Preparation method of high-elasticity and high-strength spandex fiber fabric

Abstract

The application relates to the technical field of spandex fibers, and discloses a preparation method of high-elasticity high-strength spandex fiber fabric, in which modified graphene flame retardant is used to blend and electrostatically spin polyurethane to obtain spandex fibers, and through processes such as twisting, warping and weaving, the high-elasticity high-strength spandex fiber fabric is obtained. The polymer flame retardant grafted with graphene contains a urea group structure, can form electrostatic interaction with a urethane structure in the polyurethane, makes the graphene and the spandex fiber form an electrostatic crosslinking network, strengthens the interface interaction between the graphene and the spandex fiber, and thus the breaking strength and the breaking elongation of the spandex fiber are improved, and the fiber has better strength and elasticity.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of spandex fibers, in particular to a preparation method of high-elasticity high-strength spandex fiber fabric. BACKGROUND

[0002] Spandex fibers have high elasticity and resilience and are excellent synthetic fibers, and are widely applied in the fields of textiles, clothing and the like, in order to meet the actual application of spandex fibers in functional fibers and fabrics, the elasticity, strength and the like of the spandex fibers need to be improved. Graphene is a carbon nanomaterial, has the advantages of good heat resistance and high strength, and has a wide application prospect in flame retardants, refractory materials, thermal insulation materials and the like. In the document "Preparation and Performance Research of Biomass Graphene Modified Spandex Fiber", the biomass graphene modified spandex fiber prepared by means of dry spinning has good far infrared function and antibacterial performance, and can replace traditional spandex filaments, but the problems of flammability and low strength of the spandex fibers are not solved. The application aims to prepare a modified graphene flame retardant to improve the flame retardance and strength of the spandex fibers and fabric. SUMMARY

[0003] The technical problem solved by the application is that a modified graphene flame retardant is prepared, and the problems of poor flame retardance and low strength of the spandex fibers and fabric are solved.

[0004] The technical scheme provided by the application is as follows:

[0005] A preparation method of high-elasticity high-strength spandex fiber fabric, comprising the following steps: polyurethane is added into N,N-dimethylacetamide, stirring to prepare a spinning solution, then a modified graphene flame retardant is added, ultrasonic oscillation is carried out, then the spinning solution is subjected to electrostatic spinning, the spinning voltage is 16-20 kV, the spinning speed is 1-2.5 mL / h, and the receiving distance is 12-20 cm, so that spandex fibers are obtained; the spandex fibers are subjected to twisting, warping, sizing and weaving, so that the high-elasticity high-strength spandex fiber fabric is obtained.

[0006] Further, the mass fraction of the polyurethane in the spinning solution is 12-18%.

[0007] Further, the mass of the modified graphene flame retardant is 1-8% of the mass of the polyurethane.

[0008] Further, the preparation method of the modified graphene flame retardant comprises the following steps: amino-modified graphene is added into N,N-dimethylacetamide, ultrasonic oscillation is carried out, diphenylmethane-4,4'-diisocyanate and bisamino benzimidazole phosphate are added, stirring is carried out at a temperature of 70-110 DEG C for 6-12 h, cooling is carried out, filtration is carried out, water and ethanol are sequentially washed, and drying is carried out, so that the modified graphene flame retardant is obtained.

[0009] Further, the mass ratio of the amino-modified graphene, which is sequentially modified by diphenylmethane-4,4'-diisocyanate and bisaminobenzimidazole phosphate, to the polyurethane is (80-200)%, (180-400)%, respectively.

[0010] Further, the method for preparing the bisaminobenzimidazole phosphate comprises the following steps:

[0011] S11: adding 2,2-bis(bromomethyl)-1,3-propanediol, 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide with a structural formula of and triethylamine into dichloromethane, and reacting at room temperature for 12-24 h, concentrating, washing with n-hexane, drying, and obtaining 2,2-bis(bromomethyl)-1,3-phosphonate intermediate. The reaction formula is as follows:

[0012]

[0013] S12: adding 6-nitrobenzimidazole and tetrabutylammonium bromide (TBAB) into a sodium hydroxide solution, adding the 2,2-bis(bromomethyl)-1,3-phosphonate intermediate, stirring and reacting at room temperature for 6-12 h, adding chloroform, standing and separating the organic layer, concentrating, adding the product into water, adding reduced iron powder and ammonium chloride, and reacting at a temperature of 70-85 °C for 3-8 h, cooling, adding ethyl acetate, collecting the filtrate after filtration, standing and separating the organic layer, concentrating, recrystallizing the product with ethanol, and obtaining bisaminobenzimidazole phosphate. The reaction formula is as follows:

[0014]

[0015] Further, the mass ratio of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide and triethylamine in S11 to 2,2-bis(bromomethyl)-1,3-propanediol is (140-190)% and (75-90)%, respectively.

