Amino silicone oil emulsion, method for preparing the same, and use thereof

Abstract

The present application relates to a kind of amino silicone oil emulsion and its preparation method and application, belong to silicone oil emulsion technical field.The present application provides a kind of amino silicone oil emulsion, its preparation method includes, amino silicone oil, cocamide propyl betaine, polyether modified silicone oil are mixed, obtain homogeneous oil phase, gradient is added deionized water, carry out double refinement and obtain homogeneous phase, 3-amino propyl trimethoxysilane and polyether modified polydimethylsiloxane are handled to obtain modified homogeneous phase, again join hydroxymethyl cellulose and porous nanometer silicon dioxide, after mixing, it is obtained.The present application is compounded by amino silicone oil, cocamide propyl betaine, polyether modified silicone oil, amino propyl trimethoxysilane, polyether modified polydimethylsiloxane and porous nanometer silicon dioxide, the stability of amino silicone oil is synergistically improved, and good flexibility and durability are given to fabric.

Description

Technical Field

[0001] This invention belongs to the field of silicone oil emulsion technology, and relates to an amino silicone oil emulsion, its preparation method and application. Background Technology

[0002] Amino silicone oil emulsions are stable emulsion systems formed through emulsification technology, with amino silicone oil as the main component. They are widely used in textiles and other fields. Conventional amino silicone oil emulsions mainly include three types: cationic, nonionic, and anionic. Although amino silicone oil emulsions have excellent performance, they still have limitations in practical applications. For example, cationic emulsions are easily affected by pH and may demulsify under alkaline conditions; nonionic emulsions, while having good stability, have relatively weaker softening effects; and anionic emulsions require high compatibility with other auxiliaries. Furthermore, traditional emulsions have relatively large particle sizes, resulting in insufficient penetration into the fiber and affecting the durability of the finishing effect. Summary of the Invention

[0003] The purpose of this invention is to provide an amino silicone oil emulsion, its preparation method, and its application. This invention improves the stability of amino silicone oil by compounding amino silicone oil, cocamidopropyl betaine, polyether-modified silicone oil, aminopropyltrimethoxysilane, polyether-modified polydimethylsiloxane, and porous nano-silica, thereby giving the fabric good flexibility and durability.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A method for preparing an amino silicone oil emulsion, the method comprising the following steps:

[0006] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0007] Step X2: Gradually add deionized water to the homogeneous oil phase to perform double refinement and obtain a homogeneous phase;

[0008] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0009] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0010] Further, in step X1, the mass ratio of amino silicone oil, cocamidopropyl betaine, and polyether modified silicone oil is 5.5-6.5:0.25-0.35:0.17-0.23; the mixing refers to stirring at 450-550 rpm for 8-12 minutes at 45°C.

[0011] Further, in step X2, the total mass ratio of deionized water to homogeneous oil phase used in the gradient addition of deionized water is 1:2.1-2.3; the gradient addition of deionized water refers to dividing the deionized water into 5 equal parts and adding it in 5 portions at 40°C, stirring at 7000-9000 rpm for 2-4 minutes after each addition, with a 2-minute interval between adjacent additions; the double refinement refers to first setting the pressure of the high-pressure microjet treatment to 80-120 MPa and the flow rate to 40-60 mL / min, performing the high-pressure microjet treatment twice, and then setting the ultrasonic frequency to 26-30 kHz and the ultrasonic frequency to 400-600 W, performing the ultrasonic treatment for 18-22 minutes.

[0012] Further, in step X3, the mass ratio of the homogeneous phase, 3-aminopropyltrimethoxysilane, and polyether-modified polydimethylsiloxane is 6.7-7.1:0.08-0.12:0.04-0.06; the mixing refers to stirring at 150-250 rpm for 25-35 min at 35°C; in step X4, the mass ratio of the modified homogeneous phase, sodium hydroxymethyl cellulose, and porous nano-silica is 7-7.1:0.04-0.06:0.028-0.032; the mixing refers to stirring at 80-120 rpm for 2-3 h at 40°C followed by filtration.

[0013] Further, the average particle size of the porous nano-silica in step X4 is 160-170 nm. The porous nano-silica refers to porous nano-silica microspheres modified with hydrolyzed silk fibroin. The preparation method of the porous nano-silica microspheres modified with hydrolyzed silk fibroin includes the following steps:

[0014] Step Y1: Mix tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, and stir at 400-600 rpm for 25-35 min at 40℃. Then add CaCl2 solution and stir at 300-500 rpm for 2-3 h at room temperature to obtain liposome-gel microspheres.

[0015] Step Y2: Liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol-water solution are mixed and stirred at 800-1000 rpm for 10-20 min. Tetraethyl orthosilicate and ammonia are added dropwise at a rate of 1-3 drops / s. After stirring at 25℃ for 6-8 h, the mixture is dispersed in hydrochloric acid-ethanol solution. The hexadecyltrimethylammonium bromide is removed by reflux at 60℃. After centrifugation and washing until neutral, gel microspheres with a porous nano-silica shell are obtained.

