阅读说明：本技术 一种有机无机纳米杂化无氟拒水整理剂及其制备方法 (Organic-inorganic nano hybrid fluorine-free water repellent finishing agent and preparation method thereof ) 是由 张达 郭连娣 王曰爱 沈建华 于 2021-10-13 设计创作，主要内容包括：本发明公开了一种有机无机纳米杂化无氟拒水整理剂及其制备方法,该制备方法包括以下步骤：S1、环氧基有机硅和伯氨基氟化石墨混合,加入异丙醇,高速搅拌反应0.2～1小时后,加热升温至60～80℃,继续反应3～6小时,得到半透明黏稠状液体,即纳米氟化石墨改性有机硅油；S2、将乳化剂与步骤S1中所制得的纳米氟化石墨改性有机硅油以重量比(1～3)：100的比例进行水中搅拌混合,调节pH值至中性,升温至60～85℃,搅拌0.5～1.5小时,得到有机无机纳米杂化无氟拒水整理剂。本发明提供的有机无机纳米杂化无氟拒水整理剂,用于棉织物或天然织物的拒水整理,使织物具有类似有机硅柔软剂整理织物一样柔软滑爽的手感,同时使得棉织物在整理后拒水效果非常优良。(The invention discloses an organic-inorganic nano hybrid fluorine-free water repellent finishing agent and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing epoxy organic silicon and primary amino group graphite fluoride, adding isopropanol, stirring at a high speed for reaction for 0.2-1 h, heating to 60-80 ℃, and continuing to react for 3-6 h to obtain semitransparent viscous liquid, namely nano graphite fluoride modified organic silicon oil; s2, mixing an emulsifier and the nano graphite fluoride modified organic silicone oil prepared in the step S1 in a weight ratio of (1-3): stirring and mixing the mixture in water according to the proportion of 100, adjusting the pH value to be neutral, heating to 60-85 ℃, and stirring for 0.5-1.5 hours to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent. The organic-inorganic nano hybrid fluoride-free water repellent finishing agent provided by the invention is used for water repellent finishing of cotton fabrics or natural fabrics, so that the fabrics have the same soft and smooth hand feeling as those of the fabrics finished by the organic silicon softener, and meanwhile, the water repellent effect of the cotton fabrics after finishing is very excellent.)

1. A preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent is characterized by comprising the following steps:

s1, mixing epoxy organic silicon and primary amino group graphite fluoride, adding a proper amount of isopropanol, stirring at a high speed for reaction for 0.5-1 h, heating to 60-80 ℃, and continuing to react for 3-6 h to obtain semitransparent viscous liquid, namely nano graphite fluoride modified organic silicon oil;

s2, mixing an emulsifier and the nano graphite fluoride modified organic silicone oil prepared in the step S1 in a weight ratio of (1-3): stirring and mixing the mixture in water according to the proportion of 100, adjusting the pH value to be neutral, heating to 60-85 ℃, and stirring for 0.5-1.5 hours to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

2. The preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent according to claim 1, wherein in the step S1, the mass ratio of the epoxy organosilicon to the primary amino group graphite fluoride is 1: (0.1-0.5).

3. The preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent according to claim 1, wherein in step S1, the epoxy organosilicon is prepared by the following steps:

adding octamethylcyclotetrasiloxane into a flask, heating to 70-90 ℃ in a water bath, mixing 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and deionized water according to the mass ratio of (3-7) to 1, stirring uniformly, slowly dropwise adding into the flask containing octamethylcyclotetrasiloxane, adding a strong basic catalyst, reacting for 3-6 hours, adding an end-capping agent into the reaction solution, reacting for 1-2 hours, cooling to 50-70 ℃, continuing to react for 18-24 hours, distilling the cooled solution for 30-45 minutes at the temperature of 90-110 ℃ and the pressure of 1-2 MPa, and cooling to room temperature to obtain uniform, semitransparent and viscous epoxy organosilicon; wherein the mass ratio of the octamethylcyclotetrasiloxane, the 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane, the end-capping agent and the strong basic catalyst is (30-60): 3-12): 0.05-0.6): 0.05-1.

4. The preparation method of the organic-inorganic nano-hybrid fluorine-free water repellent finishing agent according to claim 3, characterized in that the end-capping agent is selected from at least one of hexamethyldisiloxane or pentamethyldisiloxane.

