High-performance PVC composite material and preparation method thereof

Abstract

The invention relates to a high-performance PVC composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The high-performance PVC composite material comprises the following components in parts by weight: 100 parts of PVC resin, 10-20 parts of chlorinated polyethylene, 4-8 parts of a modified flame retardant, 2-4 parts of a modified anti-aging agent, 1-2 parts of a lubricant, 4-8 parts of a stabilizer, 4-10 parts of a plasticizer, 1-2 parts of a coupling agent and 10-15 parts of calcium carbonate, the high-performance PVC composite material prepared by the invention not only has a good flame-retardant effect, but also has excellent heat-resistant and aging-resistant effects.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a high-performance PVC composite material and its preparation method. Background Technology

[0002] PVC (polyvinyl chloride) is currently the second largest general-purpose plastic after polyethylene in terms of production volume. It has excellent chemical resistance, electrical insulation, acid and alkali resistance, and high structural strength. It is widely used in building pipes, medical equipment, food packaging, building water supply and drainage, and chemical technology fields.

[0003] However, ordinary PVC materials soften under high temperature and ultraviolet radiation, and continuous temperature fluctuations accelerate the aging of the material, limiting its application range. In addition, although ordinary PVC materials have a certain degree of flame retardancy, with the continuous improvement of practical application requirements, their flame retardancy is no longer sufficient to meet current needs. Therefore, the development of high-performance PVC composite materials with excellent performance has important practical significance and application value. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a high-performance PVC composite material and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-performance PVC composite material and its preparation method, comprising the following raw materials in parts by weight: 100 parts PVC resin, 10-20 parts chlorinated polyethylene, 4-8 parts modified flame retardant, 2-4 parts modified aging resistant agent, 1-2 parts lubricant, 4-8 parts stabilizer, 4-10 parts plasticizer, 1-2 parts coupling agent, and 10-15 parts calcium carbonate.

[0007] The lubricant is stearic acid;

[0008] The stabilizer is a calcium-zinc composite heat stabilizer;

[0009] The plasticizer mentioned is DOP;

[0010] The coupling agent is KH-550.

[0011] The modified flame retardant is prepared by the following method:

[0012] Step A1: Place Sb2O3 and distilled water into a planetary high-energy ball mill and perform wet ball milling at room temperature. The ball milling speed is 400 r / min and the ball milling time is 24 h. After ball milling, wash, dry at 100℃ for 10 h, and pass through a 100-mesh metal mesh sieve to obtain the intermediate.

[0013] Furthermore, the ratio of Sb₂O₃ to distilled water is 10-15g: 15-20mL;

[0014] First, the intermediate was prepared by ball milling Sb2O3 to obtain nanomaterials;

[0015] Step A2: At room temperature, place the intermediate and grinding balls in a ball mill jar, add vinyltriethoxysilane, then add ethanol-water mixed solution, adjust the pH of the system to 5, ball mill at 400 r / min for 24 h, wash, dry at 80 ℃ for 10 h, and pass through a 100 mesh metal sieve to obtain the preproduct.

[0016] Furthermore, the ratio of the intermediate, grinding ball, vinyltriethoxysilane, and ethanol-water mixed solution is 0.01-0.03 mol: 0.07-0.21 g: 0.02-0.06 mol: 10-15 mL, and the volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 1:1.

[0017] Secondly, the preproduct was prepared by reacting the hydroxyl groups of the intermediate with the silanol groups generated by the hydrolysis of vinyltriethoxysilane.

[0018] Step A3: Under nitrogen atmosphere, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene were mixed and stirred at 80°C. The preproduct was added and mixed evenly. Then azobisisobutyronitrile was added and reacted for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, washed, and vacuum dried at 60°C for 12 hours to obtain the modified flame retardant.

[0019] Furthermore, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, preproduct, and azobisisobutyronitrile is 0.01-0.03 mol: 80 mL: 0.01-0.03 mol: 0.2 g;

[0020] Finally, the modified flame retardant was prepared by reacting the carbon-carbon double bond of the preproduct with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0021] The modified anti-aging agent is prepared by the following method:

[0022] Step B1: Mix p-aminophenol and dimethyl sulfoxide evenly, slowly add allyl isothiocyanate under stirring, heat to 45-55℃, continue stirring for 3-4 hours, after the reaction is complete, filter, wash, dry, and obtain the compound.