[0016] Step Y3: Gel microspheres with porous nano-silica shells are mixed with hydrolyzed silk protein solution and impregnated at 30℃ and -0.1MPa vacuum for 1.3-1.7h. After filtration, microspheres are obtained. The microspheres are mixed with 3-aminopropyltriethoxysilane-ethanol solution and stirred at 40-80rpm at 50℃ for 3.5-4.5h. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0017] Further, in step Y1, the mass ratio of tea polyphenol liposomes, hydrolyzed silk protein solution, sodium alginate solution, and CaCl2 solution is 1:1.9-2.1:1.1-1.2:0.6-0.8; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:18.8-19.2; the sodium alginate solution is obtained by compounding sodium alginate and deionized water at a mass ratio of 1:42-46; and the mass of CaCl2 in the CaCl2 solution is 0.45-0.55 wt%.

[0018] Furthermore, the method for preparing tea polyphenol liposomes in step Y1 includes the following steps:

[0019] Step Z1: Stir soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved. Inject PBS buffer at a rate of 0.5-1.5 mL / min using a syringe pump. Set the sonication frequency to 30-50 kHz and the sonication frequency to 100-200 W for 10-30 min. Centrifuge and filter out the lower layer of free tea polyphenols to obtain tea polyphenol liposomes.

[0020] In step Z1, the mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer is 1:5.5-6.5:2.8-3.2:0.3-0.4:1.5-2.1; the PBS buffer needs to be adjusted to pH 7.2-7.6 and preheated to 60°C.

[0021] Further, in step Y2, the mass ratio of liposome-gel microspheres, hexadecyltrimethylammonium bromide, ethanol aqueous solution, tetraethyl orthosilicate, and ammonia is 1:0.14-0.16:20.7-20.9:0.6-0.8:0.12-0.16; the mass of ethanol in the ethanol aqueous solution is 18-22 wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1M HCl.

[0022] Further, in step Y3, the mass ratio of the gel microspheres with porous nano-silica shell to the hydrolyzed silk protein solution is 1:18-22; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:15-17; the mass ratio of the microspheres to the 3-aminopropyltriethoxysilane-ethanol solution is 1:5-10; and the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 2-3 wt%.

[0023] Furthermore, the amino silicone oil emulsion is applied to textile finishing.

[0024] The beneficial effects of this invention are:

[0025] (1) In the preparation process of this invention, amino silicone oil is the main component, which gives the fabric excellent softness and durability. Cocamidopropyl betaine promotes the dispersion of the oil-water phase by reducing the surface tension, and polyether-modified silicone oil enhances the interfacial film strength, forming a homogeneous and delicate emulsion. On this basis, gradient water addition treatment and double refining treatment are carried out, which, together with cocamidopropyl betaine and polyether-modified silicone oil, effectively avoids the emulsion from separating or becoming uneven, and further improves the stability of the emulsion. Then, aminopropyltrimethoxysilane is used to improve the bonding force between the emulsion and the surface of the textile, enhancing wash resistance and durability. Polyether-modified polydimethylsiloxane provides good softness, enhancing the comfort and durability of the fabric. On this basis, sodium hydroxymethyl cellulose is introduced to further improve the softness and hand feel of the plant, while porous nano silica is introduced to provide long-lasting softness and durability to the fabric. The components work together to give the fabric good softness and durability.

[0026] (2) In the preparation process, this application introduces porous nano-silica microspheres modified with hydrolyzed silk protein. The surface of the microspheres is treated with silane. The polarity of the amino group in 3-aminopropyltriethoxysilane can improve its dispersibility in amino silicone oil emulsion. It can also interact with the hydroxyl groups in the clothing fibers after subsequent treatment, thereby improving its adhesion to the fiber surface. When finishing the clothes, the hydrolyzed silk protein film on the outer surface of the microspheres is adsorbed onto the fibers through hydrogen bonds, providing immediate softness. After multiple washes, in an alkaline environment, i.e. under the treatment of laundry detergent, the pore size expands after the sodium alginate swells, and the hydrolyzed silk protein and tea polyphenol liposomes encapsulated inside are slowly released. As the number of washes gradually increases, the porous nano-silica shell breaks, and the hydrolyzed silk protein and tea polyphenol liposomes are completely released. In this way, the hydrolyzed silk protein compensates for the softness lost during washing, while the tea polyphenol nano-liposomes provide antioxidant assistance and work synergistically with the hydrolyzed silk protein to improve the yellowing resistance of the clothes. Detailed Implementation

[0027] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0028] In all embodiments and comparative examples of this invention, the amino silicone oil, cocamidopropyl betaine, and hexadecyltrimethylammonium bromide were purchased directly from the market from Greenlink (Jining) Chemical Technology Co., Ltd.; the polyether-modified silicone oil was purchased directly from the market from Zhuhai Xiande New Material Technology Co., Ltd.; the 3-aminopropyltrimethoxysilane was purchased directly from the market from Wuhan Smike Biotechnology Co., Ltd.; the polyether-modified polydimethylsiloxane and sodium hydroxymethyl cellulose were purchased directly from the market from Hubei Maidehao Biotechnology Co., Ltd.; PB S buffer solution was purchased directly from the market from Sigma-Aldrich (Shanghai) Trading Co., Ltd.; soybean lecithin, cholesterol, tea polyphenols, hydrolyzed silk protein, sodium alginate, and CaCl2 were all purchased directly from the market from Wuhan Jiangxin Biotechnology Co., Ltd.; tetraethyl orthosilicate was purchased directly from the market from Shandong Yuanjin New Materials Co., Ltd.; ammonia was purchased directly from the market from Guangdong Qiming Chemical Technology Co., Ltd.; and 3-aminopropyltriethoxysilane was purchased directly from the market from Jinan Shanzheng Trading Co., Ltd.