5. The preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent according to claim 3, characterized in that the strong basic catalyst is at least one selected from potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide.

6. The preparation method of the organic-inorganic nano-hybrid fluorine-free water repellent finishing agent according to claim 1, wherein in step S1, the primary amino group graphite fluoride is prepared by the following steps:

mixing graphite fluoride and urea, reacting for 3-6 hours under the protection of high-temperature oil bath and inert gas by magnetic stirring, cooling to room temperature after the reaction is finished, respectively and repeatedly washing with absolute ethyl alcohol and deionized water, filtering with a polytetrafluoroethylene microporous filter membrane, centrifuging, and freeze-drying to obtain powdery primary amino graphite fluoride; wherein the mass ratio of the graphite fluoride mixture to the urea is 1 (30-100).

7. The preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent according to claim 6, characterized in that after the graphite fluoride and the urea are mixed, the mixture is magnetically stirred and reacted for 3-6 hours in a high-temperature oil bath at 140-160 ℃ under the protection of nitrogen.

8. The preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent according to claim 6, wherein the graphite fluoride is nano graphite fluoride, the particle size of the nano graphite fluoride is 200-800 nm, and the fluorine content of the nano graphite fluoride is 20-60%.

9. The preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent according to claim 1, wherein the emulsifier is at least one selected from sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.

10. An organic-inorganic nano hybrid fluorine-free water repellent finishing agent prepared by the preparation method of any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of textile auxiliaries, and particularly relates to an organic-inorganic nano hybrid fluorine-free water repellent finishing agent and a preparation method thereof.

Background

Cotton fabric has the characteristics of good hygroscopicity, heat retention, softness and the like, so that cotton fiber becomes a preferred raw material in the textile industry, but the defects of water repellency, easy pollution and the like limit the wider application of the cotton fiber, so that water repellent finishing is needed to be carried out on the cotton fiber.

The water repellent finishing is an important functional finishing, wherein although the fluorine-containing water repellent can endow the fabric with excellent water repellent performance, the fluorine-containing water repellent often contains PFOS and PFOA, and the PFOS and PFOA have the problems of difficult degradation, high biological accumulation, multiple toxicity and the like and are forbidden to be applied to the functional finishing of textiles, so the development of the fluorine-free water repellent has very important significance.

The water repellent finishing in the prior art mainly has two modes: one is that a layer of hydrophobic substance is attached to the surface of the fabric, but the washing fastness of the fabric is not always required; and the other is that the water repellent agent molecules are chemically bonded with the fiber surface groups, so that the washability of the water repellent effect of the fabric can be improved. In general, the water repellent finish of fabrics is different from the water repellent finish. The waterproof finishing is to coat a layer of compact film on the surface of the fabric, and water and air can not permeate the fabric under the normal pressure state. The water repellent finishing is to fix a hydrophobic material in the fabric or on the surface of the fabric and combine the hydrophobic material with fibers in a certain way, so that the surface energy of the fabric is reduced, liquid water cannot be soaked into the fabric under the normal pressure state, but air can permeate through the fabric, but the existing water repellent in the market often cannot meet the requirements of customers in performance, and enterprises often replace the water repellent finishing with waterproof finishing in order to pursue the finishing effect, so that the air permeability is poor, and the wearing experience of the fabric is poor.

The organosilicon water repellent is a high molecular polymer with a silicon-oxygen bond as a main chain, Si atoms and O atoms on the main chain are alternately bonded, and other organic groups are directly connected on the Si atoms, so that the organosilicon water repellent has a good water repellent effect, and a fluorine material has the water repellent performance which cannot be superior to all other materials. In practical application, the water repellent effect of the organosilicon functional finishing agent is not ideal, and how to improve the water repellent performance of organosilicon by modification to achieve the water repellent effect of fluorine-containing water repellent agent as far as possible and have durability becomes a key point for researching and developing the products.

Disclosure of Invention

The invention provides an organic-inorganic nano hybrid fluorine-free water repellent finishing agent and a preparation method thereof, which can solve the defects in the prior art.

