High-insulativity PVC material and preparation method thereof

Abstract

The invention discloses a high-insulativity PVC (polyvinyl chloride) material and a preparation method thereof, tetrahydrofuran is adopted as a modifier, the surface structure of PVC is changed through a special surface treatment mode, and modified PVC resin is obtained, so that the processing plasticization of a product is improved, a plasticizer in processing is replaced, and the insulativity and precipitation resistance of the product are improved; by adding the chlorosulfonated polyethylene elastomer, the toughness of the product is improved, the toughness of the product without adding the plasticizer is compensated, and the rigid-tough balance of the product is regulated, so that the high-insulation PVC material with required strength is formed.

Description

Technical Field:

[0001] The present invention belongs to the technical field of polymer material modification and processing, and relates to a high-insulation PVC material and a preparation method thereof. Background Art

[0002] PVC (polyvinyl chloride) is polymerized from VCM (vinyl chloride) as a monomer. As a high-performance material, it is widely used in various fields, such as pipes, profiles, and films. Due to its insulation property, it is used in the cable field and has a relatively high premium space. As an insulating layer, the insulation performance of the product is required to be relatively high. The five-type powder requires a volume resistivity higher than 10^ 12 Ω·m. Currently, people will improve the volume resistivity of the product by adjusting the additive formulation, such as changing the types of plasticizers and stabilizers, but this will increase the cost, or adding some insulating additives, such as fillers like kaolin. Bi Lijing found in the research that different plasticizers have a great influence on the resistivity of the product, and the insulation performance of the product is improved by adding external insulating materials; Li Yonghe and Liu Jiadong improved the insulation performance of the product by adding additives such as nano-calcium carbonate and calcined kaolin. In order to obtain a product with the required strength and toughness, a certain proportion of plasticizer needs to be added. However, on the one hand, the added plasticizer will reduce the resistivity of the finished product, and on the other hand, it will be prone to precipitation, reducing the service life of the product. Therefore, there is a need to provide a PVC with high insulation and low precipitation performance. Summary of the Invention

[0003] In order to solve the above problems, the present invention provides a high-insulation PVC material and a preparation method thereof. The prepared PVC has the advantages of high insulation and low precipitation, and the preparation method is simple and easy to implement.

[0004] The present invention can be realized through the following technical solutions:

[0005] A high-insulation PVC material, which comprises the following components in parts by weight:

[0006] 100 parts of modified PVC resin;

[0007] 10 - 30 parts of chlorosulfonated polyethylene elastomer, preferably 15 - 25 parts;

[0008] 2 - 4 parts of heat stabilizer, preferably 2.5 - 3.5 parts;

[0009] 0.1 - 1 part of processing aid, preferably 0.3 - 0.8 part.

[0010] Preferably, the modified PVC resin is modified with tetrahydrofuran as a modifier.

[0011] Preferably, the preparation method of the modified PVC resin comprises the following steps:

[0012] Place tetrahydrofuran in a drying dish, seal the drying dish with a filter screen, then place the drying dish at the bottom of a rapid dryer, place the PVC powder around the drying dish containing tetrahydrofuran, and adjust the gas volume of the rapid dryer so that the PVC powder is suspended above the equipment to obtain modified PVC resin.

[0013] Preferably, the PVC powder is type 5 powder with an average particle size of 110 - 180 μm.

[0014] The size of the filter screen is 200 nm - 10 μm; the temperature of the rapid dryer is 70 - 100 °C, the gas volume is 60 - 100 m 3 / h, and the modification time is 4 - 6 h.

[0015] In the present invention, during the modification process, the drying dish containing tetrahydrofuran is under the dryer, and tetrahydrofuran volatilizes after being heated, and the volatilized gas contacts the powder.

[0016] Preferably, in the modified PVC resin, based on 100 parts by mass of the added PVC resin, the addition amount of the modifier is 80 - 150 parts by mass, preferably 100 - 120 parts by mass.

[0017] Preferably, the chlorosulfonated polyethylene elastomer has a molecular weight of 1000 - 5000, preferably 3000 - 4000.

