CN121161608A - Preparation method of pre-oxidized fiber-based composite flame-retardant fabric - Google Patents
Preparation method of pre-oxidized fiber-based composite flame-retardant fabricInfo
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Abstract
本申请提供一种预氧化纤维基复合阻燃织物的制备方法，属于高性能纺织品技术领域。以聚丙烯腈预氧化纤维与普通聚丙烯腈纤维构成复合纱线，将其织造得到的织物采用二浸二轧方式进行阻燃整理，得到复合阻燃织物，阻燃整理剂的制备过程为：聚二元醇与二异氰酸酯在催化剂、有机溶剂存在下反应得到聚氨酯预聚物，所述聚氨酯预聚物中加入溶有改性二氧化硅气凝胶、阻燃剂和环氧树脂的N,N‑二甲基甲酰胺混合溶液，升温至80~90℃恒温反应后，降温至45~50℃，滴加含消泡剂的去离子水，完成水包油转相和乳化，所得乳液即为阻燃整理剂，解决当下复合阻燃面料阻燃不均匀和耐洗涤性差的问题。This application provides a method for preparing a pre-oxidized fiber-based composite flame-retardant fabric, belonging to the field of high-performance textile technology. A composite yarn is constructed using pre-oxidized polyacrylonitrile fibers and ordinary polyacrylonitrile fibers. The resulting fabric is then subjected to a two-dip, two-nip flame-retardant finishing process to obtain a composite flame-retardant fabric. The preparation process of the flame-retardant finishing agent is as follows: polydiol and diisocyanate react in the presence of a catalyst and an organic solvent to obtain a polyurethane prepolymer. An N,N-dimethylformamide mixed solution containing modified silica aerogel, a flame retardant, and epoxy resin is added to the polyurethane prepolymer. After a constant temperature reaction at 80-90°C, the temperature is lowered to 45-50°C, and deionized water containing a defoamer is added dropwise to complete the oil-in-water phase inversion and emulsification. The resulting emulsion is the flame-retardant finishing agent, solving the problems of uneven flame retardancy and poor washability in current composite flame-retardant fabrics.
Description
Technical Field
The application relates to a preparation method of a pre-oxidized fiber-based composite flame-retardant fabric, and belongs to the technical field of textile finishing agents.
Background
Fire accidents not only directly threaten human life safety, but also cause immeasurable economic losses. For this reason, the development of long-lasting flame retardant textiles has become a focus of attention in the society. Flame retardant textiles are textiles which are made of flame retardant fibers or textiles which are subjected to flame retardant post-finishing, the flame retardant textiles can reduce the flammability to different degrees, the burning rate of the flame retardant textiles can be obviously delayed in the burning process, and the flame retardant textiles can be rapidly self-extinguished after leaving a fire source.
The polyacrylonitrile preoxidized fiber (PANOF), also called preoxidized fiber, is a high-performance fiber material prepared by using polyacrylonitrile precursor as a base material and through a preoxidation process. The polyacrylonitrile pre-oxidized fiber has the characteristics of good thermal stability, good flame retardance and the like, and has great application potential in the fields of protective equipment, constructional engineering, battery manufacturing, wind power generation, rail transit, aerospace and the like. However, the polyacrylonitrile pre-oxidized fiber has the defects of low strength, large brittleness, poor textile processing performance and the like besides excellent flame retardance, and seriously influences the application of the polyacrylonitrile pre-oxidized fiber in the field of flame-retardant textiles. In the prior art, the polyacrylonitrile precursor fiber is subjected to chemical pretreatment in the preparation process of the precursor fiber so as to improve the comprehensive performance of the precursor fiber, or the polyacrylonitrile precursor fiber is blended with other functional fibers so as to make up the spinnability defect of the polyacrylonitrile precursor fiber and prepare the high-performance flame-retardant fabric.
