, z is 1 to 149, and n is 1 to 149;

[0027] More preferably, z+n is from 2 to 100, z is from 1 to 99, and n is from 1 to 99; z+n is the degree of polymerization.

[0028] CH2=CR 1 CH2-O[CH2CH2O] x -[CH2CH(CH3)O] y -R 2 (II)

[0029] Among them, R 1 is methyl or hydrogen; R 2 It is hydrogen or a hydrocarbon group of 1 to 18 carbon atoms; preferably it is a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, and more preferably it is a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms.

[0030] (2) reacting the polyethylene oxide propylene oxide modified polydimethylsiloxane obtained in step (1) with a compound of general formula (III), a polymer of general formula (IV), a compound of general formula (V) and a compound of general formula (VI) in the presence of a catalyst; the reaction equation is as follows:

[0031]

[0032] R 3 q (R 4 O) 3-q Si-AH(III), q is 0 or 1.

[0033] When q is 0, R' in the obtained product is -OR 4 When q is 1, the R' in the obtained product is R 3 Group.

[0034] (CH3)3SiO-[Si(CH3)2O] m -Si(CH3)3(IV), m is 1 to 200;

[0035] (R 5 O)3Si-BO-CO-CR 6 =CH2 (V);

[0036] HO-[Si(CH3)2O] p-H(VI), p is 1 to 200; preferably 1 to 100, more preferably 1 to 30.

[0037] Preferably, in step (1), the molar ratio of silicon-hydrogen bonds in the side chain hydrogen polydimethylsiloxane (I) to unsaturated carbon-carbon bonds in the polymer (II) is 1 to 2; preferably 1 to 1.5, more preferably 1 to 1.05.

[0038] Preferably, the catalyst in step (1) is a catalyst that can promote the reaction of silicon-hydrogen bonds and unsaturated carbon-carbon bonds, and the catalyst is a coordination compound containing elements such as boron, rhodium, iron, platinum, etc., preferably a coordination compound containing platinum, and more preferably a platinum-containing complex whose ligand is isopropanol, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, n-octanol, and isooctyl alcohol;

[0039] Preferably, the amount of the catalyst used in step (1) is 1 to 30 ppm, preferably 1 to 20 ppm, and more preferably 1 to 10 ppm, all of which are based on the total mass of the reactants (the total mass of the reactants in step (1)), and the amount of the catalyst is calculated as platinum element.

[0040] Preferably, the reaction temperature in step (1) is 40 to 150°C, preferably 60 to 120°C, more preferably 80 to 120°C.

[0041] Preferably, in step (2), the amount of compound (V) used is 0.01 to 1 times, preferably 0.1 to 1 times, the amount of compound (III) used. The amount of compound (V) and compound (III) used can be adjusted by adjusting the amino group content in the co-modified polysiloxane.

[0042] Preferably, in step (2), the polymer obtained in the first step is first reacted with compound (III), polymer (IV) and polymer (VI) under the action of a catalyst at 94-96° C. for 1-3 hours, and then compound (V) is added to the system to continue the reaction for 1.5-2.5 hours. The amount of compound (IV) and compound (VI) used in step (2) is determined by the degree of polymerization of the polymer. Further preferably, the reaction is carried out at 94-96° C. under reduced pressure for 0.5-1.5 hours, and at normal pressure for 0.5-1.5 hours. The reduced pressure is -0.08-0.10 MPa.

[0043] Preferably, the catalyst in step (2) is a catalyst that can promote siloxane equilibrium, and the preferred catalyst is one of alkali metal hydroxide, linear phosphazene, and tetramethylammonium hydroxide.

[0044] Preferably, the amount of the catalyst used in step (2) is 1 to 1000 ppm (based on the total mass of the reactants in step (2)), preferably 300 to 600 ppm.

[0045] The reaction process of the method of the present invention is as follows: the first step is a silylation reaction of polydimethylsiloxane with side chain silane hydrogen and polyether containing unsaturated double bonds; the second step is to introduce aminosilane and capping groups through base-catalyzed polysiloxane equilibrium to control the size of the molecular weight; and then the introduced amino group reacts with the Michael addition reaction of α, β unsaturated carbonyl compounds to introduce trialkoxy groups into the system.

[0046] The present invention also provides the use of the amino polyether co-modified polysiloxane in a fabric finishing agent. Preferably, the fabric comprises a fabric sheet or a wire. Preferably, the amino polyether co-modified polysiloxane is in the form of an emulsion or a microemulsion.

[0047] The present invention also provides a fabric finishing agent, which is an aqueous emulsion containing the amino polyether co-modified polysiloxane.

[0048] Preferably, the mass fraction of the amino polyether co-modified polysiloxane in the aqueous emulsion is 20% to 60%, preferably 30% to 50%.

[0049] The preparation method of the fabric finishing agent containing amino polyether co-modified polysiloxane of the present invention is as follows: the polysiloxane of the present invention is mixed with water in a certain proportion, stirred and then homogenized by a rotor-stator homogenizer, a colloid mill or a high-pressure homogenizer.

[0050] Preferably, acetic acid is used to neutralize the amino groups of the polysiloxane before mixing with water.

[0051] Beneficial effects:

[0052] One or more technical solutions provided by the embodiments of the present invention have at least the following beneficial effects:

[0053] The amino polyether co-modified polysiloxane of the present invention is easily dispersed in water without other auxiliary agents, that is, self-dispersible, and produces emulsions, especially microemulsions.

