High-performance PVC composite material and preparation method thereof

Abstract

The application relates to a high-performance PVC composite material and a preparation method thereof, and belongs to the technical field of 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 modified flame retardant, 2-4 parts of modified anti-aging agent, 1-2 parts of lubricant, 4-8 parts of stabilizer, 4-10 parts of plasticizer, 1-2 parts of coupling agent and 10-15 parts of calcium carbonate. The high-performance PVC composite material prepared by the application has good flame-retardant effect, excellent heat resistance and excellent anti-aging effect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a high-performance PVC composite material and a preparation method thereof. BACKGROUND

[0002] PVC (polyvinyl chloride) material is the second largest general-purpose plastic with a yield only less than polyethylene, and is widely used in technical fields such as building pipes, medical devices, food packaging, building water supply and drainage, and chemical industry due to excellent chemical resistance, electrical insulation, acid and alkali resistance, and high structural strength.

[0003] However, ordinary PVC material will soften under high temperature and ultraviolet irradiation, and continuous temperature fluctuation will accelerate the aging of the material, thereby limiting the use range thereof; in addition, although ordinary PVC material has certain flame retardancy, the flame retardancy thereof is difficult to meet the current demand as the actual application demand is continuously improved, and therefore, it is of important practical significance and application value to develop high-performance PVC composite material with excellent performance. SUMMARY

[0004] In order to solve the above technical problems, the application provides a high-performance PVC composite material and a preparation method thereof.

[0005] The object of the application can be achieved by the following technical scheme.

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

[0007] The lubricant is stearic acid.

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

[0009] The plasticizer is DOP.

[0010] The coupling agent is KH-550.

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

[0012] Step A1: Sb2O3 and distilled water are put into a planetary high-energy ball mill, wet ball milling is carried out at room temperature, the ball milling speed is 400 r / min, the ball milling time is 24 h, after the ball milling is completed, washing, drying at 100 DEG C for 10 h, and passing through a 100-mesh metal screen to prepare an intermediate.

[0013] Further, the amount ratio of Sb2O3 and distilled water is 10-15 g: 15-20 mL;

[0014] First, the intermediate is prepared by ball-milling Sb2O3 to nano size;

[0015] Step A2: The intermediate and grinding balls are placed in a ball mill tank at room temperature, and then vinyltriethoxysilane and an ethanol-water mixed solution are added, and the pH of the system is adjusted to 5, and then ball-milling is carried out at 400 r / min for 24 h, and then the product is washed, dried at 80°C for 10 h, and sieved through a 100-mesh metal screen to obtain a pre-product;

[0016] Further, the amount ratio of the intermediate, grinding balls, vinyltriethoxysilane, and the 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 and deionized water in the ethanol-water mixed solution is 1:1;

[0017] Second, the pre-product is prepared by the reaction of the hydroxyl group of the intermediate and the silicon hydroxyl group produced by the hydrolysis of vinyltriethoxysilane;

[0018] Step A3: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene are mixed under a nitrogen atmosphere, and then the mixture is stirred at 80°C, and then the pre-product is added and mixed uniformly, and then azobisisobutyronitrile is added, and then the reaction is carried out for 24 h, and then the reaction is cooled to room temperature, and then the product is washed and dried under vacuum at 60°C for 12 h to obtain a modified flame retardant;

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

[0020] Finally, the modified flame retardant is prepared by the reaction of the carbon-carbon double bond of the pre-product and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

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

[0022] Step B1: p-aminophenol and dimethyl sulfoxide are mixed uniformly, and then allyl isothiocyanate is slowly added under stirring, and then the temperature is raised to 45-55°C, and then the stirring is continued for 3-4 h, and then the reaction is completed, and then the product is filtered, washed, and dried to obtain a compound;

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

[0024] First, the amino group of p-aminophenol and the isothiocyanate group of allyl isothiocyanate are reacted to prepare the compound;

[0025] Step B2: the compound, p-toluenesulfonyl chloride, acetone and triethylamine are mixed uniformly, stirred at room temperature for 2-3h, after the reaction is completed, rotary evaporation, washing, drying to prepare the modified anti-aging agent;

[0026] Further, the compound, p-toluenesulfonyl chloride, acetone, triethylamine are used in a ratio of 0.01-0.03mol: 0.01-0.03mol: 20mL: 0.5-0.6mL.

