Environment-friendly oil-resistant PVC slipper material and preparation process thereof

Abstract

The invention relates to the technical field of polyvinyl chloride shoe materials, and discloses an environment-friendly oil-resistant PVC slipper material and a preparation process thereof.The PVC slipper material is prepared from, by weight, 70-85 parts of polyvinyl chloride, 15-30 parts of nitrile rubber, 23-30 parts of plasticizer, 2-3.5 parts of GMA grafted CPE, 1.8-3 parts of carboxyl-terminated polyacrylonitrile and the like; in the high-temperature mixing process, an epoxy group of a GMA grafted CPE side chain and a terminal carboxyl group of polyacrylonitrile are subjected to ring-opening initiation, so that a polyacrylonitrile molecular chain is introduced into a side chain of CPE chlorinated polyethylene, a polyacrylonitrile-CPE polymer is formed and can play a role of a compatilizer, the compatibility between polyvinyl chloride and nitrile rubber is improved, and the mechanical property of the material is improved. The PVC slipper material has higher tensile property and tearing strength, and is low in oil absorption rate and excellent in oil resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of polyvinyl chloride shoe materials, and specifically to an environmentally friendly oil-resistant PVC slipper material and its preparation process. Background Art

[0002] Polyvinyl chloride has good wear resistance, electrical insulation, and corrosion resistance, and has a low production cost. It is widely used in sole materials, wires and cables, packaging materials, pipe materials, etc. Traditional polyvinyl chloride sole materials have problems such as poor mechanical strength, easy cracking, and poor oil resistance. Modifying polyvinyl chloride with rubber materials, such as nitrile rubber, styrene-butadiene rubber, ethylene propylene diene monomer rubber, polyurethane rubber, etc., can improve the comprehensive performance of polyvinyl chloride.

[0003] Nitrile rubber has good oil resistance, wear resistance, heat resistance and other properties. Combining nitrile rubber with polyvinyl chloride can give play to the advantages of both and obtain a composite material with better performance. Chinese Patent CN114196134B discloses a women's shoe with a cold-resistant sole and its preparation method. Using modified polyvinyl chloride, powdered nitrile rubber, ethyl p-aminobenzoate, etc. as raw materials, the prepared sole material has excellent cold resistance, but this patent does not improve the mechanical properties such as the tensile properties and tear strength of the polyvinyl chloride sole material. Summary of the Invention

[0004] The present invention solves the problem of poor mechanical properties of PVC slipper materials.

[0005] The technical solution of the present invention: An environmentally friendly oil-resistant PVC slipper material, characterized in that, by weight, the PVC slipper material comprises 70 - 85 parts of polyvinyl chloride, 15 - 30 parts of nitrile rubber, 23 - 30 parts of plasticizer, 2 - 3.5 parts of GMA-grafted CPE, 1.8 - 3 parts of carboxyl-terminated polyacrylonitrile, 2.2 - 3 parts of heat stabilizer, 3 - 5 parts of foaming agent, 0.2 - 0.3 parts of crosslinking agent, 1.3 - 2 parts of filler, 0.8 - 1.3 parts of auxiliary agent, 1.2 - 1.6 parts of antioxidant.

[0006] Further, the plasticizer is dioctyl terephthalate, the heat stabilizer is a calcium-zinc stabilizer, the foaming agent is azodicarbonamide, the crosslinking agent is diisopropylbenzene peroxide, the filler is zinc oxide, and the antioxidant is antioxidant 4100NA. The auxiliary agent is any one or a combination of stearic acid and zinc stearate.

[0007] Further, the preparation process of GMA-grafted CPE is as follows: By weight, 100 parts of chlorinated polyethylene, 2-5 parts of glycidyl methacrylate, and 0.3-0.6 parts of diisopropylbenzene peroxide are added to a torque rheometer, and melt grafting is carried out at 170-175 °C for 6-10 min. After cooling and discharging, the product is added to xylene, heated under reflux, and the filtered product is extracted with acetone in a Soxhlet extractor to obtain GMA-grafted CPE.

