A polysiloxane material, a method of preparation and use thereof

Abstract

This application discloses a polysiloxane material, its preparation method, and its application. The preparation method includes the following steps: S1: 5-norbornene-2-methanol is polymerized with an epoxide to obtain a first product; S2: the first product is reacted with terminal hydrogen silicone oil to obtain a second product; S3: dimethyl biphenyl diisocyanate is reacted with the second product to obtain a third product, and vanillin is added to obtain the polysiloxane material. The polysiloxane material of this application is suitable for use as an anti-wrinkle finishing agent for silk fabrics. After treatment, silk fabrics are less prone to wrinkles, the wrinkle recovery effect is significantly improved, the breaking strength of the fabric is increased, the hand feel is soft, and the by-products are environmentally friendly.

Description

Technical Field

[0001] This application relates to the field of polymer materials, specifically to a polysiloxane material, its preparation method, and its application. Background Technology

[0002] Resin deposition and covalent cross-linking are the known anti-wrinkle mechanisms. The former involves self-condensation during baking to form a network of water-insoluble macromolecular polymers that are deposited in the fiber and form hydrogen bonds with the fiber, hindering the relative slippage between fiber molecules and maintaining the stability of the fiber morphology, thereby achieving the purpose of anti-wrinkle. The latter involves forming covalent cross-links with the active groups of the fiber through its own functional groups, fixing the fiber and making it less prone to deformation.

[0003] Currently, there is a wide variety of anti-wrinkle finishing agents used on silk fabrics, with significant differences in their mechanisms of action, performance, and application limitations. Among them, N-hydroxymethylamide resin finishing agents, with compounds containing active hydroxymethyl groups as their core components, achieve anti-wrinkle effects by forming a network cross-linked structure with silk fibers. They are not only inexpensive to produce and have outstanding anti-wrinkle properties, but also possess good wash resistance and storage stability. However, their tendency to release harmful formaldehyde is a significant drawback. Dialdehyde finishing agents rely on the reaction of aldehyde groups with active groups such as hydroxyl, amino, phenolic hydroxyl, and carboxylic acid groups on silk fibers to form hemiacetal or amino alcohol structures, achieving cross-linking and anti-wrinkle effects. However, these finishing agents are relatively expensive and tend to cause yellowing of fabrics and reduce their tensile strength. Polycarboxylic acid finishing agents work by reacting carboxylic acid groups with the amino or hydroxyl groups of silk fibers to form ester or amide bonds. For example, citric acid anti-wrinkle agents are relatively inexpensive but easily cause yellowing of fabrics, while butanetetracarboxylic acid (BTCA) anti-wrinkle agents offer ideal anti-wrinkle effects but are expensive. Waterborne polyurethane (WPU) anti-wrinkle agents offer advantages such as safety, environmental friendliness, energy efficiency, and ease of use. They achieve wrinkle resistance by reacting the active isocyanate end groups with the active hydrogen groups on silk to form ester and amide bonds. Fabrics treated with WPU maintain good tensile strength and whiteness, with only a slight decrease in softness. Epoxy compound anti-wrinkle agents rely on cross-linking reactions between epoxy groups and the active hydrogen groups on silk to exert their anti-wrinkle effect. However, the improvement in wrinkle recovery after treatment is limited, and it can lead to a decrease in tensile strength and severe yellowing. Reactive silicone finishing agents primarily achieve wrinkle resistance by grafting reactive groups onto silicone molecules. These groups react with the active groups on the silk fabric to form chemical cross-links. Simultaneously, the inherent properties of silicone impart softness, drape, and resilience to the fabric, reducing stress concentration caused by chemical cross-linking and thus minimizing damage to fabric strength.

