阅读说明：本技术 一种无氟防水剂的制备方法及制得的无氟防水剂 (Preparation method of fluorine-free waterproof agent and prepared fluorine-free waterproof agent ) 是由 张春梅 朱利 付小刚 于 2019-11-07 设计创作，主要内容包括：本发明公开了一种无氟防水剂的制备方法及制得的无氟防水剂,属于织物防水整理剂的技术领域,解决了其加工稳定性差的缺点的问题。无氟防水剂的制备方法,包括以下步骤：A：将乳化剂a、乙醇a、水a、正硅酸乙酯混合,得混合物X；B：将乳化剂b、乙醇b、水b、甲基三乙基硅氧烷混合,得混合物Y；C：将混合物X和混合物Y混合,并加入硅烷偶联剂和氯铂酸,得混合物Z；D：将烷基丙烯酸酯、丙烯酸羟乙酯或丙烯酸羟丙酯、乳化剂c混合,得到混合物M；E：将混合物M和引发剂V-50混合,得混合物N；F：将混合物Z、混合物N和石蜡乳液进行混合,得混合物Q；添加pH调节剂,得到无氟防水剂,提高无氟防水剂的加工稳定性。(The invention discloses a preparation method of a fluorine-free waterproof agent and the prepared fluorine-free waterproof agent, belongs to the technical field of fabric waterproof finishing agents, and solves the problem of poor processing stability. The preparation method of the fluorine-free waterproof agent comprises the following steps: a: mixing an emulsifier a, ethanol a, water a and tetraethoxysilane to obtain a mixture X; b: mixing an emulsifier b, ethanol b, water b and methyl triethyl siloxane to obtain a mixture Y; c: mixing the mixture X and the mixture Y, and adding a silane coupling agent and chloroplatinic acid to obtain a mixture Z; d: mixing alkyl acrylate, hydroxyethyl acrylate or hydroxypropyl acrylate and an emulsifier c to obtain a mixture M; e: mixing the mixture M and an initiator V-50 to obtain a mixture N; f: mixing the mixture Z, the mixture N and the paraffin emulsion to obtain a mixture Q; and adding a pH regulator to obtain the fluorine-free waterproof agent, thereby improving the processing stability of the fluorine-free waterproof agent.)

1. A preparation method of a fluorine-free waterproof agent is characterized by comprising the following steps:

a: mixing an emulsifier a, ethanol a, water a and 4.5-7.5 parts of tetraethoxysilane, and emulsifying for 13-20min under the stirring of 7000-8500r/min to obtain a mixture X;

b: mixing an emulsifier b, ethanol b, water b and 25-30 parts of methyltriethylsiloxane, and emulsifying for 13-20min under the stirring of 7000-8500r/min to obtain a mixture Y;

c: mixing the mixture X and the mixture Y, adding 1-5 parts of silane coupling agent and 10-30ppm of chloroplatinic acid, heating to 60-85 ℃, and reacting for 1-3 hours under the condition of heat preservation to obtain a mixture Z;

d: mixing 15-20 parts of alkyl acrylate, 2-5 parts of hydroxyethyl acrylate or hydroxypropyl acrylate and 1-5 parts of emulsifier c, and homogenizing and emulsifying to obtain a mixture M;

e: mixing the mixture M with 1-5 parts of initiator V-50, heating to 65-80 ℃, preserving heat, and reacting for 2.5-4.5h under the stirring of 150-250r/min to obtain a mixture N;

f: mixing the mixture Z, the mixture N and the paraffin emulsion, heating to 40-50 ℃, preserving heat, and mixing under the stirring of 100-150r/min to obtain a mixture Q; adding a pH regulator to adjust the pH of the mixture Q to 4.5-5.5 to obtain a fluorine-free waterproof agent;

step A, step B and step D can be carried out simultaneously;

the using amount of the emulsifier a is 14-15% of the tetraethoxysilane, the using amount of the ethanol a is 4.5-6% of the tetraethoxysilane, and the using amount of the water a is 4-5% of the tetraethoxysilane;

the using amount of the emulsifier b is 16-17% of the methyl triethyl siloxane, the using amount of the ethanol b is 12-13% of the methyl triethyl siloxane, and the using amount of the water b is 8-9% of the methyl triethyl siloxane;

the emulsifier a and the emulsifier b are respectively a mixture of peregal O-10, peregal O-20 and peregal O-30, and the emulsifier c is one of a cationic emulsifier, span, tween, peregal and isomeric alcohol;

in the step F, the paraffin emulsion accounts for 10-20% of the weight of the mixture Q, the weight part ratio of the mixture Z to the mixture N is 1:1, and the solid content of paraffin in the paraffin emulsion is 15-32%;

the parts are all parts by weight.

