A kind of ablation-resistant PVC alloy material and its preparation method and application

Abstract

The present invention relates to an ablation-resistant PVC alloy material and a preparation method and application thereof, and belongs to the technical field of modified plastics. The ablation-resistant PVC alloy material of the present invention comprises the following components in parts by weight: 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 microspheres, 3-15 parts of hyperbranched polyester, 1-5 parts of silane coupling agent and 1-3 parts of lubricant. The present invention is aimed at the fact that the ablation-resistant PVC in the prior art contains a large amount of plasticizers and is mostly soft in texture, which is difficult to meet the requirements of high flame retardancy, ablation resistance and thermosetting properties. Through a large number of experimental studies, a hard ablation-resistant PVC alloy material is provided that does not contain a plasticizer component, has high flame retardancy, high heat resistance, good toughness and low density.

Description

Technical Field

[0001] The invention belongs to the technical field of modified plastics, and in particular relates to an ablation-resistant PVC alloy material and a preparation method and application thereof. Background Art

[0002] Polyvinyl chloride (PVC) is the second largest general-purpose plastic after polyethylene in terms of production. It has the advantages of high strength, corrosion resistance, flame retardancy, insulation, transparency, etc., and is widely used in technical fields such as construction, drainage, sewage, and chemical industry. Traditional ablation-resistant PVC technology is mainly used in the preparation of wires and cables, etc., which generally adds silicone rubber, ablation-resistant fillers, porcelain fillers or a large amount of plasticizer components to PVC resin, but this type of product is soft PVC, and its application field is limited to wires and cables. Summary of the invention

[0003] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a corrosion-resistant PVC alloy material and a preparation method and application thereof. The corrosion-resistant PVC alloy material of the present invention is hard PVC, which breaks the traditional corrosion-resistant idea, combines corrosion-resistant resin coating, porcelain-forming technology, and alloying technology, fills the gap in the material field, and broadens the application scope of the corrosion-resistant PVC.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is: an ablation-resistant PVC alloy material, comprising the following components by weight: 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.

[0005] In view of the fact that the ablation-resistant PVC in the prior art contains a large amount of plasticizers and is mostly soft in texture, making it difficult to meet the requirements of high flame retardancy, ablation resistance and thermosetting, the present invention provides a hard ablation-resistant PVC alloy material that does not contain a plasticizer component, has high flame retardancy, high heat resistance, good toughness and low density through a large number of experimental studies.

[0006] As a preferred embodiment of the ablation-resistant PVC alloy material of the present invention, the polymerization degree of the PVC resin is 400-700. The inventors of the present application have found that when the polymerization degree of the PVC resin is too high, the prepared material is difficult to be applied in the injection molding field, and most of the products are extrusion products, while the PVC resin with a polymerization degree of 400-700 has good fluidity and a wider range of applications. The test method for the polymerization degree of the PVC resin is gel permeation chromatography, the test temperature is 40°C, and the sample is treated with tetrahydrofuran.

[0007] As a preferred embodiment of the ablation-resistant PVC alloy material of the present invention, the glass microspheres are composite glass microspheres including high-melting point glass microspheres and low-melting point glass microspheres; the melting point of the high-melting point glass microspheres is 750-900°C; the melting point of the low-melting point glass microspheres is 500-600°C.

[0008] As a preferred embodiment of the ablation-resistant PVC alloy material of the present invention, the mass ratio of high-melting-point glass microspheres to low-melting-point glass microspheres in the composite glass microspheres is 3:7 to 7:3. The inventors of the present application have found through a large number of experimental studies that during the combustion process, a ceramic solid phase reaction occurs between the high-melting-point glass microspheres and the low-melting-point glass microspheres, and a crystalline substance is generated, a ceramic layer with holes is formed on the surface of the material, and a hard porous ceramic is formed inside. When the mass ratio of high-melting-point glass microspheres to low-melting-point glass microspheres in the composite glass microspheres is 3:7 to 7:3, the ablation resistance of the prepared PVC alloy material is better.

[0009] As a preferred embodiment of the ablation-resistant PVC alloy material of the present invention, the hyperbranched polyester is a hyperbranched polyester resin prepared with an aromatic heat-resistant polyester hyperbranched polymer as a skeleton. The inventors of the present application have found through extensive research that the addition of hyperbranched polyester can achieve a ceramic effect, which can not only improve the thermal stability of the material, but also form a skeleton ceramic layer under a high-temperature flame to block external heat, while maintaining the original shape of the material to play a self-supporting role, and the synergistic effect with glass microspheres is better.

[0010] As a preferred embodiment of the ablation-resistant PVC alloy material of the present invention, it includes at least one of the following (a)-(c):

[0011] (a) the stabilizer is an organotin stabilizer;

[0012] (b) the toughening agent is a silicon-based toughening agent;

[0013] (c) The lubricant includes polyethylene wax.

[0014] More preferably, the weight content of tin in the organic tin stabilizer is ≥19%; the weight content of silicon in the silicon toughening agent is 5-20%.