[0004] However, in silicone-modified polyurethane materials, the selection of protecting groups is a crucial step in achieving wrinkle resistance. Currently, commonly used protecting groups include alcohol-based blocking agents, phenol-based blocking agents, oxime-based blocking agents, amine-based blocking agents, imidazole-based blocking agents, bisulfite-based blocking agents, and other blocking agents containing active hydrides. However, these currently used protecting groups have significant drawbacks: the deblocking temperature is too high, leading to stringent environmental and equipment requirements; simultaneously, the deblocking process generates toxic and harmful substances, failing to meet environmental protection requirements. Therefore, the development of a silicone finishing agent with excellent wrinkle resistance without affecting the feel of silk fabrics is urgently needed. Summary of the Invention

[0005] The purpose of this application is to provide a comprehensive anti-wrinkle finishing agent for silk fabrics that has excellent anti-wrinkle properties while maintaining a smooth feel and being less prone to yellowing.

[0006] To achieve the above objectives, the technical solution adopted in this application is as follows: A polysiloxane material with the following general structural formula:

[0007] , where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

[0008] A method for preparing a polysiloxane material is provided, comprising the following preparation steps: S1: 5-norbornene-2-methanol is polymerized with an epoxide to obtain a first product; S2: the first product is reacted with a terminal hydrogen silicone oil to obtain a second product; S3: dimethyl biphenyl diisocyanate is reacted with the second product to obtain a third product, and vanillin is added to obtain the polysiloxane material.

[0009] The structural formula of the first product is , where R is 3≤x≤10, 2≤y≤8; the structural formula of the second product is , where R is , 6≤m≤20, 3≤x≤10, 2≤y≤8; the structural formula of the third product is , where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

[0010] As a preferred embodiment, the equivalent ratio of the terminal hydrogen silicone oil to the first product is 1:(2~3).

[0011] As another preferred option, the structure of the hydrogen-terminated silicone oil is as follows: Where 6≤m≤20, the number average molecular weight of the terminal hydrogen silicone oil is 500, 1000 or 1500.

[0012] As another preferred embodiment, the alkylene oxide is a mixture of ethylene oxide and propylene oxide.

[0013] As another preferred embodiment, the equivalent ratio of the second product to dimethylbiphenyl diisocyanate is 1:(1~3).

[0014] As another preferred embodiment, the equivalent ratio of the third product to the vanillin is 1:(2~3).

[0015] As another preferred embodiment, step S1 specifically involves: dissolving 5-norbornene-2-methanol in a solvent, adding a first catalyst, ethylene oxide, and propylene oxide, performing a polymerization reaction, and removing the solvent to obtain the first product; step S2 specifically involves: placing the terminal hydrogen silicone oil in a reaction vessel, adding the first product, heating to 35-45°C, adding a second catalyst, continuing to heat to 90-100°C, and maintaining the temperature for 2-6 hours to obtain the second product; step S3 specifically involves: adding dimethyl biphenyl diisocyanate to a solvent, adding the second product dropwise, heating to 30-50°C, reacting for a period of time, adding a third catalyst, continuing to heat to 65-85°C, maintaining the temperature for a period of time to obtain the third product, adding vanillin, maintaining the temperature for a period of time, removing the solvent, and obtaining the polysiloxane material.

[0016] As another preferred embodiment, the amount of the first catalyst is 2% to 6% of the total mass of the reactants in step S1, and the first catalyst is boron trifluoride diethyl ether; the amount of the second catalyst is 20 to 30 ppm, and the second catalyst is chloroplatinic acid; the amount of the third catalyst is 1% to 2% of the total mass of the reactants in step S3, and the third catalyst is dibutyltin dilaurate.

[0017] This application also provides a wrinkle-resistant finishing agent for silk fabrics, comprising the above-described polysiloxane material or the polysiloxane material prepared by any of the above-described preparation methods, an emulsifier, a solvent, and an initiator.

[0018] Compared with the prior art, the beneficial effects of this application are as follows:

[0019] (1) The polysiloxane material of this application contains vanillin, which can release isocyanate groups at a lower setting temperature and a higher deprotection rate, and then form a strong covalent bond with the active groups of silk fabric, thereby making the prepared anti-wrinkle finishing agent of silk fabric have a long-lasting and efficient anti-wrinkle effect.

