A ceramified polyolefin composite and a method for producing the same

Abstract

The application discloses a kind of ceramization polyolefin composite material and its preparation method, the ceramization polyolefin composite material is made of polyolefin resin, phosphate low-melting glass powder, wollastonite powder, mineral raw material, heat insulating agent, silane coupling agent, aluminate coupling agent, the application is by introducing heat insulating agent titanium white powder, so that the temperature of ceramization polyolefin composite material reduces under strong sunlight, with excellent heat insulation performance.In addition, the melting point of rutile titanium white powder is higher, the structure of the ceram that is burnt, has good density and strength, insulates high temperature and flame to a certain extent, can withstand a certain intensity of spray and mechanical vibration.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a ceramicized polyolefin composite material, its preparation method, and its application. Background Technology

[0002] With the rapid development of my country's economy and the increasing awareness of fire safety among the public, refractory materials are playing an increasingly important role in national production. Ceramicized polyolefin composites are a new type of fire-resistant and refractory material, but their flame retardancy, thermal stability, and mechanical properties are relatively poor, which limits the application of polyolefins in many fields.

[0003] The service life of polyolefin composites largely depends on their durability. Like most polymers, polyolefins are highly sensitive to oxidation and photoaging. Polyolefin materials can experience the adverse effects of oxidation reactions, which can occur at any stage of the polymer's life cycle. Various stabilizing agents, such as antioxidants, UV absorbers, and light stabilizers, are often added to polyolefin composites, which not only affect the mechanical properties of the composites but can also pollute the environment.

[0004] Therefore, the present invention urgently needs to provide a ceramicized polyolefin composite material and its preparation process. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a ceramicized polyolefin composite material and its preparation method. The production process is simple, the production cost is low, and energy consumption is reduced. By introducing rutile titanium dioxide as a heat-insulating agent, the ceramicized polyolefin composite material exhibits excellent heat insulation performance with reduced temperature under strong sunlight. Furthermore, rutile titanium dioxide has a high melting point, and the sintered ceramic-like structure possesses good density and strength, providing a certain degree of insulation against high temperatures and flames, and can withstand a certain intensity of spraying and mechanical vibration.

[0006] The purpose of this invention is to provide a ceramicized polyolefin composite material, its preparation method, and its application. To solve the above problems, the technical solution adopted by this invention is as follows:

[0007] In a first aspect, the present invention provides a ceramicized polyolefin composite material, said ceramicized polyolefin composite material being made of the following components in parts by mass:

[0008]

[0009] The polyolefin resin comprises the following components in parts by weight:

[0010] 7 to 13 parts of polypropylene

[0011] 15 to 25 parts of low-density linear polyethylene

[0012] 5 to 10 parts of polyolefin elastomer

[0013] The mineral raw material is one or a mixture of two or more of mica powder, halloysite powder, silica, and montmorillonite (preferably mica powder); the phosphate low-melting-point glass powder has a melting point of 300-400℃; the heat insulation agent is titanium dioxide (preferably rutile titanium dioxide); the silane coupling agent is one or a mixture of two or more of silane KH-550, silane KH-570, and silane A-172 (preferably silane A-172);

[0014] The ceramicized polyolefin composite material is prepared according to the following method:

[0015] S1: Mix anhydrous ethanol and the required amount of silane coupling agent evenly, atomize the resulting mixture into the required amount of heat insulation agent under stirring, and dry to obtain material A.

[0016] S2: Mix the phosphate low-melting-point glass powder, wollastonite powder, mineral raw materials and aluminate coupling agent evenly, and modify at 100-200℃ for 2-2.5h (preferably 110-120℃ for 2-2.5h, especially preferably 115℃ for 2h) to obtain material B;

[0017] S3: Mix all of the A material described in step S1, all of the B material described in step S2, and the total amount of polyolefin resin to obtain the ceramicized polyolefin composite material.