[0023] Furthermore, the ratio of p-aminophenol, dimethyl sulfoxide, and allyl isothiocyanate is 0.01-0.03 mol: 10-15 mL: 0.01-0.03 mol;

[0024] The compound was prepared by reacting the amino group of p-aminophenol with the isothiocyanate group of allyl isothiocyanate.

[0025] Step B2: Mix the compound, p-toluenesulfonyl chloride, acetone and triethylamine evenly, stir at room temperature for 2-3 hours, after the reaction is complete, rotary evaporate, wash and dry to obtain the modified anti-aging agent;

[0026] Furthermore, the ratio of the compound, p-toluenesulfonyl chloride, acetone, and triethylamine is 0.01-0.03 mol: 0.01-0.03 mol: 20 mL: 0.5-0.6 mL.

[0027] Finally, the modified anti-aging agent was prepared by reacting the hydroxyl group of the compound with the chlorine atom of p-toluenesulfonyl chloride.

[0028] A method for preparing a high-performance PVC composite material specifically includes the following steps:

[0029] S1. Mix PVC resin and stabilizer for 30 minutes, then add chlorinated polyethylene, modified flame retardant and modified aging resistant agent, and stir for 15-30 minutes to obtain premix.

[0030] S2. Mix the premix, lubricant, plasticizer, coupling agent and calcium carbonate evenly, place them in a twin-screw extruder, extrude and granulate at a speed of 300 r / min, and cool to room temperature to obtain a high-performance PVC composite material.

[0031] The beneficial effects of this invention are:

[0032] The high-performance PVC composite material of the present invention has good flame retardant effect, and at the same time, it also has excellent heat resistance and aging resistance, further extending its service life.

[0033] In the modified flame retardant prepared by this invention, Sb₂O₃ can react with chlorine and hydrogen free radicals generated during the combustion of the composite material to produce volatile gases, which isolate oxygen and absorb heat, reducing the heat generated during the combustion of the matrix material. Furthermore, the intermediate has a large specific surface area and good dispersibility, resulting in high flame retardant efficiency of the composite material. Simultaneously, when the composite material is subjected to significant external stress, it does not produce large particle effects that could damage the matrix material, thus enhancing the mechanical properties of the matrix material. Secondly, the Sb-O-Si formed in the preproduct can effectively reduce the nanoparticle size. The surface activity and surface energy of the particles are improved, enhancing dispersibility and flame retardant effect. The phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a phosphoraphenanthrene compound with high thermal stability, promotes the formation of a dense and continuous char layer during combustion, effectively isolating oxygen, blocking the exchange of heat and combustible gases, and synergistically retards flame with phosphorus-oxygen double bonds, extending its service life. In addition, the modified flame retardant prepared by this invention is halogen-free, which helps reduce environmental pollution and ecosystem damage, is harmless to human health, and achieves sustainable development.

[0034] In the modified anti-aging agent prepared by this invention, the thiourea compound possesses excellent anti-ozone aging and anti-thermal oxidation properties. It can capture free radicals, terminate chain reactions, and delay the aging of composite materials, thereby effectively extending service life and reducing usage costs. In addition, the sulfone structure of p-toluenesulfonyl chloride, as an electron-donating and electron-withdrawing group, can promote intramolecular charge transfer, allowing electrons in the material molecules to flow and thus achieve light absorption. It efficiently absorbs ultraviolet rays in different wavelength ranges and converts ultraviolet energy into heat or light energy, reducing the damage and aging of composite materials caused by ultraviolet rays. Furthermore, this modified anti-aging agent has good compatibility with composite materials and can be uniformly dispersed in the matrix, synergistically exerting its heat resistance and anti-aging effects. Detailed Implementation

[0035] 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.

[0036] Example 1: A method for preparing a high-performance PVC composite material, specifically including the following steps:

[0037] S1. Weigh the raw materials according to the following parts by weight: 100 parts of PVC resin, 10 parts of chlorinated polyethylene, 4 parts of modified flame retardant (prepared in this embodiment), 2 parts of modified aging resistant agent (prepared in this embodiment), 1 part of lubricant, 4 parts of stabilizer, 4 parts of plasticizer, 1 part of coupling agent, and 10 parts of calcium carbonate; mix and stir the PVC resin and calcium-zinc composite heat stabilizer for 30 minutes, then add chlorinated polyethylene, modified flame retardant and modified aging resistant agent, and stir for 15 minutes to obtain a premix;

[0038] S2. Mix the premix, stearic acid, DOP, KH-550 and calcium carbonate evenly, place them in a twin-screw extruder, extrude and granulate at a speed of 300 r / min, cool to room temperature, and obtain a high-performance PVC composite material.