[0020] (2) The raw materials for preparing polysiloxane in this application include 5-norbornene-2-polyether methanol. The norbornene structure drives the reaction activity. Its high ring strain and high electron density make the hydrosilylation reaction easier to occur and increase the rigidity of the product, making it difficult to fold. As a result, the fabric treated with the prepared anti-wrinkle finishing agent has a smooth feel and hydrophilicity.

[0021] (3) The polysiloxane material of this application introduces polyether silicone oil with double-terminated hydroxyl groups through hydrosilylation, which is beneficial to give the fabric better smoothness and avoids the influence of norbornene structure on softness.

[0022] (4) The polysiloxane material of this application, through reasonable structural design, reduces the introduction of active groups that are easily oxidized, thereby reducing the probability of material oxidation reaction and improving the yellowing problem of fabric;

[0023] (5) The anti-wrinkle finishing agent for silk fabrics of this application has excellent comprehensive performance, the by-products are non-toxic and harmless, the preparation method is simple and the yield is high, and it is suitable for large-scale production. Detailed Implementation

[0024] The present application will be further described below with reference to specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0025] The terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are intended to cover non-exclusive inclusion, for example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units that are explicitly listed, but may include other steps or units that are not explicitly listed or that are inherent to such process, method, product, or device.

[0026] This application provides a polysiloxane material with the following general structural formula:

[0027] , where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

[0028] The polysiloxane material of this application introduces vanillin groups, which can release isocyanate groups at a lower setting temperature and a higher deprotection rate, forming a strong covalent bond with the active groups of silk fabrics, thereby achieving a more durable and efficient anti-wrinkle effect. Moreover, the released byproduct vanillin is non-toxic, harmless, and environmentally friendly.

[0029] The polysiloxane material of this application introduces a norbornene structure, whose high ring strain and high electron density make it more prone to hydrosilylation reaction. At the same time, it increases the rigidity of the product, making it less prone to folding, and makes the finishing agent more stiff and smooth. The introduction of polyether into the structure increases the hydrophilicity of the product.

[0030] The polysiloxane material of this application, through structural design, is applied in the field of fabric treatment agents to give silk fabrics a long-lasting and highly effective anti-wrinkle effect, making them less prone to yellowing and giving them a smooth and comfortable feel. It is an excellent polymer material.

[0031] This application also provides a method for preparing a polysiloxane material, comprising the following preparation steps:

[0032] S1: 5-norbornene-2-methanol was polymerized with an epoxide to obtain the first product;

[0033] S2: The first product reacts with hydrogen-terminated silicone oil to obtain the second product;

[0034] S3: Dimethyl biphenyl diisocyanate and the second product are used to prepare the third product, and then vanillin is added to prepare the polysiloxane material of this application.

[0035] In some embodiments, the structural formula of the first product is: , where R is , 3≤x≤10, 2≤y≤8.

[0036] The structural formula of hydrogen-terminated silicone oil is: , where 6≤m≤20.

[0037] The structural formula of the second product is: , where R is , 6≤m≤20, 3≤x≤10, 2≤y≤8.

[0038] The structural formula of the third product is:

[0039] , where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

[0040] In some embodiments, the alkylene oxide is any one or a combination of ethylene oxide, propylene oxide, and 1,2-epoxybutane. In a preferred embodiment, the alkylene oxide is a mixture of ethylene oxide and propylene oxide.

[0041] In some embodiments, the reaction formula for polymerizing 5-norbornene-2-methanol, ethylene oxide, and propylene oxide to obtain the first product is:

[0042] , where R is , 3≤x≤10, 2≤y≤8.

[0043] In the preferred embodiment, the molar ratio of ethylene oxide to propylene oxide is 1:1.

[0044] In a more preferred embodiment, the x and y values ​​are equal, and the x and y values ​​can be 3, 5, or 7.

[0045] In some embodiments, the reaction formula between the first product and the hydrogen-terminated silicone oil is as follows:

[0046] , where R is , 6≤m≤20, 3≤x≤10, 2≤y≤8.