CN109703140a discloses a production process of flame-retardant composite cloth, wherein a mixed fiber is prepared by mixing modified acrylic fibers and acrylic pre-oxidized fibers, and the prepared fabric has excellent flame-retardant performance, but the heat-insulating performance needs to be improved. In order to improve the heat insulation performance, CN 118478570A discloses a multilayer flame-retardant composite fabric based on pre-oxidized fiber fibers and a preparation method thereof, wherein the pre-oxidized fiber fibers, modified cotton fibers and aramid fibers are blended, the obtained blended yarns are woven into an outer layer fabric and an inner layer fabric, and a layer of polyurethane flame retardant containing silica aerogel is coated on the surface of the outer layer fabric and the inner layer fabric to prepare the multilayer flame-retardant composite fabric with the heat insulation function. But toluene-2, 4-diisocyanate adopted by the method is easy to cause yellowing of finished fabrics, and the problems of washing resistance and flame retardance uniformity of flame retardance of fabrics are not considered.
Disclosure of Invention
In view of the above, the application provides a preparation method of a pre-oxidized fiber-based composite flame-retardant fabric, which solves the problems of poor flame-retardant uniformity and poor washing resistance of the current composite flame-retardant fabric.
Specifically, the application is realized by the following scheme:
a preparation method of a pre-oxidized fiber-based composite flame-retardant fabric comprises the following steps:
Step one, preparing a composite fabric, namely blending polyacrylonitrile pre-oxidized fibers and polyacrylonitrile fibers to obtain composite yarns, and weaving the composite yarns to obtain the composite fabric;
And secondly, preparing a flame retardant finishing agent, namely heating and melting polydiol, cooling to 45-50 ℃, adding diisocyanate, heating to 55-60 ℃ for reaction, adding dibutyl tin dilaurate and solvent N, N-dimethylformamide, heating to 60-70 ℃ for continuous reaction to obtain polyurethane prepolymer, adding N, N-dimethylformamide mixed solution containing modified silica aerogel, flame retardant and epoxy resin, heating to 80-90 ℃ for constant temperature reaction, cooling to 45-50 ℃, slowly dropwise adding deionized water containing a defoaming agent, rapidly adding the rest deionized water containing the defoaming agent after finishing oil-in-water inversion, and continuously emulsifying to obtain the flame retardant finishing agent.
The modified silica aerogel is obtained by modifying silica aerogel by a silane coupling agent, and has the structural formula:
the typical value range is x=10 to 20, y=10 to 20, and the chain length is controlled.
And thirdly, preparing the composite flame-retardant fabric, namely putting the composite fabric into a flame-retardant finishing agent, and performing flame-retardant finishing in a two-dipping and two-rolling mode to obtain the composite flame-retardant fabric.
Further, as preferable:
In the first step, the blending mass ratio of the polyacrylonitrile pre-oxidized fiber to the polyacrylonitrile fiber is 4-8:2-6, preferably 5-7:3-5, and the mass ratio of the polyacrylonitrile pre-oxidized fiber is 60% with 6:4 as the best.
In the second step, the second step is to carry out the process,
The preparation method of the modified silica aerogel comprises the steps of dispersing the silica aerogel in absolute ethyl alcohol at room temperature, adding triethylamine and a silane coupling agent, heating to 50-70 ℃ for constant-temperature reaction, cooling to room temperature, fully washing with deionized water, and drying in vacuum to obtain the modified silica aerogel.
The silane coupling agent is a mixture of trimethylmethoxysilane and hydroxy polydimethylsilane, and the mixing molar ratio of the trimethylmethoxysilane to the hydroxy polydimethylsilane is 1:2-5, preferably 1:3. The silica aerogel is modified by adopting the mixture of the trimethylmethoxysilane and the hydroxy polydimethylsilane, the trimethylmethoxysilane can seal the hydroxy groups on the surface of the silica aerogel, the dispersibility of the silica aerogel in a polyurethane preparation system is improved, and the hydroxy polydimethylsilane can endow the silica aerogel with proper reaction performance and good waterproof performance.
The silica aerogel is a powdery silica aerogel.
The mass ratio of the silica aerogel to the silane coupling agent is 2-3:3-5.
