CN111764159A - Fluorine-free waterproof finishing method for cotton fabric - Google Patents
Fluorine-free waterproof finishing method for cotton fabric Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract
The invention discloses a fluorine-free waterproof finishing method for cotton fabrics, which comprises the following steps: according to the mass ratio of the solid parts in the finishing liquid of 1: 0.05-1: 0.3 preparation of Long-chain alkyl modified organosilicon finishing liquid and epoxy modified nanometer SiO2Finishing liquor, namely finishing the cotton fabric by a one-bath method or a two-bath method. The one-bath method is used for finishing the cotton fabric, and the epoxy group is firstly modified by the nano SiO2Uniformly mixing the finishing liquid and the long-chain alkyl modified organic silicon finishing liquid, and then rolling and baking the cotton fabricFinishing; the two-bath method for finishing the cotton fabric is to firstly use epoxy group to modify nano SiO2The finishing liquid is used for carrying out rolling baking finishing on the cotton fabric, and then the long-chain alkyl modified organic silicon finishing liquid is used for carrying out rolling baking finishing on the cotton fabric. After the cotton fabric is finished by the fluoride-free waterproof finishing method, the waterproof finishing effect of the cotton fabric is good, the fabric is soft in hand feeling, the excellent waterproof effect is achieved, and the waterproof effect is lasting.
Description
Technical Field
The invention belongs to the technical field of dyeing and finishing processing of textiles, and particularly relates to a fluorine-free waterproof finishing method for cotton fabrics.
Background
In order to meet the continuous requirements of people on textiles, more and more textiles are endowed with functionality, and the waterproof function is an important branch. The waterproof fabric is a functional fabric which is not immersed in water under certain pressure, but the fabric has a certain moisture permeable function, so that sweat emitted by a human body can be transmitted to the outside through the fabric in a water vapor mode. The application field of the product is wide at present, and mainly comprises: field army uniform, fire-fighting, army special clothing, protective articles, army tent, sleeping bag, climbing clothes, ski wear, shoes and hats, case, shower curtain, leisure wind coat, medical articles and the like.
The application effect of the existing waterproof finishing is that PFOS finishing agent, after the cotton fabric is finished, the fluorocarbon chain on the polymer side chain of the fluorine-containing finishing agent reduces the surface energy and improves the water and oil repellent performance of the fiber surface. However, under the influence of the fact that the non-stick pan manufactured by DuPont in the United states contains organic fluorine chemicals which may cause carcinogenesis to human bodies, research on organic fluorine chemicals used for water-proof, oil-proof and stain-proof finishing of textiles is also conducted in the international market. The result shows that the organic fluorine chemicals PFOS and PFOA which are frequently used for textile three-prevention finishing in the international market at present have potential harm to the health of human bodies. Because no effective method for solving the pollution problems of PFOS and PFOA exists at home and abroad at present, finding a finishing agent or a cotton fabric finishing and weaving method capable of replacing PFOS and PFOA becomes a primary problem to be solved urgently in the dyeing and finishing industry.
At present, a plurality of fluoride-free waterproof finishing agents or finishing methods exist, and have some defects which are difficult to overcome, including that after the fabric is subjected to waterproof finishing or made into waterproof fabric, the hand feeling of part of the fabric needs to be improved, the preparation method of the functional fabric needs to be simplified, and the water washing resistance of the fabric needs to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a fluorine-free waterproof finishing method for cotton fabrics, the cotton fabrics are finished by the fluorine-free waterproof finishing method, the cotton fabrics have soft hand feeling and excellent waterproof effect, the waterproof effect is durable, and simultaneously the use amounts of two finishing liquids, namely epoxy group modified nano silicon dioxide finishing liquid and long chain alkyl modified organic silicon finishing liquid, can be flexibly adjusted according to the fabrics and actual conditions and requirements, so that the optimal waterproof finishing effect is achieved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a finishing method for fluorine-free waterproof cotton fabrics comprises the following steps: and (3) rolling, baking and finishing the cotton fabric by adopting a one-bath method or a two-bath method through the long-chain alkyl modified organic silicon finishing liquid and the epoxy modified nano-silica finishing liquid.
