Modified amino silicon oil as well as preparation method and application thereof

Abstract

The invention relates to modified amino silicone oil as well as a preparation method and application thereof, the preparation method comprises the following steps: S100, mixing 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 2-30 parts by weight of amino silane and 3-30 parts by weight of dimethyl silicone oil at the temperature of 40-100 DEG C to obtain a mixture; s200, at the temperature of 20-40 DEG C and under the stirring condition, 6-40 parts by weight of water is added into the mixture for a hydrolysis reaction, then nitrogen is introduced into a reaction system to discharge water and generated alcohol, and a hydrolysate is obtained; s300, adding 0.0001-0.005 part by weight of phosphazene base into the hydrolysate, and carrying out a first reaction at the temperature of 50-100 DEG C under the condition that nitrogen is introduced into a reaction system; adding 1-10 parts by weight of organic acid anhydride, and carrying out second reaction at the temperature of 50-100 DEG C to obtain a reaction product; and S400, carrying out low-temperature removal treatment on the reaction product to obtain the modified amino silicon oil. The modified amino silicon oil provided by the invention has the advantages of low content of organic silicon ring bodies, low volatile components and low yellowing property.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon technology, specifically relating to modified amino silicone oil, its preparation method, and its application. Background Technology

[0002] Amino silicone oil is a product of dimethyl silicone oil in which some methyl groups at the lateral and terminal positions are replaced by amino groups. Its amino groups are highly polar and reactive, and it has the characteristics of adsorption, compatibility and easy emulsification. It is widely used as a fiber finishing agent, resin modifier, coating additive, brightener and cosmetic additive.

[0003] Based on whether the polysiloxane backbone contains reactive groups other than amino groups, amino silicone oils can be divided into reactive amino silicone oils and non-reactive amino silicone oils. Compared with non-reactive amino silicone oils, reactive amino silicone oils, due to the introduction of reactive groups such as hydroxyl and alkoxy groups into the amino polysiloxane backbone, can cross-link and form a film on the fiber surface, thus improving the fiber's softness, lubrication, resilience, and bonding strength.

[0004] Currently, the main industrial route for synthesizing amino silicone oils involves polymerizing octamethylcyclotetrasiloxane (D4) or a mixture of dimethylcyclosiloxanes (DMC) with amino monomers. The resulting products are generally random copolymers, exhibiting defects such as uneven amino group distribution and low conversion rates. Furthermore, the products often contain difficult-to-remove organosilicon rings, which pose a persistent environmental hazard.

[0005] Because organosilicon products are widely used in numerous fields and have relatively stable chemical properties, large quantities of methylsiloxanes from human life and production sites migrate into the atmosphere, water, soil, and other environmental matrix through various pathways, forming persistent presences. With the development of relevant toxicological studies, reports have indicated that methylsiloxanes have toxic effects on the nervous, immune, and reproductive systems of animals, exhibiting carcinogenic and mutagenic properties. For example, in 2018, the EU stipulated that the concentration of D4, D5, and D6 in personal care products should not exceed 0.1%, and in the same year, the EU proposed listing D4, D5, and D6 on the SVHC list. The EU also proposed restrictions on D4, D5, and D6 in personal care and consumer products. Therefore, there is a need to produce high-quality amino silicone oils to meet market demands and expand the application range of products.

[0006] Currently, commercially available amino-modified silicone oils largely use N-β-aminoethyl-γ-propyl polydimethylsiloxane as a raw material to prepare amino silicone oils. These oils have two amino groups (primary and secondary amino groups) on their side chains and contain three active hydrogen atoms. They are easily oxidized and turn yellow in the presence of oxidants or when exposed to light or heat.

[0007] Chinese patent application CN112280041A discloses a method for preparing amino silicone oil using a linear polymer, a diekoxy amino monomer, and low-viscosity methyl silicone oil, comprising the following steps: (1) mixing 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 1-50 parts by weight of silanoxy amino monomer, and 1-25 parts by weight of end-capping agent at a temperature of 50-100°C to obtain a mixed material; (2) adding 1-5 parts by weight of water to the mixed material obtained in step (1) for hydrolysis, and purging nitrogen gas to remove water and alcohol to obtain a hydrolyzed material; (3) adding alkaline catalysts such as KOH solid, KOH aqueous solution, trimethylsilanotate potassium, and tetramethylammonium hydroxide to the hydrolyzed material, and carrying out a polymerization reaction at a temperature of 50-100°C to obtain a polymerized reaction material; (4) removing the polymerized reaction material to obtain amino silicone oil. This patent application uses solid KOH, aqueous KOH, potassium trimethylsilanolate, and tetramethylammonium hydroxide as catalysts, with high dosages, typically above 100 ppm. This results in an excessively fast polymerization rate that is difficult to control. Furthermore, the use of potassium trimethylsilanolate and tetramethylammonium hydroxide introduces excessive organic salts, leading to increased turbidity and affecting downstream applications.

