阅读说明：本技术 一种poss改性环氧基硅油防水整理剂及其制备方法 (POSS (polyhedral oligomeric silsesquioxane) modified epoxy silicone oil 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POSS改性环氧基硅油防水整理剂及其制备方法,该制备方法包括A1：将预设比例的单双键烷基化POSS和1,2-环氧-5-乙烯溶于氯仿中,得到硅油改性溶液；A2：将硅油改性溶液添加到加热后的氨基硅油混合反应,蒸馏后得到POSS改性环氧基硅油；A3：将POSS改性环氧基硅油去离子水乳化,得到POSS改性环氧基硅油防水整理剂。采用该方法制备得到的防水整理剂应用于整理纯棉织物,整理后的棉织物手感柔软、爽滑,表面具有类似荷叶的疏水结构结构,具有优异的防水性与耐洗涤性,防水效果明显。(The invention discloses a POSS modified epoxy silicone oil waterproof finishing agent and a preparation method thereof, wherein the preparation method comprises the following steps of A1: dissolving single-double bond alkylated POSS and 1, 2-epoxy-5-ethylene in a preset proportion into chloroform to obtain a silicone oil modified solution; a2: adding the silicone oil modified solution into the heated amino silicone oil for mixing reaction, and distilling to obtain POSS modified epoxy silicone oil; a3: and emulsifying the POSS modified epoxy silicone oil deionized water to obtain the POSS modified epoxy silicone oil waterproof finishing agent. The waterproof finishing agent prepared by the method is applied to finishing pure cotton fabrics, the finished cotton fabrics are soft and smooth in hand feeling, the surfaces of the cotton fabrics have hydrophobic structure structures similar to lotus leaves, and the waterproof finishing agent has excellent waterproofness and washing fastness and obvious waterproof effect.)

1. The POSS modified epoxy silicone oil waterproof finishing agent is characterized in that the waterproof finishing agent is obtained by emulsifying POSS modified epoxy silicone oil, and the structural formula of the POSS modified epoxy silicone oil is as follows:

wherein x is 100-1000; y is 10-100; z is 10 to 100, x, y and z are integers, and R represents an aliphatic chain.

2. The POSS modified epoxy silicone oil waterproof finishing agent as claimed in claim 1, which is characterized in that the waterproof finishing agent comprises the following raw materials in percentage by mass:

3. a preparation method of a POSS modified epoxy silicone oil waterproof finishing agent is characterized by comprising the following steps:

a1: dissolving single-double bond alkylated POSS and 1, 2-epoxy-5-ethylene in a preset proportion into chloroform to obtain a silicone oil modified solution;

a2: adding the silicone oil modified solution into the heated amino silicone oil for mixing reaction, and distilling to obtain POSS modified epoxy silicone oil;

a3: emulsifying POSS modified epoxy silicone oil deionized water to obtain the POSS modified epoxy silicone oil waterproof finishing agent.

4. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent as claimed in claim 3, wherein the step A2 is specifically that amino silicone oil is added into a flask, the temperature is increased to 25-45 ℃, then a silicone oil modified solution is added into the flask while stirring, after reaction for 4-8 hours, the mixture is distilled for 30-50 min at the pressure of 0.1-0.5 MPa and the temperature of 90-110 ℃, and chloroform is removed to obtain the POSS modified epoxy silicone oil.

5. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent as claimed in claim 3 or 4, wherein the molar ratio of the amino group in the amino silicone oil to the double bond in the silicone oil modified solution is 1: 1-1.1.

6. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent according to claim 3, wherein the step A3 is specifically that acetic acid is adopted to adjust the pH value of the POSS modified epoxy silicone oil to be neutral, then an emulsifier and the POSS modified epoxy silicone oil are mixed in a water bath, deionized water is added while stirring, and stirring is carried out for 1h, so that the POSS modified epoxy silicone oil waterproof finishing agent is obtained.

7. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent according to claim 6, wherein the amount of the emulsifier is 0.5-2% of the weight of the POSS modified epoxy silicone oil.

8. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent according to claim 6, wherein the weight ratio of the deionized water to the POSS modified epoxy silicone oil is 100: 20 to 40.

9. The POSS modified epoxy silicone oil waterproof finishing agent as claimed in claim 7, wherein the emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.

10. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent as claimed in any one of claim 6, wherein the preparation method of the amino silicone oil is as follows: mixing and stirring 75-87.5 wt% of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane aqueous solution and octamethylcyclotetrasiloxane heated to 70-90 ℃, adding a strong basic catalyst, reacting for 3-6 hours, adding an end capping agent, reacting for 1-2 hours, cooling to 50-70 ℃, and continuing to react for 18-24 hours to obtain the amino silicone oil.

11. The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent according to claim 10, wherein all raw materials of the waterproof finishing agent are octamethylcyclotetrasiloxane, (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, one-and-two-bond alkylated POSS, 1, 2-epoxy-5-hexene, strong basic catalyst of end capping agent, and emulsifier;

the dosage of the octamethylcyclotetrasiloxane is 50-95% of the total weight of all raw materials, the dosage of the N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane is 1-20% of the total weight of all raw materials, and the dosage of the end-capping agent is 0.01-0.1% of the total weight of all raw materials; the dosage of the strong alkaline catalyst is 0.01-0.1% of the total weight of all raw materials.

12. The POSS modified epoxy silicone oil waterproof finishing agent as claimed in claim 10, wherein the strong basic catalyst is any one of potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide, and the end-capping agent is hexamethyldisiloxane or pentamethyldisiloxane.

Technical Field

The invention belongs to the technical field of textile auxiliaries, and particularly relates to a POSS modified epoxy silicone oil waterproof finishing agent and a preparation method thereof.

Background

The currently used waterproof finishing agent is mainly an organic fluorine type finishing agent, and can reduce the surface energy of the fabric to the extent that oil, water and stains cannot infiltrate and penetrate the fibers. However, PFOS and PFOA in the organic fluorine chemicals frequently used for textile three-proofing finishing can cause extremely serious potential harm to human health, and are prohibited to be used in the textile industry, so people are dedicated to developing various fluorine-free waterproof agents.

Currently, there are two main types of fluoride-free waterproof finishing agents: alkane long-chain waterproof finishing agents and organosilicon waterproof finishing agents. The alkane long-chain waterproof finishing agent comprises metal soaps, pyridinium quaternary salts, aliphatic hydrocarbon melamines and fatty acid metal complexes, wherein the metal soap finishing agent is commonly used for industrial cloth which is not washed frequently and has the defect of poor washing resistance. The organic silicon compound has the characteristics of both organic compounds and inorganic compounds, so that the finished fabric has better waterproof performance, the air permeability of the fabric is not influenced, and the flexibility and the tearing performance of the fabric can be improved, therefore, the organic silicon product is an important product in the fluorine-free waterproof finishing agent. The current novel fluorine-free water-proofing agent mainly focuses on the application of new technologies such as dendritic polymers, nanotechnology, microcapsule technology, plasma technology and the like, and related products developed by utilizing the technologies.

Disclosure of Invention

The invention provides a POSS modified epoxy silicone oil waterproof finishing agent and a preparation method thereof, the waterproof finishing agent is applied to finishing of pure cotton fabrics, the finished cotton fabrics are soft and smooth in hand feeling, the surfaces of the cotton fabrics have hydrophobic structure structures similar to lotus leaves, and the waterproof finishing agent has excellent waterproofness and washing fastness and obvious waterproof effect.

In order to solve the problems, the technical scheme of the invention is as follows:

the waterproof finishing agent is obtained by emulsifying POSS modified epoxy silicone oil, and the structural formula of the POSS modified epoxy silicone oil is as follows:

wherein x is 100-1000; y is 10-100; z is 10 to 100, x, y and z are integers, and R represents an aliphatic chain.

Preferably, the waterproof finishing agent comprises the following raw materials in percentage by mass:

the invention also provides a preparation method of the POSS modified epoxy silicone oil waterproof finishing agent, which comprises the following steps:

a1: dissolving single-double bond alkylated POSS and 1, 2-epoxy-5-ethylene in a preset ratio in chloroform to obtain a silicone oil modified solution, wherein a side chain in the structure of the single-double bond alkylated POSS is connected with a double-ethylene bond, and the rest seven side chains are connected with an alkyl chain;

a2: adding the silicone oil modified solution into the heated amino silicone oil for mixing reaction, and distilling to obtain POSS modified epoxy silicone oil;

a3: emulsifying POSS modified epoxy silicone oil deionized water to obtain the POSS modified epoxy silicone oil waterproof finishing agent.

Preferably, the step A2 is to add amino silicone oil into a flask, heat the mixture to 25-45 ℃, add the silicone oil modified solution into the flask while stirring, react for 4-8 hours, distill the mixture for 30-50 min at 90-110 ℃ under 0.1-0.5 MPa, and remove chloroform to obtain the POSS modified epoxy silicone oil.