[0008] Further, the preparation process of carboxyl-terminated polyacrylonitrile is as follows: By weight, N,N-dimethylformamide, 100 parts of acrylonitrile, 2.2-3.5 parts of S,S'-bis(α,α'-methyl-α"-acetic acid) trithiocarbonate, and 0.22-0.3 parts of azobisisobutyronitrile are added to a reaction vessel. Under a nitrogen atmosphere, it is heated to 65-75 °C and reacted for 12-18 h. Ethanol is added to the solution for dilution, and after filtration, it is washed with ethanol and dried to obtain carboxyl-terminated polyacrylonitrile. The reaction formula is:

[0009]

[0010] Further, the preparation process of the environmentally friendly oil-resistant PVC slipper material is as follows: Nitrile rubber is placed in a two-roll kneader for kneading, and then polyvinyl chloride, plasticizer, GMA-grafted CPE, carboxyl-terminated polyacrylonitrile, heat stabilizer, filler, auxiliary agent, and antioxidant are added, and kneading is carried out at 100-110 °C for 10-15 min. A foaming agent and a crosslinking agent are added for kneading, and then discharged; finally, foaming is carried out in an injection molding machine at a temperature of 180-210 °C, a pressure of 10-15 MPa, and a time of 8-10 min, and then cooled to obtain the environmentally friendly oil-resistant PVC slipper material.

[0011] The technical effects of the present invention: In the present invention, polyvinyl chloride, nitrile rubber, GMA-grafted CPE, carboxyl-terminated polyacrylonitrile, plasticizer, heat stabilizer, filler, etc. are subjected to high-temperature kneading and vulcanization foaming to obtain an environmentally friendly oil-resistant PVC slipper material. During the high-temperature kneading process, the epoxy group on the side chain of GMA-grafted CPE undergoes ring-opening initiation with the carboxyl group at the end of polyacrylonitrile, thereby introducing the polyacrylonitrile molecular chain into the side chain of CPE chlorinated polyethylene to form a polyacrylonitrile-CPE polymer. Since the compatibility between chlorinated polyethylene and polyvinyl chloride is good, and the polyacrylonitrile molecular chain on the side chain also has a similar polarity to the polyacrylonitrile block molecular chain in nitrile rubber, the polyacrylonitrile-grafted CPE acts as a compatibilizer, further improving the compatibility between polyvinyl chloride and nitrile rubber, making the PVC slipper material have higher tensile properties and tear strength, and low oil absorption rate and excellent oil resistance. Specific embodiments

[0012] To make the objectives, technical solutions and beneficial effects of the present invention clearer, the preferred embodiments of the present invention will be described in detail below to facilitate understanding by those skilled in the art.

[0013] The following are polyvinyl chloride, model PVCP440, from Dongguan Zhengtao Plastic Co., Ltd.; nitrile butadiene rubber, model NBR3305E, from Dongguan Zhengtao Plastic Co., Ltd.; chlorinated polyethylene, model CPE7100, from Dongguan Chengjin Plastic Co., Ltd.; calcium-zinc stabilizer, model MC91717KA / 2, from Guangzhou Shenyue Trading Co., Ltd.

[0014] Example 1:

[0015] (1) Add 200 g of chlorinated polyethylene, 7 g of glycidyl methacrylate, and 0.9 g of diisopropylbenzene peroxide to a torque rheometer, and conduct melt grafting at 170 °C for 10 min. After cooling and discharging, the product is added to xylene, heated under reflux, filtered, and then extracted with acetone in a Soxhlet extractor to obtain GMA-grafted CPE.

[0016] (2) Add 150 mL of N,N-dimethylformamide, 100 g of acrylonitrile, 2.8 g of S,S'-bis(α,α'-methyl-α"-acetic acid) trithiocarbonate, and 0.26 g of azobisisobutyronitrile to a reaction vessel, heat to 65 °C under a nitrogen atmosphere, and react for 18 h. Dilute the solution with ethanol, filter, wash with ethanol, and dry to obtain carboxyl-terminated polyacrylonitrile.

