Organosilicon polymer, self-emulsifying silicone oil emulsion and preparation method

Abstract

The invention belongs to the field of organosilicon polymer chemistry, and particularly discloses an organosilicon polymer, a self-emulsifying silicone oil emulsion and a preparation method. The organic silicon polymer is formed by polymerizing a monomer shown in a formula I and a monomer shown in a formula II; wherein the mass ratio of the monomer shown in the formula I to the monomer shown in the formula II is (1-9): 1; in the formula I, X is 25 to 450, and R is a C1-C18 alkyl group, a phenyl group, or a C1-C18 alkyl group with 1 to 2 amino substituent groups, and in the formula II, X is 25 to 450, and R is a C1-C18 alkyl group, a phenyl group, or a C1-C18 alkyl group with 1 to 2 amino substituent groups. Starting from the initial raw material octamethylcyclotetrasiloxane, the organosilicon polymer can be prepared by only three steps; the process is short and time is reduced; because hydrogen-containing silicone oil is not involved in the preparation process, byproducts are not generated, and water washing is not needed in the preparation process, so that water consumption and energy consumption are reduced.

Description

Technical Field

[0001] This application belongs to the field of organosilicon polymer chemistry. More specifically, it relates to an organosilicon polymer, a self-emulsifying silicone oil emulsion, and a preparation method thereof. Background Art

[0002] Organosilicon finishing agents are aqueous emulsions of organosilicon polymer, with the main component being polysiloxane, and are suitable for soft finishing of natural fiber textiles such as cotton, wool, silk, linen, and human hair.

[0003] The first-generation organosilicon soft finishing agent is dimethyl silicone oil or hydroxyl silicone oil, which is a white emulsion obtained by emulsifying with a surfactant, mainly used for yarn lubrication or as a smoothing component of fabric raising agents. The second-generation organosilicon soft finishing agent is amino-modified silicone oil. Due to the introduction of amino groups with high affinity for fabrics in the molecular structure, the smoothness of the fabric is greatly improved, and it is mainly used for soft and smooth finishing of various fibers and fabrics. By combining microemulsion technology with amino silicone oil, a blue-light transparent liquid can be obtained. The product features good handfeel, but still needs improvement in terms of high electrolyte resistance and anion chemical resistance. The product is prone to oil floating under poor processing conditions, and cannot be used in the dyeing system, and the treated fabric becomes hydrophobic. To avoid this problem, scientists have developed the third-generation organosilicon soft finishing agent, polyether-modified silicone oil, whose active ingredient is polyether side-chain modified dimethyl silicone oil. The product is generally a transparent light yellow liquid, miscible with water, mainly used for hydrophilic finishing of various fibers and fabrics, with less yellowing, good compounding performance, non-sticking to rollers, and no oil floating. The disadvantage is that the handfeel is average and the cost performance is poor, and the current market share is small.

[0004] In the 1990s, Momentive Performance Materials Inc. of the United States developed a linear block polyetheramine organosilicon terpolymer fabric softener, which can be called the fourth-generation fabric softener. Since it is synthesized using terpolymerization technology, it is commonly referred to as terpolymerized silicone oil. It has greatly improved the stability and hydrophilicity of traditional fabric softeners and obtained a satisfactory handfeel, and is a very popular fabric softener at home and abroad. Its synthesis method is that terminal epoxy silicone oil (or terminal polyether epoxy silicone oil) reacts with polyetheramine to obtain crude oil, and a certain amount of surfactant is added for emulsification to prepare a silicone oil emulsion. For example, patent document CN111019139A discloses a preparation method of a self-emulsifying block copolymerized silicone oil emulsion, using terminal polyether epoxy silicone oil to react with N-N dimethylethylenediamine to generate block copolymerized silicone oil, and adjusting the ratio of polyether groups and dimethylsiloxane segments to improve the hydrophilicity of the silicone oil, thereby realizing the self-emulsification of block silicone oil. Non-patent literature "Preparation of Self-Emulsifying Block Silicone Oil" (Zhao Haowei, "New Chemical Materials", Vol. 47 No. 8 P244) uses terminal epoxy silicone oil (molecular weight M = 6000) and polyetheramine ED600 to prepare a self-emulsifying block silicone oil.

