A fluorine-free silicone-modified carbodiimide waterborne polyurethane emulsion and application thereof

Abstract

This invention relates to the technical field of fiber fabric treatment methods, mainly focusing on anti-siphon treatment agents for fabrics and their preparation process. Specifically, it relates to a fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion and its application. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion comprises 15-35% organosilicon-modified carbodiimide waterborne polyurethane polymer, 1-5% fatty acid fatty alcohol ester, 0-5% organosilicon-modified wax, 1-5% emulsifier, 2-5% co-solvent, 50-70% water, and 0-5% paraffin or natural wax. This invention, through the combination of organosilicon-modified polyurethane and carbodiimide structures, achieves both hydrophobic properties and good adhesion to fabrics. Furthermore, it maintains good hydrolysis resistance even after long-term immersion in water, making it particularly suitable for anti-siphon treatment of fabrics.

Description

Technical Field

[0001] This invention relates to the field of functional finishing agents for textiles, specifically to a fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion and its application. Background Technology

[0002] In the finishing of fabric materials, waterproofing and anti-wicking finishing technology is often used for shoelaces, webbing, and woven shoe uppers. This finishing technology changes the surface energy of the fabric material by using fluorinated C6, C8 or fluorine-free waterproofing agents, giving the fabric waterproof properties without affecting its breathability. This makes the fabric less likely to be wetted by water droplets, splashes, or soaking in humid weather, and is also a common functional finishing for functional footwear materials.

[0003] With the increasing demands for environmental protection, fluorinated materials have been gradually phased out in the textile industry due to their PFAS content. The development of fluorine-free anti-siphon materials has become a key issue in the industry.

[0004] Patent CN120052652A describes an anti-siphon treatment agent for zippers, composed of a commercially available waterborne polyurethane, a commercially available acrylic emulsion, and a commercially available carbodiimide crosslinking agent. However, the waterborne polyurethane described in this patent lacks detailed specifications, failing to indicate whether it has undergone hydrophobic modification. The carbodiimide is described as an external additive rather than grafted onto the polyurethane backbone, and it is also unclear whether the carbodiimide has undergone silicone or hydrophobic modification. Furthermore, this patent requires degreasing the fabric before applying the anti-siphon treatment.

[0005] CN115785393A describes the synthesis process of a hydrophilically modified carbodiimide, but does not specify its application in preventing siphoning. While the introduction of a hydrophilic agent can aid in the emulsification of aqueous emulsions, it is not suitable for waterproofing and preventing siphoning.

[0006] CN1131147 describes a waterborne polyurethane compounded with a fluorinated resin containing a long-chain alkyl-modified carbodiimide structure for the preparation of a waterproofing agent, but does not describe its application in preventing siphoning.

[0007] There are few patented technologies for anti-siphoning in the market. This patent makes full use of water-based carbodiimide polyurethane emulsion technology to achieve its anti-siphoning effect on fabrics. Summary of the Invention

[0008] (a) Technical problems to be solved

[0009] To address the shortcomings of existing technologies, this invention provides a fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion, which can effectively prevent moisture siphoning when applied to fabrics.

[0010] (II) Technical Solution

[0011] To achieve the above objectives, the present invention provides the following technical solution:

[0012] A fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion, comprising, by mass fraction:

[0013] Organosilicon-modified carbodiimide waterborne polyurethane polymer: 15-35%

[0014] Fatty acid fatty alcohol esters: 1-5%

[0015] Organosilicon modified wax: 0-5%

[0016] Emulsifier: 1-5%

[0017] Cosolvent: 2-5%

[0018] Water: 50-70%

[0019] Paraffin or natural wax: 0-5%.

[0020] Furthermore, the fluorine-free organosilicon-modified carbodiimide waterborne polyurethane polymer is a polyurethane polymer with an organosilicon hydrophobic modified polycarbodiimide structure, obtained by reacting organosilicon resin and diisocyanate, as shown in the following reaction formula:

[0021]

[0022] The number of n is 0≤n≤9, preferably 0≤n≤3;

[0023] The quantity of x is 0≤x≤30, preferably 3≤x≤15;

[0024] The number of m is 1≤m≤30, preferably 3≤m≤15.

