modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof
阅读说明：本技术 一种改性环氧基poss无氟防水整理剂及其制备方法 (modified epoxy group POSS fluorine-free waterproof finishing agent and preparation method thereof ) 是由 王慧荣 顾永欢 程凌燕 苏梦婷 于 2019-10-28 设计创作，主要内容包括：本发明公开了一种改性环氧基POSS无氟防水整理剂及其制备方法,该制备方法包括A1：将环氧基POSS与硬脂酸、乙酰丙酮基金属络合物以及溶剂混合,搅拌反应后得到腊状粘稠性产物,其中环氧基POSS与硬脂酸的摩尔比为1:4～7；A2：将腊状粘稠性产物减压蒸馏,然后用乙醇清洗,得到改性环氧基POSS；A3：将改性环氧基POSS配置成水溶液与乳化剂混合搅拌,得到改性环氧基POSS无氟防水整理剂。该防水整理剂制备方法简单,反应过程易操作,防水整理剂用于棉织物的防水后整理,棉织物手感柔软,能赋予棉织物的优异的防水效果和良好的耐水洗性。(The invention discloses modified epoxy group POSS fluorine-free waterproof finishing agent and a preparation method thereof, wherein the preparation method comprises the steps of A1, mixing epoxy group POSS with stearic acid, acetylacetone-based metal complex and solvent, stirring and reacting to obtain a wax-like viscous product, A2, carrying out reduced pressure distillation on the wax-like viscous product, then cleaning with ethanol to obtain modified epoxy group POSS, and A3, preparing the modified epoxy group POSS into an aqueous solution, mixing and stirring with an emulsifier to obtain the modified epoxy group POSS fluorine-free waterproof finishing agent.)
The modified epoxy group POSS fluorine-free waterproof finishing agent is characterized in that the waterproof finishing agent is obtained by emulsifying modified epoxy group POSS, and the structural formula of the modified epoxy group POSS is as follows:
Wherein X is 1-3; y is 4-7, and X and Y are integers.
The preparation method of modified epoxy group POSS fluorine-free waterproof finishing agents is characterized by comprising the following steps:
a1: mixing epoxy group POSS with stearic acid, an acetylacetone-based metal complex and a solvent, and stirring to react to obtain a wax-like viscous product, wherein the molar ratio of the epoxy group POSS to the stearic acid is 1: 4-7;
a2: distilling the waxy viscous product under reduced pressure, and then cleaning with ethanol to obtain modified epoxy group POSS;
a3: preparing the modified epoxy group POSS into an aqueous solution, mixing and stirring the aqueous solution and an emulsifier to obtain the modified epoxy group POSS fluorine-free waterproof finishing agent.
3. The preparation method of the modified epoxy POSS fluoride-free waterproof finishing agent as claimed in claim 2, wherein the step A1 is specifically as follows: adding epoxy POSS into a flask, heating to 85-105 ℃, adding stearic acid, acetylacetone-based metal complex and a solvent into the flask according to a preset proportion, uniformly mixing, stirring, and reacting for 3-8 hours to obtain the waxy viscous product.
4. The preparation method of the modified epoxy POSS fluoride-free waterproof finishing agent as claimed in claim 2 or 3, wherein in the step A1, the mixing proportion of the metal acetylacetonate complex is 0.05-5% by mass of stearic acid, and the mixing proportion of the solvent is 30-50% by mass of the mixed solution.
5. The method of claim 2 or 3, wherein the acetylacetonato metal complex is at least selected from the group consisting of acetylacetonato complex zirconium, acetylacetonato complex aluminum, acetylacetonato complex lanthanum zirconium, acetylacetonato complex iron, diacetone complex copper, diacetone complex cobalt, diacetone complex manganese, diacetone complex nickel, diacetone complex beryllium, and diacetone complex zinc.
6. The preparation method of the modified epoxy POSS fluoride-free waterproof finishing agent as claimed in claim 2 or 3, wherein the solvent is selected from of toluene and xylene.
