Side-chain amino silicon oil and preparation method thereof

Abstract

The invention belongs to the technical field of silicone oil, and particularly relates to side-chain amino silicone oil and a preparation method thereof. The side-chain amino silicon oil is prepared through an in-situ dealcoholization reaction of hydroxyl on a siloxane side chain, and the side-chain amino silicon oil is structurally characterized in that amino is connected to a siloxane main chain through a C-Si-O bond. The preparation method comprises the following steps: adding the side hydroxyl silicone oil and the monoethoxy N-substituted silane coupling agent into a reaction container at room temperature in a nitrogen atmosphere; and removing ethanol in vacuum to obtain a product. The side-chain amino silicon oil prepared by the method is controllable in viscosity and ammonia value, heating is not needed in the reaction process, no catalyst is used, the reaction time is short, no siloxane ring body low-boiling-point substance is generated, and the side-chain amino silicon oil prepared by the method has better effect than amino silicon oil prepared by a traditional method in fabric finishing.

Description

Technical Field

[0001] The invention belongs to the technical field of silicone oil, and in particular relates to side chain amino silicone oil and a preparation method thereof. Background Art

[0002] Amino silicone oil is amino-alkyl modified polysiloxane. The reactivity and polarity of the amino group endow silicone oil with excellent water-phase emulsif[iota]ability and dispersibility, and it exhibits good adsorption capacity and good compatibility on the fiber surface, so it is widely used in fabric post-finishing, personal care products, etc.

[0003] The most commonly used synthesis process in industry is the catalytic equilibrium method. This process uses cyclosiloxane monomers or hydroxyl-terminated polydimethylsiloxane and aminopropyldiethoxysilane coupling agent monomers as raw materials. Under the catalysis of metal hydroxides such as sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide, the ring opening and breaking / rearrangement of siloxane in the raw materials, the dealcoholization of siloxy groups in the coupling agent and the embedding of aminopropylsiloxane units into the polymer main chain are achieved, thereby obtaining silicone oil with amino groups randomly distributed in the siloxane main chain. Its structural feature is that the amino functional group is connected to the linear polysiloxane main chain through a CCC bond.

[0004] However, due to the presence of a strong base catalyst in the equilibrium process, the flexible siloxane bond breaks and bites back simultaneously during the reaction, resulting in the production of low-boiling products such as siloxane rings. At the same time, the dealcoholization rate of aminopropyldiethoxysilane coupling agent induced under alkaline conditions is difficult to control, resulting in a strong random distribution of amino groups in the equilibrium process, which ultimately leads to insufficient controllability of the process and poor storage stability, such as poor controllability of viscosity and ammonia value, and reduced light transmittance.

[0005] CN112280041A discloses a method for preparing a side amino silicone oil with low siloxane ring content. The method firstly stirs and mixes hydroxyl-terminated polydimethylsiloxane, an amino monomer with siloxy groups and a capping agent at a temperature of 50-100°C; then, water is added to the stirred and mixed material for hydrolysis, and nitrogen is introduced to remove moisture and alcohol to obtain a hydrolyzed material; an alkaline catalyst is added to the hydrolyzed material, and a polymerization reaction is carried out at a temperature of 50-110°C to obtain a polymerization reaction material; the polymerization reaction material is de-lowered to obtain an amino silicone oil. The amino silicone oil prepared by this method has a more uniform amino distribution and low siloxane ring content and volatile matter, but the preparation steps are cumbersome, and a polycondensation reaction can occur between the coupling agent hydrolyzates, which leads to a relatively low degree of improvement in the uniformity of the amino distribution and poor controllability of the reaction.

[0006] CN115449079A discloses a method for preparing a side amino silicone oil with improved controllability of viscosity and ammonia value. The starting materials are polydimethylsiloxane and dimethylsiloxane mixed ring bodies containing silanol end-capping, catalyst, water, and silane coupling agent are added and mixed evenly, the temperature is raised to 50-90°C for insulation for 10-120min, and then vacuum degassing is carried out, the temperature is raised to 95-145°C, the reaction is 1-4h, and finally low-boiling substances are removed in vacuum to obtain amino silicone oil, with a yield of 88%, and the entire preparation process is carried out under nitrogen protection. Although the preparation process provided by the present invention improves the viscosity of amino silicone oil and the stability of ammonia value to a certain extent, the specific operation steps are cumbersome, and there are problems of catalyst cracking odor and low-boiling substance ring body generation.

