Fast-heating long cilia strip and preparation method thereof

Abstract

The invention relates to the technical field of wool top production processes, and particularly discloses a fast-heating long cilium wool top and a preparation method thereof. The fast-heating long cilia strip is prepared from the following raw materials in parts by weight: 65 to 75 parts of PET (Polyethylene Terephthalate), 5 to 8 parts of modified hyperbranched polyester, 7 to 10 parts of graphene nanoplatelets, 5 to 8 parts of epoxy modified aerogel and 0.5 to 1 part of auxiliaries, and the modified hyperbranched polyester is prepared from the following raw materials: hydroxyl-terminated hyperbranched polyester, 3-aminopropyltriethoxysilane and methoxypolyethylene glycol. The quick-heating long cilia strip can quickly heat when being irradiated by sunlight or contacted with skin, has a continuous heat preservation effect, is softer and more comfortable compared with traditional synthetic heating fibers, cannot be stuffy while preserving heat, and realizes balance of heat preservation and ventilation.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of top production processes, in particular to a quick-heating long-fiber top and a preparation method thereof. BACKGROUND

[0002] With the improvement of people's living standards and the upgrading of consumer demand, the functionalization and comfort of textiles have become the core trend of industry development. In the fields of winter clothing, outdoor equipment and home supplies, textile materials with rapid heating and high-efficiency thermal insulation functions gradually become the research focus and market trend in the textile field because they can actively cope with cold environments and improve human comfort.

[0003] At present, the common thermal insulation materials on the market mainly include natural fibers (such as wool and cashmere) and synthetic fibers (such as acrylic and polyester). Wool and cashmere are widely used due to their natural thermal insulation performance, but their heat absorption and release process is slow, the heating speed is significantly insufficient, the price is relatively high, and the thermal insulation performance in a wet and cold environment will also decrease. Conventional synthetic fibers often increase the thickness of the material or use special spinning processes to manufacture hollow fibers to improve the static heat retention capacity, but this inevitably leads to an increase in the weight of the textile and a decrease in the air permeability, sacrificing the lightness and comfort of the textile.

[0004] In view of the related technologies in the above, the inventors found that, in order to endow the fiber with the ability of active heating or rapid heat conduction, the existing technology began to try to mix phase change, conductive or heat-conductive materials such as carbon fibers, metal fibers or metal powders into synthetic fibers. Although this method improves the electrothermal or heat-conductive performance of the material to some extent, it often cannot balance the thermal insulation performance and comfort, and in addition, the mixing of phase change, conductive or heat-conductive materials not only increases the cost, but also affects the softness and air permeability of the fabric. SUMMARY

[0005] In order to improve the rapid heating and thermal insulation performance of the fiber material and improve the air permeability and comfort of the fiber material, the application provides a quick-heating long-fiber top and a preparation method thereof.

[0006] In a first aspect, the application provides a quick-heating long-fiber top, which adopts the following technical solution: A quick-heating long-fiber top, the raw materials including 65-75 parts of PET, 5-8 parts of modified hyperbranched polyester, 7-10 parts of amino-graphene microsheet, 5-8 parts of epoxy-modified aerogel and 0.5-1 part of auxiliary agent, the raw materials of the modified hyperbranched polyester including hydroxyl-terminated hyperbranched polyester, amino-silane coupling agent and polyethylene glycol monomethyl ether.

[0007] By adopting the technical scheme, the amino graphene microsheet is used as the heat conduction component, the epoxy modified aerogel is used as the heat preservation component, the modified hyperbranched polyester is added in the PET matrix as the interface bridging agent, the residual hydroxyl groups in the modified hyperbranched polyester prepared by the hydroxyl-terminated hyperbranched polyester can undergo ring-opening reaction with the amino groups on the surface of the amino graphene microsheet and the epoxy groups in the epoxy modified aerogel in the subsequent high-temperature melting process, and stable cross-linking action is formed among the three, so that the heat conduction material and the heat preservation material are uniformly dispersed in the PET matrix, a perfect heat conduction and heat insulation network is constructed, and when the finished fiber is subjected to external heat sources such as sunlight and human body heat, the finished fiber can be uniformly and rapidly heated, so that rapid heating and persistent heat preservation are realized.