[0005] Starting from the raw material octamethylcyclotetrasiloxane, the above-mentioned technology requires four steps to synthesize. Specifically, in the first step, hydrogen-terminated silicone oil is prepared using hydrogen-containing disiloxane as the end-capping agent and concentrated sulfuric acid as the catalyst. During the preparation process, sodium bicarbonate is used to neutralize the concentrated sulfuric acid, and a large amount of water is used to wash the hydrogen-terminated silicone oil multiple times until it is neutral. Usually, when producing 1 ton of hydrogen-terminated silicone oil, about 50 kg of by-product sodium sulfate is generated, and 1 - 1.5 tons of water is consumed. This process consumes a large amount of water and generates a large amount of energy consumption. In the second step, allyl epoxy polyether and hydrogen-terminated silicone oil are used to prepare epoxy-terminated silicone oil through a hydrosilylation reaction under the catalysis of chloroplatinic acid. The use of precious metal catalysts results in high costs. Moreover, the chloroplatinic acid catalyst has requirements for the reaction system. When nitrogen, phosphorus, or sulfur elements are present in the reactants, it is easy to cause catalyst poisoning and the reaction cannot proceed. In the third step, polyetheramine or bifunctional small molecule amine is used for chain extension reaction to obtain silicone oil. In the fourth step, silicone oil, glacial acetic acid, and water are mixed and emulsified to obtain self-emulsifying block silicone oil. Summary of the Invention

[0006] Aiming at the defects of the prior art, the purpose of this application is to introduce a certain number of hydrophilic polyvinylpyrrolidone groups into the structure of silicone oil, directly emulsify without adding an emulsifier to obtain an emulsion, and achieve the self-emulsification of block silicone oil.

[0007] To achieve the above purpose, in the first aspect, this application provides an organosilicon polymer with a molecular weight of 5,000 - 200,000, which is polymerized from monomer of formula I and monomer of formula II. Among them, the mass ratio of the monomer of formula I to the monomer of formula II is (1 - 9):1;

[0008] I

[0009] II Among them, X is 25 - 450, R is phenyl, an alkyl group without substituents or a C1 - C alkyl group with 1 - 2 amino substituents. 18 alkyl.

[0010] Preferably, R includes methyl and R1 with a molar ratio of (0.4 - 80):1. R1 is an alkyl group of C2 - C, phenyl, or a C1 - C alkyl group with 1 - 2 amino substituents; the molar ratio of methyl is more than 28.5% of R. 18 alkyl, phenyl, or a C1 - C alkyl group with 1 - 2 amino substituents; 18 alkyl; the molar ratio of methyl is more than 28.5% of R.

[0011] In the second aspect, this application provides a self-emulsifying silicone oil emulsion, including 5 wt% - 25 wt% of the organosilicon polymer by mass fraction.

[0012] Preferably, the self-emulsifying silicone oil emulsion further comprises acetic acid accounting for 1 wt% - 2 wt% of the mass of the silicone polymer.

[0013] In a third aspect, the present application provides a method for preparing a silicone polymer, comprising: reacting a compound of formula III and N-vinylpyrrolidone in a mass ratio of (1 - 9):1 under the action of an initiator through a radical reaction to obtain the silicone polymer, wherein X is 25 - 450.

[0014]

[0015] III Preferably, the solvent for the radical reaction is an alcohol compound, and the mass of the solvent is 1 - 2 times the total mass of the N-vinylpyrrolidone and the compound of formula III.

[0016] As a further preference, the alcohol compound is isopropyl alcohol.

[0017] Preferably, the temperature of the radical reaction is 60°C - 80°C, and the atmosphere of the radical reaction is an inert gas.

[0018] Preferably, the mass ratio of the compound of formula III and N-vinylpyrrolidone is (1 - 9):1.

[0019] Preferably, the initiator is an azo initiator, and the mass of the initiator is 1 wt% - 2 wt% of the total mass of the N-vinylpyrrolidone and the compound of formula III.

