Fluoride-free waterproof finishing agent, emulsion with same and preparation method of emulsion

Abstract

The preparation method of the fluorine-free waterproof finishing agent emulsion comprises the following steps: adding long-chain fatty acyl chloride or long-chain fatty acid methyl ester and a catalyst into epoxy resin, carrying out a heating reaction, then adding a cosolvent, and carrying out a reaction to obtain the fluorine-free waterproof finishing agent emulsion. And adding an emulsion containing long carbon chain amine, acetic acid or formic acid and a nonionic surfactant, and cooling to room temperature in a stirring state. The emulsion containing the fluoride-free waterproof finishing agent has the characteristics of good waterproof performance and high soaping fastness during application, and the preparation method is simple.

Description

Technical Field

[0001] The invention relates to a fluorine-free waterproof finishing agent, an emulsion containing the same and a preparation method of the emulsion, and belongs to the technical field of textile auxiliaries. Background Art

[0002] As people's living standards improve, functional fabrics such as antibacterial and deodorizing, antistatic, waterproof and breathable, oil-proof and antifouling are becoming more and more popular among consumers. Among them, waterproof textiles are widely used in outdoor sportswear, industrial textiles and home textiles.

[0003] Textile waterproofing agents are important finishing agents used to give fabrics waterproof properties. Its series of products include: metal salts, fatty acid salts / metal salts, paraffins, pyridines, modified melamine resins, silicones, acrylics, polyurethanes and fluorocarbons. Among them, perfluoro compounds are an important type of waterproofing additives. They have good waterproof, oil-proof and anti-fouling effects, good hand feel and are resistant to washing. However, due to the environmental toxicity of perfluorocarbons, their use is increasingly restricted.

[0004] There are many types of fluorine-free waterproofing agents, which are mainly divided into: silicone-based fluorine-free waterproofing agents, fluorine-free water-based polyurethane waterproofing agents, acrylic-based fluorine-free water repellents, modified amino resin waterproofing agents, etc. according to the preparation process and raw materials used.

[0005] Silicone-based fluorine-free waterproofing agents are mainly copolymerized organic polymer emulsions and reactive silicone emulsions. The treated textiles have good hydrophobicity and will not affect the air permeability of the textiles. When the silicone polymer is applied to the surface of the textile, the three hydrogen atoms on the methyl group wrap the oxygen atoms like an open umbrella. The methyl group and other organic groups can shield the textile surface with high surface energy, greatly reducing its critical surface tension and producing a good hydrophobic effect. That is, the oxygen atoms in the main chain of the waterproofing agent are covered by methyl groups, making it difficult to approach hydrogen atoms in water. The waterproofing function is achieved by the mutual repulsion between the side methyl groups and the hydrogen atoms in the water molecules.

[0006] Waterborne polyurethane is mainly a reaction between isocyanate groups and some compounds containing active hydrogen. The hydrogen atoms are connected to nitrogen atoms through the transfer of hydrogen atoms, thereby generating carbamate (i.e. polyurethane). Polyurethane is a high molecular compound containing carbamate repeating units on the main chain of the molecule, which has the advantages of low temperature resistance, good flexibility, and high bonding strength. Due to the presence of polar groups such as hydrophilic groups in the polyurethane soft segment, the moisture permeability of the polyurethane hydrophilic film increases with the increase of the humidity gradient between the inside and outside of the film, and the moisture permeability changes with humidity. At the same time, the polyurethane hard segment and its hydrophobic side chain are hydrophobic, which can prevent water droplets from passing through and play a waterproof role.