[0008] The modified hyperbranched polyester has a spherical structure, which can not only synergize with the layered graphene structure, block the overlapping and aggregation of graphene microsheets caused by the close proximity of graphene microsheets, and enhance the dispersion uniformity of graphene sheets, but also reduce the aggregation between graphene and aerogel, and enhance the continuous and smooth continuity of the three-dimensional heat conduction network path in the long fiber flock. Further, the addition of the modified hyperbranched polyester enhances the air permeability of the long fiber flock, because the three-dimensional spherical structure of the hyperbranched polyester disrupts the regular arrangement of the crystallization process of PET molecules, which may slightly reduce the crystallinity of the fiber and increase the amorphous region, and the packing of the amorphous region molecular chain is relatively loose, which provides more free volume and channels for the transmission of water vapor molecules, significantly improves the air permeability of the long fiber flock fabric, significantly improves the stuffiness problem of traditional thermal materials, and realizes thermal insulation while being more breathable and dry, and the comfort is significantly improved.

[0009] Optionally, the preparation method of the modified hyperbranched polyester comprises the following steps: The hydroxyl-terminated hyperbranched polyester is dissolved in an organic solvent, and after heating, amino silane coupling agent is added dropwise, after dropping, p-toluenesulfonic acid is added, and reflux reaction is carried out, and after vacuum distillation, the amino-modified hyperbranched polyester is obtained; The amino-modified hyperbranched polyester is dissolved in an organic solvent, and polyethylene glycol monomethyl ether and triethylamine are added under ice water bath condition, and then a mixed solution of EDC and NHS is added dropwise, and after uniform stirring, the ice bath is removed, and the stirring reaction is continued, and then the reaction product is purified by post-treatment, and the modified hyperbranched polyester is obtained.

[0010] By adopting the above technical solution, the terminal hydroxyl hyperbranched polyester is first modified with an aminosilane coupling agent, providing highly active amine target sites, which effectively improves the compatibility with graphene microsheets and aerogel, resulting in stronger interfacial bonding. Graphene microsheets and aerogel can be more uniformly dispersed in the hyperbranched polyester system, ensuring the rapid heating and uniform warmth retention of the long fiber sliver. Furthermore, the introduction of hydrophilic polyethylene glycol monomethyl ether long chains into the hyperbranched polyester not only enhances the softness of the fiber but also forms denser and more continuous hydrophilic microchannels inside and on the surface of the fiber. This significantly improves the fiber's adsorption and guided transport of water vapor, while further enhancing the fiber's breathability. In synergy with the aerogel, the long fiber sliver achieves rapid heating and warmth retention while maintaining excellent breathability and moisture wicking, resulting in greater comfort.

[0011] Optionally, the molar ratio of the hydroxyl-terminated hyperbranched polyester, the aminosilane coupling agent, and the polyethylene glycol monomethyl ether is 1:(1.2-1.3):(1.3-1.4).

[0012] Optionally, the polyethylene glycol monomethyl ether has a molecular weight of 1000-2000.

[0013] By adopting the above technical solution, if the molecular weight is too small, the hydrophilic chain is too short, resulting in poor air permeability and moisture removal. If the molecular weight is too large, the compatibility with PET is even worse, and the molecular chains are prone to entanglement, making it difficult to form microchannels in the matrix. This will affect the stability of the spinning melt flow and make phase separation more likely.

[0014] Optionally, the epoxy-modified aerogel is an epoxy-modified cellulose-silica composite aerogel.

[0015] Optionally, the preparation method of the epoxy-modified cellulose-silica composite aerogel includes the following steps: Nanocellulose is dispersed in water, and after ultrasonic treatment and standing, a cellulose hydrogel is formed. A silicon source solution was obtained by pre-hydrolyzing a mixture of tetraethyl orthosilicate and ethanol. Ammonia and ethanol were added to the cellulose hydrogel, and then the silicon source solution was added dropwise under stirring. After standing, a cellulose-silica composite wet gel was obtained. The composite wet gel is impregnated in an epoxy modifier solution, heated in a water bath, and then subjected to solvent replacement and drying to obtain the final product.

[0016] Optionally, the epoxy modifier solution is a 5-8% (w / w) solution of 3-glycidyl etheroxypropyltrimethoxysilane.

[0017] By adopting the technical scheme, the nano-porous structure of the aerogel can effectively trap air and inhibit convective heat transfer and solid heat conduction, has an extremely low thermal conductivity, and has excellent warmth-keeping effect. Further, the epoxy groups are introduced into the aerogel, which can simultaneously undergo ring-opening polymerization reaction with the amino groups / hydroxyl groups of the modified hyperbranched polyester and the amino groups of the aminated graphene, realize multi-point chemical crosslinking, effectively improve the poor bonding force of the aerogel and the matrix, and form a continuous heat barrier and heat preservation network in the long-fiber fluff, so that the heat rapidly transferred by the graphene can be effectively locked in the fiber, realizing persistent heat preservation after rapid heating.

