High-strength high-temperature-resistant polyvinyl chloride material

Abstract

The invention discloses a high-strength high-temperature-resistant polyvinyl chloride material, and relates to the technical field of polyvinyl chloride materials, and the high-strength high-temperature-resistant polyvinyl chloride material comprises the following raw materials in parts by weight: 50-60 parts of polyvinyl chloride, 25-30 parts of diisononyl adipate, 0.2-0.4 part of a lubricant, 1-2 parts of zinc stearate, 20-25 parts of a modified N-phenylmaleimide copolymer, and 1.5-2.0 parts of a flame retardant. The synthesized modified N-phenylmaleimide copolymer is obtained by copolymerizing a functional monomer containing thiophene and amino, styrene, N-phenylmaleimide and acrylonitrile; the synthesized flame retardant is obtained by introducing a polysiloxane chain into Mo-MOF (Molecular Organic Framework). The high-strength high-temperature-resistant polyvinyl chloride material has excellent thermal stability, mechanical strength, light stability, flame retardance and smoke suppression, and is worthy of popularization and application.

Description

Technical Field

[0001] This invention relates to the field of polyvinyl chloride (PVC) materials technology, specifically to a high-strength, high-temperature resistant PVC material. Background Technology

[0002] Polyvinyl chloride (PVC) is one of the world's most produced plastic products. It is inexpensive and possesses advantages such as chemical resistance and good electrical insulation, making it widely used. However, PVC also has shortcomings. Its poor heat resistance is its biggest drawback; the maximum continuous operating temperature is only around 60°C. Excessive temperatures can cause PVC to soften, deform, and crack, thus shortening its lifespan and significantly limiting its application. Furthermore, PVC's light stability is insufficient; prolonged exposure to light will cause products to age, become brittle, and darken in color. Moreover, existing PVC materials have relatively limited functionality, lacking a good balance between high-temperature resistance and high strength.

[0003] Previous studies have used molybdenum ion-containing organic framework materials (Mo-MOF) to add to flexible polyvinyl chloride (PVC) materials to improve the flame retardancy and smoke suppression properties of PVC materials. However, the thermal stability of molybdenum ion-containing organic framework materials (Mo-MOF) is still insufficient.

[0004] Therefore, there is an urgent need to develop suitable modification methods to improve the thermal stability of molybdenum ion-containing organic framework materials (Mo-MOF) and apply them to polyvinyl chloride (PVC) materials. At the same time, it is necessary to improve the thermal stability and light stability of PVC materials and enhance their strength, thereby obtaining PVC materials with excellent properties such as high strength and high temperature resistance. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a high-strength, high-temperature resistant polyvinyl chloride material.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A high-strength, high-temperature resistant polyvinyl chloride (PVC) material comprises the following raw materials in parts by weight: 50-60 parts of polyvinyl chloride, 25-30 parts of diisononyl adipate, 0.2-0.4 parts of lubricant, 1-2 parts of zinc stearate, 20-25 parts of modified N-phenylmaleimide copolymer, and 1.5-2.0 parts of flame retardant; wherein the lubricant is oxidized polyethylene wax;

[0008] The preparation of the high-strength, high-temperature resistant polyvinyl chloride material includes the following steps:

[0009] Polyvinyl chloride, diisononyl adipate, lubricant, zinc stearate, and modified N-phenylmaleimide copolymer are stirred and mixed at 800-900 r / min for 10-15 min, then melt-blended at 155-165℃ for 20-25 min, cooled, and flame retardant is added and mixing is continued for 5-10 min. After pressing on a flat vulcanizing machine, high-strength, high-temperature resistant polyvinyl chloride material is obtained.

[0010] The modified N-phenylmaleimide copolymer is prepared by the following steps:

[0011] Step A1: Add 5-nitrothiophene-3-carboxylic acid to DMF, add sulfoxide under stirring, and reflux at 50-60℃ for 4-5 hours to obtain the acyl chloride product; mix alkenyl alcohol, pyridine, triethylamine and sulfoxide to obtain mixture 1; add the acyl chloride product to sulfoxide to obtain mixture 2, and add mixture 2 dropwise to mixture 1 in an ice-water bath. After the addition is complete, raise the temperature to 40-45℃ and stir at a constant temperature for 8-10 hours to obtain the nitro product;

[0012] Further, the ratio of 5-nitrothiophene-3-carboxylic acid, DMF, and dimethyl sulfoxide is 0.1-0.15 mol: 45-55 mL: 0.15-0.2 mol; the ratio of alkenyl alcohol, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 0.1-0.15 mol: 0.85-1.0 g: 9-10 g: 25-35 mL, and the alkenyl alcohol is selected from one of 3-buten-1-ol, 4-methyl-4-pentenol, and 6-hepten-1-ol; the ratio of acyl chloride product and dimethyl sulfoxide in mixture 2 is 21-23 g: 50-60 mL; and the ratio of mixture 1 to mixture 2 is 40-50 mL: 55-65 mL.

