Preparation method of high-strength PVC alloy material

Abstract

The invention discloses a preparation method of a high-strength PVC alloy material, and belongs to the technical field of modified plastics. The raw materials of the flame-retardant PVC composite material comprise the following components in parts by mass: 20-80 parts of PVC resin, 20-80 parts of ABS resin, 10-25 parts of PTFE micro powder, 1-10 parts of a heat stabilizer, 1-5 parts of a lubricant, 50-80 parts of a plasticizer, 0.1-0.5 part of an antioxidant, 10-20 parts of a halogen-free compound flame retardant and 5-20 parts of an inorganic filler. The PVC alloy material obtained by the invention not only has the advantages of impact resistance, low temperature resistance, easiness in molding and processing and the like of the ABS resin, but also has the advantages of flame retardance, chemical corrosion resistance, wear resistance, insulation, low price and the like of the PVC.

Description

Technical Field

[0001] The invention belongs to the technical field of modified plastics, and in particular relates to a method for preparing a high-strength PVC alloy material. Background Art

[0002] Polyvinyl chloride (PVC) is a general-purpose plastic with low price and good comprehensive performance. Through specific ingredients and different processing processes, it can be made into a series of products with different performances from soft to hard, and is widely used in various industries. PVC has the advantages of light weight, high strength, good electrical insulation, flame retardancy, corrosion resistance, low price and wide source of raw materials. However, when used alone, it becomes more brittle at low temperatures and has limited flame retardancy, which seriously limits the promotion and application of PVC resin and its products.

[0003] In order to make PVC more widely used, it must be modified to improve the performance of its products. PVC alloy material is a composite material obtained by extruding polyvinyl chloride as the main component, mixing with stabilizers, lubricants, toughening agents, etc., and using a variety of resins to blend and modify. The common modification method is physical blending, which mixes PVC with other polymers, usually using mechanical blending. The main purpose of blending is modification, such as improving processing performance, improving heat resistance, and improving impact resistance.

[0004] Chinese invention patent application number 201010622075.5 discloses a flame retardant PVC / ABS alloy material and a preparation method thereof, which is characterized by comprising 10-80 parts of PVC resin; 10-70 parts of ABS resin; 1-10 parts of a compatibilizer; 1-7 parts of a heat stabilizer; 1-10 parts of a filler; 1-5 parts of a flame retardant coordinator; 2-15 parts of a processing aid; and 1-15 parts of a toughening agent.

[0005] The Chinese invention patent with application number 201210199488.6 discloses a high heat-resistant polyvinyl chloride alloy material, which is characterized by including 100 parts of polyvinyl chloride; 100-160 parts of high heat-resistant resin; 10-20 parts of impact modifier; 3-7 parts of heat stabilizer; 0.4-1 part of lubricant; 1-3 parts of processing aid; 0.2-0.5 parts of antioxidant; and 5-10 parts of filler.

[0006] The Chinese invention patent with application number 202310173314.0 discloses an ablation-resistant PVC alloy material, a preparation method and an application thereof, characterized in that it includes 100 parts of PVC resin; 2-5 parts of heat stabilizer; 10-40 parts of ABS resin; 5-10 parts of toughening agent; 5-20 parts of glass microbeads; 3-15 parts of hyperbranched polyester; 1-5 parts of silane coupling agent; and 1-3 parts of lubricant.

[0007] Most of the existing technologies are modified to improve one aspect of performance, such as high temperature resistance, wear resistance, flame retardancy, ablation resistance, etc., but the low temperature resistance of PVC alloy materials is relatively poor, and there are few studies on this aspect. With the increasing application of PVC plastics, people are in urgent need of a PVC alloy material with strong comprehensive performance, so the development of a high-strength PVC alloy material is also particularly important. Summary of the invention

[0008] The invention provides a method for preparing a high-strength PVC alloy material to improve the low-temperature resistance and flame retardant performance of the PVC alloy material.

[0009] In order to solve the above technical problems, one of the purposes of the present invention is to provide a high-strength PVC alloy material, comprising the following components in parts by weight: PVC resin 20-80 parts; ABS resin 20-80 parts; 10-25 parts of PTFE micropowder; 1-10 parts of heat stabilizer; 1-5 parts of lubricant; 50-80 parts of plasticizer; Antioxidant 0.1-0.5 parts; 10-20 parts of halogen-free compound flame retardant; 5-20 parts of inorganic filler. The PVC resin is a loose PVC resin with a polymerization degree of 1300-1700. The PVC resin has the characteristics of high fluidity, UV resistance stability and good flame retardancy, can effectively improve the flame retardancy of PVC alloy materials, and effectively improve the processing performance of PVC alloy materials.