[0018] In addition, the cellulose and silica composite aerogel adopted in the present application provides more three-dimensional open porous structure, ensures air permeability, and the silica nanoparticles are uniformly dispersed in the cellulose matrix, which can further reduce the thermal conductivity and enhance the mechanical strength of the aerogel, avoid collapse during processing, and the composite aerogel has stronger bonding force with the matrix and better processing performance.

[0019] In a second aspect, the present application provides a preparation method of a fast-heating long-fiber fluff, which adopts the following technical scheme: A preparation method of a fast-heating long-fiber fluff, comprising the following steps: According to the formula, the raw materials are weighed, part of the PET, the modified hyperbranched polyester, the aminated graphene microsheet and the epoxy-modified aerogel are uniformly mixed, the additives are added and uniformly mixed to obtain a mixture, and the mixture is melt-blended, extruded and granulated to obtain a master batch; After the remaining PET is mixed with the master batch, melt spinning, cooling, oiling, drawing, heat setting, crimping, cutting and carding are performed to obtain a sliver.

[0020] By adopting the above technical scheme, the aminated graphene microsheet, the epoxy-modified aerogel, the modified hyperbranched polyester and a small amount of PET are pre-composited and granulated to ensure that the nano-filler is preliminarily and uniformly dispersed in the master batch, and then the master batch is mixed with the remaining PET chips for melt spinning, which helps to improve the hyperdispersion of graphene and aerogel in the final long-fiber fluff, effectively prevents the agglomeration of fillers, greatly reduces the hole blockage of the spinneret and the breakage rate caused by too much filler during direct blending spinning, and the spinnability and spinning stability are stronger. Further, in the spinning process, the hydroxyl groups in the modified hyperbranched polyester and the amino groups of the aminated graphene microsheet and the epoxy groups in the epoxy-modified aerogel further undergo ring-opening reaction to form a stable crosslinked network, the interface bonding is more firm, and the finished long-fiber fluff can have excellent fast-heating performance and excellent mechanical properties.

[0021] In summary, the present application has the following beneficial effects: 1、Due to the application adopts amino graphene microsheet as the heat conducting component, epoxy modified aerogel as the heat preservation component, and modified hyperbranched polyester containing end groups and amino groups as the interface bridging agent in the PET matrix, the modified hyperbranched polyester can undergo ring-opening reaction with the amino groups on the surface of the amino graphene microsheet and the epoxy groups in the epoxy modified aerogel during the subsequent high-temperature melting process, and the three are connected by stable cross-linking action, realizing the uniform dispersion of the heat conducting material and the heat preservation material in the PET matrix, and constructing a perfect heat conducting and heat insulation network, when the finished product fiber is affected by external heat sources such as sunlight and human body heat, it can uniformly and rapidly heat up, realizing rapid heating and long-lasting heating.

[0022] 2、In the application, amino silane coupling agent and polyethylene glycol monomethyl ether modified hyperbranched polyester are preferably used, which significantly improves the air permeability and moisture removal of the long fiber sliver. On the one hand, the three-dimensional spherical structure of the hyperbranched polyester disrupts the regular arrangement of PET molecules during crystallization, resulting in an increase in the amorphous region inside the fiber. The packing of the amorphous region molecular chain is more loose, providing more free volume and channels for the transmission of water vapor molecules, significantly improving the air permeability of synthetic fiber fabric. On the other hand, the hydrophilic polyethylene glycol monomethyl ether long chain not only improves the softness of the synthetic fiber, but also forms more dense and continuous hydrophilic microchannels inside and on the surface of the fiber, improving the adsorption and guided transport of water vapor, and working together with the aerogel to realize fast heating and warmth of the long fiber sliver while having excellent air permeability and moisture removal, making it more comfortable.

[0023] 3、The method of the application, by pre-complexing and granulating the amino graphene microsheet, epoxy modified aerogel and modified hyperbranched polyester with a small amount of PET, ensures that the nanofiller is initially and uniformly dispersed in the masterbatch. After mixing the masterbatch with the remaining PET chips and melting and spinning, it helps to improve the superdispersion of graphene and aerogel in the final long fiber sliver, prevent filler agglomeration and overlap, greatly reduce the nozzle blockage and breakage rate caused by excessive filler during direct blending spinning, and improve the spinnability and spinning stability. DETAILED DESCRIPTION

[0024] The application will be further described in detail below in combination with examples and comparative examples.