[0025] Preferably, R1 is a straight-chain, isomeric alkyl, or ether-alkyl structure of -C1 to C6-.

[0026] The structure of R1 is as follows: or ,

[0027] Where y and z are 1-10, more preferably, where y and z are 1-5.

[0028] Preferably, R2 is -CH3 or a C8-C18 straight-chain alkyl group;

[0029] When R2 is -CH3, the organosilicon resin is a monohydroxy organosilicon.

[0030] When R2 is a C8-C18 straight-chain alkyl group, the organosilicon resin is a long-chain alkyl-modified monohydroxy organosilicon.

[0031] Preferably, the OCN-R-NCO diisocyanate structure is one or more of toluene diisocyanate, diphenylmethane diisocyanate, aliphatic isocyanate, isoflurone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, phenylmethylene diisocyanate, and tetramethyl isophenylmethylene diisocyanate.

[0032] More preferably, the aliphatic isocyanate is hexamethylene diisocyanate.

[0033] Preferably, the catalyst 1 is an organotin or organobismuth catalyst, and its amount is 0.1%-0.5% of the mass of the isocyanate;

[0034] The catalyst 2 is an organophosphorus compound (MPPO) used in an amount of 0.3% to 0.8% of the mass of isocyanate.

[0035] Preferably, the fatty acid fatty alcohol ester is one or more of the following: a straight-chain or isomeric alkyl ester structure of C1-C29-COO-C2-C30, a fatty acid triglyceride, and a pentaerythritol stearate. More preferably, the straight-chain isomeric alkyl ester structure of C1-C29-COO-C2-C30 is a straight-chain structure of C7-C17-COO-C8-C18.

[0036] Preferably, the fatty acid triglyceride has the following structural formula:

[0037] R3 is a straight-chain or isomeric alkyl group of C1 to C30, more preferably a straight-chain alkyl group of C8 to C18;

[0038] The structural formula of the pentaerythritol stearate is:

[0039] R4 is a straight-chain or isomeric alkyl group of C1 to C30, more preferably a straight-chain alkyl group of C8 to C18.

[0040] Preferably, the organosilicon-modified wax is a long-chain alkyl-modified polydimethylsiloxane, specifically one or more of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane, and the content of the organosilicon-modified wax can be 0.

[0041] Preferably, the emulsifier is a combination of a cationic emulsifier and a nonionic emulsifier, wherein the cationic emulsifier is one or more of ammonium chloride-type cationic and amide-type cationic emulsifiers; and the nonionic emulsifier is one or more of isotridecyl alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, or Tween-type emulsifiers.

[0042] Preferably, the co-solvent is one or more selected from 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, isohexyl glycol, and diethylene glycol butyl ether.

[0043] Preferably, the paraffin wax has a melting point of 30-80℃, more preferably 40-60℃. The natural wax is one or more of beeswax, palm wax, sage wax, and cetacean wax. The content of both paraffin wax and natural wax can be 0.

[0044] This invention also discloses the application of fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion in fabric anti-siphoning.

[0045] (III) Beneficial Effects

[0046] Compared with existing technologies, this invention provides a method for preparing an aqueous polyurethane polymer emulsion and its application in anti-siphoning. By combining organosilicon-modified polyurethane with a carbodiimide structure, both hydrophobic properties and good adhesion to fabrics can be achieved, and good water-resistant properties can be maintained even after long-term immersion in water. The introduction of carbodiimide into the polyurethane structure allows the crosslinking agent groups in the aqueous polyurethane to better bond with the fabric. Furthermore, compared with long-chain alkyl groups, the organosilicon used in this invention has a lower surface tension, which can more effectively prevent water siphoning.

[0047] In addition, fluorine-free polymers can give fabrics good waterproof and anti-wicking properties, and these finishing agents do not contain fluorides, making them environmentally friendly and meeting environmental protection standards; on the other hand, compared with C6 waterproofing agents, fluorine-free waterproofing agents are also cheaper. Detailed Implementation

[0048] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0049] A fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion, comprising, by mass fraction:

[0050] Organosilicon-modified carbodiimide waterborne polyurethane polymer: 15-35%

[0051] Fatty acid fatty alcohol esters: 1-5%

[0052] Organosilicon modified wax: 0-5%

[0053] Emulsifier: 1-5%

[0054] Cosolvent: 2-5%

[0055] Water: 50-70%

[0056] Paraffin or natural wax: 0-5%.

