阅读说明：本技术 一种耐高低温低voc的pvc人造革的制备方法 (Preparation method of PVC artificial leather resistant to high and low temperatures and low VOC ) 是由 顾跃进 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种耐高低温低VOC的PVC人造革的制备方法,利用海藻酸钠对阻燃剂锡酸锌进行修饰,再将石墨烯分散到海藻酸钠盐基锡酸锌中,阻燃效果均匀；还原氧化石墨烯与海藻酸钠盐基锡酸锌具有良好的协同作用,海藻酸钠充分发挥了阻燃剂锡酸锌与PVC基体之间的桥联作用；利用N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷做硅烷偶联剂对复合聚氯乙烯进行接枝与交联,海藻酸钠中氨基与偶联剂的氨基存在竞争关系,避免基体发生团聚现象,确保了链接性的同时保证了分散性；取竹纤维制备柔性碳纤维,将正硅酸乙酯与硅烷偶联的聚氯乙烯复合物置于醇/水溶液中,制备硅烷基溶胶浸渍柔性碳纤维；在氮气保护下热处理,柔性碳纤维表面覆有Si-C-O结构,提升了皮革的柔韧性。(The invention discloses a preparation method of PVC artificial leather resistant to high and low temperature and low VOC, which is characterized in that sodium alginate is used for modifying flame retardant zinc stannate, and then graphene is dispersed into sodium alginate-based zinc stannate, so that the flame retardant effect is uniform; the reduced graphene oxide and sodium alginate-based zinc stannate have good synergistic effect, and sodium alginate fully plays a bridging role between the flame retardant zinc stannate and the PVC matrix; n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane is used as a silane coupling agent to graft and crosslink the composite polyvinyl chloride, and the competition relationship between the amino in the sodium alginate and the amino of the coupling agent exists, so that the agglomeration phenomenon of a matrix is avoided, the linkage is ensured, and the dispersibility is ensured; preparing flexible carbon fibers from bamboo fibers, putting ethyl orthosilicate and silane-coupled polyvinyl chloride compound in an alcohol/water solution, and preparing silyl sol-impregnated flexible carbon fibers; and (3) performing heat treatment under the protection of nitrogen, wherein the surface of the flexible carbon fiber is covered with a Si-C-O structure, so that the flexibility of the leather is improved.)

1. A preparation method of PVC artificial leather resistant to high and low temperature and low VOC comprises the following specific steps:

the method comprises the following steps: adding the prepared flame retardant into a PVC substrate to obtain a composite polyvinyl chloride-mixture A added with the flame retardant;

step two: grafting and crosslinking the mixture A obtained in the step one by using a coupling agent to obtain a mixture B;

step three: taking a bamboo fiber textile, carrying out hydrothermal treatment and then calcining treatment to obtain flexible carbon fibers;

step four: placing the flexible carbon fiber obtained in the third step into tetraethoxysilane and the mixture B obtained in the second step into an alcohol/water solution, adding a catalyst and a dispersing agent to prepare PVC silane-based sol-impregnated flexible carbon fiber, and carrying out heat treatment on the PVC silane-based sol-impregnated flexible carbon fiber under the protection of nitrogen to obtain composite polyvinyl chloride with the flexible carbon fiber as a substrate;

step five: and (4) preparing fluorocarbon paint, and coating the fluorocarbon paint on any side of the composite polyvinyl chloride obtained in the step four to obtain the PVC artificial leather.

2. The preparation method of PVC artificial leather resistant to high and low temperature and low VOC according to claim 1, which is characterized in that: the preparation of the flame retardant comprises the following steps: adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and (3) centrifugally separating the reaction precipitate, washing the reaction precipitate for three times by using deionized water, and drying the reaction precipitate for 24 hours in a vacuum drying oven to obtain the flame retardant sodium alginate-based zinc stannate.

3. The preparation method of the PVC artificial leather resistant to high and low temperature and low VOC according to claim 2, characterized in that: the preparation of the flame retardant comprises the following steps: taking graphene, adding a small amount of deionized water, ultrasonically stirring for 1h, and adding into a reaction kettle; adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and after the reaction is finished, pouring the product into a new reaction kettle, preserving heat for 6h at 150 ℃, finally, centrifugally separating the reaction precipitate, washing the reaction precipitate with deionized water for three times, and freeze-drying the reaction precipitate for 24h to obtain a product, namely the flame retardant: sodium alginate based zinc stannate/reduced graphene oxide.