[0025] Raw materials The raw materials used in the examples and comparative examples of the application are commercially available, specifically: PET chips are selected from Hengshui Jizhou Qinghua Plastic Factory, with a product number of PET-QH and a brand name of Qh-pet; The amino graphene microsheet is APTMS grafted graphene microsheet, with a grafting amount of APTMS of 4.6%, a particle size of 1-10 μm, and a thickness of 5-10 nm; Hydroxyl-terminated hyperbranched polyester, selected from Wuhan Hyperbranched Resin Technology Co., Ltd., H201; 3-aminopropyl triethoxysilane, kH-550, selected from Shandong Shuntai New Material Co., Ltd.; Polyethylene glycol monomethyl ether, mPEG-750, mPEG-1000, mPEG-1500, mPEG-2000 and mPEG-3000 are selected from Haian Petroleum Chemical Factory in Jiangsu Province; Nanocellulose CNF, selected from Wuhan Lanna Bai Medicine Chemical Co., Ltd., width 10-50 nm, length 0.5-3 μm; 3-glycidyloxypropyl trimethoxysilane, kH-560, selected from Shandong Shuntai New Material Co., Ltd.; Antioxidant 1010, selected from Dongguan Shanyi Plastic Co., Ltd.; Oxidized polyethylene wax, selected from Dongguan Shanyi Plastic Co., Ltd., OPE816.

[0026] Preparation examples 1.1-1.6 of modified hyperbranched polyester Preparation example 1.1 Modified hyperbranched polyester, its preparation method, comprising the following steps: S1: Under the condition of nitrogen protection, 1 mol of hydroxyl-terminated hyperbranched polyester is dissolved in anhydrous toluene according to the ratio of 1:10, heated to 80℃, 1.2 mol of 3-aminopropyl triethoxysilane is added at a rate of 1.5 mL / min, after dropping, p-toluenesulfonic acid is added, the amount of p-toluenesulfonic acid is 0.5% of the total mass of hydroxyl-terminated hyperbranched polyester and 3-aminopropyl triethoxysilane, refluxed for 10 h, the solvent and excess 3-aminopropyl triethoxysilane are removed by vacuum distillation, then the product is precipitated with excess anhydrous ether for 3 times, filtered, vacuum dried to obtain amino-modified hyperbranched polyester; S2: Under the condition of nitrogen protection, the amino-modified hyperbranched polyester obtained in step S1 is dissolved in anhydrous DMF according to the ratio of 1:10, 1.3 mol of mPEG-2000 and 1.2 equivalents of triethylamine of mPEG-2000 are added under ice water bath condition, the DMF solution of EDC·HCl and NHS equal to the molar of triethylamine is added dropwise, after stirring uniformly, the ice bath is removed, and the reaction is stirred at room temperature for 16 h, then the reaction product is precipitated in excess anhydrous cold ether for 3 times, after dialysis to remove salt impurities, vacuum drying is carried out.

[0027] Preparation example 1.2 Modified hyperbranched polyester, its preparation method, comprising the following steps: S1: Under nitrogen protection, 1 mol of terminal hydroxyl hyperbranched polyester was dissolved in anhydrous toluene at a feed-to-liquid ratio of 1:10. The mixture was heated to 90°C, and 1.3 mol of 3-aminopropyltriethoxysilane was added dropwise at a rate of 1.5 mL / min. After the addition was complete, p-toluenesulfonic acid was added. The amount of p-toluenesulfonic acid was 0.5% of the total mass of the terminal hydroxyl hyperbranched polyester and 3-aminopropyltriethoxysilane. The mixture was refluxed for 6 h. The solvent and excess 3-aminopropyltriethoxysilane were removed by vacuum distillation. The product was then precipitated three times with excess anhydrous diethyl ether, filtered, and vacuum dried to obtain amino-modified hyperbranched polyester. S2: Under nitrogen protection, the amino-modified hyperbranched polyester obtained in step S1 was dissolved in anhydrous DMF at a material-to-liquid ratio of 1:10. 1.4 mol of mPEG-1500 and 1.2 equivalents of triethylamine of mPEG-1500 were added under ice-water bath conditions. An equimolar amount of DMF solution of EDC·HCl and NHS was added dropwise. After stirring evenly, the ice bath was removed, and the reaction was stirred at room temperature for 16 h. The reaction product was then poured into excess anhydrous cold diethyl ether to precipitate three times. After dialysis to remove salt impurities, the product was dried under vacuum to obtain the final product.

