Organic silicon softening finishing agent and preparation method thereof

Abstract

The invention provides an organic silicon softening finishing agent and a preparation method thereof, the finishing agent takes amino silicon oil as a matrix, the amino silicon oil and an epoxy monomer containing an ester group, a phenyl group or a polyether chain segment are subjected to an addition reaction under the protection of nitrogen, and a multifunctional modified organic silicon polymer containing the ester group, the phenyl group or the polyether chain segment is constructed; and mixing with an emulsifier to form the organic silicon softening finishing agent. When the finishing agent is used for finishing a polyester fabric, the finishing agent can strongly interact with ester groups or benzene rings on the surfaces of fibers, endows the fabric with lasting and excellent softness, smoothness and hydrophilicity, realizes the comprehensive hand feeling of'softness, smoothness and smoothness', and meets the increasingly improved requirement of high-end polyester textiles on the comprehensive quality. The invention has the advantages of simple preparation method, low cost, environmental protection, safety, adjustable structure and the like, is suitable for large-scale industrial application, and provides technical support for high-quality after-finishing of high-end polyester textiles.

Description

Technical Field

[0001] This invention relates to the field of textile finishing agents, specifically to an organosilicon softening agent and its preparation method. Background Technology

[0002] Polyethylene terephthalate (PET) fiber, commonly known as polyester, is currently the most produced and widely used synthetic fiber in the world. For a long time, polyester has held an absolute dominant position in the global chemical fiber market due to its excellent strength, abrasion resistance, dimensional stability, and easy washing and quick drying characteristics. Its market share has remained stable at over 80% for many years, making it an indispensable basic raw material for the textile industry.

[0003] However, polyester fibers inherently possess drawbacks such as poor moisture absorption, stiff and rough hand feel, and susceptibility to static electricity, severely impacting their wearing comfort. To enhance comfort and added value, softeners are typically used in finishing processes to impart a soft, smooth, and full hand feel to the fabric. Among numerous softeners, silicone softeners, especially various modified silicone oils, have become the preferred polyester softening agents due to their low surface tension, good film-forming properties, and safety and environmental friendliness. Fabrics treated with traditional amino-modified silicone oils are smooth, elastic, soft, comfortable to the touch, and have excellent wash resistance. However, when used on polyester fabrics, they are prone to yellowing under high-temperature baking or long-term storage conditions; furthermore, their strong hydrophobicity leads to poor moisture absorption and breathability, resulting in stuffy and uncomfortable wear, significantly reducing comfort. Therefore, there is an urgent need in this field to develop a novel, structurally controllable silicone softener that combines excellent softness with superior hydrophilicity and can firmly bond with polyester fibers, fully meeting the ever-increasing demands for comprehensive quality in modern high-end polyester textiles.

[0004] Patent CN106496569A discloses a method for preparing durable hydrophilic silicone oil. It involves reacting a side-chain-terminated amino silane with a single-terminated epoxy polyether under alkaline conditions to form a molecular structure containing hydroxyethyl amino branches. This dual-reactive-group combination enhances hydrophilicity, wash resistance, and stability. However, the flexibility of this hydroxyethyl amino branched molecular structure is limited, and the reaction process is complex and difficult to control, potentially leading to unstable product quality. Patent CN120682469A discloses a method for preparing modified amino silicone oil. It introduces polar groups from polyhydroxy and polyamide structures to form hydrogen bonds with other polar groups, producing end-group hydrogen-containing amino silicone oil. This oil is then hydrosilylated with a silane containing an olefin to generate modified amino silicone oil, improving its hydrophilicity and thus enhancing the wearing comfort of textiles. This design results in a high proportion of organosilicon segments, balancing softness and film-forming properties. However, its synthesis process is complex and involves numerous steps, leading to high production costs and low efficiency. Patent CN113501962A discloses a low-yellowing hydrophilic block polyether amino silicone oil and its preparation method. By introducing a quaternary ammonium salt structure to replace the original primary and secondary amine structure, and introducing long-chain alkyl groups into the main chain, the yellowing performance and hydrophilic performance are coordinated and improved. However, further improvements are needed in terms of fabric feel and moisture absorption. Summary of the Invention