[0008] Chinese patent application CN115449079A discloses a method for preparing amino silicone oil. The method uses a mixture of dimethylsiloxanes as the starting material, adding a catalyst, water, and a silane coupling agent, mixing thoroughly, heating to 50–90°C and holding for 10–120 minutes, then performing vacuum de-lowering treatment, followed by heating to 95–145°C and reacting for 1–4 hours, and finally vacuum de-lowering treatment to obtain amino silicone oil. The entire preparation process is carried out under nitrogen protection. In this method, the dimethylsiloxane mixture is used as a dimethyl hydrolysate, containing both cyclic and linear molecules, with the cyclic molecules accounting for 50–80% of the mixture. De-lowering after polymerization results in a high low-boiling point content, increasing production energy consumption and reducing production capacity. Furthermore, the high cyclic content in the product does not meet environmental protection requirements. Summary of the Invention

[0009] In view of this, the purpose of this invention is to address the deficiencies in the prior art by providing a modified amino silicone oil, its preparation method, and its application. The modified amino silicone oil of this invention has a low content of organosilicon cyclic compounds and low volatile components, and also exhibits low yellowing properties.

[0010] The objective of this invention is achieved through the following technical solutions.

[0011] In a first aspect, the present invention provides a method for preparing modified amino silicone oil, wherein the preparation method includes the following steps:

[0012] S100. At a temperature of 40 to 100°C, 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 2 to 30 parts by weight of aminosilane and 3 to 30 parts by weight of dimethyl silicone oil are mixed to obtain a mixture.

[0013] S200. At a temperature of 20-40°C and under stirring conditions, 6-40 parts by weight of water are added to the mixture obtained in step S100 to carry out a hydrolysis reaction. Then, nitrogen gas is introduced into the reaction system to remove water and the generated alcohol, and the hydrolysis product is obtained.

[0014] S300: Add 0.0001 to 0.005 parts by weight of phosphazene base to the hydrolysis product obtained in step S200, and carry out the first reaction at a temperature of 50 to 100°C and under the condition of purging nitrogen into the reaction system; add 1 to 10 parts by weight of organic acid anhydride, and carry out the second reaction at a temperature of 50 to 100°C to obtain the reaction product.

[0015] S400: The reaction product obtained in step S300 is subjected to de-lowering treatment to obtain modified amino silicone oil.

[0016] In this invention, a first reaction is carried out by adding phosphazene base instead of potassium trimethylsilanolate as a catalyst to the hydrolysis product obtained from a mixture of hydroxyl-terminated polydimethylsiloxane, methyldialkoxyaminosilane, and dimethyl silicone oil, followed by the addition of organic acid anhydride for a second reaction. The modified amino silicone oil prepared after de-oxidation treatment has low organosilicon cyclic content, low volatile matter, and low yellowing properties. Furthermore, the use of hydroxyl-terminated polydimethylsiloxane in this invention facilitates the control of uniform amino group distribution. Adding a capping agent before hydrolysis effectively controls the degree of polymerization (viscosity) of the linear hydroxyl-terminated polydimethylsiloxane and methyldialkoxyaminosilane, preventing the viscosity of the amino silicone oil product from increasing too rapidly.

[0017] According to the preparation method provided by the present invention, the viscosity of the hydroxyl-terminated polydimethylsiloxane at 25°C can be 40–150 cs. In this invention, if the viscosity of the hydroxyl-terminated polydimethylsiloxane is higher than the above range, the hydroxyl content is too low, making polymerization difficult; conversely, if the viscosity is too low, the reaction rate is difficult to control, and the molecular weight distribution is wide. In this invention, the viscosity of the hydroxyl-terminated polydimethylsiloxane at 25°C can be 40 cs, 50 cs, 60 cs, 70 cs, 80 cs, 90 cs, 100 cs, 110 cs, 120 cs, 150 cs, or a range thereof. For example, the viscosity of the hydroxyl-terminated polydimethylsiloxane at 25°C is 40–100 cs, preferably 70–80 cs.

[0018] The inventors of this application unexpectedly discovered that, in the preparation method of this invention, using phosphazene base as a catalyst can further reduce the content of organosilicon cyclic compounds, thus lowering the requirements for raw materials. In some embodiments, the content of organosilicon cyclic compounds D4, D5, and D6 in the hydroxyl-terminated polydimethylsiloxane is each independently ≤0.5% by weight.

[0019] In this invention, the terms "octamethylcyclotetrasiloxane" and D4 can be used interchangeably; the terms "decamethylcyclopentasiloxane" and D5 can be used interchangeably; and the terms "dodecylmethylcyclotetrasiloxane" and D6 can be used interchangeably.

[0020] According to the preparation method provided by the present invention, the aminosilane is selected from N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, 3-piperazinepropylmethyldimethoxysilane, 3-piperazinepropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane, preferably N-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0021] According to the preparation method provided by the present invention, the dimethyl silicone oil has a viscosity of 2-20 cs at 25°C, preferably 10-20 cs.

