Amino silicone oil emulsion as well as preparation method and application thereof

Abstract

The invention relates to amino silicone oil emulsion as well as a preparation method and application thereof, and belongs to the technical field of silicone oil emulsion. A preparation method of the amino silicone oil emulsion comprises the following steps: mixing amino silicone oil, cocamidopropyl betaine and polyether modified silicone oil to obtain a homogeneous oil phase, adding deionized water in a gradient manner, and carrying out double refining to obtain a homogeneous phase; 3-aminopropyltrimethoxysilane and polyether modified polydimethylsiloxane are added for treatment, a modified homogeneous phase is obtained, hydroxymethyl cellulose and porous nano-silica are added, and mixing is performed to obtain the coating. Through compounding of the amino silicon oil, the cocamidopropyl betaine, the polyether modified silicon oil, the amino propyl trimethoxy silane, the polyether modified polydimethylsiloxane and the porous nano silicon dioxide, the stability of the amino silicon oil is synergistically improved, and the fabric is endowed with good flexibility and durability.

Description

Technical Field

[0001] The invention belongs to the technical field of silicone oil emulsions and relates to an amino silicone oil emulsion and a preparation method and application thereof. Background Art

[0002] Aminosilicone emulsions are stable emulsion systems formed through emulsification technology using aminosilicone oil as the primary ingredient. They are widely used in textiles and other fields. Conventional aminosilicone emulsions primarily come in three types: cationic, nonionic, and anionic. While aminosilicone emulsions offer excellent performance, they still have limitations in practical applications. For example, cationic emulsions are susceptible to pH and may demulsify under alkaline conditions; nonionic emulsions offer excellent stability but relatively weak softening effects; and anionic emulsions require high compatibility with other additives. Furthermore, the large particle size of conventional emulsions results in insufficient penetration into fibers, impacting the durability of the finishing effect. Summary of the Invention

[0003] The present invention aims to provide an aminosilicone oil emulsion, a preparation method thereof, and an application thereof. The present invention synergistically improves the stability of the aminosilicone oil and imparts good flexibility and durability to fabrics by compounding aminosilicone oil, cocamidopropyl betaine, polyether-modified silicone oil, aminopropyltrimethoxysilane, polyether-modified polydimethylsiloxane, and porous nano-silica.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

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

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

[0007] Step X2: adding deionized water to the homogeneous oil phase in a gradient manner to perform double refinement to obtain a homogeneous phase;

[0008] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

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

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

[0012] Furthermore, the mass ratio of the homogeneous phase, 3-aminopropyltrimethoxysilane, 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 150-250 rpm for 25-35 minutes at 35°C; 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 80-120 rpm for 2-3 hours at 40°C and then filtering.

[0013] Furthermore, the average particle size of the porous nano-silica in step X4 is 160-170 nm, and 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 comprises the following steps:

[0014] Step Y1, mixing tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stirring at 40° C. and 400-600 rpm for 25-35 minutes, adding CaCl2 solution, and stirring at 300-500 rpm at room temperature for 2-3 hours to obtain liposome-gel microspheres;

[0015] Step Y2: liposome-gel microspheres, cetyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 800-1000 rpm for 10-20 min, and ethyl orthosilicate and ammonia water are added simultaneously at a rate of 1-3 drops / s. After stirring at 25° C. for 6-8 h, the mixture is dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove cetyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell.

[0016] Step Y3: Mix the gel microspheres with a porous nano-silica shell and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.3-1.7 hours, filter and dry to obtain microspheres, mix the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stir at 40-80 rpm at 50°C for 3.5-4.5 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

[0017] Furthermore, in step Y1, the mass ratio of the 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 in a mass ratio of 1:18.8-19.2; the sodium alginate solution is obtained by compounding sodium alginate and deionized water in a mass ratio of 1:42-46; the mass of CaCl2 in the CaCl2 solution is 0.45-0.55wt%.

