阅读说明：本技术 一种低气味高强度耐久型pvc人造革及其制备方法 (Low-odor high-strength durable PVC artificial leather and preparation method thereof ) 是由 顾跃进 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种低气味高强度耐久型PVC人造革及其制备方法,涉及人造装饰材料技术领域技术领域。本发明先将聚氯乙烯用氢氧化钠出来后,在引发剂作用下与马来酸酐反应,制得改性聚氯乙烯,然后,将硝酸铝、硝酸镧溶于水中并加入正硅酸乙酯,于碱性条件下搅拌反应后,制得改性水滑石,将改性水滑石用氢氧化钠进行羟基化后在四氯化锡的作用下与氧化环氧大豆油接枝,制得改性增塑剂,最后,将改性聚氯乙烯与混合交联剂混合,并加入改性聚氯乙烯,搅拌混合后,充模成型,得低气味高强度耐久型PVC人造革。本发明制备的低气味高强度耐久型PVC人造革气体释放量较少,且力学性能优异。(The invention discloses low-odor high-strength durable PVC artificial leather and a preparation method thereof, and relates to the technical field of artificial decorative materials. The method comprises the steps of firstly taking out polyvinyl chloride with sodium hydroxide, reacting with maleic anhydride under the action of an initiator to prepare modified polyvinyl chloride, then dissolving aluminum nitrate and lanthanum nitrate in water, adding tetraethoxysilane, stirring and reacting under an alkaline condition to prepare modified hydrotalcite, hydroxylating the modified hydrotalcite with sodium hydroxide, grafting with epoxy soybean oil under the action of stannic chloride to prepare a modified plasticizer, finally mixing the modified polyvinyl chloride with a mixed crosslinking agent, adding the modified polyvinyl chloride, stirring and mixing, and filling a mold for molding to obtain the low-odor high-strength durable PVC artificial leather. The low-odor high-strength durable PVC artificial leather prepared by the invention has less gas release amount and excellent mechanical property.)

1. The low-odor high-strength durable PVC artificial leather is characterized by mainly comprising the following raw material components in parts by weight: 70-85 parts of modified polyvinyl chloride, 20-40 parts of modified plasticizer and 0-2 parts of mixed crosslinking agent.

2. The low-odor high-strength durable PVC artificial leather according to claim 1, wherein the modified polyvinyl chloride is prepared by pre-dehydrochlorination of polyvinyl chloride and grafting with maleic anhydride in a microwave environment under the action of an initiator.

3. The low-odor high-strength durable PVC artificial leather according to claim 2, wherein the mixed cross-linking agent is prepared by mixing hexahydrophthalic anhydride, 1-methylimidazole and tin tetrachloride according to a mass ratio of 1:1: 0.1-0.3.

4. The low-odor high-strength durable PVC artificial leather according to claim 3, wherein the modified plasticizer is prepared by preparing modified hydrotalcite containing silicon dioxide from aluminum nitrate, lanthanum nitrate and ethyl orthosilicate, hydroxylating the modified hydrotalcite containing silicon dioxide, and then reacting the hydroxylated hydrotalcite with epoxidized soybean oil under the catalysis of stannic chloride; the epoxidized soybean oil is prepared by oxidizing epoxidized soybean oil with hydrogen peroxide and formic acid under the action of sulfuric acid.

5. The low-odor high-strength durable PVC artificial leather according to claim 4, which mainly comprises the following raw material components in parts by weight: 80 parts of modified polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent.

6. A preparation method of low-odor high-strength durable PVC artificial leather is characterized by mainly comprising the following preparation steps:

(1) mixing pretreated polyvinyl chloride and acetone for swelling, adding maleic anhydride and an initiator, stirring for reaction, performing suction filtration, and drying to obtain modified polyvinyl chloride;

(2) mixing aluminum nitrate and aluminum nitrate in water, adding an ethyl orthosilicate solution, stirring and mixing, then adjusting the pH value to be alkaline by using a buffer solution, stirring and reacting, filtering and drying to obtain modified hydrotalcite;

(3) mixing the modified hydrotalcite obtained in the step (2) with a sodium hydroxide solution for reaction, filtering, washing and drying to obtain hydroxylated modified hydrotalcite;

(4) dispersing the hydroxylated modified hydrotalcite obtained in the step (3) in an organic solvent, adding oxidized epoxidized soybean oil, simultaneously dripping tin tetrachloride dispersion liquid, stirring for reaction, filtering, and drying to obtain a modified plasticizer;

(5) weighing the following components in parts by weight: 70-85 parts of modified polyvinyl chloride, 20-40 parts of modified plasticizer and 0-2 parts of mixed crosslinking agent; and mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing, and filling the mixture into a mold for molding to obtain the low-odor high-strength durable PVC artificial leather.