[0005] The main objective of this invention is to provide an organosilicon softening agent and its preparation method, solving the problems of traditional amino silicone oil finishing agents in the prior art, such as limited functionality, poor hydrophilicity, greasy feel, easy yellowing, and weak bonding with polyester fibers. The organosilicon softening agent of this invention has a simple preparation process, readily available raw materials, low cost, and low energy consumption. Furthermore, the resulting product exhibits excellent softness, hydrophilicity, smoothness, and durable washability, meeting the high standards required for comprehensive performance in high-end polyester textiles.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: A method for preparing an organosilicon softening agent includes the following steps: (1) Dissolve amino silicone oil in a solvent, heat it up and add the reactive monomer, and stir to react; (2) After the reaction is complete, the solvent is removed by vacuum evaporation to obtain the modified organosilicon polymer; (3) The above-mentioned organosilicon polymer is mixed with an emulsifier, dispersed at high speed, and then diluted with water to obtain the organosilicon softening agent.

[0007] The synthesis of the above-mentioned modified organosilicon polymers was carried out under a nitrogen atmosphere to prevent amino oxidation or side reactions, and to ensure the structural regularity and batch stability of the products.

[0008] Furthermore, the amino silicone oil has an ammonia value (based on nitrogen content) of 0.2%-0.9%.

[0009] Furthermore, the solvent is at least one of isopropanol, toluene, and tetrahydrofuran.

[0010] Furthermore, the reaction temperature in step (1) is 30-120℃, and the reaction time is 0.5-8h.

[0011] Furthermore, the reaction temperature in step (1) is 50-90℃, and the reaction time is 2-6h.

[0012] Further, the reactive monomer is at least one of the following: glycidyl acrylate, glycidyl methacrylate, diglycidyl adipic acid, glycidyl acetate, phenyl glycidyl ether, N,N,N,N-tetracyclooxypropyl-4,4-diaminodiphenylmethane, polyethylene glycol glycidyl methacrylate, polyethylene glycol p-(glycidyloxy)benzoate, ethyl acetate 2-(2-(2-glycidyloxyethoxy)ethoxy)acetyl, bisphenol A diglycidyl ether, glycidyl p-hydroxybenzoate, glycidyl 4-(2-(glycidyloxy)ethoxy)carbonyl)benzoate, and diglycidyl terephthalate.

[0013] Furthermore, the molar ratio of amino groups (based on nitrogen atoms) and epoxy groups in the amino silicone oil and reactive monomer is 1:1-2.

[0014] Furthermore, the molar ratio of amino groups (based on nitrogen atoms) and epoxy groups in the amino silicone oil and reactive monomer is 1:1-1.1 to ensure sufficient reaction and avoid excessive crosslinking.

[0015] The second aspect of the present invention provides the aforementioned silicone softening agent, which is obtained by the preparation method of the aforementioned silicone softening agent.

[0016] Furthermore, the solid content of the organosilicon softening agent is 10-30%.

[0017] A third aspect of the present invention provides the application of the aforementioned silicone softening agent in the finishing of polyester fabrics.

[0018] Furthermore, the application includes: diluting a finishing agent with a solid content of 10-30% into a finishing solution of 10-15 g / L, treating polyester fabric with a one-dip-one-puff process (puffing rate of 70-80%), and baking at 150°C for 120 seconds to obtain a finished fabric with a soft, smooth feel and good hydrophilicity.

[0019] This invention utilizes the efficient reaction between epoxy groups and amino groups to precisely introduce functional groups such as ester groups or phenyl groups into the main chain of organosilicon, constructing a modified organosilicon material with controllable structure and multiple functions. During the finishing process of polyester fabrics, the ester groups or phenyl groups in the molecule can strongly interact with corresponding groups in the polyester fiber structure, achieving firm adsorption and even interfacial anchoring. This significantly improves the durability of the finishing effect, endowing the fabric with a lasting and excellent soft hand feel, significantly enhanced hydrophilicity, and a unique "soft, smooth, and refreshing" comprehensive tactile experience. It effectively overcomes the technical bottlenecks of traditional softeners, such as single function, poor hydrophilicity, and easy oil seepage or stickiness.

[0020] The beneficial effects of this invention are as follows: 1. This invention introduces epoxy monomers containing ester groups, phenyl or polyether structures into amino silicone oil molecules, and prepares multifunctional modified organosilicon polymers through efficient addition reactions with amino groups; the polymers can generate strong interactions with functional groups such as ester groups and benzene rings on the surface of polyester fibers, achieving strong adsorption and interfacial anchoring, and significantly improving the wash fastness and durability of the finishing effect.