[0016] Further, the mass ratio of 6-nitrobenzimidazole and tetrabutylammonium bromide in S12 to 2,2-bis(bromomethyl)-1,3-phosphonate intermediate is (120-180)% and (9-14)%, respectively.

[0017] The application has the technical effect that: 2,2-bis(bromomethyl)-1,3-propanediol, 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide, 6-nitrobenzimidazole and the like are used as raw materials to prepare a novel bisaminobenzimidazole phosphate, which contains bisamino and can react with diphenylmethane-4,4'-diisocyanate on the surface of amino-modified graphene to realize graft polymerization in situ, so that the polymer flame retardant containing a benzimidazole phosphate structure is grafted to the surface of graphene to obtain modified graphene flame retardant.

[0018] The modified graphene flame retardant is blended with polyurethane, electrospun to obtain spandex fibers, and then subjected to twisting, warping, weaving and the like to obtain high-elasticity and high-strength spandex fabric. The urea structure in the polymer flame retardant can form electrostatic interaction with the urethane structure in the polyurethane to form an electrostatic crosslinking network between the graphene and the spandex fibers, thereby enhancing the interface interaction between the graphene and the spandex fibers and improving the breaking strength and elongation at break of the spandex fibers, so that the fibers have better strength and elasticity.

[0019] The application grafts the polymer flame retardant containing a benzimidazole phosphate structure to the surface of graphene, and the nitrogen-phosphorus-graphene synergistic flame-retardant effect, so that the grafted polymer flame retardant can promote the dehydration of the spandex fabric into carbon during combustion, form a continuous and stable carbon layer with the graphene, hinder the conduction of heat to the inside of the fabric, and inhibit the conduction of oxygen, thereby achieving excellent flame-retardant effect. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0021] Main raw materials: amino-modified graphene: thickness 0.6-1.2 nm; sheet diameter 0.5-5 um; amino content 4 wt%; Suzhou Kaifa New Material.

[0022] Polyurethane: effective ingredient content 100%; Dongguan Jiuru Plastic Raw Material.

[0023] 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide; purity 97%; CAS No. 4090-55-5; Anjie Chemical.

[0024] 6-nitrobenzimidazole: purity 98%; CAS No. 94-52-0; Anjie Chemical.

[0025] 2,2-dibromomethyl-1,3-propanediol; CAS No. 3296-90-0; purity: 98%

[0026] Example 1

[0027] (1) 0.2 g of 2,2-dibromomethyl-1,3-propanediol, 0.35 g of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane-2-oxide, and 0.17 g of triethylamine were added to dichloromethane, and reacted at room temperature for 24 h, concentrated, washed with n-hexane, and dried to obtain a 2,2-bis(bromomethyl)-1,3-phosphonate intermediate.

[0028] (2) 0.7 g of 6-nitrobenzimidazole, 0.052 g of tetrabutylammonium bromide were added to a 26% by mass sodium hydroxide solution, and 0.5 g of the 2,2-bis(bromomethyl)-1,3-phosphonate intermediate was added, and reacted with stirring at room temperature for 6 h, chloroform was added, and after standing and separation of the organic layer, the product was concentrated, and the product was added to water, and iron powder and ammonium chloride were added, and reacted at 85°C for 6 h, cooled, and ethyl acetate was added, and after filtration, the filtrate was collected, and after standing and separation of the organic layer, the product was concentrated, and recrystallized from ethanol to obtain a bisamino benzimidazole phosphonate.

[0029] (3) 0.1 g of an amino-modified graphene was added to N,N-dimethylacetamide, and ultrasonically agitated, and 0.08-0.2 g of diphenylmethane-4,4'-diisocyanate, and 0.18-0.4 g of the bisamino benzimidazole phosphonate were added, and reacted with stirring at 100°C for 8 h, cooled, filtered, washed with water and ethanol, and dried to obtain a modified graphene flame retardant.

