High-elasticity polyvinyl chloride material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses a high-elasticity polyvinyl chloride material and a preparation method thereof, the high-elasticity polyvinyl chloride material comprises the following raw materials by mass: 80-100 parts of polyvinyl chloride resin, 10-20 parts of a composite reinforcing material, 10-15 parts of modified collagen fiber, 2-3 parts of a stabilizer, 5-10 parts of a plasticizer, and 6-8 parts of a lubricant. The composite reinforcing material and chloride ions in polyvinyl chloride can form ionic bonds and covalent bonds, so that the interfacial compatibility of the composite reinforcing material and a polyvinyl chloride material is remarkably improved, and the elastic modulus and the mechanical property of the polyvinyl chloride are enhanced; a polymer formed by copolymerization of 1, 4-vinyl phenyl glycidyl ether and 1-carboxyl o-carborane permeate into a three-dimensional multi-layer structure of the collagenous fiber, so that the interlayer spacing of the collagenous fiber is enlarged, permeation of a polyvinyl chloride molecular chain is facilitated, the structural stability of the composite reinforced material is improved, and the elastic modulus of the polyvinyl chloride material is enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically relates to a highly elastic polyvinyl chloride material and a preparation method thereof. Background Art

[0002] Polyvinyl chloride is the third largest synthetic polymer plastic in the world in terms of production volume. It is a polymer formed by the free radical polymerization reaction of vinyl chloride monomer under the action of an initiator or light and heat. It is a multi-component plastic with advantages such as flame retardancy, corrosion resistance, abrasion resistance, insulation, low price, and wide sources of raw materials. By adding various additives and through various molding methods, different polyvinyl chloride materials can be produced, showing good physical and mechanical properties, and are widely used in fields such as pipes, plates, and profiles.

[0003] The elastic modulus of polyvinyl chloride materials will change with the change of temperature. At high temperatures, the movement of its molecular chains intensifies, resulting in a decrease in the elastic modulus. Moreover, under long-term load, polyvinyl chloride materials are prone to creep and relaxation phenomena, reducing the elastic modulus of polyvinyl chloride materials. Adding sepiolite can improve the thermal stability of polyvinyl chloride materials, and its fibrous structure can restrict the movement of polyvinyl chloride molecular chains, enhancing the elastic modulus of polyvinyl chloride materials. However, the porous structure of sepiolite has strong hygroscopicity, causing the polyvinyl chloride material to absorb water and soften, affecting the flexibility and elastic modulus of the polyvinyl chloride material. Summary of the Invention

[0004] The present invention provides a highly elastic polyvinyl chloride material and a preparation method thereof, which solve the problems that the intensification of molecular chain movement of polyvinyl chloride materials affects the elastic modulus and the hygroscopicity of sepiolite causes the polyvinyl chloride material to absorb water and soften.

[0005] The technical solution of the present invention:

[0006] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 80-100 parts of polyvinyl chloride resin, 10-20 parts of composite reinforcing material, 10-15 parts of modified collagen fiber, 2-3 parts of stabilizer, 5-10 parts of plasticizer, and 6-8 parts of lubricant;

[0007] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0008] Adding polyvinyl chloride resin, composite reinforcing material, modified collagen fiber, stabilizer, plasticizer, and lubricant into a mixer, fully mixing for 8-10 min to obtain a mixture, and extruding and granulating the mixture through a twin-screw extruder to obtain a highly elastic polyvinyl chloride material.

[0009] The composite reinforcing material is prepared by mixing and reacting sepiolite loaded with nano-titanium dioxide, imidazole monomer, and zinc nitrate hexahydrate, and then performing silane surface modification;

[0010] The sepiolite loaded with nano-titanium dioxide is prepared by mixing pretreated sepiolite with tetrabutyl titanate and subjecting them to a hydrothermal reaction;

[0011] The modified collagen fiber is obtained by mixing 4-vinylphenyl glycidyl ether, 1-carboxy-o-carborane and the surface of collagen fiber, followed by polymerization initiation;

[0012] Furthermore, the twin-screw extruder extrusion process: the temperature of the first zone is 100 - 110 °C, the temperature of the second zone is 110 - 120 °C, the temperature of the third zone is 120 - 130 °C, the temperature of the fourth zone is 125 - 135 °C, the temperature of the fifth zone is 130 - 140 °C, the temperature of the sixth zone is 125 - 135 °C, the temperature of the seventh zone is 105 - 115 °C, the temperature of the eighth zone is 105 - 115 °C, the temperature of the ninth zone is 105 - 115 °C; the screw speed is 400 - 450 r / min.

[0013] Furthermore, the degree of polymerization of the polyvinyl chloride resin is 800 - 1000.

[0014] Furthermore, the stabilizer is selected from calcium-zinc stabilizers or magnesium-aluminum-zinc stabilizers.

[0015] Furthermore, the lubricant is selected from any one of calcium stearate, zinc stearate, stearic acid, and butyl stearate.

[0016] Furthermore, the plasticizer is selected from any one of dioctyl terephthalate, dipentaerythritol ester, bis(2-propylheptyl) phthalate, ethylene carbonate, and propylene carbonate.

[0017] Furthermore, the composite reinforcing material is specifically prepared by the following steps:

[0018] A1. Add sepiolite to a hydrochloric acid solution with a concentration of 0.5 - 1.5 mol / L, stir evenly, place it in a microwave oven at 70 - 90 °C, heat for 1 - 3 h, then cool to room temperature, filter, wash, dry, grind and sieve to obtain pretreated sepiolite;

[0019] A2. Add tetrabutyl titanate and cetyltrimethylammonium bromide to deionized water, stir evenly, add the pretreated sepiolite, stir evenly, place it in a hydrothermal reaction kettle, carry out a hydrothermal reaction at 160 - 180 °C for 2 - 4 h, filter and collect the solid, place the solid in a muffle furnace, calcine at 200 - 300 °C for 30 - 50 min, cool to room temperature, take out, grind, and sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0020] A3. Add 2-methylimidazole to deionized water, stir until dissolved, add zinc nitrate hexahydrate and sepiolite loaded with nano-titanium dioxide, stir at 20 - 30 °C for 20 - 22 h, then centrifuge to collect the precipitate. Wash and dry the precipitate to obtain modified sepiolite;

[0021] A4. Mix silane, ethanol and deionized water, stir evenly, add modified sepiolite and hydrochloric acid with a mass fraction of 35 - 37% to adjust the pH to 5 - 6, stir at 40 - 50 °C for 1 - 3 h, filter, wash and dry to obtain the composite reinforcing material.

[0022] Furthermore, during the above A1 reaction process, sepiolite is treated with hydrochloric acid, so that the free metal ion magnesium ion in sepiolite is replaced and precipitated, removing surface impurities, and the internal pores of sepiolite are opened, which is beneficial to the synthesis of nanoparticles in the pores of sepiolite.