[0007] The molecular chain of acrylate polymer does not contain double bonds, so it has excellent light and heat stability, chemical stability and antioxidant properties. The ester group in the molecule forms hydrogen bonds with the hydroxyl or amide group in the textile. It is not easy to hydrolyze within the pH range of normal fiber processing. It has excellent heat resistance, light resistance, antioxidant and chemical stability. Recently, it has been widely used in textile waterproofing. Here, the acrylate emulsion used for textile waterproofing has the following advantages: non-toxic, easy to operate, simple production process, and good film-forming property. The ester group in polyacrylate easily reacts with the hydroxyl or amide group in the textile to form hydrogen bonds, thus showing excellent adhesion. The film formed on the fabric has excellent wear resistance and flexural resistance. Since the product is an aqueous emulsion, it can be combined with other water-based printing and dyeing auxiliaries in any proportion to form a coating slurry. After treatment, a continuous, transparent, soft, and highly adhesive polymer film is formed on the surface of the textile, which has excellent wear resistance and multi-flexibility. Therefore, it can be used as a permanent waterproof finishing agent.

[0008] Modified amino resin waterproofing agent is a relatively new type of waterproofing agent, with a simple and controllable synthesis process, mild conditions, less environmental pollution, and better waterproofing effect. This type of waterproofing agent has good waterproofing properties due to the large number of hydrophobic groups distributed on the periphery of the molecular structure.

[0009] However, existing waterproof finishing agents all have the problems of low bonding strength with fabrics and poor washing fastness. Summary of the invention

[0010] The object of the present invention is to provide a fluorine-free waterproof finishing agent, an emulsion containing the same and a preparation method of the emulsion. The emulsion containing the fluorine-free waterproof finishing agent has the characteristics of good waterproof performance and high soap washing fastness when used, and the preparation method is simple.

[0011] In order to achieve the above object, the technical solution adopted by the present invention is:

[0012] A fluorine-free waterproof finishing agent having the following structure:

[0013]

[0014] Wherein, R is a straight-chain alkyl group having 5 to 50 carbon atoms, and n is any integer between 2 and 20.

[0015] A fluorine-free waterproof finishing agent emulsion comprises the above-mentioned fluorine-free waterproof finishing agent and long-chain amine acetate or long-chain amine formate, wherein the carbon chains in the long-chain amine acetate and the long-chain amine formate are straight chains, and the length is any integer between 11 and 26.

[0016] The preparation method of the above-mentioned fluorine-free waterproof finishing agent emulsion is to add long-chain fatty acid chloride or long-chain fatty acid methyl ester and a catalyst to epoxy resin, add a co-solvent after heating reaction, and add an emulsion containing a long carbon chain amine, acetic acid or formic acid and a non-ionic surfactant, and cool to room temperature under stirring.

[0017] Preferably, the long-chain fatty acid chloride is at least one of stearic acid chloride and palmitic acid chloride;

[0018] The long-chain fatty acid methyl ester is at least one of methyl stearate and methyl palmitate;

[0019] The epoxy resin is bisphenol A epoxy resin, and the epoxy equivalent is 450-900 g / eq.

[0020] Preferably, when long-chain fatty acid chloride is used as the raw material, the catalyst is any one of triethylamine, N,N-dimethylbenzylamine and triisopropanolamine; when long-chain fatty acid methyl ester is used as the raw material, the catalyst is tetrabutyl titanate or tetraisopropyl titanate.

[0021] Preferably, the added mass ratio of long-chain fatty acid chloride or long-chain fatty acid methyl ester to catalyst and epoxy resin is (40-220):(0.5-20):(60-230).

[0022] Preferably, the cosolvent is at least one of dipropylene glycol, tripropylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether;

[0023] The amount of the co-solvent added is 2-15% of the total mass of the long-chain fatty acid chloride or long-chain fatty acid methyl ester, the catalyst and the epoxy resin.

[0024] Preferably, the nonionic surfactant is at least one of fatty alcohol polyoxyethylene ether, peregal O, Tween 60, Tween 80 and fatty acid polyoxyethylene ester.