[0054] The amino polyether co-modified polydimethylsiloxane of the present invention has a similar structure to traditional amino-modified polydimethylsiloxane and ternary copolymer silicone oil. Traditional amino-modified polydimethylsiloxane is prepared with aminosilane coupling agent as raw material, which can give the fiber substrate a soft effect, but its hydrophilicity is poor. The traditional ternary copolymer silicone oil introduces a polyether structure into the main chain of the molecule. Due to the introduction of the polyether, the hydrophilicity of the polysiloxane is improved, but because the silicon-oxygen-silicon chain of the siloxane main chain is destroyed, the flexibility of its molecular chain is also destroyed, so the feel of its soft finishing is poor. And due to the good hydrophilicity, the water washing resistance of the traditional ternary copolymer silicone oil is very poor. After the fiber substrate after finishing is washed many times, the effect of soft finishing is greatly reduced.

[0055] In the present invention, we introduce polyether groups on the side chains through the equilibrium reaction of polysiloxane, and on the basis of improving the hydrophilicity of silicone oil, the main chain structure of polysiloxane is not destroyed, and the softness of the main chain of polysiloxane is maintained, so it has a very good soft finishing effect. The present invention utilizes the Michael addition reaction of α, β unsaturated carbonyl compounds, and introduces the trialkoxysilane structure through the Michael addition reaction of amino group (A group in formula III) and compound formula V having both trialkoxysilyloxy and acryloxy groups, for example,

[0056]

[0057] The trialkoxy structure can react with the carbon hydroxyl group on the fiber substrate to form a chemical bond. In the aqueous emulsion, due to the influence of steric hindrance, the trialkoxysilane cannot completely and thoroughly react with the carbon hydroxyl group on the fiber substrate, so the residual alkoxy group can be hydrolyzed to produce silicon hydroxyl groups that can form hydrogen bonds with the polar groups on the fiber substrate. Therefore, the amino polyether modified polysiloxane in the present invention can not only form hydrogen bonds with the fiber substrate, but also form silicon-oxygen-carbon chemical bonds, greatly improving the water washing resistance of the fiber substrate. At the same time, since the amino polyether co-modified polysiloxane amino group in the present invention is a secondary amine or a tertiary amine, its yellowing resistance effect is significantly improved.

[0058] In the modified polysiloxane structure of the present invention, the content of the polyether group and the trialkylsilane structural unit affects its hydrophilicity, water resistance and other properties. Within a certain range, the higher the content of the polyether group, the better the hydrophilicity, and the higher the content of the trialkoxy group, the better the water resistance, but the effect is not the more the better. In the present invention, the trialkoxy group is introduced into the side chain, so the content of the alkoxy group can be arbitrarily adjusted, thereby adjusting the hydrophilicity. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 This is the infrared spectrum of the amino polyether modified polydimethylsiloxane obtained in Example 1. DETAILED DESCRIPTION

[0060] The present invention is described in detail below with reference to specific examples. Unless otherwise specified, the raw materials used in the examples of the present invention are all common commercially available products.

[0061] Embodiment 1:

[0062] A water-resistant amino-polyether co-modified polysiloxane, the structural formula or general formula of each reactant used is as follows:

[0063] Compounds of formula I: Compound of formula III Compound of formula IV Compounds of formula V Compound of formula VI

[0064] The preparation method comprises the following steps:

[0065] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (Formula I) (water content 50 ppm, silicon-hydrogen content 0.30%, degree of polymerization 90) and 787.82 g of an allyl alcohol ethoxy compound of the following formula (the molar ratio of the silicon-hydrogen bond in Formula I to the unsaturated carbon-carbon bond in Formula II is 1:1.05),

[0066] CH2=CHCH2-O-(CH2CH2O) 10.05 -H,

[0067] Its iodine value is 50.74 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.24g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinylpolydimethylsiloxane (as solvent) (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the reaction is continued for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 1500mPa.s at 25°C) is obtained, which is polyether-modified polydimethylsiloxane.

[0068] (2) 850 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, corresponding to the compound of formula VI), 12.00 g of aminoethylaminopropylmethyldimethoxysilane (corresponding to the compound of formula III, C8H 22 O2N2Si, 206.36), 66.67g trimethylsiloxy-terminated polydimethylsiloxane (polymerization degree is 19), corresponding to the compound of general formula IV) and 33.33g polyether-modified polydimethylsiloxane prepared above were mixed, the temperature was raised to 95°C, 0.78g tetramethylammonium hydroxide pentahydrate (catalyst dosage is 400ppm) was dissolved in 1g of water and added, the pressure was reduced to -0.09MPa, the reaction was maintained at 95°C for 1 hour, and then reacted at normal pressure for 1 hour, and 14.44g methacryloxypropyltrimethoxysilane (corresponding to the compound of general formula V, C 10 H 20 O5Si, 248.35, the ratio of its amount to the amount of aminoethylaminopropylmethyldimethoxysilane is about 1:1), the reaction is continued for 2 hours, and the NMR is used to 1HNMR detection showed that no vinyl group remained. The temperature was raised to 150°C and the reaction was carried out for 0.5 hour. The pressure was reduced to -0.09 MPa and the volatile substances in the product were removed to obtain a light yellow transparent silicone oil with a viscosity of 4680 mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.12 mmol / g.