[0022] According to the preparation method provided by the present invention, in step S100, the amino content of the modified amino silicone oil can be controlled by adjusting the amount of methyldialkoxyaminosilane, and the viscosity of the modified amino silicone oil can be controlled by adjusting the amount of dimethyl silicone oil.

[0023] In some embodiments, the amount of aminosilane used in step S100 may be 10 to 30 parts by weight, preferably 12.5 to 25 parts by weight; and / or the amount of dimethyl silicone oil may be 10 to 30 parts by weight, preferably 15 to 30 parts by weight.

[0024] According to the preparation method provided by the present invention, the mixing conditions in step S100 include: a temperature of 80-90°C; and / or a time of 0.5-5 hours, preferably 1-2 hours.

[0025] In this invention, the mixing in step S100 can be carried out by stirring. The stirring speed is typically 100 to 500 rpm, preferably 200 to 400 rpm.

[0026] According to the preparation method provided by the present invention, the amount of water used in step S200 can be 10 to 30 parts by weight, preferably 10 to 15 parts by weight.

[0027] According to the preparation method provided by the present invention, water in step S200 can be added all at once or in batches. In some embodiments, water in step S200 is added in two batches with a time interval of 20 to 40 minutes, and in some embodiments, the ratio of the first batch of water to the second batch of water is 1:0.2 to 1.

[0028] According to the preparation method provided by the present invention, the hydrolysis conditions in step S200 include: a temperature of 10 to 30°C and a time of 1 to 2 hours.

[0029] According to the preparation method provided by the present invention, the stirring speed in step S200 can be 100 to 500 rpm, preferably 200 to 400 rpm.

[0030] According to the preparation method provided by the present invention, in step S200, the hydrolysis reaction produces methanol or ethanol. After the hydrolysis reaction, nitrogen gas is introduced into the reaction system to remove the remaining water and the methanol or ethanol produced by the hydrolysis.

[0031] In some embodiments, the nitrogen flow rate in step S200 is 0.1–0.8 m³, based on 100 g of hydroxyl-terminated polydimethylsiloxane. 3 / min; and in some implementations 0.3–0.6m 3 / min.

[0032] According to the preparation method provided by the present invention, the nitrogen gas introduction time in step S200 can be 30 to 90 minutes, for example, 60 minutes.

[0033] According to the preparation method provided by the present invention, the phosphazene base is selected from one or more of phosphazene ligand P4-t-Bu, phosphazene ligand P1-tert-butyltris(tetramethylene), phosphazene ligand P2-ET, phosphazene ligand P2-tert-butyl, phosphazene ligand P1-tert-butyl, and phosphazene ligand P4-tert-octyl, preferably phosphazene ligand P4-t-Bu.

[0034] According to the preparation method provided by the present invention, the amount of phosphazene base used in step S300 is 0.0004 to 0.005 parts by weight.

[0035] According to the preparation method provided by the present invention, the weight ratio of the phosphazene base to the organic acid anhydride in step S300 is 1:(1500~15000).

[0036] According to the preparation method provided by the present invention, the first reaction in step S300 is carried out under the condition of introducing nitrogen gas into the reaction system, which is conducive to the removal of by-products such as water, and thus conducive to the polymerization reaction. Furthermore, the viscosity of the reaction system can be controlled by the nitrogen gas flow rate.

[0037] In some embodiments, the nitrogen flow rate in step S300 is 0.1–1.5 m³, based on 100 g of hydroxyl-terminated polydimethylsiloxane. 3 / min, in some implementations it is 0.3–1.2m 3 / min, and in some implementations 0.8–1.2m 3 / min.

[0038] According to the preparation method provided by the present invention, the temperature of the first reaction in step S300 is 75–90°C. Furthermore, in step S300, the reaction termination can be determined by measuring whether the viscosity of the reaction system stops increasing within 10 minutes.

[0039] According to the preparation method provided by the present invention, the organic acid anhydride in step S300 is selected from acetic anhydride, propionic anhydride, and phthalic anhydride, preferably acetic anhydride.

[0040] According to the preparation method provided by the present invention, the temperature of the second reaction in step S300 is 75-90°C.

[0041] According to the preparation method provided by the present invention, the second reaction in step S300 is carried out under stirring conditions. In some embodiments, the stirring speed can be 100-500 rpm, preferably 200-400 rpm.

[0042] According to the preparation method provided by the present invention, the conditions for the removal of low temperature in step S400 include: a temperature of 130-170°C, preferably 140-150°C; and a vacuum degree of 0.097-0.099 MPa.

[0043] According to the preparation method provided by the present invention, the de-lowering treatment in step S400 is carried out under stirring conditions. The stirring speed can be 100-500 rpm, preferably 200-400 rpm.

[0044] According to the preparation method provided by the present invention, there are no special limitations on the stirring method. However, it is preferable to use a double-ribbon stirring method.

[0045] In a second aspect, the present invention provides a modified amino silicone oil prepared by the method described in the first aspect.

[0046] Thirdly, the present invention provides the application of modified amino silicone oil as a finishing agent in fabric finishing.