The invention provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which comprises the following steps:

s1, mixing epoxy-based organosilicon and primary amino graphite fluoride, adding a proper amount of isopropanol, stirring at a high speed for reaction for 0.2-1 hour until the epoxy-based organosilicon, the primary amino graphite fluoride and the isopropanol are fully and uniformly mixed, heating to 60-80 ℃, and continuing to react for 3-6 hours to obtain semitransparent viscous liquid, namely the nano graphite fluoride modified organic silicone oil;

s2, mixing an emulsifier and the nano graphite fluoride modified organic silicone oil prepared in the step S1 in a weight ratio of (1-3): stirring and mixing the mixture in water according to the proportion of 100, adjusting the pH value to be neutral, heating to 60-85 ℃, and stirring for 0.5-1.5 hours to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

At present, in water repellent finishing, when a hydrophobic surface is prepared, a typical preparation route is to firstly construct a micro-nano coarse structure on a substrate by using particles and then perform hydrophobic modification on the surface by using a low-surface-energy substance. How to simplify the finishing process and hybridize the organic polysiloxane and the inorganic nanoparticles to realize the effective grafting of the organic polysiloxane and the inorganic nanoparticles, thereby solving the key problems of fabric hydrophobicity, durability, stability, environmental protection and the like, is a problem which is urgently to be solved and researched at present. According to the invention, an epoxy group in epoxy organosilicon and a primary amino group in primary amino graphite fluoride are subjected to ring-opening addition reaction, fluorine-containing graphite nanoparticles and modified organosilicon are covalently bonded together, so that the organic-inorganic nano hybrid fluorine-free water repellent finishing agent is prepared, the nano graphite fluoride in the finished coating not only can be combined with micron-sized grooves in cotton fibers to construct a cotton fabric surface with a bionic hydrophobic micro-nano structure, but also contains a large amount of fluorine elements, and the nano graphite fluoride particles have extremely excellent hydrophobicity, so that the finished fabric has excellent water repellency through the synergistic effect of an organic silicon oil film, a rough structure and the nano graphite fluoride particles.

Preferably, in step S1, the mass ratio of the epoxy silicone to the primary amino graphite fluoride is 1: (0.1-0.5).

Specifically, in step S1, the epoxy-based silicone is prepared by the following steps:

adding octamethylcyclotetrasiloxane into a flask, heating to 70-90 ℃ in a water bath, mixing 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and deionized water according to the mass ratio of (3-7) to 1, stirring uniformly, slowly dropwise adding into the flask containing octamethylcyclotetrasiloxane, adding a strong basic catalyst, reacting for 3-6 hours, adding an end-capping agent into the reaction solution, reacting for 1-2 hours, cooling to 50-70 ℃, continuing to react for 18-24 hours, distilling the cooled solution for 30-45 minutes at the temperature of 90-110 ℃ and the pressure of 1-2 MPa, and cooling to room temperature to obtain uniform, semitransparent and viscous epoxy organosilicon; wherein the mass ratio of the octamethylcyclotetrasiloxane, the 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane, the end-capping agent and the strong basic catalyst is (30-60): 3-12): 0.05-0.6): 0.05-1.

By the preparation method, the reactive epoxy group is introduced into the organic silicon side chain to prepare the organic silicon containing the epoxy group, so that the organic silicon containing the epoxy group and the primary amino group in the primary amino graphite fluoride can carry out ring-opening addition reaction.

Preferably, the blocking agent is selected from at least one of hexamethyldisiloxane or pentamethyldisiloxane.

Preferably, the strong basic catalyst is at least one selected from potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide.

Specifically, in step S1, the primary amino graphite fluoride is prepared by the following steps:

mixing graphite fluoride and urea, reacting for 3-6 hours under the protection of high-temperature oil bath and inert gas by magnetic stirring, cooling to room temperature after the reaction is finished, respectively and repeatedly washing with absolute ethyl alcohol and deionized water, filtering with a polytetrafluoroethylene microporous filter membrane, centrifuging, and freeze-drying to obtain powdery primary amino graphite fluoride; wherein the mass ratio of the graphite fluoride mixture to the urea is 1 (30-100).

The method for preparing the primary amino group graphite fluoride by using the urea melting method can control the quantity of the primary amino groups on the surface of the graphite fluoride particles according to the urea melting condition.

Specifically, after graphite fluoride and urea are mixed, the mixture is subjected to magnetic stirring reaction for 3-6 hours in a high-temperature oil bath at the temperature of 140-160 ℃ under the protection of nitrogen.

Preferably, the graphite fluoride is nano-scale graphite fluoride, the particle size of the nano-scale graphite fluoride is 200-800 nm, and the fluorine content of the nano-scale graphite fluoride is 20-60%.

