Fluorine-free silicon-containing waterproofing agent, preparation method and application thereof

Abstract

This invention provides a fluorine-free silicone-containing waterproofing agent, its preparation method, and its application, belonging to the technical field of textile functional finishing agents. The fluorine-free silicone-containing waterproofing agent provided by this invention comprises, by mass percentage: 10-15% modified silicone resin, 10-15% modified polysiloxane, 1-5% surfactant, 5-10% organic solvent, and the balance being water. This invention modifies the silicone resin using 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol, introducing shorter-chain hydrophobic groups and polar groups with stronger hydrophobicity. Simultaneously, the modified silicone resin is dissolved using polysiloxane modified with shorter-chain hydrophobic groups, thereby improving the waterproofing and wash resistance of the fluorine-free silicone-containing waterproofing agent.

Description

Technical Field

[0001] This invention belongs to the technical field of functional finishing agents for textiles, specifically relating to a fluorine-free silicone waterproofing agent, its preparation method, and its application. Background Technology

[0002] Waterproofing is applied in many areas of textiles, such as waterproof jackets, tents, bag fabrics, and umbrellas. Waterproofing agents can be divided into two main categories: fluorinated and fluorine-free. Due to the harmful effects of fluorides, fluorine-free waterproofing agents are more environmentally friendly and safer, and have therefore become the mainstream in the field of waterproofing finishing.

[0003] Fluorine-free waterproofing agents mainly fall into three categories: acrylic, polyurethane, and silicone. Acrylic waterproofing agents have a simple process, low cost, and acceptable waterproofing performance, but the hand feel of the finished fabric is significantly reduced, and hand scratches are severe. Polyurethane waterproofing agents have a better hand feel than acrylic but worse than silicone, and excellent waterproofing and wash resistance, but their process is complex and costly. Furthermore, while acrylic and polyurethane fluorine-free waterproofing agents offer good waterproofing and wash resistance, their waterproofing after washing and drying is poor, and the polymer film on the fiber surface creates a lubricating effect, resulting in significant yarn slippage after finishing. Silicone waterproofing agents offer excellent hand feel and very slight hand scratches, and yarn slippage is also very small, but their waterproofing and wash resistance are still far from meeting practical needs. Summary of the Invention

[0004] The purpose of this invention is to provide a fluorine-free silicone-containing waterproofing agent, its preparation method, and its application. The fluorine-free silicone-containing waterproofing agent provided by this invention exhibits excellent waterproofing properties, durable wash-and-dry waterproofing, a soft hand feel, and very low yarn slippage.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a fluorine-free silicone-containing waterproofing agent, which, by mass percentage, comprises the following components: 10-15% modified silicone resin, 10-15% modified polysiloxane, 1-5% surfactant, 5-10% organic solvent, and the balance being water;

[0007] The modified silicone resin is prepared by a thiol-ene click reaction initiated by an initiator with methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol;

[0008] The modified polysiloxane is prepared by hydrosilylation reaction of methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane.

[0009] Preferably, the method for preparing the modified silicone resin includes:

[0010] Methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, 3-chloro-1-propanethiol, solvent and initiator were mixed and subjected to a thiol-ene click reaction to obtain a modified silicone resin.

[0011] The methyl vinyl MQ silicone resin has an M / Q of 0.6 to 0.9, a vinyl content of 1 to 4 wt%, and a weight-average molecular weight of 4000 to 10000 g / mol; the molar ratio of vinyl to 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol in the methyl vinyl MQ silicone resin is 1:(0.6 to 0.8):(0.2 to 0.4).

[0012] Preferably, the solvent includes one or more of toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and isopropanol; the mass ratio of the solvent to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, and 3-chloro-1-propanethiol is (0.5~1):1.

[0013] Preferably, the initiator is azobisisobutyronitrile; the mass ratio of the initiator to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol is (0.1~0.5):100.

[0014] Preferably, the method for preparing the modified polysiloxane includes:

[0015] Methyl hydrogen silicone oil, vinyltris(trimethylsiloxy)silane and catalyst are mixed and subjected to hydrosilylation reaction to obtain modified polysiloxane.

[0016] Preferably, the molar ratio of Si-H in the methyl hydrogen silicone oil to vinyltris(trimethylsiloxy)silane is 1:(1~1.1).

[0017] Preferably, the surfactant includes one or more of nonionic surfactants and cationic surfactants.