[0007] CN108912333A discloses a method for preparing a high-transmittance lateral aminosilicone oil. First, an aminosilane coupling agent is mixed with water for reaction for 1 to 2 hours, and then maintained at -0.09MPa for 0.5 to 2 hours to prepare a coupling agent hydrolyzate; octamethylcyclotetrasiloxane and a catalyst tetramethylammonium hydroxide are mixed evenly under certain conditions, and then the coupling agent hydrolyzate is gradually added dropwise; then the pressure is reduced to -0.09MPa for reaction for 20 to 30 minutes, and then the temperature is raised to 90°C for reaction for 10 to 30 minutes, and then the end-capping agent hexamethyldisiloxane is added for reaction for 1 to 2 hours; finally, the temperature is raised to 150°C to deactivate the catalyst, and the temperature is raised to 180°C to remove low molecular weight compounds to obtain aminosilicone oil. Although the aminosilicone oil prepared by the present invention has a high transmittance, there are still problems of cumbersome preparation steps and low-boiling ring body pollution.

[0008] CN115819448A discloses a method for synthesizing a self-exothermic nitrogen-containing six-membered ring functionalized α-silane coupling agent, and foresees its feasibility in the green preparation of aminosiloxane materials. However, due to the high activity of diethoxy α-nitrogen substituted silane coupling agents, the dealcoholization-chain extension reaction with silanol-terminated silicone oil may lead to the problem of uncontrollable viscosity of aminosilicone oil. Summary of the invention

[0009] In view of the shortcomings of the prior art, the object of the present invention is to provide a side chain amino silicone oil which has good softness when applied to fabrics.

[0010] The invention also provides a preparation method thereof, the structure and reaction process thereof are controllable, and no low-boiling siloxane ring body is produced.

[0011] The side chain amino silicone oil of the present invention is prepared by reacting a side hydroxy silicone oil with a monoethoxy N-substituted silane coupling agent. The amino group of the side chain amino silicone oil is connected to the siloxane main chain via a C-Si-O bond. The structure of the side chain amino silicone oil is shown in Formula I:

[0012] Formula I; Wherein: R 1 and R 2 groups are the same or different neutral groups respectively, and the R 3 group is any aminomethyl group; m is an integer from 0 to 650, and n is an integer from 1 to 21.

[0013] Preferably, the R 1 , R 2 groups are independently hydrocarbyl groups having 1 to 18 carbon atoms, and more preferably hydrocarbyl groups having 1 to 6 carbon atoms.

[0014] More preferably, the R 1 , R 2 groups are independently vinyl, methyl; the R 3 groups are independently the following organic aminomethyl: .

[0015] The preparation method of the side-chain amino silicone oil described in the present invention includes the following steps: (1) At room temperature and under a nitrogen atmosphere, add side-hydroxyl silicone oil and monoethoxy N-substituted silane coupling agent to a reaction vessel for reaction; (2) Vacuum remove ethanol to obtain the product.

[0016] The monoethoxy N-substituted silane coupling agent described in step (1) has the following structural formula II:

[0017] Formula II.

[0018] The side-hydroxyl silicone oil described in step (1) is shown in the following structural formula III:

[0019] Formula III; The reaction equation of the side-chain amino silicone oil is as Figure 1 shown.

[0020] The reaction temperature described in step (1) is room temperature, and the reaction time is 5 to 60 min.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) The monoethoxy N-substituted silane coupling agent used in the present invention, the molecular structure R 3The amino group is connected to the silicon atom through a methylene group (-NC-Si). Compared with the silane coupling agent configuration (-NCCC-Si) commonly used in the existing process, the silaneoxy group in the N-substituted silane coupling agent with the structure of formula II has the reaction activity of self-catalytic dealcoholization with silanol in the absence of water, acid or alkali or organic tin catalyst.