[0017] (3) Place 1.5 kg of nitrile butadiene rubber in a two-roll mill for plasticization, then add 8.5 kg of polyvinyl chloride, 3 kg of plasticizer dioctyl terephthalate, 200 g of GMA-grafted CPE, 180 g of carboxyl-terminated polyacrylonitrile, 300 g of calcium-zinc stabilizer, 160 g of filler zinc oxide, 70 g of stearic acid, 30 g of zinc stearate, 120 g of antioxidant 4100NA, and mix at 100 °C for 15 min. Add 500 g of blowing agent azodicarbonamide and 20 g of crosslinking agent diisopropylbenzene peroxide, and conduct mixing and discharging; finally, conduct foaming in an injection molding machine at a temperature of 180 °C, a pressure of 10 MPa, and a time of 10 min, and then cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0018] Example 2:

[0019] (1) Add 200 g of chlorinated polyethylene, 10 g of glycidyl methacrylate, and 1.2 g of diisopropylbenzene peroxide to a torque rheometer, and conduct melt grafting at 175 °C for 8 min. After cooling and discharging, the product is added to xylene, heated under reflux, filtered, and then extracted with acetone in a Soxhlet extractor to obtain GMA-grafted CPE.

[0020] (2) Add 150 mL of N,N-dimethylformamide, 100 g of acrylonitrile, 3.5 g of S,S'-bis(α,α'-methyl-α"-acetic acid) trithiocarbonate, and 0.3 g of azobisisobutyronitrile into the reaction vessel. Under a nitrogen atmosphere, heat to 70 °C and react for 18 h. Add ethanol to dilute the solution, filter, wash with ethanol, and dry to obtain carboxyl-terminated polyacrylonitrile.

[0021] (3) Place 2 kg of nitrile rubber in a two-roll mill for kneading, then add 8 kg of polyvinyl chloride, 2.6 kg of plasticizer dioctyl terephthalate, 300 g of GMA-grafted CPE, 250 g of carboxyl-terminated polyacrylonitrile, 270 g of calcium-zinc stabilizer, 130 g of filler zinc oxide, 80 g of stearic acid, 30 g of zinc stearate, 130 g of antioxidant 4100NA, knead at 110 °C for 10 min, add 420 g of foaming agent azodicarbonamide and 28 g of crosslinking agent dicumyl peroxide, and carry out kneading, then discharge; finally, carry out foaming in an injection molding machine at a temperature of 210 °C, a pressure of 15 MPa, and a time of 8 min, and cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0022] Example 3:

[0023] (1) Add 200 g of chlorinated polyethylene, 4 g of glycidyl methacrylate, and 0.6 g of dicumyl peroxide into a torque rheometer, carry out melt grafting at 170 °C for 6 min, cool and discharge. Add the product into xylene, heat to reflux, filter, and then extract the product with acetone in a Soxhlet extractor to obtain GMA-grafted CPE.

[0024] (2) Add 100 mL of N,N-dimethylformamide, 100 g of acrylonitrile, 2.2 g of S,S'-bis(α,α'-methyl-α"-acetic acid) trithiocarbonate, and 0.22 g of azobisisobutyronitrile into the reaction vessel. Under a nitrogen atmosphere, heat to 75 °C and react for 12 h. Add ethanol to dilute the solution, filter, wash with ethanol, and dry to obtain carboxyl-terminated polyacrylonitrile.

