PVC composite material, preparation method and application thereof

Abstract

This invention relates to a PVC composite material, its preparation method, and its applications. The PVC composite material comprises the following components in parts by weight: 45-60 parts PVC resin, 10-35 parts SAS resin, and 5-10 parts elastomer. This PVC composite material exhibits good heat resistance, low dielectric constant, and good solvent resistance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically, to a PVC composite material, its preparation method, and its application. Background Technology

[0002] In the outdoor industry, especially in the outdoor communication equipment and outdoor construction industries, weather-resistant and hydrolysis-resistant materials are required to meet stringent environmental requirements.

[0003] Polyvinyl chloride (PVC) is a material choice for communication equipment and construction due to its good weather resistance. However, its relatively low heat resistance and high dielectric constant limit its application in high-temperature environments with stringent signal transmission requirements, such as communication boxes. Patent CN109553876A addresses the heat resistance of PVC by adding itaconic acid monobutyl ester and SG-8 type PVC resin, but it does not focus on the material's dielectric constant.

[0004] In addition, some communication equipment needs to come into contact with energy storage batteries or mechanical devices, which may be contaminated and corroded by solvents (such as heat transfer oil and lubricating oil) from the energy storage batteries or mechanical devices, thus affecting the basic mechanical properties or service life of the communication equipment components. Therefore, polyvinyl chloride materials are also required to have good solvent resistance.

[0005] Therefore, it is necessary to develop a polyvinyl chloride material with good heat resistance, low dielectric constant and good solvent resistance to meet its application requirements in corresponding outdoor scenarios. Summary of the Invention

[0006] The primary objective of this invention is to overcome the problems of poor heat resistance, high dielectric constant, and poor solvent resistance of polyvinyl chloride (PVC) materials in the current technology, and to provide a PVC composite material, its preparation method, and its application.

[0007] A further object of the present invention is to provide a method for preparing the above-mentioned PVC composite material.

[0008] A further object of the present invention is to provide the application of the above-mentioned PVC composite material in the manufacture of outdoor communication equipment.

[0009] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0010] A PVC composite material comprises the following components in parts by weight:

[0011]

[0012]

[0013] The SAS resin, according to the ISO 1133-1 standard, has a melt volumetric flow rate of 3–25 cm⁻¹ at 220°C and a load of 10 kg. 3 / 10min;

[0014] The average degree of polymerization of the PVC resin is 600 to 1500.

[0015] In this invention, SAS resin refers to silicone copolymer AS resin (styrene-acrylonitrile-silicone copolymer).

[0016] The inventors of this invention discovered through research that adding SAS resin to PVC resin, while simultaneously controlling the melt flow rate of the SAS resin and the average degree of polymerization of the PVC resin, can improve the heat resistance and solvent resistance of PVC composite materials and reduce their dielectric constant. The reason is that controlling the melt flow rate of the SAS resin and the average degree of polymerization of the PVC resin ensures good compatibility between the two during processing and injection molding, achieving good dispersion of the SAS resin in the PVC resin. This, in turn, enhances the material's heat resistance through the organosilicon segments in the molecular structure of the SAS resin, while fully utilizing its low dielectric constant characteristic to reduce the overall dielectric constant of the material. Furthermore, by controlling the amount of SAS resin within a specific range, the heat resistance, dielectric constant, and solvent resistance of the material can be effectively balanced.

[0017] Further research revealed that adding elastomers and combining them with SAS resin can further improve the solvent resistance of the material, enabling it to reach a high level of solvent resistance.

[0018] That is, the PVC composite material of the present invention has good heat resistance, low dielectric constant and good solvent resistance.

[0019] In this invention, PVC resin is used as the main resin, accounting for more than 40% of the mass of the PVC composite material.

[0020] In this invention, the average degree of polymerization of the PVC resin can be measured according to GB / T 5761-2018.

[0021] Preferably, the average degree of polymerization of the PVC resin is 900 to 1400.

[0022] Preferably, the elastomer is at least one of high-polymer powder, silicone elastomer, or acrylic elastomer.