[0018] Preferably, the heat stabilizer is one or more of calcium - zinc type and barium - zinc type heat stabilizers, and the models include one or more of CZ - 113, BZ - 830, CZ - 116, CZ - 122W, BF - 470HB; preferably barium - zinc stabilizer.

[0019] Preferably, the processing aid is one or more of acrylate (ACR), polyethylene wax, and stearic acid, preferably one or more of ACR - 201, ACR - 301, and ACR - 401.

[0020] On the other hand, the present invention also provides a preparation method of a high - insulation PVC material, including the following steps:

[0021] Mix the modified polyvinyl chloride resin, chlorosulfonated polyethylene elastomer, heat stabilizer, and processing aid evenly, and then extrude and pelletize through an extruder to obtain a high - insulation polyvinyl chloride product.

[0022] Preferably, the mixing is carried out in a high - speed mixer, the extruder is a twin - screw extruder, the temperature of the high - speed mixer is 110 - 120 °C, the heating temperature in the extruder is 130 - 160 °C, and the extrusion temperature is 130 - 160 °C.

[0023] The positive effects of the present invention are:

[0024] In the present invention, tetrahydrofuran is used as a modifier, and a special surface treatment method is adopted to change the surface structure of PVC to obtain a modified PVC resin, thereby increasing the processing plasticization of the product, replacing the plasticizer in the processing, and improving the insulation and precipitation resistance of the product.

[0025] By adding chlorosulfonated polyethylene elastomer, the toughness of the product is improved, the toughness without adding plasticizer is compensated, and the rigidity and toughness balance of the product is adjusted, so as to obtain a high-insulation cable material with the required product performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 :Schematic diagram of modified PVC processing process Specific implementation method:

[0027] The present invention is described in detail below with reference to specific embodiments.

[0028] In the following embodiments, five types of polyvinyl chloride resin powders are selected.

[0029] Polyvinyl chloride resin SG-5 was purchased from Junzheng Petrochemical; chlorosulfonated polyethylene elastomer (molecular weight 3000), barium zinc stabilizer BF-470HB, stearic acid, and ACR-201 processing aid were purchased from Aladdin.

[0030] Preparation Example 1 of Modified PVC Resin:

[0031] Place 100 parts of tetrahydrofuran solution in a drying dish, seal it with a filter screen with a size of 200nm, and then place it at the bottom of the rapid dryer. At the same time, place 100 parts of PVC resin powder around the drying dish containing tetrahydrofuran solution and place them together in the rapid dryer. Set the temperature to 70℃ and the gas volume to 60m 3 / h, ensuring that the powder is suspended above the equipment, and the drying dish containing tetrahydrofuran solution is placed under the dryer. The solution evaporates after being heated, and the volatile gas contacts the powder. After 4 hours of operation, modified PVC resin 1 is obtained.

[0032] Preparation Example 2 of Modified PVC Resin:

[0033] Place 150 parts of tetrahydrofuran solution in a drying dish, seal it with a filter screen with a size of 1um, and then place it at the bottom of the rapid dryer. At the same time, place 100 parts of PVC resin powder around the drying dish containing tetrahydrofuran solution and place them together in the rapid dryer. Set the temperature to 85℃ and the gas volume to 80m 3 / h, ensuring that the powder is suspended above the equipment. The drying dish containing the tetrahydrofuran solution is placed below the dryer. After the solution is heated, it volatilizes, and the volatilized gas contacts the powder. After operating for 5 h, modified PVC resin 2 is obtained.

[0034] Preparation Example 3 of Modified PVC Resin:

[0035] Place 100 parts of the tetrahydrofuran solution in a drying dish, seal it with a filter screen with a size of 10 μm, and then place it at the bottom of a rapid dryer. At the same time, place 100 parts of PVC resin powder around the drying dish containing the tetrahydrofuran solution, and place them together in a rapid dryer. Set the temperature to 100 °C and the gas volume to 100 m 3 / h, ensuring that the powder is suspended above the equipment. The drying dish containing the tetrahydrofuran solution is placed below the dryer. After the solution is heated, it volatilizes, and the volatilized gas contacts the powder. After operating for 6 h, modified PVC resin 3 is obtained.