[0028] Preparation Example 1.3 The modified hyperbranched polyester is prepared by means of the following steps: S1: Under nitrogen protection, 1 mol of terminal hydroxyl hyperbranched polyester was dissolved in anhydrous toluene at a feed-to-liquid ratio of 1:10. The mixture was heated to 85°C, and 1.2 mol of 3-aminopropyltriethoxysilane was added dropwise at a rate of 1.5 mL / min. After the addition was complete, p-toluenesulfonic acid was added. The amount of p-toluenesulfonic acid was 0.5% of the total mass of the terminal hydroxyl hyperbranched polyester and 3-aminopropyltriethoxysilane. The mixture was refluxed for 8 h. The solvent and excess 3-aminopropyltriethoxysilane were removed by vacuum distillation. The product was then precipitated three times with excess anhydrous diethyl ether, filtered, and vacuum dried to obtain amino-modified hyperbranched polyester. S2: Under nitrogen protection, the amino-modified hyperbranched polyester obtained in step S1 was dissolved in anhydrous DMF at a material-to-liquid ratio of 1:10. 1.4 mol of mPEG-1000 and 1.2 equivalents of triethylamine of mPEG-1000 were added under ice-water bath conditions. An equimolar amount of DMF solution of EDC·HCl and NHS was added dropwise. After stirring evenly, the ice bath was removed, and the reaction was stirred at room temperature for 16 h. The reaction product was then poured into excess anhydrous cold diethyl ether to precipitate three times. After dialysis to remove salt impurities, the product was dried under vacuum to obtain the final product.

[0029] Preparation Example 1.4 The modified hyperbranched polyester differs from that in Preparation Example 1.1 only in that the mPEG used in step S2 has a molecular weight of 750.

[0030] Preparation Example 1.5 Modified hyperbranched polyester, the difference from Preparation Example 1.1 is only that the molecular weight of mPEG used in step S2 is 3000.

[0031] Preparation Example 1.6 Modified hyperbranched polyester, the difference from Preparation Example 1.1 is only that the mPEG modification in step S2 is not carried out, and the amino-modified hyperbranched polyester obtained in step S1 is the product modified hyperbranched polyester.

[0032] Preparation Examples 2.1-2.6 of epoxy-modified aerogel Preparation Example 2.1 Preparation method of epoxy-modified cellulose-silica composite aerogel, comprising the following steps: S1: 2.5 g of nanocellulose is dispersed in 100 mL of water, and after 15 min of ultrasonic crushing treatment at 500 W, it is stirred at 800 r / min for 40 min, and then it is left to stand at room temperature for 14 h to form a cellulose hydrogel; S2: 10 mL of tetraethyl orthosilicate and 25 mL of anhydrous ethanol are mixed, 3.2 mL of water is added, 0.5 mol / L hydrochloric acid is added dropwise to adjust the pH to 4±0.1, and magnetic stirring is carried out for 30 min to obtain a silica source solution; S3: 3 mL of 1 mol / L ammonia water and 50 mL of 50 wt% ethanol aqueous solution are added to the cellulose hydrogel obtained in step S1, and then the silica source solution obtained in step S2 is added dropwise under stirring, after dropping, continue to stir for 30 min, and stand for 20 h to obtain a cellulose-silica composite wet gel; S4: 3-glycidyloxypropyltrimethoxysilane is added to anhydrous ethanol, and 5% of a modifier solution is prepared by adding ammonia water dropwise to adjust the pH to 8.5±0.1, the cellulose-silica composite wet gel is immersed in the modifier solution, heated in a 50°C water bath for 10 h, and after standing, a composite gel is obtained; S5: The composite gel is immersed in anhydrous ethanol for 8 h, the ethanol is replaced every 2 h to replace the unreacted modifier solution inside the gel, then it is soaked with tert-butyl alcohol for secondary replacement, and then it is freeze-dried, ground and sieved to obtain the product.

[0033] Preparation Example 2.2 Epoxy-modified cellulose-silica composite aerogel, the difference from Preparation Example 2.1 is only that the concentration of the modifier solution in step S4 is 7%.

[0034] Preparation Example 2.3 Epoxy-modified cellulose-silica composite aerogel, the difference from Preparation Example 2.1 is only that the concentration of the modifier solution in step S4 is 8%.

[0035] Preparation Example 2.4 An epoxy-modified cellulose aerogel, a method for preparing the same, comprising the following steps: S1: dispersing 2.5 g of nanocellulose in 100 mL of water, performing 15 min of ultrasonic crushing at 500 W, then stirring at 800 r / min for 40 min, and standing at room temperature for 14 h to form a cellulose hydrogel; S2: adding 3-glycidyloxypropyltrimethoxysilane into anhydrous ethanol, adjusting the pH to 8.5±0.1 by adding ammonia water dropwise, preparing a 5% modifier solution, immersing the cellulose hydrogel in the modifier solution, heating in a 50°C water bath for 10 h, and obtaining a wet gel after standing; S3: immersing the wet gel in anhydrous ethanol for 8 h, replacing the ethanol every 2 h to replace the unreacted modifier solution inside the gel, then immersing in tert-butyl alcohol for secondary replacement, and then performing freeze-drying, grinding, and sieving to obtain the product.

