Preparation method of multifunctional softening agent for fabric after-finishing

Abstract

The invention belongs to the technical field of textile auxiliaries, and particularly relates to a preparation method of a multifunctional softening agent, which comprises the following steps: S1, adding polyether epoxy silicone oil, amine and an organic solvent into a reaction kettle according to the metered amount, introducing dry nitrogen, uniformly stirring, heating to 70-135 DEG C, and reacting for 1-2 hours; after the reaction, adding amino silane with polyfunctional groups, and continuously reacting to obtain organic silicon crude oil; and S2, adding an emulsifier into the organic silicon crude oil obtained in the step S1 for emulsification to finally obtain the multifunctional softening agent. Cloth finished by the softening agent prepared by the preparation method provided by the invention has excellent flexibility, stiffness and smoothness and excellent fluffy and soft hand feeling.

Description

Technical Field

[0001] The invention belongs to the technical field of textile auxiliaries, and particularly relates to a method for preparing a multifunctional softener for fabric finishing. Background Art

[0002] Silicone softeners are widely used as fabric finishing auxiliaries for the softening and finishing of various textiles. They can impart excellent bulk, softness, and smoothness to textiles. They can also, through structural adjustment, impart special water-repellent or hydrophilic properties to fabrics. For clothing such as men's shirts, suits, and women's skirts, softness, comfort, and a crisp, stylish feel are generally desired, resulting in a comfortable, stylish, and upscale appearance. Chinese patents CN119265944A and CN111945433A disclose a softener for acrylic fiber finishing that imparts good bulk, softness, elasticity, and crispness. Chinese patent CN110791959A discloses a wax-print-like feel finishing agent for cotton reactive printed fabrics. Through the synergistic effect of its components, the finished fabric exhibits a crisp, bony feel, a flexible and elastic feel, a thick and fluffy texture, a smooth and smooth surface, a strong cotton texture, and bright colors, with a unique appearance and feel. However, this product has the disadvantage of large dosage and obvious impact on fabric strength. Therefore, it is urgent to develop a softener that is flexible, crisp, soft and comfortable for general fabric finishing. Summary of the Invention

[0003] The technical problem to be solved by the present invention is a method for preparing a multifunctional softener for fabric finishing, so that the fabric finished with the modified silicone emulsion produced by this technical solution has excellent flexibility and crispness and an excellent fluffy, soft and comfortable feel, and the product fabric has a wide applicability.

[0004] In order to solve the above technical problems, the present invention adopts the following technical solutions: A method for preparing a multifunctional softener comprises the following steps: S1: Add polyether epoxy silicone oil, amine and organic solvent in measured amounts into a reactor, introduce dry nitrogen, stir evenly and heat to 70-135°C. After the reaction, add multifunctional aminosilane and continue the reaction to obtain organic silicone crude oil; S2: adding an emulsifier to the organic silicon crude oil obtained in S1 and emulsifying the emulsified organic silicon crude oil to obtain a multifunctional softener.

[0005] Through the above technical solution, a ternary copolymer modified fiber softener with multiple reactive groups is obtained by polycondensation reaction of polyether epoxy silicone oil with amine and multifunctional aminosilane. The ternary copolymer modified fiber softener with multiple reactive groups has polyoxyethylene ether and / or polyoxypropylene ether structure and multifunctional structure of aminosilane embedded in the main chain of silicone oil. The polyoxyethylene ether structure can form a melt eutectic with the polyester structure at high temperature, thereby improving the bonding strength with polyester and the orientation degree on the fiber surface; polyoxypropylene ether can provide a rigid elastic structure, and the multifunctional structure of aminosilane can form a melt eutectic with the polyester structure at high temperature. The structure can better cross-link with the hydroxyl groups of cotton fabrics or the carboxyl groups of synthetic fibers, thereby greatly enhancing the bonding strength and cross-linking performance of the silicone emulsion; after adding multifunctional aminosilane, the amino group can undergo a condensation reaction with the epoxy group, and the amino group increases the formation of hydrogen bonds or covalent bonds with the hydroxyl groups of natural fibers such as cotton or the carboxyl groups of synthetic fibers; through multiple effects, the fluffiness, elasticity and activity of the fabric treated with the softener produced by the technical solution are enhanced, and when applied to cotton, polyester and their blended fibers, the fabric can have excellent activity, stiffness, and excellent fluffiness and softness.