[0018] Furthermore, the preparation method of the tea polyphenol liposomes in step Y1 comprises the following steps:

[0019] Step Z1, stirring soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved, injecting PBS buffer at a rate of 0.5-1.5 mL / min using a syringe pump, setting the ultrasonic frequency to 30-50 kHz and the ultrasonic frequency to 100-200 W, ultrasonicating for 10-30 min, and centrifuging to remove free tea polyphenols in the lower layer 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 pH of the PBS buffer needs to be adjusted to 7.2-7.6 and preheated to 60°C.

[0021] Furthermore, in step Y2, the mass ratio of the liposome-gel microspheres, hexadecyltrimethylammonium bromide, ethanol aqueous solution, tetraethyl orthosilicate, and ammonia water 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 18-22wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1M HCl.

[0022] Furthermore, in step Y3, the mass ratio of the gel microspheres with a porous nano-silica shell and 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 in a mass ratio of 1:15-17; the mass ratio of the microspheres and the 3-aminopropyltriethoxysilane-ethanol solution is 1:5-10; the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 2-3wt%.

[0023] Furthermore, the amino silicone oil emulsion is used in textile finishing.

[0024] Beneficial effects of the present invention:

[0025] (1) The present invention mainly uses amino silicone oil in the preparation process, which gives the fabric excellent softness and durability; cocamidopropyl betaine promotes oil-water phase dispersion by reducing surface tension, and polyether-modified silicone oil enhances the interfacial film strength to form a homogeneous and delicate emulsion; on this basis, gradient water addition treatment and double refinement treatment are carried out, and the two phases of cocamidopropyl betaine and polyether-modified silicone oil are coordinated to effectively avoid emulsion stratification or unevenness, thereby further improving the stability of the emulsion; then, aminopropyl trimethoxysilane is used to improve the bonding force between the emulsion and the textile surface, thereby enhancing washability and durability, and polyether-modified polydimethylsiloxane is used to provide good flexibility, thereby enhancing the comfort and durability of the fabric; on this basis, sodium hydroxymethyl cellulose is introduced to further improve the softness and feel of the plant, and porous nano-silica is introduced to provide the fabric with long-lasting softness and durability; the components work together to give the fabric good softness and durability.

[0026] (2) The present application introduces porous nano-silica microspheres modified with hydrolyzed silk protein in the preparation process. The surface of the microspheres is treated with silane. The polar properties of the amino group in 3-aminopropyltriethoxysilane can improve its dispersibility in the amino silicone oil emulsion, and can also interact with the hydroxyl groups in the subsequently treated clothing fibers to improve its adhesion to the fiber surface. When finishing clothes, the hydrolyzed silk protein film on the outer surface of the microspheres is adsorbed on the fibers through hydrogen bonds during the finishing of clothes, providing instant softness. After multiple washings, in an alkaline environment, i.e., under the treatment of laundry detergent, the pore size of the sodium alginate swells and expands, and the hydrolyzed silk protein and tea polyphenol liposomes wrapped inside are slowly released. As the number of washings gradually increases, the porous nano-silica shell breaks, and the hydrolyzed silk protein and tea polyphenol liposomes are completely released, thereby compensating for the softening components lost during washing with the help of hydrolyzed silk protein. At the same time, the tea polyphenol nano-liposomes provide antioxidant assistance, and synergistically improve the yellowing resistance of clothing with hydrolyzed silk protein. DETAILED DESCRIPTION