[0025] Preferably, the long carbon chain amine has the structural formula CH3-(CH2) m -NH2, wherein m is any integer between 10 and 25;

[0026] The content of long carbon chain amine, acetic acid or formic acid and nonionic surfactant in the emulsion is 1-5%;

[0027] The amount of the emulsion added is 1.5-3 times the total mass of the long-chain fatty acid chloride or long-chain fatty acid methyl ester, the catalyst and the epoxy resin.

[0028] Preferably, the heating reaction conditions are: 80-100°C, 2-7h;

[0029] The emulsion temperature is 70-85°C.

[0030] The beneficial effects of the present invention are:

[0031] The hydroxyl groups in the epoxy resin are reacted with fatty acid methyl ester or fatty acid chloride to esterify the hydroxyl groups to obtain a "brush-like" epoxy resin containing an epoxy resin main chain and a long-chain fatty group. Then, a long-chain amine acetate is used as one of the emulsifiers to emulsify the "brush-like" epoxy resin to obtain a fluorine-free waterproof finishing agent emulsion. The preparation method is simple and convenient.

[0032] At the same time, the long-chain amine acetate in the waterproof finishing agent emulsion will decompose and release acetic acid and long-chain amine during the high-temperature baking process of textiles. The generated long-chain amine will further react with the epoxy resin to promote the curing of the epoxy resin, further increasing the "brush-like" structure of the waterproof finishing agent, thereby improving the waterproof effect and wash fastness of the waterproof finishing agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the TEM image of sample 1#;

[0034] Figure 2 This is the TEM image of sample #3;

[0035] Figure 3 This is the TEM image of sample #5;

[0036] Figure 4 This is the TEM image of sample 7#. DETAILED DESCRIPTION

[0037] The present invention utilizes fatty acid methyl ester or fatty acid chloride to react with hydroxyl groups in epoxy resin to esterify the hydroxyl groups to obtain a "brush-like" epoxy resin containing an epoxy resin main chain and a long-chain fatty group, and then utilizes a long-chain amine acetate as one of the emulsifiers to emulsify the "brush-like" epoxy resin to obtain a fluorine-free waterproof finishing agent (the synthesis schematic diagram is as follows).

[0038]

[0039] The long-chain amine acetate emulsifier in the waterproof finishing agent emulsion will decompose and release acetic acid and long-chain amines during the high-temperature baking process of textiles. The generated long-chain amines will further react with the epoxy resin to promote the curing of the epoxy resin, further increasing the "brush-like" structure of the waterproof finishing agent, thereby improving the waterproof effect and wash fastness of the waterproof finishing agent (schematic diagram below).

[0040]

[0041] Example 1

[0042] (1) Preparation of stearic acid modified epoxy resin

[0043] Add 90g of epoxy resin CYD-011 (epoxy equivalent 450-500, produced by Baling Petrochemical) into a 1000ml dry beaker, heat to 80°C, add 90g of stearic acid chloride, stir to melt, then add 15g of catalyst triethylamine, react at 80°C for 4 hours to obtain stearic acid modified epoxy resin.

[0044] (2) Preparation of fluorine-free waterproofing agent emulsion

[0045] Preparation of surfactant solution: Add 13.6 g of octadecylamine, 15 g of acetic acid and 14.8 g of nonionic surfactant SECOL-70 (secondary alcohol polyoxyethylene ether, Jiangsu Secco Chemical Co., Ltd.) to 1000 mL of deionized water, heat to dissolve and heat to 80° C. for use.

[0046] Emulsification: Add 9 g of cosolvent dipropylene glycol to the stearic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 365 g of the above-mentioned surfactant solution while stirring, and after the addition is completed, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, numbered 1# (TEM image see Figure 1 ), solid content 33%.

[0047] Example 2

[0048] (1) Preparation of stearic acid modified epoxy resin

[0049] Add 160g of epoxy resin CYD-013 (epoxy equivalent 700-800, produced by Baling Petrochemical) into a 1000ml dry beaker, heat to 80°C, add 160g of methyl stearate, stir to melt, then add 1g of catalyst tetrabutyl titanate, react at 80°C for 7 hours to obtain stearic acid modified epoxy resin.