[0022] 2) The present invention prepares the lateral amino silicone oil by mildly and highly selectively reacting the side hydroxyl groups of the silicone oil with the silaneoxy groups in the coupling agent in an in-situ dealcoholization reaction. This process does not require the addition of a catalyst, and can avoid the influence of catalyst residues on the quality of the amino silicone oil; the preparation of traditional amino silicone oil requires the use of metal hydroxides or tetramethylammonium hydroxide as a catalyst, and then organic phosphoric acid needs to be added to neutralize the catalyst, or the catalyst needs to be removed by high-temperature cracking, and trimethylamine will be produced during the decomposition of the catalyst, which has a fishy smell and is not conducive to environmental protection.

[0023] 3) The present invention does not require heating and has a short reaction time (5min~60min for reaction at room temperature), thus avoiding the problem of the generation of low-boiling cyclosiloxane products caused by the use of alkaline catalysts under high temperature conditions, and realizing the controllable preparation of the viscosity and ammonia value of the side chain amino silicone oil. On the contrary, the preparation of traditional amino silicone oil has a high catalytic reaction temperature (80℃~160℃), a long equilibrium reaction time (2h~8h), and requires a high-temperature cracking catalyst (150℃~180℃) and removal of low-boiling products in the later stage, resulting in poor controllability and low yield (about 88%).

[0024] 4) In the amino silicone oil prepared by the present invention, the amino group is connected to the siloxane main chain through a C-Si-O bond. Compared with the traditional amino silicone oil structure in which the amino group is connected to the siloxane main chain through a CCC bond, the C-Si-O bond has better softness. Therefore, the fabric treated with the amino silicone oil of the present invention shows better softness. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is the reaction equation of side chain amino silicone oil; Figure 2 This is a GC-MS analysis of byproducts produced by the self-catalytic dealcoholization preparation of amino silicone oil in Example 1; Figure 3 This is the in-situ FT-IR monitoring diagram of the reaction process of Example 1; Figure 4 For Example 1 raw materials / products 29 Si-NMR comparison chart; Figure 5 This is the in-situ FT-IR monitoring diagram of the reaction process of Comparative Example 1; Figure 6 For the product of Example 2 1 H-NMR spectrum; Figure 7For the product of Example 3 1 H-NMR spectrum; Figure 8 For the product of Example 4 1 H-NMR spectrum; Fig. 9 For the product of Example 5 1 H-NMR spectrum; Fig.10 For the product of Example 6 1 H-NMR spectrum; Fig.11 This is the GC-MS analysis chart of low-boiling substances produced by preparing amino silicone oil using the traditional process in comparative example 3. DETAILED DESCRIPTION

[0026] The present invention will be further described below with reference to the embodiments.

[0027] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0028] 1. Preparation of pendant hydroxy silicone oil: The side hydroxy silicone oil was prepared according to patent CN115785449A: linear polydimethylsiloxane with a hydrogen side chain (provided by Shandong Dongyue Organic Silicone Materials Co., Ltd.), water and 1,4-dioxane were added to a flask, and a palladium carbon catalyst (loading amount of 10wt.%) was added under constant temperature stirring at 20°C, and then reacted for 3h, and the catalyst was filtered to remove the side chain hydroxy silicone oil. The structural formula of the linear polydimethylsiloxane with a hydrogen side chain is as follows: ; m and n are measured by the gas volume method in the chemical industry standard HG / T4804-2015.

[0029] The structural formula of pendant hydroxy silicone oil 1 is as follows: ; Specific synthesis method: The preparation method was based on the side hydroxy silicone oil, wherein the addition amount of each component was as follows: 10 kg of linear polydimethylsiloxane (hydrogen content: 0.4%) with hydrogen side chain, 25 kg of 1,4-dioxane, 2.5 kg of water, and 0.05 kg of palladium-carbon catalyst.

[0030] The structural formula of pendant hydroxy silicone oil 2 is as follows: ; Specific synthesis method: The preparation method was based on the side hydroxy silicone oil, wherein the added amount of each component was: 10 kg of linear polydimethylsiloxane (hydrogen content: 0.03%) with a hydrogen side chain, 25 kg of 1,4-dioxane, 0.3 kg of water, and 0.27 kg of palladium-carbon catalyst.