[0020] As a further preference, the azo initiator is azobisisobutyronitrile, azobisisoheptonitrile, dimethyl 2,2'-azobis(2-methylpropionate), or azoisobutyronitrile carboxamide.

[0021] As an even further preference, the azo initiator is azobisisobutyronitrile or dimethyl 2,2'-azobis(2-methylpropionate).

[0022] Preferably, the preparation method of the compound of formula III is: stirring and heating octamethylcyclotetrasiloxane, a silane coupling agent, and tetramethylammonium hydroxide to 100°C - 120°C under an inert gas atmosphere, reacting for 3 h - 4 h, then stirring and heating to 140°C - 145°C and reacting for 1 h to obtain the compound of formula III.

[0023] Preferably, the preparation method of the compound of formula III is: stirring and heating octamethylcyclotetrasiloxane, a compound of formula IV, a silane coupling agent, and tetramethylammonium hydroxide to 100°C - 120°C under an inert gas atmosphere, reacting for 3 h - 4 h, then stirring and heating to 140°C - 145°C and reacting for 1 h - 2 h to obtain the compound of formula III; wherein, R1 is C1 - C18 alkyl, phenyl, or C1-C with 1-2 amino substituents 18 alkyl

[0024] IV.

[0025] As a further preference, the chemical reaction formula for preparing the compound of formula III is specifically as follows:

[0026] wherein x = 4a + b, a is 5 to 100, and b is 5 to 50.

[0027] As a further preference, the silane coupling agent is dimethyldimethoxysilane, methylphenyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldimethoxysilane.

[0028] As a further preference, the mass of the silane coupling agent is 5 wt% to 40 wt% of octamethylcyclotetrasiloxane; the mass of tetramethyldivinyldisiloxane is 0.6 wt% to 4 wt% of octamethylcyclotetrasiloxane.

[0029] Generally speaking, compared with conventional self-emulsifying block silicone oil, this application innovates in structure, uses polyvinylpyrrolidone as the hydrophilic group, and synthesizes N-vinylpyrrolidone-side chain modified dimethylsiloxane random copolymer (PNVP-co-PDMS), that is, an organosilicon polymer, which has the following beneficial effects: 1. Starting from the initial raw material octamethylcyclotetrasiloxane, the organosilicon polymer can be prepared in at most three steps; the process is short and the time is reduced; 2. Since the preparation process does not involve hydrogen-containing silicone oil, no by-products will be generated, and the preparation process does not require water washing, so water consumption and energy consumption are reduced; 3. There is no need to use precious metal catalysts, which reduces the production cost; 4. Due to the innovation of the technical route, the most critical reaction mechanism is adjusted from "hydrosilylation" to "free radical polymerization", so even if the reactant structure contains N element (such as amino group), it will not cause catalyst poisoning and unable to react. Description of the Drawings

[0030] Figure 1 is the infrared spectrum of the side chain modified terminal vinyl silicone oil provided in Example 1 of this application; Figure 2 is the infrared spectrum of the self-emulsifying silicone oil provided in Example 1 of this application. Detailed Embodiments

[0031] In order to make the objectives, technical solutions and advantages of this application more clear and understandable, the following further details this application in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not used to limit this application.

[0032] In the ranges disclosed in this application, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this application.

[0033] This application provides a self-emulsifying silicone oil emulsion, which includes a silicone polymer with a mass fraction of 5 wt% to 25 wt%, acetic acid accounting for 1 wt% to 2 wt% of the mass of the silicone polymer, and a solvent mainly composed of deionized water and alcohol compounds. Among them, the molecular weight of the silicone polymer is 5,000 to 200,000 (when the molecular weight is less than 5,000, it is difficult to exert the performance of the softener; when the molecular weight is higher than 200,000, it may cause the obtained self-emulsifying silicone oil emulsion to be difficult to store stably at room temperature), and it is polymerized from monomer of formula I and monomer of formula II. Among them, the mass ratio of the monomer of formula I to the monomer of formula II is (1 to 9):1. If it is higher than this ratio, too much monomer of formula I may not be able to complete the self-emulsification process; if it is lower than this ratio, too much monomer of formula II will cause the function of the self-emulsifying silicone oil emulsion as a softener to decrease;

[0034] I

[0035] II Among them, X is 25 to 450 (preferably 70 to 415), and R is an alkyl group of C1-C 18 , phenyl, or an alkyl group of C1-C 18 substituted with 1 to 2 amino groups.

