A PVC composite material and its preparation method and application

Abstract

The invention discloses a PVC composite material, characterized in that, by weight, it comprises the following components: 100 parts of PVC; 25-80 parts of plasticizer; 15-45 parts of filler; 0.5-3 parts of stabilizer; 0.5-2 parts of antimony trioxide; 0.05-0.3 parts of polytetrafluoroethylene; the plasticizer is a compound of dioctyl terephthalate and didecyl phthalate, and the filler is a compound of calcium silicate and talcum powder. The present invention can significantly improve the wear resistance and melt fluidity of the flexible PVC composite material by selecting specific plasticizers and fillers, and can also improve the decline of flame retardancy caused by the addition of plasticizers in the prior art.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a PVC composite material and a preparation method and application thereof. Background Art

[0002] PVC materials are widely used in many industries, including household appliances, wires and cables, power tools, sports equipment, automobiles, etc. Its material performance advantages include weather resistance, acid and alkali resistance, chemical resistance, flame retardancy, etc. Its modification range is wide, and it can be optimized in many aspects according to actual needs.

[0003] Flexible PVC generally refers to PVC materials with more than 20 parts of plasticizer added. However, plasticizers will have a negative impact on the wear resistance and flame retardancy of PVC materials. In addition, PVC composite materials themselves have low strength, so their wear resistance is worse than other engineering resins.

[0004] Flexible PVC has a good feel and is frequently used in some products such as sheaths, pedals, handles, cable packaging materials, etc. The corresponding products have certain requirements on the wear resistance of the material. At the same time, improving the flame retardancy of flexible PVC materials is also a relatively important demand. Summary of the invention

[0005] The purpose of the present invention is to provide a PVC composite material with good wear resistance, flame retardancy and fluidity.

[0006] The present invention is achieved through the following technical solutions:

[0007] A PVC composite material, comprising the following components in parts by weight:

[0008] PVC 100 copies;

[0009] Plasticizer 25-80 parts;

[0010] 15-45 parts of filler;

[0011] Antimony trioxide 0.5-2 parts;

[0012] Polytetrafluoroethylene 0.05-0.3 parts;

[0013] Stabilizer 0.5-3 parts;

[0014] The plasticizer is a compound of dioctyl terephthalate and didecyl phthalate, with a weight ratio of (0.3-1.1):1;

[0015] The filler is a compound of calcium silicate and talcum powder, with a weight ratio of (2-5):1, and an average particle size of the filler is 1-10 microns.

[0016] Preferably, the plasticizer is a compound of dioctyl terephthalate and didecyl phthalate in a weight ratio of (0.7-0.9):1.

[0017] Preferably, the filler is a compound of calcium silicate and talc in a weight ratio of (3-4):1.

[0018] Preferably, the average particle size of the filler is in the range of 4-7 microns.

[0019] The average particle size of the polytetrafluoroethylene is in the range of 0.2-45 microns; preferably, the average particle size of the polytetrafluoroethylene is in the range of 4-16 microns.

[0020] The stabilizer is selected from metal stearate stabilizers, and the metal stearate stabilizer is selected from at least one of zinc stearate stabilizers and calcium stearate stabilizers.

[0021] According to actual needs, it can be selected whether to add 0-2 parts of lubricant, and the lubricant can be polyethylene wax. The content of PVC resin in the PVC composite material of the present invention is not less than 40wt%.

[0022] In the technical solution of the present application, 0-1.2 parts of antistatic agent, 0-0.5 parts of antibacterial agent, and 0-0.4 parts of anti-UV aging agent can also be added.

[0023] The preparation method of a PVC composite material comprises the following steps: uniformly mixing PVC, a plasticizer and a stabilizer, heating the mixture to 80-110°C, uniformly mixing the mixture with polytetrafluoroethylene and antimony trioxide, and then mixing the mixture with a filler and granulating the mixture through an extruder, wherein the temperature range of the extruder is 80-170°C (70-90°C in the first zone, 90-110°C in the second zone, 140-160°C in the third zone, 150-160°C in the fourth zone, 150-170°C in the fifth zone, and 160-180°C in the sixth zone), to obtain the PVC composite material.

[0024] Application of PVC composite material, the PVC composite material of the present invention is tested according to the test standard ISO 4649:2010, the test instrument is a rotating roller wear tester, and the volume wear loss is less than 175 mm 3 , spiral wire length is greater than 250mm, flame retardancy V-0, suitable for cable materials.