7. The method for preparing low-odor high-strength durable PVC artificial leather according to claim 6, wherein the method for preparing low-odor high-strength durable PVC artificial leather mainly comprises the following steps:

(1) mixing pretreated polyvinyl chloride and acetone according to a mass ratio of 1: 5-1: 8, mixing the mixture in a flask, swelling the mixture for 1-3 hours, adding a 10 mass percent maleic anhydride aqueous solution which is 2 times of the mass of the pretreated polyvinyl chloride and a 6 mass percent ammonium persulfate aqueous solution which is 0.5 times of the mass of the pretreated polyvinyl chloride into the flask, stirring the mixture to react, performing suction filtration to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 70 ℃ for 1-3 hours to obtain the modified polyvinyl chloride;

(2) mixing aluminum nitrate and lanthanum nitrate in a flask according to the mass ratio of 2: 1-3: 1, adding water with the mass being 8-12 times that of the aluminum nitrate into the flask, stirring and mixing, adding 20% ethyl orthosilicate ethanol solution with the volume fraction being 1 time that of the solution in the flask, stirring and mixing for 1-2 hours, adjusting the pH of the material in the flask to 8.5-9.5 by using a buffer solution, stirring and reacting for 4-6 hours, filtering to obtain a modified hydrotalcite blank, and drying the modified hydrotalcite blank for 24 hours at the temperature of 100 ℃ to obtain modified hydrotalcite;

(3) mixing the modified hydrotalcite obtained in the step (2) with a sodium hydroxide solution with the mass fraction of 5-10% according to a mass ratio of 1: 5-1: 8, stirring and reacting for 2 hours at the temperature of 80 ℃ and the rotating speed of 600-900 r/min, filtering to obtain filter residue, washing the filter residue with deionized water for 5-6 times, and drying for 12 hours at the temperature of 60 ℃ to obtain hydroxylated modified hydrotalcite;

(4) mixing the hydroxylated modified hydrotalcite obtained in the step (3) and dimethyl sulfoxide in a three-neck flask according to the mass ratio of 1: 35-1: 40, adding oxidized epoxidized soybean oil which is 1-1.2 times of the mass of the hydroxylated modified hydrotalcite into the three-neck flask, dripping tin tetrachloride dimethyl sulfoxide dispersion liquid which is 0.2-0.3 times of the mass of the hydroxylated modified hydrotalcite and has the volume fraction of 1-2% into the three-neck flask at the speed of 5-8 mL/min, stirring and reacting for 30-60 min at the temperature of 30-60 ℃ and the rotating speed of 300-400 r/min, filtering to obtain modified plasticizer blanks, and drying the modified plasticizer blanks for 2-6 h at the temperature of 60-75 ℃ to obtain modified plasticizers;

(5) weighing the following components in parts by weight: 80 parts of the modified polyvinyl chloride obtained in the step (1), 35 parts of the modified plasticizer obtained in the step (4) and 1 part of a mixed crosslinking agent; and mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing to obtain a mixture, keeping the mixture at the temperature of 170-190 ℃ for 7-12 min, filling the mold and forming to obtain the low-odor high-strength durable PVC artificial leather.

8. The method for preparing low-odor high-strength durable PVC artificial leather according to claim 7, wherein the preparation method of the pretreated PVC in the step (1) comprises the steps of mixing the PVC with 10% by mass of sodium hydroxide in a mass ratio of 1:10 to 1:20, stirring for reaction, performing suction filtration, and washing to neutrality to obtain the pretreated PVC.

9. The method of claim 7, wherein the buffer solution in the step (2) is prepared by mixing sodium carbonate and sodium hydroxide in a mass ratio of 2:1, adding water in an amount 20 times the mass of sodium carbonate, and stirring and mixing.