[0039] The modified flame retardant is prepared by the following method:

[0040] Step A1: Place 10g Sb2O3 and 15mL distilled water into a planetary high-energy ball mill and perform wet ball milling at room temperature. The ball milling speed is 400r / min and the ball milling time is 24h. After ball milling, wash, dry at 100℃ for 10h, and pass through a 100-mesh metal mesh sieve to obtain the intermediate.

[0041] Step A2: At room temperature, 0.01 mol of the intermediate and 0.07 g of grinding balls were placed in a ball mill jar, 0.02 mol of vinyltriethoxysilane was added, and then 10 mL of ethanol-water mixed solution was added. The pH of the system was adjusted to 5, and the mixture was ball milled at 400 r / min for 24 h. After washing, the mixture was dried at 80 °C for 10 h and passed through a 100-mesh metal sieve to obtain the preproduct. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution was 1:1.

[0042] Step A3: Under nitrogen atmosphere, 0.01 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 80 mL of toluene were mixed and stirred at 80 °C. 0.01 mol of the preproduct was added and mixed evenly. Then 0.2 g of azobisisobutyronitrile was added and the reaction was carried out for 24 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and vacuum dried at 60 °C for 12 h to obtain the modified flame retardant.

[0043] The modified anti-aging agent is prepared by the following method:

[0044] Step B1: Mix 0.01 mol of p-aminophenol and 10 mL of dimethyl sulfoxide evenly, and slowly add 0.01 mol of allyl isothiocyanate under stirring. Heat to 45 °C and continue stirring for 3 h. After the reaction is complete, filter, wash, and dry to obtain the compound.

[0045] Step B2: Mix 0.01 mol of the compound, 0.01 mol of p-toluenesulfonyl chloride, 20 mL of acetone and 0.5 mL of triethylamine evenly, stir at room temperature for 2 h, after the reaction is complete, rotary evaporate, wash and dry to obtain the modified anti-aging agent.

[0046] Example 2: A method for preparing a high-performance PVC composite material, specifically including the following steps:

[0047] S1. Weigh the raw materials according to the following parts by weight: 100 parts PVC resin, 15 parts chlorinated polyethylene, 6 parts modified flame retardant (prepared in this embodiment), 3 parts modified aging resistant agent (prepared in this embodiment), 1.5 parts lubricant, 6 parts stabilizer, 7 parts plasticizer, 1.5 parts coupling agent, and 12.5 parts calcium carbonate; mix and stir the PVC resin and calcium-zinc composite heat stabilizer for 30 minutes, then add chlorinated polyethylene, modified flame retardant, and modified aging resistant agent, and stir for 22.5 minutes to obtain a premix.

[0048] S2. Mix the premix, stearic acid, DOP, KH-550 and calcium carbonate evenly, place them in a twin-screw extruder, extrude and granulate at a speed of 300 r / min, cool to room temperature, and obtain a high-performance PVC composite material.

[0049] The modified flame retardant is prepared by the following method:

[0050] Step A1: Place 12.5g Sb2O3 and 17.5mL distilled water into a planetary high-energy ball mill and perform wet ball milling at room temperature. The ball milling speed is 400r / min and the ball milling time is 24h. After ball milling, wash, dry at 100℃ for 10h, and pass through a 100-mesh metal mesh sieve to obtain the intermediate.

[0051] Step A2: At room temperature, 0.02 mol of the intermediate and 0.14 g of grinding balls were placed in a ball mill jar, 0.04 mol of vinyltriethoxysilane was added, and then 12.5 mL of ethanol-water mixed solution was added. The pH of the system was adjusted to 5, and the mixture was ball milled at 400 r / min for 24 h. After washing, the mixture was dried at 80 °C for 10 h and passed through a 100-mesh metal sieve to obtain the preproduct. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution was 1:1.

[0052] Step A3: Under nitrogen atmosphere, 0.02 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 80 mL of toluene were mixed and stirred at 80 °C. 0.02 mol of the preproduct was added and mixed evenly. Then 0.2 g of azobisisobutyronitrile was added and the reaction was carried out for 24 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and vacuum dried at 60 °C for 12 h to obtain the modified flame retardant.

[0053] The modified anti-aging agent is prepared by the following method:

[0054] Step B1: Mix 0.02 mol of p-aminophenol and 12.5 mL of dimethyl sulfoxide evenly, and slowly add 0.02 mol of allyl isothiocyanate under stirring. Heat to 50 °C and continue stirring for 3.5 h. After the reaction is complete, filter, wash, and dry to obtain the compound.