[0015] As a preferred embodiment of the ablation-resistant PVC alloy material of the present invention, the ABS resin is an acrylonitrile-butadiene-styrene resin with an AN weight content of 20-23%.

[0016] The present invention also provides a preparation method of the ablation-resistant PVC alloy material, comprising the following steps: weighing PVC resin, ABS resin, heat stabilizer and lubricant, adding them into a high-speed mixer, heating and mixing to 95-105° C., adding a toughening agent and a hyperbranched polyester, continuing to heat and mix to 115-125° C., adding a silane coupling agent and glass microbeads, mixing for 2-4 minutes, discharging the mixed powder in the high-speed mixer into a low-speed mixer, cooling to 75-85° C., feeding the mixed powder into an extruder screw for granulation, and obtaining the ablation-resistant PVC alloy granular material.

[0017] The present invention also provides the use of the ablation-resistant PVC alloy material in the preparation of ablation-resistant resin coatings and electronic and electrical products. The ablation-resistant resin coatings and electronic and electrical products include motor and electrical appliance housings.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention provides an ablation-resistant PVC alloy material and a preparation method and application thereof; the ablation-resistant PVC alloy material of the present invention does not add a plasticizer, breaking the limitation that a large amount of plasticizer needs to be added to the traditional soft cable PVC; the present invention adds glass microbeads with different melting points in the preparation of the PVC alloy material, and adjusts the proportion of different melting points so that the prepared PVC alloy material has better heat resistance and flame retardancy; the present invention synergistically improves the ablation resistance of the PVC alloy material by compounding hyperbranched polyester with composite glass microbeads and combining the phase characteristics of the PVC alloy; the ablation-resistant PVC alloy material of the present invention has the characteristics of high flame retardancy, high toughness, high heat resistance and the like, and has important application and economic significance in the future replacement of thermosetting materials or iterative development of ordinary flame-retardant PVC. DETAILED DESCRIPTION

[0019] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0020] The raw materials used in the embodiments and comparative examples of the present invention are described as follows, but are not limited to these materials:

[0021] PVC resin A: degree of polymerization is 420-450, PVC JLTS-1, Sichuan Jinlu;

[0022] PVC resin B: degree of polymerization is 450-480, PVC powder S400, Japan Zhongyuan;

[0023] PVC resin C: degree of polymerization is 650-700, PVC TL-700, LG Bohai;

[0024] ABS resin A: DG-MG29 (YP), AN weight content is 20-23%, Tianjin Dagu;

[0025] ABS resin B: DG-417 (YP), AN weight content 19%, Tianjin Dagu;

[0026] Organic tin stabilizer A: YT181, tin weight content ≥ 19%, Yunnan Tin Industry;

[0027] Organic tin stabilizer B: MT-9001 (YP), tin weight content 18.5%, Sanyi Chemical;

[0028] Silicone toughening agent A: S2100 (YP-1), silicon content by weight 5-20%, Mitsubishi Chemical;

[0029] Silicone toughening agent B: S2100 (YP-2), silicon content 4% by weight, Mitsubishi Chemical;

[0030] Lubricant: polyethylene wax, 316A, Honeywell;

[0031] High melting point glass beads A: melting point 850℃, 050-20-215-A, SOVITEC;

[0032] High melting point glass microspheres B: melting point 750°C, 050-20-215-B (YP), SOVITEC;

[0033] High melting point glass microspheres C: melting point 900°C, 050-20-215-C (YP), SOVITEC;

[0034] High melting point glass beads D: melting point 1000℃, 050-20-215-D (YP), SOVITEC;

[0035] Low melting point glass beads A: melting point 550°C, 050-20-215-E (YP), SOVITEC;

[0036] Low melting point glass microspheres B: melting point 500°C, 050-20-215-F (YP), SOVITEC;

[0037] Low melting point glass microspheres C: melting point 600°C, 050-20-215-G (YP), SOVITEC;

[0038] Low melting point glass microspheres D: melting point 400°C, 050-20-215-H (YP), SOVITEC;

[0039] Hyperbranched polyester A: Hyper C403 type polyester, a hyperbranched polyester resin prepared with aromatic heat-resistant polyester hyperbranched polymer as the skeleton, Suzhou Hibote;

[0040] Hyperbranched polyester B: C403 (YP) polyester, Suzhou Hibote;

[0041] Silane coupling agent: KH550, Nanjing Xuanhao;

[0042] In the embodiments and comparative examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified; and the components used are consistent unless otherwise specified in the embodiments and comparative examples.

[0043] Examples 1 to 9, Comparative Examples 1 to 17

[0044] The components of the ablation-resistant PVC alloy materials of Examples 1 to 9 and Comparative Examples 1 to 17 of the present invention are shown in Tables 1 to 3.