[0021] 2. The modified organosilicon polymer molecular structure of the present invention has high tunability. According to the user's specific needs for properties such as softness, hydrophilicity or slipperiness, the product function can be precisely controlled by selecting different types of epoxy reactive monomers and adjusting the feeding ratio.

[0022] 3. The silicone softening agent of this invention, under conventional baking conditions, effectively bonds with the surface of polyester fibers, endowing the fabric with lasting and excellent softness, significantly improved hydrophilicity, and a unique "soft, smooth, and refreshing" overall hand feel. Experiments show that the treated polyester fabric achieves a hand feel grade of 4-5, reduces bending stiffness by more than 20%, significantly reduces the coefficient of dynamic friction, and shortens the water penetration time to 2.5-3.7s. Its performance is far superior to the blank sample and control sample, meeting the increasingly stringent requirements of high-end polyester textiles for multifunctional and high-quality finishing effects.

[0023] 4. The preparation method of this invention is simple and easy to operate; the raw materials used are all commercially available common chemicals, which are widely available and inexpensive. The reaction conditions are mild and energy consumption is low, making it easy to achieve large-scale production and with broad market application prospects. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention.

[0025] Example 1: Under a nitrogen atmosphere, 350g of amino silicone oil with an ammonia value (nitrogen content) of 0.4% was placed in a reaction flask containing 182g of isopropanol. After heating to 55℃, 14g of glycidyl methacrylate was added dropwise to the reaction flask, and the mixture was stirred for 7 hours. After the reaction was completed, the isopropanol was evaporated under reduced pressure to obtain a transparent viscous liquid, namely the organosilicon polymer. The organosilicon polymer was mixed with an emulsifier, dispersed by high-speed shearing, and then diluted with water to obtain an organosilicon softening agent with a solid content of 20%.

[0026] Example 2: Under a nitrogen atmosphere, 400g of amino silicone oil with an ammonia value (nitrogen content) of 0.6% was placed in a reaction flask containing 265g of isopropanol. After heating to 80℃, 18g of N,N,N,N-tetracyclooxypropyl-4,4-diaminodiphenylmethane was added dropwise to the reaction flask and stirred for 6h. After the reaction was completed, the isopropanol was evaporated under reduced pressure to obtain a transparent viscous liquid, i.e., an organosilicon polymer. The organosilicon polymer was mixed with an emulsifier, dispersed by high-speed shearing, and then diluted with water to obtain an organosilicon softening agent with a solid content of 20%.

[0027] Example 3: Under a nitrogen atmosphere, 300g of amino silicone oil with an ammonia value (nitrogen content) of 0.8% was placed in a reaction flask containing 247g of isopropanol. After heating to 85℃, 33g of bisphenol A diglycidyl ester was added dropwise to the reaction flask, and the mixture was stirred for 3 hours. After the reaction was completed, the isopropanol was evaporated under reduced pressure to obtain a transparent viscous liquid, namely the organosilicon polymer. The organosilicon polymer was mixed with an emulsifier, dispersed by high-speed shearing, and then diluted with water to obtain an organosilicon softening agent with a solid content of 20%.

[0028] Example 4: Under a nitrogen atmosphere, 500g of amino silicone oil with an ammonia value (nitrogen content) of 0.2% was placed in a reaction flask containing 430g of isopropanol. After heating to 75°C, 25g of polyethylene glycol glycidyl methacrylate was added dropwise to the reaction flask, and the mixture was stirred for 4 hours. After the reaction was completed, the isopropanol was evaporated under reduced pressure to obtain a transparent viscous liquid, namely the organosilicon polymer. The organosilicon polymer was mixed with an emulsifier, dispersed by high-speed shearing, and then diluted with water to obtain an organosilicon softening agent with a solid content of 20%.

[0029] Example 5: Under a nitrogen atmosphere, 300g of amino silicone oil with an ammonia value (nitrogen content) of 0.5% was placed in a reaction flask containing 220g of isopropanol. After heating to 90℃, 20g of phenyl glycidyl ether was added dropwise to the reaction flask, and the mixture was stirred for 3 hours. After the reaction was completed, the isopropanol was evaporated under reduced pressure to obtain a transparent viscous liquid, namely the organosilicon polymer. The organosilicon polymer was mixed with an emulsifier, dispersed by high-speed shearing, and then diluted with water to obtain an organosilicon softening agent with a solid content of 20%.