[0030] (4) A polyurethane was added to N,N-dimethylacetamide, and stirred to prepare a 14% by mass spinning solution, and then 1-8% by mass of the modified graphene flame retardant based on the mass of the polyurethane was added, and ultrasonically agitated, and then the spinning solution was electrospun at a voltage of 18 kV at a rate of 1.5 mL / h at a receiving distance of 15 cm to obtain a spandex fiber; the spandex fiber was twisted, beamed, sized, and woven to obtain a high-elasticity high-strength spandex fabric.

[0031] Example 2

[0032] The difference from Example 1 is that in step (3), the mass of the diphenylmethane-4,4'-diisocyanate is 0.12 g, and the mass of the bisamino benzimidazole phosphonate is 0.25 g.

[0033] Example 3

[0034] The difference from Example 1 is that the mass of the diphenylmethane-4,4'-diisocyanate in step (3) is 0.16 g, and the bisaminobenzimidazole phosphate is 0.32 g.

[0035] Example 4

[0036] The difference from Example 1 is that the mass of the diphenylmethane-4,4'-diisocyanate in step (3) is 0.12 g, and the bisaminobenzimidazole phosphate is 0.4 g.

[0037] Example 5

[0038] The difference from Example 1 is that the mass of the modified graphene flame retardant in step (4) is 3% of the mass of the polyurethane.

[0039] Example 6

[0040] The difference from Example 1 is that the mass of the modified graphene flame retardant in step (4) is 5% of the mass of the polyurethane.

[0041] Example 7

[0042] The difference from Example 1 is that the mass of the modified graphene flame retardant in step (4) is 8% of the mass of the polyurethane.

[0043] Comparative Example 1

[0044] The difference from Example 1 is that the modified graphene flame retardant in step (4) is replaced by amino-modified graphene.

[0045] Comparative Example 2

[0046] The difference from Example 1 is that no amino-modified graphene is added in step (3).

[0047] 0.08 g of diphenylmethane-4,4'-diisocyanate and 0.18 g of bisaminobenzimidazole phosphate are added to N,N-dimethylacetamide, stirred at a temperature of 100°C for 8 h, cooled, filtered, washed with water and ethanol in sequence, and dried to obtain a polymer flame retardant.

[0048] The polyurethane is added to N,N-dimethylacetamide to prepare a spinning solution with a mass fraction of 14%, then 1% of the mass of the polyurethane is added to the polymer flame retardant, ultrasonic oscillation is performed, and then the spinning solution is electrospun at a spinning voltage of 18 kV, a spinning speed of 1.5 mL / h, and a receiving distance of 15 cm to obtain a spandex fiber; the spandex fiber is twisted, beamed, sized, and woven to obtain a spandex fabric.

[0049] The flame retardant performance of the spandex fabric is tested by an oxygen index tester, and the test results are as follows:

[0050] Limiting oxygen index (%) of spandex fabric Execution standard GB / T 5454-1997 Example 1 26.2 Example 2 27.3 Example 3 28.1 Example 4 28.7 Comparative Example 1 24.3 Comparative Example 2 26.0

[0051] With the mass of diphenylmethane-4,4'-diisocyanate and the mass of bisaminobenzimidazole phosphate gradually increasing in Examples 1-4, the polymer flame retardant grafted on the surface of graphene is also more and more, and the limiting oxygen index is also more and more, the polymer flame retardant forms a synergistic flame-retardant effect with graphene, and the flame retardancy of spandex fiber fabric is obviously improved.

[0052] Comparative Example 1 uses amino-modified graphene instead of modified graphene flame retardant, graphene does not graft polymer flame retardant, and the flame-retardant effect on spandex fiber is not obvious.

[0053] Comparative Example 2 uses a polymer flame retardant instead of a modified graphene flame retardant, and there is no synergistic flame-retardant effect with graphene, and the limiting oxygen index is slightly lower than that of Example 1.

[0054] The flame-retardant performance of spandex fiber fabric is tested by an oxygen index tester, and the mechanical properties of spandex fiber are tested by an electronic single fiber strength tester.