Preferably, the molar ratio of the amino group of the amino silicone oil to the double bond in the silicone oil modified solution is 1: 1-1.1.

Preferably, the step a3 is to adjust the pH of the POSS modified epoxy silicone oil to neutral by using acetic acid, then mix the emulsifier and the POSS modified epoxy silicone oil in a water bath, add deionized water while stirring, and stir for 1 hour to obtain the POSS modified epoxy silicone oil waterproof finishing agent.

Preferably, the using amount of the emulsifier is 0.5-2% of the mass of the POSS modified epoxy silicone oil.

Preferably, the weight ratio of the deionized water to the POSS modified epoxy silicone oil is 100: 20 to 40.

Preferably, the emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.

Preferably, the preparation method of the amino silicone oil comprises the following steps: mixing and stirring 75-87.5 wt% of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane aqueous solution and octamethylcyclotetrasiloxane heated to 70-90 ℃, adding a strong basic catalyst, reacting for 3-6 hours, adding an end capping agent, reacting for 1-2 hours, cooling to 50-70 ℃, and continuing to react for 18-24 hours to obtain the amino silicone oil.

Preferably, raw materials of the waterproof finishing agent are octamethylcyclotetrasiloxane, (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, single-double-bond alkylated POSS, 1, 2-epoxy-5-hexene, a strong basic catalyst of a terminating agent and an emulsifier;

the dosage of the octamethylcyclotetrasiloxane is 50-95% of the total weight of the raw materials, the dosage of the N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane is 1-20% of the total weight of the raw materials, and the dosage of the end-capping agent is 0.01-0.1% of the total weight of the raw materials; the dosage of the strong alkaline catalyst is 0.01-0.1% of the total weight of the raw materials.

Preferably, the strong basic catalyst is any one of potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide, and the blocking agent is hexamethyldisiloxane or pentamethyldisiloxane.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:

the structural formula of the POSS modified epoxy silicone oil waterproof finishing agent provided by the invention contains alkyl, methyl silicon chain and epoxy group, and in the process of applying finishing treatment to textiles, after a film is formed after high-temperature baking, hydrophobic alkyl and methyl silicon chain are easily enriched on the surface of the film; meanwhile, a large number of alkyl POSS nano molecules are grafted on a molecular chain, and the POSS can form an uneven rough structure similar to lotus leaves on fibers, has the hydrophobicity of the lotus leaves, and further improves the waterproof effect of the finished fabric; in addition, because the side chain of the waterproof finishing agent contains an epoxy group, after high-temperature baking, the molecular chain of the waterproof agent is connected to the cotton fiber through a covalent bond, so that the water washing resistance after finishing is improved.

According to the POSS modified epoxy silicone oil waterproof finishing agent provided by the invention, silicone oil and nano particle POSS are combined together, and after the waterproof finishing agent is applied to textiles, the textiles have soft and smooth handfeel brought by the silicone oil, and the POSS is connected to a silicone oil molecular main chain through a chemical bond, so that the agglomeration phenomenon of nano particles can not occur, and the POSS nano particles can be fully exerted to enable the fiber surface to show a rough surface with an uneven micro-nano structure similar to lotus leaves.

Detailed Description

The POSS modified epoxy silicone oil waterproof finishing agent and the preparation method thereof provided by the invention are further described in detail by combining specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims.

The POSS (polyhedral oligomeric silsesquioxane) functional monomer is a three-dimensional structure of an organic-inorganic hybrid molecule, the size of the POSS functional monomer is 1-3 nm, the POSS functional monomer has 1-8 reactive organic groups, and the reactive groups comprise amino groups, epoxy groups, unsaturated double bonds, alkoxy groups, light groups, thiol groups and the like. Most monomers are monofunctional and contain only one reactive group, while multifunctional monomers contain two or more reactive groups that can react with each other to form a variety of functional monomers by appropriate chemical reactions. However, currently, POSS has not been applied to fluorine-free water repellent finishes.

Therefore, the invention provides a POSS modified epoxy silicone oil waterproof finishing agent, which is obtained by emulsifying POSS modified epoxy silicone oil, and the structural formula of the POSS modified epoxy silicone oil is as follows:

wherein x is 100-1000; y is 10-100; z is 10 to 100, x, y and z are integers, and R represents an aliphatic chain.