[0018] Preferably, the organic solvent includes one or more of tripropylene glycol, dipropylene glycol, diethylene glycol butyl ether, isohexyl glycol, and isopropanol.

[0019] This invention also provides a method for preparing the fluorine-free silicone-containing waterproofing agent described in the above technical solution, comprising:

[0020] The modified silicone resin and the modified polysiloxane are mixed to obtain the first mixture.

[0021] The surfactant, organic solvent, and water are mixed to obtain a second mixture.

[0022] Under shear conditions, the first mixture is added to the second mixture to obtain a preemulsion;

[0023] The pre-emulsion was homogenized to obtain a fluorine-free silicone waterproofing agent.

[0024] The present invention also provides the application of the fluorine-free silicone waterproofing agent described in the above technical solution in fabric finishing.

[0025] This invention provides a fluorine-free silicone-containing waterproofing agent, comprising, by weight percentage: 10-15% modified silicone resin, 10-15% modified polysiloxane, 1-5% surfactant, 5-10% organic solvent, and the balance water. The modified silicone resin is prepared by a thiol-ene click reaction initiated by an initiator with methyl vinyl MQ silicone resin and 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol. The modified polysiloxane is prepared by a hydrosilylation reaction between methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane. This invention modifies the silicone resin with 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol, introducing shorter-chain hydrophobic groups and polar groups with stronger hydrophobicity. Simultaneously, the modified silicone resin is dissolved using polysiloxane modified with shorter-chain hydrophobic groups, thus improving the waterproofing and wash resistance of the fluorine-free silicone-containing waterproofing agent. The results of the embodiments show that after the fabric is treated with the fluorine-free silicone waterproofing agent provided by the present invention, the waterproof rating of the fabric before washing is above level 4, and the waterproof rating after washing and drying is above level 3.5. At the same time, it has a good hand feel and low yarn slippage. Detailed Implementation

[0026] This invention provides a fluorine-free silicone waterproofing agent, which, by mass percentage, comprises the following components: 10-15% modified silicone resin, 10-15% modified polysiloxane, 1-5% surfactant, 5-10% organic solvent, and the balance being water.

[0027] The fluorine-free silicone waterproofing agent provided by this invention comprises 10-15% modified silicone resin by weight percentage. As one embodiment, the content of the modified silicone resin may specifically be 10%, 11%, 12%, 13%, 14%, or 15%.

[0028] In this invention, the modified silicone resin is prepared by a thiol-ene click reaction initiated by an initiator with methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol.

[0029] In this invention, the preferred method for preparing the modified silicone resin includes:

[0030] A modified silicone resin was obtained by mixing methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, 3-chloro-1-propanethiol, solvent and initiator and carrying out a thiol-ene click reaction.

[0031] In this invention, the general structural formula of the methyl vinyl MQ silicone resin is [(CH3)2(CH2=CH)SiO 1 / 2 ] a [(CH3)3SiO 1 / 2 ] b [SiO 4 / 2 ] c Among them, [(CH3)2(CH2=CH)SiO 1 / 2 ] a [(CH3)3SiO 1 / 2 ] b It is an M-structure, [SiO] 4 / 2 ] c It is a Q-structure.

[0032] In this invention, the M / Q of the methyl vinyl MQ silicone resin is preferably 0.6 to 0.9; the vinyl content of the methyl vinyl MQ silicone resin is preferably 1 to 4 wt%; and the weight-average molecular weight of the methyl vinyl MQ silicone resin is preferably 4000 to 10000 g / mol. As one embodiment, the M / Q of the methyl vinyl MQ silicone resin can specifically be 0.6, 0.7, 0.8, or 0.9; the vinyl content of the methyl vinyl MQ silicone resin can specifically be 1 wt%, 2 wt%, 3 wt%, or 4 wt%; and the weight-average molecular weight of the methyl vinyl MQ silicone resin can specifically be 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, or 10000 g / mol. This invention does not impose any special limitations on the source of the methyl vinyl MQ silicone resin; commercially available products well-known to those skilled in the art can be used to ensure that the required parameters are within the above ranges. As one implementation, the specific source of the methyl vinyl MQ silicone resin may be Jiangxi Xinjiayi New Material Co., Ltd. (model XJY-8206A), Shandong Dayi Chemical Co., Ltd. (model DY-VMQ101), or Sichuan Chenguang Boda New Material Co., Ltd. (model 6201-4).