[0027] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0028] The amino silicone oil, cocamidopropyl betaine, and cetyltrimethylammonium bromide in all the embodiments and comparative examples of the present invention were purchased directly from the market and were purchased from Green Union (Jining) Chemical Technology Co., Ltd.; the polyether-modified silicone oils were purchased directly from the market and were purchased from Zhuhai Xiande New Materials Technology Co., Ltd.; 3-aminopropyltrimethoxysilane was purchased directly from the market and was purchased from Wuhan Smack Biotechnology Co., Ltd.; polyether-modified polydimethylsiloxane and sodium hydroxymethylcellulose were purchased directly from the market and were purchased from Hubei Maidehao Biotechnology Co., Ltd.; PB S buffer was purchased directly from the market and was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.; soybean lecithin, cholesterol, tea polyphenols, hydrolyzed silk protein, sodium alginate, and CaCl2 were purchased directly from the market and were purchased from Wuhan Jiangxin Biotechnology Co., Ltd.; ethyl orthosilicate was purchased directly from the market and was purchased from Shandong Yuanjin New Materials Co., Ltd.; ammonia water was purchased directly from the market and was purchased from Guangdong Qiming Chemical Technology Co., Ltd.; 3-aminopropyltriethoxysilane was purchased directly from the market and was purchased 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 comprises the following steps:

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

[0032] Step X2: adding deionized water to the homogeneous oil phase in a gradient manner to perform double refinement to obtain a homogeneous phase;

[0033] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

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

[0036] The mass ratio of the total deionized water and the homogeneous oil phase used in the gradient addition of deionized water in step X2 of this embodiment is 1:2.1; the gradient addition of deionized water refers to dividing the deionized water into 5 parts, adding deionized water in 5 times at 40°C, stirring at 7000 rpm for 4 minutes after each addition of water, and requiring a 2-minute interval between two adjacent water additions; double refinement refers to first setting the pressure of the high-pressure microjet treatment to 80 MPa and the flow rate to 60 mL / min, performing the high-pressure microjet treatment twice, and then setting the ultrasonic frequency to 26 kHz and 400 W, and performing the ultrasonic treatment for 22 minutes.

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

[0038] The average particle size of the porous nano-silica in step X4 of this embodiment 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 comprises the following steps:

[0039] Step Y1: tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution were mixed, stirred at 400 rpm at 40° C. for 35 min, and then CaCl2 solution was added. The mixture was stirred at 300 rpm at room temperature for 3 h to obtain liposome-gel microspheres.

[0040] Step Y2: liposome-gel microspheres, cetyltrimethylammonium bromide, and ethanol aqueous solution were mixed, stirred at 800 rpm for 20 min, and tetraethyl orthosilicate and ammonia water were added simultaneously at a rate of 1 drop / s. After stirring at 25° C. for 6 h, the mixture was dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove cetyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell.

[0041] Step Y3: Mix the gel microspheres with a porous nano-silica shell and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.3 hours, filter and dry to obtain microspheres, mix the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stir at 40 rpm at 50°C for 4.5 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

[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 in a mass ratio of 1:18.8; the sodium alginate solution is obtained by compounding sodium alginate and deionized water in a mass ratio of 1:42; the mass of CaCl2 in the CaCl2 solution is 0.45wt%.

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

[0044] Step Z1, stirring soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved, injecting PBS buffer at a rate of 0.5 mL / min using a syringe pump, setting the ultrasonic frequency to 30 kHz and 100 W for 30 min, and centrifuging to remove free tea polyphenols in the lower layer to obtain tea polyphenol liposomes;

[0045] The mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer in step Z1 is 1:5.5:2.8:0.3:1.5; the pH of the PBS buffer needs to be adjusted to 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 water is 1:0.14:20.7:0.6:0.12; the mass of ethanol in the ethanol aqueous solution is 18 wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1 M HCl.

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

[0048] The amino silicone oil emulsion of this embodiment is used for textile finishing.

[0049] Example 2

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

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

[0052] Step X2: adding deionized water to the homogeneous oil phase in a gradient manner to perform double refinement to obtain a homogeneous phase;

[0053] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

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

[0056] The mass ratio of the total deionized water and the homogeneous oil phase used in the gradient addition of deionized water in step X2 of this embodiment is 1:2.3; the gradient addition of deionized water refers to dividing the deionized water into 5 parts, adding deionized water in 5 times at 40°C, stirring at 9000 rpm for 2 minutes after each addition of water, and requiring a 2-minute interval between two adjacent water additions; double refinement refers to first setting the pressure of the high-pressure microjet treatment to 120 MPa and the flow rate to 40 mL / min, performing the high-pressure microjet treatment twice, and then setting the ultrasonic frequency to 30 kHz and 600 W, and performing the ultrasonic treatment for 18 minutes.