[0047] This invention has the following advantages:

[0048] (1) In the preparation method of the present invention, phosphazene base is added to the hydrolysis product obtained from a mixture containing hydroxyl-terminated polydimethylsiloxane, methyldialkoxyaminosilane and dimethyl silicone oil to replace catalysts such as trimethylsiloxane potassium as a catalyst for the first reaction. Then, organic acid anhydride is added to carry out the second reaction. The modified amino silicone oil prepared after de-oxidation treatment has low organosilicon cyclic content and low volatile matter, and has low yellowing properties and a wide range of applications. It is not intended to be limited by theory, but it is believed that the use of organic acid anhydride for neutralization (second reaction) in the present invention neutralizes the phosphazene base and reacts with the active hydrogen on the aminosilane to carry out a partial acylation reaction, reducing the content of active hydrogen. In the subsequent application of amino silicone oil, this increases the whiteness of textile products, has low yellowing properties, and reduces the organic salts in the amino silicone oil, thus avoiding cloudiness.

[0049] Furthermore, the use of hydroxyl-terminated polydimethylsiloxane in this invention is beneficial for controlling the uniform distribution of amino groups. In addition, the addition of the capping agent before hydrolysis can effectively control the degree of polymerization (viscosity) of linear hydroxyl-terminated polydimethylsiloxane and methyldialkoxyaminosilane, thus avoiding excessively rapid viscosity growth of the amino silicone oil product.

[0050] (2) In the preparation method of the present invention, phosphazene base is used as a catalyst, which requires a small amount, has a low polymerization reaction (first reaction) temperature, and low energy consumption. In addition, the use of phosphazene base as a catalyst in the present invention can further reduce the content of organosilicon cyclic compounds, reduce the requirements for raw materials, and result in low odor.

[0051] (3) In the preparation method of the present invention, nitrogen is used to remove water, which simplifies the operation and makes the viscosity easy to control. In addition, the preparation method of the present invention is simple in process, mild in conditions, low in equipment requirements, short in production time, low in production cost, and easy to apply in industry. Attached Figure Description

[0052] Figure 1 These are the infrared spectra of the modified amino silicone oil of this invention and the amino silicone oil of the comparative example. Detailed Implementation

[0053] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0054] Unless otherwise specified, the techniques or conditions described in the examples are as described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0055] 1. Determination of molecular weight distribution by gel permeation chromatography

[0056] The molecular weight distribution of amino silicone oil was analyzed using a gel permeation chromatography system (SHODEX GPC system 21) from Showa Denko KK. The mobile phase was toluene, the flow rate was 1.0 mL / min, and the column temperature was 40 °C.

[0057] 2. Volatile matter

[0058] The volatile matter of amino silicone oil was determined using the oven drying method. Specifically, 2g of sample was weighed and dried at 150℃ for 2 hours. The weight of the sample before and after drying was measured, and the volatile matter was calculated using Formula I:

[0059] Volatile matter = (m0-m1) / m0 × 100%

[0060] Where m0 is the weight of the sample before drying, and m1 is the weight of the sample after drying.

[0061] 3. Organosilicon cyclic content

[0062] The content of organosilicon cyclic compounds was determined by GC-FID chromatography based on the internal standard method, and calculated using the following formula:

[0063] wi=(Fi×A2) / m

[0064] Wherein, wi represents the mass fraction of organosilicon cyclic compounds, in g / g;

[0065] Fi represents the correction factor for organosilicon cyclic compounds;

[0066] A2 represents the peak area of ​​the organosilicon rings in the sample;

[0067] m represents the sample mass, in grams.

[0068] 4. Infrared Spectrum

[0069] Infrared analysis was performed using a Fourier transform infrared spectrometer from Bruker.

[0070] 5. Product application test

[0071] The experiment was conducted according to the national standard GB / T 8424.2-2001 "Instrumental Evaluation Method for Relative Whiteness in Color Fastness Testing of Textiles". Specifically, it included:

[0072] Preparation of amino silicone oil emulsion: Using the reverse phase emulsification method, weigh 8g of the prepared amino silicone oil emulsion and dilute it with water to 200g, with a concentration of 40g / L;

[0073] Rolling: Adjust the double rolling mill to a working pressure of 1MPa, pour the prepared emulsion onto the rolling rollers, lay the cut cotton knitted fabric flat on the rolling rollers, and as the rolling rollers slowly rotate, immerse it in the emulsion and come out from under the rolling rollers; then repeat the same steps once more, which is two dips and two rolls.

[0074] Drying: Place the cotton knitted fabric that has been dipped and rolled twice on a special drying rack, fix it in place, and put it into an oven at 150℃ for 3 minutes.

[0075] Whiteness test: A whiteness meter was used to measure the whiteness of different parts of the treated fabric 8 times.

[0076] Example 1

[0077] (1) 100g of hydroxyl-terminated polydimethylsiloxane with a viscosity of 80cs at 25℃, 12.8g of N-aminoethyl-3-aminopropylmethyldimethoxysilane and 17.6g of dimethyl silicone oil with a viscosity of 10cs at 25℃ were added sequentially into a 500ml open reactor equipped with a double-screw ribbon and nitrogen bubbling device. The temperature was raised to 85℃ and stirred at 300 rpm for 1 hour to obtain a uniformly mixed material.