[0031] The structural formula of pendant hydroxy silicone oil 3 is as follows: ; Specific synthesis method: The preparation method was based on the side hydroxy silicone oil, wherein the added amount of each component was: 10 kg of linear polydimethylsiloxane with a hydrogen side chain (hydrogen content of 0.05%), 25 kg of 1,4-dioxane, 0.4 kg of water, and 0.27 kg of palladium-carbon catalyst.

[0032] The structural formula of pendant hydroxy silicone oil 4 is as follows: ; Specific synthesis method: The preparation method was based on the side hydroxy silicone oil, wherein the added amount of each component was: 10 kg of linear polydimethylsiloxane with a hydrogen side chain (hydrogen content of 0.01%), 25 kg of 1,4-dioxane, 0.25 kg of water, and 0.29 kg of palladium-carbon catalyst.

[0033] The structural formula of pendant hydroxy silicone oil 5 is as follows: ; Specific synthesis method: The preparation method was based on the side hydroxy silicone oil, wherein the added amount of each component was: 10 kg of linear polydimethylsiloxane (hydrogen content: 0.03%) with a hydrogen side chain, 25 kg of 1,4-dioxane, 0.3 kg of water, and 0.27 kg of palladium-carbon catalyst.

[0034] The structural formula of pendant hydroxy silicone oil 6 is as follows: ; Specific synthesis method: The preparation method was based on the side hydroxy silicone oil, wherein the added amount of each component was: 10 kg of linear polydimethylsiloxane (hydrogen content: 0.04%) with hydrogen side chains, 25 kg of 1,4-dioxane, 0.35 kg of water, and 0.28 kg of palladium-carbon catalyst.

[0035] 2. Preparation of monoethoxy N-substituted silane coupling agent: The monoethoxy N-substituted silane coupling agent is prepared by referring to patent CN115819448A: (1) At room temperature and in a nitrogen atmosphere, chloromethylethoxydimethylsilane and an organic amine are simultaneously injected into a reaction vessel, wherein the molar ratio of the organic amine to the chloromethylethoxydimethylsilane is 4:1. Under room temperature conditions, the organic amine and the chloromethylethoxydimethylsilane are respectively injected into the reaction kettle at injection rates of 14.5 L / h and 7.2 L / h. The system releases heat, the temperature rises, and the solution in the reaction vessel begins to become turbid. When the temperature is constant, the reaction is completed; (2) Excess organic amine is distilled off, and the vacuum degree is increased to distill off the monoethoxy N-substituted silane.

[0036] Preparation of N-[(ethoxydimethylsilyl)methyl]ethylenediamine: Prepared according to the above-mentioned preparation method of monoethoxy N-substituted silane coupling agent, wherein the selected organic amine is ethylenediamine; Preparation of N-[(ethoxydimethylsilyl)methyl]morpholine: Prepared according to the above-mentioned method for preparing monoethoxy N-substituted silane coupling agent, wherein the selected organic amine is morpholine; Preparation of N-[(ethoxydimethylsilyl)methyl]cyclohexylamine: prepared according to the above-mentioned preparation method of monoethoxy N-substituted silane coupling agent, wherein the selected organic amine is cyclohexylamine.

[0037] Example 1 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 5.95 kg of side hydroxy silicone oil 1 and 4.40 kg of N-[(ethoxydimethylsilyl)methyl]ethylenediamine were added to a 15 L stirred reactor. After reacting for 5 minutes, ethanol was removed under reduced pressure (-0.098 MPa) to obtain 9.13 kg of colorless and transparent side chain amino silicone oil with an ammonia value of 5.051 mmol / g, a viscosity of 20 mPa·s, and a yield of 99.1%.

[0038] The average structural formula of the product is: ; Example 1 GC-MS analysis of by-products produced by the autocatalytic dealcoholization preparation of amino silicone oil Figure 2 As shown, the only by-product detected by GC-MS was ethanol. Figure 2 The appearance of the characteristic peak of ethanol in the reaction verifies that the reaction can proceed spontaneously without a catalyst.

[0039] Example 1 In-situ FT-IR monitoring of the reaction process is shown in FIG. Figure 3 As shown, the raw materials / products 29 Si-NMR comparison chart Figure 4 As shown: Side hydroxy silicone oil: 29 Si-NMR (119 MHz, CDCl 3 ),δ(ppm):9.05((CH 3 ) 3 SiO 1 / 2 ),-54(Si-OH); Example 1 product: 29 Si-NMR (119 MHz, CDCl 3 ),δ(ppm):8.15((CH 3 ) 3 SiO 1 / 2 ),4.66((CH 2 (CH 3 ) 2 SiO 1 / 2 ),-64.01(CH 3 SiO 3 / 2 ).