[0023] Furthermore, during the above A2 reaction process, the pore structure of the pretreated sepiolite has good adsorption performance, which can adsorb tetrabutyl titanate into the pores of the pretreated sepiolite, and tetrabutyl titanate hydrolyzes to form titanium dioxide gel. Hydrothermal reaction is carried out at 160 - 180 °C to make the titanium dioxide gel crystal grow, and calcination is carried out at 200 - 300 °C to remove the residual organic matter and promote the crystallization of nano-titanium dioxide, realizing the in-situ synthesis of 50 - 100 nm nano-titanium dioxide in the pores of the pretreated sepiolite.

[0024] Furthermore, during the above A3 reaction process, the surface of sepiolite loaded with nano-titanium dioxide contains a large number of silanol structures, which can combine with zinc ions in zinc nitrate hexahydrate, so that zinc ions are adsorbed on the surface of sepiolite loaded with nano-titanium dioxide, and zinc ions can carry out a coordination reaction with the nitrogen atoms in the imidazole monomer 2-methylimidazole to form a complex with a nitrogen-zinc bond on the surface of sepiolite loaded with nano-titanium dioxide. As the coordination reaction proceeds, nitrogen-zinc coordination bonds are continuously formed between zinc ions and 2-methylimidazole molecules. These coordination bonds connect zinc ions and 2-methylimidazole molecules together, and then form a porous zinc-based metal-organic framework on the surface of sepiolite loaded with nano-titanium dioxide.

[0025] Furthermore, during the above A4 reaction process, the hydroxyl groups in the metal-organic framework on the surface of the modified sepiolite can be chemically bonded with the silanol groups generated by the hydrolysis of γ-aminopropyltriethoxysilane, so that γ-aminopropyltriethoxysilane is grafted on the surface of the modified sepiolite to form a composite reinforcing material.

[0026] Furthermore, in step A1, the dosage ratio of sepiolite to hydrochloric acid solution is (5.5 - 6.5) g : (40 - 60) mL.

[0027] Further, in step A2, the dosage ratio of tetrabutyl titanate, cetyltrimethylammonium bromide, deionized water, and pretreated sepiolite is (5 - 6) g : (0.1 - 0.3) g : (25 - 35) mL : (10 - 12) g.

[0028] Further, in step A3, the dosage ratio of 2-methylimidazole, deionized water, zinc nitrate hexahydrate, and sepiolite loaded with nano-titanium dioxide is (5.5 - 6.5) g : (60 - 80) mL : (2 - 3) g : (12 - 15) g.

[0029] Further, in step A4, the dosage ratio of silane, ethanol, deionized water, and modified sepiolite is (2 - 4) g : (90 - 100) mL : (4 - 6) mL : (5 - 6) g.

[0030] Further, the modified collagen fibers are specifically prepared by the following steps

[0031] B1. Add 4-vinylphenyl glycidyl ether to chloroform, stir evenly, add collagen fibers and boron trifluoride diethyl ether, stir and react at 80 - 100 °C for 30 - 40 min, filter, wash, and dry to obtain a solid. Add 1-carboxy-ortho-carborane and the solid to ethanol, stir evenly, add a sodium hydroxide aqueous solution with a concentration of 8 - 12 mol / L to adjust the pH to 2 - 3, stir and react at 125 - 130 °C for 1 - 2 h, filter, wash, and dry to obtain pretreated collagen fibers;

[0032] B2. Add the pretreated collagen fibers to ethanol and deionized water, stir evenly, add azobisisobutyronitrile, stir and react at 65 - 75 °C for 8 - 10 h, filter, wash, and dry to obtain modified collagen fibers.

[0033] Further, during the reaction process of B1 above, the epoxy group in 4-vinylphenyl glycidyl ether can undergo a ring-opening reaction with the oxygen-containing functional groups on the surface of collagen fibers, enabling 4-vinylphenyl glycidyl ether to graft onto the surface of collagen fibers; the hydroxyl groups generated by the ring-opening on the solid surface and the unreacted oxygen-containing functional groups on the surface of collagen fibers can react with the carboxyl groups contained in 1-carboxy-ortho-carborane, enabling 4-vinylphenyl glycidyl ether and 1-carboxy-ortho-carborane to graft onto the surface of collagen fibers.

[0034] Further, during the reaction process of B2 above, under the action of the initiator azobisisobutyronitrile, the double bonds of 4-vinylphenyl glycidyl ether polymerize on the pretreated collagen fibers, realizing the formation of a polymer on the surface of the pretreated collagen fibers to obtain modified collagen fibers.

[0035] Further, in step B1, the dosage ratio of 4-vinylphenyl glycidyl ether, chloroform, collagen fiber, and boron trifluoride diethyl ether is (0.3 - 0.7) g : (15 - 25) mL : (1 - 2) g : (0.3 - 0.5) g.

[0036] Further, in step B1, the dosage ratio of 1-carboxy-o-carborane, solid, and ethanol is (0.5 - 1) g : (3 - 4) g : (30 - 40) mL.

[0037] Further, in step B2, the dosage ratio of the pretreated collagen fiber, ethanol, deionized water, and azobisisobutyronitrile is (5 - 6) : (40 - 50) mL : (3 - 7) mL : (0.05 - 0.15) g.

[0038] Further, the sepiolite has a particle size of 20 - 25 μm and a pore size of 0.5 - 1 μm.

[0039] Further, the silane is γ-aminopropyltriethoxysilane.

[0040] The present invention has the following beneficial effects:

[0041] (1) In the technical solution of the present invention, microwave-assisted acid activation of sepiolite can remove surface impurities and open the internal pores of sepiolite, which is beneficial to the synthesis of nanoparticles in the pores of sepiolite, and the fibrous structure of sepiolite helps to improve the strength and toughness of the polyvinyl chloride material; synthesizing nano-titanium dioxide in the pores of the pretreated sepiolite can block the pores of the pretreated sepiolite, avoiding the easy moisture absorption of the pretreated sepiolite, which leads to the water absorption and softening of the polyvinyl chloride material, affecting the mechanical properties and elastic modulus of the polyvinyl chloride material. On the other hand, the synthesized nano-titanium dioxide has high mechanical strength, serving as the support framework of the pretreated sepiolite, enhancing the mechanical strength of the pretreated sepiolite, and avoiding the easy breakage of the pretreated sepiolite, which affects the mechanical properties of the polyvinyl chloride.

