Branch-shaped hydrophilic soft quaternization modified block silicone oil and preparation method thereof

Abstract

The invention relates to the field of textile finishing agents, in particular to branch-shaped hydrophilic soft quaternization modified block silicone oil and a preparation method thereof. The anti-rust agent is prepared from double-end epoxy silicone oil, diethanol amine, glycerol triglycidyl ether, isopropanol, glacial acetic acid and other raw materials. The branch-shaped silicone oil containing the quaternization structure prepared by the invention not only has the characteristics of low viscosity, high solubility, high branching, high reactivity and the like, but also contains a large number of siloxane chain segments, amino chain segments and hydrophilic polyether chain segments in the branch-shaped structure; due to the irregularity and disorder of the chain segments, the finished fabric has excellent fluffy and soft performance. In addition, an amino chain segment in the polymer structure is a quaternization structure, so that the anti-yellowing performance of the fabric can be improved; meanwhile, hydroxyalkyl is connected with nitrogen atoms in a quaternization structure and contains a large amount of hydroxyl, so that the silicone oil has excellent self-emulsifying property under the combined action of the hydroxyalkyl and a hydrophilic polyether chain segment, and the fabric is endowed with excellent hydrophilicity.

Description

Technical Field

[0001] The invention relates to the field of textile finishing agents, and in particular to a branch-shaped hydrophilic soft quaternary ammonium modified block silicone oil and a preparation method thereof. Background Art

[0002] With the rapid economic development and the continuous improvement of living standards, people's pursuit of an active and comfortable lifestyle is accompanied by an increasing demand for functional and diversified textiles, and the requirements for comfort in use are also getting higher and higher. The fabrics treated with amino silicone oil and modified amino silicone oil have significantly improved softness and smooth feel, but their hygroscopicity and storage stability are poor, and they are prone to yellowing. These shortcomings greatly affect their application value.

[0003] In recent years, with the rapid development of the silicone oil field, various functional silicone oils have sprung up, especially ternary or multi-block modified silicone oils. On the basis of the softness of amino silicone oil, embedding other functional segments in the silicon chain can give the fabric excellent hydrophilicity, resilience, fluffiness and smoothness, thereby meeting people's demand for soft, elastic, smooth and comfortable wearing fabrics. Patent CN201610632480.2 "A ternary copolymer block hydrophilic amino silicone oil and its preparation method and application" alternately arranges siloxane segments, polyether segments and amino segments. Although such a structural design gives the finished fabric excellent hydrophilicity and soft feel, the amino group on its segment structure is a primary or secondary amine group, which is easily oxidized and converted into a chromophore group, causing the fabric to yellow and affecting whiteness. Patent CN201610783241.7 "A quaternary ammonium modified block polyether amino silicone oil and its preparation method" is a quaternary ammonium modified block silicone oil prepared by the reaction of tertiary amine compounds and epoxy silicone oil. It is used on fabrics to give the fabrics an excellent soft feel and has little effect on the whiteness of the fabrics. However, the patent uses tertiary amine to modify silicone, and the nitrogen atoms in the tertiary amine structure used are all connected to methyl groups, and the methyl group is a hydrophobic group and has no reaction activity, resulting in a decrease in the hydrophilicity of the finished fabric. In addition, the above patents are all prepared with linear copolymer block silicone oils, and their main function is to give the fabric a soft, smooth feel, but almost no fluffy performance, which also reflects the problem that the existing fabric finishing agents have a single performance or difficult to be compatible with the performance, and further limits their application direction. Therefore, it is urgent to study a multifunctional fabric finishing agent that can not only have anti-yellowing properties, but also give the fabric fluffy, soft and hydrophilic properties. Summary of the invention