[0010] In the above scheme, although ABS resin has the characteristics of impact resistance, low temperature resistance, and easy molding and processing, its flame retardancy and weather resistance are extremely poor. PTFE micropowder has excellent weather resistance, cold resistance, flame retardancy, chemical stability and good dispersibility, and is easy to be evenly blended with other materials. In this application, PVC resin and ABS resin are compounded within a certain proportion range, and the flame retardancy of the compounded PVC resin and the low temperature resistance of ABS can be better exerted. A certain amount of PTFE micropowder and other additives are added. Through the synergistic fusion of the components in the system, the low temperature resistance of the system is more significantly improved while ensuring flame retardancy, and the impact strength of the overall material system is improved.

[0011] As a preferred embodiment, the ABS resin is an ABS resin having a butadiene segment content of 40-60% and an average particle size of the butadiene rubber phase less than or equal to 0.15 μm. As a preferred solution, the molecular weight of the PTFE micropowder is less than 10,000 and the average particle size is ≤15µm.

[0012] As a preferred embodiment, the heat stabilizer is a calcium-zinc composite heat stabilizer, which helps to inhibit the degradation of PVC materials and can effectively improve the stability, weather resistance and aging resistance of PVC alloy materials.

[0013] As a preferred embodiment, the lubricant is polyethylene wax (PE wax). As a preferred embodiment, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Antioxidant 1010).

[0014] As a preferred embodiment, the plasticizer is selected from one or more of diethylene glycol dibenzoate (DEDB) plasticizer, di(2-propylheptyl) adipate (LH-80) plasticizer and triethylene glycol diisooctanoate (TGDE) plasticizer.

[0015] As a preferred embodiment, the halogen-free composite flame retardant is obtained by mixing modified basic magnesium sulfate whiskers and magnesium hydroxide flame retardant in a mass ratio of 3:5; The preparation method of the modified basic magnesium sulfate whisker is as follows: mixing the basic magnesium sulfate whisker with deionized water, heating to 70-100° C., stirring evenly to obtain a whisker suspension, then adding a surface modifier, continuing stirring for 25 minutes, cooling to room temperature, and then washing and drying to obtain the modified basic magnesium sulfate whisker. The hydrophobic group of the surfactant is coated on the surface of the basic magnesium sulfate whisker, so that the whisker has good compatibility with the organic polymer material.

[0016] The surface modifier is selected from titanate coupling agent NDZ-201, titanate coupling agent NDZ-101, stearic acid, or aluminate coupling agent ASA, and the amount of the surface modifier added is 5% of the mass of the basic magnesium sulfate whisker.

[0017] The basic magnesium sulfate whisker is a 153-type, 138-type or 311-type basic magnesium sulfate whisker.

[0018] The preferred whisker length is 10-100 μm, and the whisker aspect ratio is 50-700.

[0019] As a preferred embodiment, the inorganic filler is at least one of activated calcium carbonate powder and talcum powder; In order to solve the above technical problems, the second object of the present invention is to provide a method for preparing a high-strength PVC alloy material, comprising the following preparation steps: 1) According to the PVC alloy material formula, weigh each component according to the ratio, then add PVC resin, PTFE powder, heat stabilizer, lubricant, inorganic filler, antioxidant into a high-speed mixer and stir until the material temperature is 75°C, then add plasticizer and continue stirring until the material temperature is 100-125°C, the hot mixing time is 10-15 minutes; and cool to room temperature, then add halogen-free compound flame retardant into the high-speed mixer, stir at 750 r / min at room temperature for 5-10 minutes, and get the expected; 2) The premix obtained in step 1) is sent to an internal mixer for pre-plasticization, and then sent to an extruder for repeated plasticization and plasticization, and then added from the main feed port of the twin-screw extruder, and ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated through the twin-screw extruder. The extrusion temperature of the twin-screw extruder is 165-170°C. The plasticized material passes through a metal detector and can be sent to a calender to be calendered into a film with a thickness of 0.25mm, which is drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product.