[0055] The test results are as follows:

[0056]

[0057] With the mass of modified graphene flame retardant gradually increasing, the limiting oxygen index of spandex fiber fabric is more and more large, and when the mass is 8% of the mass of polyurethane, the limiting oxygen index of spandex fiber fabric is maximum, which is 29.8%.

[0058] However, with the mass of modified graphene flame retardant gradually increasing, the breaking strength of spandex fiber increases and then decreases, and when the mass is 3% of the mass of polyurethane, the tearing strength is maximum, which is 1.95 cN / dtex. When the mass is 1% of the mass of polyurethane, the breaking elongation is maximum, which is 531.0%.

[0059] The above is only a typical example of the present application, in addition to this, the present application can have other various specific embodiments, and any technical solution formed by equivalent replacement or equivalent transformation falls within the scope of the present application.

Claims

1. A method for producing a high-elasticity high-strength spandex fabric, characterized by, The method comprises the following steps: The polyurethane is added into N,N-dimethylacetamide, stirred to prepare a spinning solution, then the modified graphene flame retardant is added and ultrasonically vibrated, and then the spinning solution is electrospun to obtain spandex fibers, wherein the spinning voltage is 16-20 kV, the spinning speed is 1-2.5 mL / h, and the receiving distance is 12-20 cm; the spandex fibers are twisted, warped, sized and woven to obtain high-elasticity and high-strength spandex fabric. The preparation method of the modified graphene flame retardant comprises the following steps: the amino-modified graphene is added into N,N-dimethylacetamide and ultrasonically vibrated, then diphenylmethane-4,4'-diisocyanate and bisaminobenzimidazole phosphate are added, and the mixture is stirred and reacted at a temperature of 70-110 DEG C for 6-12 h, then the mixture is cooled, filtered, washed with water and ethanol in sequence, and dried to obtain the modified graphene flame retardant. The bisaminobenzimidazole phosphate has a structural formula of ; The mass of the diphenylmethane-4,4'-diisocyanate and bisaminobenzimidazole phosphate is (80-200)% and (180-400)% of the mass of the amino-modified graphene in sequence. The preparation method of the bisaminobenzimidazole phosphate comprises the following steps: S11: 2,2-dibromomethyl-1,3-propanediol, 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide and triethylamine are added into dichloromethane, and the mixture is reacted at room temperature for 12-24 h, concentrated, washed with n-hexane, and dried to obtain a 2,2-bis(bromomethyl)-1,3-phosphate intermediate; S12: 6-nitrobenzimidazole and tetrabutylammonium bromide are added into a sodium hydroxide solution, and then the 2,2-bis(bromomethyl)-1,3-phosphate intermediate is added, and the mixture is stirred and reacted at room temperature for 6-12 h, then chloroform is added, the mixture is allowed to stand and separated into an organic layer, the organic layer is separated, concentrated, and the product is washed with n-hexane, and then the product is added into water, iron powder and ammonium chloride are added, and the mixture is reacted at a temperature of 70-85 DEG C for 3-8 h, then the mixture is cooled, ethyl acetate is added, the mixture is filtered to collect a filtrate, the mixture is allowed to stand and separated into an organic layer, the organic layer is separated, concentrated, and the product is recrystallized with ethanol to obtain bisaminobenzimidazole phosphate.

2. The method for preparing high-elasticity, high-strength spandex fiber fabric according to claim 1, characterized in that, The mass fraction of the polyurethane in the spinning solution is 12-18%.

3. The method for preparing high-elasticity, high-strength spandex fiber fabric according to claim 1, characterized in that, The mass of the modified graphene flame retardant is 1-8% of the mass of the polyurethane.

4. The method for preparing high-elasticity, high-strength spandex fiber fabric according to claim 1, characterized in that, In S11, the mass of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide and triethylamine is (140-190)% and (75-90)% of the mass of 2,2-dibromomethyl-1,3-propanediol in sequence.

5. The method for preparing high-elasticity, high-strength spandex fiber fabric according to claim 1, characterized in that, In S12, the mass of 6-nitrobenzimidazole and tetrabutylammonium bromide is (120-180)% and (9-14)% of the mass of the 2,2-bis(bromomethyl)-1,3-phosphate intermediate in sequence.

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