[0025] The present invention has the following beneficial effects:

[0026] The present invention finds that the absorption of different plasticizers by PVC resin is limited and parallel. The present invention can be better absorbed by selecting a specific compound plasticizer, which is beneficial to better oil absorption of PVC resin, and can significantly improve the decrease in flame retardancy and wear resistance caused by the addition of other plasticizers in the prior art; through fillers with specific particle size and ratio, calcium silicate is a porous needle structure with fire insulation and heat insulation, and talcum powder is a layered structure with lubricity, and the compounding of the two can significantly improve the wear resistance and melt fluidity of the flexible PVC composite material. Further exploration of the average particle size of polytetrafluoroethylene can further improve the wear resistance. Implementation

[0027] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0028] The sources of raw materials used in the present invention are as follows:

[0029] PVC: PVC TG-1000, Tosoh Chemical Co., Ltd.;

[0030] Dioctyl terephthalate: UN488, Liancheng Chemical;

[0031] Didecyl phthalate: Palatinol 10 P, BASF;

[0032] Commonly used compound plasticizer A in the prior art: citric acid ester ATBC / trimellitate TOTM=1:1;

[0033] The commonly used compound plasticizer B in the prior art: aliphatic dibasic acid ester DOS / citric acid ester ATBC / trimellitate ester TOTM = 1:2:3;

[0034] The commonly used compound plasticizer C in the prior art is: phthalate DOTP / citrate ATBC / trimellitate TOTM=1:2:3.

[0035] Zinc stearate stabilizer: brand RUP-110C, purchased from Aidico Investment Co., Ltd.;

[0036] Calcium silicate A: average particle size 1.1 μm, purchased from Junzhuo Chemical;

[0037] Calcium silicate B: average particle size 4.2 μm, purchased from Qianyao Technology;

[0038] Calcium silicate C: average particle size 7.0 μm, purchased from Jiangxi Aote;

[0039] Calcium silicate D: average particle size 9.6 μm, purchased from Synade Nanomaterials Co., Ltd.;

[0040] Calcium silicate E: average particle size 0.6 μm, purchased from Junzhuo Chemical;

[0041] Calcium silicate F: average particle size 16.3 μm, purchased from Jiangxi Aote;

[0042] Talc powder was purchased from Guangdong Yuanlei Powder Co., Ltd. Raw materials with different average particle sizes were obtained by grinding and screening, and the average particle size was obtained by testing with a particle size tester.

[0043] Talc A: average particle size 2.9 microns;

[0044] Talc B: average particle size 5.0 μm;

[0045] Talc C: average particle size 6.5 microns;

[0046] Talc D: average particle size 10.0 μm;

[0047] Talc E: average particle size 0.5 microns;

[0048] Talc F: average particle size 15.7 microns.

[0049] Calcium carbonate: AC-MLT02, purchased from Meilitai Chemical Co., Ltd., average particle size 2.5 μm;

[0050] Antimony trioxide: S-05N, Shanxing Antimony Industry Co., Ltd.

[0051] Polytetrafluoroethylene A: average particle size 0.2 μm, Xijia Chemical, POLY TS 30;

[0052] Polytetrafluoroethylene B: average particle size 4.5 microns, Qihong Chemical;

[0053] Polytetrafluoroethylene C: average particle size 15.6 microns, Yinyuan New Materials, FR-PT105;

[0054] Polytetrafluoroethylene D: average particle size 45.0 microns, Coward, 121;.

[0055] Lubricant:316A.

[0056] The preparation method of the PVC composite material of the embodiment and the comparative example is as follows: PVC, a plasticizer and a stabilizer are mixed uniformly, the mixture is heated to 100° C. and then mixed uniformly with polytetrafluoroethylene and antimony trioxide, and then mixed with a filler and granulated by an extruder. The temperature of the extruder is set to 80° C. in the first zone, 100° C. in the second zone, 150° C. in the third zone, 155° C. in the fourth zone, 160° C. in the fifth zone and 170° C. in the sixth zone to obtain a PVC composite material.

[0057] Various test methods:

[0058] (1) Volumetric wear: The test instrument is a rotating roller abrader and the test standard is ISO 4649:2010.

[0059] (2) Flame retardancy: The test standard is UL-94 and the sample is a 1.5 mm burning specimen.

[0060] (3) Fluidity: The spiral length is obtained by using the spiral length, injection temperature of 170°C, spiral mold thickness of 1 mm, width of 10 mm, and fixed injection pressure, holding pressure and other process conditions.