2. The method for preparing a fluorine-free water repellent according to claim 1, wherein the wax in the wax emulsion has a melting range of 55 to 65 ℃ and the emulsifier is one of disproportionated rosin potassium soap or O-10.

3. The method for producing a fluorine-free water repellent according to claim 2, wherein the paraffin wax in the paraffin wax emulsion has a solid content of 30%.

4. The method for producing a fluorine-free water repellent according to claim 1, wherein the total number of carbon atoms of the alkyl acrylate in the step D is 6 to 22.

5. The method for preparing a fluorine-free waterproofing agent according to claim 1, wherein the emulsifier a is composed of peregal O-10, peregal O-20 and peregal O-30 in a weight ratio of 3:5: 6.8.

6. The method of claim 5, wherein in step A, the amount of emulsifier a is 14.8% of ethyl orthosilicate, the amount of ethanol a is 5% of ethyl orthosilicate, and the amount of water a is 4.5% of ethyl orthosilicate.

7. The method for preparing a fluorine-free waterproofing agent according to claim 1, wherein the emulsifier b is composed of peregal O-10, peregal O-20 and peregal O-30 in a weight ratio of 3:5: 6.8.

8. The method of claim 7, wherein in step B, the amount of emulsifier B used is 16.8% of tetraethoxysilane, the amount of ethanol B used is 12.5% of tetraethoxysilane, and the amount of water B used is 8.3% of tetraethoxysilane.

9. A fluorine-free water repellent agent obtained by the production method according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of fabric waterproof finishing agents, in particular to a preparation method of a fluorine-free waterproof agent and the prepared fluorine-free waterproof agent.

Background

The fabric finishing is to apply a finishing agent on the fabric, which can change the surface property of the fabric so as to endow the fabric with special functions, and a waterproof agent can change the surface property of the fiber so that the surface of the fabric is not easy to be wetted and spread by water or oil so as to achieve the waterproof effect. The general finishing operation is to carry out the dipping treatment in the finishing agent working solution at 40-70 ℃ and then carry out the drying treatment.

The mainstream fabric waterproof agent in the market before 2015 is a fluorine long-chain C8 finishing agent, and the C8 finishing agent has excellent performance and low price. The C8 finishing agent contains PFOA (perfluorooctanoic acid and salts thereof), PFOS (perfluorooctanoic acid sulfonyl compound) and APEO (alkylphenol ethoxylates), the PFOA, the PFOS and the APEO are difficult to degrade in the environment, have biological accumulation and various toxicities, have common characteristics of persistent organic pollutants, and are considered to be novel persistent environmental pollutants which are intensively researched in the 21 st century. The 2006 european union issues statutes and specifies: the PFOS and PFOA content in the textile of the European Union of export must be less than 1ug/m²C8 on the market at that time was difficult to meet the requirements and was gradually eliminated.

After the european union issued the directive, C8 was gradually replaced by a short-chain fluorine-based finishing agent C6, C6 was PFHS (perfluorohexane sulfonyl compound or sulfonate) as a main component, and the contents of PFOS and PFOA in C6 were less than the prescribed values and were difficult to detect, so C8 was replaced by a large amount of C6; however, C6 is expensive and the effect is difficult to achieve with C8.

With increasing emphasis on global environmental protection, the united states environmental protection agency (u.s.a.) stipulates in the clear, and by 2015, C8 and C6 containing PFOA and PFOS were prohibited globally, and C4 and fluorine-free finishes were strongly recommended. In 2015, fluorine-free water-proofing agent is popularized and used in textile industry, and mainly solves the performance of fabric in washing fastness.

The various fluoride-free waterproof agents in the existing market have different reactivity ratios of water molecules and waterproof agent molecules in the fabric dyeing process due to the fact that the waterproof agent product is an emulsion mixture, so that the fabric is poor in head and tail in the processing process, namely processing instability is caused; as described above, the fluorine-free water repellent has a drawback of poor workability.