[0033] In this invention, the preferred molar ratio of vinyl groups to 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol in the methyl vinyl MQ silicone resin is 1:(0.6~0.8):(0.2~0.4).

[0034] In this invention, the solvent preferably includes one or more of toluene, xylene, butanone, methyl isobutyl ketone, and isopropanol.

[0035] In this invention, the preferred mass ratio of the solvent to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, and 3-chloro-1-propanethiol is (0.5~1):1. As one embodiment, the specific mass ratio of the solvent to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, and 3-chloro-1-propanethiol may be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1.

[0036] In this invention, the initiator is preferably azobisisobutyronitrile.

[0037] In this invention, the preferred mass ratio of the initiator to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, and 3-chloro-1-propanethiol is (0.1~0.5):100. As one embodiment, the specific mass ratio of the initiator to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, and 3-chloro-1-propanethiol may be 0.1:100, 0.2:100, 0.3:100, 0.4:100, or 0.5:100.

[0038] In this invention, the preferred method for mixing the methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, 3-chloro-1-propanethiol, solvent, and initiator is to mix the methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, 3-chloro-1-propanethiol, and solvent, and then add the initiator.

[0039] In this invention, the preferred temperature for the thiol-ene click reaction is 60-100°C; the preferred time for the thiol-ene click reaction is 1-2 hours; and the thiol-ene click reaction is preferably carried out under a nitrogen atmosphere and stirring conditions. This invention does not impose any particular limitation on the stirring method and rate; stirring techniques well-known to those skilled in the art can be used. As one embodiment, the temperature for the thiol-ene click reaction can specifically be 60°C, 70°C, 80°C, 90°C, or 100°C.

[0040] After the thiol-olefin click reaction is completed, the product of the thiol-olefin click reaction is preferably vacuum dried to obtain a modified silicone resin.

[0041] In one embodiment, the vacuum drying temperature can be 95~100℃; the vacuum drying time can be 1~3 hours. This invention does not impose any particular limitation on the vacuum degree of the vacuum drying process; any vacuum degree well-known to those skilled in the art can be used.

[0042] The present invention relates to a method for preparing modified silicone resin, which introduces short-chain hydrophobic groups and polar groups with stronger hydrophobicity through chemical modification, thereby improving the waterproof and wash-resistant properties of fluorine-free silicone waterproofing agents.

[0043] The fluorine-free silicone waterproofing agent provided by this invention further includes 10-15% modified polysiloxane by weight percentage. As one embodiment, the content of the modified polysiloxane may specifically be 10%, 11%, 12%, 13%, 14%, or 15%.

[0044] In this invention, the modified polysiloxane is prepared by hydrosilylation reaction of methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane.

[0045] In this invention, the preferred method for preparing the modified polysiloxane includes:

[0046] Methyl hydrogen silicone oil, vinyltris(trimethylsiloxy)silane and catalyst are mixed and subjected to hydrosilylation reaction to obtain modified polysiloxane.

[0047] In this invention, the molar ratio of Si-H of the methyl hydrogen silicone oil to vinyltris(trimethylsiloxy)silane is preferably 1:(1~1.1), more preferably 1:1.05.

[0048] In this invention, the catalyst is preferably a 0.99wt% chloroplatinic acid-isopropanol solution.

[0049] In this invention, the amount of catalyst added is preferably 5 to 50 ppm of the total mass of methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane, measured by Pt.

[0050] In this invention, the mixing of the methyl hydrogen silicone oil, vinyltris(trimethylsiloxy)silane, and catalyst is preferably carried out by mixing vinyltris(trimethylsiloxy)silane with the catalyst to obtain a mixture, and then adding the mixture dropwise to the methyl hydrogen silicone oil. In this invention, the dropwise addition time is preferably 1 to 1.5 hours.

[0051] In this invention, the temperature of the hydrosilylation reaction is preferably 70~130℃; the time of the hydrosilylation reaction is preferably 3~5h; and the hydrosilylation reaction is preferably carried out under a nitrogen atmosphere and stirring conditions. In this invention, the time of the hydrosilylation reaction is calculated from the time the mixture is completely added dropwise.

[0052] After the hydrosilylation reaction is completed, the product of the hydrosilylation reaction is preferably heated to 130-150°C and subjected to vacuum distillation for 1 hour to remove low molecular weight impurities, thereby obtaining modified polysiloxane.