[0069] In the product obtained in Example 1, group A is -CH2CH2CH2NHCH2CH2NH-, group B is -CH2CH2CH2-, R1 is -H, R2 is -H, R' is -CH3, R5 is -CH3, and R6 is -CH3; a=1.31, b=279.30, c=0.90, x=10.05, and y=0.

[0070] Figure 1 is the infrared spectrum of the obtained amino polyether modified polydimethylsiloxane, Figure 1 It can be seen that 3500~3200cm -1 The nearby peaks are stretching vibration peaks of amino NH, 2961-2860 cm -1 A group of peaks nearby are the stretching vibration peaks of CH3 and CH2, 1720 cm -1 The peak near is the asymmetric stretching vibration peak of C=O. Figure 1 It can be seen that there is no vinyl residue in the product and the reaction is complete.

[0071] 40 g of the prepared amino polyether-modified polydimethylsiloxane was taken, 0.29 g of acetic acid was added to neutralize the amino groups in the system, and 60 g of water was added during stirring to obtain a microemulsion.

[0072] Embodiment 2:

[0073] A water-resistant amino-polyether co-modified polysiloxane, wherein the compound of formula III is: Compound of formula V:

[0074] The preparation method comprises the following steps:

[0075] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (water content 50 ppm, silicon hydrogen content 0.30%, degree of polymerization 90) and 1478.74 g of an allyl alcohol ethoxy propoxy compound of the following formula (the molar ratio of the silicon-hydrogen bond in formula I to the unsaturated carbon-carbon bond in formula II is 1:1.05),

[0076] CH2=CHCH2-O-[CH2CH2O] 20.02 -H

[0077] Its iodine value is 27.03 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.27g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinyl polydimethylsiloxane (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the temperature is maintained for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 5500mPa.s at 25°C) is obtained, namely polyether-modified polydimethylsiloxane.

[0078] (2) 850.00 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, corresponding to the compound of general formula VI), 100.00 g of aminoethylaminopropyltrimethoxysilane (corresponding to the compound of general formula III), 66.67 g of trimethylsiloxy-terminated polydimethylsiloxane (with a degree of polymerization of 19, corresponding to the compound of general formula IV) and 33.33 g of the polyether-modified polydimethylsiloxane prepared above were mixed, the temperature was raised to 95° C., 0.93 g of tetramethylammonium hydroxide pentahydrate (the catalyst dosage was 400 ppm) was dissolved in 1 g of water and added, the pressure was reduced to -0.09 MPa, the reaction was maintained at 95° C. for 1 hour, and then the reaction was carried out at normal pressure for 1 hour, 111.69 g of methacryloxypropyltrimethoxysilane (corresponding to the compound of general formula V, the amount of which to the amount of aminoethylaminopropyltrimethoxysilane was about 1:1) was added, the reaction was continued for 2 hours, and the resultant mixture was analyzed by nuclear magnetic resonance. 1 HNMR detection showed that there was no vinyl residue. The temperature was raised to 150°C and the reaction was carried out for 0.5 hour. The pressure was reduced to -0.09 MPa, and the volatile substances in the product were removed to obtain a light yellow transparent silicone oil with a viscosity of 11240 mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.77 mmol / g.

[0079] In the product obtained in Example 2, group A is -CH2CH2CH2NHCH2CH2NH-, group B is -CH2CH2CH2-, R1 is H, R2 is -H, R' is -OCH3, R5 is -CH3, and R6 is -CH3; a=10.26, b=282.63, c=0.6, x=20.02, and y=0.

[0080] 40.00 g of the prepared amino polyether-modified polydimethylsiloxane was taken, 1.86 g of acetic acid was added, and 60.00 g of water was added while stirring to obtain a microemulsion.

[0081] Embodiment 3:

[0082] A water-resistant amino-polyether co-modified polysiloxane, the compound of formula III used is: Compounds of formula V The preparation method comprises the following steps:

[0083] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (water content 50 ppm, silicon-hydrogen content 0.15%, degree of polymerization 90) was mixed with 2090.03 g of an allyl alcohol ethoxy compound of the following formula (the molar ratio of the silicon-hydrogen bond in formula I to the unsaturated carbon-carbon bond in formula II was 1:1.05),

[0084] CH2=CHCH2-O-[CH2CH2O] 5.00 -[CH2CH(CH3)O] 15.00 -C 16 H 33 ;

[0085] Its iodine value is 19.13 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.47g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinyl polydimethylsiloxane (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the temperature is maintained for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 4356mPa.s at 25°C) is obtained, namely, polyether-modified polydimethylsiloxane.

[0086] (2) 850 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, corresponding to the compound of general formula VI), 68.5 g of aminoethylaminopropylmethyldimethoxysilane (with a degree of polymerization of 19, corresponding to the compound of general formula III), 66.67 g of trimethylsiloxy-terminated polydimethylsiloxane (with a degree of polymerization of 19, corresponding to the compound of general formula IV) and 33.33 g of the polyether-modified polydimethylsiloxane prepared above were mixed, the temperature was raised to 95° C., 0.86 g of tetramethylammonium hydroxide pentahydrate (with a catalyst amount of 400 ppm) was dissolved in 1 g of water and added, the pressure was reduced to -0.09 MPa, the temperature was maintained at 95° C. for 1 hour, and then the temperature was kept at normal pressure for 1 hour, 68.47 g of acryloyloxypropyltrimethoxysilane (with a substance amount of 1:1) was added, the reaction was continued for 2 hours, and the concentration was measured by nuclear magnetic resonance. 1HNMR detection showed that no vinyl group remained. The temperature was raised to 150°C and the reaction was carried out for 0.5 hour. The pressure was reduced to -0.09 MPa and the volatile substances in the product were removed to obtain a light yellow transparent silicone oil with a viscosity of 8389 mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.61 mmol / g.