Disclosure of Invention

The present invention has been made to overcome the drawbacks of the prior art, and a first object of the present invention is to provide a method for producing a fluorine-free water repellent which achieves the effect of obtaining a fluorine-free water repellent having good processing stability.

The second purpose of the invention is to provide a fluorine-free waterproof agent which achieves the effect of providing good processing stability for fabrics.

In order to achieve the first object, the invention provides the following technical scheme:

the technical purpose of the invention is realized by the following technical scheme:

a preparation method of a fluorine-free waterproof agent comprises the following steps:

a: mixing an emulsifier a, ethanol a, water a and 4.5-7.5 parts of tetraethoxysilane, and emulsifying for 13-20min under the stirring of 7000-8500r/min to obtain a mixture X;

b: mixing an emulsifier b, ethanol b, water b and 25-30 parts of methyltriethylsiloxane, and emulsifying for 13-20min under the stirring of 7000-8500r/min to obtain a mixture Y;

c: mixing the mixture X and the mixture Y, adding 1-5 parts of silane coupling agent and 10-30ppm of chloroplatinic acid, heating to 60-85 ℃, and reacting for 1-3 hours under the condition of heat preservation to obtain a mixture Z;

d: mixing 15-20 parts of alkyl acrylate, 2-5 parts of hydroxyethyl acrylate or hydroxypropyl acrylate and 1-5 parts of emulsifier c, and homogenizing and emulsifying to obtain a mixture M;

e: mixing the mixture M with 1-5 parts of initiator V-50, heating to 65-80 ℃, preserving heat, and reacting for 2.5-4.5h under the stirring of 150-250r/min to obtain a mixture N;

f: mixing the mixture Z, the mixture N and the paraffin emulsion, heating to 40-50 ℃, preserving heat, and mixing under the stirring of 100-150r/min to obtain a mixture Q; adding a pH regulator to adjust the pH of the mixture Q to 4.5-5.5 to obtain a fluorine-free waterproof agent;

step A, step B and step D can be carried out simultaneously;

the using amount of the emulsifier a is 14-15% of the tetraethoxysilane, the using amount of the ethanol a is 4.5-6% of the tetraethoxysilane, and the using amount of the water a is 4-5% of the tetraethoxysilane;

the using amount of the emulsifier b is 16-17% of the methyl triethyl siloxane, the using amount of the ethanol b is 12-13% of the methyl triethyl siloxane, and the using amount of the water b is 8-9% of the methyl triethyl siloxane;

the emulsifier a and the emulsifier b are respectively a mixture of peregal O-10, peregal O-20 and peregal O-30, and the emulsifier c is one of a cationic emulsifier, span, tween, peregal and isomeric alcohol;

in the step F, the paraffin emulsion accounts for 10-20% of the weight of the mixture Q, the weight part ratio of the mixture Z to the mixture N is 1:1, and the solid content of paraffin in the paraffin emulsion is 15-32%;

the parts are all parts by weight.

By adopting the technical scheme, the tetraethoxysilane in the step A is gradually hydrolyzed under the conditions of water and ethanol to form-OC₂H₅The group is substituted by-OH, the reaction equation is as follows:

further, two molecules of hydrolysis product of tetraethoxysilane are reacted, and the end parts of the two products are respectively dehydrogenated and hydroxyl to form ether group and form one molecule of water, and the reaction equation is as follows:

in the step B, the methyl triethyl siloxane is dispersed in water and ethanol and gradually hydrolyzed under high-speed stirring, and the reaction equation is as follows:

the reaction between the two hydrolysis products continues, and the reaction equation is as follows:

in the step C, the mixture X and the mixture Y are mixed, a condensation compound generated by the hydrolysis product of the tetraethoxysilane in the step A and a condensation compound generated by the hydrolysis product of the tetraethoxysilane in the step B react with a silane coupling agent, and the reaction equation is as follows:

and D, homogenizing and emulsifying hydroxyethyl methacrylate or hydroxyethyl acrylate, alkyl acrylate and an emulsifier, and uniformly dispersing all the components to prepare for the next addition polymerization reaction.

In step E, hydroxyethyl methacrylate or hydroxyethyl acrylate and alkyl acrylate are subjected to addition polymerization under the catalysis of an initiator, wherein the formula is as follows, taking hydroxyethyl methacrylate as an example:

r1 and R2 are alkyl.

