CN119711183B - Preparation method of waterproof flame-retardant multifunctional fabric - Google Patents
Preparation method of waterproof flame-retardant multifunctional fabric Download PDFInfo
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Abstract
本申请提供一种防水阻燃多功能面料的制备方法，属于功能纺织品技术领域。将二元醇加热至完全融化后，加入二异氰酸酯和阻燃剂、催化剂，反应得到聚氨酯预聚体，加入扩链剂扩链毕，再加入封端剂封端，冷却，添加乳化剂得到防水阻燃剂乳液，加水形成整理剂，将聚丙烯腈预氧化纤维面料浸渍在该整理剂中处理毕，预烘，焙烘得到多功能面料。本发明采用长烷烃链的多元醇对聚氨酯预聚体进行扩链，获得的防水剂具有良好的成膜性，在应用时无需借助交联剂或粘合剂就能坚牢的固着在纤维表面，赋予改性纺织品优异的耐洗涤性。The present application provides a method for preparing a waterproof and flame-retardant multifunctional fabric, which belongs to the technical field of functional textiles. After heating the diol until it is completely melted, diisocyanate, flame retardant and catalyst are added to react to obtain a polyurethane prepolymer, a chain extender is added to extend the chain, and then a capping agent is added to cap the end, cooled, and an emulsifier is added to obtain a waterproof and flame retardant emulsion, and water is added to form a finishing agent. The polyacrylonitrile preoxidized fiber fabric is immersed in the finishing agent and treated, pre-baked, and baked to obtain a multifunctional fabric. The present invention uses a polyol with a long alkane chain to extend the polyurethane prepolymer. The obtained waterproof agent has good film-forming properties. When used, it can be firmly fixed on the fiber surface without the help of a cross-linking agent or adhesive, giving the modified textile excellent washing resistance.
Description
Technical Field
The application relates to a preparation method of waterproof flame-retardant multifunctional fabric, and belongs to the technical field of functional textiles.
Background
The polyacrylonitrile pre-oxidized fiber has the advantages of flame retardance, high temperature resistance, acid and alkali resistance, relatively low price and the like, so that the polyacrylonitrile pre-oxidized fiber is widely applied to the fields of flame retardant fabrics, high temperature resistance filter materials, carbon/carbon composite materials, activated carbon fibers and the like. However, certain structural defects exist in the polyacrylonitrile fiber, and new defects can be continuously generated in the carbonization process due to high-temperature treatment, so that the fiber after carbonization has low crimp degree, weak cohesion and reduced strength, and the subsequent spinning process is directly influenced. In addition, when the polyacrylonitrile preoxidized fiber is subjected to external force in the using and processing process, fragments or residues after carbonization often fall off, so that the popularization and application of products are seriously affected.
Based on the problems of the existing flame-retardant fibers, the application aims to prepare the multifunctional fabric with the waterproof function and the permanent flame-retardant performance, so as to solve the defects of the polyacrylonitrile pre-oxidized fibers in the application of the textile field.
Disclosure of Invention
In view of the above, the application provides a preparation method of waterproof flame-retardant multifunctional fabric, which endows the provided fabric with both waterproof property and permanent flame retardance, so as to solve the problems of low strength, poor wearability, poor waterproof effect and the like of the traditional polyacrylonitrile pre-oxidized flame-retardant fiber.
Specifically, the application is realized by the following scheme:
a preparation method of waterproof flame-retardant multifunctional fabric comprises the following steps:
heating dihydric alcohol to be completely melted, cooling to 50-60 ℃, adding diisocyanate and a flame retardant, stirring, heating to 60-80 ℃, adding a catalyst, continuing to react to obtain a polyurethane prepolymer, adding a chain extender, continuing to react, adding a blocking agent, continuing to react, cooling to 50-60 ℃, adding an emulsifying agent twice under the stirring condition, adding the remaining emulsifying agent to continue emulsifying after the first added emulsifying agent amount is converted into oil-in-water phase, and obtaining the waterproof flame retardant emulsion, wherein the emulsifying agent is deionized water containing 1-2 g/L of defoaming agent and 30-60 g/L of surfactant.
Step two, preparing the multifunctional fabric, namely immersing the polyacrylonitrile pre-oxidized fiber fabric in a finishing agent, and then pre-baking to obtain the multifunctional fabric, wherein the finishing agent is the aqueous solution of the waterproof flame retardant prepared in the step one, the concentration is 30-60 g/L, the immersion time is 5-10 min, and the rolling allowance is 60-80%.