4. The preparation method of PVC artificial leather resistant to high and low temperature and low VOC according to claim 1, which is characterized in that: the coupling agent is: n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602).

5. The preparation method of PVC artificial leather resistant to high and low temperature and low VOC according to claim 4, characterized in that: the method for grafting and crosslinking the coupling agent and the composite polyvinyl chloride (PVC) added with the flame retardant comprises the following steps: adding the mixture A obtained in the step one into a mixing chamber of a high-speed mixer, operating at 2000 revolutions per minute, and adding a stabilizer when the temperature is 30 ℃; adding an auxiliary agent at 60 ℃; when the temperature rises to 90 ℃, the cross-linking agent KH-602 is added until the temperature reaches 105 ℃, thus obtaining a mixture B.

6. The preparation method of PVC artificial leather resistant to high and low temperature and low VOC according to claim 1, which is characterized in that: preparing the flexible carbon fiber: washing the bamboo fiber textile fabric with water and then washing with alcohol, drying, pre-oxidizing at 260 ℃ and preserving heat for 90min, raising the temperature to 600-plus-1100 ℃ at the rate of 5 ℃/min and preserving heat for 120min, calcining, taking out, washing with water and then washing with alcohol and drying to obtain the flexible carbon fiber.

7. The preparation method of PVC artificial leather resistant to high and low temperature and low VOC according to claim 1, which is characterized in that: the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: adding tetraethoxysilane, the mixture B and a dispersing agent into absolute ethyl alcohol and a hydrosolvent, fully stirring for a period of time at 100 ℃, adding ammonia water to ensure that the pH value is 8, stirring for 2-4h, and impregnating the flexible carbon fiber.

8. The method for preparing PVC artificial leather resistant to high and low temperature and low VOC according to claim 7, which is characterized in that: the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: hydroxyethyl cellulose was added as a dispersant in an amount of 0.6%.

9. The preparation method of PVC artificial leather resistant to high and low temperature and low VOC according to claim 1, which is characterized in that: the heat treatment method for dipping the flexible carbon fiber by the PVC silane-based sol in the fourth step comprises the following steps: after fully drying at normal pressure, carrying out pyrolysis in a high-temperature tube furnace under the protection of argon, setting the flow rate of argon Ar at 0.2ml/min, setting the initial temperature at 50 ℃, raising the temperature to 300 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 2 h.

10. The method for preparing PVC artificial leather resistant to high and low temperature and low VOC according to claim 9, which is characterized in that: the preparation of the fluorocarbon coating comprises the following steps: 75-85 parts of tetrafluoroethylene-vinyl ether copolymer fluorocarbon resin, 30-60 parts of acrylic resin, 4-6 parts of titanium dioxide, 1-5 parts of alumina, 1-2 parts of a waterproof agent and 1-3 parts of polyethylene wax, and mixing and stirring at 60-80 ℃ for 2-3 hours to obtain the fluorocarbon coating.

Technical Field

The invention relates to the technical field of leather, in particular to a preparation method of high-low temperature resistant low-VOC PVC artificial leather.

Background

The traditional inorganic flame retardant is widely applied to PVC composite materials due to the characteristics of wide sources and low price. However, due to the low flame retardant efficiency, the increased addition amount for satisfying the flame retardant requirement has a great influence on the mechanical properties of the polymer material.

The common fibers have the defects of brittleness and poor flexibility, and the common fibers are used as substrates to influence the flexibility of leather. The search for suitable substrate materials can improve the flexibility and resistance to damage of the leather.

Therefore, it is necessary to design a PVC artificial leather having excellent mechanical properties and high flexibility, which is resistant to high and low temperatures and low VOCs.

Disclosure of Invention

The invention aims to provide a preparation method of PVC artificial leather resistant to high and low temperature and low VOC, so as to solve the problems in the background technology.