[0018] Preferably, the polyolefin resin is composed of the following components in parts by weight:

[0019] 7 to 13 parts of polypropylene

[0020] 15 to 25 parts of low-density linear polyethylene

[0021] 5 to 10 parts of polyolefin elastomer

[0022] It should be noted that the amount of unit mass parts in polyolefin resin and the amount of unit mass parts in ceramicized polyolefin composite material may not be the same.

[0023] Furthermore, the polyolefin resin further comprises 3 to 8 parts by weight of other polyolefin resins, wherein the other polyolefin resins are one or more mixtures of high-density polyethylene, nonlinear low-density polyethylene, and ethylene-vinyl acetate. Specifically, the polyolefin resin is composed of the following components in parts by weight: 7 to 13 parts polypropylene, 15 to 25 parts low-density linear polyethylene, 5 to 10 parts polyolefin elastomer, and 3 to 8 parts other polyolefin resins.

[0024] A single matrix cannot achieve the purpose of this invention. This invention uses the interaction of composite matrices to achieve a balance between strength and elongation. For example, the tensile strength of polypropylene alone can reach 20 MPa, but it has almost no elongation at break; the elongation of a single polyolefin elastomer can reach 500%, but it has almost no strength.

[0025] In the technical solution of this invention, glass powder acts as a flux, wollastonite is fibrous and increases strength, and other minerals with high melting points act as skeleton fillers.

[0026] Preferably, the ceramicized polyolefin composite material is made of the following components in parts by weight:

[0027]

[0028] The polyolefin resin is composed of the following components in parts by weight:

[0029] 8 parts of polypropylene

[0030] 25 parts of low-density linear polyethylene

[0031] 7 parts of polyolefin elastomer

[0032] The mineral raw material is mica powder; the heat insulation agent is rutile titanium dioxide; and the silane coupling agent is silane A-172.

[0033] Preferably, the heat-insulating agent is selected from rutile titanium dioxide, which has excellent optical properties and a certain reflectivity in both the visible and infrared wavelengths, thus providing some protection against infrared radiation. Preferably, the average particle size of the heat-insulating agent is 0.3–0.5 micrometers.

[0034] Furthermore, the mass ratio of the silane coupling agent to anhydrous ethanol in step S1 is 1:1-1.2.

[0035] Furthermore, the drying process described in step S1 is carried out in a constant temperature forced-air drying oven. Even further, drying is performed at 70–90°C for 1–1.5 hours. In embodiments of the present invention, the material is stirred every ten minutes during the drying process.

[0036] In the embodiments of the present invention, the purpose of manual stirring during drying in step S1 is to accelerate the overall drying process. The purpose of uniform mixing in a high-speed mixer after drying in step S1 is to prevent the formation of small lumps. Therefore, high-speed stirring disperses the powder, which is beneficial for mixing with the matrix. Thus, in the embodiments of the present invention, step S1 is: uniformly mixing anhydrous ethanol and the required amount of silane coupling agent; atomizing the resulting mixture and spraying it into the required amount of heat-insulating agent under stirring; manually stirring during drying; and uniformly mixing in a high-speed mixer to obtain material A. Determining whether the product form is necessary is within the scope of conventional knowledge for those skilled in the art.

[0037] In step S2, stirring may be performed as needed to ensure uniform heating during modification. In embodiments of the present invention, stirring is performed every ten minutes during the modification process.

[0038] Furthermore, in step S2, the mixing is performed using a high-speed mixer, with the mixing temperature set at 50–85°C and the time at 30 minutes. In one embodiment of the invention, the temperature is 60°C.

[0039] In an embodiment of the present invention, the mixing in step S3 is accomplished using a high-speed mixer.

[0040] In addition, the present invention provides a method for applying the ceramicized polyolefin composite material.

[0041] One method is direct compression molding, and the other is extrusion granulation, drying, and injection molding.