[0029] Example 1

[0030] A method for preparing an amino silicone oil emulsion, the preparation method of this embodiment includes the following steps:

[0031] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0032] Step X2: Gradually add deionized water to the homogeneous oil phase to perform double refinement and obtain a homogeneous phase;

[0033] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0034] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0035] In this embodiment, the mass ratio of amino silicone oil, cocamidopropyl betaine, and polyether modified silicone oil in step X1 is 5.5:0.25:0.17; mixing refers to stirring at 450 rpm for 8 minutes at 45°C.

[0036] In step X2 of this embodiment, the total mass ratio of deionized water to homogeneous oil phase used in the gradient addition of deionized water is 1:2.1. Gradient addition of deionized water means that the deionized water is divided into 5 equal parts and added in 5 portions at 40°C. After each addition of water, the mixture is stirred at 7000 rpm for 4 minutes, and there is a 2-minute interval between two adjacent water additions. Double refinement means that the high-pressure microjet treatment is first set to a pressure of 80 MPa and a flow rate of 60 mL / min, and the high-pressure microjet treatment is performed twice. Then, the ultrasonic frequency is set to 26 kHz and the ultrasonic frequency is 400 W, and the ultrasonic treatment is performed for 22 minutes.

[0037] In this embodiment, the mass ratio of homogeneous phase, 3-aminopropyltrimethoxysilane, and polyether-modified polydimethylsiloxane in step X3 is 6.7:0.08:0.04; mixing refers to stirring at 150 rpm for 35 min at 35°C. In step X4, the mass ratio of modified homogeneous phase, sodium hydroxymethyl cellulose, and porous nano-silica is 7:0.04:0.028; mixing refers to stirring at 80 rpm for 3 h at 40°C followed by filtration.

[0038] In this embodiment, the average particle size of the porous nano-silica in step X4 is 160 nm. The porous nano-silica refers to porous nano-silica microspheres modified with hydrolyzed silk protein. The preparation method of the porous nano-silica microspheres modified with hydrolyzed silk protein includes the following steps:

[0039] Step Y1: Mix tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stir at 400 rpm for 35 min at 40℃, add CaCl2 solution, and stir at 300 rpm for 3 h at room temperature to obtain liposome-gel microspheres.

[0040] Step Y2: Liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 800 rpm for 20 min. Tetraethyl orthosilicate and ammonia are added dropwise at a rate of 1 drop / s. After stirring at 25 °C for 6 h, the mixture is dispersed in hydrochloric acid-ethanol solution. The hexadecyltrimethylammonium bromide is removed by reflux at 60 °C. The mixture is then centrifuged and washed until neutral to obtain gel microspheres with a porous nano silica shell.

[0041] Step Y3: Gel microspheres with porous nano-silica shells are mixed with hydrolyzed silk protein solution and impregnated at 30℃ and -0.1MPa vacuum for 1.3h. After filtration, microspheres are obtained. The microspheres are mixed with 3-aminopropyltriethoxysilane-ethanol solution and stirred at 40rpm at 50℃ for 4.5h. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0042] In step Y1 of this embodiment, the mass ratio of tea polyphenol liposomes, hydrolyzed silk protein solution, sodium alginate solution, and CaCl2 solution is 1:1.9:1.1:0.6; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:18.8; the sodium alginate solution is obtained by compounding sodium alginate and deionized water at a mass ratio of 1:42; and the mass of CaCl2 in the CaCl2 solution is 0.45 wt%.

[0043] The preparation method of tea polyphenol liposomes in step Y1 of this embodiment includes the following steps:

[0044] Step Z1: Stir soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved. Inject PBS buffer at a rate of 0.5 mL / min using a syringe pump. Set the sonication frequency to 30 kHz and 100 W and sonicate for 30 min. Centrifuge and filter out the lower layer of free tea polyphenols to obtain tea polyphenol liposomes.

[0045] In step Z1, the mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer is 1:5.5:2.8:0.3:1.5; the PBS buffer needs to be adjusted to pH 7.2 and preheated to 60°C.

[0046] In step Y2 of this embodiment, the mass ratio of liposome-gel microspheres, hexadecyltrimethylammonium bromide, ethanol aqueous solution, tetraethyl orthosilicate, and ammonia is 1:0.14:20.7:0.6:0.12; the mass of ethanol in the ethanol aqueous solution is 18wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1M HCl.