The polyglycol is any one of polycaprolactone glycol (PCL), polyether glycol (PPG), polyether glycol (PTMG) and polytetrahydrofuran glycol (PTMEG), and preferably polycaprolactone glycol (PCL).
The diisocyanate is one or a mixture of more than one of hexamethylene diisocyanate, diphenylmethane diisocyanate, pentamethylene diisocyanate and 4,4 '-dicyclohexylmethane diisocyanate, preferably a mixture of pentamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate, and the aliphatic structure and molecular chain of the pentamethylene diisocyanate do not contain benzene ring structures, so that the polyurethane has higher flexibility, and the polyurethane hydrophobic membrane is prevented from cracking in the preparation process. Therefore, the polyglycol is compounded with a certain amount of diisocyanate with a rigid cyclohexyl structure, and the fastness of the adhesive film can be properly improved while the flexibility of polyurethane is not affected. The mixing molar ratio of pentamethylene diisocyanate to 4,4' -dicyclohexylmethane diisocyanate is optimally 3:7.
The flame retardant is a derivative of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and has a structural formula of
。
The epoxy resin is any one of tetrabromobisphenol A epoxy resin, brominated phenolic epoxy resin, dibromo-quaternary pentanediol diglycidyl ether, N-diglycidyl-2, 4, 6-tribromoaniline, dibromotoluene glycidyl ether and 1, 3-diglycidyl-4, 5,6, 7-tetrabromobenzimidazolone, and is preferably tetrabromobisphenol A epoxy resin.
The defoaming agent is a defoaming agent DM8317, and the content is 0.5-1 g/L.
The molar ratio of the polyglycol, the diisocyanate, the dibutyl tin dilaurate, the modified silica aerogel, the flame retardant and the epoxy resin is 2-3:3-5:0.05-0.1:0.5-1:0.5-1:1-2.
In the third step, the consumption of the flame retardant is 80-150 g/L, the rolling allowance is 55-65%, and after pre-baking for 1-3 min at 80-90 ℃, the flame retardant is baked for 2-5 min at 160-180 ℃. Preferably, the flame retardant is used in an amount of 100g/L, the rolling allowance is 60%, and the flame retardant is baked at 80 ℃ for 2 min and then baked at 160 ℃ for 3 min.
After the surface of the composite flame-retardant fabric obtained by the scheme is coated with the adhesive, the fabric with a multilayer structure is formed by hot pressing. Preferably, the fabric of the multilayer structure is a two-layer composite flame retardant fabric, after one side of a layer of the composite flame retardant fabric is coated with the adhesive, and hot-pressing with another layer of composite flame-retardant fabric. The adhesive is polyvinylidene chloride adhesive, and the coating amount is 20-30 g/m 2. The adopted adhesive has good flame retardant effect, not only can not influence the flame retardant property of the composite flame retardant fabric obtained in the step three, but also can form a reinforcing effect on the composite flame retardant fabric treated by the flame retardant finishing agent.
The aqueous polyurethane-based flame retardant finishing agent provided by the method can be applied to the treatment of textiles so as to obtain textiles with excellent heat insulation and flame retardance and washing resistance.
The working principle and the beneficial effects of the application are summarized as follows:
1) The main reason for the poor washing resistance of the conventional composite flame-retardant fabric is that the polyurethane film with the flame-retardant component introduced is easy to absorb moisture and swell, and has poor bonding force with fibers, so that the formed flame-retardant polyurethane film falls off in the washing process. In the process of preparing the flame-retardant finishing agent, modified silica aerogel and epoxy resin are used as chain extenders. The modified silica aerogel with good waterproofness endows the prepared waterborne polyurethane-based flame retardant finishing agent with good heat insulation and hydrophobicity, and can effectively reduce the degree of moisture absorption and swelling of a polyurethane adhesive film, thereby improving the washing fastness of the finished fabric. The epoxy resin with excellent adhesive force is introduced into the polyurethane structure, so that the bonding force between polyurethane and a fiber matrix can be improved, and the polyurethane adhesive film can be endowed with good flame retardant property. And the modified silica aerogel and the epoxy resin are polyhydroxy substances, and when the modified silica aerogel and the epoxy resin are used as a chain extender, polyurethane with a three-dimensional network structure can be formed, so that the fastness of a polyurethane adhesive film is further improved, and the hydrophobicity of the polyurethane film and the binding force between the polyurethane film and a fiber matrix are remarkably improved.