[0053] In this invention, the general structural formula of the modified polysiloxane is shown in Formula I: Formula I;

[0054] In Equation I, m and n are independent integers greater than 0.

[0055] In this invention, the weight-average molecular weight of the modified polysiloxane is preferably 2000~20000 g / mol. As one embodiment, the weight-average molecular weight of the modified polysiloxane may specifically be 2000 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 12000 g / mol, 15000 g / mol, 18000 g / mol, or 20000 g / mol.

[0056] The present invention provides a method for controlling the preparation of modified polysiloxanes, which uses short-chain hydrophobic groups to modify polysiloxanes to dissolve modified silicone resins, thereby improving the waterproof and wash-resistant properties of fluorine-free silicone waterproofing agents.

[0057] The fluorine-free silicone waterproofing agent provided by this invention further includes 1-5% surfactant by weight percentage. As one embodiment, the content of the surfactant may specifically be 1%, 2%, 3%, 4%, or 5%.

[0058] In this invention, the surfactant preferably includes one or more of nonionic and cationic surfactants; the nonionic surfactant preferably includes one or more of Span 40, Span 60, Span 80, polyoxyethylene monostearate, sorbitol monostearate, sorbitol monooleate, fatty alcohol polyoxyethylene (25) ether, and polyoxyethylene octadecyl ether; the cationic surfactant preferably includes one or more of hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, docosyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride. The addition of surfactants in this invention allows for the formation of a pre-emulsion during the preparation process.

[0059] The fluorine-free silicone waterproofing agent provided by this invention further includes 5-10% organic solvent by weight percentage. As one embodiment, the content of the organic solvent may specifically be 5%, 6%, 7%, 8%, 9%, or 10%.

[0060] In this invention, the organic solvent preferably includes one or more of tripropylene glycol, dipropylene glycol, diethylene glycol butyl ether, isohexyl glycol, and isopropanol.

[0061] The fluorine-free silicone waterproofing agent provided by this invention also includes the remainder water by weight percentage.

[0062] In one implementation method, the water is deionized water.

[0063] This invention modifies silicone resin with 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol, introducing short-chain hydrophobic groups and polar groups with stronger hydrophobicity. At the same time, the modified silicone resin is dissolved with polysiloxane modified with short-chain hydrophobic groups. By controlling the composition and dosage of each component of the fluorine-free silicone waterproofing agent, the waterproofing and washability of the fluorine-free silicone waterproofing agent are improved. The treated fabric has excellent hand feel, very light hand scratches and very little yarn slippage.

[0064] This invention also provides a method for preparing the fluorine-free silicone-containing waterproofing agent described in the above technical solution, comprising:

[0065] The modified silicone resin and the modified polysiloxane are mixed to obtain the first mixture.

[0066] The surfactant, organic solvent, and water are mixed to obtain a second mixture.

[0067] Under shear conditions, the first mixture is added to the second mixture to obtain a preemulsion;

[0068] The pre-emulsion was homogenized to obtain a fluorine-free silicone waterproofing agent.

[0069] The present invention mixes modified silicone resin and modified polysiloxane to obtain a first mixture.

[0070] In this invention, the mixing temperature is preferably 80-110°C; the mixing is preferably carried out under stirring conditions. This invention does not impose any special limitations on the stirring method and rate; stirring techniques well-known to those skilled in the art can be used. This invention does not impose any special limitations on the mixing time, as long as the mixture is homogeneous.

[0071] After mixing, the present invention preferably cools the mixed product to 60-70°C to obtain a first mixture. The present invention does not have any special limitations on the cooling operation; conventional cooling methods used by those skilled in the art can be employed.

[0072] The present invention mixes surfactant, organic solvent and water to obtain a second mixture.

[0073] The present invention does not impose any special limitations on the mixing operation; any technical solution known to those skilled in the art can be used to ensure that the three are mixed evenly.

[0074] After mixing, the present invention preferably heats the mixed product to 60~70°C to obtain a second mixture.

[0075] After obtaining the first mixture and the second mixture, the present invention adds the first mixture to the second mixture under shear conditions to obtain a pre-emulsion.

[0076] In this invention, the shearing rate is preferably 4500~5500 rpm, more preferably 5000 rpm; the shearing temperature is preferably 60~70℃.

[0077] In this invention, the first mixture is preferably added at a uniform rate over a period of 2-5 minutes. Controlling the addition method of the first mixture in this invention further improves the stability of the fluorine-free silicone-containing waterproofing agent.