10. The method for preparing the low-odor high-strength durable PVC artificial leather according to claim 7, wherein the epoxidized soybean oil in the step (4) is prepared by mixing the epoxidized soybean oil with formic acid in a mass ratio of 1:4 to 1:8, adding a hydrogen peroxide mixed solution, stirring for reaction, washing with a sodium bicarbonate solution with a mass fraction of 4 to 8%, standing for layering, taking an upper oil phase, washing the oil phase with deionized water to neutrality, distilling under reduced pressure, and removing byproducts to obtain the epoxidized soybean oil.

Technical Field

The invention relates to the technical field of artificial decorative materials, in particular to low-odor high-strength durable PVC artificial leather and a preparation method thereof.

Background

The artificial leather and the synthetic leather are composite materials which simulate the tissue structure and the service performance of leather and can be used as leather substitutes. Usually, woven fabric and non-woven fabric are used to simulate the net layer of leather, and microporous high-molecular coating is used to simulate the grain layer of leather, so that the obtained artificial leather is similar to leather in both front and back sides, and can be widely used for making shoes, boots, bags, balls, etc.

In China, the earliest artificial leather was nitrocellulose varnished cloth produced by Shanghai varnished cloth production cooperative in 40 years, and the artificial leather developed by Shanghai plastic product factories in 1958 approximately, so that the development order of the artificial leather in China is formally uncovered. Thousands of manufacturing enterprises have been formed in China so far, and artificial leather has been widely applied to thousands of varieties of clothes, shoes, hats, gloves, bags, home furniture, cultural sports, industrial and agricultural and transportation lamp box advertisements, shed covers, automobiles and the like in daily life of people.

Polyvinyl chloride (PVC) has been commercialized in 1930 in the united states and germany, and is commercialized 10 years later in japan. In 1958, a Carlender machine was developed in Japan to produce PVC foamed plastic leather. The PVC artificial leather has tough leather membrane and is widely applied to vehicles, leather bags and coating materials. However, during the manufacturing process, a plasticizer must be added in order to adjust softness, and thus becomes gradually hard during use. And is not suitable for making shoes because of lack of air permeability and water vapor permeability. But PVC is still commonly used because of its low cost.

The PVC artificial leather on the market at present has unpleasant smell and has a pathogenic threat because the plasticizer used by the PVC artificial leather is volatile, and in addition, because the PVC artificial leather has a lower decomposition temperature than the processing temperature in the preparation process, the mechanical property of a PVC product is poorer, a stabilizer needs to be added to improve the physical property of PVC, but the dispersibility of the currently added stabilizer in PVC is poor, so that the mechanical property and the durability of the PVC artificial leather cannot be further improved.

Disclosure of Invention

The invention aims to provide low-odor high-strength durable PVC artificial leather and a preparation method thereof, so as to solve the problem that the elastic fiber has insufficient tensile rate at present.

The low-odor high-strength durable PVC artificial leather is characterized by mainly comprising the following raw material components in parts by weight: 70-85 parts of modified polyvinyl chloride, 20-40 parts of modified plasticizer and 0-2 parts of mixed crosslinking agent.

Preferably, the modified polyvinyl chloride is prepared by carrying out advanced dehydrochlorination on polyvinyl chloride and then grafting the polyvinyl chloride with maleic anhydride in a microwave environment under the action of an initiator.

Preferably, the mixed crosslinking agent is prepared by mixing hexahydrophthalic anhydride, 1-methylimidazole and stannic chloride according to the mass ratio of 1:1: 0.1-0.3.

The modified plasticizer is prepared by preparing modified hydrotalcite containing silicon dioxide from aluminum nitrate, lanthanum nitrate and ethyl orthosilicate, hydroxylating the modified hydrotalcite containing silicon dioxide, and reacting the hydroxylated modified hydrotalcite with epoxidized soybean oil under the catalysis of stannic chloride; the epoxidized soybean oil is prepared by oxidizing epoxidized soybean oil with hydrogen peroxide and formic acid under the action of sulfuric acid.

Preferably, the low-odor high-strength durable PVC artificial leather mainly comprises the following raw material components in parts by weight: 80 parts of modified polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent.