[0013] In step A1, the carboxyl group of 5-nitrothiophene-3-carboxylic acid reacts with thionyl chloride to generate an acyl chloride product; the acyl chloride product then reacts with an alkenyl alcohol to generate a nitro product containing a terminal carbon-carbon double bond.

[0014] Step A2: Add the nitro product to toluene, heat to 45-50℃, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1-1.5h to obtain the functional monomer.

[0015] Furthermore, the ratio of nitro product, toluene, and sodium dithionite is 33-37g: 110-120mL: 18-20g;

[0016] During step A2, the nitro group of the nitro product is reduced to an amino group, yielding an amino-containing functional monomer.

[0017] Step A3: Add sodium dodecylbenzenesulfonate and OP-10 to deionized water and stir at 80-90℃ for 10-15 min to obtain solution a; then add styrene, N-phenylmaleimide, acrylonitrile and functional monomer to methanol and stir for 20-25 min to obtain solution b; add solution b to solution a and stir for 30-40 min to obtain a pre-emulsion; first take a portion of the pre-emulsion and add ammonium persulfate and stir at 70-75℃ for 20-25 min, then raise the temperature to 80-85℃, then add the remaining pre-emulsion, and stir at a constant temperature for 2-2.5 h to obtain the modified N-phenylmaleimide copolymer;

[0018] Further, the ratio of sodium dodecylbenzenesulfonate, OP-10, and deionized water in solution a is 2-3 g: 1-2 g: 10-15 mL; the ratio of styrene, N-phenylmaleimide, acrylonitrile, functional monomer, and methanol in solution b is 30-40 g: 23-25 ​​g: 30-42 g: 4.5-5.5 g: 220-230 mL; the ratio of solution a to solution b in the preemulsion is 35-45 mL: 100-110 mL; the ratio of ammonium persulfate to the total amount of preemulsion is 0.15-0.2 g: 415-425 mL; and the volume ratio of the preemulsion taken first to the remaining preemulsion is 1-1.5: 8.5-9.

[0019] In step A3, under the initiation of ammonium persulfate, styrene, N-phenylmaleimide, acrylonitrile and functional monomers are copolymerized to obtain a modified N-phenylmaleimide copolymer containing thiophene and amino groups.

[0020] The flame retardant is prepared by the following steps:

[0021] Step B1: Add MoO3 and 4-nitroimidazole to deionized water, reflux and stir at 100-110℃ for 12-13h, cool to room temperature, centrifuge, wash the precipitate with deionized water, and then vacuum dry at 70-80℃ for 8-9h to obtain Mo-MOF.

[0022] Furthermore, the ratio of MoO3, 4-nitroimidazole, and deionized water is 15-16g: 70-72g: 230-240mL;

[0023] In step B1, the imidazole ring in 4-nitroimidazole serves as the organic ligand, and Mo... 6+ Mo-MOFs with porous structures and high specific surface area are formed by the self-assembly of metal ions through coordination bonds.

[0024] Step B2: Add Mo-MOF to toluene, heat to 45-50℃, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1-1.5h to obtain the amino product.

[0025] Furthermore, the ratio of Mo-MOF, toluene, and sodium dithionite is 9-11g:40-50mL:9-10g;

[0026] In step B2, the nitro group in Mo-MOF is reduced to an amino group, yielding an amino product;

[0027] Step B3: Add the double-ended carboxyl silicone oil to DMF, add sulfoxide under stirring, and reflux and stir at 70-80℃ for 5-6 hours to obtain acyl chloride product 1; mix the amino product, potassium carbonate and sulfoxide to obtain mixture 3, then add acyl chloride product 1 to sulfoxide and stir to obtain mixture 4. Add mixture 4 dropwise to mixture 3 under ice-water bath. After the addition is complete, heat to 60-70℃ and stir at a constant temperature for 8-10 hours. Distill under reduced pressure to obtain the flame retardant.

[0028] Furthermore, the ratio of the amount of double-ended carboxyl silicone oil, DMF, and sulfoxide is 10-12g: 60-70mL: 12-15mL; the ratio of the amount of amino product, potassium carbonate, and sulfoxide in mixture 3 is 10-12g: 0.25-0.35mol: 55-65mL; ​​the ratio of the amount of acyl chloride product 1 and sulfoxide in mixture 4 is 13-15g: 30-40mL; and the ratio of the amount of mixture 3 to mixture 4 is 75-85mL: 45-55mL.