[0036] Preparation Example 4 of Modified PVC Resin:

[0037] Place 300 parts of the tetrahydrofuran solution in a drying dish, seal it with a filter screen with a size of 10 μm, and then place it at the bottom of a rapid dryer. At the same time, place 100 parts of PVC resin powder around the drying dish containing the tetrahydrofuran solution, and place them together in a rapid dryer. Set the temperature to 150 °C and the gas volume to 100 m 3 / h, ensuring that the powder is suspended above the equipment. The drying dish containing the tetrahydrofuran solution is placed below the dryer. After the solution is heated, it volatilizes, and the volatilized gas contacts the powder. After operating for 2 h, modified PVC resin 4 is obtained.

[0038] Preparation Example 5 of Modified PVC Resin:

[0039] Place 40 parts of the tetrahydrofuran solution in a drying dish, seal it with a filter screen with a size of 10 μm, and then place it at the bottom of a rapid dryer. At the same time, place 100 parts of PVC resin powder around the drying dish containing the tetrahydrofuran solution, and place them together in a rapid dryer. Set the temperature to 60 °C and the gas volume to 60 m 3 / h, ensuring that the powder is suspended above the equipment. The drying dish containing the tetrahydrofuran solution is placed below the dryer. After the solution is heated, it volatilizes, and the volatilized gas contacts the powder. After operating for 2 h, modified PVC resin 5 is obtained.

[0040] Example 1

[0041] Weigh 100 parts by mass of modified PVC resin 1, 20 parts by mass of chlorosulfonated polyethylene elastomer, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of heating zones 1, 2, 3, and 4 in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the extruded cable in zones 1, 2, 3, and 4 are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0042] Example 2

[0043] Weigh 100 parts by mass of modified PVC resin 1, 10 parts by mass of chlorosulfonated polyethylene elastomer, 2 parts by mass of barium-zinc heat stabilizer, 0.1 part by mass of ACR, and 10 parts of dioctyl phthalate. After mixing evenly, mix them in a high-speed mixer for 5 minutes, and granulate the evenly mixed material in a twin-screw extruder. Mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of heating zones 1, 2, 3, and 4 in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the extruded cable in zones 1, 2, 3, and 4 are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0044] Example 3

[0045] Weigh 100 parts by mass of modified PVC resin 1, 30 parts by mass of chlorosulfonated polyethylene elastomer, 4 parts by mass of barium-zinc heat stabilizer, 1 part by mass of ACR, and 20 parts of dioctyl phthalate. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of heating zones 1, 2, 3, and 4 in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the extruded cable in zones 1, 2, 3, and 4 are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0046] Example 4

[0047] Weigh 100 parts by mass of modified PVC resin 2, 20 parts by mass of chlorosulfonated polyethylene elastomer, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of heating zones 1, 2, 3, and 4 in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the extruded cable in zones 1, 2, 3, and 4 are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0048] Example 5

[0049] Weigh 100 parts by mass of the modified PVC resin 3, 20 parts by mass of chlorosulfonated polyethylene elastomer, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of the first, second, third, and fourth heating zones in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the first, second, third, and fourth zones for extruding the cable are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0050] Comparative Example 1

[0051] Weigh 100 parts by mass of PVC resin, 40 parts by mass of dioctyl phthalate, 20 parts by mass of chlorosulfonated polyethylene elastomer, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of the first, second, third, and fourth heating zones in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the first, second, third, and fourth zones for extruding the cable are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0052] Comparative Example 2

[0053] Weigh 100 parts by mass of the modified PVC resin 1, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of the first, second, third, and fourth heating zones in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the first, second, third, and fourth zones for extruding the cable are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0054] Comparative Example 3

[0055] Weigh 100 parts by mass of the modified PVC resin 4, 20 parts by mass of chlorosulfonated polyethylene elastomer, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of the first, second, third, and fourth heating zones in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of the first, second, third, and fourth zones for extruding the cable are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0056] Comparative Example 4

[0057] Weigh 100 parts by mass of the modified PVC resin 5, 20 parts by mass of chlorosulfonated polyethylene elastomer, 3 parts by mass of barium-zinc heat stabilizer, and 0.5 part by mass of ACR. After mixing them evenly, mix them in a high-speed mixer for 5 minutes at a mixing temperature of 110°C, and granulate the evenly mixed material in a twin-screw extruder. The temperatures of heating zones 1, 2, 3, and 4 in the extruder are 130, 140, 150, and 160°C respectively, and the temperatures of zones 1, 2, 3, and 4 for extruding the cable are 130, 140, 150, and 160°C respectively. The test results are shown in Table 1.