[0042] (2) In the technical solution of the present invention, mixing the sepiolite loaded with nano-titanium dioxide, imidazole monomer, and zinc source for reaction forms a porous zinc-based metal-organic framework on the surface of the sepiolite loaded with nano-titanium dioxide. The synthesized metal-organic framework has good mechanical energy attenuation effect. When the polyvinyl chloride material is under long-term load, the pores and zinc-nitrogen bonds in the synthesized metal-organic framework can absorb the impact energy generated under long-term load. Through the collapse of the pores of the metal-organic framework and the breakage of the zinc-nitrogen bonds, the acting force generated under long-term load is consumed, avoiding the creep and relaxation phenomena of the polyvinyl chloride material under external force, which affect the elastic modulus of the polyvinyl chloride material. Moreover, the synthesized metal-organic framework can further fix the nanoparticles in the sepiolite loaded with nano-titanium dioxide, avoiding the shedding of nano-titanium dioxide caused by external force on the sepiolite, which affects the performance of the polyvinyl chloride material.

[0043] (3) In the technical solution of the present invention, γ-aminopropyltriethoxysilane is grafted onto the surface of modified sepiolite to form a composite reinforcing material. The amino group of γ-aminopropyltriethoxysilane on the surface of the composite reinforcing material can form ionic bonds and covalent bonds with chloride ions in polyvinyl chloride, thereby significantly improving the interfacial compatibility between the composite reinforcing material and the polyvinyl chloride material, enabling the composite reinforcing material to be dispersed in the polyvinyl chloride matrix, and enhancing the elastic modulus and mechanical properties of polyvinyl chloride.

[0044] (4) In the technical solution of the present invention, after 4-vinylphenyl glycidyl ether, 1-carboxy-ortho-carborane and collagen fiber surface are mixed and reacted, polymerization is then initiated. On the one hand, 1-carboxy-ortho-carborane contains a stable cage structure and has high thermal stability, which can improve the heat resistance of collagen fibers and avoid the thermal decomposition of collagen fibers, affecting the elastic properties of polyvinyl chloride materials. On the other hand, 4-vinylphenyl glycidyl ether on the pretreated collagen fibers is copolymerized to form a polymer. The formed polymer and 1-carboxy-ortho-carborane can penetrate into the three-dimensional multi-level structure of collagen fibers, expand the layer spacing of collagen fibers, facilitate the penetration of polyvinyl chloride molecular chains, form a randomly distributed network structure with collagen fibers, increase the action sites between the modified collagen fibers and polyvinyl chloride molecular chains, effectively hinder the detachment of polyvinyl chloride molecular chains during impact and restrict the movement of polyvinyl chloride molecular chains, improve the structural stability of the composite reinforcing material and enhance the elastic modulus of polyvinyl chloride materials, and the formed randomly distributed network structure can also improve the mechanical strength of polyvinyl chloride materials. Specific embodiments

[0045] The following will describe clearly and completely the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0046] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0047] Among them, the degree of polymerization of polyvinyl chloride resin is 900, industrial product, Huahai Petrochemical Co., Ltd.

[0048] The stabilizer is a calcium-zinc stabilizer.

[0049] The lubricant is calcium stearate.

[0050] The plasticizer is dioctyl terephthalate.

[0051] The particle size of sepiolite is 23μm and the pore diameter is 0.6μm.

[0052] The silane is γ-aminopropyltriethoxysilane.

[0053] The collagen fibers are specifically prepared by the following steps:

[0054] Add 5 g of leather shavings to 50 mL of deionized water, adjust the pH to 6 with a 1 mol / L aqueous sodium bicarbonate solution, stir at 25 °C for 1 h, filter, dry in an oven at 70 °C for 10 min, place in an ultra-centrifugal grinder with a centrifugal speed of 12,000 r / min for grinding, and pass through a 40-mesh sieve to obtain collagen fibers.

[0055] Leather shavings, industrial grade, Shandong Senlu Leather Industry Co., Ltd.

[0056] Example 1

[0057] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 80 parts of polyvinyl chloride resin, 10 parts of composite reinforcing material, 10 parts of modified collagen fibers, 2 parts of calcium-zinc stabilizer, 5 parts of dioctyl terephthalate, and 6 parts of calcium stearate;

[0058] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0059] Add polyvinyl chloride resin, composite reinforcing material, modified collagen fibers, calcium-zinc stabilizer, dioctyl terephthalate, and calcium stearate to a blender, mix well for 8 min to obtain a mixture, and extrude and pelletize the mixture through a twin-screw extruder to obtain a highly elastic polyvinyl chloride material.

[0060] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 100 °C, the temperature of the second zone is 110 °C, the temperature of the third zone is 120 °C, the temperature of the fourth zone is 125 °C, the temperature of the fifth zone is 130 °C, the temperature of the sixth zone is 125 °C, the temperature of the seventh zone is 105 °C, the temperature of the eighth zone is 105 °C, and the temperature of the ninth zone is 105 °C; the screw speed is 400 r / min.

[0061] The composite reinforcing material is specifically prepared by the following steps:

[0062] A1. Add 5.5 g of sepiolite to 40 mL of a 0.5 mol / L hydrochloric acid solution, stir evenly, place in a 70 °C microwave oven, heat for 1 h, cool to room temperature, filter, wash 3 times with absolute ethanol, wash with deionized water until the pH of the washing solution is neutral, dry in an oven at 60 °C for 10 min, place in a grinder for grinding, and pass through a 600-mesh sieve to obtain pretreated sepiolite;

[0063] A2. Add 5 g of tetrabutyl titanate and 0.1 g of cetyltrimethylammonium bromide to 25 mL of deionized water, stir evenly, add 10 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle and carry out hydrothermal reaction at 160 °C for 2 h. Filter and collect the solid. Place the solid in a muffle furnace and calcine it at 200 °C for 30 min, cool it to room temperature, take it out, grind it, and pass it through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0064] A3. Add 5.5 g of 2-methylimidazole to 60 mL of deionized water, stir until dissolved, add 2 g of zinc nitrate hexahydrate and 12 g of sepiolite loaded with nano-titanium dioxide, stir at 20 °C for 20 h, then centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate 3 times with methanol and 3 times with deionized water, and dry it in an oven at 70 °C for 15 min to obtain modified sepiolite;

[0065] A4. Mix 2 g of γ-aminopropyltriethoxysilane, 90 mL of ethanol and 4 mL of deionized water, stir evenly, add 5 g of modified sepiolite and hydrochloric acid with a mass fraction of 35% to adjust the pH to 5, stir at 40 °C for 1 h, filter and collect the precipitate, wash the precipitate 3 times with deionized water, and dry it in an oven at 100 °C for 10 min to obtain a composite reinforcing material.

[0066] The modified collagen fiber is specifically prepared by the following steps

[0067] B1. Add 0.3 g of 4-vinylphenyl glycidyl ether to 15 mL of chloroform, stir evenly, then add 1 g of collagen fiber and 0.3 g of boron trifluoride diethyl etherate, stir and react at 80 °C for 30 min, filter, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain a solid. Add 0.5 g of 1-carboxy-o-carborane and 3 g of the solid to 30 mL of ethanol, stir evenly, add sodium hydroxide aqueous solution with a concentration of 8 mol / L to adjust the pH to 2, stir and react at 125 °C for 1 h, filter, wash 3 times with deionized water, and dry in an oven at 80 °C for 10 min to obtain pretreated collagen fiber;

[0068] B2. Add 5 g of pretreated collagen fiber to 40 mL of ethanol and 3 mL of deionized water, stir evenly, add 0.05 g of azobisisobutyronitrile, stir and react at 65 °C for 8 h, filter, wash 3 times with deionized water, and dry in an oven at 60 °C for 30 min to obtain modified collagen fiber.