[0087] Example 3 The product obtained has a A group of -CH2CH2CH2NHCH2CH2NH-, a B group of -CH2-, R1 of H, and R2 of -C 16 H 33 , R' is -CH3, R5 is -CH3, R6 is -H; a=7.63, b=284.14, c=0.46, x=5, y=15.

[0088] Take 40g of the prepared amino polyether modified polydimethylsiloxane, add 1.47g of acetic acid, and add 60g of water while stirring to obtain a microemulsion. Compared with Example 1, the amount of aminosilane in this example is different, resulting in different soft finishing effects and different trialkoxy content introduced. Different trialkoxy content may lead to different finishing feel and water washability effects

[0089] Embodiment 4:

[0090] A water-resistant amino-polyether co-modified polysiloxane, the compound of formula III used is: Compound of formula V: The preparation method comprises the following steps:

[0091] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (water content 50 ppm, silicon-hydrogen content 0.30%, polymerization degree 90, corresponding to the compound of formula I) and 831.92 g of the allyl alcohol ethoxy compound of the following formula (corresponding to the compound of formula II) were mixed (the molar ratio of the silicon-hydrogen bond in formula I to the unsaturated carbon-carbon bond in formula II was 1:1.05),

[0092] CH2=C(CH3)-CH2-O-(CH2CH2O) 10.05 -CH3

[0093] Its iodine value is 48.05 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.24g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinylpolydimethylsiloxane (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the temperature is maintained for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 1300mPa.s at 25°C) is obtained, thereby obtaining polyether-modified polydimethylsiloxane.

[0094] (2) 850 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, corresponding to the compound of general formula VI), 88.00 g of piperazinylmethylmethyldimethoxysilane (with a degree of polymerization of 19, corresponding to the compound of general formula III), 66.67 g of trimethylsiloxy-terminated polydimethylsiloxane (with a degree of polymerization of 19, corresponding to the compound of general formula IV) and 200.00 g of the polyether-modified polydimethylsiloxane prepared above were mixed, the temperature was raised to 95° C., 1.04 g of tetramethylammonium hydroxide pentahydrate (with a catalyst dosage of 422 ppm) was dissolved in 1 g of water and added, the pressure was reduced to -0.09 MPa, the temperature was maintained at 95° C. for 1 hour, and then the temperature was kept at normal pressure for 1 hour, 99.19 g of methacryloxypropyltrimethoxysilane (with a molar ratio of the molar ratio of the molar ratio of the piperazinylmethyldimethoxysilane to ... 1 HNMR detection showed that no vinyl group remained. The temperature was raised to 150°C and the reaction was carried out for 0.5 hour. The pressure was reduced to -0.09 MPa and the volatile substances in the product were removed to obtain a light yellow transparent silicone oil with a viscosity of 3543 mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.61 mmol / g.

[0095] Example 4 The A group in the obtained product is The B group is -CH2CH2CH2-, R1 is -CH3, R2 is -CH3, R' is -CH3, R5 is -CH3, and R6 is -CH3; a=7.37, b=241.93, c=4.31, x=10.05, y=0.

[0096] 40 g of the prepared amino polyether-modified polydimethylsiloxane was taken, 1.47 g of acetic acid was added, and 60 g of water was added while stirring to obtain a microemulsion.

[0097] Embodiment 5:

[0098] A water-resistant amino-polyether co-modified polysiloxane, the compound of formula III used is: Compound of formula V: The preparation method comprises the following steps:

[0099] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (water content 50 ppm, silicon-hydrogen content 0.30%, degree of polymerization 90, corresponding to the compound of formula I) and 787.82 g of the allyl alcohol ethoxy compound of the following formula (corresponding to the compound of formula II) were mixed (the molar ratio of the silicon-hydrogen bond in formula I to the unsaturated carbon-carbon bond in formula II was 1:1.05),

[0100] CH2=CHCH2-O-(CH2CH2O) 10.05 -H

[0101] Its iodine value is 50.74 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.24g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinylpolydimethylsiloxane (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the temperature is maintained for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 1500mPa.s at 25°C) is obtained, thereby obtaining polyether-modified polydimethylsiloxane.