According to the scheme, dihydric alcohol, diisocyanate and a flame retardant are used as raw materials, a polyurethane prepolymer is obtained through catalysis, and then an oil-in-water inversion is carried out on a chain extension reactant to obtain an emulsion of the polyurethane-based fluorine-free waterproof flame retardant, wherein the obtained emulsion is used for padding treatment of polyacrylonitrile pre-oxidized fiber fabric, so that a finished multifunctional fabric with flame retardance and waterproofness is obtained.
Further, as preferable:
In the first step, the first step is to perform,
The molar ratio of the dihydric alcohol to the diisocyanate to the chain extender to the flame retardant is 2-6:3-15:2-4:2-10, and more preferably, the molar ratio of the dihydric alcohol to the diisocyanate to the chain extender to the flame retardant is 3-5:6:5. The addition amount of the catalyst is 0.02-0.03% of the molar amount of diisocyanate, and the blocking agent is 5-10% of the molar amount of diisocyanate.
The dihydric alcohol is any one or a plurality of compound of polycaprolactone dihydric alcohol (PCL), polyether dihydric alcohol (PPG), polyether dihydric alcohol (PTMG), polytetrahydrofuran dihydric alcohol (PTMEG) and 1, 12-dodecane dihydric alcohol, more preferably, the dihydric alcohol is a compound of polycaprolactone dihydric alcohol (such as PCL 2000) and 1, 12-dodecane dihydric alcohol, and the compound molar ratio of the polycaprolactone dihydric alcohol and the 1, 12-dodecane dihydric alcohol is 1:0.1-0.3.
The diisocyanate is one or a mixture of more than one of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI), 1, 4-cyclohexane diisocyanate (CHDI) and methylcyclohexane diisocyanate (HTDI), more preferably, the diisocyanate is a mixture of isophorone diisocyanate (IPDI) and dicyclohexylmethane-4, 4' -diisocyanate (HMDI), and the molar ratio of isophorone diisocyanate (IPDI) to dicyclohexylmethane-4, 4' -diisocyanate (HMDI) is preferably 1:2-5.
The chain extender is sorbitol stearate, such as span 60, span 80, span 40, span 20, preferably span 60.
The flame retardant is one or more of nano silicon carbide, nano graphene oxide, MXene nano sheet, carbon nano tube, carbon nano wire, nano MgO, nano ZrO 2, nano SiO 2 and nano ZnO, and preferably nano silicon carbide.
The end capping agent is R-OH, wherein the number of C atoms in R is 8-20, and cetyl alcohol is preferred.
The catalyst is dibutyl tin dilaurate.
The defoamer is defoamer DM 8317.
The surfactant is one or more of alkylphenol ethoxylates, higher fatty alcohol ethoxylates, fatty acid polyoxyethylene esters and fatty acid methyl ester ethoxylates, preferably higher fatty alcohol ethoxylates, and further preferably fatty alcohol ethoxylate O-20.
The volume ratio of the deionized water containing the defoaming agent and the surfactant is 30-40% in the first dripping process and the deionized water containing the defoaming agent and the surfactant in the second dripping process. The invention does not use common hydrophilic chain extender, and deionized water containing defoamer and surfactant is added as emulsifier during emulsification and is carried out twice. The first addition is carried out in a slow dropwise adding mode, so that the phase inversion from water-in-oil to oil-in-water can be realized, and after the phase inversion is successful, the rest deionized water containing the defoamer and the surfactant can be quickly and largely added. When the emulsifier is added at one time, polyurethane prepared by the reaction is a polymer with poor hydrophilicity, the one-time addition can cause too high water adding speed, oil-water separation is generated, emulsification failure is caused, and the adding speed is low, so that the first addition amount is added for several times and controlled to be 30-40%, the processing efficiency can be obviously improved, and the production time consumption is reduced. The waterproof flame retardant is emulsion, so that the waterproof flame retardant not only can be stored stably, but also can be spread on the surface of the fiber and permeate into the fiber during application, and further the waterproof performance and durability are improved.
In the second step, the second step is to carry out the process,
The polyacrylonitrile pre-oxidized fiber fabric is one of a polyacrylonitrile pre-oxidized fiber woven fabric and a polyacrylonitrile pre-oxidized fiber knitted fabric.