In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of PVC artificial leather resistant to high and low temperature and low VOC comprises the following specific steps:

the method comprises the following steps: adding the prepared flame retardant into a PVC substrate to obtain a composite polyvinyl chloride-mixture A added with the flame retardant;

step two: grafting and crosslinking the mixture A obtained in the step one by using a coupling agent to obtain a mixture B;

step three: taking a bamboo fiber textile, carrying out hydrothermal treatment and then calcining treatment to obtain flexible carbon fibers;

step four: placing the flexible carbon fiber obtained in the third step into tetraethoxysilane and the mixture B obtained in the second step into an alcohol/water solution, adding a catalyst and a dispersing agent to prepare PVC silane-based sol-impregnated flexible carbon fiber, and carrying out heat treatment on the PVC silane-based sol-impregnated flexible carbon fiber under the protection of nitrogen to obtain composite polyvinyl chloride with the flexible carbon fiber as a substrate;

step five: and C, preparing fluorocarbon paint, and coating one side of the composite polyvinyl chloride obtained in the step four to obtain the PVC artificial leather.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; centrifuging the reaction precipitate, washing with deionized water for three times, and drying in vacuum drying oven 24h, obtaining the flame retardant of sodium alginate-based zinc stannate.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: taking graphene, adding a small amount of deionized water, ultrasonically stirring for 1h, and adding into a reaction kettle; adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and after the reaction is finished, pouring the product into a new reaction kettle, preserving heat for 6h at 150 ℃, finally, centrifugally separating the reaction precipitate, washing the reaction precipitate with deionized water for three times, and freeze-drying the reaction precipitate for 24h to obtain a product, namely the flame retardant: sodium alginate based zinc stannate/reduced graphene oxide.

According to the above technical scheme, the coupling agent is: n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602).

According to the technical scheme, the method for grafting and crosslinking the coupling agent and the composite polyvinyl chloride (PVC) added with the flame retardant comprises the following steps: adding the mixture A obtained in the step one into a mixing chamber of a high-speed mixer, operating at 2000 revolutions per minute, and adding a stabilizer when the temperature is 30 ℃; adding an auxiliary agent at 60 ℃; when the temperature rises to 90 ℃, the cross-linking agent KH-602 is added until the temperature reaches 105 ℃, thus obtaining a mixture B.

According to the technical scheme, the preparation of the flexible carbon fiber comprises the following steps: washing the bamboo fiber textile fabric with water and then washing with alcohol, drying, pre-oxidizing at 260 ℃ and preserving heat for 90min, raising the temperature to 600-plus-1100 ℃ at the rate of 5 ℃/min and preserving heat for 120min, calcining, taking out, washing with water and then washing with alcohol and drying to obtain the flexible carbon fiber.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: adding tetraethoxysilane, the mixture B and a dispersing agent into absolute ethyl alcohol and a hydrosolvent, fully stirring for a period of time at 100 ℃, adding ammonia water to ensure that the pH value is 8, stirring for 2-4h, and impregnating the flexible carbon fiber.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: hydroxyethyl cellulose was added as a dispersant in an amount of 0.6%.

According to the technical scheme, the heat treatment method for dipping the flexible carbon fiber by the PVC silane-based sol in the fourth step comprises the following steps: after fully drying at normal pressure, carrying out pyrolysis in a high-temperature tube furnace under the protection of argon, setting the flow rate of argon Ar at 0.2ml/min, setting the initial temperature at 50 ℃, raising the temperature to 300 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 2 h.

According to the technical scheme, the preparation of the fluorocarbon coating comprises the following steps: 75-85 parts of tetrafluoroethylene-vinyl ether copolymer fluorocarbon resin, 30-60 parts of acrylic resin, 4-6 parts of titanium dioxide, 1-5 parts of alumina, 1-2 parts of a waterproof agent and 1-3 parts of polyethylene wax, and mixing and stirring at 60-80 ℃ for 2-3 hours to obtain the fluorocarbon coating.