[0023] Optionally, the high-polymer powder is at least one of ASA high-polymer powder or ABS high-polymer powder.

[0024] Preferably, the high-polymer powder is ASA high-polymer powder, which results in better properties of the PVC composite material.

[0025] In this invention, the melt volume flow rate of SAS resin can be measured according to the standard ISO 1133-1:2011.

[0026] Typically, the SAS resin contains 10–35 wt% acrylonitrile and 25–52% styrene.

[0027] Preferably, the melt volumetric flow rate of the SAS resin measured at 220°C and 10 kg load is 20–22 cm⁻¹. 3 / 10min.

[0028] Preferably, the SAS resin has a mass percentage of 16-67% relative to the PVC resin.

[0029] More preferably, the SAS resin has a mass percentage of 37% to 67% relative to the PVC resin.

[0030] More preferably, the mass percentage of the SAS resin relative to the PVC resin is 37% to 57%. By controlling the mass percentage of the SAS resin relative to the PVC resin within this range, the resulting PVC composite material has a lower dielectric constant and better heat resistance.

[0031] Preferably, the PVC composite material further includes 0.5 to 1.5 parts of a foaming agent. Adding a foaming agent to the PVC composite material system of the present invention can further reduce the dielectric constant of the material and further improve its solvent resistance.

[0032] More preferably, the foaming agent is at least one of a bicarbonate foaming agent or azodicarbonamide.

[0033] More preferably, the bicarbonate-based foaming agent is at least one of sodium bicarbonate, potassium bicarbonate, or ammonium bicarbonate.

[0034] Preferably, the PVC composite material further includes 1 to 10 parts of filler.

[0035] Optionally, the mesh size of the filler is 1000 to 5000 mesh.

[0036] Optionally, the filler is at least one of talc, barium sulfate, or calcium carbonate.

[0037] Preferably, the PVC composite material further includes 0.5 to 2 parts of heat stabilizer.

[0038] Optionally, the heat stabilizer includes, but is not limited to, at least one of calcium-zinc stabilizers, organotin stabilizers, organophosphites, epoxidized soybean oil, hydrotalcite, or calcium oxide.

[0039] Without affecting the effect of the PVC composite material of the present invention, the PVC composite material may also include 0.5 to 5 parts of other additives.

[0040] Optionally, the other additives are at least one of weather-resistant agents, antioxidants, lubricants, plasticizers, colorants, or antistatic agents.

[0041] Optionally, the weathering agent is a light stabilizer, including but not limited to at least one of phenolic light stabilizers, benzoic acid light stabilizers, pyridine light stabilizers, or hydroxybenzoic acid ester light stabilizers.

[0042] Optionally, the antioxidant is at least one of hindered phenolic antioxidants, phosphite antioxidants, metal alkyl thiophosphate antioxidants, carbamic acid antioxidants, or organosulfur antioxidants.

[0043] Optionally, the lubricant is at least one of stearate lubricants and amide lubricants.

[0044] The preparation method of the above-mentioned PVC composite material includes the following steps: mixing the components, melt extruding, and granulating to obtain the PVC composite material.

[0045] Preferably, the temperature of the melt extrusion is 160–180°C.

[0046] The application of the above-mentioned PVC composite material in the manufacture of outdoor communication equipment is also within the scope of protection of this invention.

[0047] Generally, the outdoor communication equipment is an antenna radome.

[0048] Compared with the prior art, the beneficial effects of the present invention are:

[0049] The PVC composite material of the present invention has good heat resistance, low dielectric constant and good solvent resistance. Detailed Implementation

[0050] To more clearly and completely describe the technical solution of the present invention, the present invention will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention. Various changes can be made within the scope of the claims of the present invention.

[0051] The reagents used in the various embodiments and comparative examples of this invention are described below:

[0052] PVC resin #1: Average degree of polymerization is 1000, purchased from Tianjin LG Bohai Chemical Co., Ltd., model TL-1000;

[0053] PVC resin #2: Average degree of polymerization is 700, purchased from Tianjin LG Bohai Chemical Co., Ltd., model TL-700;

[0054] PVC resin #3: Average degree of polymerization is 1300, purchased from Tianjin LG Bohai Chemical Co., Ltd., model TL-1300;

[0055] PVC resin #4: Average degree of polymerization is 450, purchased from Kaneka Chemical Co., Ltd., Japan, model S400;

[0056] PVC resin #5: Average degree of polymerization is 1800, purchased from Formosa Plastics Industrial Co., Ltd., model S 80.