2) The flame retardant introduced into the flame retardant finishing agent, the modified silica aerogel and the epoxy resin realize a synergistic effect, so that the polyurethane has excellent flame retardant property.
The flame retardant is a phosphorus flame retardant, P-H in the main structure of the flame retardant can react with active groups such as amino, hydroxyl, C=C double bonds and the like to form a series of derivatives, PO generated in the combustion process of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof can capture HO and H generated by combustion, meanwhile, phosphorus-containing aerobic acid is generated, the aerobic acid can generate polymerization reaction to generate a dehydration catalyst when subjected to strong heat, a carbon layer is catalyzed to form, and further combustion of a base material is delayed.
The epoxy resin contains halogen elements, and the halogen elements in the structure of the epoxy resin endow the epoxy resin with flame retardant effect. The flame-retardant mechanism is mainly three, namely, the bond energy of C-X of a halogen flame-retardant system is low, a part of heat can be absorbed when the halogen flame-retardant system is heated and decomposed, HX can also react with free radicals HO generated by combustion to generate halogen free radicals X, X can react with polymer chains to generate HX, HO and oxygen are prevented from reacting, finally, the existence of the flame retardant weakens Van der Waals force between the polymer chains, so that the material is in a viscous state when being heated, and the material has fluidity when being heated and can take away a part of flame and heat when flowing, thereby realizing the flame-retardant effect. The brominated flame retardant such as tetrabromobisphenol A epoxy resin has the advantages of high flame retardant efficiency, small consumption and low cost.
Silica aerogel is the best performing insulation material known so far, its pore size is lower than the mean free path of air molecules at normal pressure, so air molecules are approximately stationary in the aerogel voids, thereby avoiding convective heat transfer of air, while the extremely low bulk density of aerogel and the tortuous path of the nano-grid structure also prevent gaseous and solid heat transfer, and the void walls tending to "infinity" can minimize heat radiation. In addition, the bond energy of Si-O bonds in the silica aerogel is much larger than the bond energy of C-O bonds and C-C bonds of organic matters, the silica aerogel has better high temperature resistance than common organic compounds, and the organosilicon forms a carbonization layer at high temperature more densely and continuously, so that the further combustion of a base material can be delayed, molten drops can not be generated in the combustion process of the organosilicon, the combustion speed is low, and toxic smoke can not be discharged.
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 this embodiment, the detection parameters and methods are mainly as follows:
(1) Tensile breaking strength of fabric
Referring to GB/T3923.1-2013 determination of tensile Property breaking Strength and elongation at break of textile fabrics (strip sample method), tensile test was carried out on polyurethane film by using Instron 3655 type universal material testing machine, each sample was tested 5 times, and average value was taken.
(2) Uniformity of thermal insulation
And placing the composite flame-retardant fabric on a heating platform of a thermocouple thermometer, heating the fabric to 40 ℃, testing the temperature difference of the front and the back of 20 different parts of the fabric, and calculating the standard deviation. The larger the standard deviation value, the poorer the uniformity of distribution of the silica aerogel in the polyurethane.
(3) Wash-durable washing method
According to the standard specified in GB/T19980-2025 method for evaluating the appearance of textile products after washing and drying at home.
(4) Flame retardant Properties
The limiting oxygen index test refers to GB/T5454-1997 oxygen index method for textile combustion performance test, the limiting oxygen indexes of 20 different parts of the fabric are tested, standard deviation is calculated, the larger the standard deviation value is, the worse the flame retardance uniformity is, and the test of the damage length, smoldering time and continuous burning time refers to GB/T5455-2014 determination of the damage length, smoldering time and continuous burning time in the vertical direction of the textile combustion performance.