[0102] (2) 850 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, corresponding to the compound of formula VI), 19.50 g of aminopropylmethyldimethoxysilane (corresponding to the compound of formula III, C6H 17 NO2Si, 163.3), 66.67g trimethylsiloxy-terminated polydimethylsiloxane (polymerization degree is 19, corresponding to the compound of general formula IV) and 90.00g of the above-prepared polyether-modified polydimethylsiloxane are mixed, the temperature is raised to 95°C, 1.04g of tetramethylammonium hydroxide pentahydrate (catalyst dosage is 506.7ppm) is dissolved in 1g of water and added, the pressure is reduced to -0.09MPa, the reaction is maintained at 95°C for 1 hour, and then the reaction is carried out at normal pressure for 1 hour, and 34.68g of methacryloxypropyltriethoxysilane (corresponding to the compound of general formula V, C 13 H 26 O5Si, 290.43, the ratio of its amount to the amount of aminopropylmethyldimethoxysilane is about 1:1), the reaction is continued for 2 hours, and the NMR is used to determine the 1HNMR detection showed that there was no vinyl residue. The temperature was raised to 150°C and the reaction was carried out for 0.5 hour. The pressure was reduced to -0.09 MPa and the volatile substances in the product were removed to obtain a light yellow transparent silicone oil with a viscosity of 2140 mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.11 mmol / g.

[0103] In the product obtained in Example 5, the A group is -CH2CH2CH2NH-, the B group is -CH2CH2CH2-, R1 is -H, R2 is -H, R' is -CH3, R5 is -CH3CH2, and R6 is -CH3; a=2.49, b=264.35, c=2.27, x=10.05, y=0.

[0104] 40 g of the prepared amino polyether-modified polydimethylsiloxane was taken, 0.27 g of acetic acid was added, and 60 g of water was added while stirring to obtain a microemulsion.

[0105] Embodiment 6:

[0106] A water-resistant amino-polyether co-modified polysiloxane, the compound of formula III used is: Compound of formula V: The preparation method comprises the following steps:

[0107] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (water content 50 ppm, silicon-hydrogen content 0.30%, degree of polymerization 90, corresponding to the compound of formula I) and 787.82 g of the allyl alcohol ethoxy compound of the following formula (corresponding to the compound of formula II) were mixed (the molar ratio of the silicon-hydrogen bond in formula I to the unsaturated carbon-carbon bond in formula II was 1:1.05),

[0108] CH2=CHCH2-O-(CH2CH2O) 10.05 -H

[0109] Its iodine value is 50.74 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.24g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinylpolydimethylsiloxane (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the temperature is maintained for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 1500mPa.s at 25°C) is obtained, thereby obtaining polyether-modified polydimethylsiloxane.

[0110] (2) 50 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, corresponding to the compound of general formula VI), 24.00 g of aminoethylaminopropylmethyldimethoxysilane (corresponding to the compound of general formula III), 66.67 g of trimethylsiloxy-terminated polydimethylsiloxane (with a degree of polymerization of 19, corresponding to the compound of general formula IV) and 200.00 g of the polyether-modified polydimethylsiloxane prepared above were mixed, the temperature was raised to 95° C., 0.30 g of tetramethylammonium hydroxide pentahydrate (the catalyst dosage was 440 ppm) was dissolved in 1 g of water and added, the pressure was reduced to -0.09 MPa, the temperature was maintained at 95° C. for 1 hour, and then the temperature was kept at normal pressure for 1 hour, 38.67 g of methacryloxypropyltriisopropoxysilane (corresponding to the compound of general formula V, the amount of which to the amount of aminoethylaminopropylmethyldimethoxysilane was about 1:1) was added, the reaction was continued for 2 hours, and the reaction was carried out using nuclear magnetic resonance. 1 HNMR detection showed that no vinyl group remained. The temperature was raised to 150°C and the reaction was carried out for 0.5 hour. The pressure was reduced to -0.09 MPa and the volatile substances in the product were removed to obtain a light yellow transparent silicone oil with a viscosity of 722 mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.61 mmol / g.

[0111] In the product obtained in Example 6, the A group is -CH2CH2CH2NHCH2CH2NH-, the B group is -CH2CH2CH2-, R1 is -H, R2 is -H, R' is -CH3, R5 is -CH(CH3)2, and R6 is -CH3; a=2.13, b=42.67, c=4.43, x=10.05, and y=0.

[0112] 40 g of the prepared amino polyether-modified polydimethylsiloxane was taken, 1.47 g of acetic acid was added, and 60 g of water was added while stirring to obtain a microemulsion.

[0113] Embodiment 7:

[0114] A water-resistant amino-polyether co-modified polysiloxane, the compound of formula III used is: Compound of formula V: The preparation method comprises the following steps:

[0115] (1) 500 g of trimethylsiloxy-terminated side-chain hydrogen-based polydimethylsiloxane (water content 50 ppm, silicon-hydrogen content 0.30%, degree of polymerization 90, corresponding to the compound of formula I) and 787.82 g of the allyl alcohol ethoxy compound of the following formula (corresponding to the compound of formula II) were mixed (the molar ratio of the silicon-hydrogen bond in formula I to the unsaturated carbon-carbon bond in formula II was 1:1.05),

[0116] CH2=CHCH2-O-(CH2CH2O) 10.05 -H;

[0117] Its iodine value is 50.74 (iodine value refers to the number of grams of iodine consumed in the process of adding to the unsaturated position of fat for every 100g of the material to be studied). Nitrogen protection is carried out, and the mixture is heated to 80°C, and 0.24g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α,ω-divinylpolydimethylsiloxane (viscosity of 1000mPa.s at 25°C) is added. The temperature of the reaction mixture rises by about 10°C, and the temperature is maintained for 3 hours. No silicon-hydrogen bond remains in infrared detection, and a light yellow transparent liquid (viscosity of 1500mPa.s at 25°C) is obtained, thereby obtaining polyether-modified polydimethylsiloxane.