[0057] SAS resin #1: UMG S351 from Japan, with a melt volumetric flow rate of 21 cm³ / s at 220°C and a 10 kg load. 3 / 10min;

[0058] SAS resin #2: UMG TW15G from Japan, with a melt volumetric flow rate of 3 cm³ at 220°C and a 10 kg load. 3 / 10min;

[0059] AS Resin 1#: Melt volumetric flow rate of 21 cm⁻¹ was measured at 220°C and 10 kg according to ASTM D1238-2010. 3 / 10min, prepared by blending KFA-130 and KFA-180 in a 1:1 mass ratio, wherein KFA-130 and KFA-180 were obtained from Liaoning Jinfeng;

[0060] Silicone masterbatch: The carrier is AS resin, Guangzhou Yinyuan New Materials, AS500SR.

[0061] Elastomer 1#: ASA high-polymer powder, Kumho, XC640;

[0062] Elastomer 2#: Acrylic elastomer, KANEKA, M-210;

[0063] Foaming agent #1: Azodicarbonamide, purity ≥99%, commercially available;

[0064] Foaming agent #2: Sodium bicarbonate foaming agent, commercially available;

[0065] Filler #1: Talc powder, 3000 mesh, commercially available;

[0066] Heat stabilizer 1#: Organotin stabilizer, commercially available;

[0067] Other additives #1: Weathering agent, antioxidant, and lubricant are mixed in a mass ratio of 1:0.3:1. The weathering agent is a UV absorber (UV-3808), the antioxidant is a hindered phenolic antioxidant (antioxidant 1010), and the lubricant is a stearate lubricant (glyceryl monostearate), all of which are commercially available products.

[0068] Unless otherwise specified, all components (e.g., foaming agent 1#, filler 1#, other additives 1#) used in each parallel embodiment and comparative example are the same commercially available products.

[0069] The performance of the PVC composite materials provided in the embodiments and comparative examples of this invention was determined according to the following test methods:

[0070] (1) Heat resistance: ISO 75-2-2013, the load during the test was 1.8 MPa;

[0071] (2) Dielectric constant: Measured according to ASTM D 150-11;

[0072] (3) Solvent resistance: The injection-molded samples of each embodiment and comparative example were divided into group A and group B. The initial tensile strength of group A samples was tested according to JIS K7113-1995. Group B samples were immersed in a mixture of heat transfer oil and internal combustion engine lubricating oil at 50°C (mass ratio 1:1) for 20 hours, and their tensile strength was tested according to JIS K7113-1995. The tensile strength retention rate was calculated as follows: tensile strength retention rate = tensile strength of group B sample / tensile strength of group A sample.

[0073] The PVC composite materials of the embodiments and comparative examples of the present invention were prepared by the following preparation method:

[0074] Weigh each component according to the formula; mix the components, add them to a twin-screw extruder for melt blending, extrusion granulation, and the PVC composite material is obtained. The temperature of the twin-screw extruder is 165-170℃ in zones one and two, 170-175℃ in zones three and five, and 175-180℃ in zones six and ten.

[0075] Examples 1-13

[0076] Examples 1-13 provide a series of PVC composite materials, the formulations of which are shown in Table 1.

[0077] Table 1. Formulations (parts by weight) for Examples 1-13

[0078]

[0079]

[0080] Comparative Examples 1-8

[0081] Comparative Examples 1–8 provide a series of PVC composite materials, the formulations of which are shown in Table 2.

[0082] Table 2 shows the formulations (parts by weight) for Comparative Examples 1–8.

[0083]

[0084] The properties of the PVC composite materials of each embodiment and comparative example were determined according to the test methods mentioned above, and the test results are shown in Table 3.