[0030] Example 6: Under a nitrogen atmosphere, 350g of amino silicone oil with an ammonia value (nitrogen content) of 0.7% was placed in a reaction flask containing 225g of isopropanol. After heating to 80℃, 25g of glycidyl acetate was added dropwise to the reaction flask, and the mixture was stirred for 3 hours. After the reaction was completed, the isopropanol was evaporated under reduced pressure to obtain a transparent viscous liquid, namely the organosilicon polymer. The organosilicon polymer was mixed with an emulsifier, dispersed by high-speed shearing, and then diluted with water to obtain an organosilicon softening agent with a solid content of 20%.

[0031] Comparative Example 1: The silicone softening agent was prepared using Example 1, except that glycidyl methacrylate was replaced with allyl glycidyl ether.

[0032] Comparative Example 2: The silicone softening agent was prepared using Example 1, except that the amount of glycidyl methacrylate used was 8.4g.

[0033] Comparative Example 3: The silicone softening agent was prepared using Example 1, except that the amount of glycidyl methacrylate used was 43g.

[0034] Comparative Example 4: The silicone softening agent was prepared using Example 1, except that the amount of isopropanol used was 68g.

[0035] Comparative Example 5: The silicone softening agent was prepared using Example 1, except that the amount of isopropanol used was 440g.

[0036] Performance testing: The silicone softening agents prepared in the above examples and comparative examples were diluted to a finishing solution of 10 g / L. Polyester fabrics were treated using a one-dip-one-puff method, and baked at 150°C for 120 seconds. After the fabric samples cooled, the hand feel was evaluated. The test method is as follows: (1) Hand feel level: The hand feel of the fabric is mainly evaluated based on its soft and smooth style. Ten people are invited to blind touch and score the fabric, and the hand feel is divided into 1 to 5 levels, with 5 being the best and 1 being the worst. Finally, the average score of the 10 people is combined.

[0037] (2) Bending stiffness: Tested using a YG821 fabric style tester. The lower the bending stiffness, the better the flexibility.

[0038] (3) Coefficient of kinetic friction: Tested using a YG821 fabric style tester. The smaller the coefficient of kinetic friction, the better the fabric smoothness.

[0039] (4) Hydrophilicity: Lay the fabric horizontally, and after the 1mL dropper absorbs water, drop 1 drop of water from about 10cm away from the fabric surface. Measure the time it takes for the water droplet to spread and completely penetrate the fabric surface. The shorter the time, the better the hydrophilicity.

[0040] The test results are shown in Table 1.

[0041] Table 1. Performance Evaluation of Organosilicon Softeners Obtained in Examples and Comparative Examples

[0042] As shown in Table 1, Examples 1-6 significantly improved the hand feel of polyester fabrics. Examples 1 and 3 achieved a hand feel grade of 5, exhibiting an excellent overall "soft, smooth, and refreshing" feel, far superior to the blank sample and the comparative example. This indicates that the present invention, by introducing reactive epoxy monomers, not only enhances the softness but also avoids the problems of oiliness and stickiness associated with traditional silicone oils, giving the fabric a dry and comfortable feel. The bending stiffness of Examples 1-6 was significantly lower than that of the blank sample and the comparative example, indicating a substantial improvement in fabric softness. The dynamic friction coefficient was generally reduced to between 5.08 and 6.53, with Examples 4-5 exhibiting particularly excellent smoothness. Furthermore, the water penetration time of Examples 1-6 was less than 3.72 seconds, with Example 4 requiring only 2.53 seconds, significantly better than the blank sample and Comparative Example 1. This demonstrates that the finishing agent of the present invention effectively improves the hydrophilicity of polyester fabrics, solving the technical problems of poor moisture absorption and wicking, and stuffiness caused by the strong hydrophobicity of traditional amino silicone oils.