[0078] Preferably, after the first mixture is added, the material is sheared for 2-5 minutes to obtain a pre-emulsion.

[0079] After obtaining the pre-emulsion, the present invention performs homogenization treatment on the pre-emulsion to obtain a fluorine-free silicone waterproofing agent.

[0080] In this invention, the pressure of the homogenization process is preferably 25-35 MPa, more preferably 30 MPa; the number of homogenization processes is preferably 2-4; and the temperature of the homogenization process is preferably 60-70°C.

[0081] After homogenization, the present invention preferably cools and filters the homogenized product sequentially to obtain a fluorine-free silicone waterproofing agent.

[0082] The present invention does not impose any special limitations on the cooling operation; any cooling technique known to those skilled in the art can be used to cool the material to room temperature.

[0083] In this invention, the mesh size of the filter screen during filtration is preferably 200 to 400 mesh.

[0084] The present invention also provides the application of the fluorine-free silicone waterproofing agent described in the above technical solution in fabric finishing.

[0085] In this invention, the preferred application includes: mixing a fluorine-free silicone waterproofing agent with water to obtain a finishing solution; mixing the finishing solution with a fabric, and then sequentially soaking, rolling, and baking the fabric to obtain the treated fabric.

[0086] As one embodiment, the concentration of the fluorine-free silicone waterproofing agent in the finishing solution can be 40 g / L.

[0087] The present invention does not have a special limitation on the amount of finishing liquid used, as long as it can cover the fabric.

[0088] In this invention, the soaking temperature is preferably 20~40℃; the soaking time is preferably 1~5s; the liquid content after rolling is preferably 40~80wt%; the baking temperature is preferably 130~180℃; and the baking time is preferably 0.5~2min.

[0089] Fabrics treated with the fluorine-free silicone waterproofing agent of this invention exhibit excellent waterproofing performance before and after washing and drying, as well as excellent hand feel, very light hand scratches, and very little yarn slippage.

[0090] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0091] Example 1

[0092] A fluorine-free silicone waterproofing agent is composed of 10% modified silicone resin, 15% modified polysiloxane, 3% surfactant (octadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene (25) ether in a mass ratio of 1:2), 7% organic solvent (isohexanediol) and the balance deionized water.

[0093] The modified silicone resin was prepared as follows: 120g of methyl vinyl MQ silicone resin (M / Q=0.8, weight average molecular weight=6000g / mol, vinyl content 2wt%, XJY-8206A from Jiangxi Xinjiayi New Material Co., Ltd.), 8.06g of 2-(trimethylsilane)ethanethiol and 4.42g of 3-chloro-1-propanethiol were dissolved in 120g of butanone, heated to 70℃, and 0.5g of azobisisobutyronitrile was added. The mixture was kept at this temperature for 2h under nitrogen protection and continuous stirring. After the reaction was completed, the material was taken out and dried under vacuum at 100℃ for 3h to obtain the modified silicone resin.

[0094] The method for preparing modified polysiloxane is as follows: 100g of methyl hydrogen silicone oil (viscosity: 60mm) is added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel. 2 / s (25℃), hydrogen content: 0.18wt%, Shanghai Maclean Biochemical Technology Co., Ltd.), turn on the stirrer and nitrogen protection and heat to 90℃, mix 69g vinyltris(trimethylsiloxy)silane with 0.99wt% chloroplatinic acid-isopropanol solution (Pt is measured as 10ppm of the total mass of methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane) to obtain a mixture, add the mixture dropwise to methyl hydrogen silicone oil through a dropping funnel, the dropwise addition time is 1h, after the dropwise addition is completed, heat to 110℃ and continue to react for 3h, after the reaction is completed, heat to 130℃ and remove low molecular weight impurities by vacuum distillation for 1h to obtain modified polysiloxane; the weight average molecular weight of modified polysiloxane is 6000g / mol;

[0095] The preparation method of the fluorine-free silicone waterproofing agent is as follows: the modified silicone resin and the modified polysiloxane are stirred and dissolved at 90°C, and then cooled to 70°C to obtain the first mixture.

[0096] The surfactant, organic solvent and deionized water were mixed and heated to 60°C. The mixture was sheared at a rate of 5000 rpm. During the shearing process, the first mixture was added at a uniform rate over 3 minutes. After the addition was completed, the shearing process continued for another 3 minutes to obtain a pre-emulsion.