[0029] In step B3, the carboxyl groups in the double-ended carboxyl silicone oil react with thionyl chloride to generate acyl chloride product 1; acyl chloride product 1 reacts with the amino groups in the amino product to generate Mo-MOF containing polysiloxane chains, i.e., flame retardant.

[0030] Beneficial effects of the present invention: The present invention discloses a high-strength, high-temperature resistant polyvinyl chloride material, comprising polyvinyl chloride, diisononyl adipate, lubricant, zinc stearate, modified N-phenylmaleimide copolymer and flame retardant as raw materials. The synthesized modified N-phenylmaleimide copolymer is obtained by copolymerizing styrene, N-phenylmaleimide, and acrylonitrile with functional monomers containing thiophene and amino groups. The modified N-phenylmaleimide copolymer is consistent with the ordinary N-phenylmaleimide copolymer obtained by copolymerizing styrene, N-phenylmaleimide, and acrylonitrile, and can effectively improve the thermal stability and mechanical strength of PVC materials. When PVC materials are exposed to ultraviolet radiation, thiophene can effectively absorb ultraviolet energy and convert it into lower-energy heat energy for release. After thiophene participates in copolymerization, its compatibility in the matrix is ​​enhanced, and it is less prone to migration and failure, thereby effectively improving the light stability of PVC materials. The amino groups in the modified N-phenylmaleimide copolymer can neutralize the HCl produced during the thermal decomposition of PVC, effectively weakening the catalytic effect of HCl on PVC degradation. Together with N-phenylmaleimide, which has heat-resistant modification properties, it synergistically improves the thermal stability of PVC materials intramolecularly.

[0031] The synthesized flame retardant was obtained by introducing polysiloxane chains into Mo-MOF. During combustion, molybdenum ions are oxidized to form nano-molybdenum oxide with a high specific surface area and high dispersion in the matrix. This allows for more complete contact with the polyvinyl chloride material and catalytic reaction to form char, thereby effectively improving the flame retardancy and smoke suppression of the material. The Si-O-Si and Si-C bonds in the polysiloxane chains have high bond energies and require high energy to break, thus enhancing the thermal stability of Mo-MOF. Furthermore, the polysiloxane chains generate a cracked char layer during combustion. The silicon-oxygen chain segments in the char layer help form a continuous silicate protective layer, which synergistically enhances the flame retardancy of the polyvinyl chloride material intramolecularly with Mo-MOF.

[0032] In summary, the high-strength, high-temperature resistant polyvinyl chloride material of the present invention has excellent thermal stability, mechanical strength, light stability, flame retardancy, and smoke suppression properties, and is worthy of widespread use. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Example 1

[0035] A modified N-phenylmaleimide copolymer is prepared by the following steps:

[0036] Step A1: 5-Nitrothiophene-3-carboxylic acid was added to DMF, and sulfoxide was added with stirring. The mixture was refluxed and stirred at 50°C for 4 hours to obtain the acyl chloride product. 3-Buten-1-ol, pyridine, triethylamine, and dimethyl sulfoxide were mixed to obtain mixture 1. The acyl chloride product was added to dimethyl sulfoxide to obtain mixture 2. Mixture 2 was added dropwise to mixture 1 in an ice-water bath. After the addition was complete, the temperature was raised to 40°C and the mixture was stirred and stirred at a constant temperature for 8 hours to obtain the nitro... The product; the ratio of 5-nitrothiophene-3-carboxylic acid, DMF, and dimethyl sulfoxide is 0.1 mol: 45 mL: 0.15 mol; the ratio of 3-buten-1-ol, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 0.1 mol: 0.85 g: 9 g: 25 mL; the ratio of acyl chloride product and dimethyl sulfoxide in mixture 2 is 21 g: 50 mL; the ratio of mixture 1 to mixture 2 is 40 mL: 55 mL.

[0037] Step A2: Add the nitro product to toluene, heat to 45°C, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1 hour to obtain the functional monomer; the ratio of nitro product, toluene and sodium dithionite is 33g:110mL:18g.