[0027] Finally, the hydroxyl group of the compound and the chlorine atom of p-toluenesulfonyl chloride are reacted to prepare the modified anti-aging agent.

[0028] A preparation method of a high-performance PVC composite material, specifically comprising the following steps:

[0029] S1, the PVC resin and the stabilizer are mixed and stirred for 30min, then the chlorinated polyethylene, the modified flame retardant and the modified anti-aging agent are added and stirred for 15-30min to prepare a premix;

[0030] S2, the premix, the lubricant, the plasticizer, the coupling agent and the calcium carbonate are mixed uniformly, placed in a double-screw extruder, extruded and granulated at a rotating speed of 300r / min, and cooled to room temperature to prepare the high-performance PVC composite material.

[0031] The beneficial effects of the present application are:

[0032] The high-performance PVC composite material of the present application has good flame-retardant effect, and also has excellent heat resistance and anti-aging effect, further prolonging the service life.

[0033] The Sb2O3 in the modified flame retardant prepared by the application can react with chlorine free radicals and hydrogen free radicals generated by the combustion of the composite material to generate volatile gas, isolate oxygen and absorb heat, thereby reducing the heat generated in the combustion process of the matrix material. In addition, the intermediate has a large specific surface area and good dispersibility, so that the flame retardant efficiency of the composite material is high. At the same time, when the composite material is subjected to a large external stress, no large particle effect is generated to split the matrix material, thereby enhancing the mechanical properties of the matrix material. Secondly, the Sb-O-Si formed in the pre-product can effectively reduce the surface activity and surface energy of the nanoparticles, improve the dispersibility and flame retardant effect. The phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a high-thermal-stability phosphaphenanthrene compound, promotes the formation of a dense and continuous carbon layer during combustion, effectively isolates oxygen, blocks the exchange of heat and flammable gas, and synergistically retards combustion with the phosphorus-oxygen double bond, thereby prolonging the service life. In addition, the modified flame retardant prepared by the application is halogen-free, which helps to reduce pollution to the environment and damage to the ecosystem, is harmless to human health, and realizes sustainable development.

[0034] In the modified anti-aging agent prepared by the application, the thiourea of the compound has good ozone aging resistance and thermal oxidation resistance, can capture free radicals, terminate chain reactions, delay the aging of the composite material, thereby effectively prolonging the service life and reducing the use cost. In addition, the sulfone group structure of p-toluenesulfonyl chloride as an electron-withdrawing group can promote intramolecular charge transfer, so that the electrons in the material molecules can flow to achieve light absorption, efficiently absorb ultraviolet rays of different wavelength ranges, and convert the ultraviolet energy into heat or light energy, thereby reducing the damage and aging of the composite material caused by ultraviolet rays. In addition, the modified anti-aging agent has good compatibility with the composite material, can be uniformly dispersed in the matrix, and synergistically plays a heat-resistant and anti-aging role. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0036] Embodiment 1: A preparation method of a high-performance PVC composite material, specifically comprising the following steps:

[0037] S1, the raw materials are weighed by parts by weight, 100 parts of PVC resin, 10 parts of chlorinated polyethylene, 4 parts of modified flame retardant (prepared by this example), 2 parts of modified anti-aging agent (prepared by this example), 1 part of lubricant, 4 parts of stabilizer, 4 parts of plasticizer, 1 part of coupling agent, 10 parts of calcium carbonate; the PVC resin and calcium zinc composite heat stabilizer are mixed and stirred for 30 min, then the chlorinated polyethylene, the modified flame retardant and the modified anti-aging agent are added and stirred for 15 min to prepare a premix;

[0038] S2, the premix, stearic acid, DOP, KH-550 and calcium carbonate are uniformly mixed and placed in a double screw extruder, extruded and granulated at a rotating speed of 300 r / min, cooled to room temperature to prepare a high-performance PVC composite material;

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

[0040] Step A1: 10g of Sb2O3 and 15mL of distilled water are placed in a planetary high-energy ball mill, wet ball milling is carried out at room temperature, the ball milling speed is 400r / min, the ball milling time is 24h, after ball milling, washing, drying at 100℃ for 10h, passing through a 100 mesh metal screen, to prepare an intermediate;

[0041] Step A2: at room temperature, 0.01mol of the intermediate and 0.07g of the milling ball are placed in the ball mill tank, 0.02mol of vinyl triethoxysilane is added, 10mL of ethanol-water mixed solution is added, the pH of the system is adjusted to 5, ball milling is carried out at 400r / min for 24h, washing, drying at 80℃ for 10h, passing through a 100 mesh metal screen, to prepare a pre-product, the volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 1:1;