[0036] The preparation method of the above-mentioned silicone polymer includes the following steps: S1. Octamethylcyclotetrasiloxane, a compound of formula IV, a silane coupling agent, and tetramethylammonium hydroxide are gradually heated and reacted under an inert gas (such as nitrogen) atmosphere to obtain a compound of formula III; considering the reaction rate and the stability of the catalyst tetramethylammonium hydroxide, it is preferably to first stir and heat up to 100°C to 120°C, react for 3h to 4h, and then stir and heat up to 140°C to 145°C, react for 1h to 2h; among them, R1 is C1-C 18alkyl, phenyl, or C1-C with 1-2 amino substituents 18 When R is methyl, in order to obtain the corresponding silicone polymer, in this reaction, the compound of formula IV can be not used, and only octamethylcyclotetrasiloxane and silane coupling agent are used as reaction raw materials;

[0037] III

[0038] IV The specific chemical reaction formula is as follows: ; (1) or (2) where x = 4a + b, a is 5 to 100, b is 5 to 50; usually a:b is (0.1 to 80):1, so when R1 is not methyl, the molar ratio of methyl in R to R1 is (0.4 to 80):1; that is, the molar fraction of methyl is more than 28.5% of R.

[0040] Among them, the silane coupling agent can be dimethyldimethoxysilane, methylphenyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldimethoxysilane; the mass of the silane coupling agent is 5 wt% to 40 wt% of octamethylcyclotetrasiloxane; the mass of tetramethyldivinyldisiloxane is 0.6 wt% to 4 wt% of octamethylcyclotetrasiloxane.

[0041] S2. React the compound of formula III and N-vinylpyrrolidone with a mass ratio of (1 to 9):1 under the action of an initiator by carrying out a radical reaction in an atmosphere of an inert gas (such as nitrogen) to obtain a solution of the silicone polymer. Considering the boiling point of the solvent and the stability of the initiator comprehensively, the reaction temperature is preferably 60°C to 80°C; among them, the solvent for the radical reaction is an alcohol compound such as isopropanol, and the solvent is 1 to 2 times the total mass of N-vinylpyrrolidone and the compound of formula III. Therefore, in the obtained solution, the mass fraction of the silicone polymer is 33.3% to 50%. Too little solvent will result in too low molecular weight of the generated silicone polymer, and too much will result in too little content of the silicone polymer in the product; Among them, the initiator is an azo initiator (such as azodiisobutyronitrile, azodiisopentanenitrile, dimethyl azodiisobutyrate, azoisobutyronitrile formamide, etc.); considering the reaction efficiency and the molecular weight of the resulting organosilicon polymer needs to be controlled within 5,000 - 200,000, the mass of the initiator is 1 wt% - 2 wt% of the total mass of N-vinylpyrrolidone and the compound of formula III.

[0042] It should be noted that whether it is the intermediate compound of formula III in the process, the finally obtained organosilicon polymer, or the monomer of formula I contained therein, due to the nature of the polymer, parameters such as the length of the molecular chain and the ratio of monomers are not exactly the same for each molecule during a single preparation process. The range of X, and parameters such as the molar ratio of methyl and R1 in the molecule represent the average value rather than the molecular weight of each individual polymer molecule.