The temperature of the pre-baking is 80-100 ℃ and the duration is 3-10 min.
The baking temperature is 130-170 ℃ and the baking time is 3-6 min.
The finished waterproof flame-retardant multifunctional fabric obtained by the scheme has the following beneficial effects:
(1) The polyurethane monomer is obtained by reacting the dihydric alcohol and the diisocyanate, and under the action of the catalyst, the nanoscale flame retardant and the polyurethane monomer are uniformly mixed and then subjected to polymerization reaction to form the polyurethane prepolymer, so that the distribution uniformity of the nano flame retardant material in polyurethane is effectively improved, and the waterproof flame retardant is also a premise of uniform flame retardance.
(2) The polyurethane prepolymer with flame retardance is subjected to chain extension, polyol with long alkane chain is used as a chain extender, monohydric alcohol with long alkane chain is used as a blocking agent, and the prepared chain extension product has fewer hydrophilic groups in structure, excellent hydrophobic property, water resistance and good film forming property, and can be firmly fixed on the surface of fiber without a crosslinking agent or an adhesive during application, so that the modified textile is endowed with excellent washing resistance. Particularly, when the chain extender adopts sorbitol stearate substances such as span 60, span 80, span 40, span 20 and the like, the structure of the chain extender contains 3 hydroxyl groups, and the chain extender can react with isocyanate-terminated polyurethane prepolymer to generate polymer with a network structure, so that the waterproof performance and the durability of the polymer can be improved, the water dipping grade reaches 5 levels, the water dipping grade can still be kept at 5 levels after 50 times of water washing, and the film forming performance is excellent.
(3) Besides the waterproof and flame-retardant functions, the waterproof and flame-retardant multifunctional fabric provided by the scheme can form a compact film on the surface of the fiber and resist external tensile force together with the fiber, and in addition, the waterproof and flame-retardant can penetrate into the fiber to repair the original defects of the fiber to a certain extent, so that the effect of improving the mechanical strength of the fabric is achieved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more apparent, the technical solutions of the present application will be further described in detail below with reference to specific examples in the embodiments of the present application, and it should be understood that the specific embodiments described herein are only for explaining the present application and are not intended to limit the technical solutions of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In addition, the terms "first," "second," are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features. The meaning of "a plurality of" is two or more, unless specifically defined otherwise.
The waterproof flame-retardant multifunctional fabric and the unmodified polyacrylonitrile pre-oxidized fiber fabric prepared by the comparative example and the example are subjected to hydrophobic effect, washing resistance, mechanical strength and flame retardant performance analysis. The washing method during the detection of the washability is carried out according to the specification of the household washing and drying procedure for the textile test of GB/T8629-2017, the hydrophobic effect is carried out according to the specification of the water-dipping method for detecting and evaluating the waterproof performance of the textile of GB/T4745-2012, the flame retardant property is carried out according to the specification of the measurement of the damage length, smoldering and continuous burning time in the vertical direction of the combustion performance of the textile of GB/T5455-2014, and the mechanical strength is carried out according to the specification of the measurement of the breaking strength and the breaking elongation (strip method) of the part 1 of the tensile performance of the textile fabric of GB/T3923.1-2013.
Example 1
(1) Preparation of waterproof flame retardant:
Adding 0.15mol of dihydric alcohol (the compound molar ratio of polycaprolactone dihydric alcohol PCL2000 to 1, 12-dodecanediol is 1:0.2) into a three-neck round bottom flask of 500 mL, heating in an oven until the dihydric alcohol is completely melted, cooling to 50 ℃, adding 0.30mol of diisocyanate (the molar ratio of IPDI to HMDI is 1:3) and 10g of flame retardant nano silicon carbide, stirring for 60min at 500r/min, heating to 80 ℃, adding 0.05g of catalyst dibutyl tin dilaurate and 7mLDMF, continuing to react for 90min to obtain a polyurethane prepolymer, adding 0.1mol of chain extender span 60 and 10mLDMF, continuing to react for 90min, adding 0.07mol of end-capping agent cetyl alcohol, continuing to react for 60min, cooling to 50 ℃, dropwise adding 70mL of deionized water containing 2 g/L of defoamer DM 8317 and 40g/L of surfactant fatty alcohol polyoxyethylene ether O-20 under the stirring condition of 1500 r/min, after the oil phase is completely wrapped with water, adding min mL of the surfactant, continuing to turn to obtain the emulsion without the residual fluorine, and continuing to obtain the flame retardant emulsion without the residual fluorine.