[0038] Step A3: Add sodium dodecylbenzenesulfonate and OP-10 to deionized water and stir at 80°C for 10 min to obtain solution a; then add styrene, N-phenylmaleimide, acrylonitrile, and functional monomers to methanol and stir for 20 min to obtain solution b; add solution b to solution a and stir for 30 min to obtain a pre-emulsion; first, take a portion of the pre-emulsion and add ammonium persulfate and stir at 70°C for 20 min, then raise the temperature to 80°C, and then add the remaining pre-emulsion, and stir at a constant temperature for 2 h to obtain modified N-phenylmaleimide. The mixture contains an imide copolymer; in solution a, the ratio of sodium dodecylbenzenesulfonate, OP-10, and deionized water is 2g:1g:10mL; in solution b, the ratio of styrene, N-phenylmaleimide, acrylonitrile, functional monomer, and methanol is 30g:23g:30g:4.5g:220mL; in the preemulsion, the ratio of solution a to solution b is 35mL:100mL; the ratio of ammonium persulfate to the total amount of preemulsion is 0.15g:415mL; and the volume ratio of the preemulsion taken first to the remaining preemulsion is 1:9.

[0039] Example 2

[0040] A modified N-phenylmaleimide copolymer is prepared by the following steps:

[0041] Step A1: 5-Nitrothiophene-3-carboxylic acid was added to DMF, and sulfoxide was added under stirring. The mixture was refluxed and stirred at 55°C for 4.5 h to obtain the acyl chloride product. 4-Methyl-4-pentenol, pyridine, triethylamine, and sulfoxide were stirred and mixed to obtain mixture 1. The acyl chloride product was added to sulfoxide to obtain mixture 2. Mixture 2 was added dropwise to mixture 1 in an ice-water bath. After the addition was complete, the temperature was raised to 42°C and the mixture was stirred and stirred at a constant temperature for 9 h to obtain the nitro product. The ratio of 5-nitrothiophene-3-carboxylic acid, DMF, and dimethyl sulfoxide in mixture 1 is 0.13 mol: 50 mL: 0.17 mol; the ratio of 4-methyl-4-pentenol, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 0.13 mol: 0.92 g: 9.5 g: 30 mL; the ratio of acyl chloride product and dimethyl sulfoxide in mixture 2 is 22 g: 55 mL; the ratio of mixture 1 to mixture 2 is 45 mL: 60 mL.

[0042] Step A2: Add the nitro product to toluene, heat to 47°C, turn on reflux and stir, then add sodium dithionite, and reflux and stir for another 1.3 h to obtain the functional monomer; the ratio of nitro product, toluene and sodium dithionite is 35g:115mL:19g.

[0043] Step A3: Add sodium dodecylbenzenesulfonate and OP-10 to deionized water and stir at 85°C for 13 min to obtain solution a; then add styrene, N-phenylmaleimide, acrylonitrile, and functional monomers to methanol and stir for 23 min to obtain solution b; add solution b to solution a and stir for 35 min to obtain a pre-emulsion; first, take a portion of the pre-emulsion and add ammonium persulfate and stir at 72°C for 23 min, then raise the temperature to 83°C, and then add the remaining pre-emulsion, and stir at a constant temperature for 2.3 h to obtain modified N-phenylmaleimide. Amine copolymer; the ratio of sodium dodecylbenzenesulfonate, OP-10, and deionized water in solution a is 2.5g:1.5g:13mL; the ratio of styrene, N-phenylmaleimide, acrylonitrile, functional monomer, and methanol in solution b is 35g:24g:36g:5.0g:225mL; the ratio of solution a to solution b in the preemulsion is 40mL:105mL; the ratio of ammonium persulfate to the total amount of preemulsion is 0.17g:420mL; and the volume ratio of the preemulsion taken first to the remaining preemulsion is 1.2:8.8.

[0044] Example 3

[0045] A modified N-phenylmaleimide copolymer is prepared by the following steps:

[0046] Step A1: Add 5-nitrothiophene-3-carboxylic acid to DMF, add sulfoxide under stirring, and reflux at 60°C for 5 hours to obtain the acyl chloride product; mix 6-hepten-1-ol, pyridine, triethylamine, and sulfoxide to obtain mixture 1; add the acyl chloride product to sulfoxide to obtain mixture 2. In an ice-water bath, add mixture 2 dropwise to mixture 1. After the addition is complete, raise the temperature to 45°C and stir for 10 hours to obtain the nitro... The product; the ratio of 5-nitrothiophene-3-carboxylic acid, DMF, and dimethyl sulfoxide is 0.15 mol: 55 mL: 0.2 mol; the ratio of 6-hepten-1-ol, pyridine, triethylamine, and dimethyl sulfoxide in mixture 1 is 0.15 mol: 1.0 g: 10 g: 35 mL; the ratio of acyl chloride product and dimethyl sulfoxide in mixture 2 is 23 g: 60 mL; the ratio of mixture 1 to mixture 2 is 50 mL: 65 mL.

[0047] Step A2: Add the nitro product to toluene, heat to 50°C, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1.5 h to obtain the functional monomer; the ratio of nitro product, toluene and sodium dithionite is 37 g: 120 mL: 20 g.