[0047] In step Y3 of this embodiment, the mass ratio of gel microspheres with porous nano-silica shells to hydrolyzed silk protein solution is 1:18; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:15; the mass ratio of microspheres to 3-aminopropyltriethoxysilane-ethanol solution is 1:5; the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 2wt%.

[0048] The amino silicone oil emulsion in this embodiment is applied to textile finishing.

[0049] Example 2

[0050] A method for preparing an amino silicone oil emulsion, the preparation method of this embodiment includes the following steps:

[0051] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0052] Step X2: Gradually add deionized water to the homogeneous oil phase to perform double refinement and obtain a homogeneous phase;

[0053] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0054] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0055] In this embodiment, the mass ratio of amino silicone oil, cocamidopropyl betaine, and polyether modified silicone oil in step X1 is 6.5:0.35:0.23; mixing refers to stirring at 550 rpm for 8 minutes at 45°C.

[0056] In step X2 of this embodiment, the total mass ratio of deionized water to homogeneous oil phase used in the gradient addition of deionized water is 1:2.3. Gradient addition of deionized water means that the deionized water is divided into 5 equal parts and added in 5 portions at 40°C. After each addition of water, the mixture is stirred at 9000 rpm for 2 minutes, and there is a 2-minute interval between two adjacent water additions. Double refinement means that the high-pressure microjet treatment is first set to a pressure of 120 MPa and a flow rate of 40 mL / min, and the high-pressure microjet treatment is performed twice. Then, the ultrasonic frequency is set to 30 kHz and the ultrasonic frequency is 600 W, and the ultrasonic treatment is performed for 18 minutes.

[0057] In this embodiment, the mass ratio of homogeneous phase, 3-aminopropyltrimethoxysilane, and polyether-modified polydimethylsiloxane in step X3 is 7.1:0.12:0.06; mixing refers to stirring at 250 rpm for 25 min at 35°C. In step X4, the mass ratio of modified homogeneous phase, sodium hydroxymethyl cellulose, and porous nano-silica is 7.1:0.06:0.032; mixing refers to stirring at 120 rpm for 2 h at 40°C followed by filtration.

[0058] In this embodiment, the average particle size of the porous nano-silica in step X4 is 170 nm. The porous nano-silica refers to porous nano-silica microspheres modified with hydrolyzed silk protein. The preparation method of the porous nano-silica microspheres modified with hydrolyzed silk protein includes the following steps:

[0059] Step Y1: Mix tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stir at 600 rpm for 25 min at 40℃, add CaCl2 solution, and stir at 500 rpm for 2 h at room temperature to obtain liposome-gel microspheres.

[0060] Step Y2: Liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 1000 rpm for 10 min. Tetraethyl orthosilicate and ammonia are added dropwise at a rate of 3 drops / s. After stirring at 25℃ for 8 h, the mixture is dispersed in hydrochloric acid-ethanol solution. The hexadecyltrimethylammonium bromide is removed by reflux at 60℃. After centrifugation and washing until neutral, gel microspheres with a porous nano silica shell are obtained.

[0061] Step Y3: Gel microspheres with porous nano-silica shells are mixed with hydrolyzed silk protein solution and impregnated at 30℃ and -0.1MPa vacuum for 1.7h. After filtration, microspheres are obtained. The microspheres are mixed with 3-aminopropyltriethoxysilane-ethanol solution and stirred at 80rpm at 50℃ for 3.5h. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0062] In this embodiment, the mass ratio of tea polyphenol liposomes, hydrolyzed silk protein solution, sodium alginate solution, and CaCl2 solution in step Y1 is 1:2.1:1.2:0.8; the hydrolyzed silk protein solution is prepared by mixing hydrolyzed silk protein powder and deionized water at a mass ratio of 1:19.2; the sodium alginate solution is prepared by mixing sodium alginate and deionized water at a mass ratio of 1:46; and the mass of CaCl2 in the CaCl2 solution is 0.55 wt%.

[0063] The preparation method of tea polyphenol liposomes in step Y1 of this embodiment includes the following steps:

[0064] Step Z1: Stir soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved. Inject PBS buffer at a rate of 1.5 mL / min using a syringe pump. Set the sonication frequency to 50 kHz and 200 W and sonicate for 10 min. Centrifuge and filter out the lower layer of free tea polyphenols to obtain tea polyphenol liposomes.

[0065] In step Z1, the mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer is 1:6.5:3.2:0.4:2.1; the PBS buffer needs to be adjusted to pH 7.6 and preheated to 60°C.

[0066] In step Y2 of this embodiment, the mass ratio of liposome-gel microspheres, hexadecyltrimethylammonium bromide, ethanol aqueous solution, tetraethyl orthosilicate, and ammonia is 1:0.16:20.9:0.8:0.16; the mass of ethanol in the ethanol aqueous solution is 22wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1M HCl.

[0067] In step Y3 of this embodiment, the mass ratio of the gel microspheres with porous nano-silica shell to the hydrolyzed silk protein solution is 1:22; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:17; the mass ratio of the microspheres to the 3-aminopropyltriethoxysilane-ethanol solution is 1:10; and the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 3wt%.