7. The preparation method of the modified epoxy POSS fluoride-free waterproof finishing agent of claim 2, wherein in the step A2, the modified epoxy POSS is obtained by distilling a waxy viscous product under the conditions of pressure of 0.1-0.5 MPa and temperature of 60-90 ℃ for 30-50 min under reduced pressure, removing the solvent, and washing with ethanol.
8. The preparation method of the modified epoxy group POSS fluoride-free waterproof finishing agent according to claim 2, characterized in that in the step A3, the modified epoxy group POSS is prepared into an aqueous solution with the mass percent of 20-40%, the temperature is raised to 40-80 ℃, then the modified epoxy group POSS aqueous solution with the preset proportion is mixed with an emulsifier, and the mixture is rapidly stirred for 1h to obtain the modified epoxy group POSS fluoride-free waterproof finishing agent.
9. The preparation method of the modified epoxy POSS fluoride-free waterproof finishing agent as claimed in claim 2 or 8, wherein the modified epoxy POSS aqueous solution and the emulsifier are mixed in a mass ratio of 100: 0.5-5.
10. The preparation method of the modified epoxy POSS fluoride-free waterproof finishing agent as claimed in claim 2 or 8, wherein the emulsifier is selected from any or any combination of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether or isomeric tridecanol polyoxyethylene ether.
Technical Field
The invention belongs to the technical field of textile auxiliaries, and particularly relates to modified epoxy group POSS fluorine-free waterproof finishing agents and a preparation method thereof.
Background
Along with the improvement of living standard of people, the demand of people on fabrics is various, the demand on functional textiles is more and more, the demand is higher and higher, and the requirements comprise non-ironing, antibacterial, soft, flame retardant or waterproof functions and the like, wherein, the waterproof function finishing is types of extremely important functional textiles, has been widely used for outdoor textile and clothing, the best waterproof effect is the fluorine-containing polyacrylate finishing agent, especially containing-C8F17The finishing agent with the group as the main component has the best effect, namely people generally refer to the C8 type waterproofing agent for short. The fabric treated with the waterproof finishing agent has extremely low surface energy, is difficult to wet on the surface of the fabric, and has the most excellent waterproof effect.
However, the molecular material of the waterproof agent contains harmful substances of perfluorooctanoic acid, or the generation of perfluorooctanoic acid is easy to cause, so that the waterproof agent is limited and applied or forbidden by European Union, America and other developed countries, and at present, main fluorocarbon waterproof agent suppliers around the world collectively decide to stop the production and sale of products, so that more and more enterprises start to turn to a substitute of the product, namely, a fluorine-free waterproof finishing agent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides modified epoxy group POSS fluorine-free waterproof finishing agents and a preparation method thereof, the preparation method of the waterproof finishing agent is simple, the reaction process is easy to operate, the waterproof finishing agent is used for the waterproof after-finishing of cotton fabrics, the cotton fabrics have soft hand feeling, the excellent waterproof effect and good washing resistance of the cotton fabrics can be endowed, and the POSS is polymeric oligomeric silsesquioxane in the whole course and is named as cage type polysilsesquioxane in the Chinese language.
In order to solve the problems, the technical scheme of the invention is as follows:
modified epoxy group POSS fluoride-free waterproof finishing agent, wherein the waterproof finishing agent is obtained by emulsifying modified epoxy group POSS, and the structural formula of the modified epoxy group POSS is as follows:
Wherein X is 1-3; y is 4-7, and X and Y are integers.
The invention also provides a preparation method of the modified epoxy group POSS fluorine-free waterproof finishing agent, which comprises the following steps:
a1: epoxy POSS is mixed with stearic acid, acetylacetone-based metal complex and solvent, and wax-like viscous products are obtained after stirring reaction, wherein the molar ratio of the epoxy POSS to the stearic acid is 1: 4-7;
a2: distilling the waxy viscous product under reduced pressure, and then cleaning with ethanol to obtain modified epoxy group POSS;
a3: preparing the modified epoxy group POSS into an aqueous solution, mixing and stirring the aqueous solution and an emulsifier to obtain the modified epoxy group POSS fluorine-free waterproof finishing agent.
