Fluorine-free organic silicon modified carbodiimide waterborne polyurethane emulsion and application thereof

Abstract

The invention relates to the technical field of fiber fabric treatment methods, mainly embodied in a fabric anti-siphon treatment agent and a preparation process thereof, and particularly relates to a fluoride-free organic silicon modified carbodiimide waterborne polyurethane emulsion and application thereof. The fluorine-free organic silicon modified carbodiimide waterborne polyurethane emulsion is prepared from 15 to 35 percent of organic silicon modified carbodiimide waterborne polyurethane polymer, 1 to 5 percent of fatty acid fatty alcohol ester, 0 to 5 percent of organic silicon modified wax, 1 to 5 percent of emulsifier, 2 to 5 percent of cosolvent, 50 to 70 percent of water and 0 to 5 percent of paraffin or natural wax. By combining organic silicon modified polyurethane with a carbodiimide structure, the hydrophobic property can be met, meanwhile, the good binding force with the fabric can be achieved, the good hydrolysis resistance can be kept by soaking a solution in water for a long time, and the anti-siphon finishing agent is especially suitable for anti-siphon treatment of the fabric.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of textile functional finishing agent, in particular to a fluorine-free organic silicon modified carbodiimide water-based polyurethane emulsion and its application. BACKGROUND

[0002] In the finishing of fabric materials, waterproof and anti-siphon finishing technology is often used for shoelaces, ribbons and woven uppers. This finishing technology changes the surface energy of the fabric material by using fluorocarbon six, carbon eight waterproof agent or fluorine-free waterproof agent, which gives the fabric material waterproof properties without affecting its air permeability, so that the fabric material is not easily wetted by water droplets or splashed water in wet weather. It is also a common functional finishing for functional shoe materials.

[0003] With the requirements of environmental protection, fluorine materials have been gradually eliminated in the textile field due to the influence of PFAS, and the development of fluorine-free anti-siphon has become a key issue in the industry.

[0004] CN120052652A describes a commercially available water-based polyurethane anti-siphon treatment agent composed of commercially available acrylic emulsion and commercially available carbodiimide crosslinking agent for zipper treatment. The water-based polyurethane described in this patent is not detailed, and it is not stated whether the water-based polyurethane is hydrophobically modified. Carbodiimide is added externally rather than grafted onto the polyurethane backbone, and it is not stated whether the carbodiimide is organically modified or hydrophobically modified. At the same time, the fabric needs to be deoiled before anti-siphon.

[0005] CN115785393A describes the synthesis process of a hydrophilically modified carbodiimide, which is not applicable to anti-siphon. The introduction of hydrophilic agents can help emulsify water-based emulsions but is not suitable for waterproofing and anti-siphon.

[0006] CN1131147 describes a water-based polyurethane with a long-chain alkyl modified carbodiimide structure compounded with fluorine-containing resin for preparing a waterproof agent, but does not mention its application in anti-siphon.

[0007] There are few patent technologies for anti-siphon in the market, and this patent makes full use of water-based carbodiimide polyurethane emulsion technology to achieve its anti-siphon effect on fabric. SUMMARY

[0008] (I) Technical problems solved In view of the deficiencies of the prior art, the present application provides a fluorine-free organic silicon modified carbodiimide water-based polyurethane emulsion, which can effectively prevent the siphon phenomenon of water in fabric.

[0009] (II) Technical solutions To achieve the above object, the present application provides the following technical solutions. A fluorine-free silicone-modified carbodiimide waterborne polyurethane emulsion, according to mass fraction, comprises: Silicone-modified carbodiimide waterborne polyurethane polymer: 15-35% Fatty acid fatty alcohol ester: 1-5% Silicone-modified wax: 0-5% Emulsifier: 1-5% Co-solvent: 2-5% Water: 50-70% Paraffin wax or natural wax: 0-5%.

[0010] Further, the fluorine-free silicone-modified carbodiimide waterborne polyurethane polymer is a silicone hydrophobic modified polycarbodiimide structure polyurethane polymer, which is obtained by reaction of silicone resin and diisocyanate structure, and the reaction formula is as follows:

[0011] Wherein the number of n is 0≤n≤9, preferably 0≤n≤3; Wherein the number of x is 0≤x≤30, preferably 3≤x≤15; Wherein the number of m is 1≤m≤30, preferably 3≤m≤15.