[0048] Step A3: Add sodium dodecylbenzenesulfonate and OP-10 to deionized water and stir at 90°C for 15 min to obtain solution a; then add styrene, N-phenylmaleimide, acrylonitrile, and functional monomers to methanol and stir for 25 min to obtain solution b; add solution b to solution a and stir for 40 min to obtain a pre-emulsion; first, take a portion of the pre-emulsion and add ammonium persulfate and stir at 75°C for 25 min, then raise the temperature to 85°C, and then add the remaining pre-emulsion, and stir at a constant temperature for 2.5 h to obtain modified N-phenylmaleimide. The mixture contains an imide copolymer; in solution a, the ratio of sodium dodecylbenzenesulfonate, OP-10, and deionized water is 3g:2g:15mL; in solution b, the ratio of styrene, N-phenylmaleimide, acrylonitrile, functional monomer, and methanol is 40g:25g:42g:5.5g:230mL; in the preemulsion, the ratio of solution a to solution b is 45mL:110mL; the ratio of ammonium persulfate to the total amount of preemulsion is 0.2g:425mL; and the volume ratio of the preemulsion taken first to the remaining preemulsion is 1.5:8.5.

[0049] Example 4

[0050] A flame retardant, the preparation of which includes the following steps:

[0051] Step B1: Add MoO3 and 4-nitroimidazole to deionized water, reflux and stir at 100℃ for 12h, cool to room temperature, centrifuge, wash the precipitate with deionized water, and then vacuum dry at 70℃ for 9h to obtain Mo-MOF; the ratio of MoO3, 4-nitroimidazole and deionized water is 15g:70g:230mL;

[0052] Step B2: Add Mo-MOF to toluene, heat to 45°C, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1 hour to obtain the amino product; the ratio of Mo-MOF, toluene and sodium dithionite is 9g:40mL:9g.

[0053] Step B3: Add the double-ended carboxyl silicone oil (supplier: Hubei Xinyuhong Biomedical Technology Co., Ltd.) to DMF, add sulfoxide under stirring, and reflux at 70°C for 5 hours to obtain acyl chloride product 1; mix the amino product, potassium carbonate, and sulfoxide to obtain mixture 3, then add acyl chloride product 1 to sulfoxide and stir to obtain mixture 4. Under an ice-water bath, add mixture 4 dropwise to mixture 3. After the addition is complete, raise the temperature to 60°C. The reaction was carried out at 0℃ with constant stirring for 8 hours, followed by vacuum distillation to obtain the flame retardant. The ratio of double-terminated carboxyl silicone oil, DMF, and sulfoxide was 10g:60mL:12mL. The ratio of amino product, potassium carbonate, and dimethyl sulfoxide in mixture 3 was 10g:0.25mol:55mL. The ratio of acyl chloride product 1 and dimethyl sulfoxide in mixture 4 was 13g:30mL. The ratio of mixture 3 to mixture 4 was 75mL:45mL.

[0054] Example 5

[0055] A flame retardant, the preparation of which includes the following steps:

[0056] Step B1: Add MoO3 and 4-nitroimidazole to deionized water, reflux and stir at 105℃ for 12.5h, cool to room temperature, centrifuge, wash the precipitate with deionized water, and then vacuum dry at 75℃ for 8.5h to obtain Mo-MOF; the ratio of MoO3, 4-nitroimidazole and deionized water is 15.5g:71g:235mL;

[0057] Step B2: Add Mo-MOF to toluene, heat to 47°C, turn on reflux and stir, then add sodium dithionite, and reflux and stir for another 1.3 h to obtain the amino product; the ratio of Mo-MOF, toluene and sodium dithionite is 10 g: 45 mL: 9.5 g.

[0058] Step B3: Add the double-ended carboxyl silicone oil (supplier: Hubei Xinyuhong Biomedical Technology Co., Ltd.) to DMF, add sulfoxide under stirring, and reflux at 75°C for 5.5 h to obtain acyl chloride product 1; mix the amino product, potassium carbonate, and sulfoxide to obtain mixture 3, then add acyl chloride product 1 to sulfoxide and stir to obtain mixture 4. Add mixture 4 dropwise to mixture 3 under an ice-water bath. After the addition is complete, heat to [temperature missing]. The reaction was carried out at 65℃ with constant stirring for 9 hours, followed by vacuum distillation to obtain the flame retardant. The ratio of double-terminated carboxyl silicone oil, DMF, and sulfoxide was 11g:65mL:13.5mL. The ratio of amino product, potassium carbonate, and dimethyl sulfoxide in mixture 3 was 11:0.30mol:60mL. The ratio of acyl chloride product 1 and dimethyl sulfoxide in mixture 4 was 14g:35mL. The ratio of mixture 3 to mixture 4 was 80mL:50mL.