[0043] S3. According to the mass fraction of the organosilicon polymer mentioned above being 5 wt% - 25 wt% and the mass fraction of acetic acid being 1 wt% - 2 wt%, calculate the masses of glacial acetic acid and deionized water required to prepare the self-emulsifying silicone oil emulsion; if the mass fraction of the organosilicon polymer is lower than 5 wt%, there will be too few active ingredients in the self-emulsifying silicone oil emulsion, which is not conducive to transportation and storage; if the mass fraction of the organosilicon polymer is higher than 25 wt%, it may cause stratification (i.e., separation of the oil phase and the water phase) during storage; and when in use, it is difficult to dilute to the use concentration. After mixing the obtained solution of the organosilicon polymer with glacial acetic acid, add deionized water in multiple portions and continuously stir, then a self-emulsifying silicone oil emulsion that can be stably stored at room temperature can be obtained. Adding glacial acetic acid can form a double ionization layer, which helps to improve the storage stability of the self-emulsifying silicone oil emulsion; if it is lower than 1 wt%, the double ionization layer is not fully formed; if it is higher than 2 wt%, it cannot further improve the stability of the self-emulsifying silicone oil emulsion and will cause the acidity of the self-emulsifying silicone oil emulsion to be too high.

[0044] The embodiments of the present application will be described below with reference to the accompanying drawings.

[0045] The embodiments of the present application are implemented on the premise of the technical solution of the present application, and detailed implementation manners and processes are given, but the protection scope of the present application is not limited to the following embodiments. For the process parameters not specified in the following embodiments, they are usually in accordance with conventional conditions.

[0046] Example 1 S1: Place 168 g of octamethylcyclotetrasiloxane (molecular weight 296.62), 2.2 g of tetramethyldivinyldisiloxane (molecular weight 186.4), 13.4 g of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (molecular weight 206.36), and 0.168 g of tetramethylammonium hydroxide in a three-necked flask. Under nitrogen protection, stir and heat to 110 °C and react for 4 h. Continue to stir and heat to 145 °C and react for 1 h. Remove low-boiling substances under reduced pressure to obtain side-chain modified vinyl-terminated silicone oil.

[0047] Based on the mass and molecular weight of the reactants, it can be inferred that in this example, R1 is , a = 48, b = 5.5, X = 197.5.

[0048] S2: Place 100 g of side-chain modified vinyl-terminated silicone oil, 18 g of N-vinylpyrrolidone, 173 g of isopropanol, and 1.8 g of initiator azobisisobutyronitrile in a three-necked flask. Under nitrogen protection, heat to 70 °C and keep the temperature for reaction for 12 h. Cool to room temperature to obtain an organosilicon polymer with a mass fraction of about 40.3%.

[0049] S3: Place 50 g of the above organosilicon polymer and 0.5 g of glacial acetic acid in a beaker, stir for 15 minutes, then add 49.5 g of deionized water (add slowly in several portions) and keep stirring to obtain a silicone oil emulsion with a mass fraction of 20%.

[0050] Example 2 S1: Place 180 g of octamethylcyclotetrasiloxane (molecular weight 296.62), 7.2 g of tetramethyldivinyldisiloxane (molecular weight 186.4), 37.1 g of dimethyldimethoxysilane (molecular weight 120.22), and 0.18 g of tetramethylammonium hydroxide in a three-necked flask. Under nitrogen protection, stir and heat to 110 °C and react for 4 h. Continue to stir and heat to 145 °C and react for 1 h. Remove low-boiling substances under reduced pressure to obtain side-chain modified vinyl-terminated silicone oil.

[0051] Based on the mass and molecular weight of the reactants, it can be inferred that in this example, R1 is methyl, a = 15.7, b = 8, X = 70.8.

[0052] S2: Place 50 g of side-chain modified vinyl-terminated silicone oil, 50 g of N-vinylpyrrolidone, 200 g of isopropanol, and 2 g of initiator dimethyl azobisisobutyrate in a three-necked flask. Under nitrogen protection, heat to 70 °C and keep the temperature for reaction for 12 h. Cool to room temperature to obtain an organosilicon polymer with a mass fraction of about 33%.

[0053] S3: Place 50 g of the above silicone polymer and 1 g of glacial acetic acid in a beaker, stir for 15 minutes, then add 31.5 g of deionized water (slowly added in multiple portions) and continue stirring to obtain a silicone oil emulsion with a mass fraction of 20%.