(2) Preparation of waterproof flame-retardant multifunctional fabric
The padding method is adopted to prepare the waterproof flame-retardant multifunctional fabric, namely, the waterproof flame-retardant emulsion prepared in the step (1) is added with water to form a finishing liquid with the waterproof flame-retardant concentration of 40g/L, the polyacrylonitrile pre-oxidized fiber fabric is immersed in the finishing liquid for 8min, the padding residual rate is 60%, and after being pre-baked for 6min at 80 ℃, the fabric is baked for 4min at 150 ℃.
Comparative example 1
This comparative example was set up identically to example 1, except that no flame retardant was added in step (1), the waterproof flame retardant was prepared as follows:
Adding 0.15mol of dihydric alcohol (the compound molar ratio of polycaprolactone dihydric alcohol PCL2000 to 1, 12-dodecanediol is 1:0.2) into a three-neck round bottom flask of 500 mL, heating in an oven until the dihydric alcohol is completely melted, cooling to 50 ℃, adding 0.30mol of diisocyanate (the molar ratio of IPDI to HMDI is 1:3), stirring for 60min at 500r/min, heating to 80 ℃, adding 0.05g of catalyst dibutyl tin dilaurate and 7mLDMF, continuing to react for 90min to obtain a polyurethane prepolymer, adding 0.1mol of chain extender span 60 and 10mLDMF, continuing to react for 90min, adding 0.07mol of end-capping agent hexadecanol, continuing to react for 60min, cooling to 50 ℃, dropwise adding 70mL of deionized water containing 2 g/L of defoamer DM 8317 and 40g/L of surfactant fatty alcohol polyoxyethylene ether O-20 under the stirring condition of 1500: 1500 r/min, after the emulsion is completed into oil-in-water phase inversion, adding the rest 130mL of surfactant and min mL of the surfactant, and continuing to emulsify the emulsion to complete the emulsification.
Performance tests were performed on unmodified fabrics (i.e., pre-oxidized polyacrylonitrile fiber fabrics before impregnation), fabrics treated in example 1 and comparative example 1, and are specifically shown in table 1.
TABLE 1 impact of flame retardant on fabric properties
。
As can be seen from the table 1,
The continuous burning time of the unmodified fabric is about 0.17s, the smoldering time is 0.16s, the damage length is up to 60mm, the breaking strength is 400N, and the water dipping grade is 2-3.
Compared with the unmodified fabric, the continuous burning time of the embodiment 1 is reduced to 0.13s, the ignition time is less than 0.10 s, the damage length is reduced to about 43mm, and the flame retardant property is obviously improved. The flame retardant is not added in the preparation process of the comparative example 1, the flame retardant performance of the fabric is slightly reduced, and the reason for the phenomenon is probably that the polyurethane film has combustibility, the continuous combustion time is prolonged, but the flame retardant performance is not obviously changed due to the thinner polyurethane film.
Compared with unmodified fabric, the preparation method has the advantage of remarkably improving mechanical property and waterproof property. The water dipping grades of the example 1 and the comparative example 1 are increased from 2-3 grades of the unmodified fabric to 5 grades, the breaking strength is increased from 400N of the unmodified fabric to 570N and 550N respectively, and the breaking strength and the water dipping grade are obviously improved. The difference between the breaking strength of the example 1 and the breaking strength of the comparative example 1 also shows that whether the flame retardant is added and participates in the synthesis process of the waterproof flame retardant has no obvious effect on the waterproof performance of the fabric under the same preparation condition, but has a certain improvement effect on the breaking strength.