Preferably, the emulsifier is at least one selected from sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.

The invention provides an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which is prepared by adopting the preparation method.

Compared with the prior art, the invention has the following beneficial effects:

1. the preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent provided by the invention effectively avoids the application of C8 materials, introduces a fluorine-containing material with the most excellent water repellency, introduces a reactive epoxy group into an organic silicon side chain by adopting an alkaline catalytic organic silicon monomer, bonds a polymer and nano microspheres together by utilizing the epoxy group in organic silicon and the primary amino group of modified graphite fluoride, and obtains the water repellent finishing agent after water emulsification.

2. The water repellent finishing agent prepared by the preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent provided by the invention is used for water repellent finishing of cotton fabrics or natural fabrics, so that the fabrics have soft and smooth handfeel similar to those of the fabrics finished by the organic silicon softener, and meanwhile, the water repellent effect of the cotton fabrics after finishing is very excellent by forming a rough and hydrophobic surface similar to lotus leaves.

3. In the preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent, the number of primary amino groups on the surface of graphite fluoride particles can be controlled according to the urine melting condition; when the nano graphite fluoride modified organic silicon oil is prepared, epoxy groups in epoxy organic silicon are more than the number of primary amino groups in the surface of graphite fluoride particles, so that the nano graphite fluoride modified organic silicon oil contains a large number of unreacted epoxy groups, and the epoxy groups can react with hydroxyl groups on cotton fibers during post-finishing baking, so that the binding power of a water-repellent finishing agent and the cotton fibers is increased, a film can be formed on the surface of the cotton fibers after finishing, the air permeability is good, the washability of a finished fabric can be improved, and the long-term durability of a water-repellent effect is ensured.

4. The water repellent finishing agent prepared by the preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent provided by the invention has better conductivity of graphite fluoride particles, so that the finished fabric still can keep better antistatic property.

Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.

Drawings

FIG. 1 is an infrared spectrum of a primary aminogroup graphite fluoride prepared in example 1;

FIG. 2 is a surface topography of fibers after finishing cotton fabrics by using the organic-inorganic nano hybrid fluorine-free water repellent finishing agent prepared in example 2.

Detailed Description

In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.

Example 1

The preparation method of the primary amino group graphite fluoride by adopting a urea melting method comprises the following steps:

5g of nanoscale graphite fluoride (specification D50, fluorine content 40%) and 250g of urea are placed in a three-necked flask, nitrogen is introduced into the flask, and the mixture is heated and stirred in a high-temperature oil bath at 150 ℃ for 5 hours. And after the reaction is finished, cooling to room temperature, repeatedly washing the product with absolute ethyl alcohol and deionized water for three times, then filtering for 3 times by using a polytetrafluoroethylene microporous filter membrane, centrifuging, and then carrying out freeze-drying treatment on the treated product to finally obtain powdery primary amino group graphite fluoride.

FIG. 1 is an infrared spectrum of the primary aminofluorographite prepared in this example, in which 1149cm is plotted^-1The peak obviously appears at 1730cm and belongs to the C-F stretching vibration peak^-1And 1550cm^-1The sharp absorption peak appears, which can be classified as the bending vibration peak of C ═ O and C-N or the stretching vibration combined absorption peak of C-N, and shows that the amino and fluorine atoms on the urea are successfully introduced into the graphite fluoride by the preparation method.

Example 2

The embodiment provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which specifically comprises the following steps: adding 86.21g of octamethylcyclotetrasiloxane into a flask, heating to 80 ℃ in a water bath, mixing 17.24g of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane with 2.59g of deionized water, stirring uniformly, slowly and dropwise adding into the three-neck flask, adding 0.34g of potassium hydroxide, and reacting for 5 hours; adding 0.52g of hexamethyldisiloxane into the solution, reacting for 2 hours, cooling to 60 ℃, continuing to react for 18 hours, distilling the cooled solution at 110 ℃ and 1MPa for 30 minutes, cooling to room temperature to obtain uniform and translucent epoxy-based organic silicon, adding 43.10g of primary amino group graphite fluoride prepared in the embodiment 1 and a proper amount of isopropanol, stirring for half an hour at the rotating speed of 5000r/min (wherein the stirring is performed to fully and uniformly mix the epoxy-based organic silicon, the primary amino group graphite fluoride and the isopropanol, and a person skilled in the art can adaptively adjust the stirring time according to the specific stirring and mixing conditions), heating to 70 ℃, continuing to react for 6 hours to obtain nano graphite fluoride modified organic silicon oil, finally adding 1.54g of sodium dodecyl benzene sulfonate and 250mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour (the stirring effect is to ensure that the nano graphite fluoride modified organic silicon oil and the sodium dodecyl benzene sulfonate fully react) to obtain the organic-inorganic nano hybrid fluoride-free water repellent finishing agent.