Specifically, the mass ratio of the long-chain alkyl modified organosilicon finishing liquid to the epoxy modified nano-silica finishing liquid is 1: 0.05-1: 0.3.
specifically, the one-bath method comprises the following steps: firstly, mixing the long-chain alkyl modified organic silicon finishing liquid and the epoxy modified nano-silica finishing liquid, and then rolling, baking and finishing the cotton fabric.
Specifically, the two-bath method comprises the following steps: firstly, the epoxy group modified nano silicon dioxide finishing liquid is adopted to perform rolling baking finishing on cotton fabrics, and then the long-chain alkyl modified organic silicon finishing liquid is adopted to perform rolling baking finishing on the cotton fabrics finished by the epoxy group modified nano silicon dioxide finishing liquid.
The rolling baking finishing comprises the following steps: diluting epoxy-modified nano-silica finishing liquid and long-chain alkyl-modified organic silicon finishing liquid or mixed finishing liquid thereof to 50-200 g/L, then carrying out a double-dipping and double-rolling process on cotton fabrics in the finishing liquid, wherein the rolling residue rate is 65-75%, then predrying for 4-7 minutes at 100-110 ℃, then baking for 2-4 minutes at 170-190 ℃, and then cooling.
Preferably, the preparation method of the long-chain alkyl modified organosilicon finishing liquid comprises the following steps: the emulsifier and the long-chain alkyl modified organic silicone oil are mixed according to the weight ratio of (1-3): stirring and mixing the long-chain alkyl modified organic silicon finishing liquid in water according to the proportion of 100, adjusting the pH to be neutral by using an acetic acid solution, heating to 60-85 ℃, and stirring for 1h to obtain the long-chain alkyl modified organic silicon finishing liquid.
Preferably, the preparation method of the long-chain alkyl modified organic silicone oil comprises the following steps: adding an octamethylcyclotetrasiloxane linear body, 1/5-3/5 catalyst and distilled water into a reaction container, stirring, heating to 90-100 ℃, reacting for 1.5-2.5 h, cooling to 60 ℃, adding long-carbon-chain trimethoxy silane and the rest catalyst, heating to 100-130 ℃, reacting for 1-3 h, cooling, decompressing, distilling and removing low-boiling-point substances to obtain transparent viscous liquid, namely the long-chain alkyl modified organic silicone oil; .
Wherein, the linear body of octamethylcyclotetrasiloxane is 85-95%, the long carbon chain silane coupling agent is 4-10%, the catalyst is 0.1-0.4%, and the balance is distilled water, and the sum of the weight percentages of the raw materials is 100%.
Preferably, the preparation method of the epoxy modified nano silica finishing liquid comprises the following steps:
the preparation method of the epoxy group modified nano silicon dioxide comprises the following steps: adding nano silicon dioxide into toluene, performing ultrasonic dispersion for 30min at 20-30 ℃ to obtain a suspension, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and long-carbon-chain trimethoxy silane into the suspension, performing ultrasonic dispersion for 5min, performing magnetic stirring reflux for 4-8 h under the reaction condition of 80-100 ℃, centrifuging, washing for multiple times, and drying to obtain the epoxy group modified nano silicon dioxide;
and then placing the epoxy group modified nano silicon dioxide into distilled water, and performing ultrasonic treatment for 30 minutes at the temperature of 20-30 ℃ to obtain the epoxy group modified nano silicon dioxide finishing liquid.
Wherein, the toluene accounts for 88 to 97 percent, the nano silicon dioxide accounts for 2 to 8 percent, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane accounts for 1 to 4 percent, the long carbon chain silane coupling agent accounts for 0.5 to 1.5 percent, and the sum of the weight percentages of the raw materials is 100 percent.
Preferably, the particle size of the nano silicon dioxide is 30nm to 100 nm.
Preferably, the long carbon chain trimethoxy silane is at least one of octyl trimethoxy silane, dodecyl trimethoxy silane, hexadecyl trimethoxy silane and octadecyl trimethoxy silane.