[0012] Preferably, R1 is a linear, isomeric alkyl, or ether alkyl structure of -C1-C6-; The structure of R1 is Or , Wherein y, z are 1-10, more preferably wherein y, z are 1-5.

[0013] Preferably, R2 is -CH3 or a linear alkyl of C8-C18. When R2 is -CH3, the silicone resin is a single hydroxyl silicone.

[0014] When R2 is a linear alkyl of C8-C18, the silicone resin is a long-chain alkyl-modified single hydroxyl silicone.

[0015] Preferably, the OCN-R-NCO diisocyanate structure is one or more of toluene diisocyanate, diphenylmethane diisocyanate, aliphatic isocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate.

[0016] More preferably, the aliphatic isocyanate is hexamethylene diisocyanate.

[0017] Preferably, the catalyst 1 is an organotin or organobismuth catalyst, and the amount of the catalyst 1 is 0.1%-0.5% of the mass of the isocyanate; The catalyst 2 is an organophosphorus compound (referred to as MPPO), and the amount of the catalyst 2 is 0.3%-0.8% of the mass of the isocyanate.

[0018] Preferably, the fatty acid fatty alcohol ester is one or more of a C1-C29-COO-C2-C30 linear or isomeric alkyl ester structure, a fatty acid glycerol triester, and a pentaerythritol stearate. More preferably, the C1-C29-COO-C2-C30 linear or isomeric alkyl ester structure is a C7-C17-COO-C8-C18 linear structure.

[0019] Preferably, the fatty acid glycerol triester has the following structural formula: The R3 is a C1-C30 linear or isomeric alkyl group, and more preferably a C8-C18 linear alkyl group. The pentaerythritol stearate has the following structural formula: The R4 is a C1-C30 linear or isomeric alkyl group, and more preferably a C8-C18 linear alkyl group.

[0020] Preferably, the organosilicon-modified wax is a long-chain alkyl-modified polydimethylsiloxane, and is one or more of a hexadecyl-modified polydimethylsiloxane, an octadecyl-modified polydimethylsiloxane, and a docosyl-modified polydimethylsiloxane. The content of the organosilicon-modified wax can be 0.

[0021] Preferably, the emulsifier is a combination of a cationic emulsifier and a non-ionic emulsifier. The cationic emulsifier is one or more of an ammonium chloride type cationic emulsifier and an amide type cationic emulsifier. The non-ionic emulsifier is one or more of isomeric tridecanol polyoxyethylene ether, castor oil polyoxyethylene ether, and a Tween type emulsifier.

[0022] Preferably, the co-solvent is one or more of 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, isohexylene glycol, and diethylene glycol butyl ether.

[0023] Preferably, the paraffin wax is a paraffin wax with a melting point of 30-80℃, and more preferably a paraffin wax with a melting point of 40-60℃. The natural wax is one or more of beeswax, palm wax, small turbid tree wax, and whale wax. The content of the paraffin wax and the natural wax can both be 0.

[0024] The application also discloses an application of the fluorine-free organosilicon-modified carbodiimide water-based polyurethane emulsion in fabric anti-syphoning.

[0025] (Three) beneficial effects Compared with the prior art, the application provides a preparation method of a water-based polyurethane polymer emulsion and application thereof in anti-siphon, and the combination of organic silicon modified polyurethane and a carbodiimide structure can meet the hydrophobic performance and good bonding force with the fabric, and the long-term water immersion liquid can maintain good water resistance. The introduction of carbodiimide into the polyurethane structure enables the water-based polyurethane containing a crosslinking agent group to be better combined with the fabric. Compared with a long-chain alkyl group, the organic silicon adopted in the application has lower surface tension, and can more effectively prevent the siphon phenomenon of water.

[0026] In addition, the fluorine-free polymer can give the fabric good waterproof and anti-siphon performance, and the finishing agent does not contain fluorine, is environmentally friendly, and meets the environmental protection standard; on the other hand, compared with a C6 waterproof agent, the fluorine-free waterproof agent is also more cost-effective. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the application, not all the embodiments.