[0047] In some embodiments, the reaction formula for preparing the third product by reacting dimethylbiphenyl diisocyanate with the second product is as follows:

[0048] , where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

[0049] In some embodiments, the reaction formula for the reaction between the third product and vanillin is as follows:

[0050]

[0051] Where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

[0052] In some embodiments, step S1 specifically involves: dissolving 5-norbornene-2-methanol in a solvent, adding a first catalyst, ethylene oxide, and propylene oxide, and reacting to obtain a first product. The amount of the first catalyst is 2% to 6% of the total mass of the reactants, more preferably, the amount of the first catalyst is 4% of the total mass of the reactants.

[0053] In the preferred embodiment, the first catalyst is boron trifluoride diethyl ether.

[0054] In the preferred embodiment, the solvent in step S1 is 1,2-dichloroethane. The amount of solvent added can be calculated based on the solid content in the reaction system to ensure that the solid content of the reaction is approximately 70%.

[0055] The first product prepared in this application is 5-norbornene-2-polyether methanol, wherein the norbornene structure drives the reactivity, and its high ring strain and high electron density make it more susceptible to hydrosilylation reaction. At the same time, it increases the rigidity of the product, making it less prone to folding, thus making the subsequent finishing agent more rigid. Polyether is also introduced into the structure of the first product to increase the hydrophilicity of the product.

[0056] In some embodiments, step S2 specifically involves: placing the terminal hydrogen silicone oil in a reaction vessel, adding an excess of the first product, heating to 35-45 °C and adding a second catalyst, continuing to heat to 90-100 °C and maintaining the temperature for 2-6 hours to obtain the second product.

[0057] In the preferred embodiment, the number average molecular weight of the hydrogen-terminated silicone oil is 500, 1000 or 1500, and its solid content is 90%.

[0058] Preferably, the equivalent ratio of the terminal hydrogen silicone oil to the first product is 1:(2~3). In a more preferred embodiment, the equivalent ratio of the terminal hydrogen silicone oil to the first product is 4:9.

[0059] Preferably, the second catalyst is chloroplatinic acid, and the amount of the second catalyst is 20~30 ppm.

[0060] This application ingeniously introduces siloxane segments into polyether alcohols via hydrosilylation to prepare a second product, which is a polyether silicone oil with hydroxyl groups at both ends. This increases the smoothness of the product and can reduce the insufficient softness caused by the polyurethane structure and norbornene structure when used as a fabric finishing agent.

[0061] In some embodiments, step S3 specifically involves: adding dimethylbiphenyl diisocyanate to a solvent, adding the second product dropwise and heating to 30-50 °C for a period of time, adding a third catalyst and continuing to heat to 65-85 °C, maintaining the temperature for a period of time to obtain the third product, adding vanillin to the system, maintaining the temperature for a period of time to remove the solvent, and obtaining the polysiloxane material of this application.

[0062] The structural formula of dimethylbiphenyl diisocyanate is: Its molecular weight is 264.

[0063] In some embodiments, the equivalence ratio of the second product to dimethylbiphenyl diisocyanate is 1:(1~3). Preferably, the equivalence ratio of the second product to dimethylbiphenyl diisocyanate is 4:5.

[0064] The structural formula of vanillin is: Its molecular weight is 152.

[0065] In a preferred embodiment, the equivalence ratio of the third product to vanillin is 1:(2~3). In a more preferred embodiment, the equivalence ratio of the third product to vanillin is 2:5.

[0066] This application incorporates vanillin during the preparation process, resulting in a lower setting temperature for the finishing agent used on silk fabrics. Furthermore, the isocyanate groups protected by vanillin can efficiently remove the protective agent, allowing most of the isocyanates to regain their activity. The isocyanate groups form a strong covalent bond with the active groups of the silk fabric, thereby achieving a more durable and efficient anti-wrinkle effect. Moreover, the vanillin byproduct released is non-toxic, harmless, and environmentally friendly.

[0067] In some embodiments, the amount of the third catalyst is 1% to 2% of the total mass of the reactants; more preferably, the amount of the third catalyst is 1% of the total mass of the reactants. In some embodiments, the third catalyst is dibutyltin dilaurate.