[0040] Example 1 Si-OC during the reaction process 2 H 5 (948cm -1 The infrared absorption peak near ) gradually disappears; 29 In the Si-NMR spectrum, Si-OH at -54ppm disappears, and NC-Si in the product appears at 4.6ppm. The above results prove the self-catalytic dealcoholation characteristics of this process: no catalyst is required, the reaction energy consumption is low at room temperature, and no cyclic siloxane is produced.

[0041] Comparative Example 1 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 5.95 kg of hydroxyl silicone oil 1 and 4.75 kg of commercially available coupling agent: N-β-(aminoethyl)-γ-aminopropyldimethylethoxysilane were added to a 15 L stirred reactor. Figure 5 As shown, within 2 h, Si-O-CH 2 CH 3 (948cm -1 There is no significant change in the infrared absorption peak intensity of the silane coupling agent, which indicates that the silane alkoxy group of the traditional silane coupling agent does not have the self-catalytic dealcoholization performance with the silanol group.

[0042] Example 2 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 9.39 kg of side hydroxy silicone oil 2 and 0.61 kg of N-[(ethoxydimethylsilyl)methyl]morpholine were added to a 15L stirred reactor. After 15 minutes of reaction, ethanol was removed under reduced pressure (-0.098 MPa) to obtain 9.80 kg of colorless transparent side chain amino silicone oil, with an ammonia value of 0.301 mmol / g, a viscosity of 1000 mPa·s, and a yield of 99.6%. The average structural formula of the product is: ; Example 2 Product 1 H-NMR Figure 6 As shown: 1 HNMR (400 MHz, CDCl 3 ), δ (ppm): 3.67 (d, 12H, -O-CH 2 -), 2.41 (d, 12H, -OCH 2 -CH 2 -), 1.90 (s, 6H, -Si-CH 2 -), 0.17-0.01 (m, 825H, -Si-CH 3 ).

[0043] Example 3 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 9.03 kg of side hydroxy silicone oil 3 and 0.96 kg of N-[(ethoxydimethylsilyl)methyl]cyclohexylamine were added to a 15L stirred reactor. After reacting for 25 minutes, ethanol was removed under reduced pressure (-0.098 MPa) to obtain 9.75 kg of colorless transparent side chain amino silicone oil with an ammonia value of 0.452 mmol / g, a viscosity of 2000 mPa·s, and a yield of 99.5%. The average structural formula of the product is: ; Example 3 Product 1 H-NMR Figure 7 As shown: 1 H-NMR (CDCl 3 , 400MHz), δ (ppm): 2.25 (t, 9H, -CH-), 2.04 (d, 18H, -Si-CH 2 -), 1.90-1.81 (d, 18H, -CH(CH 2 ) 5 -), 1.70 (dt, 18H, -CH(CH 2 ) 5 -), 1.58 (d, 18H, -CH(CH2 ) 5 -), 1.18 (dq, 27H, -NH-CH(CH 2 ) 5 )、1.01(m,18H,-CH(CH 2 ) 5 -), 0.15-0.05 (m, 1599H, -Si-CH 3 ).

[0044] Example 4 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 9.77 kg of side hydroxy silicone oil 4 and 0.23 kg of N-[(ethoxydimethylsilyl)methyl]ethylenediamine were added to a 15L stirred reactor. After 30 minutes of reaction, ethanol was removed under reduced pressure (-0.098 MPa) to obtain 9.88 kg of colorless and transparent side chain amino silicone oil, with an ammonia value of 0.261 mmol / g, a viscosity of 2300 mPa·s, and a yield of 99.5%. The average structural formula of the product is: ; Example 4 Product 1 H-NMR Figure 8 As shown: 1 HNMR (400 MHz, CDCl 3 ), δ (ppm): 6.06 (dd, 2H, -CH=CH 2 ), 5.87 (dd, 2H, -CH=CH 2 ), 5.67 (dd, 2H, -CH=CH 2 ), 2.74 (t, 6H, -CH 2 -NH 2 ), 2.64 (dd, 6H, -CH 2 -CH 2 -NH 2 ), 2.03 (d, 6H, -Si-CH 2 -), 1.81 (s, 9H, -NH-, -NH 2 ), 0.17-0.03 (m, 1839H, -Si-CH 3 ).