Specifically, the step a1 specifically includes: adding epoxy POSS into a flask, heating to 85-105 ℃, adding stearic acid, acetylacetone-based metal complex and a solvent into the flask according to a preset proportion, uniformly mixing, stirring, and reacting for 3-8 hours to obtain the waxy viscous product.
Preferably, in the step a1, the mixing ratio of the metal acetylacetonate complex is 0.05-5% by mass of stearic acid, the mixing ratio of the solvent is 30-50% by mass of the mixed solution, and the metal acetylacetonate complex is used as the catalyst, and the amount of the metal acetylacetonate complex is less than 0.05% by mass of stearic acid, so that the reaction is incomplete and the reaction cannot proceed in a specific direction; if the amount is more than 5% of stearic acid, byproducts may be generated.
Preferably, the acetylacetonato-based metal complex is at least selected from the group consisting of acetylacetonato zirconium, acetylacetonato aluminum, acetylacetonato lanthanum zirconium, acetylacetonato iron, acetylacetonato copper, acetylacetonato cobalt, acetylacetonato manganese, acetylacetonato nickel, acetylacetonato beryllium, and acetylacetonato zinc.
Preferably, the solvent is of toluene or xylene, and further steps are preferably toluene.
Preferably, in the step a2, the waxy viscous product is distilled under reduced pressure at a pressure of 0.1 to 0.5MPa and a temperature of 60 to 90 ℃ for 30 to 50min, the solvent is removed, and the solvent is washed with ethanol to obtain the modified epoxy group POSS.
Preferably, in the step a3, the modified epoxy group POSS is prepared into an aqueous solution with a mass percentage of 20-40%, the temperature is raised to 40-80 ℃, then the modified epoxy group POSS aqueous solution with a preset proportion is mixed with an emulsifier, and the mixture is rapidly stirred for 1 hour, so as to obtain the modified epoxy group POSS fluorine-free waterproof finishing agent.
Preferably, the modified epoxy POSS aqueous solution and the emulsifier are mixed in a mass ratio of 100: 0.5-5, and the proportion of the emulsifier is limited in that too little emulsifier is not beneficial to emulsification, and too much emulsifier generates side effects, and the effect is not good.
Preferably, the emulsifier is selected from kinds of or any combination of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether or isomeric tridecanol polyoxyethylene ether.
The invention also provides modified epoxy group POSS fluorine-free waterproof finishing agents, which are prepared by the method in the embodiment.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
the invention utilizes an acetylacetone-based metal complex as a catalyst, so that an epoxy group in epoxy-based POSS and a carboxyl group in stearic acid are subjected to esterification reaction, and the acetylacetone-based metal complex is adopted to catalyze the esterification reaction of the epoxy group and the carboxyl group, experiments show that the acetylacetone-based metal complex catalyst has good catalytic activity and extremely high catalytic efficiency, and can not catalyze redundant epoxy groups to perform ring-opening self-polymerization reaction, so that the viscosity of a product is hardly changed in months.
In addition, the proportion of epoxy groups in the epoxy group POSS is more than that of carboxyl of stearic acid, and an acetylacetone-based metal complex is used as a catalyst, so that the redundant epoxy groups can not generate ring-opening self-polymerization reaction, and the finally obtained fluorine-free waterproof finishing agent also contains the epoxy groups, so that the epoxy groups react with hydroxyl on the surface to form a stable covalent bond when the finishing is baked at high temperature, thereby increasing the cohesiveness of the epoxy groups and fibers, improving the washing resistance of the finished fabric, and ensuring the long-acting property of the waterproof effect.
Detailed Description
The following steps will be made in detail with reference to specific examples to illustrate the preparation of modified epoxy POSS fluorine-free water-repellent finishing agents and water-repellent textiles in accordance with the present invention.
modified epoxy group POSS fluoride-free waterproof finishing agent, which is obtained by emulsifying the modified epoxy group POSS, wherein the structural formula of the modified epoxy group POSS is as follows:
Wherein X is 1-3; y is 4-7, and X and Y are integers.