[0025] (3) Place 3 kg of nitrile rubber in a two-roll mill for kneading, then add 7 kg of polyvinyl chloride, 2.3 kg of plasticizer dioctyl terephthalate, 350 g of GMA-grafted CPE, 300 g of carboxyl-terminated polyacrylonitrile, 220 g of calcium-zinc stabilizer, 200 g of filler zinc oxide, 50 g of stearic acid, 50 g of zinc stearate, 160 g of antioxidant 4100NA, knead at 110 °C for 12 min, add 300 g of foaming agent azodicarbonamide and 30 g of crosslinking agent dicumyl peroxide, and carry out kneading, then discharge; finally, carry out foaming in an injection molding machine at a temperature of 190 °C, a pressure of 15 MPa, and a time of 8 min, and cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0026] Comparative Example 1: The difference between this comparative example and Example 1 is that GMA-grafted CPE and carboxyl-terminated polyacrylonitrile are not added.

[0027] (1) Place 1.5 kg of nitrile rubber in a two-roll plasticizer and plasticize it. Then add 8.5 kg of polyvinyl chloride, 3 kg of plasticizer dioctyl terephthalate, 300 g of calcium-zinc stabilizer, 160 g of filler zinc oxide, 70 g of stearic acid, 30 g of zinc stearate, 120 g of antioxidant 4100NA, and mix at 100 °C for 15 min. Add 500 g of blowing agent azodicarbonamide and 20 g of crosslinking agent dicumyl peroxide, and mix. Discharge the material. Finally, foam in an injection molding machine at a temperature of 180 °C, a pressure of 10 MPa, and a time of 10 min, and then cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0028] Comparative Example 2: The difference between this comparative example and Example 1 is that GMA-grafted CPE is not added.

[0029] (1) Place 1.5 kg of nitrile rubber in a two-roll plasticizer and plasticize it. Then add 8.5 kg of polyvinyl chloride, 3 kg of plasticizer dioctyl terephthalate, 180 g of carboxyl-terminated polyacrylonitrile, 300 g of calcium-zinc stabilizer, 160 g of filler zinc oxide, 70 g of stearic acid, 30 g of zinc stearate, 120 g of antioxidant 4100NA, and mix at 100 °C for 15 min. Add 500 g of blowing agent azodicarbonamide and 20 g of crosslinking agent dicumyl peroxide, and mix. Discharge the material. Finally, foam in an injection molding machine at a temperature of 180 °C, a pressure of 10 MPa, and a time of 10 min, and then cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0030] Comparative Example 3: The difference between this comparative example and Example 1 is that carboxyl-terminated polyacrylonitrile is not added.

[0031] (1) Place 1.5 kg of nitrile rubber in a two-roll plasticizer and plasticize it. Then add 8.5 kg of polyvinyl chloride, 3 kg of plasticizer dioctyl terephthalate, 200 g of GMA-grafted CPE, 300 g of calcium-zinc stabilizer, 160 g of filler zinc oxide, 70 g of stearic acid, 30 g of zinc stearate, 120 g of antioxidant 4100NA, and mix at 100 °C for 15 min. Add 500 g of blowing agent azodicarbonamide and 20 g of crosslinking agent dicumyl peroxide, and mix. Discharge the material. Finally, foam in an injection molding machine at a temperature of 180 °C, a pressure of 10 MPa, and a time of 10 min, and then cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0032] Comparative Example 4: The difference between this comparative example and Example 1 is that chlorinated polyethylene is used instead of GMA-grafted CPE.

[0033] (1) Place 1.5 kg of nitrile rubber in a two-roll plasticizer for plasticizing, then add 8.5 kg of polyvinyl chloride, 3 kg of plasticizer dioctyl terephthalate, 200 g of chlorinated polyethylene, 180 g of carboxyl-terminated polyacrylonitrile, 300 g of calcium-zinc stabilizer, 160 g of filler zinc oxide, 70 g of stearic acid, 30 g of zinc stearate, 120 g of antioxidant 4100NA, mix at 100 °C for 15 min, add 500 g of foaming agent azodicarbonamide and 20 g of crosslinking agent dicumyl peroxide, mix, and discharge; finally, carry out foaming in an injection molding machine at a temperature of 180 °C, a pressure of 10 MPa, and a time of 10 min, and cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0034] Comparative Example 5: The difference between this comparative example and Example 1 is that polyacrylonitrile is used instead of carboxyl-terminated polyacrylonitrile.