[0042] Step A3: under nitrogen environment, 0.01mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 80mL of toluene are mixed, stirring at 80℃, 0.01mol of the pre-product is mixed uniformly, then 0.2g of azobisisobutyronitrile is added, the reaction is carried out for 24h, after the reaction is completed, cooling to room temperature, washing, drying at 60℃ under vacuum for 12h, to prepare a modified flame retardant;

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

[0044] Step B1: 0.01mol of p-aminophenol and 10mL of dimethyl sulfoxide are mixed uniformly, 0.01mol of allyl isothiocyanate is slowly added under stirring, the temperature is raised to 45℃, and the stirring is continued for 3h, after the reaction is completed, filtration, washing, drying, to prepare a compound;

[0045] Step B2: 0.01 mol of the compound, 0.01 mol of p-toluenesulfonyl chloride, 20 mL of acetone and 0.5 mL of triethylamine were uniformly mixed, stirred at room temperature for 2 h, after the reaction was completed, rotary evaporation, washing, drying, to prepare the modified anti-aging agent.

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

[0047] S1, the raw materials were weighed according to the weight parts, 100 parts of PVC resin, 15 parts of chlorinated polyethylene, 6 parts of modified flame retardant (prepared by this embodiment), 3 parts of modified anti-aging agent (prepared by this embodiment), 1.5 parts of lubricant, 6 parts of stabilizer, 7 parts of plasticizer, 1.5 parts of coupling agent, 12.5 parts of calcium carbonate; the PVC resin and calcium-zinc composite heat stabilizer were mixed and stirred for 30 min, then the chlorinated polyethylene, modified flame retardant and modified anti-aging agent were added and stirred for 22.5 min to prepare a premix;

[0048] S2, the premix, stearic acid, DOP, KH-550 and calcium carbonate were uniformly mixed and placed in a double-screw extruder, extruded and granulated at a rotation speed of 300 r / min, and cooled to room temperature to prepare a high-performance PVC composite material;

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

[0050] Step A1: 12.5 g of Sb2O3 and 17.5 mL of distilled water were placed in a planetary high-energy ball mill and wet ball milled at room temperature, the ball milling speed was 400 r / min, the ball milling time was 24 h, after the ball milling was completed, washing, drying at 100℃ for 10 h, and sieving through a 100 mesh metal screen to prepare an intermediate;

[0051] Step A2: 0.02 mol of the intermediate and 0.14 g of grinding balls were placed in a ball mill tank at room temperature, 0.04 mol of vinyltriethoxysilane was added, then 12.5 mL of an ethanol-water mixed solution was added, the pH of the system was adjusted to 5, and ball milling was carried out at 400 r / min for 24 h, then washing, drying at 80℃ for 10 h, and sieving through a 100 mesh metal screen to prepare a pre-product, the volume ratio of ethanol to deionized water in the ethanol-water mixed solution was 1:1;

[0052] Step A3: 0.02 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 80 mL of toluene were mixed under a nitrogen atmosphere, stirred at 80℃, 0.02 mol of the pre-product was uniformly mixed, then 0.2 g of azobisisobutyronitrile was added, the reaction was carried out for 24 h, after the reaction was completed, the system was cooled to room temperature, washed, and dried at 60℃ under vacuum for 12 h to prepare a modified flame retardant;

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

[0054] Step B1: 0.02 mol of p-aminophenol and 12.5 mL of dimethyl sulfoxide were mixed uniformly, 0.02 mol of allyl isothiocyanate was slowly added under stirring, the temperature was raised to 50°C, and stirring was continued for 3.5 h. After the reaction was completed, filtration, washing, and drying were performed to obtain the compound;

[0055] Step B2: 0.02 mol of the compound, 0.02 mol of p-toluenesulfonyl chloride, 20 mL of acetone, and 0.55 mL of triethylamine were mixed uniformly, stirring was performed at room temperature for 2.5 h, and after the reaction was completed, rotary evaporation, washing, and drying were performed to obtain the modified anti-aging agent.