[0006] Optionally, the amine is one or more of diamine, polyamine or small molecule amine.

[0007] Optionally, the diamine is a polyetheramine in the D series, ED series and T series; the polyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine; and the small molecule amine is ethylenediamine, hexamethylenediamine, tetramethylhexamethylenediamine.

[0008] Optionally, the molar ratio of the amine to the allyl polyether epoxy silicone oil is 0.7-1.8:1.

[0009] Optionally, the multifunctional aminosilane is one or more of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, bis-(3-trimethoxysilylpropyl)amine, and bis-(3-triethoxysilylpropyl)amine.

[0010] Optionally, the multifunctional aminosilane is aminopropyltriethoxysilane or bis-(3-triethoxysilylpropyl)amine.

[0011] Optionally, the molar ratio of the multifunctional aminosilane to the polyether epoxy silicone oil is 0.2-2.2:1.

[0012] Through the above technical solution, after adding multi-functional aminosilane, the amino group can undergo condensation reaction with the epoxy group. The amino group increases the formation of hydrogen bonds or covalent bonds with the hydroxyl group of natural fibers such as cotton or the carboxyl group of synthetic fibers, thereby increasing the fluffiness and flexibility of the fabric; the multi-reactive groups are hydrolyzed and condensed, and the cross-linking degree is increased, which can increase the stiffness and flexibility of the fabric.

[0013] Optionally, the emulsifier is one or more of fatty alcohol polyoxyethylene ether or isomeric alcohol polyoxyethylene ether.

[0014] Optionally, the emulsifier is compounded from one to four fatty alcohol polyoxyethylene ethers with different HLB values, and the HLB value of the fatty alcohol polyoxyethylene ether is 10-13, which is represented by the following general formula: RO-(CH2CH2O)nH, (R is C 10～18 hydrocarbon group, n=3-25).

[0015] Optionally, the preparation method of the polyether epoxy silicone oil is as follows: hydrogen-terminated silicone oil and allyl polyether epoxy and / or organic solvent are added to a reaction kettle, dry nitrogen is introduced, and the mixture is stirred evenly and then heated to 50-70°C. A catalyst solution is added and then the temperature is further raised to 75-115°C for reaction. After the reaction, a transparent polyether epoxy silicone oil is obtained. The reaction formula of the polyether epoxy silicone oil is as follows (m, p, and q are any numbers of 25≤m≤350, 5≤p≤45, and 0≤q≤25, respectively): .

[0016] Through the above technical scheme, the polyether epoxy silicone oil obtained by the preparation method of the polyether epoxy silicone oil in the present invention has no characteristic silicon-hydrogen absorption peak when detected by infrared detection, indicating that the silicon-hydrogen addition rate of the preparation method exceeds 98%, which can meet the requirements of the polyether epoxy silicone oil required for the preparation of the softener of the present invention, thereby maintaining the activity, crispness, fluffiness and softness of the fabric at a relatively excellent level.

[0017] Optionally, the molar ratio of the allyl polyether epoxy to the hydrogen-terminated silicone oil is 1.9-2.2:1.

[0018] Optionally, the molecular weight of the hydrogen-terminated silicone oil is 2000-25000, and the molecular weight of the allyl polyether epoxy is 300-2000.

[0019] Optionally, the catalyst is chloroplatinic acid or Castro's platinum, and the catalyst dosage is 6-20 ppm.

[0020] Optionally, the organic solvent is one or a combination of isopropyl alcohol, ethylene glycol monobutyl ether or butanol.

[0021] Optionally, the allyl polyether epoxy structure contains polyoxyethylene polyether and / or polyoxypropylene ether groups.

[0022] Optionally, the allyl polyether epoxy is selected from allyl polyether epoxy with a molecular weight of 600 or 800 containing polyoxyethylene polyether and polyoxypropylene ether.