[0068] The amino silicone oil emulsion in this embodiment is applied to textile finishing.

[0069] Example 3

[0070] A method for preparing an amino silicone oil emulsion, the preparation method of this embodiment includes the following steps:

[0071] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0072] Step X2: Gradually add deionized water to the homogeneous oil phase to perform double refinement and obtain a homogeneous phase;

[0073] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0074] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0075] In this embodiment, the mass ratio of amino silicone oil, cocamidopropyl betaine, and polyether modified silicone oil in step X1 is 6:0.3:0.2; mixing refers to stirring at 500 rpm for 10 minutes at 45°C.

[0076] In step X2 of this embodiment, the total mass ratio of deionized water to homogeneous oil phase used in the gradient addition of deionized water is 1:2.2. Gradient addition of deionized water means that the deionized water is divided into 5 equal parts and added in 5 portions at 40°C. After each addition of water, the mixture is stirred at 8000 rpm for 3 minutes, and there is a 2-minute interval between two adjacent water additions. Double refinement means that the high-pressure microjet treatment is first set to a pressure of 100 MPa and a flow rate of 50 mL / min, and the high-pressure microjet treatment is performed twice. Then, the ultrasonic frequency is set to 28 kHz and the ultrasonic frequency is 500 W, and the ultrasonic treatment is performed for 20 minutes.

[0077] In this embodiment, the mass ratio of homogeneous phase, 3-aminopropyltrimethoxysilane, and polyether-modified polydimethylsiloxane in step X3 is 6.9:0.1:0.05; mixing refers to stirring at 200 rpm for 30 min at 35°C. In step X4, the mass ratio of modified homogeneous phase, sodium hydroxymethyl cellulose, and porous nano-silica is 7.05:0.05:0.03; mixing refers to stirring at 100 rpm for 2.5 h at 40°C followed by filtration.

[0078] In this embodiment, the average particle size of the porous nano-silica in step X4 is 165 nm. The porous nano-silica refers to porous nano-silica microspheres modified with hydrolyzed silk protein. The preparation method of the porous nano-silica microspheres modified with hydrolyzed silk protein includes the following steps:

[0079] Step Y1: Mix tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stir at 500 rpm for 30 min at 40℃, add CaCl2 solution, and stir at 400 rpm for 2.5 h at room temperature to obtain liposome-gel microspheres.

[0080] Step Y2: Liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 900 rpm for 15 min. Tetraethyl orthosilicate and ammonia are added dropwise at a rate of 2 drops / s. After stirring at 25℃ for 7 h, the mixture is dispersed in hydrochloric acid-ethanol solution. Hexadecyltrimethylammonium bromide is removed by reflux at 60℃. After centrifugation and washing until neutral, gel microspheres with porous nano silica shells are obtained.

[0081] Step Y3: Gel microspheres with porous nano-silica shells are mixed with hydrolyzed silk protein solution and impregnated at 30℃ and -0.1MPa vacuum for 1.5h. After filtration, microspheres are obtained. The microspheres are mixed with 3-aminopropyltriethoxysilane-ethanol solution and stirred at 60rpm at 50℃ for 4h. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0082] In this embodiment, the mass ratio of tea polyphenol liposomes, hydrolyzed silk protein solution, sodium alginate solution, and CaCl2 solution in step Y1 is 1:2:1.15:0.7; the hydrolyzed silk protein solution is obtained by mixing hydrolyzed silk protein powder and deionized water at a mass ratio of 1:19; the sodium alginate solution is obtained by mixing sodium alginate and deionized water at a mass ratio of 1:44; and the mass of CaCl2 in the CaCl2 solution is 0.5 wt%.

[0083] The preparation method of tea polyphenol liposomes in step Y1 of this embodiment includes the following steps:

[0084] Step Z1: Stir soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved. Inject PBS buffer at a rate of 1 mL / min using a syringe pump. Set the sonication frequency to 40 kHz and 150 W and sonicate for 20 min. Centrifuge and filter out the lower layer of free tea polyphenols to obtain tea polyphenol liposomes.

[0085] In step Z1, the mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer is 1:6:3:0.35:1.8; the PBS buffer needs to be adjusted to pH 7.4 and preheated to 60°C.

[0086] In step Y2 of this embodiment, the mass ratio of liposome-gel microspheres, hexadecyltrimethylammonium bromide, ethanol aqueous solution, tetraethyl orthosilicate, and ammonia is 1:0.15:20.8:0.7:0.14; the mass of ethanol in the ethanol aqueous solution is 20wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1M HCl.

[0087] In step Y3 of this embodiment, the mass ratio of gel microspheres with porous nano-silica shells to hydrolyzed silk protein solution is 1:20; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:16; the mass ratio of microspheres to 3-aminopropyltriethoxysilane-ethanol solution is 1:7.5; the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 2.5 wt%.

[0088] The amino silicone oil emulsion in this embodiment is applied to textile finishing.

[0089] Example 4

[0090] Based on Example 3, cocamidopropyl betaine in step X1 was removed and replaced with an equal weight of polyether-modified silicone oil, while other conditions remained the same as in Example 3.