[0020] The beneficial effects of the present invention are: The present application compounds PVC resin and ABS resin, and the low-temperature resistance and flame retardant properties of the compounded system can be better exerted. At the same time, a certain amount of PTFE micropowder, modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant are added in proportion to form a halogen-free compound flame retardant system. The PTFE micropowder itself has excellent heat resistance, weather resistance, cold resistance, chemical stability, high flame retardancy and other properties, and the basic magnesium sulfate whisker has excellent properties such as flame retardancy and smoke suppression, and enhanced mechanical properties of materials. Through the synergistic fusion of various components in the system, while achieving flame retardancy, it can also improve the impact strength and low-temperature resistance of the overall material system, improve the mechanical properties of the alloy, and achieve energy conservation and emission reduction to the greatest extent. The PVC alloy material has the advantages of ABS resin such as impact resistance, low-temperature resistance, and easy molding and processing, and has the advantages of PVC such as flame retardancy, corrosion resistance, weather resistance, and low price, thereby obtaining a cost-effective alloy material. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application. All other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0022] Example 1 A high-strength PVC alloy material, prepared according to the following mass proportions: 80 parts of PVC resin, 20 parts of ABS resin, 15 parts of PTFE, 75 parts of DEDB, 5 parts of calcium zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 10 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 5 parts of inorganic filler. The halogen-free composite flame retardant used in this embodiment is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5. Specifically, the preparation method of modified basic magnesium sulfate whisker is as follows: 1) 1000mL of deionized water is measured and placed in a beaker; 2) 25g of 311 type basic magnesium sulfate whisker (whisker length 30μm, whisker aspect ratio 200) is weighed and added to the beaker in the above 1); 3) The beaker in the above 2) is placed in a 75°C constant temperature water bath, and stirred with an electric stirrer until the whiskers are uniformly dispersed into a suspension, and the stirring speed is 700r / min; 4) After the temperature is constant, a titanate coupling agent NDZ-201 with a mass fraction of 5% of the basic magnesium sulfate whisker is added, and stirring is continued for 20min; 5) The beaker is taken out, cooled at room temperature, and then washed with deionized water, filtered, and dried to finally obtain modified basic magnesium sulfate whisker.

[0023] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1300), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, active calcium carbonate powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then DEDB powder is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 165°C. The plasticized material passes through a metal detector and is then fed into a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this embodiment are shown in Table 1. Example 2 A high-strength PVC alloy material, prepared according to the following mass proportions: 70 parts of PVC resin, 30 parts of ABS resin, 10 parts of PTFE, 55 parts of DEDB, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 15 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 15 parts of inorganic filler. The halogen-free composite flame retardant used in this embodiment is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5. Specifically, the preparation method of modified basic magnesium sulfate whisker is as follows: 1) 1000mL of deionized water is measured and placed in a beaker; 2) 25g of 153 type basic magnesium sulfate whisker (whisker length 80μm, whisker aspect ratio 100) is weighed and added to the beaker in the above 1); 3) the beaker in the above 2) is placed in a 75°C constant temperature water bath, and stirred with an electric stirrer until the whiskers are uniformly dispersed into a suspension, and the stirring speed is 700r / min; 4) after the constant temperature is reached, a titanate coupling agent NDZ-101 with a mass fraction of 5% of the basic magnesium sulfate whisker is added, and stirring is continued for 20min; 5) the beaker is taken out, cooled at room temperature, and then washed with deionized water, filtered, and dried to finally obtain modified basic magnesium sulfate whisker. A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1500), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, active calcium carbonate powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then DEDB powder is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 165°C. The plasticized material passes through a metal detector and is then fed into a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this embodiment are shown in Table 1.

[0024] Example 3 A high-strength PVC alloy material, prepared according to the following mass proportions: 70 parts of PVC resin, 30 parts of ABS resin, 15 parts of PTFE, 55 parts of LH-80, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 20 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 20 parts of inorganic filler.

[0025] The halogen-free composite flame retardant used in this embodiment is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5. Specifically, the preparation method of modified basic magnesium sulfate whisker is as follows: 1) 1000mL of deionized water is measured and placed in a beaker; 2) 25g of 311 type basic magnesium sulfate whisker (whisker length 50μm, whisker aspect ratio 700) is weighed and added to the beaker in the above 1); 3) the beaker in the above 2) is placed in a 75°C constant temperature water bath, and stirred with an electric stirrer until the whiskers are uniformly dispersed into a suspension, and the stirring speed is 700r / min; 4) after the temperature is constant, a titanate coupling agent NDZ-201 with a mass fraction of 5% of the basic magnesium sulfate whisker is added, and stirring is continued for 20min; 5) the beaker is taken out, cooled at room temperature, and then washed with deionized water, filtered, and dried to finally obtain modified basic magnesium sulfate whisker.