[0036] Preparation Example 2.5 An epoxy-modified silica aerogel, a method for preparing the same, comprising the following steps: S1: mixing 10 mL of tetraethyl orthosilicate, 25 mL of anhydrous ethanol, and 3.2 mL of water, stirring uniformly, adjusting the pH to 4±0.1 by adding 0.5 mol / L hydrochloric acid dropwise, performing pre-hydrolysis by magnetic stirring for 30 min to obtain a precursor solution, adjusting the pH to 7.5±0.1 by adding 1 mol / L ammonia water, stirring uniformly, standing for 10 h, and then adding 50 mL of 50 wt% ethanol aqueous solution to stand for 16 h to obtain a silica wet gel; S2: adding 3-glycidyloxypropyltrimethoxysilane into anhydrous ethanol, adjusting the pH to 8.5±0.1 by adding ammonia water dropwise, preparing a 5% modifier solution, immersing the silica wet gel in the modifier solution, heating in a 50°C water bath for 10 h, and obtaining a wet gel after standing; S3: immersing the wet gel in anhydrous ethanol for 8 h, replacing the ethanol every 2 h to replace the unreacted modifier solution inside the gel, then immersing in tert-butyl alcohol for secondary replacement, and then performing freeze-drying, grinding, and sieving to obtain the product.

[0037] Preparation Example 2.6 A cellulose-silica composite aerogel, which is different from Preparation Example 2.1 only in that no epoxy modification is performed in S4. Example

[0038] Example 1 A fast heating long-fiber top, according to parts by weight, the raw materials include 65 parts of PET chips, 5 parts of modified hyperbranched polyester prepared in preparation example 1.1, 7 parts of amino graphene microsheet, 5 parts of epoxy modified cellulose-silica composite aerogel prepared in preparation example 2.1, 0.4 parts of antioxidant 1010 and 0.6 parts of oxidized polyethylene wax; The preparation method of the above fast heating long-fiber top, comprising the following steps: S1: according to the formula, the raw materials are weighed, 1 / 3 of the PET chips, the modified hyperbranched polyester, the amino graphene microsheet and the epoxy modified cellulose-silica composite aerogel are mixed uniformly, the antioxidant 1010 and the oxidized polyethylene wax are added and continue to mix uniformly to obtain a mixture, and the mixture is added into a twin-screw extruder for melt blending, extrusion and granulation at 250 DEG C to obtain a master batch; S2: the remaining PET chips are mixed with the master batch, and then melt spinning at 260 DEG C, oiling after bundling, drawing, heat setting, crimping, cutting and carding into a top.

[0039] Example 2 A fast heating long-fiber top, according to parts by weight, the raw materials include 72 parts of PET chips, 7.1 parts of modified hyperbranched polyester prepared in preparation example 1.2, 8.4 parts of amino graphene microsheet, 6.5 parts of epoxy modified cellulose-silica composite aerogel prepared in preparation example 2.2, 0.4 parts of antioxidant 1010 and 0.6 parts of oxidized polyethylene wax; The preparation method of the above fast heating long-fiber top, comprising the following steps: S1: according to the formula, the raw materials are weighed, 1 / 3 of the PET chips, the modified hyperbranched polyester, the amino graphene microsheet and the epoxy modified cellulose-silica composite aerogel are mixed uniformly, the antioxidant 1010 and the oxidized polyethylene wax are added and continue to mix uniformly to obtain a mixture, and the mixture is added into a twin-screw extruder for melt blending, extrusion and granulation at 250 DEG C to obtain a master batch; S2: the remaining PET chips are mixed with the master batch, and then melt spinning at 260 DEG C, oiling after bundling, drawing, heat setting, crimping, cutting and carding into a top.

[0040] Example 3 A fast heating long-fiber top, according to parts by weight, the raw materials include 75 parts of PET chips, 8 parts of modified hyperbranched polyester prepared in preparation example 1.3, 10 parts of amino graphene microsheet, 8 parts of epoxy modified cellulose-silica composite aerogel prepared in preparation example 2.3, 0.4 parts of antioxidant 1010 and 0.6 parts of oxidized polyethylene wax; The preparation method of the above fast heating long-fiber top, comprising the following steps: S1: according to the formula, the raw materials are weighed, 1 / 3 of the PET chips, modified hyperbranched polyester, amino graphene microsheet and epoxy modified cellulose-silica composite aerogel are uniformly mixed, antioxidant 1010 and oxidized polyethylene wax are added and uniformly mixed to obtain a mixture, and the mixture is added to a twin-screw extruder for melt blending, extrusion and granulation at 255°C to obtain a masterbatch; S2: the remaining PET chips are mixed with the masterbatch, and then melt spun at 280°C, oiled after bundling, drawn, heat set, crimped, cut and carded into slivers.