[0118] (2) 850 g of α, ω-dihydroxy polydimethylsiloxane (with a degree of polymerization of 50, to obtain polyether-modified polydimethylsiloxane), 62.00 g of aminoethylaminopropylmethyldimethoxysilane (corresponding to the compound of general formula III), 20.00 g of trimethylsiloxy-terminated polydimethylsiloxane (with a degree of polymerization of 19, corresponding to the compound of general formula IV) and 33.33 g of the polyether-modified polydimethylsiloxane prepared above were mixed, the temperature was raised to 95° C., 0.78 g of tetramethylammonium hydroxide pentahydrate (the catalyst dosage was 400 ppm) was dissolved in 1 g of water and added, the pressure was reduced to -0.09 MPa, the reaction was maintained at 95° C. for 1 hour, and then the reaction was carried out at normal pressure for 1 hour, 7.46 g of methacryloxypropyltriisopropoxysilane (corresponding to the compound of general formula V, the amount of which to the amount of aminoethylaminopropylmethyldimethoxysilane was about 0.1:1) was added, the reaction was continued for 2 hours, and the resultant was analyzed by nuclear magnetic resonance. 1 HNMR detection showed that there was no vinyl residue. The temperature was raised to 150°C, the reaction was carried out for 0.5 hour, and the pressure was reduced to -0.09MPa to remove the volatile substances in the product to obtain a light yellow transparent silicone oil with a viscosity of 40000mPa.s at 25°C. The ammonia value of the amino polyether co-modified polysiloxane was 0.62mmol / g.

[0119] In the product obtained in Example 7, the A group is -CH2CH2CH2NHCH2CH2NH-, the B group is -CH2CH2CH2-, R1 is -H, R2 is -H, R' is -CH3, R5 is -CH3, and R6 is -CH3; a=20.35, b=803.84, c=2.73, x=10.05, and y=0.

[0120] 40 g of the prepared amino polyether-modified polydimethylsiloxane was taken, 1.48 g of acetic acid was added, and 60 g of water was added while stirring to obtain a microemulsion.

[0121] Comparative Example 1:

[0122] A modified polysiloxane, namely a conventional amino silicone oil, is modified with pure amino groups and comprises the following preparation methods:

[0123] 479.40 g of α, ω-dihydroxypolydimethylsiloxane (degree of polymerization: 50) and 30.9 g of aminoethylaminopropylmethyldimethoxysilane were added to a reaction kettle, the pressure was reduced to -0.09 MPa, the temperature was raised to 80°C, 0.08 g of sodium hydroxide aqueous solution (mass fraction 50%) was added, and the pressure was continued to be reduced until the viscosity did not change, to obtain aminosilicone oil with an ammonia value of 0.61 mmol / g.

[0124] Take 40g of the above amino silicone oil, add 4g of TO-10 and mix evenly, add 60g of water while stirring continuously, and add 1.4g of acetic acid to neutralize to obtain a microemulsion.

[0125] Comparative Example 2:

[0126] A modified polysiloxane, i.e. a conventional ternary copolymer silicone oil, comprises the following preparation methods:

[0127] 500g of α, ω-dihydropolydimethylsiloxane (water content 50ppm, hydrogen content 0.04%) and 27.4g of allyl glycidyl ether were added to a reactor, nitrogen protection, the temperature was raised to 80°C, and 0.06g of a solution of 2.7% (in terms of elemental platinum) of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in α, ω-divinyldimethylpolysiloxane (viscosity of 1000mPa.s at 25°C) was added. The temperature of the reaction mixture rose by about 6°C, and the temperature was maintained for 3 hours. No silicon-hydrogen bonds remained in the infrared detection. Nitrogen was bubbled to remove the unreacted allyl glycidyl ether, and a light yellow transparent liquid was obtained.

[0128] Add 162g ED-900 and 441g ethylene glycol monobutyl ether to the above product, heat to 130°C, keep the temperature for 4 hours, add 21.6g acetic acid for neutralization, and obtain a light yellow transparent ternary copolymer silicone oil with an ammonia value of 0.32mmol / g. Take 40g of the above product and mix it evenly with 2g TO-10, add 60g water while stirring continuously, and obtain a microemulsion.

[0129] The amino polyether co-modified polysiloxane performance test method of the present invention is:

[0130] Hydrophilicity: Use the static water drop method. Drop a drop of water at a height of 1 cm from the fabric, and judge the difference in hydrophilicity based on the time it takes for the water drop to completely diffuse.

[0131] Hand feel: After cooling and rehydration, the finished fabric samples were evaluated comprehensively by several experienced hand feel evaluation professionals in terms of smoothness, softness, fluffiness, etc. The hand feel of the original fabric was rated as 1 point, and the best hand feel evaluation was 5 points, and the average value was taken.

[0132] Washing resistance: The polyester fabric was treated with the products of the embodiment and the comparative example respectively. The treated fabric was washed 5 times at home and its feel and hydrophilicity were compared. The padding dosage was 10 g / L. Padding process: the emulsion dosage was 30 g / L, one dip and one padding (rolling rate 60%), drying (100°C), setting (150°C, 30 seconds), and moisture regain for 4 hours.

[0133] Yellowing property: Use padding method to soften polyester whitening cloth or fabric that is easy to change color. Use SF600X Datacolor colorimeter to measure the whiteness value of polyester whitening cloth before and after softening.