As optimization, the preparation method of the low-odor high-strength durable PVC artificial leather mainly comprises the following preparation steps:

(1) mixing pretreated polyvinyl chloride and acetone for swelling, adding maleic anhydride and an initiator, stirring for reaction, performing suction filtration, and drying to obtain modified polyvinyl chloride;

(2) mixing aluminum nitrate and aluminum nitrate in water, adding an ethyl orthosilicate solution, stirring and mixing, then adjusting the pH value to be alkaline by using a buffer solution, stirring and reacting, filtering and drying to obtain modified hydrotalcite;

(3) mixing the modified hydrotalcite obtained in the step (2) with a sodium hydroxide solution for reaction, filtering, washing and drying to obtain hydroxylated modified hydrotalcite;

(4) dispersing the hydroxylated modified hydrotalcite obtained in the step (3) in an organic solvent, adding oxidized epoxidized soybean oil, simultaneously dripping tin tetrachloride dispersion liquid, stirring for reaction, filtering, and drying to obtain a modified plasticizer;

(5) weighing the following components in parts by weight: 70-85 parts of modified polyvinyl chloride, 20-40 parts of modified plasticizer and 0-2 parts of mixed crosslinking agent; and mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing, and filling the mixture into a mold for molding to obtain the low-odor high-strength durable PVC artificial leather.

As optimization, the preparation method of the low-odor high-strength durable PVC artificial leather mainly comprises the following preparation steps:

(1) mixing pretreated polyvinyl chloride and acetone according to a mass ratio of 1: 5-1: 8, mixing the mixture in a flask, swelling the mixture for 1-3 hours, adding a 10 mass percent maleic anhydride aqueous solution which is 2 times of the mass of the pretreated polyvinyl chloride and a 6 mass percent ammonium persulfate aqueous solution which is 0.5 times of the mass of the pretreated polyvinyl chloride into the flask, stirring the mixture to react, performing suction filtration to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 70 ℃ for 1-3 hours to obtain the modified polyvinyl chloride;

(2) mixing aluminum nitrate and lanthanum nitrate in a flask according to the mass ratio of 2: 1-3: 1, adding water with the mass being 8-12 times that of the aluminum nitrate into the flask, stirring and mixing, adding 20% ethyl orthosilicate ethanol solution with the volume fraction being 1 time that of the solution in the flask, stirring and mixing for 1-2 hours, adjusting the pH of the material in the flask to 8.5-9.5 by using a buffer solution, stirring and reacting for 4-6 hours, filtering to obtain a modified hydrotalcite blank, and drying the modified hydrotalcite blank for 24 hours at the temperature of 100 ℃ to obtain modified hydrotalcite;

(3) mixing the modified hydrotalcite obtained in the step (2) with a sodium hydroxide solution with the mass fraction of 5-10% according to a mass ratio of 1: 5-1: 8, stirring and reacting for 2 hours at the temperature of 80 ℃ and the rotating speed of 600-900 r/min, filtering to obtain filter residue, washing the filter residue with deionized water for 5-6 times, and drying for 12 hours at the temperature of 60 ℃ to obtain hydroxylated modified hydrotalcite;

(4) mixing the hydroxylated modified hydrotalcite obtained in the step (3) and dimethyl sulfoxide in a three-neck flask according to the mass ratio of 1: 35-1: 40, adding oxidized epoxidized soybean oil which is 1-1.2 times of the mass of the hydroxylated modified hydrotalcite into the three-neck flask, dripping tin tetrachloride dimethyl sulfoxide dispersion liquid which is 0.2-0.3 times of the mass of the hydroxylated modified hydrotalcite and has the volume fraction of 1-2% into the three-neck flask at the speed of 5-8 mL/min, stirring and reacting for 30-60 min at the temperature of 30-60 ℃ and the rotating speed of 300-400 r/min, filtering to obtain modified plasticizer blanks, and drying the modified plasticizer blanks for 2-6 h at the temperature of 60-75 ℃ to obtain modified plasticizers;

(5) weighing the following components in parts by weight: 80 parts of the modified polyvinyl chloride obtained in the step (1), 35 parts of the modified plasticizer obtained in the step (4) and 1 part of a mixed crosslinking agent; and mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing to obtain a mixture, keeping the mixture at the temperature of 170-190 ℃ for 7-12 min, filling the mold and forming to obtain the low-odor high-strength durable PVC artificial leather.

And (2) optimally, the preparation method of the pretreated polyvinyl chloride in the step (1) comprises the steps of mixing the polyvinyl chloride with 10% of sodium hydroxide in a mass ratio of 1: 10-1: 20, stirring for reaction, carrying out suction filtration, and washing to be neutral to obtain the pretreated polyvinyl chloride.

Optimally, the buffer solution in the step (2) is prepared by mixing sodium carbonate and sodium hydroxide according to the mass ratio of 2:1, adding water with the mass of 20 times that of the sodium carbonate, and stirring and mixing.