Preferably, the waterproof finishing agent comprises the following raw materials in percentage by mass:

the structural formula of the POSS modified epoxy silicone oil waterproof finishing agent provided by the invention contains alkyl, methyl silicon chain and epoxy group, and in the process of applying finishing treatment to textiles, after a film is formed after high-temperature baking, hydrophobic alkyl and methyl silicon chain are easily enriched on the surface of the film; meanwhile, a large number of alkyl POSS nano molecules are grafted on a molecular chain, and the POSS can form an uneven rough structure similar to lotus leaves on fibers, has the hydrophobicity of the lotus leaves, and further improves the waterproof effect of the finished fabric; in addition, because the side chain of the waterproof finishing agent contains an epoxy group, after high-temperature baking, the molecular chain of the waterproof agent is connected to the cotton fiber through a covalent bond, so that the water washing resistance after finishing is improved.

According to the POSS modified epoxy silicone oil waterproof finishing agent provided by the invention, silicone oil and nano particle POSS are combined together, and after the waterproof finishing agent is applied to textiles, the textiles have soft and smooth handfeel brought by the silicone oil, and the POSS is connected to a silicone oil molecular main chain through a chemical bond, so that the agglomeration phenomenon of nano particles can not occur, and the POSS nano particles can be fully exerted to enable the fiber surface to show a rough surface with an uneven micro-nano structure similar to lotus leaves.

The invention also provides a preparation method of the POSS modified epoxy silicone oil waterproof finishing agent, which comprises the following steps:

a1: dissolving single-double bond alkylated POSS and 1, 2-epoxy-5-ethylene in a preset proportion into chloroform to obtain a silicone oil modified solution;

a2: adding the silicone oil modified solution into heated amino silicone oil for mixing reaction, and distilling to obtain POSS modified epoxy silicone oil, wherein a side chain in the structure of single-double bond alkylated POSS is connected with a double-olefinic bond, and the rest seven side chains are connected with alkyl chains;

a3: and emulsifying the POSS modified epoxy silicone oil deionized water to obtain the POSS modified epoxy silicone oil waterproof finishing agent.

The preparation method of the POSS modified epoxy silicone oil waterproof finishing agent provided by the invention is simple in steps and convenient to operate.

Specifically, the step A2 is to add amino silicone oil into a flask, heat the mixture to 25-45 ℃, add a silicone oil modified solution into the flask while stirring, react for 4-8 hours, distill the mixture for 30-50 min at 90-110 ℃ under the pressure of 0.1-0.5 MPa, and remove chloroform to obtain the POSS modified epoxy silicone oil.

Further, the molar ratio of the amino silicone oil to the silicone oil modified solution is 1: 1-1.1.

Specifically, step A3 is to adjust the pH of the POSS modified epoxy silicone oil to be neutral by using acetic acid, then carry out water bath mixing on the emulsifier and the POSS modified epoxy silicone oil, add deionized water while stirring, and stir for 1h to obtain the POSS modified epoxy silicone oil waterproof finishing agent.

Furthermore, the using amount of the emulsifier is 0.5-2% of the weight of the POSS modified epoxy silicone oil.

Further, the weight ratio of the deionized water to the POSS modified epoxy silicone oil is 100: 20 to 40.

Further, the emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.

Specifically, the preparation method of the amino silicone oil comprises the following steps: mixing and stirring 75-87.5 wt% of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane aqueous solution and octamethylcyclotetrasiloxane heated to 70-90 ℃, adding a strong basic catalyst, reacting for 3-6 hours, adding an end capping agent, reacting for 1-2 hours, cooling to 50-70 ℃, and continuing to react for 18-24 hours to obtain the amino silicone oil.

Furthermore, the raw materials of the waterproof finishing agent are octamethylcyclotetrasiloxane, (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, single-double-bond alkylated POSS, 1, 2-epoxy-5-hexene, a strong basic catalyst of a terminating agent and an emulsifier;

the dosage of the octamethylcyclotetrasiloxane is 50-95% of the total weight of the raw materials, the dosage of the N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxysilane is 1-20% of the total weight of the raw materials, and the dosage of the end-capping agent is 0.01-0.1% of the total weight of the raw materials; the dosage of the strong alkaline catalyst is 0.01-0.1% of the total weight of the raw materials.

Further, the strong basic catalyst is any one of potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide, and the end-capping reagent is hexamethyldisiloxane or pentamethyldisiloxane.