Example 1
The pre-oxidized fiber-based composite flame retardant fabric of the embodiment is prepared by the following method:
(1) Preparation of the fabric:
The polyacrylonitrile pre-oxidized fiber and the common polyacrylonitrile fiber are compounded to prepare yarn, and the yarn is woven into a composite fabric. Wherein the mass ratio of the polyacrylonitrile preoxidized fiber is 60 percent, and the mass ratio of the common polyacrylonitrile fiber is 40 percent.
(2) Preparation of modified silica aerogel:
dispersing 25 g silicon dioxide aerogel in 500 mL absolute ethyl alcohol at room temperature, adding 10mL triethylamine, providing alkalinity in the reaction process and catalyzing hydrolysis of a silane coupling agent, dropwise adding a mixture of 10 g trimethylmethoxysilane and 30 g hydroxy polydimethylsilane (preferably dihydroxy-terminated polydimethylsiloxane) in 60 min under the stirring condition of 300 r/min, continuing stirring 60 min after the dropwise adding, then heating to 60 ℃ at 2 ℃ per min, reacting at a constant temperature for 120 min, cooling to room temperature, fully washing with deionized water, and vacuum drying to obtain the modified silicon dioxide aerogel.
(3) Preparation of flame retardant finishing agent
Putting 30 g polycaprolactone diol (PCL) into a three-neck flask, heating and melting the PCL in a constant-temperature blast drying oven at 115 ℃, cooling the PCL after the PCL is completely melted, adding 40 g diisocyanate (the compound molar ratio of pentamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate is 3:7) at 50 ℃, heating the PCL to 60 ℃, reacting the PCL with 60 min, adding 0.5mL dibutyl tin dilaurate and 10g N, N-dimethylformamide, continuously reacting the PCL with 60 min at 60 ℃, then adding 30 mL of N, N-dimethylformamide solution containing 8g modified silica aerogel, 10g 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative and 10g tetrabromobisphenol A epoxy resin mixture, heating to 80 ℃, reacting 120 min at constant temperature, cooling to 50 ℃, slowly dropwise adding 50mL of deionized water containing 1g defoamer DM8317 under the condition of 1500 r/min, quickly adding 150 mL of deionized water containing 1g defoamer DM8317 after finishing oil-in-water inversion, and continuing emulsifying 180 min to obtain the flame retardant finishing agent.
(4) The preparation of the composite flame-retardant fabric comprises the steps of immersing the composite fabric in the step (1) in a finishing agent for flame-retardant finishing by adopting a two-soaking and two-rolling method, wherein the finishing agent contains 100 g/L of the flame-retardant finishing agent prepared in the step (3), the rolling surplus rate is 60%, pre-baking the composite flame-retardant fabric at 80 ℃ for 2min, and baking the composite flame-retardant fabric at 160 ℃ for 3 min.
(5) The preparation of the pre-oxidized fiber and the composite flame-retardant fabric comprises the steps of coating polyvinylidene chloride adhesive on the surface of the composite flame-retardant fabric obtained in the step (4) by adopting a single-sided coating technology, coating the polyvinylidene chloride adhesive with the coating amount of 30 g/m 2, and bonding the pre-oxidized fiber and the composite flame-retardant fabric with the composite flame-retardant fabric obtained in the other step (4) by adopting a hot pressing method to form the pre-oxidized fiber and the composite flame-retardant fabric with the multilayer structure.
Comparative example 1
This comparative example was identical to the setup of example 1, except that in step (1), the mass ratio of polyacrylonitrile pre-oxidized fiber was replaced with 40%.
Comparative example 2
This comparative example was identical to the setup of example 1, except that in step (1), the mass ratio of polyacrylonitrile pre-oxidized fiber was replaced with 80%.
Comparative example 3
This comparative example was the same as the setup of example 1, except that the silica aerogel was not modified, and the modified silica aerogel in step (3) was replaced with an unmodified silica aerogel.