[0134] Table 1 Performance evaluation of fabric after finishing

[0135]

[0136] As can be seen from Table 1, the amino polyether co-modified polysiloxane prepared in the present invention is used to finish the fabric, and better soft finishing effect, yellowing resistance effect (the data of whiteness before and after finishing reflect the yellowing resistance effect), hydrophilic effect and water washing resistance effect can be obtained than the traditional ternary copolymer silicone oil and amino modified polydimethylsiloxane. Due to the presence of alkoxy groups, the siloxane copolymer can be more stably bonded to the fabric surface, and after multiple washings, the fabric still shows good softness and hydrophilic effects. At the same time, since the amino group is changed from the original primary amine to the secondary amine, its yellowing resistance effect is improved to a certain extent.

Claims

1. A water-resistant amino-polyether co-modified polysiloxane, characterized in that: Its structural formula is: ； Wherein, the group A is a group containing an amino group, B is an alkane group consisting of 1 to 8 -CH2-, wherein R 1 is hydrogen or methyl, R 2 is a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms; x+y is 1 to 200, x is 1 to 200, y is 0 to 199; a is 1 to 50; b is 5 to 1500; c is 0.1 to 10; wherein R' is R 3 Or -OR 4 Group, R 3 is a hydrocarbon group having 1 to 18 carbon atoms, R 4 is a hydrocarbon group of 1 to 18 carbon atoms; R 5 is a hydrocarbon group of 1 to 18 carbon atoms; R 6 A hydrogen atom or a methyl group.

2. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: x+y is 2~98, x is 2~50, and y is 0~48.

3. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: x+y is 2~25, x is 2~25, y is 0~18.

4. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: a is 1~21; b is 40~850.

5. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: c is 0.4~5, x+y is 10~21, x is 5~21, and y is 0~15.

6. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: The amino group is at least one of a secondary amino group and a tertiary amino group.

7. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: A group is selected from -CH2CH2CH2NH-, -CH2CH2CH2NHCH2CH2NH-, -CH2CH2CH2OCH2CH2NH-, -CH2CH2CH2NHCH2CH2CH2NH-, One of; The B group is one of methylene -CH2-, dimethylene -CH2CH2-, and trimethylene -CH2CH2CH2-.

8. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: R 2 It is a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms.

9. The water-washable amino-polyether co-modified polysiloxane according to claim 8, characterized in that: R 2 It is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.

10. The water-washable amino-polyether co-modified polysiloxane according to claim 8, characterized in that: The R 2 It is one of alkyl, alkenyl and aryl.

11. The water-washable amino-polyether co-modified polysiloxane according to claim 8, characterized in that: R 2 It is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dodecyl, hexadecyl, allyl, phenyl and benzyl.

12. The water-washable amino-polyether co-modified polysiloxane according to claim 11, characterized in that: R 2 It is -H and an alkyl group having 1 to 16 carbon atoms.

13. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: R 3 , R 4 , R 5 The groups are each one of chain alkyl, cycloalkyl and aryl.

14. The water-washable amino-polyether co-modified polysiloxane according to claim 13, characterized in that: R 3 , R 4 , R 5 The groups are respectively one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, naphthyl, o- / m- / p-methylphenyl, xylyl, ethylphenyl, benzyl, α-phenylethyl or β-phenylethyl.

15. The water-washable amino-polyether co-modified polysiloxane according to claim 14, characterized in that: R 3 , R 4 , R 5 The groups are respectively hydrocarbon groups having 1 to 6 carbon atoms.

16. The water-washable amino-polyether co-modified polysiloxane according to claim 15, characterized in that: R 3 , R 4 , R 5 The radicals are each a hydrocarbon radical having 1 to 3 carbon atoms.

17. The water-washable amino-polyether co-modified polysiloxane according to claim 15, characterized in that: R 3 , R 4 , R 5 The groups are each one of methyl, ethyl, and n-propyl.

18. The water-washable amino-polyether co-modified polysiloxane according to any one of claims 1 to 17, characterized in that: R 3 , R 4 The group is -CH3; R 5 It is one of -CH3, -CH3CH2, and -CH(CH3)2.

19. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: The content of amino groups in the co-modified polysiloxane is 0.05-0.9 mmol / g, and the content of amino groups is the amount of substances contained in nitrogen atoms per gram of sample.

20. The water-washable amino-polyether co-modified polysiloxane according to claim 19, characterized in that: The amino content is 0.1~0.8mmol / g.

21. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: The viscosity of the co-modified polymer is 100-200000 mPa.s.

22. The water-washable amino-polyether co-modified polysiloxane according to claim 1, characterized in that: The viscosity of the co-modified polymer is 200-100000 mPa.s.

23. The water-washable amino-polyether co-modified polysiloxane according to claim 22, characterized in that: The viscosity of the co-modified polymer is 500-50000 mPa.s.

24. The water-washable amino-polyether co-modified polysiloxane according to claim 23, characterized in that: The viscosity of the co-modified polymer is 700-40000 mPa.s.