[0035] (1) Add 400 mL of N,N-dimethylformamide, 100 g of acrylonitrile, and 0.9 g of azobisisobutyronitrile to a reaction vessel, heat to 70 °C in a nitrogen atmosphere, react for 3 h, dilute the solution with ethanol, filter, wash with ethanol, and dry to obtain polyacrylonitrile.

[0036] (2) Place 1.5 kg of nitrile rubber in a two-roll plasticizer for plasticizing, then add 8.5 kg of polyvinyl chloride, 3 kg of plasticizer dioctyl terephthalate, 200 g of GMA-grafted CPE, 180 g of polyacrylonitrile, 300 g of calcium-zinc stabilizer, 160 g of filler zinc oxide, 70 g of stearic acid, 30 g of zinc stearate, 120 g of antioxidant 4100NA, mix at 100 °C for 15 min, add 500 g of foaming agent azodicarbonamide and 20 g of crosslinking agent dicumyl peroxide, mix, and discharge; finally, carry out foaming in an injection molding machine at a temperature of 180 °C, a pressure of 10 MPa, and a time of 10 min, and cool to obtain an environmentally friendly oil-resistant PVC slipper material.

[0037] Make the PVC slipper material into a specimen of 20 cm × 8 cm × 1 cm, dry and weigh it, add it to gasoline, soak for 72 h, take it out, hang it for 30 min, drain and wipe the residual gasoline on the surface, weigh it, and calculate the oil absorption rate W. W = (m - m0) / m0, the smaller the oil absorption rate, the better the oil absorption performance and oil resistance performance.

[0038] The tensile properties of the slipper material are tested according to the national standard GB / T 6344-2008. The tear strength is tested according to the national standard GB / T10808-2006.

[0039] Table 1 Performance test of PVC slipper material

[0040]

[0041] After testing, compared with Comparative Example 1, in the PVC slipper materials of Examples 1-3, GMA-grafted CPE and carboxyl-terminated polyacrylonitrile are added. During the high-temperature mixing process, the epoxy groups on the side chains of GMA-grafted CPE initiate ring-opening with the carboxyl termini of polyacrylonitrile, thereby introducing polyacrylonitrile molecular chains into the side chains of CPE (chlorinated polyethylene) to form polyacrylonitrile-CPE polymers. Since the compatibility between chlorinated polyethylene and polyvinyl chloride is good, and the polyacrylonitrile molecular chains on the side chains also have similar polarities to the polyacrylonitrile block molecular chains in nitrile rubber, the polyacrylonitrile-grafted CPE acts as a compatibilizer, further improving the compatibility between polyvinyl chloride and nitrile rubber, making the PVC slipper material have higher tensile properties and tear strength, and having a low oil absorption rate and excellent oil resistance.

[0042] In Comparative Example 2, GMA-grafted CPE was not added, and the compatibility between carboxyl-terminated polyacrylonitrile and polyvinyl chloride was poor, unable to further improve the compatibility between polyvinyl chloride and nitrile rubber, and unable to effectively improve the mechanical properties such as the tear strength of the PVC slipper material.

[0043] In Comparative Example 3, carboxyl-terminated polyacrylonitrile was not added, and the compatibility between GMA-grafted CPE and nitrile rubber was not good, unable to further improve the compatibility between polyvinyl chloride and nitrile rubber, and unable to effectively improve the mechanical properties such as the tear strength of the PVC slipper material.

[0044] The chlorinated polyethylene in Comparative Example 4 does not contain epoxy groups, cannot react with carboxyl-terminated nitrile rubber, and does not form polyacrylonitrile-CPE polymers, unable to further improve the compatibility between polyvinyl chloride and nitrile rubber, and unable to effectively improve the mechanical properties such as the tear strength of the PVC slipper material.