[0004] In order to solve the above problems, the present invention aims to provide a branch-like hydrophilic soft quaternary ammonium modified block silicone oil and a preparation method thereof, and a hydrophilic soft branch-like quaternary ammonium modified block silicone oil is prepared by reacting a self-made branch-like structure quaternary ammonium intermediate with a double-ended epoxy polyether silicone oil, wherein the branch-like structure contains a large amount of siloxane segments, hydrophilic polyether segments, and quaternary ammonium structure segments. The group of the quaternary ammonium structure itself can enhance the softness, anti-yellowing and hydrophilicity of the silicone oil itself, and the nitrogen atoms in the quaternary ammonium structure are all connected to hydroxyalkyl groups, so that the whole structure contains a large amount of hydroxyl segments. The abundance of polyether segments and hydroxyl segments provides excellent hydrophilic properties to the fabric, and also makes the silicone oil have excellent self-emulsification. At the same time, the disorder of the branch-like structure contributes to the excellent fluffiness of the finished fabric, while the siloxane segments provide good softness.

[0005] The technical solution of the present invention is as follows: A method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil, the preparation method comprising the following steps: (1) Add diethanolamine to the solvent, condense and reflux, start stirring, and drop propylene glycol triglycidyl ether into the reaction solution. After the dropwise addition is completed, heat up and keep the temperature to react to obtain a branched tertiary amine intermediate; (2) taking the branched tertiary amine intermediate, adding acid to acidify it, and obtaining a branched quaternary ammonium structure-containing intermediate; (3) Adding double-terminal epoxy polyether silicone oil, branch-shaped quaternary ammonium structure intermediate, and solvent into a reaction vessel with a condensation reflux system, stirring and heating to react, thereby obtaining a branch-shaped hydrophilic soft quaternary ammonium modified block silicone oil.

[0006] The reaction formula of the branched intermediate containing quaternary ammonium structure is as follows:

[0007] The reaction formula of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil is as follows:

[0008] The R segment is .

[0009] Wherein m is an integer between 100 and 200, and n is an integer between 10 and 15.

[0010] Preferably, in the method, the solvent is one or a combination of isopropanol and ethylene glycol monobutyl ether.

[0011] In the step (2), the acid is one or a combination of glacial acetic acid and lauric acid.

[0012] Preferably, in step (3), the number average molecular weight of the double-terminal epoxy polyether silicone oil is 10,000-14,000.

[0013] Preferably, in step (1), the mass ratio of the solvent, diethanolamine and propylene glycol triglycidyl ether is 150: (310-320): (250-270).

[0014] Preferably, in step (1), after the dropwise addition is completed, the temperature is raised to 60-80° C. and the reaction is kept warm for 4-8 hours.

[0015] Preferably, in step (2), the mass ratio of the branched tertiary amine intermediate, the acid and the solvent is (30-50): (40-60): (40-60), and the acidification time is 0.1-24 hours.

[0016] Preferably, in step (3), the mass ratio of the double-ended epoxy polyether silicone oil, the branched quaternary ammonium structure, and the solvent intermediate is 800: (30-50): (500-600); the mixture is heated to 83-86° C. and kept warm for 6-10 hours.

[0017] A branch-shaped hydrophilic soft quaternary ammonium modified block silicone oil is prepared by any of the preparation methods of the branch-shaped hydrophilic soft quaternary ammonium modified block silicone oil. The advantages of the present invention are: The invention prepares a branch-shaped hydrophilic soft block silicone oil by reacting a self-made branch-shaped quaternary ammonium structure intermediate with double-ended epoxy polyether silicone oil. The self-made intermediate structure contains three tertiary amine groups, and can react with double-ended epoxy silicone oil under the action of acid to obtain a branch-shaped silicone oil containing quaternary ammonium structure. The prepared block silicone oil not only has the characteristics of low viscosity, high solubility, high branching and high reactivity, but also contains a large number of siloxane segments, amino segments, hydroxyl segments and hydrophilic polyether segments in the branch-shaped structure. The amino group in the amino segment is a quaternary ammonium group, which can improve the softness, yellowing resistance and hydrophilicity of the silicone oil itself, and the nitrogen atoms in the quaternary ammonium structure are all connected to hydroxyalkyl groups, bringing a large number of hydroxyl groups to the entire segment, which synergistically acts with the hydrophilic polyether segment to give the fabric excellent hydrophilicity, and at the same time has good low yellowing performance.