[0028] A fluorine-free organic silicon modified carbodiimide water-based polyurethane emulsion, according to mass fraction, comprises: Organic silicon modified carbodiimide water-based polyurethane polymer: 15-35% Fatty acid fatty alcohol ester: 1-5% Organic silicon modified wax: 0-5% Emulsifier: 1-5% Co-solvent: 2-5% Water: 50-70% Paraffin wax or natural wax: 0-5%.

[0029] The organic silicon modified carbodiimide water-based polyurethane polymer is an organic silicon hydrophobic modified poly-carbodiimide structure polyurethane polymer, which is obtained by reaction of organic silicon resin and diisocyanate structure, and the reaction formula is as follows:

[0030] Wherein the number of n is 0 Wherein the number of x is 0 Wherein the number of m is 0

[0031] Wherein R1 is a linear, isomeric alkyl group or ether alkyl group structure with a length of C1-C6; The structure of R1 is or , wherein y, z are 1-5.

[0032] Preferably, said R2 is -CH3 or is a C8-C18 linear alkyl group; When R2 is -CH3, said silicone resin is a monohydroxyhydrocarbon silicone.

[0033] When R2 is a C8-C18 linear alkyl group, said silicone resin is a long chain alkyl modified monohydroxyhydrocarbon silicone.

[0034] The OCN-R-NCO diisocyanate structure is a mixture of toluene diisocyanate, diphenyl methane diisocyanate, aliphatic isocyanate, isophorone diisocyanate. Among them, the aliphatic isocyanate is hexamethylene diisocyanate.

[0035] Catalyst 1 is an organotin or organobismuth catalyst, the amount of which is 0.1%-0.5% of the mass of the isocyanate; Catalyst 2 is an organophosphorus compound, the amount of which is 0.3% to 0.8% of the mass of the isocyanate.

[0036] The fatty acid fatty alcohol ester is a C7-C17-COO-C8-C18 linear structure.

[0037] The fatty acid triglyceride structure is: R3 is a C10-C15 linear alkyl group; The structure of pentaerythritol stearate is: R4 is a C10-C15 linear alkyl group.

[0038] The silicone-modified wax is a long-chain alkyl-modified polydimethylsiloxane, which is a mixture of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane.

[0039] The emulsifier is a combination of a cationic emulsifier and a nonionic emulsifier, wherein the cationic emulsifier is a mixture of ammonium chloride type cationic and amide type cationic emulsifiers; the nonionic emulsifier is a mixture of isomeric tridecanol polyoxyethylene ether, castor oil polyoxyethylene ether, and Tween emulsifier.

[0040] The co-solvent is a mixture of 1,2 propylene glycol, dipropylene glycol, tripropylene glycol, isohexylene glycol, and diethylene glycol butyl ether.

[0041] The paraffin wax is a paraffin wax with a melting point of 40-60°C, and the natural wax is one of beeswax, palm wax, small turbid tree wax, and whale wax, or a mixture thereof.

[0042] Specific synthesis process Step S1: Synthesis of silicone-modified polyurethane The monohydroxy silicone or long-chain alkyl-modified monohydroxy silicone is reacted with isocyanate in the presence of solvent MIBK (methyl isobutyl ketone) and an appropriate amount of catalyst 1 (organic tin) at 70-90°C for 3-5 hours, and then NCO is tested using di-n-butylamine until the theoretical value is reached.

[0043] Step S2: Synthesis of carbodiimide structure Carbodiimide synthesis: reaction at 90-120°C for 10-20 hours in the presence of an appropriate amount of catalyst 2, and then infrared spectroscopy is used to detect until the isocyanate group disappears. Then, the temperature is lowered to 60°C, and silicone wax, paraffin wax, natural wax, and long-chain fatty acid ester are added, and the mixture is kept for half an hour to obtain a silicone-modified carbodiimide polyurethane reaction solution Step S3: Emulsion synthesis The water, cosolvent, and emulsifier are heated and stirred until uniform, and then mixed with the above-mentioned silicone-modified carbodiimide polyurethane reaction solution under high-speed shearing, and then homogenized 4 times (30-40 MPa pressure) to obtain a homogenized solution containing solvent.