[0091] Example 5

[0092] Based on Example 3, the polyether-modified silicone oil in step X1 was removed and replaced with an equal weight of cocamidopropyl betaine, while other conditions remained the same as in Example 3.

[0093] Example 6

[0094] Based on Example 3, 3-aminopropyltrimethoxysilane in step X3 was removed and replaced with an equal weight of polyether-modified polydimethylsiloxane, while other conditions remained the same as in Example 3.

[0095] Example 7

[0096] Based on Example 3, the polyether-modified polydimethylsiloxane in step X3 was removed and replaced with an equal weight of 3-aminopropyltrimethoxysilane, while other conditions remained the same as in Example 3.

[0097] Example 8

[0098] Based on Example 3, the porous nano-silica in step X4 was removed and replaced with an equal weight of nano-silica with an average particle size of 165nm (purchased from Hubei Xinyuhong Biomedical Technology Co., Ltd.), while other conditions remained the same as in Example 3.

[0099] Example 9

[0100] Based on Example 3, the tea polyphenol liposomes in step Y1 were removed and replaced with an equal weight of tea polyphenols, while other conditions remained the same as in Example 3.

[0101] Comparative Example 1

[0102] Based on Example 3, while keeping other conditions consistent, the preparation method of the amino silicone oil emulsion was changed to the following steps:

[0103] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0104] Step X2: Mix the homogeneous oil phase and deionized water at a mass ratio of 1:2.3 and perform double refining to obtain a homogeneous phase;

[0105] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0106] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0107] Comparative Example 2

[0108] Based on Example 3, while keeping other conditions consistent, the preparation method of the amino silicone oil emulsion was changed to the following steps:

[0109] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0110] Step X2: Gradually add deionized water to the homogeneous oil phase, set the pressure of the high-pressure microjet treatment to 100MPa and the flow rate to 50mL / min, and perform the high-pressure microjet treatment twice to obtain a homogeneous phase;

[0111] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0112] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0113] Comparative Example 3

[0114] Based on Example 3, while keeping other conditions consistent, the preparation method of the amino silicone oil emulsion was changed to the following steps:

[0115] Step X1: Mix amino silicone oil, cocamidopropyl betaine, and polyether-modified silicone oil to obtain a homogeneous oil phase;

[0116] Step X2: Gradually add deionized water to the homogeneous oil phase, set the ultrasonic frequency to 28kHz and the ultrasonic frequency to 500W, and ultrasonically treat for 20 minutes to obtain a homogeneous phase;

[0117] Step X3: Add 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase and mix to obtain the modified homogeneous phase;

[0118] Step X4: Add sodium hydroxymethyl cellulose and porous nano silica to the modified homogeneous phase, and mix to obtain the final product.

[0119] Comparative Example 4

[0120] Based on Example 3, while keeping other conditions consistent, the preparation method of the amino silicone oil emulsion was changed to the following steps:

[0121] Step X1: Amino silicone oil, cocamidopropyl betaine, polyether-modified silicone oil, 3-aminopropyltrimethoxysilane, polyether-modified polydimethylsiloxane, sodium hydroxymethyl cellulose and porous nano silica are mixed and stirred at 100 rpm for 190 min at 40 °C. Deionized water is added in a gradient for double refinement to obtain an amino silicone oil emulsion.

[0122] Comparative Example 5

[0123] Based on Example 3, while keeping other conditions consistent, the porous silica nanospheres were not modified with hydrolyzed silk protein. The specific preparation method includes the following steps:

[0124] Step Y1: Mix tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stir at 500 rpm for 30 min at 40℃, add CaCl2 solution, and stir at 400 rpm for 2.5 h at room temperature to obtain liposome-gel microspheres.

[0125] Step Y2: Liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 900 rpm for 15 min. Tetraethyl orthosilicate and ammonia are added dropwise at a rate of 2 drops / s. After stirring at 25℃ for 7 h, the mixture is dispersed in hydrochloric acid-ethanol solution. Hexadecyltrimethylammonium bromide is removed by reflux at 60℃. After centrifugation and washing until neutral, gel microspheres with porous nano silica shells are obtained.

[0126] Step Y3: Gel microspheres with porous nano-silica shells are mixed with 3-aminopropyltriethoxysilane-ethanol solution and stirred at 60 rpm for 4 h at 50 °C. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0127] Comparative Example 6

[0128] Based on Example 3, while keeping other conditions consistent, the preparation method of porous silica nanospheres modified with hydrolyzed silk protein was changed to the following steps:

[0129] Step Y1: Mix tea polyphenol liposomes and hydrolyzed silk protein solution, and stir at 400 rpm for 3 hours at room temperature to obtain the contents;

[0130] Step Y2: Mix the contents, hexadecyltrimethylammonium bromide, and ethanol aqueous solution, stir at 900 rpm for 15 min, add tetraethyl orthosilicate and ammonia water dropwise at a rate of 2 drops / s, stir at 25℃ for 7 h, then disperse in hydrochloric acid-ethanol solution, reflux at 60℃ to remove hexadecyltrimethylammonium bromide, centrifuge, wash until neutral, and obtain microspheres with porous nano silica shells;