[0069] Example 2

[0070] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 90 parts of polyvinyl chloride resin, 15 parts of composite reinforcing material, 13 parts of modified collagen fiber, 2.5 parts of calcium-zinc stabilizer, 8 parts of dioctyl terephthalate, and 7 parts of calcium stearate;

[0071] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0072] Add polyvinyl chloride resin, composite reinforcing material, modified collagen fiber, calcium-zinc stabilizer, dioctyl terephthalate, and calcium stearate to a blender, mix well for 9 min to obtain a mixture, and extrude the mixture through a twin-screw extruder and pelletize to obtain the highly elastic polyvinyl chloride material.

[0073] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 105 °C, the temperature of the second zone is 115 °C, the temperature of the third zone is 125 °C, the temperature of the fourth zone is 130 °C, the temperature of the fifth zone is 135 °C, the temperature of the sixth zone is 130 °C, the temperature of the seventh zone is 110 °C, the temperature of the eighth zone is 110 °C, and the temperature of the ninth zone is 110 °C; the screw speed is 430 r / min.

[0074] The composite reinforcing material is specifically prepared by the following steps:

[0075] A1. Add 6 g of sepiolite to 50 mL of hydrochloric acid solution with a concentration of 1 mol / L, stir evenly, place it in a microwave oven at 80 °C, heat for 2 h, cool to room temperature, filter, wash 3 times with absolute ethanol, wash with deionized water until the washing liquid is neutral in pH, place it in an oven at 60 °C and dry for 10 min, and place it in a grinder to grind to obtain pretreated sepiolite;

[0076] A2. Add 5.5 g of tetrabutyl titanate and 0.2 g of cetyltrimethylammonium bromide to 30 mL of deionized water, stir evenly, add 11 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle and carry out a hydrothermal reaction at 170 °C for 3 h, filter and collect the solid, place the solid in a muffle furnace, calcine at 250 °C for 40 min, cool to room temperature, take out, grind, and pass through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0077] A3. Add 6 g of 2-methylimidazole to 70 mL of deionized water, stir until dissolved, add 2.5 g of zinc nitrate hexahydrate and 13 g of sepiolite loaded with nano-titanium dioxide, stir at 25 °C for 21 h, then centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate 3 times with methanol and 3 times with deionized water, and dry in an oven at 70 °C for 15 min to obtain modified sepiolite;

[0078] A4. Mix 3 g of γ-aminopropyltriethoxysilane, 95 mL of ethanol and 5 mL of deionized water, stir evenly, add 5.5 g of modified sepiolite and hydrochloric acid with a mass fraction of 36% to adjust the pH to 5.5, stir at 45 °C for 2 h, filter to collect the precipitate, wash the precipitate 3 times with deionized water, and dry it in an oven at 100 °C for 10 min to obtain the composite reinforcing material.

[0079] The modified collagen fiber is specifically prepared by the following steps

[0080] B1. Add 0.5 g of 4-vinylphenyl glycidyl ether to 20 mL of chloroform, stir evenly, then add 1.5 g of collagen fiber and 0.4 g of boron trifluoride diethyl ether complex, stir and react at 90 °C for 35 min, filter, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain a solid. Add 0.7 g of 1-carboxy-ortho-carborane and 3.5 g of the solid to 35 mL of ethanol, stir evenly, add a sodium hydroxide aqueous solution with a concentration of 10 mol / L to adjust the pH to 2.5, stir and react at 127 °C for 1.5 h, filter, wash 3 times with deionized water, and dry in an oven at 80 °C for 10 min to obtain the pretreated collagen fiber;

[0081] B2. Add 5.5 g of the pretreated collagen fiber to 45 mL of ethanol and 5 mL of deionized water, stir evenly, add 0.1 g of azobisisobutyronitrile, stir and react at 70 °C for 9 h, filter, wash 3 times with deionized water, and dry in an oven at 60 °C for 30 min to obtain the modified collagen fiber.

[0082] Example 3

[0083] A high-elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 100 parts of polyvinyl chloride resin, 20 parts of composite reinforcing material, 15 parts of modified collagen fiber, 3 parts of calcium-zinc stabilizer, 10 parts of dioctyl terephthalate, 8 parts of calcium stearate;

[0084] A preparation method of a high-elastic polyvinyl chloride material, comprising the following preparation steps:

[0085] Add the polyvinyl chloride resin, composite reinforcing material, modified collagen fiber, calcium-zinc stabilizer, dioctyl terephthalate, and calcium stearate to a mixer, mix well for 10 min to obtain a mixture, and extrude and pelletize the mixture through a twin-screw extruder to obtain the high-elastic polyvinyl chloride material.

[0086] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 110 °C, the temperature of the second zone is 120 °C, the temperature of the third zone is 130 °C, the temperature of the fourth zone is 135 °C, the temperature of the fifth zone is 140 °C, the temperature of the sixth zone is 135 °C, the temperature of the seventh zone is 115 °C, the temperature of the eighth zone is 115 °C, the temperature of the ninth zone is 115 °C; the screw speed is 450 r / min.

[0087] The composite reinforcing material is specifically prepared by the following steps:

[0088] A1. Add 6.5 g of sepiolite to 60 mL of hydrochloric acid solution with a concentration of 1.5 mol / L, stir evenly, place it in a 90 °C microwave oven, heat for 3 h, then cool to room temperature, filter, wash with absolute ethanol 3 times, wash with deionized water until the washing liquid is neutral in pH, place it in a 60 °C oven to dry for 10 min, and place it in a grinder to grind to obtain pretreated sepiolite;

[0089] A2. Add 6 g of tetrabutyl titanate and 0.3 g of cetyltrimethylammonium bromide to 35 mL of deionized water, stir evenly, add 12 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle and carry out hydrothermal reaction at 180 °C for 4 h, filter and collect the solid, place the solid in a muffle furnace, calcine at 300 °C for 50 min, cool to room temperature, take out, grind, and pass through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0090] A3. Add 6.5 g of 2-methylimidazole to 80 mL of deionized water, stir until dissolved, add 3 g of zinc nitrate hexahydrate and 15 g of sepiolite loaded with nano-titanium dioxide, stir at 30 °C for 22 h, then centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate with methanol 3 times and deionized water 3 times, and dry in a 70 °C oven for 15 min to obtain modified sepiolite;

[0091] A4. Mix 4 g of γ-aminopropyltriethoxysilane, 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 6 g of modified sepiolite and hydrochloric acid with a mass fraction of 37% to adjust the pH to 6, stir at 50 °C for 3 h, filter and collect the precipitate, wash the precipitate with deionized water 3 times, and dry in a 100 °C oven for 10 min to obtain the composite reinforcing material.