[0058] The test results are as follows

[0059] 1) Test the properties of a high-insulation PVC material prepared in Examples 1-5 and Comparative Examples 1-4. The test results are shown in the following table:

[0060] Table 1. Physical and Mechanical Property Tests of Each Example and Comparative Product

[0061]

[0062]

[0063] The above experiments prove that:

[0064] Using tetrahydrofuran as a modifier and through a special surface treatment method to change the skin structure of PVC, the obtained modified PVC resin can improve the processing plasticization of the product, replace the plasticizer in the processing, enhance the insulation and exudation resistance of the product; by adding chlorosulfonated polyethylene elastomer with a certain molecular weight, the toughness of the product can be enhanced to make up for the toughness without adding plasticizer.

Claims

1. A highly insulating PVC material, which comprises the following components in parts by weight: 100 parts of modified PVC resin; 10 - 30 parts of chlorosulfonated polyethylene elastomer, preferably 15 - 25 parts; 2 - 4 parts of heat stabilizer, preferably 2.5 - 3.5 parts; 0.1 - 1 part of processing aid, preferably 0.3 - 0.8 part.

2. The highly insulating PVC material according to claim 1, wherein, The preparation method of the modified PVC resin comprises the following steps: Place tetrahydrofuran in a drying dish, seal the drying dish with a filter screen, then place the drying dish at the bottom of a rapid dryer, place the PVC powder around the drying dish containing tetrahydrofuran, and adjust the gas volume of the rapid dryer to suspend the PVC powder above the equipment to obtain the modified PVC resin.

3. The highly insulating PVC material according to claim 2, wherein, The PVC powder is type-five powder with an average particle size of 110 - 180 μm.

4. The highly insulating PVC material according to claim 2 or 3, wherein, The size of the filter screen is 200 nm - 10 μm; and / or, the temperature of the rapid dryer is 70 - 100 °C, and the gas volume is 60 - 100 m 3 / h; and / or, the modification time is 4 - 6 h.

5. The highly insulating PVC material according to any one of claims 2 - 4, wherein, In the modified PVC resin, based on 100 parts by mass of the added PVC resin, the addition amount of the modifier is 80 - 150 parts by mass, preferably 100 - 120 parts by mass.

6. The highly insulating PVC material according to any one of claims 1 - 5, wherein, The chlorosulfonated polyethylene elastomer has a molecular weight of 1000 - 5000, preferably 3000 - 4000.

7. The highly insulating PVC material according to any one of claims 1 - 6, wherein, The heat stabilizer is one or more of calcium-zinc type and barium-zinc type heat stabilizers, and the models include one or more of CZ-113, BZ-830, CZ-116, CZ-122W, BF-470HB; preferably barium-zinc stabilizer.

8. The highly insulating PVC material according to any one of claims 1 - 7, wherein, The processing aid is one or more of acrylate (ACR), polyethylene wax, and stearic acid, preferably one or more of ACR-201, ACR-301, and ACR-401.

9. The preparation method of the highly insulating PVC material according to any one of claims 1 - 8, wherein, It includes the following steps: Mix the modified polyvinyl chloride resin, chlorosulfonated polyethylene elastomer, heat stabilizer, and processing aid evenly, and then obtain a high-insulation polyvinyl chloride product by extrusion granulation through an extruder.

10. The preparation method according to claim 9, wherein, The mixing is carried out in a high-speed mixer. The extruder is a twin-screw extruder. The temperature of the high-speed mixer is 110 - 120 °C, the heating temperature in the extruder is 130 - 160 °C, and the temperature of the extruded cable is 130 - 160 °C.

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