[0043] Analysis of the examples and comparative examples shows that: Comparative Example 1 uses allyl glycidyl ether without ester or phenyl groups, which has low activity and cannot form a uniform and dense film. The softener treated with this material has poor compatibility with polyester fabric, resulting in a decrease in the smoothness and softness of the treated fabric. In Comparative Example 2, when the molar ratio of amino to epoxy groups increases, there is an excess of amino silicone oil, and some amino groups do not react, leading to the loss of functional groups and a decrease in the ability to bind with fibers, resulting in a decrease in the hydrophilicity of the treated fabric. In Comparative Example 3, when the molar ratio of amino to epoxy groups decreases, there is an excess of epoxy groups, leading to excessive cross-linking or gelation, resulting in excessively high system viscosity and difficulty in uniform dispersion. The hydrophilicity of the treated fabric increases, but its hand feel deteriorates. In Comparative Example 4, the amount of isopropanol is too small, resulting in incomplete reaction of the system and affecting the product quality. The smoothness and softness of the treated fabric decrease. In Comparative Example 5, the amount of isopropanol is too large, resulting in a decrease in the content of active substances in the system, a low reaction conversion rate, and affecting the film-forming performance. The smoothness and softness of the treated fabric decrease. The above results demonstrate that the present invention achieves performance optimization of organosilicon softening agents by selecting appropriate monomers, precise molar ratio control, and optimized solvent systems.

[0044] In summary, this invention constructs a novel multifunctional modified organosilicon softener by introducing reactive epoxy monomers containing ester groups, phenyl groups, or polyether structures into amino silicone oil. This achieves synergistic optimization of softness, smoothness, and hydrophilicity, and provides a long-lasting finishing effect with high wash fastness. It overcomes the problems of single function, greasy hand feel, and poor hydrophilicity in existing technologies, meeting the increasingly demanding requirements for comprehensive quality in high-end polyester textiles and possessing good prospects for industrial application.

[0045] The above embodiments are merely preferred technical solutions of the present invention and should not be considered as limitations on the present invention. The scope of protection of the present invention should be limited to the technical solutions described in the claims, including equivalent substitutions of the technical features described in the claims. That is, equivalent substitutions and improvements within this scope are also within the scope of protection of the present invention.

Claims

1. A method for preparing an organosilicon softening agent, characterized in that: Includes the following steps: (1) Dissolve amino silicone oil in a solvent, heat it up and add the reactive monomer, and stir to react; (2) After the reaction is complete, the solvent is removed by vacuum evaporation to obtain the modified organosilicon polymer; (3) The above-mentioned organosilicon polymer is mixed with an emulsifier, dispersed at high speed, and then diluted with water to obtain the organosilicon softening agent.

2. The method for preparing an organosilicon softening agent according to claim 1, characterized in that: The amino silicone oil has an ammonia value (based on nitrogen content) of 0.2%-0.9%.

3. The method for preparing an organosilicon softening agent according to claim 1, characterized in that: The solvent in step (1) is at least one of isopropanol, toluene, and tetrahydrofuran.

4. The method for preparing an organosilicon softening agent according to claim 1, characterized in that: The reaction temperature in step (1) is 30-120℃, and the reaction time is 0.5-8h.

5. The method for preparing an organosilicon softening agent according to claim 4, characterized in that: The reaction temperature in step (1) is 50-90℃ and the reaction time is 2-6h.

6. The method for preparing an organosilicon softening agent according to claim 1, characterized in that: The reactive monomer is at least one of the following: glycidyl acrylate, glycidyl methacrylate, diglycidyl adipic acid, glycidyl acetate, phenyl glycidyl ether, N,N,N,N-tetracyclooxypropyl-4,4-diaminodiphenylmethane, polyethylene glycol glycidyl methacrylate, polyethylene glycol p-(glycidyloxy)benzoate, ethyl acetate 2-(2-(2-glycidyloxyethoxy)ethoxy)acetyl, bisphenol A diglycidyl ether, glycidyl p-hydroxybenzoate, glycidyl 4-(2-(glycidyloxy)ethoxy)carbonyl)benzoate, and diglycidyl terephthalate.

7. The method for preparing an organosilicon softening agent according to claim 1, characterized in that: The molar ratio of the amino silicone oil to the amino (based on nitrogen atoms) and epoxy groups in the reactive monomer is 1:1-2.

8. The method for preparing an organosilicon softening agent according to claim 7, characterized in that: The molar ratio of the amino silicone oil to the amino (based on nitrogen atoms) and epoxy groups in the reactive monomer is 1:1-1.

1.

9. An organosilicon softening agent, characterized in that, It is obtained by the preparation method described in any one of claims 1 to 8.

10. The application of the silicone softening agent according to claim 9 in the finishing of polyester fabrics.

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