[0092] The modified collagen fiber is specifically prepared by the following steps

[0093] B1. Add 0.7 g of 4-vinylphenyl glycidyl ether to 25 mL of chloroform, stir evenly, then add 2 g of collagen fiber and 0.5 g of boron trifluoride diethyl etherate, stir and react at 100 °C for 40 min, filter, wash with deionized water 3 times, and dry in a 70 °C oven for 10 min to obtain a solid. Add 1 g of 1-carboxy-ortho-carborane and 4 g of the solid to 40 mL of ethanol, stir evenly, add sodium hydroxide aqueous solution with a concentration of 12 mol / L to adjust the pH to 3, stir and react at 130 °C for 2 h, filter, wash with deionized water 3 times, and dry in an 80 °C oven for 10 min to obtain pretreated collagen fiber;

[0094] B2. Add 6 g of pretreated collagen fibers to 50 mL of ethanol and 7 mL of deionized water, stir evenly, add 0.15 g of azobisisobutyronitrile, stir and react at 75 °C for 10 h, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 30 min to obtain modified collagen fibers.

[0095] Comparative Example 1

[0096] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 100 parts of polyvinyl chloride resin, 20 parts of composite reinforcing material, 15 parts of modified collagen fibers, 3 parts of calcium zinc stabilizer, 10 parts of dioctyl terephthalate, and 8 parts of calcium stearate;

[0097] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0098] Add polyvinyl chloride resin, composite reinforcing material, modified collagen fibers, calcium zinc stabilizer, dioctyl terephthalate, and calcium stearate to a blender, mix well for 10 min to obtain a mixture, and extrude and pelletize the mixture through a twin-screw extruder to obtain a highly elastic polyvinyl chloride material.

[0099] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 110 °C, the temperature of the second zone is 120 °C, the temperature of the third zone is 130 °C, the temperature of the fourth zone is 135 °C, the temperature of the fifth zone is 140 °C, the temperature of the sixth zone is 135 °C, the temperature of the seventh zone is 115 °C, the temperature of the eighth zone is 115 °C, and the temperature of the ninth zone is 115 °C; the screw speed is 450 r / min.

[0100] The composite reinforcing material is specifically prepared by the following steps:

[0101] A1. Add 6.5 g of sepiolite to 60 mL of hydrochloric acid solution with a concentration of 1.5 mol / L, stir evenly, place it in a 90 °C microwave oven, heat for 3 h, cool to room temperature, filter, wash with absolute ethanol 3 times, wash with deionized water until the washing liquid is neutral in pH, dry in an oven at 60 °C for 10 min, and grind in a grinder to obtain pretreated sepiolite;

[0102] A2. Add 6.5 g of 2-methylimidazole to 80 mL of deionized water, stir until dissolved, add 3 g of zinc nitrate hexahydrate and 15 g of pretreated sepiolite, stir at 30 °C for 22 h, centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate with methanol 3 times, wash with deionized water 3 times, and dry in an oven at 70 °C for 15 min to obtain modified sepiolite;

[0103] A3. Mix 4 g of γ-aminopropyltriethoxysilane, 100 mL of ethanol, and 6 mL of deionized water, stir evenly, add 6 g of modified sepiolite and hydrochloric acid with a mass fraction of 37% to adjust the pH to 6, stir at 50 °C for 3 h, filter to collect the precipitate, wash the precipitate 3 times with deionized water, and dry it in an oven at 100 °C for 10 min to obtain the composite reinforcing material.

[0104] The modified collagen fibers are specifically prepared by the following steps

[0105] B1. Add 0.7 g of 4-vinylphenyl glycidyl ether to 25 mL of chloroform, stir evenly, then add 2 g of collagen fibers and 0.5 g of boron trifluoride diethyl ether complex, stir and react at 100 °C for 40 min, filter, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain a solid. Add 1 g of 1-carboxy-o-carborane and 4 g of the solid to 40 mL of ethanol, stir evenly, add an aqueous sodium hydroxide solution with a concentration of 12 mol / L to adjust the pH to 3, stir and react at 130 °C for 2 h, filter, wash 3 times with deionized water, and dry in an oven at 80 °C for 10 min to obtain the pretreated collagen fibers;

[0106] B2. Add 6 g of the pretreated collagen fibers to 50 mL of ethanol and 7 mL of deionized water, stir evenly, add 0.15 g of azobisisobutyronitrile, stir and react at 75 °C for 10 h, filter, wash 3 times with deionized water, and dry in an oven at 60 °C for 30 min to obtain the modified collagen fibers.

[0107] Comparative Example 2

[0108] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 100 parts of polyvinyl chloride resin, 20 parts of composite reinforcing material, 15 parts of modified collagen fibers, 3 parts of calcium-zinc stabilizer, 10 parts of dioctyl terephthalate, and 8 parts of calcium stearate;

[0109] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0110] Add the polyvinyl chloride resin, composite reinforcing material, modified collagen fibers, calcium-zinc stabilizer, dioctyl terephthalate, and calcium stearate to a mixer, mix thoroughly for 10 min to obtain a mixture, and extrude and pelletize the mixture through a twin-screw extruder to obtain the highly elastic polyvinyl chloride material.

[0111] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 110 °C, the temperature of the second zone is 120 °C, the temperature of the third zone is 130 °C, the temperature of the fourth zone is 135 °C, the temperature of the fifth zone is 140 °C, the temperature of the sixth zone is 135 °C, the temperature of the seventh zone is 115 °C, the temperature of the eighth zone is 115 °C, and the temperature of the ninth zone is 115 °C; the screw speed is 450 r / min.

[0112] The composite reinforcing material is specifically prepared by the following steps:

[0113] A1. Add 6.5 g of sepiolite to 60 mL of hydrochloric acid solution with a concentration of 1.5 mol / L, stir evenly, place it in a microwave oven at 90 °C, heat for 3 h, then cool to room temperature, filter, wash 3 times with absolute ethanol, wash with deionized water until the washing liquid is neutral in pH, place it in an oven at 60 °C and dry for 10 min, and then place it in a grinder for grinding to obtain pretreated sepiolite;

[0114] A2. Add 6 g of tetrabutyl titanate and 0.3 g of cetyltrimethylammonium bromide to 35 mL of deionized water, stir evenly, add 12 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle and carry out hydrothermal reaction at 180 °C for 4 h, filter and collect the solid, place the solid in a muffle furnace, calcine at 300 °C for 50 min, cool to room temperature, take it out, grind, and pass through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0115] A3. Mix 4 g of γ-aminopropyltriethoxysilane, 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 6 g of sepiolite loaded with nano-titanium dioxide and hydrochloric acid with a mass fraction of 37% to adjust the pH to 6, stir at 50 °C for 3 h, filter and collect the precipitate, wash the precipitate 3 times with deionized water, and dry in an oven at 100 °C for 10 min to obtain the composite reinforcing material.