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

[0058] The average particle size of the porous nano-silica in step X4 of this embodiment 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 comprises the following steps:

[0059] Step Y1: tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution were mixed, stirred at 600 rpm at 40° C. for 25 min, and then CaCl2 solution was added. The mixture was stirred at 500 rpm at room temperature for 2 h to obtain liposome-gel microspheres.

[0060] Step Y2: liposome-gel microspheres, cetyltrimethylammonium bromide, and ethanol aqueous solution were mixed, stirred at 1000 rpm for 10 minutes, and tetraethyl orthosilicate and ammonia water were added simultaneously at a rate of 3 drops / s. After stirring at 25° C. for 8 hours, the mixture was dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove cetyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell layer;

[0061] Step Y3: Mix the gel microspheres with a porous nano-silica shell and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.7 hours, filter and dry to obtain microspheres, mix the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stir at 80 rpm at 50°C for 3.5 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

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

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

[0064] Step Z1, stirring soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved, injecting PBS buffer at a rate of 1.5 mL / min using a syringe pump, setting the ultrasonic frequency to 50 kHz and 200 W, ultrasonicating for 10 minutes, and centrifuging to remove free tea polyphenols in the lower layer to obtain tea polyphenol liposomes;

[0065] The mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer in step Z1 is 1:6.5:3.2:0.4:2.1; the pH of the PBS buffer needs to be adjusted to 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 water is 1:0.16:20.9:0.8:0.16; the mass of ethanol in the ethanol aqueous solution is 22 wt%; and the hydrochloric acid-ethanol solution is 50% ethanol aqueous solution of 0.1 M HCl.

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

[0068] The amino silicone oil emulsion of this embodiment is used for textile finishing.

[0069] Example 3

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

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

[0072] Step X2: adding deionized water to the homogeneous oil phase in a gradient manner to perform double refinement to obtain a homogeneous phase;

[0073] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

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

[0076] The mass ratio of the total deionized water and the homogeneous oil phase used in the gradient addition of deionized water in step X2 of this embodiment is 1:2.2; the gradient addition of deionized water refers to dividing the deionized water into 5 parts, adding deionized water in 5 times at 40°C, stirring at 8000 rpm for 3 minutes after each addition of water, and requiring a 2-minute interval between two adjacent water additions; double refinement refers to first setting the pressure of the high-pressure microjet treatment to 100 MPa and the flow rate to 50 mL / min, performing the high-pressure microjet treatment twice, and then setting the ultrasonic frequency to 28 kHz and 500 W, and performing the ultrasonic treatment for 20 minutes.

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

[0078] The average particle size of the porous nano-silica in step X4 of this embodiment 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 comprises the following steps:

[0079] Step Y1, tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution were mixed, stirred at 500 rpm at 40° C. for 30 min, and then CaCl2 solution was added. The mixture was stirred at 400 rpm at room temperature for 2.5 h to obtain liposome-gel microspheres;

[0080] Step Y2: liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution were mixed, stirred at 900 rpm for 15 minutes, and tetraethyl orthosilicate and ammonia water were added simultaneously at a rate of 2 drops / s. After stirring at 25° C. for 7 hours, the mixture was dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove hexadecyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell layer;

[0081] Step Y3: Mix the gel microspheres with a porous nano-silica shell layer and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.5 hours, filter and dry to obtain microspheres, mix the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stir at 60 rpm at 50°C for 4 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

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

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

[0084] Step Z1, stirring soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved, injecting PBS buffer at a rate of 1 mL / min using a syringe pump, setting the ultrasonic frequency to 40 kHz and 150 W for 20 min, and centrifuging to remove free tea polyphenols in the lower layer to obtain tea polyphenol liposomes;

[0085] The mass ratio of tea polyphenols, soybean lecithin, cholesterol, anhydrous ethanol, and PBS buffer in step Z1 is 1:6:3:0.35:1.8; the pH of the PBS buffer needs to be adjusted to 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 water is 1:0.15:20.8:0.7:0.14; the mass of ethanol in the ethanol aqueous solution is 20 wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1 M HCl.