[0045] Example 5 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 9.44 kg of side hydroxy silicone oil 2 and 0.56 kg of N-[(ethoxydimethylsilyl)methyl]ethylenediamine were added to a 15L stirred reactor. After 45 minutes of reaction, ethanol was removed under reduced pressure (-0.098 MPa) to obtain 9.83 kg of colorless and transparent side chain amino silicone oil, with an ammonia value of 0.586 mmol / g, a viscosity of 3300 mPa·s, and a yield of 99.8%. The average structural formula of the product is: ; Example 5 Product 1 H-NMR Fig. 9 As shown: 1 H-NMR (400 MHz, CDCl 3 ), δ (ppm): 2.74 (t, 20H, -CH 2 -NH 2 ), 2.64 (dd, 20H, -CH 2 -CH 2 -NH 2 ), 2.03 (d, 20H, -Si-CH 2 -), 1.81 (s, 30H, -NH-, -NH 2 ), 0.25-0.02 (m, 2808H, -Si-CH 3 ).

[0046] Example 6 The preparation method of the side chain amino silicone oil comprises the following steps: At room temperature and nitrogen atmosphere, 9.18 kg of side hydroxy silicone oil 6 and 0.81 kg of N-[(ethoxydimethylsilyl)methyl]morpholine were added to a 15L stirred reactor. After 60 minutes of reaction, ethanol was removed under reduced pressure (-0.098 MPa) to obtain 9.77 kg of colorless transparent side chain amino silicone oil with an ammonia value of 0.403 mmol / g, a viscosity of 5000 mPa·s, and a yield of 99.6%. The average structural formula of the product is: ; Example 6 Product 1 H-NMR Fig.10 As shown: 1 HNMR (400 MHz, CDCl 3 ), δ (ppm): 3.66 (d, 84H, -O-CH 2 -), 2.42 (d, 84H, -OCH 2 -CH 2 -), 1.90 (s, 42H, -Si-CH2 -), 0.15-0.01 (m, 4107H, -Si-CH 3 ).

[0047] Comparative Example 2 The preparation method of the amino silicone oil comprises the following steps: 10kg of hydroxyl-terminated silicone oil (commercially available brand: Dow PMX-0156) and 0.63kg of N-β-(aminoethyl)-α-aminomethyldiethoxymethylsilane were stirred at room temperature for 1.5h, and ethanol was removed under reduced pressure to obtain 10.3kg of side-chain amino silicone oil (yield 99.0%), with an ammonia value of 0.575mmol / g and a viscosity of 80000mPa·s. Five groups of parallel experiments were carried out according to this step, and the viscosity of the side-chain amino silicone oil obtained each time fluctuated greatly (ranging from 60000mPa·s to 100000mPa·s). This comparative experiment shows that although the diethoxy N-substituted silane coupling agent with a structure similar to that of general formula II can undergo dealcoholization reaction with hydroxyl-terminated silicone oil under anhydrous conditions, the diethoxy functional group in the coupling agent is used as a reaction site, and its autocatalytic activity leads to the dealcoholization-chain extension reaction, resulting in the viscosity of the final amino silicone oil being uncontrollable.

[0048] Comparative Example 3 The preparation method of the amino silicone oil comprises the following steps: 9.32 kg hydroxyl-terminated silicone oil (commercially available brand: Dow PMX-0156), 0.21 kg end-capping agent MD 5 M, 0.46kg of the hydrolyzate of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH602) was put into a 15L reactor, stirred and mixed evenly, heated to 80°C under a vacuum degree of -0.098MPa and dehydrated at a constant temperature for 0.5h, stopped vacuuming, heated to 80°C, added 5g of tetramethylammonium hydroxide crystals, heated to 105°C, reacted at a constant temperature for 6h, then heated to 137°C, kept at a constant temperature for 1h to decompose the catalyst, then heated to 140°C, removed low-boiling substances at a constant temperature for 1h under a vacuum degree of -0.098MPa, cooled to obtain 8.90kg of side chain amino silicone oil (yield 89.5%), with an ammonia value of 0.581mmol / g, a viscosity of 3200mPa·s, and 1.02kg of by-product siloxane ring body.