[0116] The modified collagen fiber is specifically prepared by the following steps

[0117] B1. Add 0.7 g of 4-vinylphenyl glycidyl ether to 25 mL of chloroform, stir evenly, then add 2 g of collagen fiber and 0.5 g of boron trifluoride diethyl etherate, stir and react at 100 °C for 40 min, filter, wash 3 times with deionized water, dry in an oven at 70 °C for 10 min to obtain a solid, add 1 g of 1-carboxy-ortho-carborane and 4 g of the solid to 40 mL of ethanol, stir evenly, add sodium hydroxide aqueous solution with a concentration of 12 mol / L to adjust the pH to 3, stir and react at 130 °C for 2 h, filter, wash 3 times with deionized water, and dry in an oven at 80 °C for 10 min to obtain pretreated collagen fiber;

[0118] B2. Add 6 g of pretreated collagen fiber to 50 mL of ethanol and 7 mL of deionized water, stir evenly, add 0.15 g of azobisisobutyronitrile, stir and react at 75 °C for 10 h, filter, wash 3 times with deionized water, and dry in an oven at 60 °C for 30 min to obtain the modified collagen fiber.

[0119] Comparative Example 3

[0120] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 100 parts of polyvinyl chloride resin, 20 parts of modified sepiolite, 15 parts of modified collagen fiber, 3 parts of calcium-zinc stabilizer, 10 parts of dioctyl terephthalate, and 8 parts of calcium stearate;

[0121] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0122] Add polyvinyl chloride resin, modified sepiolite, modified collagen fiber, calcium-zinc stabilizer, dioctyl terephthalate, and calcium stearate into a blender, mix well for 10 min to obtain a mixture, and extrude and pelletize the mixture through a twin-screw extruder to obtain the highly elastic polyvinyl chloride material.

[0123] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 110 °C, the temperature of the second zone is 120 °C, the temperature of the third zone is 130 °C, the temperature of the fourth zone is 135 °C, the temperature of the fifth zone is 140 °C, the temperature of the sixth zone is 135 °C, the temperature of the seventh zone is 115 °C, the temperature of the eighth zone is 115 °C, and the temperature of the ninth zone is 115 °C; the screw speed is 450 r / min.

[0124] The composite reinforcing material is specifically prepared by the following steps:

[0125] A1. Add 6.5 g of sepiolite to 60 mL of hydrochloric acid solution with a concentration of 1.5 mol / L, stir evenly, place it in a 90 °C microwave oven, heat for 3 h, cool to room temperature, filter, wash 3 times with absolute ethanol, wash with deionized water until the washing liquid is neutral in pH, place it in a 60 °C oven to dry for 10 min, and place it in a grinder to grind to obtain pretreated sepiolite;

[0126] A2. Add 6 g of tetrabutyl titanate and 0.3 g of cetyltrimethylammonium bromide to 35 mL of deionized water, stir evenly, add 12 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle, carry out hydrothermal reaction at 180 °C for 4 h, filter and collect the solid, place the solid in a muffle furnace, calcine at 300 °C for 50 min, cool to room temperature, take out, grind, and pass through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0127] A3. Add 6.5 g of 2-methylimidazole to 80 mL of deionized water, stir until dissolved, add 3 g of zinc nitrate hexahydrate and 15 g of sepiolite loaded with nano-titanium dioxide, stir at 30 °C for 22 h, then centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate 3 times with methanol and 3 times with deionized water, and dry it in a 70 °C oven for 15 min to obtain modified sepiolite.

[0128] The modified collagen fiber is specifically prepared by the following steps

[0129] B1. Add 0.7 g of 4-vinylphenyl glycidyl ether to 25 mL of chloroform, stir evenly, then add 2 g of collagen fiber and 0.5 g of boron trifluoride diethyl ether complex. Stir and react at 100 °C for 40 min. After filtration, wash with deionized water three times, and dry in an oven at 70 °C for 10 min to obtain a solid. Add 1 g of 1-carboxy-ortho-carborane and 4 g of the solid to 40 mL of ethanol, stir evenly, add sodium hydroxide aqueous solution with a concentration of 12 mol / L to adjust the pH to 3, stir and react at 130 °C for 2 h. After filtration, wash with deionized water three times, and dry in an oven at 80 °C for 10 min to obtain pretreated collagen fiber;

[0130] B2. Add 6 g of pretreated collagen fiber to 50 mL of ethanol and 7 mL of deionized water, stir evenly, add 0.15 g of azobisisobutyronitrile, stir and react at 75 °C for 10 h. After filtration, wash with deionized water three times, and dry in an oven at 60 °C for 30 min to obtain modified collagen fiber.

[0131] Comparative Example 4

[0132] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 100 parts of polyvinyl chloride resin, 20 parts of composite reinforcing material, 15 parts of modified collagen fiber, 3 parts of calcium-zinc stabilizer, 10 parts of dioctyl terephthalate, and 8 parts of calcium stearate;

[0133] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0134] Add polyvinyl chloride resin, composite reinforcing material, modified collagen fiber, calcium-zinc stabilizer, dioctyl terephthalate, and calcium stearate to a mixer, mix thoroughly for 10 min to obtain a mixture. The mixture is extruded by a twin-screw extruder and pelletized to obtain a highly elastic polyvinyl chloride material.

[0135] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 110 °C, the temperature of the second zone is 120 °C, the temperature of the third zone is 130 °C, the temperature of the fourth zone is 135 °C, the temperature of the fifth zone is 140 °C, the temperature of the sixth zone is 135 °C, the temperature of the seventh zone is 115 °C, the temperature of the eighth zone is 115 °C, and the temperature of the ninth zone is 115 °C; the screw speed is 450 r / min.