[0041] Example 4 A fast heating long fiber sliver, which is only different from example 1 in that the modified hyperbranched polyester in the raw materials is obtained by preparation example 1.4.

[0042] Example 5 A fast heating long fiber sliver, which is only different from example 1 in that the modified hyperbranched polyester in the raw materials is obtained by preparation example 1.5.

[0043] Example 6 A fast heating long fiber sliver, which is only different from example 1 in that the epoxy modified cellulose-silica composite aerogel in the raw materials is replaced by equal mass of epoxy modified cellulose aerogel prepared by preparation example 2.4.

[0044] Example 7 A fast heating long fiber sliver, which is only different from example 1 in that the epoxy modified cellulose-silica composite aerogel in the raw materials is replaced by equal mass of epoxy modified silica aerogel prepared by preparation example 2.5.

[0045] Comparative example Comparative example 1 A fast heating long fiber sliver, which is only different from example 1 in that the modified hyperbranched polyester in the raw materials is obtained by preparation example 1.6.

[0046] Comparative example 2 A fast heating long fiber sliver, which is only different from example 1 in that no modified hyperbranched polyester is added, and the modified hyperbranched polyester in the raw materials is replaced by equal mass of PET chips.

[0047] Comparative example 3 A fast heating long fiber sliver, which is only different from example 1 in that the epoxy modified cellulose-silica composite aerogel in the raw materials is replaced by equal mass of cellulose-silica composite aerogel prepared by preparation example 2.6.

[0048] Comparative example 4 A fast heating long-fiber hair strip, which is only different from example 1 in that no epoxy-modified aerogel is added, and the epoxy-modified aerogel in the raw material is replaced with an equal amount of PET chip.

[0049] Performance detection test After the fast heating long-fiber hair strips prepared from examples 1-7 and comparative examples 1-4 are respectively woven into cloth, the following relevant performance detection tests are carried out.

[0050] According to the relevant provisions of GB / T 30127-2013, the far infrared emissivity and far infrared irradiation temperature rise are detected; According to the relevant provisions of GB / T 11048-2018, the heat retention rate is calculated and detected; According to the relevant provisions of GB / T 5453-1997, the air permeability test is carried out by an air permeability tester.

[0051] Table 1 According to the performance detection results of examples 1-3 in table 1, it can be seen that the fabric made of the fast heating long-fiber hair strip of the application has a far infrared emissivity of ≥90%, a far infrared irradiation temperature rise of ≥3℃, and a heat retention rate of ≥50%, which shows that the long-fiber hair strip of the application can quickly generate heat and has the ability of persistent heat retention, and at the same time, the fabric prepared from the long-fiber hair strip of the application has excellent air permeability, solves the stuffy feeling caused by the traditional fast heating synthetic fiber during heat retention, realizes heat retention while being more breathable, and has higher comfort.

[0052] According to the performance detection tests of examples 1 and 4-5, it can be seen that when the molecular weight of polyethylene glycol monomethyl ether in the modified hyperbranched polyester of the raw material is 1000-2000, not only can dense and continuous hydrophilic microchannels be formed in the fiber interior and surface to improve the air permeability of the fabric, but also can assist in improving the dispersity of graphene and aerogel in the PET matrix to build a continuous heat conduction and heat retention network, thereby improving the rapid heat generation and heat retention performance of the fiber.

[0053] If the molecular weight of the hydrophilic chain is too low, the air permeation channel will be reduced, the air permeability will be reduced, and the dispersion of graphene will be affected, resulting in a decrease in the rapid heat generation capacity of the fiber; if the molecular weight is too high, the air permeability of the fiber will decrease, which may be because the entanglement of the molecular chain reduces the air permeation channel, and also adversely affects the dispersion of graphene microsheets, reducing the rapid heat generation capacity of the fiber.

[0054] It can be seen from Comparative Example 1 that the rapid heat generation and air permeability of the fiber are both significantly reduced because the effective hydrophilic microchannels cannot be built inside the fiber, and the dispersibility of graphene is also significantly affected, without introducing polyethylene glycol monomethyl ether long chains in the hyperbranched polyester; it can be seen from Comparative Example 2 that the rapid heat generation and air permeability of the fiber are both significantly reduced, which also proves that the modified hyperbranched polyester can act as an interfacial bridging agent to undergo ring-opening reaction with the amino groups on the surface of the aminated graphene microsheets and the epoxy groups in the epoxy-modified aerogel during the subsequent high-temperature melting process, and the three are stably cross-linked between them, realizing the uniform dispersion of the thermal conductive material and the thermal insulation material in the PET matrix, building a perfect thermal conduction and insulation network, so that the finished fiber can be uniformly and rapidly heated when affected by external heat sources such as sunlight and human body heat, realizing rapid heating and long-lasting heating, and the air permeability and moisture-wicking property of the long fiber top can be significantly improved.