Preferably, the emulsifier is any one of or a compound of any combination of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether and isomeric tridecanol polyoxyethylene ether.
Preferably, the catalyst is tetramethylammonium hydroxide or potassium hydroxide.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
the embodiment of the invention provides a fluorine-free waterproof finishing method for cotton fabrics, which is characterized in that a long-chain alkyl modified organic silicon finishing liquid and an epoxy modified nano silicon dioxide finishing liquid are used for rolling, baking and finishing the cotton fabrics by a one-bath method or a two-bath method, and epoxy modified nano SiO is used for finishing the cotton fabrics2The epoxy group in the epoxy resin undergoes ring-opening addition reaction in the baking process to react SiO2Covalently bonding with cotton fiber to obtain nano SiO2The particles are fixed on the cellulose fiber in an aiming way, so that the surface of the cotton fiber forms an uneven structure similar to a lotus leaf, and meanwhile, the cotton fiber and the nano SiO2The particles are coated with a layer of long-chain alkyl modified organic silicon with hydrophobic property, so that the particles have the same effect as lotus leaves, the waterproof effect of the cotton fabric is greatly enhanced, and a more lasting finishing effect is generated;
meanwhile, the long-chain alkyl modified organosilicon finishing liquid is adopted, the long-chain trimethoxy silane is contained in the molecular structure of organosilicon, independent silicon hydroxyl groups are formed after methoxy hydrolysis and can be used as crosslinking monomers, the long-chain alkyl modified organosilicon can form a lightly crosslinked interpenetrating network structure and is coated or attached on cotton fibers in a larger area, so that the binding power with cotton fabrics is increased, a film can be formed on the surfaces of the cotton fabrics after baking, the washing resistance of the finished fabrics can be improved, and the long-acting property of the waterproof effect is ensured.
Nano SiO2The particles have excellent characteristics and excellent chemical stability, are widely applied to textiles, can endow the textiles with special functions, but the nano SiO2Like other nanometer materials, the nanometer material has large specific surface area, is easy to agglomerate, has poor dispersion stability in the application and storage processes, has no affinity to fibers, is easy to fall off after cotton fabric treatment, is difficult to be fixed on the fiber surface, and therefore, the fabric loses the waterproof capability. Therefore, for nano SiO2The particles are subjected to surface modification, the agglomeration problem of the nano particles is solved, the dispersion stability is improved, and epoxy groups are introduced to nano SiO2The particles are modified, and the epoxy group modified nano silicon dioxide can be connected to cotton fibers through covalent bonds after being baked, so that the washing fastness is good, the epoxy group modified nano silicon dioxide is not easy to fall off, and the waterproof effect is durable.
In the preparation method of the long-chain alkyl modified silicone oil provided by the embodiment of the invention, the reaction raw materials comprise long-carbon-chain trimethoxy silane, octamethylcyclotetrasiloxane linear body and the like, methoxy is hydrolyzed into silicon hydroxyl in water, and the silicon hydroxyl is subjected to polycondensation reaction to obtain a fatty chain, so that the long-chain alkyl modified silicone oil has the fatty chain in the structure, and the finally finished fabric has soft hand feeling.
Detailed Description
The fluorine-free waterproof finishing method for cotton fabrics provided by the invention is further described in detail by combining specific embodiments. Advantages and features of the present invention will become apparent from the following description and from the claims.
Example 1
Preparing long-chain alkyl modified organic silicon finishing liquid: adding 87.6g of octamethylcyclotetrasiloxane linear body, 0.18g of tetramethylammonium hydroxide and 3.8g of distilled water into a reaction vessel, stirring, heating to 85 ℃ for reaction for 2 hours, cooling to 60 ℃, adding 6.4g of hexadecyltrimethoxysilane and 0.22g of tetramethylammonium hydroxide into the reaction vessel, heating to 120 ℃, reacting for 2 hours, cooling, reducing pressure and distilling to remove low-boiling-point substances to obtain the long-chain alkyl modified silicone oil. Then 2.6g of sodium dodecyl sulfate and the long-chain alkyl modified organic silicon oil are added into water to be stirred and mixed, the pH value of the mixture is adjusted to be neutral by using an acetic acid solution, the temperature is increased to 75 ℃, and the mixture is stirred at a high speed for 1 hour to obtain the long-chain alkyl modified organic silicon finishing liquid.