Comparative example 2
This comparative example was identical to the setup of example 1, except that no end-capping agent was added in step (1), and the waterproof flame retardant was prepared as follows:
Adding 0.15mol of dihydric alcohol (the compound molar ratio of polycaprolactone dihydric alcohol PCL2000 to 1, 12-dodecanediol is 1:0.2) into a three-neck round bottom flask of 500 mL, heating in an oven until the dihydric alcohol is completely melted, cooling to 50 ℃, adding 0.30mol of diisocyanate (the molar ratio of IPDI to HMDI is 1:3) and 10g of flame retardant nano silicon carbide, stirring for 60min at 500r/min, heating to 80 ℃, adding 0.05g of catalyst dibutyl tin dilaurate and 7mLDMF, continuing to react for 90min to obtain a polyurethane prepolymer, adding 0.1mol of chain extender span 60 and 10mLDMF, continuing to react for 90min, cooling to 50 ℃, dropwise adding 70mL of deionized water containing 2 g/L of defoamer DM 8317 and 40g/L of surfactant fatty alcohol polyoxyethylene ether O-20 under the stirring condition of 1500 r/min, after the emulsion is completely oil-in-water phase inversion, adding the rest 130mL of deionized water containing the defoamer and the surfactant min, and continuing to obtain the flame retardant emulsion.
The fabric obtained by dipping modification in comparative example 2 is tested for waterproof performance, and the water wetting performance is 4-5 grades. This is because the end-capping agent is not added, the chain-extended product is not end-capped, the molecular chain end thereof contains a small amount of hydroxyl groups and carboxyl groups, whereas example 1 is added with the end-capping agent, and the molecular chain end of the resulting waterproof flame retardant is an alkyl chain after the end-capping reaction is completed. The hydrophilic group hydroxyl groups cause a decrease in hydrophobic and water-resistant properties compared to the alkyl chain.
Comparative example 3
This comparative example was set identically to example 1, except that the chain extender in step (1) was replaced with 2, 2-dimethylolpropionic acid and the waterproof flame retardant was prepared as follows:
Adding 0.15mol of dihydric alcohol (the compound molar ratio of polycaprolactone dihydric alcohol PCL2000 to 1, 12-dodecane dihydric alcohol is 1:0.2) into a three-neck round bottom flask of 500mL, heating in an oven until the dihydric alcohol is completely melted, cooling to 50 ℃, adding 0.30mol of diisocyanate (the molar ratio of IPDI to HMDI is 1:3) and 10g of flame retardant nano silicon carbide, stirring for 60min at 500r/min, heating to 80 ℃, adding 0.05g of catalyst dibutyl tin dilaurate and 7mLDMF, continuing to react for 90min to obtain a polyurethane prepolymer, adding 0.1mol of chain extender 2, 2-dimethylolpropionic acid and 10mLDMF, continuing to react for 90min, adding 0.07mol of end-capping agent hexadecanol, continuing to react for 60min, cooling to 50 ℃, dropwise adding 70mL of deionized water containing 2 g/L of surfactant DM 8317 and 40g/L of surfactant fatty alcohol polyoxyethylene ether O-20 under the stirring condition of 1500 r/min, after the foaming agent phase inversion is completed, adding water to obtain min mL of residual emulsion, and continuing to emulsify the emulsion after the foaming to obtain min mL of the residual emulsion.
The emulsion prepared by the scheme is used for impregnating and modifying the polyacrylonitrile pre-oxidized fiber fabric (the process is the same as that of the embodiment 1), the waterproof performance of the modified fabric is detected, the water wetting performance of the modified fabric is 2-3 levels, and the water wetting performance of the modified fabric is 2 levels after washing for 50 times.
The structure of the emulsion obtained by using the chain extender of the comparative example contains a large amount of hydrophilic carboxyl groups and a certain amount of terminal hydrophilic hydroxyl groups, so that the hydrophobic property is inferior to that of example 1, while the structure of the chain extension product obtained by using the polyol chain extension of the long alkane chain of example 1 does not contain hydrophilic groups and is better in the water dipping grade parameter correspondingly.
Comparative example 4
Comparative example 4, CN116396454a, was prepared without prepolymer.
In the comparative example 4, the super-hydrophobic high molecular compound is constructed by the condensation reaction of polyurethane and a long-chain hydroxyl compound, the surface energy of the fabric can be obviously reduced by finishing the super-hydrophobic high molecular compound on the surface of the fabric, and meanwhile, the hard segment of the polyurethane effectively enhances the bonding fastness of the product and the fiber. The invention is applied to the fluorine-free waterproof finishing of fabrics, and can endow the fabrics with high-efficiency waterproof performance and excellent washability. The water-soaking performance is 5 grades, and the water-soaking performance is 3-4 grades after washing for 50 times.