[0085] Table 3. Performance test results of PVC composite materials in each example and comparative example.

[0086] Test Results Heat resistance / °C Dielectric constant Solvent resistance % Example 1 72 3.0 74 Example 2 70 3.4 72 Example 3 74 2.8 64 Example 4 72 3.5 70 Example 5 68 3.3 73 Example 6 75 3.0 68 Example 7 76 2.9 64 Example 8 69 3.0 64 Example 9 74 3.2 73 Example 10 74 3.1 72 Example 11 71 3.1 69 Example 12 68 2.7 65 Example 13 70 2.9 70 Comparative Example 1 50 3.6 80 Comparative Example 2 72 3.4 59 Comparative Example 3 52 3.4 77 Comparative Example 4 78 2.8 50 Comparative Example 5 76 3.0 55 Comparative Example 6 65 3.1 50 Comparative Example 7 67 3.4 60 Comparative Example 8 60 3.5 76 .

[0087] As can be seen from Table 3:

[0088] The heat distortion temperature of the PVC composite materials in Examples 1 to 13 is all above 68°C, the dielectric constant is all below 3.5, and the tensile strength retention rate in solvent resistance is all above 64%, indicating that the PVC composite materials of the present invention have good heat resistance, low dielectric constant and good solvent resistance.

[0089] Comparative Example 1, without the addition of SAS resin, resulted in a PVC composite material with poor heat resistance and a high dielectric constant. Comparative Example 2, with the addition of AS resin, resulted in a PVC composite material with poor solvent resistance and a higher dielectric constant compared to Example 1. Comparative Example 3, with too little SAS resin, resulted in a PVC composite material with poor heat resistance and a higher dielectric constant compared to Example 1. Comparative Example 4, with too much SAS resin, resulted in a PVC composite material with poor solvent resistance. Comparative Example 5, without the addition of an elastomer, resulted in a PVC composite material with poor solvent resistance. Comparative Example 6, with the addition of PVC resin of too low a degree of polymerization, resulted in a PVC composite material with poor solvent and heat resistance. Comparative Example 7, with the addition of PVC resin of too high a degree of polymerization, resulted in poor compatibility between PVC and SAS resin, resulting in a PVC composite material with poor solvent and heat resistance and a higher dielectric constant compared to Example 1. Comparative Example 8, with the addition of AS resin as a carrier in a silicone masterbatch, resulted in a PVC composite material with poor heat resistance and a higher dielectric constant compared to Example 1.

[0090] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A PVC composite material, characterized in that, The components include the following parts by weight: 45-60 parts of PVC resin 10-35 parts of SAS resin 5-10 parts of elastomer, The melt volume flow rate of the SAS resin measured at 220°C and 10 kg load was 3~22 cm⁻¹. 3 / 10min; The average degree of polymerization of the PVC resin is 600~1400.

2. The PVC composite material according to claim 1, characterized in that, The average degree of polymerization of the PVC resin is 900~1400.

3. The PVC composite material according to claim 1, characterized in that, The elastomer is at least one of high-polymer powder, silicone elastomer, or acrylic elastomer.

4. The PVC composite material according to claim 1, characterized in that, The melt volume flow rate of the SAS resin measured at 220°C and 10 kg load was 20-22 cm⁻¹. 3 / 10min.

5. The PVC composite material according to claim 1, characterized in that, The mass percentage of the SAS resin relative to the PVC resin is 16-67%.

6. The PVC composite material according to claim 1, characterized in that, The PVC composite material also includes 0.5 to 1.5 parts of foaming agent.

7. The PVC composite material according to claim 1, characterized in that, The PVC composite material also includes 1 to 10 parts of filler.

8. The PVC composite material according to claim 1, characterized in that, The PVC composite material also includes 0.5 to 5 parts of other additives.

9. A method for preparing the PVC composite material according to any one of claims 1 to 8, characterized in that, The process includes the following steps: mixing the components, melt extruding, and granulating to obtain the PVC composite material.

10. The use of the PVC composite material according to any one of claims 1 to 8 in the manufacture of outdoor communication equipment.

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