[0045] The polyacrylonitrile in Comparative Example 5 does not contain carboxyl groups, cannot react with the epoxy groups of GMA-grafted CPE, and does not form polyacrylonitrile-CPE polymers, unable to further improve the compatibility between polyvinyl chloride and nitrile rubber, and unable to effectively improve the mechanical properties such as the tear strength of the PVC slipper material.

Claims

1. An environmentally friendly oil-resistant PVC slipper material, characterized in that: In terms of weight, the PVC slipper material includes 70-85 parts of polyvinyl chloride, 15-30 parts of nitrile rubber, 23-30 parts of plasticizer, 2-3.5 parts of GMA grafted CPE, 1.8-3 parts of carboxyl-terminated polyacrylonitrile, 2.2-3 parts of heat stabilizer, 3-5 parts of foaming agent, 0.2-0.3 parts of cross-linking agent, 1.3-2 parts of filler, 0.8-1.3 parts of auxiliary agent, and 1.2-1.6 parts of antioxidant.

2. The environmentally friendly oil-resistant PVC slipper material according to claim 1, characterized in that: The plasticizer is dioctyl terephthalate, and the heat stabilizer is calcium zinc stabilizer.

3. The environmentally friendly oil-resistant PVC slipper material according to claim 1, characterized in that: The foaming agent is azodicarbonamide, and the cross-linking agent is dicumyl peroxide.

4. The environmentally friendly oil-resistant PVC slipper material according to claim 1, characterized in that: The filler is zinc oxide, and the antioxidant is antioxidant 4100NA.

5. The environmentally friendly oil-resistant PVC slipper material according to claim 1, characterized in that: The auxiliary agent is any one or a combination of stearic acid and zinc stearate.

6. The environmentally friendly oil-resistant PVC slipper material according to claim 1, characterized in that: The preparation process of the GMA grafted CPE is as follows: chlorinated polyethylene, glycidyl methacrylate and dicumyl peroxide are added into a torque rheometer, melt-grafted at 170-175° C. for 6-10 minutes, cooled and discharged, the product is added into xylene, heated and refluxed, the product is filtered, extracted with acetone in a Soxhlet extractor, and the GMA grafted CPE is obtained.

7. The environmentally friendly oil-resistant PVC slipper material according to claim 6, characterized in that: In terms of weight, the amount of the chlorinated polyethylene is 100 parts, the amount of glycidyl methacrylate is 2-5 parts, and the amount of dicumyl peroxide is 0.3-0.6 parts.

8. The environmentally friendly oil-resistant PVC slipper material according to claim 1, characterized in that: The preparation process of the carboxyl-terminated polyacrylonitrile is as follows: N,N-dimethylformamide, acrylonitrile, S,S'-bis(α,α'-methyl-α"-acetic acid) trithiocarbonate and azobisisobutyronitrile are added into a reaction container, heated to 65-75° C. in a nitrogen atmosphere, reacted for 12-18 hours, ethanol was added to dilute the solution, filtered, washed with ethanol, and dried to obtain the carboxyl-terminated polyacrylonitrile.

9. The environmentally friendly oil-resistant PVC slipper material according to claim 8, characterized in that: In terms of weight, the amount of acrylonitrile is 100 parts, the amount of S,S'-bis(α,α'-methyl-α"-acetic acid) trithiocarbonate is 2.2-3.5 parts, and the amount of azobisisobutyronitrile is 0.22-0.3 parts.

10. A process for preparing the environmentally friendly oil-resistant PVC slipper material according to any one of claims 1 to 9, characterized in that: The preparation process is as follows: placing the nitrile rubber in a double-roll plasticizing machine for plasticizing, then adding polyvinyl chloride, plasticizer, GMA grafted CPE, terminal carboxyl polyacrylonitrile, heat stabilizer, filler, additive, antioxidant, mixing at 100-110° C. for 10-15 minutes, adding a foaming agent and a cross-linking agent, mixing, and discharging; finally, foaming in an injection molding machine at a temperature of 180-210° C., a pressure of 10-15 MPa, a time of 8-10 minutes, cooling, and obtaining an environmentally friendly oil-resistant PVC slipper material.

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