[0078] (2) At 20℃, 5g of water was added to a reactor containing the stirred and mixed materials, and the mixture was stirred for 0.5 hours. Another 5g of water was added, and the mixture was stirred for another 0.5 hours. Nitrogen gas was then introduced for 1 hour to purge excess water and methanol, yielding the hydrolyzed material. The stirring speed was 300 rpm, and the nitrogen gas flow rate was 0.3 mg / min. 3 / min.

[0079] (3) Add 0.0004 g of phosphazene ligand P4-t-Bu to the reactor containing the hydrolyzed material, and react at 85°C while simultaneously introducing nitrogen gas. Stop introducing nitrogen gas when the viscosity of the reaction system no longer increases within 10 minutes to obtain the polymerization reaction material. The nitrogen gas introduction rate is 0.8 m³ / g. 3 / h.

[0080] After stopping the nitrogen flow into the reactor, add 6g of acetic anhydride to the reactor and neutralize for 2 hours at 85°C with stirring at 300 rpm.

[0081] (4) The material was subjected to de-lowering treatment at 140℃, 0.099MPa vacuum and 300 rpm stirring to obtain a colorless and transparent modified amino silicone oil with a viscosity of 3200 mPa·s.

[0082] Example 2

[0083] (1) 100g of hydroxyl-terminated polydimethylsiloxane with a viscosity of 80cs at 25℃, 20.75g of N-aminoethyl-3-aminopropylmethyldimethoxysilane and 27.0g of dimethyl silicone oil with a viscosity of 10cs at 25℃ were added sequentially into a 500ml open reactor equipped with a double-screw ribbon and nitrogen bubbling device. The temperature was raised to 85℃ and stirred at a speed of 300 rpm for 1 hour to obtain a uniformly mixed material.

[0084] (2) At 20℃, 7.5g of water was added to a reactor containing the stirred and mixed materials, and the mixture was stirred for 0.5 hours. Another 7.5g of water was added, and the mixture was stirred for another 0.5 hours. Nitrogen gas was then introduced for 1 hour to purge excess water and methanol, yielding the hydrolyzed material. The stirring speed was 300 rpm, and the nitrogen gas flow rate was 0.6 mg / min. 3 / h.

[0085] (3) Add 0.0045 g of phosphazene ligand P4-t-Bu to the reactor containing the hydrolyzed material, and react at 85°C while simultaneously introducing nitrogen gas. Stop introducing nitrogen gas when the viscosity of the reaction system no longer increases within 10 minutes to obtain the polymerization reaction material. The nitrogen gas introduction rate is 0.8 m³ / g. 3 / min.

[0086] After stopping the nitrogen flow into the reactor, add 8.0g of acetic anhydride to the reactor and neutralize for 2 hours at 85°C with stirring at 300 rpm.

[0087] (4) The material was subjected to de-lowering treatment at 140℃, 0.099MPa vacuum and 300 rpm stirring to obtain a colorless and transparent modified amino silicone oil with a viscosity of 2900 mPa·s.

[0088] Example 3

[0089] (1) 100g of hydroxyl-terminated polydimethylsiloxane with a viscosity of 70cs at 25℃, 20.75g of N-aminoethyl-3-aminopropylmethyldimethoxysilane and 27.0g of dimethyl silicone oil with a viscosity of 10cs at 25℃ were added sequentially into a 500ml open reactor equipped with a double-screw ribbon and nitrogen bubbling device. The temperature was raised to 85℃ and stirred at 300 rpm for 1 hour to obtain a uniformly mixed material.

[0090] (2) At 20℃, 7.5g of water was added to a reactor containing the stirred and mixed materials, and the mixture was stirred for 0.5 hours. Another 7.5g of water was added, and the mixture was stirred for another 0.5 hours. Nitrogen gas was then introduced for 1 hour to purge excess water and methanol, yielding the hydrolyzed material. The stirring speed was 300 rpm, and the nitrogen gas flow rate was 0.5mg / min. 3 / min.

[0091] (3) Add 0.0045 g of phosphazene ligand P4-t-Bu to the reactor containing the hydrolyzed material, and react at 85°C while simultaneously introducing nitrogen gas. Stop introducing nitrogen gas when the viscosity of the reaction system no longer increases within 10 minutes to obtain the polymerization reaction material. The nitrogen gas introduction rate is 1.0 m³ / g. 3 / min.

[0092] After stopping the nitrogen flow into the reactor, add 8.0g of acetic anhydride to the reactor and neutralize for 2 hours at 85°C with stirring at 300 rpm.

[0093] (4) The material was subjected to de-lowering treatment at 140℃, 0.099MPa vacuum and 300 rpm stirring to obtain a colorless and transparent modified amino silicone oil with a viscosity of 2700 mPa·s.