The polyurethane prepolymer is chain-extended by using the polyol with long alkane chain, and the obtained waterproof agent has good film forming property, can be firmly fixed on the surface of the fiber without a cross-linking agent or an adhesive during application, but has better washing resistance than that of comparative example 4. Taking example 1 as an example, the polyurethane prepolymer prepared from the dihydric alcohol and the diisocyanate is chain-extended by using the polyalcohol with long alkane chain, the prepared waterproof agent has good bonding fastness with fibers, and the formed film has good flexibility and is not easy to break during washing, and the water-soaking performance of the obtained modified fabric is still kept at 5 levels after the obtained modified fabric is washed for 50 times. In contrast, the polyurethane waterproofing agent directly prepared from the diol and the isocyanate in comparative example 4 has poor flexibility, and cracks and even falls off due to the external force during washing.
Example 2
The same arrangement as in example 1 is provided with the difference that the diol addition is 0.05 mol and the chain extender span 60 is 0.17: 0.17 mol.
Example 3
The same arrangement as in example 1 is provided with the difference that the diol addition is 0.25 mol and the chain extender span 60 is 0.03 mol.
Performance tests were performed on unmodified fabrics (i.e., pre-oxidized polyacrylonitrile fiber fabrics before impregnation), fabrics treated in example 1 and comparative example 1, and are specifically shown in table 2.
TABLE 2 influence of the amount of glycol and chain extender on the waterproof Properties of the fabrics
。
Table 2 can be seen:
1) When not washed, the fabric prepared in example 1 had the best water pick-up rating, and the waterproofing agent prepared in example 3 had the smallest water pick-up rating. After 50 times of washing, the water dipping grades of the fabrics prepared in the example 1 are not changed obviously, the water dipping grades of the fabrics prepared in the examples 2 and 3 are reduced obviously, and the water dipping grade of the fabric prepared in the example 2 is reduced more than that of the fabric prepared in the example 3.
2) The influence of the chain extender and the dihydric alcohol is mainly represented by waterproof performance. As can be seen from comparative example 1 and examples 1-1 to 1-5, when the amount of the chain extender is small, a small amount of isocyanate groups remaining in the polyurethane molecular structure are liable to react with water, which affects the emulsifying property and thus the water repellency, and when the amount of the chain extender is too large, the unreacted chain extender molecules contain hydrophilic hydroxyl groups, which deteriorates the water repellency. As can be seen from comparative examples 1, examples 1-6 to examples 1-9, when the amount of the diol is small, the molecular chain of the polyurethane prepolymer is short, the prepared waterproofing agent is poor in film forming property, and is liable to fall off during washing, so that the waterproofing property is poor. When the consumption of dihydric alcohol is more, the terminal group of the prepolymer is hydroxyl and can not react with the chain extender, so that the finished product contains more terminal hydroxyl, thereby affecting the waterproof performance of the product. Thus, the optimum molar ratio of diol, diisocyanate to chain extender is 0.15:0.30:0.10.
The above examples only represent a few possible embodiments of the invention, which are described in more detail and are not to be construed as limiting the scope of the invention, nor are they intended to limit the scope of the invention as claimed. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, and it is intended to include the present invention in all equivalent implementations or modifications.
Claims (10)
1. The preparation method of the waterproof flame-retardant multifunctional fabric is characterized by comprising the following steps of:
Heating dihydric alcohol to be completely melted, cooling to 50-60 ℃, adding diisocyanate and a flame retardant, stirring, heating to 60-80 ℃, adding a catalyst, continuing to react to obtain a polyurethane prepolymer, adding a chain extender, continuing to react, then adding a blocking agent, continuing to react, cooling to 50-60 ℃, adding an emulsifying agent twice under the stirring condition, adding the residual emulsifying agent to continue to emulsify after the first added emulsifying agent is converted into oil-in-water phase, and obtaining a waterproof flame retardant emulsion, wherein the emulsifying agent is deionized water containing 1-2 g/L of a defoaming agent and 30-60 g/L of a surfactant;
The mole ratio of the dihydric alcohol to the diisocyanate to the chain extender to the flame retardant is 2-6:3-15:2-4:2-10, the catalyst addition amount is 0.02-0.03% of the diisocyanate mole amount, the end capping agent is 5-10% of the diisocyanate mole amount, the dosage mole ratio of the dihydric alcohol to the diisocyanate to the chain extender satisfies 0.15:0.30:0.10,
The dihydric alcohol is one or more of polycaprolactone dihydric alcohol PCL, polyether dihydric alcohol PPG, polyether dihydric alcohol PTMG, polytetrahydrofuran dihydric alcohol PTMEG and 1, 12-dodecane dihydric alcohol,
The chain extender is a sorbitol stearate compound,
The end capping agent is R-OH, the number of C atoms in R is 8-20,
And step two, immersing the polyacrylonitrile pre-oxidized fiber fabric in a finishing agent for finishing treatment, pre-baking and baking to obtain the multifunctional fabric, wherein the finishing agent is the aqueous solution of the waterproof flame retardant emulsion prepared in the step one, the concentration is 30-60 g/L, the immersing time is 5-10 min, and the rolling allowance is 60-80%.