[0057] The organosilicon-modified carbodiimide waterborne polyurethane polymer is a polyurethane polymer with an organosilicon hydrophobic modification polycarbodiimide structure, obtained by reacting organosilicon resin and diisocyanate, as shown in the following reaction formula:

[0058]

[0059] The number of n is 0 < n ≤ 9, preferably 0 < n ≤ 3;

[0060] The quantity of x is 0 < x ≤ 30, preferably 3 ≤ x ≤ 15, and more preferably 7 ≤ x ≤ 10;

[0061] The quantity of m is 0 < m ≤ 30, preferably 3 ≤ m ≤ 15, and more preferably 7 ≤ m ≤ 10.

[0062] Where R1 is a straight-chain, isomeric alkyl, or ether-alkyl structure of -C1 to C6;

[0063] The structure of R1 is as follows: or ,

[0064] Where y and z are 1-5.

[0065] Preferably, R2 is -CH3 or a C8-C18 straight-chain alkyl group;

[0066] When R2 is -CH3, the organosilicon resin is a monohydroxy organosilicon.

[0067] When R2 is a C8-C18 straight-chain alkyl group, the organosilicon resin is a long-chain alkyl-modified monohydroxy organosilicon.

[0068] The OCN-R-NCO diisocyanate structure is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, aliphatic isocyanate, and isoflurone diisocyanate. The aliphatic isocyanate is hexamethylene diisocyanate.

[0069] Catalyst 1 is an organotin or organobismuth catalyst, and its dosage is 0.1%-0.5% of the mass of isocyanate;

[0070] Catalyst 2 is an organophosphorus compound, and its amount is 0.3% to 0.8% of the mass of isocyanate.

[0071] Fatty acid fatty alcohol esters have a straight-chain structure of C7~C17-COO-C8~C18.

[0072] The structural formula of fatty acid triglycerides is:

[0073] R3 is a straight-chain alkyl group of C10 to C15;

[0074] The structural formula of pentaerythritol stearate is:

[0075] R4 is a C10 to C15 straight-chain alkyl group.

[0076] The organosilicon-modified wax is a long-chain alkyl-modified polydimethylsiloxane, which is a mixture of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane.

[0077] The emulsifier is a mixture of cationic and nonionic emulsifiers, wherein the cationic emulsifier is a mixture of ammonium chloride-type cationic and amide-type cationic emulsifiers; and the nonionic emulsifier is a mixture of isotridecyl alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, and Tween-type emulsifiers.

[0078] The co-solvent is a mixture of 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, isohexyl glycol, and diethylene glycol butyl ether.

[0079] Paraffin wax is paraffin wax with a melting point of 40-60℃, and natural wax is one of beeswax, palm wax, tung oil wax, whale wax, or a mixture thereof.

[0080] Specific synthesis process

[0081] Step S1: Synthesis of Organosilicon-Modified Polyurethane

[0082] Monohydroxy organosilicon or long-chain alkyl-modified monohydroxy organosilicon is reacted with isocyanate in the presence of solvent MIBK (methyl isobutyl ketone) and an appropriate amount of catalyst 1 (organotin) at 70-90°C for 3-5 hours. Then, the NCO is tested using di-n-butylamine until it reaches the theoretical value.

[0083] Step S2: Synthesis of carbodiimide structure

[0084] Synthesis of carbodiimide: Under the condition of a suitable catalyst 2, the reaction was carried out at 90-120℃ for 10-20 hours, and the reaction was monitored by infrared spectroscopy until the isocyanate groups disappeared. Then, the temperature was lowered to 60℃, and organosilicon wax, paraffin wax, natural wax, and long-chain fatty acid esters were added. The mixture was kept at this temperature for half an hour to obtain an organosilicon-modified carbodiimide polyurethane reaction solution.

[0085] Step S3: Emulsion Synthesis

[0086] Water, cosolvent, and emulsifier are heated and stirred together until homogeneous. Then, they are mixed with the above-mentioned organosilicon-modified carbodiimide polyurethane reaction solution under high-speed shearing. The mixture is then homogenized four times under a pressure of 30-40 MPa to obtain a homogeneous solution containing solvent.