[0061] Table 1: Content of each component (parts by weight) and test results of PVC composite materials in Examples 1-6

[0062] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PVC 100 100 100 100 100 100 Zinc stearate stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 Dioctyl terephthalate 11.6 16.7 20.6 23.6 25 26.1 Didecyl phthalate 38.4 33.3 29.4 26.4 25 23.9 Calcium silicate types A A A A A A Calcium silicate content 24 24 24 24 24 24 Types of talcum powder A A A A A A Talc content 6 6 6 6 6 6 Polytetrafluoroethylene A 0.1 0.1 0.1 0.1 0.1 0.1 Antimony trioxide 1 1 1 1 1 1 <![CDATA[Volume wear, mm 3 > 169.2 166.4 148.3 150.1 167.5 171.8 Helix length, mm 260 265 285 280 265 255 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0

[0063] It can be seen from Examples 1-6 that when the compounding ratio of the plasticizer of the present invention is (0.3-1.1):1, the wear resistance, processing and flame retardancy of the material are all maintained at a high level; the preferred weight ratio is (0.7-0.9):1.

[0064] Table 2: Content of each component (parts by weight) and test results of PVC composite materials of Examples 7-13

[0065] Example 7 Example 8 Example 9 Example 10 Embodiment 11 Example 12 Embodiment 13 PVC 100 100 100 100 100 100 100 Zinc stearate stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Dioctyl terephthalate 20.6 20.6 20.6 20.6 20.6 20.6 20.6 Didecyl phthalate 29.4 29.4 29.4 29.4 29.4 29.4 29.4 Calcium silicate types B C D A A A A Calcium silicate content 24 24 24 24 20 22.5 25 Types of talcum powder B C D D A A A Talc content 6 6 6 6 10 7.5 5 Polytetrafluoroethylene A 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antimony trioxide 1 1 1 1 1 1 1 <![CDATA[Volume wear, mm 3 > 143.1 152.2 170.3 151.7 174.3 155.6 172.9 Helix length, mm 280 275 260 273 260 275 255 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0

[0066] It can be seen from Examples 3 / 7-10 that the larger the average particle size of the filler, the shorter the spiral length. When the average particle size of the preferred filler is 4-7 microns, the wear resistance and processability of the material are better.

[0067] It can be seen from Examples 3 / 11-13 that when the preferred filler ratio is calcium silicate: talc = (3-4):1, the wear resistance and processability of the material are better.

[0068] Table 3: Content of each component (parts by weight) and test results of PVC composite materials of Examples 13-17

[0069] Embodiment 13 Embodiment 14 Embodiment 15 Example 16 Embodiment 17 PVC 100 100 100 100 100 Zinc stearate stabilizer 1.5 1.5 1.5 0.5 3 Dioctyl terephthalate 20.6 20.6 20.6 8.3 40 Didecyl phthalate 29.4 29.4 29.4 16.7 40 Calcium Silicate A 24 24 24 12 36 Talc A 6 6 6 3 9 Polytetrafluoroethylene B 0.1 0.05 0.3 Polytetrafluoroethylene C 0.1 Polytetrafluoroethylene D 0.1 Antimony trioxide 1 1 1 0.5 2 <![CDATA[Volume wear, mm 3 > 143.2 146.3 157.5 174.4 164.2 Helix length, mm 280 275 260 275 255 Flame retardant V-0 V-0 V-0 V-0 V-0

[0070] It can be seen from Examples 3 / 13-15 that when the average particle size of TPFE is optimized, the wear resistance of the material is better, and the length of the spiral line can reach more than 275 mm, maintaining good processing performance.

[0071] Table 4: Content of each component (parts by weight) and test results of PVC composite materials in comparative examples 1-7

[0072] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 PVC 100 100 100 100 100 100 100 Zinc stearate stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Dioctyl terephthalate 8.3 28.3 20.6 20.6 20.6 20.6 20.6 Didecyl phthalate 41.7 21.7 29.4 29.4 29.4 29.4 29.4 Calcium silicate types A A E F F A A Calcium silicate content 24 24 24 24 24 15 25.7 Types of talcum powder A A E F A A A Talc content 6 6 6 6 6 15 4.3 Polytetrafluoroethylene A 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antimony trioxide 1 1 1 1 1 1 1 <![CDATA[Volume wear, mm 3 > 197.7 183.4 196.1 194.5 190.5 187.4 183.2 Helix length, mm 250 230 210 230 239 245 225 Flame retardant V-1 V-1 V-1 V-2 V-1 V-1 V-1

[0073] It can be seen from Comparative Examples 1-2 that when the compounding ratio of dioctyl terephthalate and didecyl phthalate is not within the scope of the present invention, the flame retardancy and wear resistance of the material deteriorate.