Preparation of epoxy modified nano SiO2Finishing liquid: in a reaction vessel90.8g of toluene was added with 4g of nano SiO2(average particle size of 80nm), ultrasonically dispersing for 30min at room temperature to obtain uniform suspension, adding 3g of coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1.2g of octyl trimethoxy silane, ultrasonically dispersing for 5min, magnetically stirring and refluxing for 6h at the temperature of 90 ℃, centrifuging, washing for multiple times, and drying to obtain the epoxy group modified nano SiO2. Before finishing cotton fabric, epoxy group modified nano SiO2Putting the mixture into distilled water, and carrying out ultrasonic treatment for 30 minutes to obtain the epoxy group modified nano SiO2And (4) finishing liquor.
According to the mass ratio of the solid parts in the finishing liquid of 1: 0.15 preparation of Long-chain alkyl modified organosilicon finishing liquid and epoxy modified nanometer SiO2The finishing liquid is prepared by modifying nano SiO with epoxy group2Uniformly mixing the finishing liquid and the long-chain alkyl modified organic silicon finishing liquid, then diluting to 100g/L, carrying out two-dipping two-rolling process finishing on the pure cotton plain woven fabric in the diluted mixed finishing liquid, wherein the rolling residue rate is 70%, then predrying for 5 minutes at 105 ℃, then baking for 3 minutes at 180 ℃, and then cooling.
Example 2
Preparing long-chain alkyl modified organic silicon finishing liquid: adding 88.6g of octamethylcyclotetrasiloxane linear body, 0.12g of tetramethylammonium hydroxide and 5.66g of distilled water into a reaction vessel, stirring, heating to 95 ℃ for reaction for 2 hours, cooling to 60 ℃, 5.4g of dodecyltrimethoxysilane and 0.22g of tetramethylammonium hydroxide, heating to 120 ℃, reacting for 2 hours, cooling, reducing pressure, distilling to remove low-boiling-point substances, and obtaining the long-chain alkyl modified silicone oil. Then adding 1.5g of sodium dodecyl sulfate, 0.8g of isomeric dodecyl alcohol polyoxyethylene ether and the long-chain alkyl modified organic silicon oil into water, stirring and mixing, adjusting the pH value to be neutral by using an acetic acid solution, heating to 75 ℃, and stirring at a high speed for 1 hour to obtain the long-chain alkyl modified organic silicon finishing liquid.
Preparation of epoxy modified nano SiO2Finishing liquid: 90.8g of toluene is added into a reaction vessel with 4g of nano SiO2(average particle diameter of 80nm), ultrasonic dispersing at room temperature for 30min to obtain uniform suspension, and adding 3g of even suspensionCoupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1.2g octyl trimethoxy silane are subjected to ultrasonic dispersion for 5min, then magnetic stirring reflux is carried out for 6h under the reaction condition that the temperature is 90 ℃, centrifugation is carried out, washing is carried out for multiple times, and drying is carried out, thus obtaining the epoxy modified nano SiO2. Before finishing cotton fabric, epoxy group modified nano SiO2Putting the mixture into distilled water, and carrying out ultrasonic treatment for 30 minutes to obtain epoxy group modified nano SiO2And (4) finishing liquor.
According to the mass ratio of the solid parts in the finishing liquid of 1: 0.25 preparation of Long-chain alkyl modified organosilicon finishing liquid and epoxy modified nanometer SiO2The finishing liquid is prepared by modifying nano SiO with epoxy group2Uniformly mixing the finishing liquid and the long-chain alkyl modified organic silicon finishing liquid, then diluting the mixed finishing liquid to 150g/L, carrying out two-dipping two-rolling process finishing on plain woven fabric of pure cotton in the diluted mixed finishing liquid, wherein the rolling residual rate is 70%, then predrying for 4 minutes at 110 ℃, then baking for 3 minutes at 180 ℃, and then cooling.