In the preparation method of the organic-inorganic nano hybrid fluorine-free water repellent finishing agent, isopropanol serves as a dispersion medium, and the specific dosage of the isopropanol is adjusted according to the dispersion and wetting conditions of the nano fluorine-containing graphite oxide.

Example 3

The embodiment provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which specifically comprises the following steps: 87.51g of octamethylcyclotetrasiloxane is added into a flask, the temperature is raised to 80 ℃ in a water bath, 21.07g of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and 3.51g of deionized water are mixed, stirred uniformly, slowly and dropwise added into the three-neck flask, and then 0.53g of potassium hydroxide is added for reaction for 3 hours; adding 0.71g of hexamethyldisiloxane into the solution, reacting for 1 hour, cooling to 70 ℃, continuing to react for 18 hours, distilling the cooled solution at 110 ℃ and 1MPa for 30 minutes, cooling to room temperature to obtain uniform and semitransparent epoxy organosilicon, adding 36.76g of primary amino group graphite fluoride prepared in example 1 and a proper amount of isopropanol, stirring for half an hour at the rotating speed of 5000r/min, heating to 70 ℃, continuing to react for 6 hours to obtain nano graphite fluoride modified organic silicone oil, finally adding 1.54g of sodium dodecyl benzene sulfonate and 250mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

Example 4

The embodiment provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which specifically comprises the following steps: 85.91g of octamethylcyclotetrasiloxane is added into a flask, the temperature is raised to 80 ℃ in a water bath, 15.46g of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and 4.31g of deionized water are mixed, stirred uniformly, slowly and dropwise added into the three-neck flask, and then 0.52g of potassium hydroxide is added for reaction for 3 hours; adding 0.86g of hexamethyldisiloxane into the solution, reacting for 2 hours, cooling to 50 ℃, continuing to react for 24 hours, distilling the cooled solution at 110 ℃ and 1MPa for 30 minutes, cooling to room temperature to obtain uniform and semitransparent epoxy organosilicon, adding 42.96g of primary amino group graphite fluoride prepared in the embodiment 1 and a proper amount of isopropanol, stirring at 5000r/min for half an hour, heating to 70 ℃, continuing to react for 6 hours to obtain nano graphite fluoride modified organic silicone oil, finally adding 3.16g of sodium dodecyl sulfate and 250mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

Example 5

The embodiment provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which specifically comprises the following steps: adding 99.88g of octamethylcyclotetrasiloxane into a flask, heating to 80 ℃ in a water bath, mixing 9.99g of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and 3.01g of deionized water, stirring uniformly, slowly and dropwise adding into the three-neck flask, adding 0.49g of potassium hydroxide, and reacting for 5 hours; adding 0.68g of hexamethyldisiloxane into the solution, reacting for 1 hour, cooling to 70 ℃, continuing to react for 18 hours, distilling the cooled solution at 110 ℃ and 1MPa for 30 minutes, cooling to room temperature to obtain uniform and semitransparent epoxy organosilicon, adding 35.96g of primary amino group graphite fluoride prepared in example 1 and a proper amount of isopropanol, stirring for half an hour at the rotating speed of 5000r/min, heating to 70 ℃, continuing to react for 6 hours to obtain nano graphite fluoride modified organic silicone oil, finally adding 4.01g of sodium dodecyl benzene sulfonate and 250mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