[0018] The large amount of siloxane segments in the dendrite structure and its disordered nature provide excellent softness and fluffy properties for the finished fabric. Therefore, the dendrite-shaped hydrophilic soft quaternary ammonium modified block silicone oil of the present invention combines good hydrophilicity, low yellowing property and finishing effect. This multi-performance composite fabric finishing agent has a good market prospect. DETAILED DESCRIPTION

[0019] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. The embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the protection scope of the present invention.

[0020] Example 1 1. Add 310 parts of diethanolamine to a reaction flask equipped with a condensation reflux device, start stirring, and then uniformly add 260 parts of propylene glycol triglycidyl ether to the flask container through a constant pressure dropping funnel. After the addition is completed, heat to 60°C and keep warm for 4 hours to obtain a branched tertiary amine structure intermediate.

[0021] 2. Add 50 parts of the branched tertiary amine intermediate, 60 parts of acid and 60 parts of solvent into a sealed bottle and mix evenly. Acidify for 1 hour to obtain a branched quaternary ammonium structure intermediate.

[0022] 3. Add 800 parts of double-ended epoxy polyether silicone oil with a number average molecular weight of 14,000, 30 parts of branched quaternary ammonium structure intermediate, and 500 parts of solvent into a reaction flask equipped with a condensation reflux device, start stirring, heat the reaction container to 85°C, and keep the reaction within this temperature range for 8 hours to obtain a branched hydrophilic soft quaternary ammonium modified block silicone oil.

[0023] The solvent was isopropanol and the acid was glacial acetic acid.

[0024] Example 2 1. Add 320 parts of diethanolamine to a reaction flask equipped with a condensation reflux device, start stirring, and then uniformly add 260 parts of propylene glycol triglycidyl ether to the flask container through a constant pressure dropping funnel. After the addition is completed, heat to 70°C and keep warm for 6 hours to obtain a branched tertiary amine structure intermediate.

[0025] 2. Add 50 parts of the branched tertiary amine intermediate, 60 parts of acid and 60 parts of solvent into a sealed bottle and mix evenly. Acidify for 1 hour to obtain a branched quaternary ammonium structure intermediate.

[0026] 3. Add 800 parts of double-ended epoxy polyether silicone oil with a number average molecular weight of 10,000, 60 parts of branched quaternized intermediate, and 500 parts of solvent into a reaction flask equipped with a condensation reflux device, start stirring, heat the reaction container to 85°C, and keep the reaction within this temperature range for 8 hours to obtain a branched hydrophilic soft quaternized modified block silicone oil.

[0027] The solvent was isopropanol and the acid was glacial acetic acid.

[0028] Example 3 1. Add 320 parts of diethanolamine to a reaction flask equipped with a condensation reflux device, start stirring, and then uniformly add 260 parts of propylene glycol triglycidyl ether to the flask container through a constant pressure dropping funnel. After the addition is completed, heat to 70°C and keep warm for 8 hours to obtain a branched tertiary amine structure intermediate.

[0029] 2. Add 50 parts of the branched tertiary amine intermediate, 60 parts of acid and 60 parts of solvent into a sealed bottle and mix evenly. Acidify for 1 hour to obtain a branched quaternary ammonium structure intermediate.

[0030] 3. Add 800 parts of double-ended epoxy polyether silicone oil with a number average molecular weight of 10,000, 60 parts of branched quaternized intermediate, and 500 parts of solvent into a reaction flask equipped with a condensation reflux device, start stirring, heat the reaction container to 85°C, and keep the reaction within this temperature range for 8 hours to obtain a branched hydrophilic soft quaternized modified block silicone oil.

[0031] The solvent was isopropanol and the acid was glacial acetic acid.