Example 3
Preparing long-chain alkyl modified organic silicon finishing liquid: adding 87.6g of octamethylcyclotetrasiloxane linear body, 0.18g of tetramethylammonium hydroxide and 3.8g of distilled water into a reaction vessel, stirring, heating to 85 ℃ for reaction for 2h, cooling to 60 ℃, heating to 120 ℃ for reaction for 2h, cooling to reduce pressure, distilling to remove low-boiling-point substances, and obtaining the long-chain alkyl modified silicone oil. Then 2.6g of sodium dodecyl sulfate and the long-chain alkyl modified organic silicon oil are added into water to be stirred and mixed, the pH value of the mixture is adjusted to be neutral by using an acetic acid solution, the temperature is increased to 75 ℃, and the mixture is stirred at a high speed for 1 hour to obtain the long-chain alkyl modified organic silicon finishing liquid.
Preparation of epoxy modified nano SiO2Finishing liquid: 90.6g of toluene was added to 5.1g of nano SiO in a reaction vessel2(average particle diameter of 60nm), ultrasonic dispersing at room temperature for 30min to obtain uniform suspension, adding 2.9g coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1.4g hexadecyl trimethoxy silane, ultrasonic dispersing for 5min, and magnetically stirring at 90 deg.CRefluxing for 6h, centrifuging, washing for multiple times and drying to obtain epoxy modified nano SiO2. Before finishing cotton fabric, epoxy group modified nano SiO2Distilled water is treated by ultrasonic for 30 minutes to obtain epoxy modified nano SiO2And (4) finishing liquor.
According to the mass ratio of the solid parts in the finishing liquid of 1: 0.15 preparation of Long-chain alkyl modified organosilicon finishing liquid and epoxy modified nanometer SiO2Finishing liquid, firstly, epoxy group is used for modifying nano SiO2The finishing liquid is used for carrying out rolling baking finishing on the cotton fabric, and then the long-chain alkyl modified organic silicon finishing liquid is used for carrying out rolling baking finishing on the cotton fabric. The rolling baking finishing is to firstly respectively modify epoxy groups into nano SiO2Diluting the finishing liquid and the long-chain alkyl modified organic silicon finishing liquid to 100g/L, and coating the plain woven fabric of pure cotton on epoxy modified nano SiO2Carrying out two-dipping and two-rolling process finishing in finishing liquid, wherein the rolling residue rate is 70%, pre-drying at 105 ℃ for 6 minutes, baking at 180 ℃ for 3 minutes, and cooling to room temperature; then the epoxy group is used for modifying the nano SiO2The plain woven fabric of the pure cotton finished by the finishing liquid is subjected to secondary soaking and secondary rolling process finishing in the long-chain alkyl modified organic silicon finishing liquid, the rolling residual rate is 70 percent, the pure cotton is pre-dried for 6 minutes at 105 ℃, then is baked for 3 minutes at 180 ℃, and is cooled to room temperature.
Example 4
Preparing long-chain alkyl modified organic silicon finishing liquid: adding 88.6g of octamethylcyclotetrasiloxane linear body, 0.12g of tetramethylammonium hydroxide and 5.66g of distilled water into a reaction vessel, stirring, heating to 95 ℃ for reaction for 2 hours, cooling to 60 ℃, 5.4g of dodecyltrimethoxysilane and 0.22g of tetramethylammonium hydroxide, heating to 120 ℃, reacting for 2 hours, cooling, reducing pressure, distilling to remove low-boiling-point substances, and obtaining the long-chain alkyl modified silicone oil. Then adding 1.5g of sodium dodecyl sulfate, 0.8g of isomeric dodecyl alcohol polyoxyethylene ether and the long-chain alkyl modified organic silicon oil into water, stirring and mixing, adjusting the pH value to be neutral by using an acetic acid solution, heating to 75 ℃, and stirring at a high speed for 1 hour to obtain the long-chain alkyl modified organic silicon finishing liquid.