2. The method for preparing the waterproof flame-retardant multifunctional fabric according to claim 1, wherein the dihydric alcohol is a compound of polycaprolactone dihydric alcohol PCL and 1, 12-dodecanediol, and the compound molar ratio of the polycaprolactone dihydric alcohol PCL to the 1, 12-dodecanediol is 1:0.1-0.3.
3. The method for preparing the waterproof flame-retardant multifunctional fabric according to claim 1, wherein the diisocyanate is one or a mixture of more than one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, 1, 4-cyclohexane diisocyanate and methylcyclohexane diisocyanate.
4. The method for preparing the waterproof flame-retardant multifunctional fabric according to claim 3, wherein the diisocyanate is a mixture of isophorone diisocyanate and dicyclohexylmethane-4, 4 '-diisocyanate, and the molar ratio of isophorone diisocyanate to dicyclohexylmethane-4, 4' -diisocyanate is 1:2-5.
5. The method for preparing the waterproof flame-retardant multifunctional fabric as claimed in claim 1, wherein the flame retardant is one or more of nano silicon carbide, nano graphene oxide, MXene nano sheet, carbon nano tube, carbon nano wire, nano MgO, nano ZrO 2, nano SiO 2 and nano ZnO.
6. The method for preparing the waterproof flame-retardant multifunctional fabric as claimed in claim 1, wherein the chain extender is one of span 60, span 80, span 40 and span 20.
7. The method for preparing the waterproof flame-retardant multifunctional fabric according to claim 1, wherein the first added emulsifier accounts for 30-40% of the total emulsifier in volume percent.
8. The method for preparing the waterproof flame-retardant multifunctional fabric as claimed in claim 1, wherein the defoaming agent is a defoaming agent DM 8317, and the surfactant is one or more of alkylphenol ethoxylates, high-carbon fatty alcohol ethoxylates, fatty acid polyoxyethylene esters and fatty acid methyl ester ethoxylates.
9. The method for preparing the waterproof flame-retardant multifunctional fabric of claim 1, wherein the polyacrylonitrile pre-oxidized fiber fabric is one of a polyacrylonitrile pre-oxidized fiber woven fabric and a polyacrylonitrile pre-oxidized fiber knitted fabric.
10. The preparation method of the waterproof flame-retardant multifunctional fabric is characterized in that the pre-baking temperature is 80-100 ℃ and the duration is 3-10 min, and the baking temperature is 130-170 ℃ and the duration is 3-6 min.
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| WO2015056763A1 (en) * | 2013-10-17 | 2015-04-23 | 東レ・オペロンテックス株式会社 | Polyurethane elastic fiber and method for producing same |
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| JP4632351B2 (en) * | 2005-01-31 | 2011-02-16 | 日華化学株式会社 | Polyurethane resin aqueous dispersion and method for producing flame retardant polyester fiber using the same |
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| CN107759763B (en) * | 2017-11-01 | 2020-08-04 | 北京中纺化工股份有限公司 | Washing-resistant flame-retardant synergist for textiles and preparation method and application thereof |
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| CN115821587B (en) * | 2022-12-23 | 2024-06-21 | 太仓宝霓实业有限公司 | Durable flame retardant for fabric and preparation method thereof |
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| WO2011014783A1 (en) * | 2009-07-31 | 2011-02-03 | Akzo Nobel N.V. | Hybrid copolymer compositions |
| WO2015056763A1 (en) * | 2013-10-17 | 2015-04-23 | 東レ・オペロンテックス株式会社 | Polyurethane elastic fiber and method for producing same |
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