[0044] Step S4: Desolventization: the above-mentioned homogenized solution containing solvent is distilled under reduced pressure to remove the solvent MIBK, and a silicone-modified polycarbodiimide water-based polyurethane emulsion is obtained.

[0045] Example 1 According to the mass fraction, a three-necked flask is added with hydroxy silicone with a molecular weight of about 2000 at 14.5% mass fraction, solvent MIBK at 14.2% mass fraction, and 3% mass fraction MDI-100 and an appropriate amount of the first catalyst organic bismuth, and then heated to 85°C for 3 hours, and then heated to 100°C for 10 hours with the second catalyst MPPO. The temperature is lowered to 60 degrees, and 2.5% mass fraction of triglyceride and 1% mass fraction of paraffin wax are added to obtain a silicone-modified carbodiimide polyurethane reaction solution.

[0046] At the same time, another beaker is prepared with 59.5% mass fraction of water, 1.2% mass fraction of emulsifier (emulsifier is Tween 80, dicocoalkyl ammonium chloride, and isomeric tridecanol polyoxyethylene ether each 1 / 3), and 4% mass fraction of cosolvent (dipropylene glycol), which is heated to 60 degrees and stirred until uniform, and then quickly stirred with the above-mentioned silicone-modified carbodiimide polyurethane reaction solution, and then homogenized 4 times at a homogenization pressure of 40 MPa.

[0047] After homogenization, desolventization is performed to remove MIBK to obtain a silicone-modified carbodiimide polyurethane emulsion. The solid content is about 25%.

[0048] Example 2 The silicone-modified carbodiimide polyurethane reaction solution was prepared by using silicone-modified wax instead of paraffin wax, and the solid content was about 25%.

[0049] Example 3 The silicone-modified carbodiimide polyurethane emulsion was prepared by using the same mass fraction of long-chain alkyl-modified hydrocarbon silicone with a molecular weight of 3000 instead of MDI-100, and the solid content was about 25%.

[0050] Example 4 The silicone-modified carbodiimide polyurethane emulsion was prepared by using the same mass fraction of TDI instead of MDI-100, and the solid content was about 25%.

[0051] Example 5 The silicone-modified carbodiimide polyurethane emulsion was prepared by using the same mass fraction of IPDI instead of MDI-100, and the solid content was about 25%.

[0052] Specific examples; examples 6-10

[0053] Example 6

[0054] The silicone-modified carbodiimide polyurethane reaction solution was prepared by adding 12.1% mass fraction of hydrocarbon silicone with a molecular weight of about 2000, 14.2% mass fraction of solvent MIBK, and 6% mass fraction of MDI-100 and an appropriate amount of first catalyst organic bismuth into a three-necked flask, and then reacting at 85°C for 3 hours, and then reacting at 100°C for 10 hours by adding second catalyst MPPO. After cooling to 60 degrees, 2% mass fraction of triglyceride and 1% mass fraction of paraffin were added to obtain the silicone-modified carbodiimide polyurethane reaction solution.

[0055] At the same time, another beaker was prepared by heating 59.5% mass fraction of water, 1.2% mass fraction of emulsifier (emulsifier was Tween 80, dicocoalkyl ammonium chloride, isomeric tridecanol polyoxyethylene ether, each 1 / 3) and 4% mass fraction of cosolvent (dipropylene glycol) to 60 degrees and stirring uniformly, and then the silicone-modified carbodiimide polyurethane reaction solution was quickly stirred and homogenized 4 times at a pressure of 40 MPa.

[0056] After homogenization, the solvent was removed to obtain the silicone-modified carbodiimide polyurethane emulsion. The solid content was about 25%.

[0057] Example 7 The silicone-modified carbodiimide polyurethane emulsion was prepared by using IPDI instead of MDI-100, and the solid content was 25%.

[0058] Example 8 The same as example 6, but using TDI instead of MDI-100, the final product is silicone modified carbodiimide polyurethane emulsion. Its solid content is 25%.

[0059] Example 9 The same as example 6, using silicone modified wax instead of paraffin wax to get silicone modified carbodiimide polyurethane reaction liquid, its solid content is about 25%.

[0060] Example 10 The same as example 6, but using silicone modified by long chain alkyl with about 3000 molecular weight instead of hydroxyl silicone, the final product is silicone modified carbodiimide polyurethane emulsion. Its solid content is 25%.