[0074] It can be seen from Comparative Examples 3-5 that when the average particle size of the filler is not within the range of the present invention, the wear resistance and processability of the material deteriorate, and when the average particle size of the filler is too large, the flame retardancy also decreases;

[0075] It can be seen from Comparative Examples 6-7 that when the ratio of the filler is not within the scope of the present invention, the wear resistance, processability and flame retardancy of the material deteriorate. Needle-shaped calcium silicate itself has high thermal insulation and flame retardancy, and its insertion in layered talc makes the material interface more uniform and uniform, and a suitable compounding ratio is conducive to flame retardancy.

[0076] Table 5: Content of each component (parts by weight) and test results of PVC composite materials in comparative examples 8-9

[0077] Comparative Example 8 Comparative Example 9 PVC 100 100 Zinc stearate stabilizer 1.5 1.5 Dioctyl terephthalate 20.6 20.6 Didecyl phthalate 29.4 29.4 Calcium silicate types A Calcium silicate content 24 Types of talcum powder A Talc content 24 Calcium carbonate 6 6 Polytetrafluoroethylene A 0.1 0.1 Antimony trioxide 1 1 <![CDATA[Volume wear, mm 3 > 191.3 185.6 Helix length, mm 215 210 Flame retardant V-1 V-1

[0078] It can be seen from Comparative Examples 7-8 that if other filling compounds are used, it is difficult to simultaneously achieve the technical effects of the present invention.

[0079] Table 6: Comparative Examples 10-12 PVC composite material component content (parts by weight) and test results

[0080] Comparative Example 10 Comparative Example 11 Comparative Example 12 PVC 100 100 100 Zinc stearate stabilizer 1.5 1.5 1.5 Types of commonly used compound plasticizers in the prior art A B C Commonly used compound plasticizer content in existing technology 50 50 50 Calcium silicate types A A A Calcium silicate content 24 24 24 Types of talcum powder A A A Talc content 6 6 6 Polytetrafluoroethylene A 0.1 0.1 0.1 Antimony trioxide 1 1 1 <![CDATA[Volume wear, mm 3 > 187.4 183.2 188.6 Helix length, mm 220 230 220 Flame retardant V-1 V-1 V-1

[0081] It can be seen from Comparative Examples 9-11 that the existing commonly used plasticizer formulations easily cause a decrease in flame retardancy and formability, and also have a negative impact on the wear resistance of the flame retardant and scratch resistant solutions of the present application.

Claims

1. A PVC composite material, characterized in that: By weight, the raw materials include the following components: PVC 100 copies; Plasticizer 25-80 parts; 15-45 parts of filler; Antimony trioxide 0.5-2 parts; Polytetrafluoroethylene 0.05-0.3 parts; Stabilizer 0.5-3 parts; The plasticizer is a compound of dioctyl terephthalate and didecyl phthalate, with a weight ratio of (0.3-1.1):1; The filler is a compound of calcium silicate and talcum powder, with a weight ratio of (2-5):1, and an average particle size of the filler is 1-10 microns.

2. The PVC composite material according to claim 1, characterized in that: The plasticizer is a compound of dioctyl terephthalate and didecyl phthalate, with a weight ratio of (0.7-0.9):

1.

3. The PVC composite material according to claim 1, characterized in that: The filler is a compound of calcium silicate and talc in a weight ratio of (3-4):

1.

4. The PVC composite material according to claim 1, characterized in that: The average particle size of the filler is in the range of 4-7 microns.

5. The PVC composite material according to claim 1, characterized in that: The average particle size of the polytetrafluoroethylene is in the range of 0.2-45 microns.

6. The PVC composite material according to claim 5, characterized in that: The average particle size of the polytetrafluoroethylene is in the range of 4-16 microns.

7. The PVC composite material according to claim 1, characterized in that: The stabilizer is selected from metal stearate stabilizers, and the metal stearate stabilizer is selected from at least one of zinc stearate stabilizers and calcium stearate stabilizers.

8. The PVC composite material according to claim 1, characterized in that: By weight, 0-2 parts of lubricant are also included.

9. The method for preparing the PVC composite material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: uniformly mixing PVC, a plasticizer and a stabilizer, heating the mixture to 80-110° C., uniformly mixing the mixture with polytetrafluoroethylene and antimony trioxide, and then mixing the mixture with a filler and granulating the mixture through an extruder at a temperature range of 80-170° C. to obtain a PVC composite material.

10. Use of the PVC composite material according to any one of claims 1 to 7, characterized in that: For cable materials.