[0136] The composite reinforcing material is specifically prepared by the following steps:

[0137] A1. Add 6.5 g of sepiolite to 60 mL of hydrochloric acid solution with a concentration of 1.5 mol / L, stir evenly, place it in a 90 °C microwave oven, after heating for 3 h, cool to room temperature, filter, wash with absolute ethanol three times, wash with deionized water until the pH of the washing solution is neutral, dry in an oven at 60 °C for 10 min, and grind in a grinder to obtain pretreated sepiolite;

[0138] A2. Add 6 g of tetrabutyl titanate and 0.3 g of cetyltrimethylammonium bromide to 35 mL of deionized water, stir evenly, add 12 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle and carry out hydrothermal reaction at 180 °C for 4 h. Filter and collect the solid. Place the solid in a muffle furnace and calcine it at 300 °C for 50 min, cool it to room temperature, take it out, grind it, and pass it through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0139] A3. Add 6.5 g of 2-methylimidazole to 80 mL of deionized water, stir until dissolved, add 3 g of zinc nitrate hexahydrate and 15 g of sepiolite loaded with nano-titanium dioxide, stir at 30 °C for 22 h, then centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate 3 times with methanol and 3 times with deionized water, and dry it in an oven at 70 °C for 15 min to obtain modified sepiolite;

[0140] A4. Mix 4 g of γ-aminopropyltriethoxysilane, 100 mL of ethanol and 6 mL of deionized water, stir evenly, add 6 g of modified sepiolite and hydrochloric acid with a mass fraction of 37% to adjust the pH to 6, stir at 50 °C for 3 h, filter and collect the precipitate, wash the precipitate 3 times with deionized water, and dry it in an oven at 100 °C for 10 min to obtain a composite reinforcing material.

[0141] The modified collagen fiber is specifically prepared by the following steps

[0142] B1. Add 0.7 g of 4-vinylphenyl glycidyl ether to 25 mL of chloroform, stir evenly, then add 2 g of collagen fiber and 0.5 g of boron trifluoride diethyl etherate, stir and react at 100 °C for 40 min, filter, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain a solid;

[0143] B2. Add 6 g of the solid to 50 mL of ethanol and 7 mL of deionized water, stir evenly, add 0.15 g of azobisisobutyronitrile, stir and react at 75 °C for 10 h, filter, wash 3 times with deionized water, and dry in an oven at 60 °C for 30 min to obtain the modified collagen fiber.

[0144] Comparative Example 5

[0145] A highly elastic polyvinyl chloride material, comprising the following raw materials in parts by mass: 100 parts of polyvinyl chloride resin, 20 parts of composite reinforcing material, 15 parts of collagen fiber, 3 parts of calcium-zinc stabilizer, 10 parts of dioctyl terephthalate, and 8 parts of calcium stearate;

[0146] A preparation method of a highly elastic polyvinyl chloride material, comprising the following preparation steps:

[0147] Add polyvinyl chloride resin, composite reinforcing material, collagen fiber, calcium zinc stabilizer, dioctyl terephthalate, and calcium stearate to a blender, mix well for 10 min to obtain a mixed material, and extrude and granulate the mixed material through a twin-screw extruder to obtain a high-elastic polyvinyl chloride material.

[0148] Among them, the extrusion process of the twin-screw extruder: the temperature of the first zone is 110 °C, the second zone is 120 °C, the third zone is 130 °C, the fourth zone is 135 °C, the fifth zone is 140 °C, the sixth zone is 135 °C, the seventh zone is 115 °C, the eighth zone is 115 °C, and the ninth zone is 115 °C; the screw speed is 450 r / min.

[0149] The composite reinforcing material is specifically prepared by the following steps:

[0150] A1. Add 6.5 g of sepiolite to 60 mL of hydrochloric acid solution with a concentration of 1.5 mol / L, stir evenly, place it in a 90 °C microwave oven, after heating for 3 h, cool to room temperature, filter, wash 3 times with absolute ethanol, wash with deionized water until the washing solution is neutral in pH, place it in an oven at 60 °C for drying for 10 min, and place it in a grinder for grinding to obtain pretreated sepiolite;

[0151] A2. Add 6 g of tetrabutyl titanate and 0.3 g of cetyltrimethylammonium bromide to 35 mL of deionized water, stir evenly, add 12 g of pretreated sepiolite, stir at a rate of 600 r / min for 30 min, then place it in a hydrothermal reaction kettle, carry out hydrothermal reaction at 180 °C for 4 h, filter and collect the solid, place the solid in a muffle furnace, calcine at 300 °C for 50 min, cool to room temperature, take out, grind, and pass through a 500-mesh sieve to obtain sepiolite loaded with nano-titanium dioxide;

[0152] A3. Add 6.5 g of 2-methylimidazole to 80 mL of deionized water, stir until dissolved, add 3 g of zinc nitrate hexahydrate and 15 g of sepiolite loaded with nano-titanium dioxide, stir at 30 °C for 22 h, then centrifuge at a rate of 2500 r / min for 10 min, collect the precipitate, wash the precipitate 3 times with methanol, wash 3 times with deionized water, and dry in an oven at 70 °C for 15 min to obtain modified sepiolite;

[0153] A4. Mix 4 g of γ-aminopropyltriethoxysilane, 100 mL of ethanol, and 6 mL of deionized water, stir evenly, add 6 g of modified sepiolite and hydrochloric acid with a mass fraction of 37% to adjust the pH to 6, stir at 50 °C for 3 h, filter and collect the precipitate, wash the precipitate 3 times with deionized water, and dry in an oven at 100 °C for 10 min to obtain the composite reinforcing material.

[0154] The high-elasticity polyvinyl chloride materials prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests.

[0155] The above-prepared high-elasticity polyvinyl chloride materials were injection-molded using ASTM standards. The dimensions of the specimen were length × width × thickness = 170 mm × 13 mm × 3.2 mm. According to ASTM D638-14 standards, with a tensile speed of 5 mm / min, the elastic modulus, tensile strength, and flexural strength of the high-elasticity polyvinyl chloride materials were measured.

[0156] Compressive strength test: The compressive strength of the above-prepared high-elasticity polyvinyl chloride materials was tested according to ASTM D695-2015 CN standards; as shown in Table 1 below.

[0157] Table 1 Performance tests of the high-elasticity polyvinyl chloride materials prepared in Examples 1-3 and Comparative Examples 1-4

[0158]

[0159] As can be seen from the data in Table 1, the high-elasticity polyvinyl chloride materials prepared in Examples 1-3 have relatively high elastic modulus and mechanical strength. In Comparative Example 1, the sepiolite loaded with nano-titanium dioxide was replaced with pretreated sepiolite to prepare a composite reinforcing material, which was added to the high-elasticity polyvinyl chloride material. The mechanical strength and elastic modulus decreased, proving that synthesizing nano-titanium dioxide in the pores of pretreated sepiolite can block the pores of pretreated sepiolite, improve the mechanical properties and elastic modulus of the polyvinyl chloride material, and the high-strength nano-titanium dioxide serves as the support framework of pretreated sepiolite to enhance the mechanical strength of pretreated sepiolite.

[0160] In Comparative Example 2, the modified sepiolite was replaced with a composite reinforcing material prepared from sepiolite loaded with nano-titanium dioxide, which was added to the high-elasticity polyvinyl chloride material. The mechanical strength and elastic modulus decreased, indicating that forming a porous zinc-based metal-organic framework on the surface of sepiolite loaded with nano-titanium dioxide can prevent creep and relaxation phenomena of the polyvinyl chloride material under external forces, affecting the elastic modulus of the polyvinyl chloride material.