[0061] The raw materials used in the above examples of the present application are described as follows: Raw materials Abbreviation or explanation Monohydroxy silicone Molecular weight 2000 Long chain alkyl-modified monohydroxy silicone Molecular weight 3000 4.4 Diphenylmethane diisocyanate MDI Toluene diisocyanate TDI Isophorone diisocyanate IPDI Hexamethylene diisocyanate HDI Silicone-modified wax Long chain alkyl-modified silicone wax Triglyceride GTS Organophosphorus catalyst MPPO Paraffin wax No. 58: Paraffin wax having a melting point of about 58°C containing semi-refined and full-refined Carbodiimide catalyst MPPO Methyl isobutyl ketone MIBK Isotridecanol polyoxyethylene ether Emulsifier Tween 80 Emulsifier Castor oil polyoxyethylene ether Emulsifier Dicoco dimethyl ammonium chloride Emulsifier Dipropylene glycol DPG Beeswax Natural wax Palm wax Natural wax Candelilla wax Natural wax ECO-BARRIER X-904E Fukusen materials waterproofing agent ECO-BARRIER 101Z Fukusen materials waterproofing crosslinking agent Comparative Example 1 ECO-BARRIER X-904E, fluoro-free waterproof, anti-siphon treatment agent, Fujian New Material Co., Ltd. Comparative Example 2 Commercially available fluoro-free anti-siphon sample.

[0062] Preparation of working solution The above examples and comparative samples are prepared into 60g / l working solution with additional waterproof crosslinking agent 10g / l. The following common fabrics are used for padding treatment, and then after 170 degree 90 second treatment, the anti-siphon test is carried out according to the test method described in the patent: Anti-siphon test The anti-siphon test is divided into static anti-siphon test and dynamic anti-siphon test. Dynamic anti-siphon test is tested by professional test instrument, and is represented by detailed numerical value; static anti-siphon test is carried out by static suspension method, and the following three items are observed and recorded: whether the tested sample appears liquid climbing (siphon) phenomenon, the time of siphon appearance, and the highest height of siphon climbing. The detailed rules of static anti-siphon test are as follows: 1) Test apparatus: Anti-siphon tester; ruler; green ink.

[0063] 2) Sampling requirements: The sample is cut into 150*30mm 3) Test requirements: l Immersion position: 10mm; l Hanging time: 0.5h, 2h and 24h 4) Test steps: The above emulsion is prepared into a treatment liquid with water, and a fabric sample is dipped and treated, and then dried in an oven to obtain a sample treated by anti-siphon At the same time, red water is filled in the anti-siphon tester.

[0064] The sample is hung vertically on the siphon tester, and the height of the sample is adjusted so that the part of the sample immersed in water is 10 mm. After the sample is set, the timing is started.

[0065] After 0.5 hours, the height of the water level rising on the sample is observed. If the height exceeds 10 mm, the test is ended, and the result is determined as unqualified, recorded as NO. If the height does not exceed 10 mm, the test is continued, recorded as OK.

[0066] After 2 hours, the height of the water level rising on the sample is observed again, as above.

[0067] After 24 hours, the height of the water level rising on the sample is observed again, as above.

[0068] Test results of Examples 1-5: Shoe material large-pore canvas: 0.5 hour result 2 hour result 24 hour result Example 1 OK OK OK Example 2 OK OK OK Example 3 OK OK OK Example 4 OK OK OK Example 5 OK OK NO Comparative Example 1 OK OK OK Comparative Example 2 OK NO - Shoe lace screen cloth: 0.5 hour result 2 hour result 24 hour result Example 1 OK OK OK Example 2 OK OK OK Example 3 OK OK OK Example 4 OK OK OK Example 5 OK OK NO Comparative Example 1 OK NO - Comparative Example 2 OK OK NO Test results of Examples 6-10 Shoe material large-pore canvas: 0.5 hour result 2 hour result 24 hour result Example 6 OK OK OK Example 7 OK OK NO Example 8 OK OK OK Example 9 OK OK NO Example 10 OK OK OK Comparative Example 1 OK OK NO Comparative Example 2 OK NO - Shoe lace screen cloth: 0.5 hour result 2 hour result 24 hour result Example 6 OK OK OK Example 7 OK OK NO Example 8 OK OK OK Example 9 OK OK NO Example 10 OK OK OK Comparative Example 1 OK OK NO Comparative Example 2 OK NO - It can be seen from the above test results that various fabrics show good and stable anti-siphon effect by using the fluorine-free water-based polyurethane anti-siphon emulsion of the application.