[0054] Example 3 S1: Place 224.7 g (molecular weight 296.62) of octamethylcyclotetrasiloxane, 1.4 g (molecular weight 186.4) of tetramethyldivinyldisiloxane, 13.8 g (molecular weight 182.29) of methylphenyldimethoxysilane, and 0.22 g of tetramethylammonium hydroxide in a three-necked flask. Under nitrogen protection, stir and heat to 110 °C, react for 4 h, continue stirring and heating to 145 °C, react for 1 h, and remove low-boiling substances under reduced pressure to obtain a side-chain modified vinyl-terminated silicone oil. Based on the mass and molecular weight of the reactants, it can be inferred that in this example, R1 is phenyl, a = 101, b = 10.1, and X = 414.1.

[0055] S2: Place 90 g of the side-chain modified vinyl-terminated silicone oil, 10 g of N-vinylpyrrolidone, 100 g of isopropanol, and 1 g of initiator azobisisobutyronitrile in a three-necked flask. Under nitrogen protection, heat to 70 °C, hold the reaction for 12 h, and cool to room temperature to obtain a silicone polymer with a mass fraction of 50%.

[0056] S3: Place 50 g of the above silicone polymer and 1 g of glacial acetic acid in a beaker, stir for 15 minutes, then add 74.5 g of deionized water (slowly added in multiple portions) and continue stirring to obtain a silicone oil emulsion with a mass fraction of 20%.

[0057] Example 4 Repeat Example 1 with the same steps, except that in step S1, 23.3 g (molecular weight 358.4) is used to replace 13.4 g of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, that is, R1 is an alkyl group of C 18

[0058] Example 5 Repeat Example 1 with the same steps, except that in step S1, the mass of octamethylcyclotetrasiloxane is 85.6 g and the mass of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane is 33.5 g, that is, the corresponding a = 8, b = 20, and X = 52.

[0059] Example 6 Repeat Example 1 with the same steps, except that in step S3, the mass of deionized water added is 30.1 g, and the mass fraction of the obtained silicone oil emulsion is 25%.

[0060] Example 7​ The silicone oil emulsion finally obtained in Example 1 was mixed with three times its mass of deionized water to obtain a silicone oil emulsion with a mass fraction of 5%.

[0061] Comparative Example 1 100 g of hydrogen-terminated silicone oil (M = 8000), 12 g of allyl epoxy polyether (M = 480), and 5.6 g of absolute ethanol were mixed evenly, stirred and heated to 65 °C, 0.3 mL of chloroplatinic acid catalyst was added, kept warm for 3 h, cooled to 40 °C and taken out to obtain epoxy polyether-terminated silicone oil.

[0062] 100 g of the above epoxy polyether-terminated silicone oil was mixed evenly with 1.5 g of N, N-dimethylethylenediamine, stirred and heated to 100 °C for reaction for 8 h until the solution became transparent, and taken out after cooling to room temperature to obtain block copolymerized silicone oil.

[0063] 40 g of the above block copolymerized silicone oil and 2 g of glacial acetic acid were placed in a beaker, stirred for 15 minutes, then 158 g of deionized water (added slowly in several portions) was added and stirring was continued to prepare a silicone oil emulsion with a mass fraction of 20%.

[0064] Comparative Example 2 (Zhao Haowei. "Preparation of Self-emulsifying Block Silicone Oil") 120 g of epoxy-terminated silicone oil (M = 6000), 16.8 g of polyetheramine ED-600, and 136.8 g of ethylene glycol monobutyl ether were placed in a three-necked flask, heated to 80 °C, and kept warm for reaction for 10 h. 50 g of the above self-emulsifying block silicone oil and 1 g of glacial acetic acid were placed in a beaker, stirred for 15 minutes, then 74 g of deionized water (added slowly in several portions) was added and stirring was continued to prepare a clear and transparent silicone oil emulsion with a mass fraction of 20%.