[0055] Step B2: Mix 0.02 mol of the compound, 0.02 mol of p-toluenesulfonyl chloride, 20 mL of acetone and 0.55 mL of triethylamine evenly, stir at room temperature for 2.5 h, and after the reaction is complete, rotary evaporate, wash and dry to obtain the modified anti-aging agent.

[0056] Example 3: A method for preparing a high-performance PVC composite material, specifically including the following steps:

[0057] S1. Weigh the raw materials according to the following parts by weight: 100 parts of PVC resin, 20 parts of chlorinated polyethylene, 8 parts of modified flame retardant (prepared in this embodiment), 4 parts of modified aging resistant agent (prepared in this embodiment), 2 parts of lubricant, 8 parts of stabilizer, 10 parts of plasticizer, 2 parts of coupling agent, and 15 parts of calcium carbonate; mix and stir the PVC resin and calcium-zinc composite heat stabilizer for 30 minutes, then add chlorinated polyethylene, modified flame retardant and modified aging resistant agent, and stir for 30 minutes to obtain a premix;

[0058] S2. Mix the premix, stearic acid, DOP, KH-550 and calcium carbonate evenly, place them in a twin-screw extruder, extrude and granulate at a speed of 300 r / min, cool to room temperature, and obtain a high-performance PVC composite material.

[0059] The modified flame retardant is prepared by the following method:

[0060] Step A1: Place 15g Sb2O3 and 20mL distilled water into a planetary high-energy ball mill and perform wet ball milling at room temperature. The ball milling speed is 400r / min and the ball milling time is 24h. After ball milling, wash, dry at 100℃ for 10h, and pass through a 100-mesh metal mesh sieve to obtain the intermediate.

[0061] Step A2: At room temperature, 0.03 mol of the intermediate and 0.21 g of grinding balls were placed in a ball mill jar, 0.06 mol of vinyltriethoxysilane was added, and then 15 mL of ethanol-water mixed solution was added. The pH of the system was adjusted to 5, and the mixture was ball milled at 400 r / min for 24 h. After washing, the mixture was dried at 80 °C for 10 h and passed through a 100-mesh metal sieve to obtain the preproduct. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution was 1:1.

[0062] Step A3: Under nitrogen atmosphere, 0.03 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 80 mL of toluene were mixed and stirred at 80 °C. 0.03 mol of the preproduct was added and mixed evenly. Then 0.2 g of azobisisobutyronitrile was added and the reaction was carried out for 24 h. After the reaction was completed, the mixture was cooled to room temperature, washed, and vacuum dried at 60 °C for 12 h to obtain the modified flame retardant.

[0063] The modified anti-aging agent is prepared by the following method:

[0064] Step B1: Mix 0.03 mol of p-aminophenol and 15 mL of dimethyl sulfoxide evenly, and slowly add 0.03 mol of allyl isothiocyanate under stirring. Heat to 55 °C and continue stirring for 4 h. After the reaction is complete, filter, wash, and dry to obtain the compound.

[0065] Step B2: Mix 0.03 mol of the compound, 0.03 mol of p-toluenesulfonyl chloride, 20 mL of acetone and 0.6 mL of triethylamine evenly, stir at room temperature for 3 h, after the reaction is complete, rotary evaporate, wash and dry to obtain the modified anti-aging agent.

[0066] Comparative Example 1: This comparative example is a high-performance PVC composite material. The difference between this example and Example 3 is that an equal amount of magnesium hydroxide is used instead of the modified flame retardant prepared in Example 3. All other aspects are the same.

[0067] Comparative Example 2: This comparative example is a high-performance PVC composite material. The difference between this example and Example 3 is that an equal amount of UV-531 is used instead of the modified aging resistant agent prepared in Example 3. All other aspects are the same.

[0068] Performance testing: The high-performance PVC composite materials obtained in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, and the oxygen index was tested according to GB / T 2406.2-2009. A high oxygen index indicates that the material is not easily combustible, while a low oxygen index indicates that the material is easily combustible. The samples were placed in a UV aging chamber at 60°C and 0.86 w / cm². 2 After 1000 hours of ultraviolet light exposure, the difference in yellow index was measured; a larger difference indicates poorer anti-aging performance. Differential thermal analysis was used to test thermal stability in oxygen at 210℃, with the oxidation induction period (min) as the indicator. The test results are shown in Table 1 below.