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

[0088] The amino silicone oil emulsion of this embodiment is used for textile finishing.

[0089] Example 4

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

[0091] Example 5

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

[0093] Example 6

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

[0095] Example 7

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

[0097] Example 8

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

[0099] Example 9

[0100] On the basis of Example 3, the tea polyphenol liposomes in step Y1 were removed and replaced with tea polyphenols of equal weight. Other conditions remained the same as in Example 3.

[0101] Comparative Example 1

[0102] On the basis of Example 3, keeping other conditions the same, the preparation method of the amino silicone oil emulsion was changed to the following steps:

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

[0104] Step X2: mixing the homogenized oil phase and deionized water in a mass ratio of 1:2.3, and performing double refinement to obtain a homogeneous phase;

[0105] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

[0107] Comparative Example 2

[0108] On the basis of Example 3, keeping other conditions the same, the preparation method of the amino silicone oil emulsion was changed to the following steps:

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

[0110] Step X2: adding deionized water to the homogeneous oil phase in a gradient manner, setting the high-pressure microfluidization pressure to 100 MPa and the flow rate to 50 mL / min, and performing the high-pressure microfluidization treatment twice to obtain a homogeneous phase;

[0111] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

[0113] Comparative Example 3

[0114] On the basis of Example 3, keeping other conditions the same, the preparation method of the amino silicone oil emulsion was changed to the following steps:

[0115] Step X1: mixing 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 28 kHz and the ultrasonic frequency to 500 W, and perform ultrasonic treatment for 20 minutes to obtain a homogeneous phase;

[0117] Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase;

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

[0119] Comparative Example 4

[0120] On the basis of Example 3, keeping other conditions the same, 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 hydroxymethylcellulose and porous nano-silica are mixed, stirred at 100 rm at 40°C for 190 min, and deionized water is added in a gradient manner for double refinement to obtain an amino silicone oil emulsion.

[0122] Comparative Example 5

[0123] On the basis of Example 3, other conditions were kept the same, and the porous nano-silica microspheres were not modified with hydrolyzed silk protein. The specific preparation method included the following steps:

[0124] Step Y1, tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution were mixed, stirred at 500 rpm at 40° C. for 30 min, and then CaCl2 solution was added. The mixture was stirred at 400 rpm at room temperature for 2.5 h to obtain liposome-gel microspheres;

[0125] Step Y2: liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution were mixed, stirred at 900 rpm for 15 minutes, and tetraethyl orthosilicate and ammonia water were added simultaneously at a rate of 2 drops / s. After stirring at 25° C. for 7 hours, the mixture was dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove hexadecyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell layer;

[0126] Step Y3: Mix the gel microspheres with a porous nano-silica shell layer with a 3-aminopropyltriethoxysilane-ethanol solution, stir at 60 rpm at 50°C for 4 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

[0127] Comparative Example 6

[0128] On the basis of Example 3, keeping other conditions the same, the preparation method of porous nano-silica microspheres modified with hydrolyzed silk protein was changed to the following steps:

[0129] Step Y1, mixing the tea polyphenol liposomes and the hydrolyzed silk protein solution, and stirring at 400 rpm at room temperature for 3 hours to obtain a content;

[0130] Step Y2: Mix the contents, hexadecyltrimethylammonium bromide, and ethanol aqueous solution, stir at 900 rpm for 15 minutes, add tetraethyl orthosilicate and ammonia solution simultaneously at a rate of 2 drops / s, stir at 25°C for 7 hours, and then disperse in a hydrochloric acid-ethanol solution. Reflux at 60°C to remove hexadecyltrimethylammonium bromide, centrifuge, and wash until neutral to obtain microspheres with a porous nano-silica shell.