[0065] Comparative Example 3 Example 1 was repeated with the same steps, except that in step S2, the side-chain modified vinyl-terminated silicone oil and N-vinylpyrrolidone were 75 g and 43 g respectively. After keeping warm for reaction for 12 hours and cooling to room temperature, the obtained organosilicon polymer had a large viscosity, poor fluidity, and presented a jelly-like state. According to the preparation method of the silicone oil emulsion in Example 1, the organosilicon polymer could not be dispersed and an emulsion could not be obtained; this might be due to the too high proportion of N-vinylpyrrolidone, so that a certain amount of by-product polyvinylpyrrolidone was generated during the reaction; its compatibility with the obtained organosilicon polymer was poor, and the comprehensive performance was an increase in viscosity and poor fluidity.

[0066] Comparative Example 4 Example 1 was repeated with the same steps, except that in step S2, the side-chain modified vinyl-terminated silicone oil and N-vinylpyrrolidone were 107 g and 11 g respectively.

[0067] Experimental result verification Infrared spectrum test The side-chain modified vinyl-terminated silicone oil and self-emulsifying silicone oil obtained in Example 1 were tested using a Fourier transform infrared spectrometer (model: Thermo Fisher Nicolet iS10, purchased from Thermo Fisher Scientific, USA). The resolution of the infrared spectrometer was 4 cm -1 , scanned 32 times, and the test range was 4000~400 cm -1 . The obtained infrared spectra are shown in Figure 1 and Figure 2 respectively.

[0068] Figure 1 It can be seen that the characteristic absorption peak of unsaturated hydrogen is at 3047.65 cm -1 , the characteristic absorption peak of C=C is at 1594.76 cm -1 , the stretching vibration absorption peaks of Si-O-Si are at 1096.22 cm -1 and 1016.57 cm-1, the characteristic absorption peaks of Si-CH3 are at 1260.91 cm -1 , 864.54 cm -1 , 799.69 cm -1 , the characteristic absorption peaks of -CH3 are at 2963.08 cm -1 and 2905.41 cm -1 , the characteristic absorption peaks of saturated C-H bending vibration are at 1445.24 cm -1 and 1412.59 cm -1 , the characteristic absorption peak of Si-C stretching vibration is at 702.72 cm -1 , indicating that the side-chain modified vinyl-terminated silicone oil was obtained through the reaction, and vinyl was introduced into the silicone oil structure, with the structural formula being III. (Based on this, a radical polymerization reaction can be carried out. Figure 2 It can be seen that the characteristic absorption peak of carbonyl is at 1660.75 cm -1 , and the other peaks are the characteristic absorption peaks of siloxane. There are no characteristic absorption peaks of unsaturated hydrogen and C=C, indicating that N-vinylpyrrolidone reacts with the side-chain modified vinyl-terminated silicone oil.

[0069] Meanwhile, based on Example 1, the type of the R1 group was changed, and the reaction temperature and reaction time in the silane coupling reaction in Step S1 and the radical reaction in Step S2 were adjusted. After estimation, the molecular weights of the obtained organosilicon polymers were all between 5,000 and 200,0000.

[0070] Heat resistance stability test Experimental method: The silicone oil emulsions prepared in the examples and comparative examples were placed in an oven at 50 °C for 2 weeks. After that, the stability was observed, whether there was stratification or demulsification.

[0071] The experimental results are shown in Table 1.

[0072] Table 1 Heat Resistance Stability Test Results

[0073] Performing heat resistance stability tests on Examples 4 - 7 can also obtain the same results as Examples 1 - 3.

[0074] Electrolyte (sodium sulfate) Resistance Stability Experimental method: Add 9 times the volume of water to the silicone oil emulsion obtained by preparing the examples and comparative examples, configure it into a working solution with a silicone oil emulsion content of 100 g / L in a glass beaker, add 0.1 g / L of reactive yellow, then add sodium sulfate according to a certain concentration, keep it warm at a temperature of 50 °C for 60 minutes. After that, pour out the working solution and observe the stability.

[0075] The experimental results are shown in Table 2.

[0076] Table 2 Electrolyte Resistance Stability Test Results

[0077] Performing heat resistance stability tests on Examples 4 - 6 can also obtain the same results as Examples 1 - 3.