[0094] Example 4

[0095] The raw materials and operations are basically the same as in Example 2, except that 0.2g of D4 organosilicon cyclic compound is added in step (1).

[0096] Example 5

[0097] The raw materials and operations are basically the same as in Example 2, except that 0.4g of D4 organosilicon cyclic compound is added in step (1).

[0098] Example 6

[0099] The raw materials and operations are basically the same as in Example 2, except that in step (3), an equimolar amount of phosphazene ligand P2-ET is used instead of phosphazene ligand P4-t-Bu.

[0100] Example 7

[0101] The raw materials and operations are basically the same as in Example 2, except that in step (3), phthalic anhydride is used instead of acetic anhydride in equal molar amounts.

[0102] Comparative Example 1

[0103] (1) 100g of hydroxyl-terminated polydimethylsiloxane with a viscosity of 80cs at 25℃, 20.75g of N-aminoethyl-3-aminopropylmethyldimethoxysilane and 27.0g of dimethyl silicone oil with a viscosity of 10cs at 25℃ were added sequentially into a 500mL open reactor equipped with a double-screw and nitrogen bubbling device. The temperature was raised to 85℃ and stirred at 300 rpm for 1 hour to obtain a uniformly mixed material.

[0104] (2) At 20℃, 7.5g of water was added to a reactor containing the stirred and mixed materials, and the mixture was stirred for 0.5 hours. Another 7.5g of water was added, and the mixture was stirred for another 0.5 hours. Nitrogen gas was then introduced for 1 hour to purge excess water and methanol, yielding the hydrolyzed material. The stirring speed was 300 rpm, and the nitrogen gas flow rate was 0.6 mg / min. 3 / min.

[0105] (3) Add 0.04 g of potassium trimethylsilanolate to the reactor containing the hydrolyzed material, and react at 85°C while simultaneously introducing nitrogen gas. Stop introducing nitrogen gas when the viscosity of the reaction system no longer increases within 10 minutes to obtain the polymerization reaction material. The nitrogen gas introduction rate is 0.8 m³ / g. 3 / min.

[0106] Stop the nitrogen flow into the reactor, add 0.03g of silicon-based phosphate to the reactor, and neutralize for 2 hours at 85°C with stirring at 300 rpm.

[0107] (4) The material was subjected to desaturation treatment at 140℃, 0.099MPa vacuum and 300 rpm stirring to obtain colorless and transparent amino silicone oil with a viscosity of 3000mPa.S.

[0108] Comparative Example 2

[0109] (1) 100g of hydroxyl-terminated polydimethylsiloxane with a viscosity of 70cs at 25℃, 20.75g of N-aminoethyl-3-aminopropylmethyldimethoxysilane and 27.0g of dimethyl silicone oil with a viscosity of 10cs at 25℃ were added sequentially into a 500mL open reactor equipped with a double-screw and nitrogen bubbling device. The temperature was raised to 85℃ and stirred at 300 rpm for 1 hour to obtain a uniformly mixed material.

[0110] (2) At 20℃, 7.5g of water was added to a reactor containing the stirred and mixed materials, and the mixture was stirred for 0.5 hours. Another 7.5g of water was added, and the mixture was stirred for another 0.5 hours. Nitrogen gas was then introduced for 1 hour to purge excess water and methanol, yielding the hydrolyzed material. The stirring speed was 300 rpm, and the nitrogen gas flow rate was 0.5mg / min. 3 / min.

[0111] (3) Add 0.021 g of potassium trimethylsilanolate to the reactor containing the hydrolyzed material, and react at 85°C while simultaneously introducing nitrogen gas. Stop introducing nitrogen gas when the viscosity of the reaction system no longer increases within 10 minutes to obtain the polymerization reaction material. The nitrogen gas introduction rate is 1.0 m³ / g. 3 / min.

[0112] Stop the nitrogen flow into the reactor, add 0.032g of silicon-based phosphate to the reactor, and neutralize for 2 hours at 85°C with stirring at 300 rpm.

[0113] (4) The material was subjected to de-lowering treatment at 140℃, 0.099MPa vacuum and 300 rpm stirring to obtain colorless and transparent amino silicone oil with a viscosity of 2700 mPa·s.

[0114] Comparative Example 3

[0115] The raw materials and operations are basically the same as in Example 2, except that in step (3), 0.02 g of potassium trimethylsilanolate is used instead of 0.0045 g of phosphazene ligand P4-t-Bu.

[0116] Comparative Example 4

[0117] The raw materials and operations are basically the same as in Example 2. The only difference is that acetic anhydride is not added in step (3). After stopping the nitrogen gas supply to the reactor, the mixture is treated for 2 hours at 85°C with stirring at 300 rpm.

[0118] Comparative Example 5

[0119] The raw materials and operations are basically the same as in Example 2, except that 0.4 g of D4 organosilicon cyclic compound is added in step (1); and 0.02 g of potassium trimethylsilanolate is used instead of 0.0045 g of phosphazene ligand P4-t-Bu in step (3).