[0087] Step S4:

[0088] Solvent removal: The solvent MIBK is removed by vacuum distillation of the above homogenized liquid containing solvent to obtain the organosilicon-modified polycarbodiimide waterborne polyurethane emulsion.

[0089] Example 1

[0090] According to the mass fractions, 14.5% by mass of a hydrocarbon hydroxyl organosilicon with a molecular weight of approximately 2000, 14.2% by mass of MIBK solvent, 3% by mass of MDI-100, and an appropriate amount of the first catalyst, organobismuth, were added to a three-necked flask. The mixture was heated to 85°C and reacted for 3 hours. Then, the temperature was raised to 100°C, and the second catalyst, MPPO, was added, and the reaction was carried out for 10 hours. The mixture was then cooled to 60°C, and 2.5% by mass of triglycerides and 1% by mass of paraffin were added to obtain the organosilicon-modified carbodiimide polyurethane reaction solution.

[0091] Meanwhile, in another beaker, prepare 59.5% water, 1.2% emulsifier (1 / 3 each of Tween 80, biscocoyl ammonium chloride, and isotridecyl alcohol polyoxyethylene ether), and 4% cosolvent (dipropylene glycol). Heat to 60 degrees Celsius and stir until homogeneous. Then, rapidly stir with the above-mentioned organosilicon-modified carbodiimide polyurethane reaction solution and homogenize under high pressure four times at a pressure of 40 MPa.

[0092] After homogenization, solvent removal was performed to remove MIBK, yielding an organosilicon-modified carbodiimide polyurethane emulsion with a solid content of approximately 25%.

[0093] Example 2

[0094] Similar to Example 1, an organosilicon-modified wax was used to replace paraffin to obtain an organosilicon-modified carbodiimide polyurethane reaction solution with a solid content of approximately 25%.

[0095] Example 3

[0096] The procedure is the same as in Example 1, but a silicone-modified carbodiimide polyurethane emulsion is obtained by using the same mass fraction of long-chain alkyl-modified hydrocarbon hydroxyl organosilicon with a molecular weight of 3000. Its solid content is approximately 25%.

[0097] Example 4

[0098] Similar to Example 1, but with the same mass fraction of TDI replacing MDI-100, a silicone-modified carbodiimide polyurethane emulsion was finally obtained. Its solid content was approximately 25%.

[0099] Example 5

[0100] Similar to Example 1, but with MDI-100 replaced by the same mass fraction of IPDI, a silicone-modified carbodiimide polyurethane emulsion was finally obtained. Its solid content was approximately 25%.

[0101] Specific embodiments; Embodiments 6-10

[0102] Example 6

[0103] According to the mass fraction, 12.1% by mass of a hydrocarbon-hydroxyl organosilicon with a molecular weight of approximately 2000, 14.2% by mass of MIBK solvent, 6% by mass of MDI-100, and an appropriate amount of the first catalyst, organobismuth, were added to a three-necked flask. The mixture was heated to 85°C and reacted for 3 hours. Then, the temperature was raised to 100°C, and the second catalyst, MPPO, was added, and the reaction was carried out for 10 hours. The mixture was then cooled to 60°C, and 2% by mass of triglycerides and 1% by mass of paraffin were added to obtain the organosilicon-modified carbodiimide polyurethane reaction solution.

[0104] Meanwhile, in another beaker, prepare 59.5% water, 1.2% emulsifier (1 / 3 each of Tween 80, biscocoyl ammonium chloride, and isotridecyl alcohol polyoxyethylene ether), and 4% cosolvent (dipropylene glycol). Heat to 60 degrees Celsius and stir until homogeneous. Then, rapidly stir with the above-mentioned organosilicon-modified carbodiimide polyurethane reaction solution and homogenize under high pressure four times at a pressure of 40 MPa.

[0105] After homogenization, solvent removal was performed to remove MIBK, yielding an organosilicon-modified carbodiimide polyurethane emulsion with a solid content of approximately 25%.

[0106] Example 7

[0107] Similar to Example 6, but with IPDI replacing MDI-100, a silicone-modified carbodiimide polyurethane emulsion was finally obtained. Its solid content was 25%.