[0050] (2) Preparation of fluorine-free waterproofing agent emulsion

[0051] Preparation of surfactant solution: add 70 g of octadecylamine, 70 g of acetic acid and 40 g of nonionic surfactant Tween 80 (Haian Petrochemical Plant) into 2000 mL of deionized water, heat to dissolve and heat to 80° C. for later use.

[0052] Emulsification: add 33 g of cosolvent tripropylene glycol to the stearic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 640 g of the heated surfactant solution while stirring, and after the addition is completed, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, No. 2, with a solid content of 33%.

[0053] Example 3

[0054] (1) Preparation of palmitic acid modified epoxy resin

[0055] Add 200 g of epoxy resin E12 (Nanya Electronic Materials (Kunshan) Co., Ltd., epoxy equivalent 900-1000) to a 1000 ml dry beaker, heat to 80°C, add 195 g of palmitic acid chloride, stir to melt, then add 15 g of catalyst N,N-dimethylbenzylamine, react at 80°C for 4 hours to obtain palmitic acid-modified epoxy resin.

[0056] (2) Preparation of fluorine-free waterproofing agent emulsion

[0057] Preparation of surfactant solution: add 20 g of hexadecylamine, 20 g of acetic acid and 20 g of non-ionic surfactant Tween 60 (Haian Petrochemical Plant) into 1000 mL of deionized water, heat to dissolve and heat to 80° C. for later use.

[0058] Emulsification: Add 31.6 g of ethylene glycol monobutyl ether as a cosolvent to the palmitic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 790 g of the heated surfactant solution while stirring, and after the addition is complete, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, No. 3# (TEM image see Figure 2 ), solid content 33%.

[0059] Example 4

[0060] (1) Preparation of palmitic acid modified epoxy resin

[0061] Add 100 g of epoxy resin E12 (Nanya Electronic Materials (Kunshan) Co., Ltd., epoxy equivalent 900-1000) to a 1000 ml dry beaker, heat to 80°C, add 71 g of methyl palmitate, stir to melt, then add 8 g of catalyst triisopropanolamine, react at 80°C for 2 hours to obtain palmitic acid-modified epoxy resin.

[0062] (2) Preparation of fluorine-free waterproofing agent emulsion

[0063] Preparation of surfactant solution: Add 12 g of hexadecylamine, 13 g of acetic acid and 12 g of nonionic surfactant SECOL-50 (secondary alcohol polyoxyethylene ether, Jiangsu Secco Chemical Co., Ltd.) to 1000 mL of deionized water, heat to dissolve, heat to 80° C., and set aside.

[0064] Emulsification: Add 8.5 g of the cosolvent ethylene glycol monoethyl ether to the palmitic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 340 g of the heated surfactant solution while stirring, and after the addition is completed, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, No. 4, with a solid content of 33%.

[0065] Example 5

[0066] (1) Preparation of palmitic acid modified epoxy resin

[0067] Add 100 g of epoxy resin CYD-014A (epoxy equivalent 710-800, Baling Petrochemical) into a 1000 ml dry beaker, heat to 80°C, add 71 g of methyl palmitate, stir to melt, then add 8 g of catalyst triisopropanolamine, react at 80°C for 2 hours to obtain palmitic acid-modified epoxy resin.

[0068] (2) Preparation of fluorine-free waterproofing agent emulsion

[0069] Preparation of surfactant solution: Add 12 g of hexadecylamine, 13 g of acetic acid and 12 g of nonionic surfactant SECOL-50 (secondary alcohol polyoxyethylene ether, Jiangsu Secco Chemical Co., Ltd.) to 1000 mL of deionized water, heat to dissolve and heat to 80° C. for use.

[0070] Emulsification: Add 8.5 g of ethylene glycol monoethyl ether as a cosolvent to the palmitic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 340 g of the heated surfactant solution while stirring, and after the addition is complete, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, No. 5# (TEM image see Figure 3 ), solid content 33%.