[0068] In some embodiments, the solvent in step S3 is butanone, and the amount of solvent added can be calculated based on the solid content in the reaction system to ensure that the solid content of the reaction is about 70%.

[0069] In some embodiments, it is assumed that the efficiency of removing solvent or water by depressurization in each of the above steps is almost 99.9%, ensuring that the reactants are relatively pure substances except for the reaction process which is carried out under conditions of 70% solid content.

[0070] The polysiloxane material of this application contains a small number of easily oxidized active groups in its structure, which makes it less prone to yellowing after being applied to silk fabrics and maintains stable performance.

[0071] This application also provides a wrinkle-resistant finishing agent for silk fabrics, comprising the above-mentioned polysiloxane material, emulsifier, solvent and initiator.

[0072] The anti-wrinkle finishing agent for silk fabrics disclosed in this application utilizes polyether segments to enhance the hydrophilicity of silk fabrics, norbornene structures to improve the structural rigidity of silk fabrics, giving them a certain degree of stiffness, and siloxane segments to enhance their smoothness. The anti-wrinkle finishing agent contains few easily oxidized groups, thus reducing the likelihood of yellowing. The vanillin groups are suitable for protecting the isocyanate groups, resulting in a long-lasting and highly effective anti-wrinkle effect. Furthermore, the agent is non-toxic and harmless, making it a comprehensive, environmentally friendly product and an excellent polymer material.

[0073] Example 1

[0074] A polysiloxane material is prepared according to the following steps:

[0075] S1: Under an inert gas atmosphere, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 184 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 132 parts by mass of ethylene oxide and 174 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product. The molecular weight of the first product is approximately 430.

[0076] S2: Under inert gas protection, 968 parts by mass of the first product were added to the reaction vessel, followed by 556 parts by mass of hydrogen-terminated silicone oil with a molecular weight of 500. After the addition was complete, the temperature was raised to about 40 °C, chloroplatinic acid was added, and the temperature was raised to 95 °C. The reaction was maintained at this temperature for 4 h until the system became transparent. After filtration and rotary evaporation, the second product was obtained. The second product was a polyether silicone oil with a molecular weight of about 1468 and two hydroxyl groups.

[0077] S3: Add 330 parts by mass of dimethyl biphenyl diisocyanate and 758 parts by mass of butanone to the reaction vessel to adjust the viscosity. Add the second product dropwise and heat to about 40 °C. Add dibutyltin dilaurate and continue to heat to 75 °C. After reacting at this temperature for 3 h, the third product is obtained. Add 380 parts by mass of vanillin to the system and react at 70 °C for 3 h. Remove butanone under reduced pressure to obtain the polysiloxane material of Example 1.

[0078] Example 2

[0079] In step S1, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 272 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 220 parts by mass of ethylene oxide and 290 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product. The molecular weight of the first product was approximately 634.

[0080] In step S2, the molecular weight of the second product obtained is approximately 1926. In step S3, 967 parts by mass of butanone are added to adjust the viscosity. The other preparation steps are consistent with the preparation steps in Example 1, and the polysiloxane material of Example 2 is obtained.

[0081] Example 3

[0082] In step S1, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 359 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 308 parts by mass of ethylene oxide and 406 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product. The molecular weight of the first product was approximately 838.

[0083] In step S2, the molecular weight of the second product obtained is approximately 2386. In step S3, 1164 parts by mass of butanone are added to adjust the viscosity. The other preparation steps are consistent with the preparation steps in Example 1, and the polysiloxane material of Example 3 is obtained.

[0084] Example 4

[0085] In step S2, 1111 parts by mass of terminal hydrogen silicone oil with a molecular weight of 1000 were added dropwise to obtain a second product with a molecular weight of approximately 1968. In step S3, 985 parts by mass of methyl ethyl ketone (MEK) were added as solvent. The other preparation steps were consistent with those in Example 1 to obtain the polysiloxane material of Example 4.

[0086] Example 5

[0087] In step S1, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 272 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 220 parts by mass of ethylene oxide and 290 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product. The molecular weight of the first product was approximately 634.