[0023] Optionally, the reaction temperature of the preparation method of the polyether epoxy silicone oil is 75-95°C.

[0024] Optionally, the reaction time of the preparation method of the polyether epoxy silicone oil is 2-16 hours.

[0025] The preparation method of the present invention has the following beneficial effects: 1. The ternary copolymer modified softener with multiple reactive groups of the present invention has a polyoxyethylene ether and / or polyoxypropylene ether structure and a multifunctional structure of aminosilane embedded in the main chain, which can impart excellent flexibility and stiffness to cotton, polyester and their blended fibers, and has a unique style, making it particularly suitable for treating clothing that requires stiffness. 2. By adjusting the ratio of polyether epoxy silicone oil to amine and multifunctional aminosilane, the proportion of groups providing softness, elasticity, stiffness and activity in the final modified silicone oil can be adjusted, so that the finished fabric has excellent activity, stiffness, outstanding fluffiness and softness; 3. The preparation method of the softener of the present invention is simple, the raw materials are readily available, the overall production cycle is suitable, and it is easy to promote in industry. DETAILED DESCRIPTION

[0026] The present invention will be further described below through specific implementation methods, but the protection scope of the present invention is not limited thereto.

[0027] The feeding amounts of the following embodiments are all calculated by mass.

[0028] Preparation Example 1 Preparation of chloroplatinic acid isopropanol catalyst solution Dissolve chloroplatinic acid solid powder in an appropriate amount of isopropanol and shake evenly to obtain a chloroplatinic acid catalyst solution, which is then placed in a dark container and sealed and stored in a light-shielded manner.

[0029] Preparation Example 2 Preparation of polyether epoxy silicone oil

[0030] Preparation Example 2-1, a method for preparing polyether epoxy silicone oil: 100 parts of hydrogen-terminated silicone oil (molecular weight of 8000) and 21 parts of allyl polyether epoxy containing polyoxyethylene ether and polyoxypropylene ether groups (molecular weight of 800) were added into the reactor, and dry nitrogen was introduced to replace the oxygen in the reactor. After stirring evenly, the temperature was raised to 60°C, and 10ppm of chloroplatinic acid isopropanol catalyst solution was added. The temperature was then continued to be raised to 90°C for reaction. After the reaction was carried out for 8 hours, a transparent polyether epoxy silicone oil with a molecular weight of 9600 was obtained. No silicon-hydrogen characteristic absorption peak was detected by infrared detection, or no bubbles were generated by the bubble method.

[0031] Preparation Example 2-2, a method for preparing polyether epoxy silicone oil: 100 parts of hydrogen-terminated silicone oil (molecular weight of 10,000) and 12 parts of allyl polyether epoxy containing polyoxyethylene ether and polyoxypropylene ether groups (molecular weight of 600) were added into the reactor, and dry nitrogen was introduced to replace the oxygen in the reactor. After stirring evenly, the temperature was raised to 60°C, and 12 ppm of chloroplatinic acid isopropanol catalyst solution was added. The temperature was then continued to be raised to 85°C for reaction. After the reaction was carried out for 8 hours, a transparent polyether epoxy silicone oil with a molecular weight of 11,200 was obtained. No silicon-hydrogen characteristic absorption peak was detected by infrared detection, or no bubbles were generated by the bubble method.

[0032] Preparation Example 2-3, a method for preparing polyether epoxy silicone oil: Dissolve chloroplatinic acid solid powder in an appropriate amount of isopropanol and shake evenly to obtain a chloroplatinic acid catalyst solution, which is then placed in a dark container and sealed and protected from light. Add 100 parts of hydrogen-terminated silicone oil (molecular weight 8000), 13.13 parts of allyl polyether epoxy containing only polyoxyethylene ether groups (molecular weight 500), and 12.57 parts of ethylene glycol monobutyl ether to a reactor, stir evenly, then heat to 60°C. Add 12 ppm of the chloroplatinic acid isopropanol catalyst solution, and continue heating to 95°C for reaction. After 12 hours of reaction, a transparent polyether epoxy silicone oil with a molecular weight of 9000 is obtained. No characteristic silicon-hydrogen absorption peaks are detected by infrared spectroscopy or by bubble detection using the bubble method.