[0108] Example 8

[0109] Similar to Example 6, but with TDI replacing MDI-100, a silicone-modified carbodiimide polyurethane emulsion was finally obtained. Its solid content was 25%.

[0110] Example 9

[0111] Similar to Example 6, an organosilicon-modified wax was used to replace paraffin to obtain an organosilicon-modified carbodiimide polyurethane reaction solution with a solid content of approximately 25%.

[0112] Example 10

[0113] Similar to Example 6, but using a long-chain alkane-modified hydroxyl organosilicon with a molecular weight of approximately 3000 to replace the hydrocarbon hydroxyl organosilicon, the final product is an organosilicon-modified carbodiimide polyurethane emulsion. Its solid content is 25%.

[0114] The following is a description of the raw materials used in the above embodiments of the present invention:

[0115] raw materials Abbreviation or Explanation Monohydroxy organosilicon Molecular weight 2000 Long-chain alkyl-modified monohydroxy organosilicon Molecular weight 3000 4,4-Diphenylmethane diisocyanate MDI Toluene diisocyanate TDI Isophorone diisocyanate IPDI Hexamethylene diisocyanate HDI Organosilicon modified wax Long-chain alkyl modified silicone wax Triglycerides GTS Organophosphorus catalysts MPPO Paraffin No. 58: Paraffin wax with a melting point of approximately 58°C includes semi-refined and fully refined varieties. Carbodiimide catalyst MPPO Methyl isobutyl ketone MIBK Isomeric tridecyl alcohol polyoxyethylene ether emulsifier Twain 80 emulsifier Castor oil polyoxyethylene ether emulsifier Di-coconut dimethylammonium chloride emulsifier dipropylene glycol DPG beeswax Natural wax palm wax Natural wax Candelilla wax Natural wax ECO-BARRIER X-904E Fuke New Material Waterproofing Agent ECO-BARRIER 101Z Fuke New Materials Waterproof Crosslinking Agent

[0116] Comparative Example 1

[0117] ECO-BARRIER X-904E, a fluorine-free waterproof and anti-siphon treatment agent from Fuke New Materials.

[0118] Comparative Example 2

[0119] Commercially available fluorine-free anti-siphon samples.

[0120] Working fluid preparation

[0121] The above-described examples and comparative samples were prepared into a 60 g / L working solution with an added 10 g / L waterproof crosslinking agent. Several common fabrics were used for padding treatment, followed by a 170°C, 90-second treatment, and then an anti-siphon test was conducted according to the test method described in the patent:

[0122] Anti-siphon test

[0123] Anti-siphon testing is divided into static anti-siphon testing and dynamic anti-siphon testing. Dynamic anti-siphon testing is conducted using specialized testing instruments and expressed through detailed numerical values. Static anti-siphon testing employs a static suspension method, observing and recording three aspects from the lateral and cross-sectional perspectives: whether liquid creep (siphoning) occurs in the tested sample, the time of siphoning occurrence, and the maximum height of the siphon creep. The details of the static anti-siphon testing primarily used in this patent are as follows:

[0124] 1) Testing equipment:

[0125] Anti-siphon tester; ruler; green ink.

[0126] 2) Sampling requirements:

[0127] The sample was cut into 150*30mm pieces.

[0128] 3) Test requirements:

[0129] Immersion area: 10mm;

[0130] Hanging time: 0.5 hours, 2 hours, and 24 hours

[0131] 4) Test steps:

[0132] The above emulsion was mixed with water to prepare a treatment solution. The fabric sample was then impregnated with the solution and dried in an oven to obtain the anti-siphon treatment sample.

[0133] Meanwhile, red water was added to the anti-siphon tester.

[0134] Suspend the sample vertically on the siphon tester and adjust the height of the sample so that 10 mm of it is submerged in water. Start timing after the sample is set up.

[0135] After 0.5 hours, observe the water level rise of the sample. If it exceeds 10 mm, the test is terminated, and the result is deemed unqualified. Record it as NO. If it does not exceed 10 mm, continue the test and record it as OK.

[0136] Two hours later, observe whether the water level rise of the sample exceeds 10 mm, as above.

[0137] After 24 hours, observe whether the water level rise of the sample exceeds 10 mm, as above.