Preparation of epoxy modified nano SiO2Finishing liquid: in a reaction vessel90.6g of toluene is added with 5.1g of nano SiO2(average particle size is 60nm), ultrasonically dispersing for 30min at room temperature to obtain uniform suspension, adding 2.9g of coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1.4g of hexadecyl trimethoxy silane, ultrasonically dispersing for 5min, magnetically stirring and refluxing for 6h at the reaction condition of 90 ℃, centrifuging, washing for multiple times, and drying to obtain the epoxy group modified nano SiO2. Before finishing cotton fabric, epoxy group modified nano SiO2Distilled water is treated by ultrasonic for 30 minutes to obtain epoxy modified nano SiO2And (4) finishing liquor.
According to the mass ratio of the solid parts in the finishing liquid of 1: 0.25 preparation of Long-chain alkyl modified organosilicon finishing liquid and epoxy modified nanometer SiO2Finishing liquid, firstly, epoxy group is used for modifying nano SiO2The finishing liquid is used for carrying out rolling baking finishing on the cotton fabric, and then the long-chain alkyl modified organic silicon finishing liquid is used for carrying out rolling baking finishing on the cotton fabric. The rolling baking finishing is to firstly respectively modify epoxy groups into nano SiO2Diluting the finishing liquid and the long-chain alkyl modified organic silicon finishing liquid to 80g/L, and coating the plain woven fabric of pure cotton on epoxy modified nano SiO2Carrying out two-dipping and two-rolling process finishing in finishing liquid, wherein the rolling residue rate is 70%, pre-drying at 110 ℃ for 4 minutes, baking at 180 ℃ for 3 minutes, and cooling to room temperature; then epoxy group is modified to nano SiO2The plain woven fabric of the pure cotton finished by the finishing liquid is subjected to secondary soaking and secondary rolling process finishing in the long-chain alkyl modified organic silicon finishing liquid, the rolling residual rate is 70 percent, the pure cotton is pre-dried for 4 minutes at 110 ℃, then is baked for 3 minutes at 180 ℃, and then is cooled to room temperature.
Water spray tests were conducted according to AATCC 22-2010 standards after initial and 10 wash cycles of the samples prepared in examples 1-4 above. After the wash cycle, the fabrics were drum dried prior to spray testing. Drying for 30 minutes at a typical roller drying temperature of 60-65 ℃. 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 finished fabrics of examples 1-4
From the measurement results of the examples 1 to 4 in the table 1, the method can adopt a one-bath method and a two-bath method to carry out waterproof finishing on the cotton fabric, the finished cotton fabric has high waterproof grade, can still keep better washing resistance effect after 10 times of cyclic washing, and meanwhile, the textile fabric also has better softness and has the effect similar to the effect after finishing by using a softener.
The embodiments of the present invention have been described in detail with reference to the examples, but the present invention is not limited to the embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (12)
1. A finishing method for fluorine-free waterproof cotton fabrics is characterized by comprising the following steps: and (3) rolling, baking and finishing the cotton fabric by adopting a one-bath method or a two-bath method through the long-chain alkyl modified organic silicon finishing liquid and the epoxy modified nano-silica finishing liquid.
2. The fluorine-free waterproof finishing method for cotton fabrics according to claim 1, characterized in that the long-chain alkyl modified organosilicon finishing liquid and the epoxy modified nano-silica finishing liquid are mixed according to a solid part mass ratio of 1: 0.05-1: 0.3.
3. the finishing method of the fluorine-free waterproof cotton fabric according to claim 2, wherein the one-bath method is as follows: firstly, mixing the long-chain alkyl modified organic silicon finishing liquid and the epoxy modified nano-silica finishing liquid, and then rolling, baking and finishing the cotton fabric.
4. The finishing method of the fluorine-free waterproof cotton fabric according to claim 2, characterized in that the two-bath method is: firstly, the epoxy group modified nano silicon dioxide finishing liquid is adopted to perform rolling baking finishing on cotton fabrics, and then the long-chain alkyl modified organic silicon finishing liquid is adopted to perform rolling baking finishing on the cotton fabrics finished by the epoxy group modified nano silicon dioxide finishing liquid.