[0088] In step S2, 1111 parts by mass of terminal hydrogen silicone oil with a molecular weight of 1000 are added dropwise to obtain a second product with a molecular weight of approximately 2426. In step S3, 1181 parts by mass of butanone are added to adjust the viscosity. The other preparation steps are consistent with the preparation steps in Example 1 to obtain the polysiloxane material of Example 5.

[0089] Example 6

[0090] In step S1, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 359 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 308 parts by mass of ethylene oxide and 406 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product, which has a molecular weight of approximately 838.

[0091] In step S2, 1111 parts by mass of terminal hydrogen silicone oil with a molecular weight of 1000 are added dropwise to obtain a second product with a molecular weight of approximately 2886. In step S3, 1378 parts by mass of butanone are added to adjust the viscosity. The other preparation steps are consistent with the preparation steps in Example 1 to obtain the polysiloxane material of Example 6.

[0092] Example 7

[0093] In step S2, 1667 parts by mass of terminal hydrogen silicone oil with a molecular weight of 1500 were added dropwise to obtain a second product with a molecular weight of approximately 2468. In step S3, 1199 parts by mass of butanone were added to adjust the viscosity. The other preparation steps were consistent with the preparation steps in Example 1 to obtain the polysiloxane material of Example 7.

[0094] Example 8

[0095] In step S1, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 272 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 220 parts by mass of ethylene oxide and 290 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product. The molecular weight of the first product was approximately 634.

[0096] In step S2, 1667 parts by mass of terminal hydrogen silicone oil with a molecular weight of 1500 were added dropwise to obtain a second product with a molecular weight of approximately 2926. In step S3, 1359 parts by mass of butanone were added to adjust the viscosity. The other preparation steps were consistent with the preparation steps in Example 1 to obtain the polysiloxane material of Example 8.

[0097] Example 9

[0098] In step S1, 124 parts by mass of 5-norbornene-2-methanol were dissolved in 359 parts by mass of 1,2-dichloroethane. Boron trifluoride diethyl ether was added as a catalyst, and 308 parts by mass of ethylene oxide and 406 parts by mass of propylene oxide were added dropwise. After polymerization at 0 °C for 4 hours, water was added to quench the polymerization. Water and 1,2-dichloroethane were removed by separation and vacuum to obtain the first product. The molecular weight of the first product was approximately 838.

[0099] In step S2, 1667 parts by mass of terminal hydrogen silicone oil with a molecular weight of 1500 were added dropwise to obtain a second product with a molecular weight of approximately 3386. In step S3, 1592 parts by mass of butanone were added to adjust the viscosity. The other preparation steps were consistent with the preparation steps in Example 1 to obtain the polysiloxane material of Example 9.

[0100] Comparative Example 1

[0101] Use commercially available glyoxal anti-wrinkle finishing agent.

[0102] Comparative Example 2

[0103] Use commercially available citric acid anti-wrinkle finishing agent.

[0104] Comparative Example 3

[0105] Use commercially available water-based polyurethane anti-wrinkle finishing agent.

[0106] Comparative Example 4

[0107] Vanillin was not added in step S3, and the other preparation steps were the same as those in Example 5 to obtain the material of Comparative Example 4.

[0108] Comparative Example 5

[0109] The second product (containing a polyether alcohol-5-norborneol polysiloxane backbone) with a molecular weight of approximately 2426 prepared in S1 and S2 of Example 5 was replaced with a bihydroxyl-terminated silicone oil of similar molecular weight and used in S3 of Example 5 to prepare Comparative Example 5. The specific reaction steps were as follows: 330 parts by mass of dimethyl biphenyl diisocyanate and 1181 parts by mass of butanone were added to the reaction vessel to adjust the viscosity. 2476 parts by mass of bihydroxyl-terminated silicone oil with a content of 98% and a molecular weight of approximately 2426 were added dropwise and the temperature was raised to about 40 °C. Dibutyltin dilaurate was added and the temperature was further raised to 75 °C. After reacting at this temperature for 3 h, 380 parts by mass of vanillin were added to the system and reacted at 70 °C for 3 h. The butanone was removed under reduced pressure to obtain the material of Comparative Example 5.