And step F, uniformly mixing the obtained organic silicon emulsion, acrylic ester emulsion and paraffin emulsion according to a compounding ratio to obtain the fluorine-free waterproof agent. The fluorine-free water repellent includes silicone emulsions prepared in steps A, B and D, acrylic emulsions prepared in steps E and F, and paraffin wax emulsions.

In the preparation process of the organic silicon emulsion, water is used as a dispersion medium, and ethyl orthosilicate is used for preparing polyalkyl silsesquioxane emulsion; in the process of emulsion polymerization, the tetraethoxysilane and water, and the monomer hydrolysate can react without a specific reaction active center, so that micelle nucleation, droplet nucleation and homogeneous nucleation can exist after the methyltriethylsiloxane is added. Hydrolyzing and polycondensing ethyl orthosilicate to generate polysiloxane oligomer with low molecular weight, thereby forming latex particles; in the initial stage of the reaction, the tetraethoxysilane is hydrolyzed and condensed to generate more oligomers, so that the particle size of the latex particles is increased relatively quickly and is dispersed, and meanwhile, partial monomer liquid drops exist; along with the reaction, the oligomers in the system increase, the hydrolysis polycondensation reaction continues to occur among the oligomers, the particle size increases, and the particle size distribution gradually narrows, so that uniform and stable emulsion is formed, and uniform film-forming property is provided for the fluorine-free waterproof agent.

The fluorine-free waterproof agent contains long-chain aliphatic hydrocarbon, methyl and ethoxy with continuous branched chains and polar groups; polar groups or reactive groups are directionally adsorbed on the fiber surface, and alkyl long chains and continuously arranged methyl and ethoxy are arranged on the fabric surface. When the fluorine-free waterproof agent is used for high-temperature baking finishing, under the action of a catalyst (generally acrylamide) and heat, the waterproof agent can form a network polymer with fiber molecules, and methyl, ethoxy and long-chain aliphatic hydrocarbon are densely and directionally arranged on the fiber surface to form a water repellent layer, so that the waterproof treatment of the fabric is realized.

Meanwhile, under the high-temperature condition, an Si-O-Si bond and oxygen in the air are subjected to oxidation reaction to form an alcohol group, and the alcohol group is further reacted with a hydroxyl group of cellulose in the fabric to generate an ether group, so that the binding force between the fluorine-free waterproof agent and the fiber is improved, and the fiber has washable water repellency; the air permeability of the fabric can be ensured because the fluorine-free waterproof agent is connected with the fiber through covalent bonds, and the water repellent layer is formed by the oriented arrangement of molecules on the outer surface of the fabric instead of a coating.

When the fluorine-free waterproof agent molecules enter the surfaces of the fibers and the fabric and in fiber pores, covalent bonds can be formed and combined with the fibers at high temperature to form a three-dimensional network structure under the combined action of the fibers and the waterproof agent molecules, and a uniform protection mechanism with the gap of only 100nm can be formed on the surfaces of the fibers. The specific surface area of the surface of the article contacted with foreign substances is greatly improved, so that water drops and the like under normal temperature and normal pressure are difficult to enter the fiber and the fabric through gaps, a special surface effect is generated, and the waterproof finishing of the fabric is realized.

In the process of dyeing the fabric, water molecules and fluorine-free waterproofing agent molecules have different reactivity ratios; the addition of a proper amount of paraffin emulsion can form an effect similar to emulsion micelles, and the emulsion can be used as a protective colloid of the fluorine-free water-proofing agent, and simultaneously reduce the surface tension and increase the stability of the fluorine-free water-proofing agent padding liquid. Meanwhile, from the experimental result, the addition of the paraffin emulsion can improve the water repellency effect and can also increase the washing resistance.

More preferably: the melting range of the paraffin in the paraffin emulsion is 55-65 ℃, and the emulsifier is one of disproportionated rosin potassium soap or O-10.

By adopting the technical scheme, the paraffin is a hydrocarbon mixture with the carbon number of about 18-30, and the main component is straight-chain paraffin, and a small amount of paraffin with individual branch chains and monocyclic cycloalkane with long side chains. The temperature of the fluorine-free water-proofing agent is generally 40-70 ℃ when in use, and the paraffin is just matched with the melting range of the paraffin at the treatment temperature, so that the paraffin in the working solution of the fluorine-free water-proofing agent is in a molten state.