[0078] Alkali (soda ash) Resistance Stability Test Experimental method: Add 9 times the volume of water to the silicone oil emulsion obtained by preparing the examples and comparative examples, configure it into a working solution with a silicone oil emulsion content of 100 g / L in a glass beaker, add 0.1 g / L of reactive yellow, then add soda ash according to a certain concentration, keep it warm at a temperature of 50 °C for 60 minutes. After that, pour out the working solution and observe the stability.

[0079] The experimental results are shown in Table 3.

[0080] Table 3 Alkali Resistance Stability Test Results

[0081] Performing heat resistance stability tests on Examples 4 - 6 can also obtain the same results as Examples 1 - 3.

[0082] It can be seen from the data in the above three tables that compared with the self - emulsifying silicone oil synthesized from terminal epoxy polyether silicone oil and polyamine compounds or the self - emulsifying silicone oil synthesized from terminal epoxy silicone oil and polyetheramine, the self - emulsifying silicone oil prepared in this application also has good heat resistance, electrolyte resistance, and alkali resistance, with a stable emulsion state and stable application performance; while for Comparative Example 4, due to the too low content of N - vinylpyrrolidone, it does not exhibit the same performance.

[0083] As described above, it is only the specific implementation manner of the present application. However, the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application can easily think of changes or substitutions, which should all be covered within the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A silicone polymer, characterized in that, It is polymerized from the monomer of formula I and the monomer of formula II; wherein, the mass ratio of the monomer of formula I to the monomer of formula II is (1~9):1; I II Among them, X is 25 to 450, and R is an alkyl group of C1-C 18 , phenyl, or an alkyl group of C1-C with 1-2 amino substituents 18 .

2. The silicone polymer as claimed in claim 1, wherein The molecular weight is 5000~200000.

3. The silicone polymer as claimed in claim 1, wherein R contains more than 28.5% methyl in terms of molar ratio.

4. An auto-emulsifying silicone oil emulsion comprising the organosilicon polymer according to any one of claims 1 to 3, characterized in that, The mass fraction of the silicone polymer is 5wt%~25wt%.

5. The preparation method of the organosilicon polymer according to any one of claims 1-3, characterized in that, The organosilicon polymer is obtained by a radical reaction of a compound of Formula III and N-vinylpyrrolidone with a mass ratio of (1-9):1 under the action of an initiator, wherein X is 25-450, and R is an alkyl group of C1-C 18 alkyl, phenyl, or C1-C 18 alkyl substituted with 1-2 amino groups; III.

6. The preparation method according to claim 5, characterized in that, The temperature of the radical reaction is 60°C~80°C, and the atmosphere of the radical reaction is an inert gas; the mass ratio of the compound of formula III to N-vinylpyrrolidone is (1~9):

1.

7. The preparation method according to claim 5, characterized in that, The initiator is an azo initiator, and the mass of the initiator is 1wt~2wt% of the total mass of N-vinylpyrrolidone and the compound of formula III.

8. The preparation method according to claim 5, characterized in that, The preparation method of the compound of formula III is: octamethylcyclotetrasiloxane, the compound of formula IV, a silane coupling agent, and tetramethylammonium hydroxide are stirred and heated to 100°C~120°C under an inert gas atmosphere, reacted for 3h~4h, then stirred and heated to 140°C~145°C, and reacted for 1h~2h to obtain the compound of formula III; Among them, R1 is an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkyl group having 1 to 5 carbon atoms substituted with 1 or 2 amino groups 18 Among them, R1 is an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkyl group having 1 to 5 carbon atoms substituted with 1 or 2 amino groups 18 alkyl group IV.

9. The preparation method according to claim 8, characterized in that, The specific reaction formula for the preparation of the compound of formula III is: Wherein, x = 4a + b, a is 5~100, and b is 5~50.

10. The preparation method according to claim 8, characterized in that, The mass of the silane coupling agent is 5wt%~40wt% of octamethylcyclotetrasiloxane; the mass of tetramethyldivinyldisiloxane is 0.6wt%~4wt% of octamethylcyclotetrasiloxane.

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