Comparative example 4
This comparative example was set up identically to example 1, except that in step (3), the preparation of the finish was as follows:
Putting 30g polycaprolactone diol (PCL) into a three-neck flask, heating and melting the PCL in a constant-temperature blast drying oven at 115 ℃, cooling the PCL after the PCL is completely melted, adding 40 g diisocyanate (the compound molar ratio of pentamethylene diisocyanate to 4,4' -dicyclohexylmethane diisocyanate is 3:7) at 50 ℃, heating the PCL to 60 ℃, reacting the PCL with 60min, adding 0.5 mL dibutyl tin dilaurate and 10g N, N-dimethylformamide, continuously reacting the PCL with 60 ℃ with 60min, then adding an N, N-dimethylformamide solution 30mL dissolved with 8g modified silica aerogel, heating the PCL to 80 ℃, reacting the PCL with 120 min at constant temperature, cooling the PCL to 50 ℃, slowly dripping deionized water 50mL containing 1g defoamer DM8317 under the condition of 1500 r/min, rapidly adding deionized water 150 mL which is not added with 1g defoamer DM8317 after oil-in-water phase inversion is completed, and continuously emulsifying the PCL with 180 to obtain the emulsifier.
Comparative example 5
This comparative example was set up identically to example 1, except that in step (3), the preparation of the finish was as follows:
Putting 30 g polycaprolactone diol (PCL) into a three-neck flask, heating and melting the PCL in a constant-temperature blast drying oven at 115 ℃, cooling the mixture after the mixture is completely melted, adding 40g diisocyanate (the compound molar ratio of pentamethylene diisocyanate to 4,4' -dicyclohexylmethane diisocyanate is 3:7) at 50 ℃, heating the mixture to 60 ℃, adding 0.5 mL dibutyl tin dilaurate and 10 g of N, N-dimethylformamide after the reaction of 60 min, continuously reacting the mixture at 60 ℃, then adding an N, N-dimethylformamide solution 30mL dissolved with 8g modified silica aerogel and 10 g tetrabromobisphenol A type epoxy resin mixture, heating the mixture to 80 ℃, carrying out constant-temperature reaction of 120 min, cooling the mixture to 50 ℃, slowly dropwise adding 50 3995 containing 1 g defoamer DM8317 under the condition of 1500 r/min, rapidly adding deionized water which is not completely added with 1 g defoamer DM8317 after the water oil-in-water phase inversion, and continuously obtaining the deionized water of 5859180.
Comparative example 6
This comparative example was set up identically to example 1, except that in step (3), the preparation of the finish was as follows:
Putting 30 g polycaprolactone diol (PCL) into a three-neck flask, heating and melting the PCL in a constant-temperature blast drying oven at 115 ℃, cooling the mixture after the PCL is completely melted, adding 40 g diisocyanate (the compound molar ratio of pentamethylene diisocyanate to 4,4' -dicyclohexylmethane diisocyanate is 3:7) at 50 ℃, heating the mixture to 60 ℃, reacting the mixture 60min, adding 0.5 mL dibutyl tin dilaurate and 10 g of N, N-dimethylformamide, continuously reacting the mixture 60min at 60 ℃, then adding N, N-dimethylformamide solution 30mL dissolved with 8g modified silica aerogel and 10 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, heating the mixture to 80 ℃, reacting the mixture 120 min at constant temperature, cooling the mixture to 50 ℃, slowly dropwise adding deionized water 50mL containing 1g defoamer DM8317 under the condition of 1500 r/min, finishing the oil-in-water phase, rapidly adding the defoamer DM8317, and continuously obtaining the emulsifier min, and carrying out the emulsion min.
Comparative example 7
Example 5 with CN118478570a is comparative example 7.
(1) Effect of polyacrylonitrile preoxidized fiber mass ratio on fabric properties
The results of the effect of the mass ratio of polyacrylonitrile pre-oxidized fibers on the tensile breaking strength and the polar oxygen index of the composite flame retardant fabric are shown in table 1.