[0033] Preparation Example 3 Preparation of Ordinary Epoxy-Terminated Silicone Oil Dissolve chloroplatinic acid solid powder in an appropriate amount of isopropanol and shake evenly to obtain a chloroplatinic acid catalyst solution, which is then placed in a dark container and sealed and stored in a dark place. Add 100 parts of 8000 molecular weight end-hydrogen silicone oil and 3.71 parts of allyl glycidyl ether to a reactor, introduce dry nitrogen to replace the oxygen in the reactor, stir evenly, then heat to 60°C, add 12ppm of chloroplatinic acid isopropanol catalyst solution, and continue to heat to 90°C for reaction. After reacting for 12 hours, a transparent ordinary end-epoxy silicone oil with a molecular weight of approximately 8200 is obtained. No characteristic silicon-hydrogen absorption peak is detected by infrared detection or bubble detection by bubble method.

[0034] Example 1 A method for preparing a multifunctional softener for fabric finishing comprises the following steps: S1: 100 parts of the polyether epoxy silicone oil prepared in Preparation Example 2-1, 2.44 parts of triethylenetetramine, and 25.6 parts of isopropyl alcohol solvent were added to a reactor in measured amounts, and dry nitrogen was introduced to replace the oxygen in the reactor. After stirring evenly, the temperature was raised to 82°C and maintained at this temperature for 10 hours. 1.85 parts of aminopropyltriethoxysilane was added and the reaction was continued for 4 hours to obtain an active, stiff, and softening agent organic silicone crude oil with a solid content of about 80%. The appearance was a light yellow to brownish red transparent uniform solution; S2: Take 20 parts of the above-mentioned active and stiff softener silicone crude oil, 4 parts of isomeric tridecanol polyoxyethylene ether and 1.2 parts of glacial acetic acid and add them to an emulsifier, start emulsification mixing, and then slowly add 54.8 parts of deionized water for phase inversion emulsification to obtain an active and stiff softener silicone emulsion with a solid content of about 20%. The emulsion has an appearance of a transparent to translucent light yellow uniform solution.

[0035] Example 2 A method for preparing a multifunctional softener for fabric finishing comprises the following steps: S1: 100 parts of the polyether epoxy silicone oil prepared in Preparation Example 2-2, 3.39 parts of D230, and 25.8 parts of isopropyl alcohol solvent were added to a reactor in measured amounts, and dry nitrogen was introduced to replace the oxygen in the reactor. After stirring evenly, the temperature was raised to 80°C, and the temperature was maintained for 8 hours. Then, 1 part of aminopropyltriethoxysilane was added and the reaction was continued for 4 hours to obtain an active, stiff, and softening agent organic silicone crude oil with a solid content of about 80%. The appearance was a light yellow to brownish red transparent uniform solution, and the appearance of the emulsion was a transparent to translucent light yellow uniform solution; S2: Take 20 parts of the above-mentioned active and stiff softener silicone crude oil, 4 parts of fatty alcohol polyoxyethylene ether and 1.2 parts of glacial acetic acid and add them into an emulsifier, start emulsification mixing, and then slowly add 54.8 parts of deionized water for phase inversion emulsification to obtain an active and stiff softener silicone emulsion with a solid content of about 20%.

[0036] Example 3 A method for preparing a multifunctional softener for fabric finishing comprises the following steps: S1: 100 parts of the polyether epoxy silicone oil prepared in Preparation Example 2-3, 3.16 parts of tetraethylene pentamine, and 11.5 parts of ethylene glycol monobutyl ether solvent were added to a reaction kettle according to measured amounts, stirred evenly, and then heated to 95°C. After maintaining this temperature for 12 hours, 1.85 parts of aminopropyl triethoxysilane was added and the reaction was continued for 4 hours to obtain an active, stiff, and softening silicone crude oil with a solid content of about 80%. The appearance was a light yellow to brownish red transparent uniform solution; S2: Take 20 parts of the above-mentioned active and stiff softener silicone crude oil, 4 parts of a mixed emulsifier of isomeric tridecyl alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and 1.2 parts of glacial acetic acid and add them to an emulsifier, start emulsification mixing, and then slowly add 54.8 parts of deionized water for phase inversion emulsification to obtain an active and stiff softener silicone emulsion with a solid content of about 20%. The emulsion has an appearance of a transparent to translucent light yellow uniform solution.