And (3) optimally, mixing the epoxidized soybean oil and formic acid according to a mass ratio of less than 1: 4-1: 8, adding a hydrogen peroxide mixed solution, stirring for reaction, washing with a sodium bicarbonate solution with a mass fraction of 4-8%, standing for layering, taking an upper oil phase, washing the oil phase to be neutral with deionized water, carrying out reduced pressure distillation, and removing byproducts to obtain the epoxidized soybean oil.

Compared with the prior art, the invention has the beneficial effects that:

the invention uses modified polyvinyl chloride and adds modified plasticizer when preparing low-odor high-strength durable PVC artificial leather.

The invention uses modified plasticizer to prepare low-odor high-strength durable PVC artificial leather, the modified plasticizer takes hydrotalcite as base material, silicon dioxide microspheres are formed on the hydrotalcite by coprecipitation, and the silicon dioxide microspheres are taken as adsorption points of epoxidized soybean oil to connect the epoxidized soybean oil with the hydrotalcite; firstly, hydrotalcite is a special layered hydroxide, and contains metal ions, after the hydrotalcite is added into polyvinyl chloride, the alkaline ions in the hydrotalcite can react with hydrogen chloride released by polyvinyl chloride at high temperature, so that the degradation of the polyvinyl chloride by the hydrogen chloride is slowed down, and the strength of the polyvinyl chloride is improved; secondly, silica microspheres are formed on the surface of the hydrotalcite in a codeposition mode, the existence of the silica microspheres can increase the contact area between the modified hydrotalcite and the polyvinyl chloride base body on one hand, so that the tensile property of the product is improved, fine holes around the hydrotalcite are increased due to the increase of the contact area, so that the toughness of the product is improved, on the other hand, after the silica is hydroxylated, the hydroxyl groups on the surface of the silica are increased, epoxy groups in the epoxy soybean oil are oxidized to open rings under the action of tin tetrachloride and can react with the hydroxyl groups on the surface of the silica, so that the silica can be used as adsorption points of the epoxy soybean oil to play a connecting role; after the silica-linked epoxidized soybean oil in the hydrotalcite is added into the modified polyvinyl chloride, the epoxidized soybean oil has excellent dispersibility in the modified polyvinyl chloride, so that after the modified plasticizer is added into the modified polyvinyl chloride, the modified plasticizer can be dispersed in a product under the action of the epoxidized soybean oil, and further the strength of the product is further improved.

The modified polyvinyl chloride used for preparing the low-odor high-strength durable PVC artificial leather is prepared by modifying polyvinyl chloride with maleic anhydride, the release amount of hydrogen chloride is reduced when the modified polyvinyl chloride is used for preparing the artificial leather, so that the strength of the product is improved, and secondly, the maleic anhydride grafted with the polyvinyl chloride oxidizes epoxy groups in epoxidized soybean oil to react under the action of a mixed cross-linking agent, so that a more complex cross-linking network can be formed in the product, and the strength of the product is further improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the method for testing each index of the low-odor high-strength durable PVC artificial leather manufactured in the following examples is as follows:

odor grade: the low-odor high-strength durable PVC artificial leather obtained in each example and the comparative example product were tested according to QB/T2725.

Testing the strength; the low-odor high-strength durable PVC artificial leather obtained in each example and comparative example was cut into a 20X 5X 1mm sample, and the breaking strength was measured using a universal tensile tester.

Example 1

A low-odor high-strength durable PVC artificial leather mainly comprises the following components in parts by weight: 80 parts of modified polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent.

(1) Mixing pretreated polyvinyl chloride and acetone according to a mass ratio of 1:5, mixing the mixture in a flask, swelling for 1h, adding a 10 mass percent maleic anhydride aqueous solution which is 2 times of the mass of the pretreated polyvinyl chloride and a 6 mass percent ammonium persulfate aqueous solution which is 0.5 times of the mass of the pretreated polyvinyl chloride into the flask, stirring and reacting for 2h at the temperature of 30 ℃ and the rotating speed of 300r/min, performing suction filtration to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 70 ℃ for 2h to obtain the modified polyvinyl chloride;