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

[0057] S1: The raw materials were weighed according to the weight parts, 100 parts of PVC resin, 20 parts of chlorinated polyethylene, 8 parts of modified flame retardant (prepared by the present example), 4 parts of modified anti-aging agent (prepared by the present example), 2 parts of lubricant, 8 parts of stabilizer, 10 parts of plasticizer, 2 parts of coupling agent, and 15 parts of calcium carbonate; the PVC resin and calcium-zinc composite heat stabilizer were mixed and stirred for 30 min, then the chlorinated polyethylene, modified flame retardant, and modified anti-aging agent were added and stirred for 30 min to obtain a premix;

[0058] S2: The premix, stearic acid, DOP, KH-550, and calcium carbonate were uniformly mixed and placed in a double-screw extruder, extrusion granulation was performed at a rotation speed of 300 r / min, and cooling was performed to room temperature to obtain a high-performance PVC composite material;

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

[0060] Step A1: 15 g of Sb2O3 and 20 mL of distilled water were placed in a planetary high-energy ball mill, wet ball milling was performed at room temperature, the ball milling rotation speed was 400 r / min, the ball milling time was 24 h, after the ball milling was completed, washing, drying at 100°C for 10 h, and passing through a 100-mesh metal screen were performed to obtain an intermediate;

[0061] Step A2: 0.03 mol of the intermediate and 0.21 g of grinding balls were placed in a ball mill tank at room temperature, 0.06 mol of vinyltriethoxysilane was added, 15 mL of an ethanol-water mixed solution was added, the system pH was adjusted to 5, ball milling was performed at 400 r / min for 24 h, washing, drying at 80°C for 10 h, and passing through a 100-mesh metal screen were performed to obtain a pre-product, and the volume ratio of ethanol to deionized water in the ethanol-water mixed solution was 1:1;

[0062] Step A3: 0.03 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 80 mL of toluene were mixed under nitrogen atmosphere, stirred at 80°C, 0.03 mol of the pre-product was added and mixed uniformly, 0.2 g of azobisisobutyronitrile was added, the reaction was carried out for 24 h, after the reaction was completed, it was cooled to room temperature, washed, and dried at 60°C under vacuum for 12 h to obtain the modified flame retardant;

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

[0064] Step B1: 0.03 mol of p-aminophenol and 15 mL of dimethyl sulfoxide were mixed uniformly, 0.03 mol of allyl isothiocyanate was slowly added under stirring, and the temperature was raised to 55°C, and the stirring was continued for 4 h, after the reaction was completed, it was filtered, washed, and dried to obtain the compound;

[0065] Step B2: 0.03 mol of the compound, 0.03 mol of p-toluenesulfonyl chloride, 20 mL of acetone, and 0.6 mL of triethylamine were mixed uniformly, stirred at room temperature for 3 h, after the reaction was completed, it was rotary evaporated, washed, and dried to obtain the modified anti-aging agent.

[0066] Comparative Example 1: This comparative example is a high-performance PVC composite material, which is different from Example 3 in that an equal amount of magnesium hydroxide is used instead of the modified flame retardant prepared in Example 3, and the rest is the same.

[0067] Comparative Example 2: This comparative example is a high-performance PVC composite material, which is different from Example 3 in that an equal amount of UV-531 is used instead of the modified anti-aging agent prepared in Example 3, and the rest is the same.

[0068] Performance test: the high-performance PVC composite materials prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, the oxygen index was tested according to GB / T 2406.2-2009, the higher the oxygen index, the less flammable the material, and the lower the oxygen index, the more flammable the material; the samples were placed in a UV aging oven with conditions of 60°C, 0.86 w / cm 2 , ultraviolet light illumination for 1000 h, the difference value of the yellow index change was tested, the larger the difference value, the worse the anti-aging performance; the thermal stability was tested by differential thermal analysis method in high temperature oxygen at 210°C, taking the oxidation induction period (min) as the index; the test results are shown in Table 1:

[0069] Table 1

[0070]

[0071] From the data of the test in Table 1, it can be seen that the high-performance PVC composite material prepared by the application has good flame-retardant effect, and from Table 1, it can also be seen that the high-performance PVC composite material prepared by the application has good heat resistance and aging resistance effect, and prolongs the service life.

[0072] The above is only an example and description of the concept of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or replace them with similar ways, as long as they do not deviate from the concept of the application or exceed the scope defined by the present claims, which shall belong to the protection scope of the application.

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 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. 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.

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, 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.

6. The method for preparing a high-performance PVC composite material according to claim 1, 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.

7. 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.

8. A high-performance PVC composite material, characterized in that, Prepared by the preparation method according to any one of claims 1-7.

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