[0059] Example 6

[0060] A flame retardant, the preparation of which includes the following steps:

[0061] Step B1: Add MoO3 and 4-nitroimidazole to deionized water, reflux and stir at 110℃ for 13h, cool to room temperature, centrifuge, wash the precipitate with deionized water, and then vacuum dry at 80℃ for 8h to obtain Mo-MOF; the ratio of MoO3, 4-nitroimidazole and deionized water is 16g:72g:240mL;

[0062] Step B2: Add Mo-MOF to toluene, heat to 50°C, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1.5 h to obtain the amino product; the ratio of Mo-MOF, toluene and sodium dithionite is 11 g: 50 mL: 10 g.

[0063] Step B3: Add the double-ended carboxyl silicone oil (supplier: Hubei Xinyuhong Biomedical Technology Co., Ltd.) to DMF, add sulfoxide under stirring, and reflux at 80°C for 6 hours to obtain acyl chloride product 1; mix the amino product, potassium carbonate, and sulfoxide to obtain mixture 3, then add acyl chloride product 1 to sulfoxide and stir to obtain mixture 4. Under an ice-water bath, add mixture 4 dropwise to mixture 3. After the addition is complete, raise the temperature to 70°C. The reaction was carried out at 0℃ with constant temperature stirring for 10 hours, followed by vacuum distillation to obtain the flame retardant. The ratio of double-terminated carboxyl silicone oil, DMF, and sulfoxide was 12g:70mL:15mL. The ratio of amino product, potassium carbonate, and dimethyl sulfoxide in mixture 3 was 12g:0.35mol:65mL. The ratio of acyl chloride product 1 and dimethyl sulfoxide in mixture 4 was 15g:40mL. The ratio of mixture 3 to mixture 4 was 85mL:55mL.

[0064] Example 7

[0065] A high-strength, high-temperature resistant polyvinyl chloride material comprises the following raw materials in parts by weight: 50 parts polyvinyl chloride, 25 parts diisononyl adipate, 0.2 parts lubricant, 1 part zinc stearate, 20 parts modified N-phenylmaleimide copolymer, and 1.5 parts flame retardant; wherein the lubricant is oxidized polyethylene wax;

[0066] The preparation of the high-strength, high-temperature resistant polyvinyl chloride material includes the following steps:

[0067] Polyvinyl chloride (supplier: Dongguan Changping Senhai Plastics Trading Company), diisononyl adipate, lubricant, zinc stearate, and the modified N-phenylmaleimide copolymer obtained in Example 1 were stirred and mixed at 800 r / min for 10 min, then melt-blended at 155°C for 20 min, cooled, and the flame retardant obtained in Example 4 was added and mixed for another 5 min. After pressing on a flat vulcanizing machine, a high-strength, high-temperature resistant polyvinyl chloride material was obtained.

[0068] Example 8

[0069] A high-strength, high-temperature resistant polyvinyl chloride material comprises the following raw materials in parts by weight: 55 parts polyvinyl chloride, 27 parts diisononyl adipate, 0.3 parts lubricant, 1.5 parts zinc stearate, 23 parts modified N-phenylmaleimide copolymer, and 1.7 parts flame retardant; wherein the lubricant is oxidized polyethylene wax;

[0070] The preparation of the high-strength, high-temperature resistant polyvinyl chloride material includes the following steps:

[0071] Polyvinyl chloride (supplier: Dongguan Changping Senhai Plastics Trading Company), diisononyl adipate, lubricant, zinc stearate, and the modified N-phenylmaleimide copolymer obtained in Example 2 were stirred and mixed at 800 r / min for 13 min, then melt-blended at 160°C for 23 min, cooled, and the flame retardant obtained in Example 5 was added and the mixture was stirred for another 8 min. After pressing on a flat vulcanizing machine, a high-strength, high-temperature resistant polyvinyl chloride material was obtained.

[0072] Example 9

[0073] A high-strength, high-temperature resistant polyvinyl chloride material comprises the following raw materials in parts by weight: 60 parts polyvinyl chloride, 30 parts diisononyl adipate, 0.4 parts lubricant, 2 parts zinc stearate, 25 parts modified N-phenylmaleimide copolymer, and 2.0 parts flame retardant; wherein the lubricant is oxidized polyethylene wax;

[0074] The preparation of the high-strength, high-temperature resistant polyvinyl chloride material includes the following steps:

[0075] Polyvinyl chloride (supplier: Dongguan Changping Senhai Plastics Trading Company), diisononyl adipate, lubricant, zinc stearate, and the modified N-phenylmaleimide copolymer obtained in Example 3 were stirred and mixed at 900 r / min for 15 min, then melt-blended at 165°C for 25 min, cooled, and the flame retardant obtained in Example 6 was added and mixed for another 10 min. After pressing on a flat vulcanizing machine, a high-strength, high-temperature resistant polyvinyl chloride material was obtained.