(2) mixing aluminum nitrate and lanthanum nitrate in a flask according to the mass ratio of 2:1, adding water with the mass being 10 times that of the aluminum nitrate into the flask, stirring and mixing, adding an ethyl orthosilicate ethanol solution with the volume fraction being 20% and the volume being 1 time that of the solution in the flask into the flask, stirring and mixing for 1h, then adjusting the pH value of the materials in the flask to 9 by using a buffer solution, stirring and reacting for 5h under the conditions that the temperature is 40 ℃ and the rotating speed is 300r/min, filtering to obtain a modified hydrotalcite blank, and drying the modified hydrotalcite blank for 24h under the condition that the temperature is 100 ℃ to obtain modified hydrotalcite;

(3) mixing the modified hydrotalcite obtained in the step (2) with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1:5, mixing, stirring and reacting for 2 hours at the temperature of 80 ℃ and the rotating speed of 600r/min, filtering to obtain filter residue, washing the filter residue for 5 times by using deionized water, and drying for 12 hours at the temperature of 60 ℃ to obtain hydroxylated modified hydrotalcite;

(4) mixing the hydroxylated modified hydrotalcite obtained in the step (3) with dimethyl sulfoxide according to the mass ratio of 1:35 in a three-neck flask, adding oxidized epoxidized soybean oil with the mass 1 time that of the hydroxylated modified hydrotalcite into the three-neck flask, simultaneously dripping tin tetrachloride dimethyl sulfoxide dispersion liquid with the volume fraction of 1% and the mass 0.2 time that of the hydroxylated modified hydrotalcite into the three-neck flask at the speed of 5mL/min, stirring and reacting for 40min at the temperature of 40 ℃ and the rotating speed of 350r/min, filtering to obtain a modified plasticizer blank, and drying the modified plasticizer blank for 3h at the temperature of 60 ℃ to obtain a modified plasticizer;

(5) weighing the following components in parts by weight: 80 parts of the modified polyvinyl chloride obtained in the step (1), 35 parts of the modified plasticizer obtained in the step (4) and 1 part of a mixed crosslinking agent; mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing to obtain a mixture, keeping the mixture at the temperature of 180 ℃ for 12min, filling the mold and forming to obtain the low-odor high-strength durable PVC artificial leather.

Optimally, the preparation method of the pretreated polyvinyl chloride in the step (1) comprises the steps of mixing the polyvinyl chloride with 10% by mass of sodium hydroxide according to the mass ratio of 1:10, stirring for reaction, carrying out suction filtration, and washing to be neutral to obtain the pretreated polyvinyl chloride.

Optimally, the buffer solution in the step (2) is prepared by mixing sodium carbonate and sodium hydroxide according to the mass ratio of 2:1, adding water with the mass of 20 times that of the sodium carbonate, and stirring and mixing.

And (3) optimally, mixing the epoxidized soybean oil with formic acid according to the mass ratio of less than 1:5, adding a hydrogen peroxide mixed solution, stirring for reaction, washing with a sodium bicarbonate solution with the mass fraction of 5%, standing for layering, taking an upper oil phase, washing the oil phase to be neutral by deionized water, distilling under reduced pressure, and removing byproducts to obtain the epoxidized soybean oil.

Example 2

A low-odor high-strength durable PVC artificial leather mainly comprises the following components in parts by weight: 80 parts of modified polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent.

(1) Mixing aluminum nitrate and lanthanum nitrate in a flask according to the mass ratio of 2:1, adding water with the mass being 10 times that of the aluminum nitrate into the flask, stirring and mixing, adding an ethyl orthosilicate ethanol solution with the volume fraction being 20% and the volume being 1 time that of the solution in the flask into the flask, stirring and mixing for 1h, then adjusting the pH value of the materials in the flask to 9 by using a buffer solution, stirring and reacting for 5h under the conditions that the temperature is 40 ℃ and the rotating speed is 300r/min, filtering to obtain a modified hydrotalcite blank, and drying the modified hydrotalcite blank for 24h under the condition that the temperature is 100 ℃ to obtain modified hydrotalcite;

(2) mixing the modified hydrotalcite obtained in the step (1) with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1:5, mixing, stirring and reacting for 2 hours at the temperature of 80 ℃ and the rotating speed of 600r/min, filtering to obtain filter residue, washing the filter residue for 5 times by using deionized water, and drying for 12 hours at the temperature of 60 ℃ to obtain hydroxylated modified hydrotalcite;