[0161] In Comparative Example 3, the composite reinforcing material was replaced with modified sepiolite, which was added to the high-elasticity polyvinyl chloride material. The mechanical strength and elastic modulus decreased, indicating that grafting γ-aminopropyltriethoxysilane on the surface of modified sepiolite significantly improved the interfacial compatibility between the composite reinforcing material and the polyvinyl chloride material, enabling the composite reinforcing material to be dispersed in the polyvinyl chloride matrix and enhancing the elastic modulus and mechanical properties of the polyvinyl chloride.

[0162] In Comparative Example 4, the pretreated collagen fibers were replaced with modified collagen fibers prepared in solid form and added to the highly elastic polyvinyl chloride material. The mechanical strength and elastic modulus decreased, demonstrating that 1-carboxy-ortho-carborane contains a stable cage structure, has high thermal stability, can improve the heat resistance of collagen fibers, and avoid the thermal decomposition of collagen fibers, which affects the elastic properties of the polyvinyl chloride material.

[0163] In Comparative Example 5, the modified collagen fibers were replaced with collagen fibers and added to the highly elastic polyvinyl chloride material. The mechanical strength and elastic modulus decreased, demonstrating that the copolymerization of 4-vinylphenyl glycidyl ether to form a polymer and 1-carboxy-ortho-carborane can penetrate into the three-dimensional multi-level structure of collagen fibers, expand the layer spacing of collagen fibers, increase the interaction sites between the modified collagen fibers and the polyvinyl chloride molecular chains, and effectively prevent the polyvinyl chloride molecular chains from being detached during impact and restrict the movement of the polyvinyl chloride molecular chains.

[0164] In the description of the specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0165] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A highly elastic polyvinyl chloride material, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of polyvinyl chloride resin, 10-20 parts of composite reinforcement material, 10-15 parts of modified collagen fiber, 2-3 parts of stabilizer, 5-10 parts of plasticizer and 6-8 parts of lubricant; The composite reinforcement material is prepared by mixing sepiolite loaded with nano-titanium dioxide, imidazole monomer and zinc nitrate hexahydrate, and then surface-modifying with silane. The nano-titanium dioxide loaded sepiolite is prepared by mixing pretreated sepiolite with tetrabutyl titanate and subjecting the mixture to a hydrothermal reaction; The modified collagen fiber is obtained by mixing 4-vinylphenyl glycidyl ether, 1-carboxyl o-carborane and the surface of the collagen fiber and then initiating polymerization.

2. A highly elastic polyvinyl chloride material according to claim 1, characterized in that: The composite reinforced material is specifically prepared by the following steps: A1. Add sepiolite to a concentration of 0.5-1.5 mol / L hydrochloric acid solution, stir evenly, place in a microwave oven at 70-90 ℃, heat for 1-3h, cool to room temperature, filter, wash, dry, grind and sieve to obtain pretreated sepiolite; A2. Tetrabutyl titanate and hexadecyltrimethylammonium bromide were added to deionized water, stirred evenly, and pretreated sepiolite was added, stirred evenly, placed in a hydrothermal reactor, and subjected to a hydrothermal reaction at 160-180 ° C for 2-4h, the solid was collected by filtration, and the solid was placed in a muffle furnace, calcined at 200-300 ° C for 30-50min, cooled to room temperature, removed, ground, and sieved to obtain a sepiolite loaded with nano-titanium dioxide; A3. 2-methylimidazole was added to deionized water and stirred until dissolved, zinc nitrate hexahydrate and nano-titanium dioxide-loaded sepiolite were added, stirred at 20-30 ° C for 20-22h, and the precipitate was collected by centrifugation, the precipitate was washed and dried to obtain a modified sepiolite; A4. Mix silane, ethanol and deionized water, stir evenly, add modified sepiolite and 35-37% hydrochloric acid by mass to adjust the pH to 5-6, stir at 40-50°C for 1-3h, filter, wash and dry to obtain a composite reinforced material.

3. A highly elastic polyvinyl chloride material according to claim 2, characterized in that: In step A1, the ratio of the sepiolite to the hydrochloric acid solution is (5.5-6.5) g: (40-60) mL.

4. A highly elastic polyvinyl chloride material according to claim 2, characterized in that: In step A2, the amount ratio of tetrabutyl titanate, hexadecyltrimethylammonium bromide, deionized water, and pretreated sepiolite is (5-6) g: (0.1-0.3) g: (25-35) mL: (10-12) g.

5. The high elastic polyvinyl chloride material according to claim 2, characterized in that: In step A3, the ratio of 2-methylimidazole, deionized water, zinc nitrate hexahydrate, and nano-titanium dioxide-loaded sepiolite is (5.5-6.5) g: (60-80) mL: (2-3) g: (12-15) g; In step A4, the ratio of the amount of silane, ethanol, deionized water, and modified sepiolite is (2-4) g: (90-100) mL: (4-6) mL: (5-6) g.

6. The high elastic polyvinyl chloride material according to claim 1, characterized in that: The modified collagen fiber is specifically prepared by the following steps: B1. Add 4-vinylphenyl glycidyl ether to chloroform, stir evenly, add collagen fibers and boron trifluoride ethyl ether, stir and react at 80-100° C. for 30-40 min, filter, wash and dry to obtain a solid, add 1-carboxyl o-carborane and the solid to ethanol, stir evenly, add 8-12 mol / L sodium hydroxide aqueous solution to adjust the pH to 2-3, stir and react at 125-130° C. for 1-2 h, filter, wash and dry to obtain pretreated collagen fibers; B2. Add the pretreated collagen fibers to ethanol and deionized water, stir evenly, add azobisisobutyronitrile, stir and react at 65-75° C. for 8-10 hours, filter, wash and dry to obtain modified collagen fibers.

7. A highly elastic polyvinyl chloride material according to claim 6, characterized in that: In step B1, the amount ratio of 4-vinylphenyl glycidyl ether, chloroform, collagen fiber, and boron trifluoride ether is (0.3-0.7) g: (15-25) mL: (1-2) g: (0.3-0.5) g; the amount ratio of 1-carboxyl o-carborane, solid, and ethanol is (0.5-1) g: (3-4) g: (30-40) mL.

8. The high elastic polyvinyl chloride material according to claim 6, characterized in that: In step B2, the ratio of the pretreated collagen fibers, ethanol, deionized water, and azobisisobutyronitrile is (5-6): (40-50) mL: (3-7) mL: (0.05-0.15) g.

9. A method for preparing a highly elastic polyvinyl chloride material according to any one of claims 1 to 8, characterized in that: The method comprises the following preparation steps: Add polyvinyl chloride resin, composite reinforcement material, modified collagen fiber, stabilizer, plasticizer and lubricant into a mixer and mix them thoroughly for 8-10 minutes to obtain a mixture. The mixture is extruded through a twin-screw extruder and granulated to obtain a high-elastic polyvinyl chloride material.

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