[0120] Performance Characterization

[0121] The prepared amino silicone oil was characterized by infrared spectroscopy, and the results are as follows: Figure 1 As shown. Figure 1 Middle, 3764cm -1 3700cm -1 The peak represents free -OH; 2963 cm⁻¹ -1 The CH3 peak has a protrusion to the left of it, which is a -NH peak, at 1598 cm⁻¹. -1 1445cm -1 -NH peak; 2963 cm⁻¹ -1 2905cm -1CH3 peak; 1261 cm⁻¹ -1 The peak is Si-CH3; 1093 cm⁻¹ -1 Peaks with a degree of polymerization greater than 5 Si-O chain segments; 800 cm⁻¹ -1 864cm -1 The peak is Si(CH3)2. Figure 1 Curve 1 shows the spectrum of the modified amino silicone oil in Example 2, and curve 2 shows the spectrum of the amino silicone oil in Comparative Example 1. Figure 1 As can be seen, compared with Comparative Example 1, the modified amino silicone oil in Example 2 has a higher spectral density at 1598 cm⁻¹. -1 1445cm -1 The -NH peak at that location decreased significantly.

[0122] The amino silicone oils prepared in each example and comparative example were characterized by GC-FID chromatography, and the contents of various organosilicon rings are shown in Table 2. Additionally, Table 1 shows the retention times of various organosilicon rings.

[0123] The amino silicone oils prepared in each example and comparative example were characterized by gel permeation chromatography, and the results are shown in Table 3.

[0124] The whiteness of the amino silicone oils prepared in each example and comparative example was tested, and the results are shown in Table 4.

[0125] Table 1 Retention times of various organosilicon rings

[0126] Components Retention time / min D3 5.799 D4 9.252 D5 11.240 D6 12.931

[0127] Table 2. Cyclic content of amino silicone oils

[0128]

[0129]

[0130] As shown in Table 2, the amino silicone oil prepared by this invention has a low content of organosilicon cyclic compounds and low volatile matter. In particular, as can be seen from Examples 2 and 4-5 and Comparative Example 5, the method of this invention can effectively reduce the content of organosilicon cyclic compounds, has a low odor, and has relatively low requirements for the quality of raw materials.

[0131] Table 3 Molecular weight distribution

[0132] Hydroxyl-terminated polydimethylsiloxane Mw / Mn Amino silicone oil Mw / Mn Example 1 1.82 1.87 Example 2 1.82 1.90 Example 3 1.74 1.81 Example 4 1.82 1.95 Example 5 1.82 1.99 Example 6 1.82 1.90 Example 7 1.82 1.91 Comparative Example 1 1.82 1.93 Comparative Example 2 1.74 1.92 Comparative Example 3 1.82 1.89 Comparative Example 4 1.82 1.88 Comparative Example 5 1.82 2.21

[0133] As shown in Table 3, the amino silicone oil prepared by this invention has a narrow molecular weight distribution. In particular, as shown in Examples 2 and 4-5 and Comparative Example 5, the preparation of this invention still exhibits a narrow molecular weight distribution even when the raw materials contain a high content of organosilicon cyclic compounds.

[0134] Table 4 Whiteness Test Data

[0135] Serial Number Amino silicone oil emulsion 1 2 3 4 5 6 7 8 average value 0# blank 83.05 83.46 84.62 86.62 85.62 85.2 82.62 83.99 84.40 1# Example 1 80.12 79.98 80.04 81.82 80.62 83.85 81.46 80.06 80.99 2# Example 2 78.44 78.89 81.05 82.64 78.81 79.08 81.7 79.58 80.02 3# Example 3 80.51 80.92 81.09 82.07 80.28 82.01 81.76 82.17 81.35 4# Example 4 79.23 78.95 80.86 81.68 79.63 79.57 81.42 79.13 80.06 5# Example 5 78.79 79.64 82.03 80.36 79.44 78.52 80.69 79.84 79.91 6# Example 6 78.12 79.24 79.45 77.85 79.03 78.31 79.68 78.39 78.76 7# Example 7 78.23 77.48 80.39 80.13 78.63 78.33 80.32 78.14 78.96 8# Comparative Example 1 77.15 76.63 74.78 76.93 77.03 75.85 75.61 75.19 76.15 9# Comparative Example 2 77.99 75.05 75.37 76.02 73.34 74.93 74.52 77.16 75.55 10# Comparative Example 3 78.11 77.24 75.36 77.67 78.03 76.08 75.43 76.69 76.83 11# Comparative Example 4 76.37 75.84 74.97 76.18 76.39 75.65 74.78 74.83 75.63 12# Comparative Example 5 76.58 75.47 74.65 76.67 76.6 75.26 75.11 75.96 75.79

[0136] As shown in Table 4, the modified amino silicone oil prepared by this invention has high whiteness and low yellowing. Specifically, as shown in Example 2 and Comparative Examples 1 and 3-5, in this invention, the modified amino silicone oil prepared by adding phosphazene base instead of potassium trimethylsiloxane as a catalyst to the hydrolysis product obtained from a mixture containing hydroxyl-terminated polydimethylsiloxane, methyldialkoxyaminosilane, and dimethyl silicone oil for a first reaction, followed by the addition of an organic acid anhydride for a second reaction, and then undergoing de-lowering treatment, has low organosilicon cyclic content and low volatile matter content, and exhibits low yellowing.