[0049] The low-boiling substances produced by this synthesis route were investigated using GC-MS analysis technology. The GC-MS analysis of low-boiling substances produced by the traditional process for preparing amino silicone oil in Example 3 is shown in the figure below. Fig.11 As shown. Fig.11 It can be found that the main by-product of the traditional process for preparing amino silicone oil is low molecular weight cyclosiloxane (D 3 ~D 7 ).

[0050] Application Examples Take 200g of the side chain amino silicone oil obtained in the above Example 5 and Comparative Example 3 respectively, add 50g AEO3 (fatty alcohol polyoxyethylene ether-3EO) and 50g AEO9 (fatty alcohol polyoxyethylene ether-9EO), stir for 10min at a speed of 1000r / min, add 50g acetic acid aqueous solution (concentration of 10wt.%), stir for 5min at a speed of 600r / min, add 650g water in 3 times, stir for 5min at a speed of 600r / min, and obtain side chain amino silicone oil softeners 1 and 2 with a solid content of 30%. The blank group is a polydimethyl silicone oil with the same viscosity as Example 5 instead of the side amino silicone oil in Example 5 to prepare softener 3.

[0051] Use deionized water to prepare the above softener into a solution with a solid content of 3.0wt%, soak the cut cotton fabric, use a two-immersion and two-rolling method with a rolling rate of 80%, then pre-bake at 100℃ for 2min, bake at 130℃ for 2min, and finally place it in a dryer for equilibration for 24h before testing the feel and whiteness.

[0052] Hand feel test: The hand feel of fabric is the result of personal subjective judgment. In this experiment, we evaluated the hand feel of fabrics in two aspects: soft and smooth. We invited 7 people to grade the hand feel by blind touch, and divided it into 1 to 5 levels, with 5 being the best and 1 being the worst. Finally, we ranked the hand feel of the finished fabrics based on the average of the seven people's scores.

[0053] Whiteness test: Place the treated sample on the sample holder of the whiteness meter, and then measure the whiteness of the fabric according to GB8425-1987. Each sample must be measured three times in different parts while keeping the warp and weft directions consistent, and then take the average value.

[0054] The test results are shown in Table 1 below: Table 1 Softener 1-3 test results

[0055] Tests show that the emulsion prepared from ethylenediamine silicone oil with a C-Si-O side chain is more beneficial to fabric treatment than the emulsion prepared from the conventional product KH602 amino silicone oil, and can significantly improve the softness of the fabric.

Claims

1. A side chain amino silicone oil, characterized in that: The side chain amino silicone oil is prepared by reacting the side hydroxy silicone oil with the monoethoxy N-substituted silane coupling agent. The amino group of the side chain amino silicone oil is connected to the siloxane main chain through a C-Si-O bond. The structure is shown in Formula I: Formula I; in: The R1 and R2 groups are respectively the same or different neutral groups, the R3 group is any aminomethyl group; m is an integer of 0 to 650, and n is an integer of 1 to 21.

2. The side chain amino silicone oil according to claim 1, characterized in that The R1 and R2 groups are independently hydrocarbon groups.

3. The side chain amino silicone oil according to claim 2, characterized in that The R1 and R2 groups are independently vinyl and methyl.

4. The side chain amino silicone oil according to claim 1, characterized in that The R3 groups are independently the following organic aminomethyl groups: 。 5. A method for preparing the side chain amino silicone oil according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) Adding pendant hydroxy silicone oil and monoethoxy N-substituted silane coupling agent into a reaction container at room temperature and under nitrogen atmosphere to react; (2) Ethanol is removed under vacuum to obtain the product.

6. The method for preparing the side chain amino silicone oil according to claim 5, characterized in that: The monoethoxy N-substituted silane coupling agent in step (1) has the following structural formula II: Formula II.

7. The method for preparing the side chain amino silicone oil according to claim 5, characterized in that: The reaction temperature in step (1) is room temperature, and the reaction time is 5 to 60 minutes.

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