Compared with the prior art, the invention has the following beneficial effects: in the invention, the raw materials are mixed,

(1) sodium alginate is used for modifying the flame retardant zinc stannate to prepare the sodium alginate-based zinc stannate flame retardant, the sodium alginate is used as an aminopolysaccharide containing a polyhydroxy structure and contains rich active functional groups, and then graphene is dispersed into the sodium alginate-based zinc stannate to prepare the sodium alginate-based zinc stannate/reduced graphene oxide hybrid material, and the flame retardant sodium alginate-based zinc stannate can be uniformly dispersed in a matrix, so that the reduced graphene oxide can be uniformly dispersed in the matrix, the agglomeration phenomenon can not occur, and the flame retardant effect is uniform; the reduced graphene oxide and sodium alginate-based zinc stannate have good synergistic effect, so that the flame retardant and smoke suppression performance of the PVC composite material is effectively improved, and the toughness of PVC is improved; sodium alginate fully plays a bridging role between the flame retardant zinc stannate and the PVC matrix, strengthens acting force between the flame retardant and the PVC matrix, and enhances the compatibility of the flame retardant and the PVC matrix; the oxygen-containing carbon ring of the sodium alginate can be used as a carbon forming agent, and has a certain improvement effect on the flame retardant property of the high polymer material; in addition, the toughness of the PVC composite material is further improved by reducing the graphene oxide;

(2) n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602) is used as a silane coupling agent to graft and crosslink the flame retardant-added composite polyvinyl chloride (PVC), so that not only can the terminal amino group on the chain be grafted, but also the imino group in the chain can be subjected to graft reaction with the unstable chlorine position on the PVC chain, thereby improving the grafting rate; the competition relationship between the amino group in the sodium alginate and the amino group of the coupling agent is realized, the agglomeration phenomenon of the composite polyvinyl chloride is avoided, the chaining property is ensured, and the dispersibility is ensured; the addition of the silane coupling agent also enhances the thermal stability of the polyvinyl chloride;

(3) taking bamboo fiber, and heating at high temperature to prepare flexible carbon fiber; putting a polyvinyl chloride compound with coupled tetraethoxysilane and silane into an alcohol/water solution, carrying out hydrolytic polymerization condensation reaction under the catalysis of hydrochloric acid and ammonia water, adding hydroxyethyl cellulose serving as a dispersing agent, and preparing silyl sol impregnated flexible carbon fibers; carrying out heat treatment under the protection of nitrogen, wherein the surface of the flexible carbon fiber is coated with a Si-C-O structure, the distribution is uniform, the fibers are partially bonded with each other, the lap joint bonding combination is good, and the fibers which are arranged in parallel and bonded are tightly bonded together; the treatment enables polyvinyl chloride and the flexible carbon fiber substrate to be well combined together, improves the flexibility of leather, and enhances the oxidation resistance of the surface of the flexible carbon fiber by the Si-C-O structure.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides the technical scheme that: a preparation method of PVC artificial leather resistant to high and low temperature and low VOC comprises the following specific steps:

the method comprises the following steps: adding the prepared flame retardant into a PVC substrate to obtain a composite polyvinyl chloride-mixture A added with the flame retardant;

step two: grafting and crosslinking the mixture A obtained in the step one by using a coupling agent to obtain a mixture B;

step three: taking a bamboo fiber textile, carrying out hydrothermal treatment and then calcining treatment to obtain flexible carbon fibers;

step four: placing the flexible carbon fiber obtained in the third step into tetraethoxysilane and the mixture B obtained in the second step into an alcohol/water solution, adding a catalyst and a dispersing agent to prepare PVC silane-based sol-impregnated flexible carbon fiber, and carrying out heat treatment on the PVC silane-based sol-impregnated flexible carbon fiber under the protection of nitrogen to obtain composite polyvinyl chloride with the flexible carbon fiber as a substrate;

step five: and C, preparing fluorocarbon paint, and coating one side of the composite polyvinyl chloride obtained in the step four to obtain the PVC artificial leather.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and (3) centrifugally separating the reaction precipitate, washing the reaction precipitate for three times by using deionized water, and drying the reaction precipitate for 24 hours in a vacuum drying oven to obtain the flame retardant sodium alginate-based zinc stannate.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: taking graphene, adding a small amount of deionized water, ultrasonically stirring for 1h, and adding into a reaction kettle; adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and after the reaction is finished, pouring the product into a new reaction kettle, preserving heat for 6h at 150 ℃, finally, centrifugally separating the reaction precipitate, washing the reaction precipitate with deionized water for three times, and freeze-drying the reaction precipitate for 24h to obtain a product, namely the flame retardant: sodium alginate based zinc stannate/reduced graphene oxide.