25. The method for preparing the water-washable amino-polyether co-modified polysiloxane according to any one of claims 1 to 24, characterized in that: The following steps are involved: (1) The trimethylsiloxy-terminated side chain hydrogen polydimethylsiloxane of formula I reacts with the polyethylene oxide propylene oxide of formula II in the presence of a catalyst to obtain polyethylene oxide propylene oxide-modified polydimethylsiloxane. The reaction equation is as follows: ； wherein z+n is 2 to 200; z is 1 to 199; n is 1 to 199; R 1 is methyl or hydrogen; R 2 It is hydrogen or a hydrocarbon group of 1 to 18 carbon atoms; (2) reacting the polyethylene oxide propylene oxide modified polydimethylsiloxane obtained in step (1) with a compound of formula III, a polymer of formula IV, a compound of formula V and a compound of formula VI in the presence of a catalyst; the reaction equation is as follows: wherein q is 0 or 1, m is 1 to 200, and p is 1 to 200.

26. The preparation method according to claim 25, characterized in that: In step (1), z+n is 2 to 150, z is 1 to 149, n is 1 to 149, and z+n is the degree of polymerization.

27. The preparation method according to claim 25, characterized in that: In step (1), z+n is 2 to 100, z is 1 to 99, and n is 1 to 99.

28. The preparation method according to claim 25, characterized in that: The amount of the catalyst used in step (1) is 1-30 ppm, which is based on the total mass of the reactants in step (1), and the amount of the catalyst is calculated as platinum element; the reaction temperature in step (1) is 40-150°C.

29. The preparation method according to claim 28, characterized in that: The amount of the catalyst used in step (1) is 1-20 ppm, and the reaction temperature in step (1) is 60-120°C.

30. The preparation method according to claim 28, characterized in that: The amount of the catalyst used in step (1) is 1-10 ppm, and the reaction temperature in step (1) is 80-120°C.

31. The preparation method according to claim 25, characterized in that: The catalyst in step (1) is a catalyst that can promote the reaction of silicon-hydrogen bonds and unsaturated carbon-carbon bonds.

32. The preparation method according to claim 31, characterized in that: The catalyst in step (1) is a coordination compound containing one or more elements selected from boron, rhodium, iron and platinum; the molar ratio of the silicon-hydrogen bond in the side chain hydrogen-based polydimethylsiloxane represented by formula I in step (1) to the unsaturated carbon-carbon bond in the polymer represented by formula II is 1 to 2.

33. The preparation method according to claim 31, characterized in that: The catalyst in step (1) is a coordination compound containing platinum element; in step (1), the molar ratio of silicon-hydrogen bonds in the side chain hydrogen-based polydimethylsiloxane represented by formula I to unsaturated carbon-carbon bonds in the polymer represented by formula II is 1 to 1.

5.

34. The preparation method according to claim 31, characterized in that: The catalyst in step (1) is one of the platinum-containing complexes whose ligands are isopropanol, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, n-octanol, and isooctyl alcohol; in step (1), the molar ratio of the silicon-hydrogen bond in the side chain hydrogen-based polydimethylsiloxane represented by formula I to the unsaturated carbon-carbon bond in the polymer represented by formula II is 1 to 1.

05.

35. The preparation method according to claim 25, characterized in that: In step (2), p is 1 to 100, and the amount of the compound represented by formula V used is 0.01 to 1 times the amount of the compound represented by formula III used.

36. The preparation method according to claim 25, characterized in that: In step (2), p is 1 to 30; the amount of the compound represented by formula V used is 0.1 to 1 times the amount of the compound represented by formula III used.

37. The preparation method according to claim 25, characterized in that: In step (2), the polymer obtained in the first step is firstly reacted with the compound represented by formula III, the polymer represented by formula IV and the polymer represented by formula VI under the action of a catalyst at 94-96° C. for 1-3 hours, and then the compound represented by formula V is added to the system and the reaction is continued for 1.5-2.5 hours.

38. The preparation method according to claim 37, characterized in that: The reaction was carried out under reduced pressure at 94-96°C for 0.5-1.5h, and then under normal pressure for 0.5-1.5h; the reduced pressure was -0.08-0.10MPa.

39. The preparation method according to claim 25, characterized in that: The catalyst in step (2) is a catalyst that can promote the balance of siloxane; the amount of the catalyst in step (2) is 1 to 1000 ppm, and the amount is calculated based on the total mass of the reactants in step (2).

40. The preparation method according to claim 25, characterized in that: The catalyst in step (2) is one of alkali metal hydroxide, linear phosphazene and tetramethylammonium hydroxide; the amount of the catalyst in step (2) is 300-600 ppm.

41. Use of the co-modified polysiloxane according to any one of claims 1 to 24 or the co-modified polysiloxane prepared by the method according to any one of claims 25 to 40 in a fabric finishing agent.

42. The use according to claim 41, characterized in that The fabric includes fabric sheets or threads.

43. The use according to claim 41, characterized in that The amino polyether co-modified polysiloxane is in the form of emulsion or microemulsion.

44. A fabric finishing agent, characterized in that The fabric finishing agent is an aqueous emulsion containing the modified polysiloxane according to any one of claims 1 to 24 or the modified polysiloxane prepared by the method according to any one of claims 25 to 40.

45. The fabric finishing agent according to claim 44, characterized in that The mass fraction of the modified polysiloxane in the aqueous emulsion is 20% to 60%.

46. ​​The fabric finishing agent according to claim 45, characterized in that The mass fraction of the modified polysiloxane in the aqueous emulsion is 30% to 50%.

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