[0026] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1700), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, active calcium carbonate powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then LH-80 powder is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; and then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then fed into a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this embodiment are shown in Table 1.

[0027] Example 4 A high-strength PVC alloy material, prepared according to the following mass proportions: 60 parts of PVC resin, 40 parts of ABS resin, 20 parts of PTFE, 55 parts of LH-80, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 20 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 15 parts of inorganic filler.

[0028] The halogen-free composite flame retardant used in this embodiment is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5. Specifically, the preparation method of modified basic magnesium sulfate whisker is as follows: 1) 1000mL of deionized water is measured and placed in a beaker; 2) 25g of 138 type basic magnesium sulfate whisker (whisker length 100μm, whisker aspect ratio 50) is weighed and added to the beaker in the above 1); 3) the beaker in the above 2) is placed in a 75°C constant temperature water bath, and stirred with an electric stirrer until the whiskers are uniformly dispersed into a suspension, and the stirring speed is 700r / min; 4) after the temperature is constant, an aluminate coupling agent ASA with a mass fraction of 5% of the basic magnesium sulfate whisker is added, and stirring is continued for 20min; 5) the beaker is taken out, cooled at room temperature, and then washed with deionized water, filtered, and dried to finally obtain modified basic magnesium sulfate whisker.

[0029] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1300), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, talcum powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then LH-80 is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 165°C. The plasticized material passes through a metal detector and is then fed into a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this embodiment are shown in Table 1.

[0030] Example 5 A high-strength PVC alloy material, prepared according to the following mass proportions: 60 parts of PVC resin, 40 parts of ABS resin, 10 parts of PTFE, 55 parts of TGDE, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 10 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 10 parts of inorganic filler.

[0031] The halogen-free composite flame retardant used in this embodiment is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5. Specifically, the preparation method of modified basic magnesium sulfate whisker is as follows: 1) 1000mL of deionized water is measured and placed in a beaker; 2) 25g of 138 type basic magnesium sulfate whisker (whisker length 80μm, whisker aspect ratio 160) is weighed and added to the beaker in the above 1); 3) the beaker in the above 2) is placed in a 75°C constant temperature water bath, and stirred with an electric stirrer until the whiskers are uniformly dispersed into a suspension, and the stirring speed is 700r / min; 4) after the temperature is constant, 5% phthalate coupling agent NDZ-201 of the basic magnesium sulfate whisker mass fraction is added, and stirring is continued for 20min; 5) the beaker is taken out, cooled at room temperature, and then washed with deionized water, filtered, and dried to finally obtain modified basic magnesium sulfate whisker.

[0032] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1500), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, talcum powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then TGDE is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then fed into a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this embodiment are shown in Table 1.

[0033] Example 6 A high-strength PVC alloy material, prepared according to the following mass proportions: 80 parts of PVC resin, 20 parts of ABS resin, 20 parts of PTFE, 75 parts of TGDE, 5 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 20 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 20 parts of inorganic filler.

[0034] The halogen-free composite flame retardant used in this embodiment is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5. Specifically, the preparation method of modified basic magnesium sulfate whisker is as follows: 1) 1000mL of deionized water is measured and placed in a beaker; 2) 25g of 153 type basic magnesium sulfate whisker (whisker length 50μm, whisker aspect ratio 120) is weighed and added to the beaker in the above 1); 3) the beaker in the above 2) is placed in a 75°C constant temperature water bath, and stirred with an electric stirrer until the whiskers are uniformly dispersed into a suspension, and the stirring speed is 700r / min; 4) after the constant temperature is reached, stearic acid with a mass fraction of 5% of the basic magnesium sulfate whisker is added, and stirring is continued for 20min; 5) the beaker is taken out, cooled at room temperature, and then washed with deionized water, filtered, and dried to finally obtain modified basic magnesium sulfate whisker.

[0035] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1700), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, talcum powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then TGDE is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then fed into a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this embodiment are shown in Table 1.

[0036] Comparative Example 1 A high-strength PVC alloy material, the formula composition is as follows 80 parts of PVC resin, 20 parts of ABS resin, 75 parts of TGDE, 5 parts of calcium zinc composite heat stabilizer, 10100.2 parts of antioxidant, 20 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 20 parts of talcum powder.