According to the above technical scheme, the coupling agent is: n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602).

According to the technical scheme, the method for grafting and crosslinking the coupling agent and the composite polyvinyl chloride (PVC) added with the flame retardant comprises the following steps: adding the mixture A obtained in the step one into a mixing chamber of a high-speed mixer, operating at 2000 revolutions per minute, and adding a stabilizer when the temperature is 30 ℃; adding an auxiliary agent at 60 ℃; when the temperature rises to 90 ℃, the cross-linking agent KH-602 is added until the temperature reaches 105 ℃, thus obtaining a mixture B.

According to the technical scheme, the preparation of the flexible carbon fiber comprises the following steps: washing the bamboo fiber textile fabric with water and then washing with alcohol, drying, pre-oxidizing at 260 ℃ and preserving heat for 90min, raising the temperature to 600-plus-1100 ℃ at the rate of 5 ℃/min and preserving heat for 120min, calcining, taking out, washing with water and then washing with alcohol and drying to obtain the flexible carbon fiber.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: adding tetraethoxysilane, the mixture B and a dispersing agent into absolute ethyl alcohol and a hydrosolvent, fully stirring for a period of time at 100 ℃, adding ammonia water to ensure that the pH value is 8, stirring for 2-4h, and impregnating the flexible carbon fiber.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: hydroxyethyl cellulose was added as a dispersant in an amount of 0.6%.

According to the technical scheme, the heat treatment method for dipping the flexible carbon fiber by the PVC silane-based sol in the fourth step comprises the following steps: after fully drying at normal pressure, carrying out pyrolysis in a high-temperature tube furnace under the protection of argon, setting the flow rate of argon Ar at 0.2ml/min, setting the initial temperature at 50 ℃, raising the temperature to 300 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 2 h.

According to the technical scheme, the preparation of the fluorocarbon coating comprises the following steps: 75-85 parts of tetrafluoroethylene-vinyl ether copolymer fluorocarbon resin, 30-60 parts of acrylic resin, 4-6 parts of titanium dioxide, 1-5 parts of alumina, 1-2 parts of a waterproof agent and 1-3 parts of polyethylene wax, and mixing and stirring at 60-80 ℃ for 2-3 hours to obtain the fluorocarbon coating.

Example 1

A preparation method of PVC artificial leather resistant to high and low temperature and low VOC comprises the following specific steps:

the method comprises the following steps: adding the prepared flame retardant into a PVC substrate to obtain a composite polyvinyl chloride-mixture A added with the flame retardant;

step two: grafting and crosslinking the mixture A obtained in the step one by using a coupling agent to obtain a mixture B;

step three: taking a bamboo fiber textile, carrying out hydrothermal treatment and then calcining treatment to obtain flexible carbon fibers;

step four: placing the flexible carbon fiber obtained in the third step into tetraethoxysilane and the mixture B obtained in the second step into an alcohol/water solution, adding a catalyst and a dispersing agent to prepare PVC silane-based sol-impregnated flexible carbon fiber, and carrying out heat treatment on the PVC silane-based sol-impregnated flexible carbon fiber under the protection of nitrogen to obtain composite polyvinyl chloride with the flexible carbon fiber as a substrate;

step five: and C, preparing fluorocarbon paint, and coating one side of the composite polyvinyl chloride obtained in the step four to obtain the PVC artificial leather.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and (3) centrifugally separating the reaction precipitate, washing the reaction precipitate for three times by using deionized water, and drying the reaction precipitate for 24 hours in a vacuum drying oven to obtain the flame retardant sodium alginate-based zinc stannate.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: taking graphene, adding a small amount of deionized water, ultrasonically stirring for 1h, and adding into a reaction kettle; adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; pouring the product into a new reaction kettle after the reaction is finished, preserving heat for 6 hours at 150 ℃, finally centrifugally separating the reaction precipitate, washing with deionized water for three times,and (5) freeze-drying for 24 hours to obtain a product, namely a flame retardant: sodium alginate based zinc stannate/reduced graphene oxide.

According to the above technical scheme, the coupling agent is: n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602).