Example 6

The embodiment provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which specifically comprises the following steps: 100.13g of octamethylcyclotetrasiloxane is added into a flask, the temperature is raised to 80 ℃ in a water bath, 12.02g of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and 6.01g of deionized water are mixed, stirred uniformly, slowly and dropwise added into the three-neck flask, and then 0.79g of potassium hydroxide is added for reaction for 4 hours; adding 0.99g of hexamethyldisiloxane into the solution, reacting for 1.5 hours, cooling to 60 ℃, continuing to react for 20 hours, distilling the cooled solution at 110 ℃ and 1MPa for 30 minutes, cooling to room temperature to obtain uniform and semitransparent viscous epoxy organosilicon, adding 30.04g of primary amino group graphite fluoride prepared in example 1 and a proper amount of isopropanol, stirring for half an hour at the rotation speed of 5000r/min, heating to 70 ℃, continuing to react for 6 hours to obtain nano graphite fluoride modified organic silicone oil, finally adding 1.99g of sodium dodecyl sulfate and 250mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

Example 7

The embodiment provides a preparation method of an organic-inorganic nano hybrid fluorine-free water repellent finishing agent, which specifically comprises the following steps: adding 111.69g of octamethylcyclotetrasiloxane into a flask, heating to 80 ℃ in a water bath, mixing 10.05g of 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane and 4.91g of deionized water, stirring uniformly, slowly and dropwise adding into the three-neck flask, adding 0.56g of potassium hydroxide, and reacting for 5 hours; adding 0.45g of hexamethyldisiloxane into the solution, reacting for 2 hours, cooling to 60 ℃, continuing to react for 18 hours, distilling the cooled solution at 110 ℃ and 1MPa for 30 minutes, cooling to room temperature to obtain uniform and semitransparent epoxy organosilicon, adding 22.34g of primary amino group graphite fluoride prepared in example 1 and a proper amount of isopropanol, stirring at 5000r/min for half an hour, heating to 70 ℃, continuing to react for 6 hours to obtain nano graphite fluoride modified organic silicone oil, finally adding 3.04g of sodium dodecyl benzene sulfonate and 250mL of water, stirring and mixing, adjusting the pH value to be neutral, heating to 80 ℃, and stirring for 1 hour to obtain the organic-inorganic nano hybrid fluorine-free water repellent finishing agent.

Test examples

The organic-inorganic nano-hybrid fluorine-free water repellent finishing agent prepared in the embodiments 2 to 7 is subjected to water repellent effect detection, the organic-inorganic nano-hybrid fluorine-free water repellent finishing agent is diluted to 100g/L, then plain woven fabric of pure cotton is subjected to the traditional two-dipping two-rolling process treatment in the diluted finishing liquid, the rolling residue rate is 65-75%, and then the plain woven fabric is pre-dried at 100 ℃ for 6 minutes, then is baked at 180 ℃ for 3 minutes, and is cooled to room temperature.

The initial and 10 wash cycles of the sample prepared above were followed by a water spray test according to AATCC 22-2010 standard. After the wash cycle, the fabrics were drum dried prior to spray testing. Typical drum drying temperatures are 60-65 ℃ for 30 minutes. According to the spray test rating chart, a rating of 100 means no adhesion or wetting of the surface of the fabric, a rating of 90 means slight random adhesion or wetting of the surface of the fabric, a rating of 80 means surface wetting of the fabric at the spray point, a rating of 70 means partial wetting of the surface of the fabric beyond the spray point, and a rating of 50 means complete wetting of the entire surface of the fabric.

TABLE 1 comparison of the Properties of the organic-inorganic nano-hybrid fluorine-free water repellent finish fabrics obtained in examples 2-5

Finishing agent	Hand feeling	Initial	10 washing cycles
				Not finished	Difference (D)	50	50
Example 2	Softness	100	90
				Example 3	Softness	100	90
Example 4	Softness	100	90
				Example 5	Softness	100	80
Example 6	Softness	100	80
				Example 7	Softness	100	80

As can be seen from Table 1, after the organic-inorganic nano hybrid fluoride-free water repellent finishing agent is used for finishing, the water repellent grade is high, the better washing resistance effect can be still kept after 10 times of cyclic washing, and meanwhile, the textile fabric has better softness and smoothness and has the hand feeling effect similar to that of the fabric finished by the organic silicon softener.

As can be seen from fig. 2, after the organic-inorganic nano hybrid fluorine-free water repellent finishing agent in example 2 is used for finishing, the rough structure of the surface of the cotton fiber is remarkably improved, and the surface of the cotton fiber has an obvious convex shape of particles, and the particles are tightly coated on the surface of the fiber with a micrometer scale, so that the micro-nano structure on the cotton fabric is realized.

The foregoing disclosure discloses only the preferred embodiments of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.