[0055] It can be seen from the performance detection test of Examples 1 and 6-7 that the cellulose and silica composite aerogel has a more significant effect on improving the warmth and air permeability of the fiber than the single cellulose or single silica aerogel in the scheme of the present application. The lack of silica in Example 6 reduces the thermal conductivity, and the warmth retention rate decreases significantly. The lack of the three-dimensional porous structure of cellulose in Example 7 reduces the air permeability.

[0056] It can be seen from Comparative Example 3 that the dispersibility and interfacial bonding between the hyperbranched polyester, graphene microsheets and aerogel and the matrix are poor, and the raw materials are aggregated, the thermal conduction and thermal insulation network is discontinuous, the heat generation and warmth retention performance is reduced, and the effect of the modified hyperbranched polyester and the aerogel on improving the air permeability is significantly inhibited, without epoxy modification of the composite aerogel; it can be seen from Comparative Example 4 that the warmth retention performance of the fiber is significantly reduced, without adding epoxy-modified aerogel.

[0057] The specific embodiments are merely an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, and the modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A fast-heating long fiber sliver, characterized in that, By weight, the raw materials include 65-75 parts PET, 5-8 parts modified hyperbranched polyester, 7-10 parts aminated graphene microsheets, 5-8 parts epoxy modified aerogel, and 0.5-1 parts additives. The raw materials for the modified hyperbranched polyester include hydroxyl-terminated hyperbranched polyester, aminosilane coupling agent, and polyethylene glycol monomethyl ether.

2. The fast-heating long fiber sliver according to claim 1, characterized in that, The method for preparing the modified hyperbranched polyester includes the following steps: Hydroxyl-terminated hyperbranched polyester was dissolved in an organic solvent, heated, and then aminosilane coupling agent was added dropwise. After the addition was complete, p-toluenesulfonic acid was added, the mixture was refluxed, and then distilled under reduced pressure to obtain amino-modified hyperbranched polyester. Amino-modified hyperbranched polyester was dissolved in an organic solvent, and polyethylene glycol monomethyl ether and triethylamine were added under ice-water bath conditions. Then, a mixed solution of EDC and NHS was added dropwise. After stirring evenly, the ice bath was removed, and the reaction was continued with stirring. The reaction product was then purified by post-treatment to obtain the final product.

3. The fast-heating long fiber sliver according to claim 2, characterized in that, The molar ratio of the hydroxyl-terminated hyperbranched polyester, the aminosilane coupling agent, and the polyethylene glycol monomethyl ether is 1:(1.2-1.3):(1.3-1.4).

4. The fast-heating long fiber sliver according to claim 2, characterized in that, The molecular weight of the polyethylene glycol monomethyl ether is 1000-2000.

5. The fast-heating long fiber sliver according to claim 1, characterized in that, The epoxy-modified aerogel is an epoxy-modified cellulose-silica composite aerogel.

6. The fast-heating long fiber sliver according to claim 5, characterized in that, The preparation method of the epoxy-modified cellulose-silica composite aerogel includes the following steps: Nanocellulose is dispersed in water, and after ultrasonic treatment and standing, a cellulose hydrogel is formed. A silicon source solution was obtained by pre-hydrolyzing a mixture of tetraethyl orthosilicate and ethanol. Ammonia and ethanol were added to the cellulose hydrogel, and then the silicon source solution was added dropwise under stirring. After standing, a cellulose-silica composite wet gel was obtained. The composite wet gel is impregnated in an epoxy modifier solution, heated in a water bath, and then subjected to solvent replacement and drying to obtain the final product.

7. The fast-heating long fiber sliver according to claim 6, characterized in that, The epoxy modifier solution is a 5-8% (w / w) solution of 3-glycidyl etheroxypropyltrimethoxysilane.

8. The method for preparing the fast-heating long fiber sliver according to any one of claims 1-7, characterized in that, Includes the following steps: Weigh the raw materials according to the formula, mix a portion of PET, modified hyperbranched polyester, aminated graphene microsheets and epoxy modified aerogel evenly, add the additives and continue to mix evenly to obtain a mixture, and then melt-blend and extrude granulate the mixture to obtain masterbatch. The remaining PET is mixed with the masterbatch and then melt-spun, cooled, bundled and oiled, stretched, heat-set, crimped, cut and combed into strips to obtain the final product.

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