[0032] Comparative Example 1 1. Based on Example 3, 320 parts of diethanolamine were added to a reaction flask equipped with a condensing reflux device, stirring was started, and then 260 parts of propylene glycol triglycidyl ether were uniformly added dropwise to the flask container through a constant pressure dropping funnel. After the addition was completed, the temperature was raised to 50°C and the reaction was kept warm for 8 hours to obtain a branched tertiary amine structure intermediate.

[0033] 2. Add 50 parts of the branched tertiary amine intermediate, 60 parts of acid and 60 parts of solvent into a sealed bottle and mix evenly. Acidify for 1 hour to obtain a branched quaternary ammonium structure intermediate.

[0034] 3. Add 800 parts of double-ended epoxy polyether silicone oil with a number average molecular weight of 10,000, 60 parts of branched quaternized intermediate, and 500 parts of solvent into a reaction flask equipped with a condensation reflux device, start stirring, heat the reaction container to 85°C, and keep the reaction within this temperature range for 8 hours to obtain a branched hydrophilic soft quaternized modified block silicone oil.

[0035] The solvent was isopropanol and the acid was glacial acetic acid.

[0036] Comparative Example 2 1. Based on Example 3, 320 parts of diethanolamine were added to a reaction flask equipped with a condensing reflux device, stirring was started, and then 260 parts of propylene glycol triglycidyl ether were uniformly added dropwise to the flask container through a constant pressure dropping funnel. After the addition was completed, the temperature was raised to 70°C and the reaction was kept warm for 8 hours to obtain a branched tertiary amine structure intermediate.

[0037] 2. Add 50 parts of the branched tertiary amine intermediate, 60 parts of acid and 60 parts of solvent into a sealed bottle and mix evenly. Acidify for 1 hour to obtain a branched quaternary ammonium structure intermediate.

[0038] 3. Add 800 parts of double-ended epoxy polyether silicone oil with a number average molecular weight of 20,000, 30 parts of branched quaternized intermediate, and 500 parts of solvent into a reaction flask equipped with a condensation reflux device, start stirring, heat the reaction container to 85°C, and keep the reaction within this temperature range for 8 hours to obtain a branched hydrophilic soft quaternized modified block silicone oil.

[0039] The solvent was isopropanol and the acid was glacial acetic acid.

[0040] Comparative Example 3 It is the commercially available silicone softener RH-NB-8973, a product developed by Ningbo Runhe High-tech Materials Technology Co., Ltd.

[0041] Block silicone oil application evaluation process: Preparation of emulsion of block silicone oil The above-mentioned example samples and commercially available benchmark samples of the same type and style were emulsified using the same emulsification process to obtain a silicone oil emulsion with a solid content of 24% to 25%.

[0042] Fabric finishing process Fabrics used: white pure cotton double-sided knitted fabric, yellow polyester-cotton knitted fabric, white chemical fiber feather yarn.

[0043] Fabric finishing process: padding working solution (hydrophilic soft quaternary ammonium modified block silicone oil emulsion 10g / L, two dips and two pads, padding rate (white pure cotton double-sided knitted fabric 80%~90%, yellow polyester-cotton knitted fabric 70%~80%, white chemical fiber feather yarn 70%~80%) → baking (white pure cotton double-sided knitted fabric 150℃×90s, yellow polyester-cotton knitted fabric 165℃×90s, white chemical fiber feather yarn 180℃×160s) → cooling and regaining moisture for 24 hours → testing performance.

[0044] Application performance testing Hydrophilic performance evaluation Evaluation of hydrophilic performance: Spread the fabric horizontally, use a standard dropper to drop a drop of water on the fabric surface from about 10 cm away from the fabric surface, and measure the time it takes for the water drop to wetting, diffuse, and completely penetrate the fabric surface under static conditions. The shorter the time, the better the hydrophilic performance.

[0045] Yellowing performance evaluation Spread the fabric horizontally and place it under a fabric whiteness meter to test its whiteness. The larger the whiteness value, the lower the yellowing property. Softness performance evaluation The compression ratio of the fabric was tested using a fabric style meter (N﹒cm / cm2 ), the larger the value, the better the fluffiness; use a fabric style meter to test the bending factor of the fabric, the larger the active rate value, the better the softness.