[0110] Emulsification process: 100 parts by weight of the polysiloxane material prepared in the above embodiments, 25 parts by weight of emulsifier 1350 / 1370, 250 parts by weight of water and 2.5 parts by weight of acetic acid are mechanically emulsified to obtain a transparent emulsion with a slight bluish tint, namely the polysiloxane finishing agent, with a polysiloxane content of about 25%.

[0111] Finishing process: The amount of polysiloxane finishing agent is 30 g / L. The finishing is carried out by two dips and two pads at room temperature with a padding rate of 80%. Then, it is pre-dried at 80 ℃ for 30 min and then baked at 130 ℃ for 3 min.

[0112] Performance evaluation test

[0113] 1. The wrinkling performance of fabrics was characterized by dry wrinkle recovery angle (DCRA) and wet wrinkle recovery angle (WCRA). The YG541B fully automatic fabric wrinkle elasticity tester was used to measure the wrinkle recovery angle of silk fabrics before and after finishing, referring to the standard GB / T 3819—1997 "Textiles - Determination of Crease Recovery - Recovery Angle Method". Five measurements were taken in each direction, and the average values ​​were added together. A blank sample was also tested for comparison.

[0114] 2. Retention rate of breaking strength of fabric: The breaking strength of silk fabric before and after finishing was determined by using a breaking strength tester in accordance with GB / T 3923.1—1997 "Textiles - Tensile properties of fabrics - Part 1: Determination of breaking strength and elongation at break - Strip method" and the retention rate of breaking strength of fabric was calculated.

[0115] 3. Whiteness test and evaluation: The whiteness of the blue light was measured using an intelligent whiteness meter in accordance with GB / T 17644-2008 "Test Method for Whiteness and Color of Textile Fibers". The test was performed 5 times and the average value was taken.

[0116] 4. Hand feel evaluation test: The overall hand feel is evaluated by touch, using a 1-5 point rating system, with 1 point being the worst and 5 points being the best. Ten people evaluate at the same time, and the average value is taken.

[0117] 5. Hydrophilicity evaluation test: According to the AATCC 79-2010 "Textiles Water Absorption" test standard, a video contact angle tensiometer is used to record the time required for the water droplet to disappear from the surface of a horizontally laid-out fabric when dropped from a certain height onto the fabric surface under static conditions. The shorter the water droplet disappearance time, the more hydrophilic the fabric. Five tests are performed and the average value is taken.

[0118] The performance test results of each embodiment and each comparative example are recorded in Table 1.

[0119] Table 1 Performance test results of finishing agents in each example and comparative example

[0120]

[0121] Analyzing the performance evaluation data of the silk fabrics in Table 1, the wrinkle recovery angle and breakage retention rate of each embodiment are higher than those of the original fabric and comparative examples 1, 2 and 3. Among them, Example 5 has the largest wrinkle recovery angle and the breakage retention rate is close to that of the original fabric, so it has the best wrinkle resistance.

[0122] The anti-wrinkle finishing agents prepared in the various embodiments of this application, after treating silk fabrics, have higher anti-wrinkle performance and lower yellowing degree compared with commercially available acetaldehyde anti-wrinkle finishing agents, citric acid anti-wrinkle finishing agents and water-based polyurethane anti-wrinkle finishing agents. The treated silk fabrics have improved anti-wrinkle effect, making the clothes more durable and beautiful.

[0123] The anti-wrinkle finishing agent of this application gives silk fabrics a better soft and smooth feel and hydrophilicity. The feel is better than commercially available finishing agent materials. Furthermore, the higher the polyether content in the polysiloxane material, the better the hydrophilicity and feel.

[0124] Analysis of the performance test results of Example 5 and Comparative Example 4 shows that the polysiloxane material protected by vanillin can achieve better anti-wrinkle effect and tensile strength retention rate, and the anti-yellowing effect is also improved to a certain extent.