[0131] Step Y3: Microspheres with porous nano-silica shells are mixed with hydrolyzed silk protein solution and immersed in the mixture at 30°C and -0.1MPa vacuum for 1.5 h. After filtration, microspheres are obtained. The microspheres are then mixed with 3-aminopropyltriethoxysilane-ethanol solution and stirred at 50°C and 60 rpm for 4 h. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0132] Comparative Example 7

[0133] Based on Example 3, while keeping other conditions consistent, the preparation method of porous silica nanospheres modified with hydrolyzed silk protein was changed to the following steps:

[0134] Step Y1: Mix tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stir at 500 rpm for 30 min at 40℃, add CaCl2 solution, and stir at 400 rpm for 2.5 h at room temperature to obtain liposome-gel microspheres.

[0135] Step Y2: Liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 900 rpm for 15 min. Tetraethyl orthosilicate and ammonia are added dropwise at a rate of 2 drops / s. After stirring at 25℃ for 7 h, the mixture is dispersed in hydrochloric acid-ethanol solution. Hexadecyltrimethylammonium bromide is removed by reflux at 60℃. After centrifugation and washing until neutral, gel microspheres with porous nano silica shells are obtained.

[0136] Step Y3: Gel microspheres with porous nano-silica shells are mixed with hydrolyzed silk protein solution and immersed in the mixture at 30℃ and -0.1MPa vacuum for 1.5h. After centrifugation, washing, and drying, porous nano-silica microspheres modified with hydrolyzed silk protein are obtained.

[0137] 1. Using the amino silicone oil emulsions prepared in Examples 1-8 and Comparative Examples 1-4 as samples, 10 mL of each sample was kept at 60°C for 24 h as Group A; 10 mL of each sample was bottled, sealed, and placed in a high and low temperature shock test chamber, and used alternately at -10°C and 45°C for 3 cycles within 24 h as Group B; whether the emulsions in Group A and Group B separated into layers was observed, and the results are recorded in Table 1 below.

[0138] Table 1

[0139]

[0140] As shown in Table 1, the amino silicone oil emulsion prepared by the present invention can still maintain a good state, be stable and not separate into layers under high temperature and alternating high and low temperature environments.

[0141] 2. Using the amino silicone oil emulsions prepared in Examples 1-9 and Comparative Examples 1-7 as samples, the samples were prepared into a 30 g / L sample solution with deionized water. The sample solution was used to treat bleached pure cotton fabric. The fabric was immersed in a two-dip, two-nip process for 1 min, dried at 100°C for 5 min, and set at 180°C for 30 s to obtain the treated fabric. The hand feel (i.e., softness) of the treated fabric was measured using a blind test method, and the hand feel of the fabric was evaluated according to a scale of 1-5, with grade 1 being the worst and grade 5 being the best. The fabric was immersed in a 2 g / L laundry detergent solution, rubbed at 40°C for 3 min, washed with cold water, and dried. This process was repeated 20 times. The whiteness was measured using a WSB-2A whiteness meter, and the hand feel of the fabric was measured using a blind test method. The results are shown in Table 2 below.

[0142] Table 2

[0143]

[0144]

[0145] As shown in Table 2, the amino silicone oil emulsion prepared by this invention can effectively improve the softness and whiteness of fabrics when applied to fabric finishing.

[0146] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A process for the preparation of an amino silicone oil emulsion, characterized by: The preparation method comprises the following steps: Step X1, mixing amino silicone oil, cocamidopropyl betaine and polyether modified silicone oil to obtain a homogeneous oil phase; Step X2, adding deionized water to the homogeneous oil phase in a gradient to perform double refinement to obtain a homogeneous phase; Step X3, adding 3-aminopropyltrimethoxysilane and polyether modified polydimethylsiloxane to the homogeneous phase to obtain a modified homogeneous phase; Step X4, adding sodium hydroxymethyl cellulose and porous nanosilica to the modified homogeneous phase, and mixing to obtain the product; In step X2, the total deionized water and the homogeneous oil phase are mixed in a mass ratio of 1:2.1-2.3; the gradient addition of deionized water refers to that the deionized water is evenly divided into 5 parts, and the deionized water is added in 5 times at 40°C; after each addition, the stirring speed is 7000-9000 rpm for 2-4 min, and the interval between adjacent two times of water addition is 2 min; the double refinement refers to that the pressure of high-pressure microjet treatment is 80-120 MPa, the flow rate is 40-60 mL / min, the high-pressure microjet treatment is performed twice, then the ultrasonic frequency is 26-30 kHz, the ultrasonic frequency is 400-600 W, and the ultrasonic treatment is performed for 18-22 min; In step X4, the average particle size of the porous nanosilica is 160-170 nm; the porous nanosilica refers to the hydrolyzed silk protein modified porous nanosilica microspheres; the preparation method of the hydrolyzed silk protein modified porous nanosilica microspheres comprises the following steps: Step Y1, mixing tea polyphenol liposomes, hydrolyzed silk protein solution and sodium alginate solution, stirring at 400-600 rpm for 25-35 min at 40°C, then adding CaCl2 solution, stirring at 300-500 rpm for 2-3 h at room temperature to obtain liposome-gel microspheres; Step Y2, mixing the liposome-gel microspheres, cetyltrimethylammonium bromide and ethanol aqueous solution, stirring at 800-1000 rpm for 10-20 min, adding tetraethyl orthosilicate and ammonia water at a speed of 1-3 drops / s, stirring at 25°C for 6-8 h, then dispersing in hydrochloric acid-ethanol solution, removing cetyltrimethylammonium bromide by refluxing at 60°C, centrifuging and washing to neutral to obtain gel microspheres with a porous nanosilica shell layer; Step Y3, mixing the gel microspheres with a porous nanosilica shell layer and a hydrolyzed silk protein solution, immersing at 30°C under a vacuum of-0.1 MPa for 1.3-1.7 h, filtering to obtain microspheres, mixing the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stirring at 40-80 rpm for 3.5-4.5 h at 50°C, centrifuging, washing and drying to obtain hydrolyzed silk protein modified porous nanosilica microspheres.