[0037] Comparative Example 1 A method for preparing a softener comprises the following steps: S1: 100 parts of the conventional epoxy-terminated silicone oil prepared in Preparation Example 3, 4.6 parts of D230, and 69.7 parts of isopropyl alcohol solvent were added to a reactor in measured amounts. Dry nitrogen was introduced to replace the oxygen in the reactor. After stirring evenly, the temperature was raised to 82°C and maintained at this temperature for 12 hours to obtain a softening finishing agent organic silicone crude oil having a light yellow to brownish red transparent uniform solution. S2: 20 parts of the above-mentioned softening agent silicone crude oil, 4 parts of isomeric tridecyl alcohol polyoxyethylene ether and 1.2 parts of glacial acetic acid were added to an emulsifier, emulsification mixing was started, and then 54.8 parts of deionized water were slowly added for phase inversion emulsification to obtain a softening agent silicone emulsion with a solid content of approximately 16%. The emulsion has an appearance of a transparent to translucent light yellow uniform solution.

[0038] Comparative Example 2 A method for preparing a softener comprises the following steps: S1: 100 parts of the polyether epoxy silicone oil prepared in Preparation Example 2-3, 3.16 parts of tetraethylene pentamine, and 11.1 parts of ethylene glycol monobutyl ether solvent were added to a reaction kettle according to measured amounts, stirred evenly, and then heated to 95°C. This temperature was maintained for 12 hours to obtain a flexible and stiff softening agent organic silicone crude oil with a solid content of about 80%, which was a light yellow to brownish red transparent uniform solution; S2: Take 20 parts of the above-mentioned active and stiff softener silicone crude oil, 4 parts of a mixed emulsifier of isomeric tridecyl alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and 1.2 parts of glacial acetic acid and add them to an emulsifier, start emulsification mixing, and then slowly add 54.8 parts of deionized water for phase inversion emulsification to obtain an active and stiff softener silicone emulsion with a solid content of about 20%. The emulsion has an appearance of a transparent to translucent light yellow uniform solution.

[0039] Performance evaluation: The softeners prepared in Examples 1-3 and Comparative Examples 1-2 and two commercial softeners (T3030, 786) were applied to polyester knitted fabrics, nylon four-way stretch fabrics and cotton woven fabrics. The finishing process is as follows: liquid preparation → one dip and one roll → baking (170℃×90s) → moisture regain for 24h → evaluation.

[0040] The amount of the 20% solid content organosilicon emulsion obtained in Examples 1-3 and Comparative Example 2 was 6 g / L, and the amount of the 16% solid content organosilicon emulsion obtained in Comparative Example 1 was 7.5 g / L. The commercially available softener was also used at the same solid content, with a residual rate of 80%. The evaluation results are shown in Table 1 below: Application performance testing: ① Handfeel evaluation: The fabric is evaluated by hand touch on a scale of 1 to 5, with 1 being the worst and 5 being the best. Five people evaluate the fabric simultaneously, and the average is taken. Evaluation includes: flexibility, stiffness, fluffiness, and softness.