TABLE 1 influence of the Polyacrylonitrile preoxidized fiber mass fraction on the fabric properties
。
As can be seen from Table 1, the flame retardant properties of the fabric increased with a greater mass ratio of polyacrylonitrile pre-oxidized fibers, reaching an optimum at 60%. In addition, the tensile breaking strength of the fabric gradually decreases as the mass ratio of the polyacrylonitrile pre-oxidized fibers increases. From this, the optimal mass ratio of polyacrylonitrile preoxidized fiber is 60%.
(2) Influence of silica aerogel modification on flame retardance uniformity and wash fastness
The effect of modification on the uniformity of distribution of silica aerogel in polyurethane flame retardant is shown in table 2.
TABLE 2 influence of silica aerogel modification on flame retardance uniformity and wash fastness
。
As can be seen from the data in table 2:
The heat insulation performance of the polyurethane flame retardant finishing fabric (example 1) prepared by adding the modified silica aerogel is better than that of the polyurethane flame retardant finishing fabric (comparative example 3) prepared by adding the unmodified silica aerogel, and the standard deviation is smaller, so that the flame retardant uniformity of the fabric obtained by the example is better.
Meanwhile, the fabric prepared in example 1 had a wash resistance superior to that of the fabric prepared in comparative example 3, and the limiting oxygen index decreased slightly after washing 10 times. This is because the polyurethane synthesis system is a hydrophobic environment, and a large amount of silicon hydroxyl groups (si—oh) contained on the surface of the unmodified silica aerogel are likely to aggregate by hydrogen bonding, so that the polyurethane is unevenly dispersed, and the heat insulation of the polyurethane is uneven. And the aggregated silica aerogel can increase the pores in the polyurethane adhesive film, so that the water absorption of the adhesive film is improved. In addition, the mixture modified silica aerogel of the trimethylmethoxysilane and the hydroxy polydimethylsilane can endow polyurethane with good hydrophobic property, so that the washing resistance of the composite flame-retardant fabric is improved.
(3) Synergistic effect of flame retardant finishing agent
The synergy in the flame retardant finish is mainly represented between several components of the modified silica aerogel, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative and tetrabromobisphenol a type epoxy resin, as shown in table 3.
TABLE 3 synergistic effect of flame retardants
。
As can be seen from the data in table 3, the flame retardant effect of the modified silica aerogel alone was relatively poor (comparative example 4), and the composite flame retardant effect of the modified silica aerogel and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative was superior to that of the modified silica aerogel and the tetrabromobisphenol a epoxy resin. And the flame retardant effect of example 1 is better than that of the comparative example, the modified silica aerogel, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative and the tetrabromobisphenol A epoxy resin have better synergistic flame retardant effect.
(4) Performance comparison with a bid
The performance of the composite flame retardant fabric prepared in example 1 is shown in table 4 against the product performance given in comparative example 7 (example 5 in CN 118478570A).
TABLE 4 results of performance comparisons of the application and the bid products
。
As can be seen from table 4, the fabric prepared in example 1 has comparable tensile breaking strength to that of the multilayer flame retardant fabric provided in comparative example 7, but the heat insulating property, flame retardant property and laundering resistance are significantly better than those of comparative example 7. The invention is characterized in that the silica aerogel is subjected to double modification of functionalization and hydrophobization, so that the distribution uniformity of the silica aerogel in polyurethane is improved, and meanwhile, the polyurethane flame retardant is endowed with good hydrophobicity.
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 (9)
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Citations (8)
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| CN119711183A (en) * | 2025-02-25 | 2025-03-28 | 浙江技立新材料股份有限公司 | Preparation method of waterproof flame-retardant multifunctional fabric |
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| US20110237144A1 (en) * | 2008-12-08 | 2011-09-29 | Albemarle Corporation | Phosphorus flame retardants and applications therefor |
| US20120142240A1 (en) * | 2010-12-07 | 2012-06-07 | Basf Se | Polyurethane composite material |
| CN112225865A (en) * | 2020-10-26 | 2021-01-15 | 陕西科技大学 | A kind of hydrophobic flame retardant water-based polyurethane and preparation method thereof |
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