[0097] The pre-emulsion was homogenized three times at 30 MPa, cooled, and then filtered to obtain a fluorine-free silicone waterproofing agent.

[0098] Example 2

[0099] A fluorine-free silicone waterproofing agent is composed of 10% modified silicone resin, 15% modified polysiloxane, 3% surfactant (octadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene (25) ether in a mass ratio of 1:2), 7% organic solvent (isohexanediol) and the balance deionized water.

[0100] The modified silicone resin was prepared as follows: 120g of methyl vinyl MQ silicone resin (M / Q=0.8, weight average molecular weight=6000g / mol, vinyl content 3wt%, DY-VMQ101 from Shandong Dayi Chemical Co., Ltd.), 12.09g of 2-(trimethylsilane)ethanethiol and 6.64g of 3-chloro-1-propanethiol were dissolved in 120g of butanone, heated to 70℃, and 0.5g of azobisisobutyronitrile was added. The mixture was kept at this temperature for 2h under nitrogen protection and continuous stirring. After the reaction was completed, the material was taken out and dried under vacuum at 100℃ for 3h to obtain the modified silicone resin.

[0101] The preparation method of the modified polysiloxane is the same as in Example 1;

[0102] The preparation method of the fluorine-free silicone waterproofing agent is the same as in Example 1.

[0103] Example 3

[0104] A fluorine-free silicone waterproofing agent is composed of 10% modified silicone resin, 15% modified polysiloxane, 3% surfactant (octadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene (25) ether in a mass ratio of 1:2), 7% organic solvent (isohexanediol) and the balance deionized water.

[0105] The modified silicone resin was prepared as follows: 120g of methyl vinyl MQ silicone resin (M / Q=0.8, weight average molecular weight=8000g / mol, vinyl content 3wt%, 6201-4 from Sichuan Chenguang Boda New Material Co., Ltd.), 12.09g of 2-(trimethylsilane)ethanethiol and 6.64g of 3-chloro-1-propanethiol were dissolved in 120g of butanone, heated to 70℃, and 0.5g of azobisisobutyronitrile was added. The mixture was kept at this temperature for 2h under nitrogen protection and continuous stirring. After the reaction was completed, the material was taken out and dried under vacuum at 100℃ for 3h to obtain the modified silicone resin.

[0106] The preparation method of the modified polysiloxane is the same as in Example 1;

[0107] The preparation method of the fluorine-free silicone waterproofing agent is the same as in Example 1.

[0108] Example 4

[0109] A fluorine-free silicone waterproofing agent is composed of 10% modified silicone resin, 15% modified polysiloxane, 3% surfactant (octadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene (25) ether in a mass ratio of 1:2), 7% organic solvent (isohexanediol) and the balance deionized water.

[0110] The modified silicone resin was prepared as follows: 120g of methyl vinyl MQ silicone resin (M / Q=0.8, weight average molecular weight=6000g / mol, vinyl content 3wt%, DY-VMQ101 from Shandong Dayi Chemical Co., Ltd.), 12.09g of 2-(trimethylsilane)ethanethiol and 6.64g of 3-chloro-1-propanethiol were dissolved in 120g of butanone, heated to 70℃, and 0.5g of azobisisobutyronitrile was added. The mixture was kept at this temperature for 2h under nitrogen protection and continuous stirring. After the reaction was completed, the material was taken out and dried under vacuum at 100℃ for 3h to obtain the modified silicone resin.

[0111] The modified polysiloxane is prepared by adding 100g of methyl hydrogen silicone oil (viscosity: 60mm) to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel in a certain proportion. 2 / s (25℃), hydrogen content: 0.55wt%, Shanghai Maclean Biochemical Technology Co., Ltd.), turn on the stirrer and nitrogen protection and heat to 90℃, mix 186.4g of vinyltris(trimethylsiloxy)silane with 0.99wt% chloroplatinic acid-isopropanol solution (Pt is measured as 10ppm of the total mass of methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane) to obtain a mixture, add the mixture dropwise to methyl hydrogen silicone oil through a dropping funnel, the dropwise addition time is 1h, after the dropwise addition is completed, heat to 110℃ and continue to react for 3h, after the reaction is completed, heat to 130℃ and remove low molecular weight impurities by vacuum distillation for 1h to obtain modified polysiloxane; the weight average molecular weight of modified polysiloxane is 10000g / mol;

[0112] The preparation method of the fluorine-free silicone waterproofing agent is the same as in Example 1.