5. The finishing method of the fluorine-free waterproof cotton fabric according to claim 1, wherein the preparation method of the long-chain alkyl modified organosilicon finishing liquid comprises the following steps: the emulsifier and the long-chain alkyl modified organic silicone oil are mixed according to the weight ratio of (1-3): stirring and mixing the long-chain alkyl modified organic silicon finishing liquid in water according to the proportion of 100, adjusting the pH to be neutral by using an acetic acid solution, heating to 60-85 ℃, and stirring for 1h to obtain the long-chain alkyl modified organic silicon finishing liquid.
6. The finishing method of the fluorine-free waterproof cotton fabric according to claim 5, wherein the preparation method of the long-chain alkyl modified organic silicone oil comprises the following steps: adding an octamethylcyclotetrasiloxane linear body, 1/5-3/5 catalyst and distilled water into a reaction container, stirring, heating to 90-100 ℃, reacting for 1.5-2.5 h, cooling to 60 ℃, adding long-carbon-chain trimethoxy silane and the rest catalyst, heating to 100-130 ℃, reacting for 1-3 h, cooling, decompressing, distilling and removing low-boiling-point substances to obtain the long-chain alkyl modified organic silicon oil;
wherein, the linear body of octamethylcyclotetrasiloxane is 85-95%, the long carbon chain silane coupling agent is 4-10%, the catalyst is 0.1-0.4%, and the balance is distilled water, and the sum of the weight percentages of the raw materials is 100%.
7. The finishing method of the fluorine-free waterproof cotton fabric according to claim 1, wherein the preparation method of the epoxy-modified nano-silica finishing liquid comprises the following steps:
adding nano silicon dioxide into toluene, performing ultrasonic dispersion for 30min at 20-30 ℃ to obtain a suspension, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and long-carbon-chain trimethoxy silane into the suspension, performing ultrasonic dispersion for 5min, performing magnetic stirring reflux for 4-8 h under the reaction condition of 80-100 ℃, centrifuging, washing for multiple times, and drying to obtain the epoxy group modified nano silicon dioxide;
then placing the epoxy group modified nano silicon dioxide into distilled water, and carrying out ultrasonic treatment for 30 minutes at the temperature of 20-30 ℃ to obtain an epoxy group modified nano silicon dioxide finishing liquid;
wherein, the toluene accounts for 88 to 97 percent, the nano silicon dioxide accounts for 2 to 8 percent, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane accounts for 1 to 4 percent, the long carbon chain silane coupling agent accounts for 0.5 to 1.5 percent, and the sum of the weight percentages of the raw materials is 100 percent.
8. The finishing method of the fluorine-free and waterproof cotton fabric according to claim 7, wherein the particle size of the nano-silica is 30nm to 100 nm.
9. The fluorine-free waterproof finishing method for cotton fabrics according to claim 6 or 7, characterized in that the long carbon chain trimethoxy silane is at least one of octyl trimethoxy silane, dodecyl trimethoxy silane, hexadecyl trimethoxy silane and octadecyl trimethoxy silane.
10. The finishing method for the fluorine-free waterproof of the cotton fabric according to claim 5, wherein the emulsifier is any one of or a compound of any combination of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxypropylene ether and isomeric tridecanol polyoxyethylene ether.
11. The fluorine-free water repellent finishing method for cotton fabrics according to claim 6, characterized in that the catalyst is tetramethylammonium hydroxide or potassium hydroxide.
12. The finishing method of the fluorine-free water proofing of cotton fabrics according to claim 3 or 4, characterized in that the roll-baking finishing is: diluting epoxy-modified nano-silica finishing liquid and long-chain alkyl-modified organic silicon finishing liquid or mixed finishing liquid thereof to 50-200 g/L, then carrying out a double-dipping and double-rolling process on cotton fabrics in the finishing liquid, wherein the rolling residue rate is 65-75%, then predrying for 4-7 minutes at 100-110 ℃, then baking for 2-4 minutes at 170-190 ℃, and then cooling.
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