[0071] Example 6

[0072] (1) Preparation of stearic acid modified epoxy resin

[0073] Add 110 g of epoxy resin CYD-011A (epoxy equivalent 530-570, Baling Petrochemical) into a 1000 ml dry beaker, heat to 95 ° C, add 118 g of stearic acid chloride, stir to melt, then add 6 g of catalyst N, N-dimethylbenzylamine, react at 80 ° C for 7 hours to obtain stearic acid modified epoxy resin.

[0074] (2) Preparation of fluorine-free waterproofing agent emulsion

[0075] Preparation of surfactant solution: add 36 g of octadecylamine, 37 g of acetic acid and 30 g of nonionic surfactant fatty acid polyoxyethylene ester (12EO) (Haian Petrochemical) to 1000 mL of deionized water, heat to dissolve and heat to 80° C. for use.

[0076] Emulsification: Add 8.5 g of the cosolvent ethylene glycol monoethyl ether to the palmitic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 456 g of the heated surfactant solution while stirring, and after the addition is completed, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, No. 6, with a solid content of 30%.

[0077] Example 7

[0078] (1) Preparation of stearic acid modified epoxy resin

[0079] Add 110 g of epoxy resin CYD-011A (epoxy equivalent 530-570, Baling Petrochemical) into a 1000 ml dry beaker, heat to 95°C, add 118 g of methyl stearate, stir to melt, then add 1.2 g of tetraisopropyl titanate as catalyst, react at 80°C for 7 hours to obtain stearic acid modified epoxy resin.

[0080] (2) Preparation of fluorine-free waterproofing agent emulsion

[0081] Preparation of surfactant solution: add 25 g of octadecylamine, 28 g of acetic acid and 20 g of nonionic surfactant Peregal O(9EO) (Haian Petrochemical) to 1000 mL of deionized water, heat to dissolve, heat to 80° C., and set aside.

[0082] Emulsification: Add 22.8 g of cosolvent dipropylene glycol to the palmitic acid-modified epoxy resin of step (1), heat to 80°C, slowly add 456 g of the heated surfactant solution while stirring, and after the addition is complete, continue stirring and cool to room temperature to obtain a waterproofing agent emulsion, No. 7# (TEM image see Figure 4 ), solid content 30%.

[0083] Performance Testing

[0084] (1) Emulsion stability test

[0085] The prepared fluorine-free waterproofing agent emulsion was sealed in 20 ml test tubes, placed in ovens at room temperature (20°C) and 45°C, and left to stand for 7 days. The upper 2 cm emulsion of the test tube was taken with a rubber-tipped pipette, and the solid content A1 of the taken emulsion was measured and compared with the solid content A0 of the original emulsion. The emulsion precipitation rate was calculated according to the following formula:

[0086]

[0087] The greater the precipitation rate, the worse the emulsion stability.

[0088] The test results are shown in Table 1.

[0089] Table 1 Fluorine-free waterproofing agent emulsion stability test results

[0090]

[0091]

[0092] It can be seen from Table 1 that the waterproofing agent emulsions prepared in Examples 1-7 have good stability and almost no sedimentation occurs.

[0093] (2) Emulsion particle size detection

[0094] The prepared fluorine-free water repellent emulsion (1# / 3# / 5# / 7#) was diluted to 3% concentration with deionized water, and the particle size of the water repellent emulsion was measured with a Spectra 300TEM transmission electron microscope (300kV, Thermo Fisher) after the emulsion was dipped on a copper mesh. The test results are attached. Figure 1-4 As can be seen from the attached figure, the particle size of the prepared emulsion is less than 1 micron.

[0095] (3) Waterproof performance test

[0096] The prepared waterproof finishing agent was diluted with deionized water to 30-50 g / L, and then impregnated into pure cotton fabric and pure polyester fabric respectively. Then, the fabric was pre-baked at 100° C., baked at 180° C. for 90 seconds, cooled to room temperature, and tested for waterproof performance.