According to the technical scheme, the method for grafting and crosslinking the coupling agent and the composite polyvinyl chloride (PVC) added with the flame retardant comprises the following steps: adding the mixture A obtained in the step one into a mixing chamber of a high-speed mixer, operating at 2000 revolutions per minute, and adding a stabilizer when the temperature is 30 ℃; adding an auxiliary agent at 60 ℃; when the temperature rises to 90 ℃, the cross-linking agent KH-602 is added until the temperature reaches 105 ℃, thus obtaining a mixture B.

According to the technical scheme, the preparation of the flexible carbon fiber comprises the following steps: washing the bamboo fiber textile fabric with water, then washing with alcohol, drying, pre-oxidizing at 260 ℃ and preserving heat for 90min, then raising the temperature to 700 ℃ at the rate of 5 ℃/min and preserving heat for 120min, calcining, taking out, washing with water, then washing with alcohol, and drying to obtain the flexible carbon fiber.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: adding tetraethoxysilane, the mixture B and a dispersing agent into absolute ethyl alcohol and a water solvent, fully stirring for a period of time at 100 ℃, adding ammonia water to enable the pH value to be 8, stirring for 3 hours, and dipping the flexible carbon fibers.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: hydroxyethyl cellulose was added as a dispersant in an amount of 0.6%.

According to the technical scheme, the heat treatment method for dipping the flexible carbon fiber by the PVC silane-based sol in the fourth step comprises the following steps: after fully drying at normal pressure, carrying out pyrolysis in a high-temperature tube furnace under the protection of argon, setting the flow rate of argon Ar at 0.2ml/min, setting the initial temperature at 50 ℃, raising the temperature to 300 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 2 h.

According to the technical scheme, the preparation of the fluorocarbon coating comprises the following steps: 75 parts of tetrafluoroethylene-vinyl ether copolymer fluorocarbon resin, 40 parts of acrylic resin, 4 parts of titanium dioxide, 2 parts of alumina, 1 part of waterproof agent and 2 parts of polyethylene wax, and mixing and stirring for 2 hours at the temperature of 60-80 ℃ to obtain the fluorocarbon coating.

Example 2

A preparation method of PVC artificial leather resistant to high and low temperature and low VOC comprises the following specific steps:

the method comprises the following steps: adding the prepared flame retardant into a PVC substrate to obtain a composite polyvinyl chloride-mixture A added with the flame retardant;

step two: grafting and crosslinking the mixture A obtained in the step one by using a coupling agent to obtain a mixture B;

step three: taking a bamboo fiber textile, carrying out hydrothermal treatment and then calcining treatment to obtain flexible carbon fibers;

step four: placing the flexible carbon fiber obtained in the third step into tetraethoxysilane and the mixture B obtained in the second step into an alcohol/water solution, adding a catalyst and a dispersing agent to prepare PVC silane-based sol-impregnated flexible carbon fiber, and carrying out heat treatment on the PVC silane-based sol-impregnated flexible carbon fiber under the protection of nitrogen to obtain composite polyvinyl chloride with the flexible carbon fiber as a substrate;

step five: and C, preparing fluorocarbon paint, and coating one side of the composite polyvinyl chloride obtained in the step four to obtain the PVC artificial leather.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂Stirring O and deionized water until the O and the deionized water are dissolved, and marking as a solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and (3) centrifugally separating the reaction precipitate, washing the reaction precipitate for three times by using deionized water, and drying the reaction precipitate for 24 hours in a vacuum drying oven to obtain the flame retardant sodium alginate-based zinc stannate.

According to the technical scheme, the preparation of the flame retardant comprises the following steps: taking graphene, adding a small amount of deionized water, ultrasonically stirring for 1h, and adding into a reaction kettle; adding Na into a reaction kettle₂SnO₃·3H₂Stirring the O and the deionized water until the O and the deionized water are completely dissolved, and marking as a solution A; adding sodium alginate and Zn (CH) into another container₃COO)₂·2H₂O and deionized water, stirring until dissolved, recordingIs solution B; dripping the two solutions into a reflux device within half an hour, stirring, keeping the temperature at 80 ℃ for condensation reflux, and reacting for 3 hours; and after the reaction is finished, pouring the product into a new reaction kettle, preserving heat for 6h at 150 ℃, finally, centrifugally separating the reaction precipitate, washing the reaction precipitate with deionized water for three times, and freeze-drying the reaction precipitate for 24h to obtain a product, namely the flame retardant: sodium alginate based zinc stannate/reduced graphene oxide.