[0037] The halogen-free composite flame retardant used in this comparative example is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5, wherein the preparation method of the modified basic magnesium sulfate whisker is the same as that of Example 6.

[0038] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1700), calcium zinc composite heat stabilizer, PE wax, talcum powder, and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then TGDE is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then sent to a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this comparative example are shown in Table 2.

[0039] Comparative Example 2 A high-strength PVC alloy material, the formula composition is as follows: 70 parts of PVC resin, 30 parts of ABS resin, 15 parts of PTFE, 55 parts of LH-80, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 20 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 20 parts of activated calcium carbonate powder.

[0040] The halogen-free composite flame retardant used in this comparative example is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:1, wherein the preparation method of the modified basic magnesium sulfate whisker is the same as that of Example 3.

[0041] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1700), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, active calcium carbonate powder and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then LH-80 is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; and then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then sent to a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this comparative example are shown in Table 2.

[0042] Comparative Example 3 A high-strength PVC alloy material, the formula composition is as follows: 70 parts of PVC resin, 30 parts of ABS resin, 15 parts of PTFE, 55 parts of LH-80, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 20 parts of halogen-free compound flame retardant, 2 parts of PE wax, and 20 parts of activated calcium carbonate powder.

[0043] The halogen-free composite flame retardant used in this comparative example is prepared by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 1:1, wherein the preparation method of the modified basic magnesium sulfate whisker is the same as that of Example 3.

[0044] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1700), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, active calcium carbonate powder and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then LH-80 is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, then a halogen-free compound flame retardant is added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; and then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then sent to a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this comparative example are shown in Table 2.

[0045] Comparative Example 4 A high-strength PVC alloy material, the formula composition is as follows: 70 parts of PVC resin, 30 parts of ABS resin, 15 parts of PTFE, 55 parts of LH-80, 4 parts of calcium-zinc composite heat stabilizer, 0.2 parts of antioxidant 1010, 20 parts of basic magnesium sulfate whisker, 2 parts of PE wax, and 20 parts of activated calcium carbonate powder.

[0046] A preparation method of a high-strength PVC alloy material is as follows: PVC resin (polymerization degree 1700), PTFE micropowder, calcium-zinc composite heat stabilizer, PE wax, active calcium carbonate powder and antioxidant 1010 are placed in a high-speed mixer and stirred until the material temperature is 75°C, then LH-80 is added and stirred until the material temperature is 100-125°C, and the hot mixing time is 10-15 minutes; and cooled to room temperature, and then basic magnesium sulfate whiskers are added to the high-speed mixer, and stirred at 750 r / min for 5-10 minutes at room temperature to obtain a premix; and then the premix is ​​sent to an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded and granulated by the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 170°C. The plasticized material passes through a metal detector and is then sent to a calender to be calendered into a 0.25 mm thick film, which is then drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product. The performance test results of the high-strength PVC alloy material prepared in this comparative example are shown in Table 2.

[0047] Table 1 Relevant properties of low temperature resistant flame retardant PVC alloy materials prepared in Examples 1-6 Table 2 PVC alloy materials prepared in Comparative Examples 1-4 From the comparison of the data of Example 3 and Comparative Example 2 and Comparative Example 3 in Table 1 and Table 2, it can be seen that when the modified basic magnesium sulfate whisker and the magnesium hydroxide flame retardant are matched in a mass ratio of 3:1 and 1:1, the mechanical properties of the PVC alloy material are not greatly affected, but the flame retardant properties of the PVC alloy material are reduced to a certain extent. Therefore, the optimal mass ratio of the modified basic magnesium sulfate whisker and the magnesium hydroxide flame retardant compound flame retardant is 3:5.

[0048] From the comparison of the data of Example 3 and Comparative Example 4 in Table 1 and Table 2, it can be seen that when the halogen-free composite flame retardant system composed of unmodified basic magnesium sulfate whiskers and magnesium hydroxide flame retardant is added to the alloy material, the mechanical properties of the PVC alloy material are reduced to a certain extent, but the effect on the flame retardant properties is not significant. The halogen-free composite flame retardant system composed of modified basic magnesium sulfate whiskers and magnesium hydroxide flame retardant has the effect of enhancing the flame retardancy of the PVC alloy material, and the PVC alloy material obtained by adding the halogen-free composite flame retardant system has good comprehensive mechanical properties. With the increase in the amount of the halogen-free composite flame retardant system added, the flame retardant properties and mechanical properties of the PVC alloy material are improved to a certain extent, and the flame retardant grade reaches UL-94 V-0.