2. The method for preparing an amino silicone oil emulsion according to claim 1, characterized in that: The mass ratio of the amino silicone oil, cocamide propyl betaine, and polyether modified silicone oil in step X1 is 5.5-6.5:0.25-0.35:0.17-0.23; the mixing refers to stirring at 45℃ with a stirring speed of 450-550 rpm for 8-12 min.

3. The method for preparing an amino silicone oil emulsion according to claim 1, characterized in that: The mass ratio of the homogeneous phase, 3-aminopropyl trimethoxysilane, and polyether modified polydimethylsiloxane in step X3 is 6.7-7.1:0.08-0.12:0.04-0.06; the mixing refers to stirring at 35℃ with a stirring speed of 150-250 rpm for 25-35 min; the mass ratio of the modified homogeneous phase, sodium hydroxymethyl cellulose, and porous nano-silica in step X4 is 7-7.1:0.04-0.06:0.028-0.032; the mixing refers to stirring at 40℃ with a stirring speed of 80-120 rpm for 2-3 h and then filtering.

4. The method for preparing an amino silicone oil emulsion according to claim 1, characterized in that: The mass ratio of the tea polyphenol liposome, hydrolyzed silk protein solution, sodium alginate solution, and CaCl2 solution in step Y1 is 1:1.9-2.1:1.1-1.2:0.6-0.8; the hydrolyzed silk protein solution is obtained by compounding hydrolyzed silk protein powder and deionized water at a mass ratio of 1:18.8-19.2; the sodium alginate solution is obtained by compounding sodium alginate and deionized water at a mass ratio of 1:42-46; the mass of CaCl2 in the CaCl2 solution is 0.45-0.55 wt%.

5. The method for preparing an amino silicone oil emulsion according to claim 1, characterized in that: The preparation method of the tea polyphenol liposome in step Y1 comprises the following steps: In step Z1, soybean phospholipid, cholesterol, tea polyphenol, and anhydrous ethanol are stirred at 50℃ until completely dissolved, an injection pump is used to inject PBS buffer at a rate of 0.5-1.5 mL / min, the ultrasonic frequency is set to 30-50 kHz, the ultrasonic frequency is 100-200 W, ultrasonic treatment is performed for 10-30 min, and the lower layer of free tea polyphenol is removed by centrifugation to obtain tea polyphenol liposomes; The mass ratio of the tea polyphenol, soybean phospholipid, cholesterol, anhydrous ethanol, and PBS buffer in step Z1 is 1:5.5-6.5:2.8-3.2:0.3-0.4:1.5-2.1; the pH of the PBS buffer needs to be adjusted to 7.2-7.6 and preheated to 60℃.

6. The method for preparing an amino silicone oil emulsion according to claim 1, characterized in that: The mass ratio of the liposome-gel microspheres, cetyltrimethylammonium bromide, ethanol aqueous solution, tetraethyl orthosilicate, and ammonia water in step Y2 is 1:0.14-0.16:20.7-20.9:0.6-0.8:0.12-0.16; the mass of ethanol in the ethanol aqueous solution is 18-22 wt%; the hydrochloric acid-ethanol solution is a 0.1 M HCl solution in 50% ethanol aqueous solution.

7. The method for preparing an amino silicone oil emulsion according to claim 1, characterized in that: The mass ratio of the gel microspheres with the porous nanosilica shell in step Y3 to the hydrolyzed silk fibroin solution is 1:18-22; the hydrolyzed silk fibroin solution is obtained by compounding hydrolyzed silk fibroin powder and deionized water according to a mass ratio of 1:15-17; the mass ratio of the microspheres to the 3-aminopropyltriethoxysilane-ethanol solution is 1:5-10; the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 2-3 wt%.

8. Use of an amino silicone emulsion prepared by the process according to any one of claims 1 to 7. The amino silicone oil emulsion is applied to textile finishing.

Images