More preferably: the paraffin wax emulsion has a solid content of 30%.

By adopting the technical scheme, experiments show that the fluorine-free waterproof agent of the paraffin emulsion with the solid content acts on the fabric, so that the fabric can obtain better processing stability. Meanwhile, the concentration of the water repellent in use is generally 30 to 35%, and more preferably: the total number of carbon atoms of the alkyl acrylate in the step D is 6-22.

By adopting the technical scheme, the acrylic ester with the carbon atom number has proper glass transition temperature, the obtained acrylic emulsion has rigidity and flexibility, and branched chains of the acrylic emulsion can be better arranged on the surface of the fabric without influencing the flexibility of the fabric.

More preferably: the emulsifier a is composed of peregal O-10, peregal O-20 and peregal O-30 in a weight portion ratio of 3:5: 6.8.

By adopting the technical scheme, experiments show that the fluorine-free waterproof agent obtained by using the combined emulsifier has uniform water repellent effect of the finished fabric, and the emulsification effect in the emulsification process can be reflected from the side surface.

More preferably: in the step A, the using amount of the emulsifier a is 14.8 percent of the tetraethoxysilane, the using amount of the ethanol a is 5 percent of the tetraethoxysilane, and the using amount of the water a is 4.5 percent of the tetraethoxysilane.

By adopting the technical scheme, experiments show that the fluorine-free waterproof agent obtained by using the using amount has better water repellent effect on the finished fabric, so that the waterproof agent forms a uniform water repellent layer on the surface of the fabric, and the emulsification effect in the emulsification process can be reflected from the side surface.

More preferably: the emulsifier b is composed of peregal O-10, peregal O-20 and peregal O-30 in a weight portion ratio of 3:5: 6.8.

By adopting the technical scheme, experiments show that the fluorine-free waterproof agent obtained by using the combined emulsifier has better water repellent effect on the finished fabric, so that the waterproof agent forms a uniform water repellent layer on the surface of the fabric, and the emulsification effect in the emulsification process can be reflected from the side surface.

More preferably: in the step B, the using amount of the emulsifier B is 16.8 percent of the tetraethoxysilane, the using amount of the ethanol B is 12.5 percent of the tetraethoxysilane, and the using amount of the water B is 8.3 percent of the tetraethoxysilane.

By adopting the technical scheme, experiments show that the fluorine-free waterproof agent obtained by using the using amount has better water repellent effect on the finished fabric, so that the waterproof agent forms a uniform water repellent layer on the surface of the fabric, and the emulsification effect in the emulsification process can be reflected from the side surface.

In order to achieve the second object, the invention provides the following technical scheme: a fluorine-free water repellent agent obtained by the production method according to any one of claims 1 to 8.

By adopting the technical scheme, when the fluorine-free waterproof agent is used for finishing the fabric, the fluorine-free waterproof agent has good processing stability, good water repellency and water washing resistance.

In conclusion, the invention has the following beneficial effects:

1. the paraffin emulsion is adopted to serve as a protective colloid of the fluorine-free waterproof agent, so that the stability of the dipping and rolling liquid of the fluorine-free waterproof agent is improved.

2. By adopting organic silicon emulsion and acrylic emulsion, polar groups or reaction groups of the waterproof agent are directionally adsorbed on the surface of the fiber, and alkyl long chains and continuously arranged methyl and ethyl groups are arranged on the surface of the fabric to form a water repellent layer, so that the waterproof treatment of the fabric is realized; the Si-O-Si bond is oxidized to form an alcohol group, and the alcohol group reacts with hydroxyl in the fabric to generate an ether group, so that the binding force between the fluorine-free waterproof agent and the fiber is improved, and the washing resistance is improved.

3. By adopting the combined emulsifier a and emulsifier b, the fluorine-free waterproof agent has tiny and uniform emulsion particles, molecules of the fluorine-free waterproof agent enter the surfaces of the fibers and the fabric and the accessible area, and a uniform protector with gaps of only 100nm can be formed on the surfaces of the fibers by utilizing a three-dimensional net-shaped three-dimensional structure. Greatly increasing the specific surface area of the surface of the article when the surface of the article is contacted with foreign substances and improving the waterproof effect.

Detailed Description