[0069] In other embodiments, other mass fractions can also be selected, and the fluorine-free silicone-modified carbodiimide water-based polyurethane emulsion includes, by mass fraction: silicone-modified carbodiimide water-based polyurethane polymer 30%, fatty acid fatty alcohol ester 5%, emulsifier 2%, cosolvent 5%, and water 58%; or includes: silicone-modified carbodiimide water-based polyurethane polymer 35%, fatty acid fatty alcohol ester 5%, emulsifier 2%, cosolvent 5%, water 50%, and natural wax 3%; or includes: silicone-modified carbodiimide water-based polyurethane polymer 19%, fatty acid fatty alcohol ester 2%, emulsifier 2%, cosolvent 2%, water 70%, and natural wax 5%; or includes: silicone-modified carbodiimide water-based polyurethane polymer 15%, fatty acid fatty alcohol ester 5%, emulsifier 5%, cosolvent 5%, and water 70%.

[0070] The silicone-modified carbodiimide waterborne polyurethane polymer is a silicone hydrophobically modified polyurethane polymer with a polyurethane polymer structure of a silicone hydrophobically modified carbodiimide, which is obtained by reacting a silicone resin and a diisocyanate structure, and the reaction formula is as follows:

[0071] wherein the number of n is 0≤n≤9, preferably 0≤n≤3; wherein the number of x is 0≤x≤30, preferably 3≤x≤15, more preferably 7≤x≤10; wherein the number of m is 1

[0072] wherein in one embodiment, n is 0, x is 8, and m is 8; wherein in one embodiment, n is 0, x is 0, and m is 10; wherein in one embodiment, n is 2, x is 8, and m is 8; Of course, in other embodiments, n, x, and m can be other numbers.

[0073] wherein R1 is a linear, isomeric alkyl, or ether alkyl structure of -C1-C6-; The structure of R1 is or , wherein y and z are 1-5, and in the present embodiment, y is 3 and z is 3.

[0074] Preferably, R2 is -CH3 or a linear alkyl of C8-C18. When R2 is -CH3, the silicone resin is a hydroxyl silicone resin.

[0075] When R2 is a linear alkyl of C8-C18, the silicone resin is a long-chain alkyl-modified hydroxyl silicone resin, and in the present embodiment, R2 is a linear alkyl of C10-C15.

[0076] The diisocyanate structure of OCN-R-NCO is a mixture of toluene diisocyanate, diphenyl methane diisocyanate, aliphatic isocyanate, and isoflurane diisocyanate. Among them, the aliphatic isocyanate is hexamethylene diisocyanate.

[0077] Catalyst 1 is an organotin or organobismuth catalyst, and the amount used is 0.1%-0.5% of the mass of the isocyanate; in the present embodiment, catalyst 1 is an organobismuth catalyst, and the amount used is 0.3% of the mass of the isocyanate. Catalyst 2 is an organophosphorus compound, and the amount used is 0.3% to 0.8% of the mass of the isocyanate, and in the present embodiment, the amount used is 0.5%.

[0078] The fatty acid fatty alcohol ester is a linear structure of C7-C17-COO-C8-C18.

[0079] The fatty acid triglyceride has the following structure: R3 is a linear alkyl group of C10-C15; The pentaerythritol stearate has the following structure: R4 is a linear alkyl group of C10-C15.

[0080] The silicone-modified wax is a long-chain alkyl-modified polydimethylsiloxane, which is a mixture of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane.

[0081] The emulsifier is a mixture of a cationic emulsifier and a nonionic emulsifier, wherein the cationic emulsifier is a mixture of an ammonium chloride type cation and an amide type cationic emulsifier; and the nonionic emulsifier is a mixture of isomeric tridecanol polyoxyethylene ether, castor oil polyoxyethylene ether, and Tween emulsifier.