According to the above technical scheme, the coupling agent is: n-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602).

According to the technical scheme, the method for grafting and crosslinking the coupling agent and the composite polyvinyl chloride (PVC) added with the flame retardant comprises the following steps: adding the mixture A obtained in the step one into a mixing chamber of a high-speed mixer, operating at 2000 revolutions per minute, and adding a stabilizer when the temperature is 30 ℃; adding an auxiliary agent at 60 ℃; when the temperature rises to 90 ℃, the cross-linking agent KH-602 is added until the temperature reaches 105 ℃, thus obtaining a mixture B.

According to the technical scheme, the preparation of the flexible carbon fiber comprises the following steps: washing the bamboo fiber textile fabric with water, then washing with alcohol, drying, pre-oxidizing at 260 ℃ and preserving heat for 90min, then raising the temperature to 800 ℃ at the rate of 5 ℃/min and preserving heat for 120min, calcining, taking out, washing with water, then washing with alcohol, and drying to obtain the flexible carbon fiber.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: adding tetraethoxysilane, the mixture B and a dispersing agent into absolute ethyl alcohol and a water solvent, fully stirring for a period of time at 100 ℃, adding ammonia water to enable the pH value to be 8, stirring for 4 hours, and dipping the flexible carbon fibers.

According to the technical scheme, the method for impregnating the flexible carbon fiber by the PVC silane-based sol comprises the following steps: hydroxyethyl cellulose was added as a dispersant in an amount of 0.6%.

According to the technical scheme, the heat treatment method for dipping the flexible carbon fiber by the PVC silane-based sol in the fourth step comprises the following steps: after fully drying at normal pressure, carrying out pyrolysis in a high-temperature tube furnace under the protection of argon, setting the flow rate of argon Ar at 0.2ml/min, setting the initial temperature at 50 ℃, raising the temperature to 300 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 30min, and then raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 2 h.

According to the technical scheme, the preparation of the fluorocarbon coating comprises the following steps: 85 parts of tetrafluoroethylene-vinyl ether copolymer fluorocarbon resin, 50 parts of acrylic resin, 6 parts of titanium dioxide, 4 parts of alumina, 2 parts of waterproof agent and 2 parts of polyethylene wax, and mixing and stirring at 80 ℃ for 3 hours to obtain the fluorocarbon coating.

In order to verify the practical effect of the invention, the following tests are specially carried out for verification:

experiment 1 utilizes the effect of sodium alginate on zinc stannate on its flame retardancy

Taking PVC resin, dividing into three groups, adding no flame retardant into No. 1, adding zinc stannate into No. 2, adding sodium alginate-based zinc stannate with the same mass as No. 2 into No. 3, and measuring the combustion temperature of three groups of samples when the OI value is 20.9 according to GB/T2406.1-2008, wherein the results are shown in Table 1:

sample (I)	Temperature of combustion
		Control group No. 1	89℃
Number 2	158℃
		No. 3	173℃

TABLE 1 measurement of the burning temperature at 20.9 OI value

As can be seen from Table 1, the sodium alginate-based zinc stannate as a flame retardant has a better flame retardant performance than pure zinc stannate.

Experiment 2 mechanical Properties of leather Material of the present invention

2.1 tensile Property test: the test was carried out using ISO527-2 (1996) standard. The sample size was 100X 70X 1mm3 and the drawing speed was 200 mm/min. Each spline was tested in parallel 5 times and averaged.

2.2 impact strength test: the sample is frozen under the condition of-30 for 3h, and then the impact resistance of the sample is tested by notch impact on a pendulum clock impact tester. The sample size was 49.2X 4.1X 5.8mm 3.

Sample (I)	Elongation in exercise (%)	Tensile Strength (MPa)	Impact Strength (kJ/m)2）
				PVC	452	24.1	1.72
The invention is finished product	364	17.5	2.83

TABLE 2 mechanical property test data of PVC and PVC composite leather material

As can be seen from Table 2, the mechanical properties of the PVC leather material of the invention are greatly improved.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.