[0046] The hydrophilic performance applicability evaluation results of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil emulsion of the present invention and the comparative silicone oil emulsion are shown in Table 1: Table 1 Comparison of hydrophilicity of example samples and comparative samples

[0047] As can be seen from Table 1, after the fabric is finished with the emulsion made of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil of the present invention, the hydrophilic property is significantly better than that of the control sample.

[0048] The anti-yellowing performance applicability evaluation results of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil emulsion of the present invention and the comparative silicone oil emulsion are shown in Table 2: Table 2 Comparison of hydrophilicity of example samples and comparative samples

[0049] As shown in Table 2, after the fabric is finished with the emulsion made of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil of the present invention, the anti-yellowing performance is significantly better than that of the control sample.

[0050] The softness performance applicability evaluation results of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil emulsion of the present invention and the comparative silicone oil emulsion are shown in Table 3: Table 3 Comparison of softness of example samples and comparative samples

[0051] As shown in Table 3, after the fabric is finished with the emulsion made of the dendritic hydrophilic soft quaternary ammonium modified block silicone oil of the present invention, the softness is obviously better than that of the control sample.

[0052] By comparing Example 3 with Comparative Examples 1-3, it can be seen that the ratio of reactants, reaction time, temperature and molecular weight of the epoxy-terminated silicone oil in preparing the branched tertiary amine structure intermediate will affect the performance of the final product, the hydrophilic, soft, quaternary ammonium modified block silicone oil. In the technical route of the present invention, Example 3 is the best route, with the best fluffy, soft, hydrophilic and anti-yellowing properties.

[0053] The technical solution of the present invention is explained through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above specific embodiments to be implemented. Any improvements made by technicians in the relevant field based on the present invention, or equivalent replacement of the materials selected by the present invention, etc., fall within the scope of protection of the patent.

Claims

1. A method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil, characterized in that: The preparation method comprises the following steps: (1) Add diethanolamine to the solvent, condense and reflux, start stirring, and drop propylene glycol triglycidyl ether into the reaction solution. After the dropwise addition is completed, heat up and keep the temperature to react to obtain a branched tertiary amine intermediate; (2) taking a branched tertiary amine intermediate, adding an acid and a solvent to acidify it, thereby obtaining a branched quaternary ammonium structure-containing intermediate; (3) Adding double-terminal epoxy polyether silicone oil, branch-shaped quaternary ammonium structure intermediate, and solvent into a reaction vessel with a condensation reflux system, stirring and heating to react, thereby obtaining a branch-shaped hydrophilic soft quaternary ammonium modified block silicone oil.

2. The method for preparing a branch-like hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the method, the solvent is one or a combination of isopropanol and ethylene glycol monobutyl ether.

3. The method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the step (2), the acid is one or a combination of glacial acetic acid and lauric acid.

4. The method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the step (3): the number average molecular weight of the double-terminal epoxy polyether silicone oil is 8000-14000.

5. The method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the step (1), the mass ratio of the solvent, diethanolamine and propylene glycol triglycidyl ether is 150: (310-320): (250-270).

6. The method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the step (1), after the dropwise addition is completed, the temperature is raised to 60-70° C. and the reaction is kept at this temperature for 4-8 hours.

7. The method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the step (2), the mass ratio of the branched tertiary amine intermediate to the acid and the solvent is (30-50): (40-60): (40-60), and the acidification time is 0.1-24 hours.

8. The method for preparing a dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to claim 1, characterized in that: In the step (3), the mass ratio of the double-terminal epoxy polyether silicone oil, the branched quaternary ammonium structure-containing intermediate, and the solvent is 800: (30-50): (500-600); Stir and heat to 83-86°C, and keep the temperature for 6-10 hours.

9. A dendritic hydrophilic soft quaternary ammonium modified block silicone oil, characterized in that: The method for preparing the dendritic hydrophilic soft quaternary ammonium modified block silicone oil according to any one of claims 1 to 8 is obtained.

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