[0097] Fabric: 70D twill white polyester taffeta, red cotton poplin (specification 40S, 110*70).

[0098] Washing process: 2g / L soap flakes, washing at 40℃, drying naturally after washing, and then washing again. After 10 cycles, test the water resistance of the waterproofing agent.

[0099] Waterproof performance: Refer to GB4745-1997 fabric waterproof water test, judge the water situation of fabric by human eyes, and the waterproof effect is divided into 5 levels, with 5 being the best and 1 being the worst. The test results are shown in Table 2.

[0100] Table 2 Waterproof performance test of fluorine-free waterproof agent

[0101]

[0102]

[0103] As can be seen from Table 2, the waterproofing agents prepared in Examples 1-7 have good waterproofing effects, and can achieve grade 5 waterproofing on polyester fabrics, grade 4-5 waterproofing on pure cotton fabrics, and some products can achieve grade 5 waterproofing. After 10 cycles of washing, the waterproofing properties of the two fabrics are still good.

[0104] The above is only a preferred implementation of the patent of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the patent of the present invention. These improvements and modifications should also be regarded as the scope of protection of the patent of the present invention.

Claims

1. A fluorine-free waterproof finishing agent, characterized in that: Has the following structure: Wherein, R is a straight-chain alkyl group having 5 to 50 carbon atoms, and n is any integer between 2 and 20.

2. A fluorine-free waterproof finishing agent emulsion, characterized in that: The invention comprises the fluorine-free waterproof finishing agent according to claim 1 and long-chain amine acetate or long-chain amine formate, wherein the carbon chains in the long-chain amine acetate and the long-chain amine formate are straight chains, and the length is any integer between 11 and 26.

3. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 2, characterized in that: The method is to add long-chain fatty acid chloride or long-chain fatty acid methyl ester and a catalyst to the epoxy resin, add a co-solvent after heating for reaction, and add an emulsion containing a long-chain amine, acetic acid or formic acid and a non-ionic surfactant, and cool to room temperature under stirring.

4. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: The long-chain fatty acid chloride is at least one of stearic acid chloride and palmitic acid chloride; The long-chain fatty acid methyl ester is at least one of methyl stearate and methyl palmitate; The epoxy resin is bisphenol A epoxy resin, and the epoxy equivalent is 450-900 g / eq.

5. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: When long-chain fatty acid chloride is used as the raw material, the catalyst is any one of triethylamine, N,N-dimethylbenzylamine and triisopropanolamine; when long-chain fatty acid methyl ester is used as the raw material, the catalyst is tetrabutyl titanate or tetraisopropyl titanate.

6. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: The mass ratio of long-chain fatty acid chloride or long-chain fatty acid methyl ester to catalyst and epoxy resin is (40-220):(0.5-20):(60-230).

7. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: The cosolvent is at least one of dipropylene glycol, tripropylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; The amount of the co-solvent added is 2-15% of the total mass of the long-chain fatty acid chloride or long-chain fatty acid methyl ester, the catalyst and the epoxy resin.

8. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: The nonionic surfactant is at least one of fatty alcohol polyoxyethylene ether, peregal O, Tween 60, Tween 80 and fatty acid polyoxyethylene ester.

9. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: The structural formula of long carbon chain amines is CH3-(CH2) m -NH2, wherein m is any integer between 10 and 25; The content of long carbon chain amine, acetic acid or formic acid and nonionic surfactant in the emulsion is 1-5%; The amount of the emulsion added is 1.5-3 times the total mass of the long-chain fatty acid chloride or long-chain fatty acid methyl ester, the catalyst and the epoxy resin.

10. The method for preparing the fluorine-free waterproof finishing agent emulsion according to claim 3, characterized in that: The conditions for the heating reaction are: 80-100°C, 2-7h; The emulsion temperature is 70-85°C.

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