[0082] The co-solvent is a mixture of 1.2 propylene glycol, dipropylene glycol, tripropylene glycol, isohexylene glycol, and diethylene glycol butyl ether.

[0083] The paraffin wax is a paraffin wax with a melting point of 40-60°C, and the natural wax is a mixture of beeswax, palm wax, small turbid tree wax, and whale wax.

Claims

1. A fluorine-free silicone-modified carbodiimide aqueous polyurethane emulsion, characterized by: According to the mass fraction, including: Silicone-modified carbodiimide aqueous polyurethane polymer: 15-35% Fatty acid fatty alcohol ester: 1-5% Emulsifier: 1-5% Co-solvent: 2-5% Water: 50-70%.

2. The silicone-modified carbodiimide aqueous polyurethane emulsion of claim 1, characterized in that: The silicone-modified carbodiimide aqueous polyurethane polymer is a silicone hydrophobic modified polycarbodiimide structure polyurethane polymer obtained by reacting organic silicon, diisocyanate structure, and the reaction formula is as follows: ， Wherein R1 is a linear, isomeric alkyl, or ether alkyl structure of -C1-C6-; R2 is -CH3 or a linear alkyl of C8-C18; Wherein the number of n is 0≤n≤9, Wherein the number of x is 0≤x≤30, Wherein the number of m is 1 3. The fluorine-free silicone-modified carbodiimide aqueous polyurethane emulsion of claim 2, characterized in that: The catalyst 1 is an organotin or organobismuth catalyst, and the amount is 0.1%-0.5% of the mass of isocyanate; The catalyst 2 is an organophosphorus compound, and the amount is 0.3% to 0.8% of the mass of isocyanate. 4.The fluorine-free silicone-modified carbodiimide waterborne polyurethane emulsion of claim 2, characterized in that: The OCN-R-NCO diisocyanate structure is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, benzene diisocyanate, and tetramethyl m-xylylene diisocyanate.

5. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 1, characterized in that: The fatty acid fatty alcohol ester is one or more of a linear or isomeric alkyl ester structure of C1-C29-COO-C2-C30, a fatty acid triglyceride, and pentaerythritol stearate.

6. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 5, characterized in that: The fatty acid triglyceride structural formula is: R3 is a C1-C30 linear or isomeric alkyl group, The pentaerythritol stearate structural formula is: R4 is a C1-C30 linear or isomeric alkyl group.

7. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 1, characterized in that: The emulsifier is a combination of a cationic emulsifier and a non-ionic emulsifier, wherein the cationic emulsifier is one or more of an ammonium chloride type cation, an amide type cationic emulsifier; the non-ionic emulsifier is one or more of isomeric tridecanol polyoxyethylene ether, castor oil polyoxyethylene ether, or Tween emulsifier.

8. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 1, characterized in that: The co-solvent is one or more of 1.2 propylene glycol, dipropylene glycol, tripropylene glycol, isohexylene glycol, and diethylene glycol butyl ether. 9.The fluorine-free silicone-modified carbodiimide waterborne polyurethane emulsion of claim 1, characterized in that: The structure of R1 is or , Wherein y, z is 1-10.

10. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 2, characterized in that: When R2 is -CH3, the silicone is a single hydrocarbon-containing silicone.

11. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 2, characterized in that: When R2 is a linear alkyl of C8-C18, the silicone is a long-chain alkyl-modified single hydrocarbon-containing silicone.

12. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 1, characterized in that: According to the mass fraction, it also includes silicone-modified wax, and paraffin wax or natural wax, The content of the silicone-modified wax is ≤5% The content of the paraffin wax or natural wax is ≤5%.

13. The fluorine-free silicone-modified carbodiimide aqueous polyurethane emulsion according to claim 12, characterized in that: The paraffin wax is a paraffin wax with a melting point of 30-80℃, and the natural wax is one or more of beeswax, palm wax, small turbid tree wax, and whale wax.

14. The fluorine-free silicone-modified carbodiimide-containing aqueous polyurethane emulsion according to claim 12, characterized in that: The silicone-modified wax is a long-chain alkyl-modified polydimethylsiloxane, which is one or more of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane.

15. Use of the fluorine-free silicone-modified carbodiimide aqueous polyurethane emulsion according to any one of claims 1 to 14 for fabric anti-syphoning.

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