(3) mixing the hydroxylated modified hydrotalcite obtained in the step (2) and dimethyl sulfoxide in a three-neck flask according to the mass ratio of 1:35, adding oxidized epoxidized soybean oil accounting for 1 time of the mass of the hydroxylated modified hydrotalcite into the three-neck flask, simultaneously dripping tin tetrachloride dimethyl sulfoxide dispersion liquid accounting for 1% of the volume fraction and accounting for 0.2 time of the mass of the hydroxylated modified hydrotalcite into the three-neck flask at the speed of 5mL/min, stirring and reacting for 40min at the temperature of 40 ℃ and the rotating speed of 350r/min, filtering to obtain a modified plasticizer blank, and drying the modified plasticizer blank for 3h at the temperature of 60 ℃ to obtain a modified plasticizer;

(4) weighing the following components in parts by weight: 80 parts of polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent; mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing to obtain a mixture, keeping the mixture at the temperature of 180 ℃ for 12min, filling the mold and forming to obtain the low-odor high-strength durable PVC artificial leather.

Optimally, the buffer solution in the step (1) is prepared by mixing sodium carbonate and sodium hydroxide according to the mass ratio of 2:1, adding water with the mass of 20 times that of the sodium carbonate, and stirring and mixing.

And (3) optimally, mixing the epoxidized soybean oil with formic acid according to the mass ratio of less than 1:5, adding a hydrogen peroxide mixed solution, stirring for reaction, washing with a sodium bicarbonate solution with the mass fraction of 5%, standing for layering, taking an upper oil phase, washing the oil phase to be neutral by deionized water, distilling under reduced pressure, and removing byproducts to obtain the epoxidized soybean oil.

Example 3

A low-odor high-strength durable PVC artificial leather mainly comprises the following components in parts by weight: 80 parts of modified polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent.

(1) Mixing pretreated polyvinyl chloride and acetone according to a mass ratio of 1:5, mixing the mixture in a flask, swelling for 1h, adding a 10 mass percent maleic anhydride aqueous solution which is 2 times of the mass of the pretreated polyvinyl chloride and a 6 mass percent ammonium persulfate aqueous solution which is 0.5 times of the mass of the pretreated polyvinyl chloride into the flask, stirring and reacting for 2h at the temperature of 30 ℃ and the rotating speed of 300r/min, performing suction filtration to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 70 ℃ for 2h to obtain the modified polyvinyl chloride;

(2) mixing aluminum nitrate and lanthanum nitrate in a flask according to the mass ratio of 2:1, adding water with the mass being 10 times that of the aluminum nitrate into the flask, stirring and mixing, adjusting the pH value of materials in the flask to 9 by using a buffer solution, stirring and reacting for 5 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified hydrotalcite blank, and drying the modified hydrotalcite blank for 24 hours at the temperature of 100 ℃ to obtain hydrotalcite;

(3) mixing the hydrotalcite obtained in the step (2) with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1:5, mixing, stirring and reacting for 2 hours at the temperature of 80 ℃ and the rotating speed of 600r/min, filtering to obtain filter residue, washing the filter residue for 5 times by using deionized water, and drying for 12 hours at the temperature of 60 ℃ to obtain hydroxylated hydrotalcite;

(4) mixing the hydroxylated hydrotalcite obtained in the step (3) and dimethyl sulfoxide in a three-neck flask according to the mass ratio of 1:35, adding oxidized epoxidized soybean oil accounting for 1 time of the mass of the hydroxylated hydrotalcite into the three-neck flask, dripping tin tetrachloride dimethyl sulfoxide dispersion liquid accounting for 1% of the volume fraction and accounting for 0.2 time of the mass of the hydroxylated hydrotalcite into the three-neck flask at the speed of 5mL/min, stirring and reacting for 40min at the temperature of 40 ℃ and the rotating speed of 350r/min, filtering to obtain modified plasticizer blank, and drying the modified plasticizer blank for 3h at the temperature of 60 ℃ to obtain modified plasticizer;

(5) weighing the following components in parts by weight: 80 parts of the modified polyvinyl chloride obtained in the step (1), 35 parts of the modified plasticizer obtained in the step (4) and 1 part of a mixed crosslinking agent; mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing to obtain a mixture, keeping the mixture at the temperature of 180 ℃ for 12min, filling the mold and forming to obtain the low-odor high-strength durable PVC artificial leather.