[0138] Test results from Examples 1-5:

[0139] Large-hole canvas for shoe materials:

[0140] Results in 0.5 hours Results in 2 hours 24-hour results 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 -

[0141] Shoelace mesh fabric:

[0142] Results in 0.5 hours Results in 2 hours 24-hour results 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

[0143] Test Results Examples 6-10

[0144] Large-hole canvas for shoe materials:

[0145] Results in 0.5 hours Results in 2 hours 24-hour results 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 -

[0146] Shoelace mesh fabric:

[0147] Results in 0.5 hours Results in 2 hours 24-hour results 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 -

[0148] The test results above show that, using the fluorine-free waterborne polyurethane anti-siphon emulsion of the present invention, various fabrics exhibit good and stable anti-siphon effects.

[0149] In other embodiments, other mass fractions can also be used. A fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion, by mass fraction, comprises: 30% organosilicon-modified carbodiimide waterborne polyurethane polymer, 5% fatty acid fatty alcohol ester, 2% emulsifier, 5% cosolvent, and 58% water; or comprises: 35% organosilicon-modified carbodiimide waterborne polyurethane polymer, 5% fatty acid fatty alcohol ester, 2% emulsifier, 5% cosolvent, 50% water, and 3% natural wax; or comprises: 19% organosilicon-modified carbodiimide waterborne polyurethane polymer, 2% fatty acid fatty alcohol ester, 2% emulsifier, 2% cosolvent, 70% water, and 5% natural wax; or comprises: 15% organosilicon-modified carbodiimide waterborne polyurethane polymer, 5% fatty acid fatty alcohol ester, 5% emulsifier, 5% cosolvent, and 70% water.

[0150] The organosilicon-modified carbodiimide waterborne polyurethane polymer is a polyurethane polymer with an organosilicon hydrophobic modification polycarbodiimide structure, obtained by reacting organosilicon resin and diisocyanate, as shown in the following reaction formula:

[0151]

[0152] The number of n is 0≤n≤9, preferably 0≤n≤3;

[0153] The quantity of x is 0≤x≤30, preferably 3≤x≤15, and more preferably 7≤x≤10;

[0154] The quantity of m is 1 < m ≤ 30, preferably 3 ≤ m ≤ 15, and more preferably 7 ≤ m ≤ 10.

[0155] In one embodiment, n is 0, x is 8, and m is 8;

[0156] In one embodiment, n is 0, x is 0, and m is 10;

[0157] In one embodiment, n is 2, x is 8, and m is 8;

[0158] Of course, in other embodiments, n, x, and m can be other numbers.

[0159] Where R1 is a straight-chain, isomeric alkyl, or ether-alkyl structure of -C1 to C6;

[0160] The structure of R1 is as follows: or ,

[0161] Where y and z are 1-5, and in this embodiment y is 3 and z is 3.

[0162] Preferably, R2 is -CH3 or a C8-C18 straight-chain alkyl group;

[0163] When R2 is -CH3, the organosilicon resin is a hydroxyl organosilicon resin.

[0164] When R2 is a C8-C18 straight-chain alkyl group, the silicone resin is a long-chain alkyl-modified hydroxyl silicone resin. In this embodiment, R2 is a C10-C15 straight-chain alkyl group.

[0165] The OCN-R-NCO diisocyanate structure is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, aliphatic isocyanate, and isoflurone diisocyanate. The aliphatic isocyanate is hexamethylene diisocyanate.

[0166] Catalyst 1 is an organotin or organobismuth catalyst, and its dosage is 0.1%-0.5% of the mass of isocyanate; in this embodiment, catalyst 1 is an organobismuth catalyst, and its dosage is 0.3% of the mass of isocyanate. Catalyst 2 is an organophosphorus compound, and its dosage is 0.3% to 0.8% of the mass of isocyanate; in this embodiment, it is 0.5%.

[0167] Fatty acid fatty alcohol esters have a straight-chain structure of C7~C17-COO-C8~C18.

[0168] The structural formula of fatty acid triglycerides is:

[0169] R3 is a straight-chain alkyl group of C10 to C15;

[0170] The structural formula of pentaerythritol stearate is:

[0171] R4 is a C10 to C15 straight-chain alkyl group.