[0131] Step Y3: Mix the microspheres with a porous nano-silica shell and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.5 hours, filter and dry to obtain microspheres, mix the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stir at 60 rpm at 50°C for 4 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

[0132] Comparative Example 7

[0133] On the basis of Example 3, keeping other conditions the same, the preparation method of porous nano-silica microspheres modified with hydrolyzed silk protein was changed to the following steps:

[0134] Step Y1, tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution were mixed, stirred at 500 rpm at 40° C. for 30 min, and then CaCl2 solution was added. The mixture was stirred at 400 rpm at room temperature for 2.5 h to obtain liposome-gel microspheres;

[0135] Step Y2: liposome-gel microspheres, hexadecyltrimethylammonium bromide, and ethanol aqueous solution were mixed, stirred at 900 rpm for 15 minutes, and tetraethyl orthosilicate and ammonia water were added simultaneously at a rate of 2 drops / s. After stirring at 25° C. for 7 hours, the mixture was dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove hexadecyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell layer;

[0136] Step Y3: Mix the gel microspheres with a porous nano-silica shell layer and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.5 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

[0137] 1. The amino silicone oil emulsions prepared in Examples 1-8 and Comparative Examples 1-4 were used as samples. 10 mL of the sample was placed at 60°C for 24 h, forming Group A. 10 mL of the sample was bottled, sealed, and placed in a high and low temperature shock test chamber, alternately at -10°C and 45°C for three cycles within 24 h, forming Group B. The emulsions in Groups A and B were observed for stratification, and the results are shown in Table 1 below.

[0138] Table 1

[0139]

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

[0141] 2. The amino silicone oil emulsion prepared in Example 1-9 and Comparative Example 1-7 was used as a sample, and the sample was prepared into a 30 g / L sample solution with deionized water. The sample solution was used to finish the pure cotton bleached cloth, and the two-immersion and two-padding process was adopted for 1 min, dried at 100 ° C for 5 min, and set at 180 ° C for 30 s to obtain the finished fabric; the feel (ie, softness) of the finished fabric was measured by a blind test method, and the feel of the fabric was evaluated according to 1-5 levels, where level 1 was the worst and level 5 was the best; the fabric was immersed in a 2 g / L washing powder solution, scrubbed at 40 ° C for 3 min, washed with cold water and dried, and repeated 20 times. The whiteness was measured using a WSB-2A whiteness meter, and the fabric feel was measured by a blind test method, and the records were shown in Table 2 below.

[0142] Table 2

[0143]

[0144]

[0145] As can be seen from Table 2, the amino silicone oil emulsion prepared by the present invention can be used in fabric finishing to effectively improve the softness and whiteness of the fabric.

[0146] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any indirect modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing an amino silicone oil emulsion, characterized in that: 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 manner to perform double refinement to obtain a homogeneous phase; Step X3, adding 3-aminopropyltrimethoxysilane and polyether-modified polydimethylsiloxane to the homogeneous phase, and mixing to obtain a modified homogeneous phase; Step X4: add sodium hydroxymethyl cellulose and porous nano-silica to the modified homogeneous phase and mix to obtain the product.

2. The method for preparing an amino silicone oil emulsion according to claim 1, wherein: 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 45° C. and 450-550 rpm for 8-12 min.

3. The method for preparing an amino silicone oil emulsion according to claim 1, wherein: The mass ratio of the total deionized water and the homogeneous oil phase used in the gradient addition of deionized water in step X2 is 1:2.1-2.3; the gradient addition of deionized water refers to dividing the deionized water into 5 parts, adding deionized water in 5 times at 40°C, stirring at 7000-9000 rpm for 2-4 minutes after each addition of water, and a 2-minute interval is required between two adjacent water 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, the ultrasonic frequency to 400-600 W, and the ultrasonic treatment for 18-22 minutes.