[0076] Comparative Example 1

[0077] Compared with Example 9, the functional monomer in step A3 of the preparation process of the modified N-phenylmaleimide copolymer was replaced with the nitro product in step A1, and no amino group was introduced. The rest was completely the same as in Example 9, and a high-strength, high-temperature resistant polyvinyl chloride material was obtained.

[0078] Comparative Example 2

[0079] Compared with Example 9, the 5-nitrothiophene-3-carboxylic acid in the preparation process of the modified N-phenylmaleimide copolymer was replaced with p-nitrobenzoic acid, thiophene was not introduced, and the rest was completely the same as in Example 9, to obtain a high-strength, high-temperature resistant polyvinyl chloride material.

[0080] Comparative Example 3

[0081] Compared with Example 9, the flame retardant was replaced with the Mo-MOF obtained in step B1, that is, no polysiloxane chain was introduced, and everything else was exactly the same as in Example 9, to obtain a high-strength, high-temperature resistant polyvinyl chloride material.

[0082] Comparative Example 4

[0083] Compared with Example 9, the flame retardant was replaced with polysiloxane chain, and Mo-MOF was not included. Everything else was exactly the same as in Example 9, and a high-strength, high-temperature resistant polyvinyl chloride material was obtained.

[0084] The high-strength, high-temperature resistant polyvinyl chloride material prepared by this invention was further tested below, and the test results are as follows.

[0085] Tensile strength: measured by a universal testing machine. The test sample was processed into a type 1A specimen according to the requirements of GB / T1040.2-2022. There were 5 valid test specimens and the tensile rate was 50 mm / min.

[0086] Vicat softening temperature: Tested according to GB / T1633-2000, heating rate is 50℃ / h, load is 10N;

[0087] Light stability: The material was placed under an intensity of 1000 W / m 2 After irradiation under ultraviolet light for 72 hours, the tensile strength retention rate was measured.

[0088] Oxygen index test: Refer to ASTM D2863 standard, the sample size is 130.0mm × 6.5mm × 3.0mm;

[0089] Smoke density test: Referencing ISO 5659-2 standard, the sample size was 75.0mm × 75.0mm × 1.0mm, and the heating power was 25kW / m². 2 Record the maximum smoke density;

[0090] The test results are recorded in Table 1;

[0091] Table 1: Test Results

[0092]

[0093] According to the data in Table 1, the high-strength, high-temperature resistant polyvinyl chloride (PVC) material of the present invention exhibits excellent mechanical strength, thermal stability, light stability, flame retardancy, and smoke suppression properties. Comparing Example 9 with Comparative Example 1, it can be seen that without the introduction of amino groups into the modified N-phenylmaleimide copolymer, it cannot synergistically improve the thermal stability of the PVC material intramolecularly with N-phenylmaleimide, which has a heat-resistant modification effect. The Vicat softening temperature of the PVC material decreases, indicating a decline in its thermal stability. Comparing Example 9 with Comparative Example 2, it can be seen that without the introduction of thiophene into the modified N-phenylmaleimide copolymer, the tensile strength retention rate decreases after ultraviolet irradiation, indicating a decline in the light stability of the PVC material. Comparing Example 9 with Comparative Example 3, it can be seen that replacing the flame retardant with Mo-MOF, without introducing polysiloxane chains, results in a decrease in the thermal stability of Mo-MOF and a reduction in its flame retardant and smoke suppression properties. Comparing Example 9 with Comparative Example 4, it can be seen that when the flame retardant is replaced with a polysiloxane chain and Mo-MOF is not introduced, the flame retardant performance decreases and the smoke suppression performance decreases significantly.