[0137] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing modified amino silicone oil, wherein, The preparation method includes the following steps: S100. At a temperature of 20-100°C, 100 parts by weight of hydroxyl-terminated polydimethylsiloxane, 2-30 parts by weight of aminosilane and 3-30 parts by weight of dimethyl silicone oil are mixed to obtain a mixture. S200. At a temperature of 20-40°C and under stirring conditions, 6-40 parts by weight of water are added to the mixture obtained in step S100 to carry out a hydrolysis reaction. Then, nitrogen gas is introduced into the reaction system to remove water and the generated alcohol, and the hydrolysis product is obtained. S300: Add 0.0001 to 0.005 parts by weight of phosphazene base to the hydrolysis product obtained in step S200, and carry out the first reaction at a temperature of 50 to 100°C and under the condition of purging nitrogen into the reaction system; add 1 to 10 parts by weight of organic acid anhydride, and carry out the second reaction at a temperature of 50 to 100°C to obtain the reaction product. S400: The reaction product obtained in step S300 is subjected to de-lowering treatment to obtain modified amino silicone oil.

2. The preparation method according to claim 1, wherein, The hydroxyl-terminated polydimethylsiloxane has a viscosity of 40–150 cs at 25°C, preferably 40–100 cs, and more preferably 70–80 cs. And / or, the contents of organosilicon cyclic compounds D4, D5 and D6 in the hydroxyl-terminated polydimethylsiloxane are each independently ≤0.5% by weight.

3. The preparation method according to claim 1 or 2, wherein, The aminosilane is selected from N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, 3-piperazinepropylmethyldimethoxysilane, 3-piperazinepropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane, preferably N-aminoethyl-3-aminopropylmethyldimethoxysilane; And / or, the viscosity of the dimethyl silicone oil at 25°C is 2-20 cs, preferably 10-20 cs.

4. The preparation method according to any one of claims 1-3, wherein, The amount of aminosilane used in step S100 is 10 to 30 parts by weight, preferably 12.5 to 25 parts by weight; and / or the amount of dimethyl silicone oil used is 10 to 30 parts by weight, preferably 15 to 30 parts by weight. And / or, the mixing conditions in step S100 include: a temperature of 80-90°C; and / or, a time of 0.5-5 hours, preferably 1-2 hours.

5. The preparation method according to any one of claims 1-4, wherein, In step S200, water is added in two batches with an interval of 20 to 40 minutes. The ratio of the first batch of water to the second batch of water is 1:0.2 to 1. And / or, the amount of water used in step S200 is 10 to 30 parts by weight, preferably 10 to 15 parts by weight; And / or, the hydrolysis conditions in step S200 include: a temperature of 10–30°C; and a time of 1–2 hours; And / or, based on 100g of hydroxyl-terminated polydimethylsiloxane, the nitrogen flow rate in step S200 is 0.1–0.8 m³. 3 / min, preferably 0.3–0.6m 3 / min; And / or, the nitrogen gas introduction time in step S200 is 30 to 90 minutes, for example, 60 minutes.

6. The preparation method according to any one of claims 1-5, wherein, The phosphazene base is selected from one or more of phosphazene ligand P4-t-Bu, phosphazene ligand P1-tert-butyltris(tetramethylene), phosphazene ligand P2-ET, phosphazene ligand P2-tert-butyl, phosphazene ligand P1-tert-butyl, and phosphazene ligand P4-tert-octyl, preferably phosphazene ligand P4-t-Bu. And / or, in step S300, the amount of phosphazene base used is 0.0004 to 0.005 parts by weight; And / or, in step S300, the weight ratio of the phosphazene base to the organic acid anhydride is 1:(1500-15000); And / or, based on 100g of hydroxyl-terminated polydimethylsiloxane, the nitrogen flow rate in step S300 is 0.1–1.5m³. 3 / min, preferably 0.3~1.2m 3 / min, more preferably 0.8 to 1.2 m 3 / min; And / or, the temperature of the first reaction in step S300 is 75–90°C.

7. The preparation method according to any one of claims 1-6, wherein, The organic acid anhydride mentioned in step S300 is selected from acetic anhydride, propionic anhydride, and phthalic anhydride, preferably acetic anhydride; And / or, the temperature of the second reaction in step S300 is 75–90°C.

8. The preparation method according to any one of claims 1-7, wherein, The conditions for the removal of low temperature in step S400 include: a temperature of 130-170°C, preferably 140-150°C; and a vacuum degree of 0.097-0.099 MPa.

9. The modified amino silicone oil prepared by any one of claims 1-8.

10. The application of the modified amino silicone oil according to claim 9 as a finishing agent in fabric finishing.

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