Optimally, the preparation method of the pretreated polyvinyl chloride in the step (1) comprises the steps of mixing the polyvinyl chloride with 10% by mass of sodium hydroxide according to the mass ratio of 1:10, stirring for reaction, carrying out suction filtration, and washing to be neutral to obtain the pretreated polyvinyl chloride.

Optimally, the buffer solution in the step (2) is prepared by mixing sodium carbonate and sodium hydroxide according to the mass ratio of 2:1, adding water with the mass of 20 times that of the sodium carbonate, and stirring and mixing.

And (3) optimally, mixing the epoxidized soybean oil with formic acid according to the mass ratio of less than 1:5, adding a hydrogen peroxide mixed solution, stirring for reaction, washing with a sodium bicarbonate solution with the mass fraction of 5%, standing for layering, taking an upper oil phase, washing the oil phase to be neutral by deionized water, distilling under reduced pressure, and removing byproducts to obtain the epoxidized soybean oil.

Comparative example

A low-odor high-strength durable PVC artificial leather mainly comprises the following components in parts by weight: 80 parts of modified polyvinyl chloride, 35 parts of modified plasticizer and 1 part of mixed crosslinking agent.

(1) Mixing pretreated polyvinyl chloride and acetone according to a mass ratio of 1:5, mixing the mixture in a flask, swelling for 1h, adding a 10 mass percent maleic anhydride aqueous solution which is 2 times of the mass of the pretreated polyvinyl chloride and a 6 mass percent ammonium persulfate aqueous solution which is 0.5 times of the mass of the pretreated polyvinyl chloride into the flask, stirring and reacting for 2h at the temperature of 30 ℃ and the rotating speed of 300r/min, performing suction filtration to obtain a filter cake, and performing vacuum drying on the filter cake at the temperature of 70 ℃ for 2h to obtain the modified polyvinyl chloride;

(2) weighing the following components in parts by weight: 80 parts of the modified polyvinyl chloride obtained in the step (1), 35 parts of epoxidized soybean oil and 1 part of mixed cross-linking agent; mixing the modified polyvinyl chloride with the mixed cross-linking agent, adding the modified polyvinyl chloride, stirring and mixing to obtain a mixture, keeping the mixture at the temperature of 180 ℃ for 12min, filling the mold and forming to obtain the low-odor high-strength durable PVC artificial leather.

Optimally, the preparation method of the pretreated polyvinyl chloride in the step (1) comprises the steps of mixing the polyvinyl chloride with 10% by mass of sodium hydroxide according to the mass ratio of 1:10, stirring for reaction, carrying out suction filtration, and washing to be neutral to obtain the pretreated polyvinyl chloride.

Optimally, the buffer solution in the step (2) is prepared by mixing sodium carbonate and sodium hydroxide according to the mass ratio of 2:1, adding water with the mass of 20 times that of the sodium carbonate, and stirring and mixing.

And (3) optimally, mixing the epoxidized soybean oil with formic acid according to the mass ratio of less than 1:5, adding a hydrogen peroxide mixed solution, stirring for reaction, washing with a sodium bicarbonate solution with the mass fraction of 5%, standing for layering, taking an upper oil phase, washing the oil phase to be neutral by deionized water, distilling under reduced pressure, and removing byproducts to obtain the epoxidized soybean oil.

Examples of effects

Table 1 below gives the results of performance analysis of the low-odor high-strength durable PVC artificial leather using examples 1 to 3 of the present invention and a comparative example.

TABLE 1

	Example 1	Example 2	Example 3	Comparative example
					Odor grade	1	≤2	1	≤2
Tensile breaking Strength (MPa)	69.2	64.9	46.3	21.5

From the comparison of experimental data of example 1 and comparative example in table 1, it can be found that the use of modified polyvinyl chloride and modified plasticizer in the preparation of PVC artificial leather can effectively improve the mechanical strength of the product and reduce the release of harmful gases from PVC artificial leather to some extent; from the comparison of experimental data of example 1 and example 2, it can be found that when polyvinyl chloride is not modified when PVC artificial leather is prepared, polyvinyl chloride cannot form a more complex cross-linked network with a modifying plasticizer, thereby affecting the mechanical properties of the product to a certain extent, and from the comparison of experimental data of example 1 and example 3, when silica is not added to the modifying plasticizer when PVC artificial leather is prepared, oxidized epoxidized soybean oil cannot be combined with hydrotalcite, so that hydrotalcite is not well dispersed, thereby greatly affecting the mechanical properties of the product.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.