[0172] The organosilicon-modified wax is a long-chain alkyl-modified polydimethylsiloxane, which is a mixture of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane.

[0173] The emulsifier is a mixture of cationic and nonionic emulsifiers, wherein the cationic emulsifier is a mixture of ammonium chloride-type cationic and amide-type cationic emulsifiers; and the nonionic emulsifier is a mixture of isotridecyl alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, and Tween-type emulsifiers.

[0174] The co-solvent is a mixture of 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, isohexyl glycol, and diethylene glycol butyl ether.

[0175] Paraffin wax is a type of wax with a melting point of 40-60℃, while natural wax is a mixture of beeswax, palm wax, tung oil wax, and whale wax.

Claims

1. A fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion, characterized in that: According to quality score, including: Organosilicon-modified carbodiimide waterborne polyurethane polymer: 15-35% Fatty acid fatty alcohol esters: 1-5% Emulsifier: 1-5% Cosolvent: 2-5% Water: 50-70%, The organosilicon-modified carbodiimide waterborne polyurethane polymer is a polyurethane polymer with an organosilicon hydrophobic modified polycarbodiimide structure, obtained by reacting organosilicon and diisocyanate structures, as shown in the following reaction formula: ， Where R1 is a straight-chain, isomeric alkyl, or ether-alkyl structure of -C1 to C6; R2 is -CH3 or a straight-chain alkyl group of C8 to C18; The number of n is 0 ≤ n ≤ 9. The quantity of x is 0 ≤ x ≤ 30. The number of m is 1 < m ≤ 30.

2. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 1, characterized in that: The catalyst 1 is an organotin or organobismuth catalyst, and its dosage is 0.1%-0.5% of the mass of the isocyanate; The catalyst 2 is an organophosphorus compound, and its amount is 0.3% to 0.8% of the mass of isocyanate.

3. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 2, characterized in that: The OCN-R-NCO diisocyanate structure is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isoflurone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, phenylmethylene diisocyanate, and tetramethyl isophenylmethylene diisocyanate.

4. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 1, characterized in that: The fatty acid fatty alcohol ester is one or more of the following: a straight-chain or isomeric alkyl ester structure of C1~C29-COO-C2~C30, a fatty acid triglyceride, and a pentaerythritol stearate.

5. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 4, characterized in that: The structural formula of the fatty acid triglyceride is: R3 is a C1-C30 straight-chain or isomeric alkyl group. The structural formula of the pentaerythritol stearate is: R4 is a C1 to C30 straight-chain or isomeric alkyl group.

6. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 1, characterized in that: The emulsifier is a combination of cationic and nonionic emulsifiers, wherein the cationic emulsifier is one or more of ammonium chloride-type cationic and amide-type cationic emulsifiers; and the nonionic emulsifier is one or more of isotridecyl alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, or Tween-type emulsifiers.

7. The fluorine-free organosilicon-modified carbodiimide waterborne 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, isohexyl glycol, and diethylene glycol butyl ether.

8. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 1, characterized in that: The structure of R1 is as follows: or , Where y and z are 1-10.

9. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 3, characterized in that: When R2 is -CH3, the organosilicon is an organosilicon containing a single hydrocarbon hydroxyl group.

10. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 2, characterized in that: When R2 is a C8-C18 straight-chain alkyl group, the organosilicon is a long-chain alkyl-modified monohydroxy organosilicon.

11. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 1, characterized in that: Based on mass fraction, it also includes silicone-modified waxes, as well as paraffin or natural waxes. The content of the organosilicon-modified wax is ≤5%. The content of the paraffin or natural wax is ≤5%.

12. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 11, characterized in that: The paraffin wax is paraffin wax with a melting point of 30-80℃, and the natural wax is one or more of beeswax, palm wax, tung oil wax, and whale wax.

13. The fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion according to claim 11, characterized in that: The organosilicon-modified wax is a long-chain alkyl-modified polydimethylsiloxane, specifically one or more of hexadecyl-modified polydimethylsiloxane, octadecyl-modified polydimethylsiloxane, and docosyl-modified polydimethylsiloxane.

14. The application of the fluorine-free organosilicon-modified carbodiimide waterborne polyurethane emulsion of any one of claims 1-13 in fabric anti-siphoning.

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