[0045] Table 1 Compositions of the ablation-resistant PVC alloy materials of Examples 1 to 9 (parts by weight)

[0046]

[0047]

[0048] Table 2 Compositions of the ablation-resistant PVC alloy materials of Comparative Examples 1 to 10 (parts by weight)

[0049]

[0050] Table 3 Compositions (parts by weight) of the ablation-resistant PVC alloy materials of Comparative Examples 11 to 17

[0051]

[0052]

[0053] The preparation method of the ablation-resistant PVC alloy material of Examples 1 to 9 and Comparative Examples 1 to 17 of the present invention comprises the following steps: weighing PVC resin, ABS resin, heat stabilizer, and lubricant and adding them into a high-speed mixer, heating and mixing to 100° C., adding a toughening agent and a hyperbranched polyester, continuing to heat and mix to 120° C., adding a silane coupling agent and glass microbeads, mixing for 3 minutes, discharging the mixed powder in the high-speed mixer into a low-speed mixer, cooling to 80° C., feeding the mixed powder into an extruder screw for granulation, and obtaining the ablation-resistant PVC alloy granular material.

[0054] The ablation-resistant PVC alloy materials of Examples 1 to 9 and Comparative Examples 1 to 17 were subjected to performance tests, and the performance test method is specifically as follows:

[0055] (1) Ablation resistance test: Use a 5VA 500W flame to burn for 3 minutes and count the number of 2.5mm square plates burned through (5 pieces). The ablation resistance flame standard is: 5VA flame requirements specified in UL94; the size of the burning test square plate is: 150*150*2.5mm.

[0056] (2) Hardness test of materials after combustion: The hardness test adopts ASTM D2240 standard, actual test, and 1s reading.

[0057] (3) Heat deformation temperature test: using ASTM D648 standard, test condition 0.45MPa.

[0058] (4) Toughness test: The cantilever beam notched impact strength is used as the evaluation index, and the test standard is:

[0059] ASTM D256 Standard

[0060] The test results are shown in Table 3.

[0061] Table 4 Performance test results of ablation-resistant PVC alloy materials of Examples 1 to 9

[0062]

[0063] Table 5 Performance test results of ablation-resistant PVC alloy materials of comparative examples 1 to 17

[0064]

[0065] It can be seen from Table 4 and Table 5 that the addition of glass microspheres with different melting points has a great influence on the ablation resistance of the prepared PVC alloy material. Comparison of Examples 3, 6, 7, Comparative Examples 14 and 15 shows that the addition of high-melting-point glass microspheres with a melting point of 750-900°C and low-melting-point glass microspheres with a melting point of 500-600°C can significantly improve the ablation resistance of the PVC alloy material; Comparison of Examples 3, 8, 9, Comparative Examples 7, 8 and 16 shows that when the mass ratio of high-melting-point glass microspheres to low-melting-point glass microspheres is 3:7 to 7:3, the ablation resistance of the prepared PVC alloy material is better; Comparison of Example 3, Comparative Examples 10 and 17 shows that, compared with no addition of hyperbranched polyester or ordinary hyperbranched polyester, the addition of a hyperbranched polyester resin prepared with an aromatic heat-resistant polyester hyperbranched polymer as a skeleton can not only improve the thermal stability of the material, but also form a skeleton ceramic layer under a high-temperature flame to block external heat, while maintaining the original shape of the material and playing a self-supporting role.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A PVC alloy material resistant to ablation, characterized in that: The invention comprises the following components in parts by weight: 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; The glass microspheres are composite glass microspheres including high-melting-point glass microspheres and low-melting-point glass microspheres; the melting point of the high-melting-point glass microspheres is 750-900° C.; the melting point of the low-melting-point glass microspheres is 500-600° C.; The mass ratio of the high-melting-point glass microbeads to the low-melting-point glass microbeads in the glass microbeads is 3:7 to 7:

3.

2. The ablation-resistant PVC alloy material according to claim 1, characterized in that: The polymerization degree of the PVC resin is 400-700.

3. The ablation-resistant PVC alloy material according to claim 1, characterized in that: The hyperbranched polyester is a hyperbranched polyester resin prepared with an aromatic heat-resistant polyester hyperbranched polymer as a skeleton.

4. The ablation-resistant PVC alloy material according to claim 1, characterized in that: Includes at least one of the following (a)-(c): (a) the stabilizer is an organotin stabilizer; (b) the toughening agent is a silicon-based toughening agent; (c) The lubricant includes polyethylene wax.

5. The ablation-resistant PVC alloy material according to claim 1, characterized in that: The ABS resin is an acrylonitrile-butadiene-styrene resin with an AN weight content of 20-23%.

6. The method for preparing the ablation-resistant PVC alloy material according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: weighing PVC resin, ABS resin, heat stabilizer and lubricant, adding them into a high-speed mixer, heating and mixing to 95-105° C., adding a toughening agent and a hyperbranched polyester, continuing to heat and mix to 115-125° C., adding a silane coupling agent and glass microbeads, mixing for 2-4 minutes, discharging the mixed powder in the high-speed mixer into a low-speed mixer, cooling to 75-85° C., feeding the mixed powder into an extruder screw for granulation, and obtaining the ablation-resistant PVC alloy particle material.

7. Use of the ablation-resistant PVC alloy material according to any one of claims 1 to 5 in the preparation of ablation-resistant resin coatings and electronic and electrical products.

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