[0125] Analyzing the performance test results of Example 5 and Comparative Example 5, this application introduces a 5-norborneol-2-polyether methanol structure into polysiloxane, which allows the prepared anti-wrinkle finishing agent to retain a good anti-wrinkle effect while further improving the hydrophilicity and hand feel of silk fabrics, thereby enhancing the user's wearing comfort.

[0126] In summary, the polysiloxane material prepared in this application is suitable for use in anti-wrinkle finishing agents for silk fabrics. The treated silk fabrics have better anti-wrinkle effect, lower yellowing performance, and better hand feel and hydrophilicity, making it a preferred solution for silk fabrics that pursue comprehensive performance.

[0127] The basic principles, main features, and advantages of this application have been described above. Those skilled in the art should understand that this application is not limited to the above embodiments. The embodiments and descriptions in the specification are merely the principles of this application. Various changes and modifications can be made to this application without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claims. The scope of protection claimed by this application is defined by the appended claims and their equivalents.

Claims

1. A polysiloxane material, characterized in that, The general structural formula is: Where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

2. The method for preparing the polysiloxane material as described in claim 1, characterized in that, The preparation steps include the following: S1: 5-norbornene-2-methanol was polymerized with an epoxide to obtain the first product; S2: The first product reacts with hydrogen-terminated silicone oil to obtain the second product; S3: Dimethyl biphenyl diisocyanate reacts with the second product to obtain a third product, and vanillin is added to obtain the polysiloxane material; The structural formula of the first product is , where R is 3≤x≤10, 2≤y≤8; The structural formula of the second product is , where R is , 6≤m≤20, 3≤x≤10, 2≤y≤8; The structural formula of the third product is as follows: , where R is , 6≤m≤20, 2≤n≤5, 3≤x≤10, 2≤y≤8.

3. The preparation method according to claim 2, characterized in that, The equivalent ratio of the terminal hydrogen silicone oil to the first product is 1:(2~3).

4. The preparation method according to claim 2, characterized in that, The structural formula of the hydrogen-terminated silicone oil is: Where 6≤m≤20, the number average molecular weight of the terminal hydrogen silicone oil is 500, 1000 or 1500.

5. The preparation method according to claim 2, characterized in that, The epoxide is a mixture of ethylene oxide and propylene oxide.

6. The preparation method according to claim 2, characterized in that, The equivalent ratio of the second product to dimethylbiphenyl diisocyanate is 1:(1~3).

7. The preparation method according to claim 2, characterized in that, The equivalent ratio of the third product to the vanillin is 1:(2~3).

8. The preparation method according to claim 5, characterized in that, The S1 step specifically involves: dissolving 5-norbornene-2-methanol in a solvent, adding the first catalyst, the ethylene oxide, and the propylene oxide, performing a polymerization reaction, and removing the solvent to obtain the first product; The S2 step specifically involves: placing the hydrogen-terminated silicone oil in a reaction vessel, adding the first product, heating to 35-45°C and adding the second catalyst, continuing to heat to 90-100°C and maintaining the temperature for 2-6 hours to obtain the second product; The S3 step is as follows: the dimethyl biphenyl diisocyanate is added to the solvent, the second product is added dropwise and the temperature is raised to 30~50 ℃ and reacted for a period of time, the third catalyst is added and the temperature is raised to 65~85 ℃, and the reaction is maintained for a period of time to obtain the third product. The vanillin is added, and the reaction is maintained for a period of time to remove the solvent to obtain the polysiloxane material.

9. The preparation method according to claim 8, characterized in that, The amount of the first catalyst is 2% to 6% of the total mass of the reactants in step S1, and the first catalyst is boron trifluoride diethyl ether; the amount of the second catalyst is 20 to 30 ppm, and the second catalyst is chloroplatinic acid; the amount of the third catalyst is 1% to 2% of the total mass of the reactants in step S3, and the third catalyst is dibutyltin dilaurate.

10. A wrinkle-resistant finishing agent for silk fabrics, characterized in that, It includes the polysiloxane material as described in claim 1 or the polysiloxane material prepared by any of the preparation methods described in claims 2 to 9, emulsifier, solvent and initiator.

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