[0049] It can be seen from the data of Example 6 and Comparative Example 1 in Table 1 and Table 2 that when PTFE powder is added, the low-temperature impact strength of the PVC alloy material is significantly improved, but the effect on the mechanical properties of the PVC alloy material is not significant, indicating that the use of PTFE powder can significantly improve the low-temperature impact strength of the PVC alloy material and effectively enhance the low-temperature resistance of the PVC alloy material.

Claims

1. A high-strength PVC alloy material, characterized in that: The raw materials consist of the following components in parts by weight: PVC resin 20-80 parts; ABS resin 20-80 parts; 10-25 parts of PTFE micropowder; 1-10 parts of heat stabilizer; 1-5 parts of lubricant; 50-80 parts of plasticizer; Antioxidant 0.1-0.5 parts; 10-20 parts of halogen-free compound flame retardant; 5-20 parts of inorganic filler; The inorganic filler is at least one of activated calcium carbonate powder and talcum powder; The plasticizer is selected from one or more of diethylene glycol dibenzoate plasticizer, di(2-propylheptyl)adipate plasticizer and triethylene glycol diisooctanoate plasticizer.

2. The high-strength PVC alloy material according to claim 1, characterized in that: The PVC resin is a loose PVC resin with a polymerization degree of 1300-1700.

3. The high-strength PVC alloy material according to claim 1, characterized in that: The ABS resin has a butadiene segment content of 40-60% and an average particle size of the butadiene rubber phase less than or equal to 0.15 μm.

4. The high-strength PVC alloy material according to claim 1, characterized in that: The molecular weight of the PTFE micropowder is less than 10,000, and the average particle size is ≤15µm.

5. The high-strength PVC alloy material according to claim 1, characterized in that: The heat stabilizer is a calcium-zinc composite heat stabilizer.

6. The high-strength PVC alloy material according to claim 1, characterized in that: The antioxidant is antioxidant 1010; the lubricant is polyethylene wax.

7. The high-strength PVC alloy material according to claim 1, characterized in that: The halogen-free composite flame retardant is obtained by mixing modified basic magnesium sulfate whisker and magnesium hydroxide flame retardant in a mass ratio of 3:5; The preparation method of the modified basic magnesium sulfate whisker is as follows: mixing basic magnesium sulfate whisker with deionized water, heating to 70-100° C., stirring evenly to obtain a whisker suspension, then adding a surface modifier, continuing stirring for 25 minutes, cooling to room temperature, and then washing and drying to obtain the modified basic magnesium sulfate whisker.

8. The high-strength PVC alloy material according to claim 7, characterized in that: The basic magnesium sulfate whisker is a 153-type, 138-type or 311-type basic magnesium sulfate whisker, the whisker length is 10-100 μm, and the whisker aspect ratio is 50-700.

9. The high-strength PVC alloy material according to claim 7, characterized in that: The surface modifier is selected from titanate coupling agent NDZ-201, titanate coupling agent NDZ-101, stearic acid or aluminate coupling agent ASA, and the added amount of the surface modifier is 5% of the mass of the basic magnesium sulfate whisker.

10. A method for preparing the high-strength PVC alloy material according to any one of claims 1 to 9, characterized in that: The specific steps are as follows: 1) According to the PVC alloy material formula, weigh each component according to the ratio, then add PVC resin, PTFE powder, heat stabilizer, lubricant, inorganic filler, antioxidant into a high-speed mixer and stir until the material temperature is 75°C, then add plasticizer and continue stirring until the material temperature is 100-125°C, the hot mixing time is 10-15 minutes; and cool to room temperature, then add halogen-free compound flame retardant into the high-speed mixer, stir at 750 r / min at room temperature for 5-10 minutes, and get the expected; 2) The premix obtained in step 1) is fed into an internal mixer for pre-plasticization, and then transported to an extruder for repeated plasticization and plasticization, and then added from the main feeding port of the twin-screw extruder, and ABS resin is fed from the middle section of the twin-screw extruder through a side feeder, and extruded into granules through the twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 165-170° C. The plasticized material passes through a metal detector and can be sent to a calender to be calendered into a film with a thickness of 0.25 mm, which is drawn out through a take-off roller, and then cooled, thickness measured, and rolled to obtain a PVC calendered film product.

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