The invention also provides a preparation method of modified epoxy group POSS fluorine-free waterproof finishing agents, which comprises the following steps:
a1: epoxy POSS is mixed with stearic acid, acetylacetone-based metal complex and solvent, and wax-like viscous products are obtained after stirring reaction, wherein the molar ratio of the epoxy POSS to the stearic acid is 1: 4-7;
a2: distilling the waxy viscous product under reduced pressure, and then cleaning with ethanol to obtain modified epoxy group POSS, wherein the structural formula of the modified epoxy group POSS is as follows:
Wherein X is 1-3; y is 4-7, and X and Y are integers;
a3: preparing the modified epoxy group POSS into an aqueous solution, mixing and stirring the aqueous solution and an emulsifier to obtain the modified epoxy group POSS fluorine-free waterproof finishing agent.
It should be noted that POSS (cage silsesquioxane) is kinds of important nano-scale cage organic-inorganic hybrid molecules, each POSS microsphere has 8R groups on the surface, the R groups are organic groups, or more are reactive functional groups, and epoxy group POSS as a raw material of the invention is to replace all eight R groups in POSS with epoxy groups, all are reactive functional groups.
The invention uses acetylacetone-based metal complex as a catalyst, so that an esterification reaction is carried out on an epoxy group in epoxy-based POSS and a carboxyl group in stearic acid, a fatty chain is grafted on the surface of each POSS microsphere (the R group of POSS is replaced by the fatty chain), a wax-like viscous product is obtained, then the wax-like viscous product is subjected to reduced pressure distillation to obtain modified epoxy-based POSS, the modified epoxy-based POSS is emulsified, the obtained modified epoxy-based POSS fluorine-free waterproof finishing agent has hydrophobicity, and after the cotton fabric is subjected to post-finishing, the fabric has a waterproof effect.
In addition, the acetylacetone-based metal complex is used as a catalyst, experiments show that the catalyst has good catalytic activity and extremely high catalytic efficiency, and can not catalyze redundant epoxy groups to generate ring-opening self-polymerization reaction, and the viscosity of the product is almost unchanged within months.
Specifically, step a1 specifically includes: adding epoxy POSS into a three-neck flask, heating to 85-105 ℃, adding stearic acid, acetylacetone-based metal complex and a solvent into the flask according to a preset proportion, uniformly mixing, stirring, and reacting for 3-8 hours to obtain a waxy viscous product.
Preferably, in the step a1, the mixing ratio of the metal acetylacetonate complex is 0.05-5% by mass of stearic acid, and the mixing ratio of the solvent is 30-50% by mass of the mixed solution.
Preferably, the metal acetylacetonate complex is at least selected from the group consisting of tris (acetylacetonate) complex zirconium (iii), tris (acetylacetonate) complex aluminum (iii), tris (acetylacetonate) complex lanthanum zirconium (ii), tetrakis (acetylacetonate) complex iron (iii), bis (acetylacetonate) complex copper (ii), bis (acetylacetonate) complex cobalt (ii), bis (acetylacetonate) complex manganese (iii), bis (acetylacetonate) complex nickel (ii), bis (acetylacetonate) complex beryllium (ii), and bis (acetylacetonate) complex zinc (ii).
Preferably, the solvent is of toluene or xylene, and further steps are preferably toluene.
Preferably, in the step A2, the waxy viscous product is subjected to reduced pressure distillation under the conditions of the pressure of 0.1-0.5 MPa and the temperature of 60-90 ℃ for 30-50 min, the solvent is removed, and the product is washed with ethanol to obtain the modified epoxy group POSS.
Preferably, in the step A3, the modified epoxy group POSS is prepared into an aqueous solution with the mass percentage of 20-40%, the temperature is raised to 40-80 ℃, then the modified epoxy group POSS aqueous solution with a preset proportion is mixed with an emulsifier, and the mixture is rapidly stirred for 1 hour to obtain the modified epoxy group POSS fluorine-free waterproof finishing agent.
Preferably, the modified epoxy group POSS aqueous solution and the emulsifier are mixed in a mass ratio of 100: 0.5-5.
Preferably, the emulsifier is selected from kinds of or any combination of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether or isomeric tridecanol polyoxyethylene ether.
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