[0041] The test results are shown in Table 1 below: Table 1 Sensitivity Stiffness Fluffiness Softness Example 1 5 5 5 4-5 Example 2 5 5 5 4-5 Example 3 4-5 4-5 4-5 5 Comparative Example 1 1 1 1-2 4-5 Comparative Example 2 1-2 1-2 2-3 4-5 Commercially available softener (786) 2 1-2 1-2 4-5 Commercially available softener (T3030) 2-3 2-3 2-3 4-5 From the data of Examples 1-3, Comparative Examples 1-2 and commercially available softeners in Table 1, it can be seen that the flexibility, stiffness and fluffiness of the fabric treated with the softener prepared by the present invention are significantly improved compared with the two commercially available softeners and the softener obtained in Comparative Examples 1-2. At the same time, the softness of the fabric is not reduced compared with the fabric treated with the commercially available softener, and the softness is even better. The fabric is given the comprehensive properties of flexibility, stiffness and fluffiness, which shows that the softener of the present invention not only meets the requirements of the market, but also significantly improves the wearing performance of the fabric and the special style requirements of the fabric for flexibility and stiffness. The polyoxypropylene (PO) group in the polyether structure of the active and stiff softener of the present invention and the amino group of the aminosilane with multiple reactive groups form hydrogen bonds or covalent bonds with the hydroxyl groups of natural fibers such as cotton or the carboxyl groups of synthetic fibers, thereby increasing the fluffiness and stiffness of the fabric; the multi-reactive groups undergo hydrolysis and polycondensation, and the cross-linking degree is increased, which can increase the stiffness and stiffness of the fabric; the amino groups in the aminosilane with multiple reactive groups and the multi-reactive groups work together to enhance the stiffness and stiffness of the fabric.

[0042] The test results of Example 3 compared to Comparative Example 2 in the table above show that Example 3 of the present invention significantly improves the flexibility, stiffness, bulk, and softness compared to Comparative Example 2. This shows that after the addition of the multifunctional aminosilane, the amino groups can undergo a polycondensation reaction with the epoxy groups. The amino groups form hydrogen bonds or covalent bonds with the hydroxyl groups of natural fibers such as cotton or the carboxyl groups of synthetic fibers, thereby increasing the bulk and flexibility of the fabric. The multi-reactive groups undergo hydrolysis and polycondensation, and the increased degree of crosslinking can increase the stiffness, elasticity, and flexibility of the fabric.

[0043] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a multifunctional softener, characterized in that: The steps include: S1: Add polyether epoxy silicone oil, amine and organic solvent in measured amounts into a reactor, introduce dry nitrogen, stir evenly and heat to 70-135°C. After the reaction, add multifunctional aminosilane and continue the reaction to obtain organic silicone crude oil; S2: adding an emulsifier to the organic silicon crude oil obtained in S1 and emulsifying the emulsified organic silicon crude oil to obtain a multifunctional softener.

2. The method for preparing a multifunctional softener according to claim 1, wherein: The amine is one or more of diamine, polyamine or small molecule amine.

3. The method for preparing a multifunctional softener according to claim 1, characterized in that: The multifunctional aminosilane is one or more of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, bis-(3-trimethoxysilylpropyl)amine, and bis-(3-triethoxysilylpropyl)amine.

4. The method for preparing a multifunctional softener according to claim 3, wherein: The multifunctional aminosilane is aminopropyltriethoxysilane or bis-(3-triethoxysilylpropyl)amine.

5. The method for preparing a multifunctional softener according to claim 3, characterized in that: The molar ratio of the multifunctional aminosilane to the polyether epoxy silicone oil is 0.2-2.2:

1.

6. The method for preparing a multifunctional softener according to claim 1, characterized in that: The emulsifier is one or more of fatty alcohol polyoxyethylene ether or isomeric alcohol polyoxyethylene ether.

7. The method for preparing a multifunctional softener according to claim 1, characterized in that: The preparation method of the polyether epoxy silicone oil comprises the following steps: adding hydrogen-terminated silicone oil, allyl polyether epoxy and / or organic solvent into a reaction kettle, introducing dry nitrogen, stirring evenly, heating to 50-70° C., adding a catalyst solution, and then continuing to heat to 75-115° C. for reaction, to obtain transparent polyether epoxy silicone oil.

8. The method for preparing a multifunctional softener according to claim 7, characterized in that: The molar ratio of the allyl polyether epoxy to the hydrogen-terminated silicone oil is 1.9-2.2:

1.

9. The method for preparing a multifunctional softener according to claim 7, wherein: The molecular weight of the hydrogen-terminated silicone oil is 2000-25000, and the molecular weight of the allyl polyether epoxy is 300-2000.

10. The method for preparing a multifunctional softener according to claim 7, wherein: The catalyst is chloroplatinic acid or Castro platinum, and the catalyst dosage is 6-20 ppm.