[0094] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A high-strength, high-temperature resistant polyvinyl chloride material, characterized in that: The raw materials include the following parts by weight: 50-60 parts of polyvinyl chloride, 25-30 parts of diisononyl adipate, 0.2-0.4 parts of lubricant, 1-2 parts of zinc stearate, 20-25 parts of modified N-phenylmaleimide copolymer, and 1.5-2.0 parts of flame retardant; The modified N-phenylmaleimide copolymer is prepared by the following steps: Step A1: Add 5-nitrothiophene-3-carboxylic acid to DMF, then add sulfoxide, and stir to react to obtain the acyl chloride product; stir and mix alkenyl alcohol, pyridine, triethylamine and sulfoxide to obtain mixture 1; add the acyl chloride product to sulfoxide to obtain mixture 2, add mixture 2 dropwise to mixture 1, and stir to react to obtain the nitro product; Step A2: Add the nitro product to toluene, then add sodium dithionite and stir to react and obtain the functional monomer; Step A3: Add sodium dodecylbenzenesulfonate and OP-10 to deionized water and stir to obtain solution a; then add styrene, N-phenylmaleimide, acrylonitrile and functional monomer to methanol and stir to obtain solution b; add solution b to solution a and stir to obtain a pre-emulsion; first take a portion of the pre-emulsion and add ammonium persulfate and stir, then add the remaining pre-emulsion and stir to obtain the modified N-phenylmaleimide copolymer.

2. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: The lubricant is oxidized polyethylene wax; in step A1, the ratio of 5-nitrothiophene-3-carboxylic acid, DMF, and thionyl chloride is 0.1-0.15 mol: 45-55 mL: 0.15-0.2 mol.

3. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: In step A1, the ratio of alkenyl alcohol, pyridine, triethylamine and dimethyl sulfoxide in mixture 1 is 0.1-0.15 mol: 0.85-1.0 g: 9-10 g: 25-35 mL, and the alkenyl alcohol is selected from one of 3-buten-1-ol, 4-methyl-4-pentenol and 6-hepten-1-ol.

4. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: In step A1, the ratio of acyl chloride product to dimethyl sulfoxide in mixture 2 is 21-23g: 50-60mL; the ratio of mixture 1 to mixture 2 is 40-50mL: 55-65mL.

5. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: In step A2, the ratio of nitro product, toluene, and sodium dithionite is 33-37g: 110-120mL: 18-20g.

6. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: In step A3, the ratio of sodium dodecylbenzenesulfonate, OP-10, and deionized water in solution a is 2-3g: 1-2g: 10-15mL; the ratio of styrene, N-phenylmaleimide, acrylonitrile, functional monomer, and methanol in solution b is 30-40g: 23-25g: 30-42g: 4.5-5.5g: 220-230mL.

7. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: In step A3, the volume ratio of solution a to solution b in the pre-emulsion is 35-45 mL: 100-110 mL; the volume ratio of ammonium persulfate to the total amount of pre-emulsion is 0.15-0.2 g: 415-425 mL; and the volume ratio of the pre-emulsion taken first to the remaining pre-emulsion is 1-1.5: 8.5-9.

8. The high-strength, high-temperature resistant polyvinyl chloride material according to claim 1, characterized in that: The flame retardant is prepared by the following steps: Step B1: Add MoO3 and 4-nitroimidazole to deionized water, reflux and stir at 100-110℃ for 12-13h, cool to room temperature, centrifuge, wash the precipitate with deionized water, and then vacuum dry at 70-80℃ for 8-9h to obtain Mo-MOF. Step B2: Add Mo-MOF to toluene, heat to 45-50℃, turn on reflux and stir, then add sodium dithionite, and reflux and stir for 1-1.5h to obtain the amino product. Step B3: Add the double-ended carboxyl silicone oil to DMF, add thionyl chloride while stirring, and reflux and stir at 70-80℃ for 5-6 hours to obtain acyl chloride product 1; mix the amino product, potassium carbonate and thionyl chloride to obtain mixture 3, then add acyl chloride product 1 to thionyl chloride and stir to obtain mixture 4. Add mixture 4 dropwise to mixture 3 under an ice-water bath. After the addition is complete, raise the temperature to 60-70℃ and stir at a constant temperature for 8-10 hours. Distill under reduced pressure to obtain the flame retardant.

9. A high-strength, high-temperature resistant polyvinyl chloride material according to claim 8, characterized in that: In step B1, the ratio of MoO3, 4-nitroimidazole and deionized water is 15-16g: 70-72g: 230-240mL; in step B2, the ratio of Mo-MOF, toluene and sodium dithionite is 9-11g: 40-50mL: 9-10g.

10. A high-strength, high-temperature resistant polyvinyl chloride material according to claim 8, characterized in that: In step B3, the ratio of the amount of double-ended carboxyl silicone oil, DMF, and sulfoxide is 10-12g: 60-70mL: 12-15mL; the ratio of the amount of the amino product, potassium carbonate, and dimethyl sulfoxide in mixture 3 is 10-12g: 0.25-0.35mol: 55-65mL; ​​the ratio of the amount of the acyl chloride product 1 and dimethyl sulfoxide in mixture 4 is 13-15g: 30-40mL; and the ratio of the amount of mixture 3 to mixture 4 is 75-85mL: 45-55mL.

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