[0113] Comparative Example 1

[0114] 20g of methyl vinyl MQ silicone resin (M / Q=0.8, weight average molecular weight=6000g / mol, vinyl content 3wt%, DY-VMQ101 from Shandong Dayi Chemical Co., Ltd.) and 30g of polydimethylsiloxane (weight average molecular weight 6000g / mol) were heated to 90℃ and stirred to dissolve. After complete dissolution, the temperature was lowered to 70℃ to obtain the first mixture. 2g of octadecyltrimethylammonium chloride, 4g of fatty alcohol polyoxyethylene (25) ether, 14g of isohexyl glycol and 130g of deionized water were mixed and heated to 60℃. The mixture was sheared at a high speed of 5000r / min, and the first mixture was added uniformly over 3min. After the addition was completed, shearing continued for another 3min to obtain a pre-emulsion. The pre-emulsion was homogenized at a pressure of 30MPa for 3 times. After homogenization, the mixture was cooled and filtered to obtain a fluorine-free waterproofing agent.

[0115] Comparative Example 2

[0116] 120g of methyl vinyl MQ silicone resin (M / Q=0.8, weight average molecular weight=6000g / mol, vinyl content 3wt%, DY-VMQ101 from Shandong Dayi Chemical Co., Ltd.), 12.09g of 2-(trimethylsilane)ethanethiol and 6.64g of 3-chloro-1-propanethiol were dissolved in 120g of butanone, heated to 70℃, and 0.5g of azobisisobutyronitrile was added. The reaction was carried out under nitrogen protection and continuous stirring for 2h. After the reaction was completed, the material was taken out and vacuum dried at 100℃ for 3h to obtain modified silicone resin.

[0117] 20g of modified silicone resin and 30g of polydimethylsiloxane (weight average molecular weight 6000g / mol) were heated to 90℃ and stirred to dissolve. After complete dissolution, the mixture was cooled to 70℃ to obtain the first mixture. 2g of octadecyltrimethylammonium chloride, 4g of fatty alcohol polyoxyethylene (25) ether, 14g of isohexyl glycol and 130g of deionized water were mixed and heated to 60℃. The mixture was sheared at a high speed of 5000r / min, while the first mixture was added uniformly over 3 minutes. After the addition was completed, shearing continued for another 3 minutes to obtain a pre-emulsion. The pre-emulsion was homogenized at a pressure of 30MPa for 3 times. After homogenization, the mixture was cooled and filtered to obtain a fluorine-free waterproofing agent.

[0118] Comparative Example 3

[0119] Commercially available silicone-based fluorine-free waterproofing agent NR-8800.

[0120] Comparative Example 4

[0121] Commercially available fluorine-free acrylic waterproofing agent X-201Pro.

[0122] Comparative Example 5

[0123] Commercially available polyurethane fluorine-free waterproofing agent X-904EW.

[0124] Application examples

[0125] The waterproofing agents of Examples 1-4 and Comparative Examples 1-5 were diluted with water to 40 g / L, and then 300T polyester spring spun yarn was subjected to soaking, rolling and baking treatment in sequence. The soaking temperature was 20℃ and the time was 2s. The liquid content after rolling was 60wt%. The baking temperature was 170℃ and the baking time was 60s, and the treated fabric was obtained.

[0126] The performance of each treated fabric was evaluated according to the following test standards, and the results are shown in Table 1:

[0127] (1) Waterproof performance test, in accordance with GB / T 4745-2012 Test and evaluation of waterproof performance of textiles - water-soaking method;

[0128] (2) Washability test, according to GB / T 8629-2017 Textiles Test Household Washing and Drying Procedure, 4N procedure;

[0129] (3) Hand feel test, refer to AATCC EP5 fabric hand feel evaluation procedure for evaluation, level 1 is the softest, level 5 is the stiffest;

[0130] (4) Hand scratch test: Use your fingers to scratch the surface of the fabric sample with uniform force, observe the surface marks and evaluate them according to the following standards:

[0131] ○: There are slight scratches.

[0132] △: There are obvious scratch marks.

[0133] ×: There are very obvious hand scratches;

[0134] (5) Yarn slippage test: The test shall be conducted in accordance with GB / T 13772.2-2018 "Determination of anti-slippage of yarn at seam of textile woven fabric - Part 2: constant load method" with a load of 120N and the weft (warp) slippage amount shall be tested.