[0069] Table 1

[0070]

[0071] As can be seen from the test data in Table 1, the high-performance PVC composite material prepared by the present invention has good flame retardant effect. Table 1 also shows that the high-performance PVC composite material prepared by the present invention has good heat resistance and aging resistance, thus extending its service life.

[0072] 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 method for preparing a high-performance PVC composite material, characterized in that, Specifically, the following steps are included: S1. Weigh the raw materials according to the following parts by weight: 100 parts PVC resin, 10-20 parts chlorinated polyethylene, 4-8 parts modified flame retardant, 2-4 parts modified aging resistant agent, 1-2 parts lubricant, 4-8 parts stabilizer, 4-10 parts plasticizer, 1-2 parts coupling agent, and 10-15 parts calcium carbonate; mix the PVC resin and stabilizer and stir for 30 minutes, then add the chlorinated polyethylene, modified flame retardant and modified aging resistant agent, and stir for 15-30 minutes to obtain the premix. S2. Mix the premix, lubricant, plasticizer, coupling agent and calcium carbonate evenly, place them in a twin-screw extruder, extrude and granulate at a speed of 300 r / min, cool to room temperature, and obtain a high-performance PVC composite material. The modified flame retardant is prepared by the following method: Step A1: Place Sb2O3 and distilled water into a planetary high-energy ball mill and perform wet ball milling at room temperature. The ball milling speed is 400 r / min and the ball milling time is 24 h. After ball milling, wash, dry at 100℃ for 10 h, and pass through a 100-mesh metal mesh sieve to obtain the intermediate. Step A2: At room temperature, place the intermediate and grinding balls in a ball mill jar, add vinyltriethoxysilane, then add ethanol-water mixed solution, adjust the pH of the system to 5, ball mill at 400 r / min for 24 h, wash, dry at 80 ℃ for 10 h, and pass through a 100 mesh metal sieve to obtain the preproduct. Step A3: Under nitrogen atmosphere, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene are mixed and stirred at 80°C. The preproduct is added and mixed evenly, and then azobisisobutyronitrile is added. The reaction is carried out for 24 hours. After the reaction is completed, the mixture is cooled to room temperature, washed, and vacuum dried at 60°C for 12 hours to obtain the modified flame retardant.

2. The method for preparing a high-performance PVC composite material according to claim 1, characterized in that, In step A1, the ratio of Sb2O3 to distilled water is 10-15g:15-20mL.

3. The method for preparing a high-performance PVC composite material according to claim 1, characterized in that, In step A2, the ratio of the intermediate, grinding ball, vinyltriethoxysilane, and ethanol-water mixed solution is 0.01-0.03 mol: 0.07-0.21 g: 0.02-0.06 mol: 10-15 mL, and the volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 1:

1.

4. The method for preparing a high-performance PVC composite material according to claim 1, characterized in that, In step A3, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, preproduct, and azobisisobutyronitrile is 0.01-0.03 mol: 80 mL: 0.01-0.03 mol: 0.2 g.

5. The method for preparing a high-performance PVC composite material according to claim 1, characterized in that, The modified anti-aging agent is prepared by the following method: Step B1: Mix p-aminophenol and dimethyl sulfoxide evenly, slowly add allyl isothiocyanate under stirring, heat to 45-55℃, continue stirring for 3-4 hours, after the reaction is complete, filter, wash, dry, and obtain the compound. Step B2: Mix the compound, p-toluenesulfonyl chloride, acetone and triethylamine evenly, stir at room temperature for 2-3 hours, after the reaction is complete, rotary evaporate, wash and dry to obtain the modified anti-aging agent.

6. The method for preparing a high-performance PVC composite material according to claim 5, characterized in that, In step B1, the ratio of p-aminophenol, dimethyl sulfoxide, and allyl isothiocyanate is 0.01-0.03 mol: 10-15 mL: 0.01-0.03 mol.

7. The method for preparing a high-performance PVC composite material according to claim 5, characterized in that, In step B2, the ratio of the compound, p-toluenesulfonyl chloride, acetone, and triethylamine is 0.01-0.03 mol: 0.01-0.03 mol: 20 mL: 0.5-0.6 mL.

8. The method for preparing a high-performance PVC composite material according to claim 1, characterized in that, The lubricant is stearic acid, the stabilizer is calcium-zinc composite heat stabilizer, the plasticizer is DOP, and the coupling agent is KH-550.

9. A high-performance PVC composite material, characterized in that, Prepared by the preparation method according to any one of claims 1-8.

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