4. The method for preparing an amino silicone oil emulsion according to claim 1, wherein: 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 minutes at 35°C; 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 80-120 rpm for 2-3 hours at 40°C and then filtering.

5. The method for preparing an amino silicone oil emulsion according to claim 1, wherein: 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 protein. The preparation method of the porous nano-silica microspheres modified with hydrolyzed silk protein comprises the following steps: Step Y1, mixing tea polyphenol liposomes, hydrolyzed silk protein solution, and sodium alginate solution, stirring at 40° C. and 400-600 rpm for 25-35 minutes, adding CaCl2 solution, and stirring at 300-500 rpm at room temperature for 2-3 hours to obtain liposome-gel microspheres; Step Y2: liposome-gel microspheres, cetyltrimethylammonium bromide, and ethanol aqueous solution are mixed and stirred at 800-1000 rpm for 10-20 min, and ethyl orthosilicate and ammonia water are added simultaneously at a rate of 1-3 drops / s. After stirring at 25° C. for 6-8 h, the mixture is dispersed in a hydrochloric acid-ethanol solution, refluxed at 60° C. to remove cetyltrimethylammonium bromide, centrifuged, and washed until neutral to obtain gel microspheres with a porous nano-silica shell. Step Y3: Mix the gel microspheres with a porous nano-silica shell and the hydrolyzed silk protein solution, immerse them at 30°C and -0.1 MPa vacuum for 1.3-1.7 hours, filter and dry to obtain microspheres, mix the microspheres with 3-aminopropyltriethoxysilane-ethanol solution, stir at 40-80 rpm at 50°C for 3.5-4.5 hours, centrifuge, wash, and dry to obtain porous nano-silica microspheres modified with hydrolyzed silk protein.

6. The method for preparing an amino silicone oil emulsion according to claim 5, wherein: In step Y1, the mass ratio of the 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 in a mass ratio of 1:18.8-19.2; the sodium alginate solution is obtained by compounding sodium alginate and deionized water in a mass ratio of 1:42-46; the mass of CaCl2 in the CaCl2 solution is 0.45-0.55wt%.

7. The method for preparing an amino silicone oil emulsion according to claim 5, wherein: The preparation method of tea polyphenol liposomes in step Y1 comprises the following steps: Step Z1, stirring soybean lecithin, cholesterol, tea polyphenols and anhydrous ethanol at 50°C until completely dissolved, injecting PBS buffer at a rate of 0.5-1.5 mL / min using a syringe pump, setting the ultrasonic frequency to 30-50 kHz and the ultrasonic frequency to 100-200 W, ultrasonicating for 10-30 min, and centrifuging to remove free tea polyphenols in the lower layer to obtain tea polyphenol liposomes; 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 pH of the PBS buffer needs to be adjusted to 7.2-7.6 and preheated to 60°C.

8. The method for preparing an amino silicone oil emulsion according to claim 5, wherein: The mass ratio of the liposome-gel microspheres, hexadecyltrimethylammonium 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 18-22wt%; and the hydrochloric acid-ethanol solution is a 50% ethanol aqueous solution of 0.1M HCl.

9. The method for preparing an amino silicone oil emulsion according to claim 5, wherein: In step Y3, the mass ratio of the gel microspheres with a porous nano-silica shell and 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 in a mass ratio of 1:15-17; the mass ratio of the microspheres and the 3-aminopropyltriethoxysilane-ethanol solution is 1:5-10; the mass of 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane-ethanol solution is 2-3wt%.

10. An application of the aminosilicone oil emulsion prepared by the preparation method of the aminosilicone oil emulsion according to any one of claims 1 to 9, characterized in that: The amino silicone oil emulsion is used for textile finishing.

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