[0135] Table 1. Properties of fabrics treated with waterproofing agent in Examples 1-4 and Comparative Examples 1-5.

[0136]

[0137] As shown in Table 1, compared to Comparative Examples 1 and 2, Examples 1-4 chemically grafted short-chain hydrophobic and polar groups into the silicone resin structure, and simultaneously grafted dendritic short-chain hydrophobic groups into the polysiloxane structure. Therefore, they exhibit better water resistance and washability than the commercially available silicone waterproofing agents in Comparative Examples 1, 2, and 3. Furthermore, since the grafted groups are short chains, yarn slippage did not change significantly. Example 2 showed better water resistance than Example 1 because the silicone resin in Example 2 had a higher vinyl content and more grafted hydrophobic and polar groups. Example 3 showed slightly better water resistance than Example 2, but a slightly worse hand feel, which is due to the larger molecular weight of the silicone resin in Example 3. Examples 1-4 showed significantly better hand feel, less scratching, significantly lower yarn slippage, and better water resistance after washing and drying compared to the acrylate and polyurethane waterproofing agents in Comparative Examples 4 and 5.

[0138] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A fluorine-free silicone-containing waterproofing agent, characterized in that, By weight percentage, it comprises the following components: 10-15% modified silicone resin, 10-15% modified polysiloxane, 1-5% surfactant, 5-10% organic solvent, and the balance being water; The modified silicone resin is prepared by a thiol-ene click reaction initiated by an initiator with methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol; The modified polysiloxane is prepared by hydrosilylation reaction of methyl hydrogen silicone oil and vinyltris(trimethylsiloxy)silane.

2. The fluorine-free silicon-containing water repellent agent according to claim 1, characterized by, The method for preparing the modified silicone resin includes: Methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, 3-chloro-1-propanethiol, solvent and initiator were mixed and subjected to a thiol-ene click reaction to obtain a modified silicone resin. The methyl vinyl MQ silicone resin has an M / Q of 0.6 to 0.9, a vinyl content of 1 to 4 wt%, and a weight-average molecular weight of 4000 to 10000 g / mol; the molar ratio of vinyl to 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol in the methyl vinyl MQ silicone resin is 1:(0.6 to 0.8):(0.2 to 0.4).

3. The fluorine-free silicon-containing water repellent agent according to claim 2, characterized by, The solvent includes one or more of toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and isopropanol; the mass ratio of the solvent to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol, and 3-chloro-1-propanethiol is (0.5~1):

1.

4. The fluorine-free silicon-containing water repellent agent according to claim 2, characterized by, The initiator is azobisisobutyronitrile; the mass ratio of the initiator to the total mass of methyl vinyl MQ silicone resin, 2-(trimethylsilane)ethanethiol and 3-chloro-1-propanethiol is (0.1~0.5):

100.

5. The fluorine-free silicon-containing water repellent agent according to claim 1, characterized by, The method for preparing the modified polysiloxane includes: Methyl hydrogen silicone oil, vinyltris(trimethylsiloxy)silane and catalyst are mixed and subjected to hydrosilylation reaction to obtain modified polysiloxane.

6. The fluorine-free silicon-containing water repellent agent according to claim 5, characterized by, The molar ratio of Si-H in the methyl hydrogen silicone oil to vinyltris(trimethylsiloxy)silane is 1:(1~1.1).

7. The fluorine-free silicone-containing waterproofing agent according to claim 1, characterized in that, The surfactant includes one or more of nonionic and cationic surfactants.

8. The fluorine-free silicone-containing waterproofing agent according to claim 1, characterized in that, The organic solvent includes one or more of tripropylene glycol, dipropylene glycol, diethylene glycol butyl ether, isohexyl glycol, and isopropanol.

9. A method for preparing the fluorine-free silicone-containing waterproofing agent according to any one of claims 1 to 8, characterized in that, include: The modified silicone resin and the modified polysiloxane are mixed to obtain the first mixture. The surfactant, organic solvent, and water are mixed to obtain a second mixture. Under shear conditions, the first mixture is added to the second mixture to obtain a preemulsion; The pre-emulsion was homogenized to obtain a fluorine-free silicone waterproofing agent.

10. The application of the fluorine-free silicone waterproofing agent according to any one of claims 1 to 8 in fabric finishing.

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