[0042] Preferably, the extrusion granulation is performed using a twin-screw extruder. Further, the temperature of the feeding section of the twin-screw extruder is 120℃~140℃, the temperature of the conveying section is 140℃~170℃, the temperature of the plasticizing section is 170℃~190℃, and the temperature of the die section is 160~180℃. Preferably, the temperature is 130℃ for the feeding section, 150℃ for the conveying section, 175℃ for the plasticizing section, and 160℃ for the die section.

[0043] Preferably, the drying is performed using a constant temperature forced-air drying oven. Further, the drying conditions are a temperature of 60–70°C and a time of 3–4 hours.

[0044] Preferably, the injection molding is performed using an injection molding machine. Further, the temperature of each zone of the injection molding machine is 160–180°C. Preferably, the temperature of each zone of the injection molding machine is 175°C, 175°C, 175°C, and 170°C.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0046] 1. Adding titanium dioxide to the composite material allows it to shield and reflect most of the ultraviolet light. Furthermore, the synergistic interaction between titanium dioxide and ceramic powder improves the long-term thermal aging performance of the composite material, resulting in a high-strength, weather-resistant polyolefin composite material.

[0047] 2. By controlling the amount of raw materials and the preparation method in the composite material preparation process, the tensile strength of the prepared composite material can reach 10.64 MPa, the elongation at break can reach 464%, and after aging at 135℃ for 96 hours, its tensile strength increases to over 12 MPa. It also exhibits excellent heat insulation under strong sunlight, ensuring that the mechanical properties and weather resistance of the composite material remain at a high level. It can meet the requirements for long-term use under strong outdoor sunlight conditions.

[0048] 3. The ceramic-like structure formed by adding rutile titanium dioxide has good density and strength, isolates high temperature and flame to a certain extent, and becomes harder at 800℃ and 900℃. The surface is smooth and has high hardness. When struck, it produces a crisp sound of porcelain forming. It can withstand a certain intensity of spraying and mechanical vibration. Detailed Implementation

[0049] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0050] In the following examples, the low-density polyethylene (Shanghai Yesuo International Trade Co., Ltd.) is non-linear low-density polyethylene. All high-speed mixers in the following examples operate at a speed of 600 r / min.

[0051] Example 1

[0052] Step 1: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. The resulting spray is then passed through 15 parts of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., model rutile) under stirring.

[0053] After achieving the mixed coating of R-996 (D50 is 0.381 microns), it is placed in a constant temperature forced-air drying oven at 75°C for 1 hour (stirred manually once every 10 minutes). Then, it is added to a high-speed mixer at room temperature and mixed evenly for 30 minutes to obtain material A.

[0054] Step 2: According to the weight ratio, add 17 parts of phosphate low melting point glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 20 parts of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), 8 parts of mica powder (Lingshou County Huayuan Mica Co., Ltd.), and 0.2 parts of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 75℃ and the time to 30 minutes. After removing it, immediately place it in a constant temperature forced-air drying oven at 110℃ for 2 hours (stir manually once every 10 minutes). After cooling, material B is obtained.

[0055] Step 3: Add all of component A, component B, 7 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 7 parts high-density polyethylene (China Petroleum & Chemical Corporation, model 5000S), 16 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), and 10 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain the ceramicized polyolefin composite material. The mixture of polyolefin composite materials was transferred to a twin-screw extruder. The processing temperatures of each section of the extruder were 120°C for the feeding section, 150°C for the conveying section, 175°C for the plasticizing section, and 165°C for the die section. The extrusion was granulated, and then the particles were dried at 65°C for 3 hours. The dried particles were then placed into an injection molding machine with temperatures of 170°C, 170°C, 170°C, and 170°C for each part. After injection molding, ceramicized polyolefin material samples were taken out for testing.

[0056] Example 2

[0057] Step 1: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. The resulting spray is then passed through 17 parts of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., model rutile) under stirring.

[0058] After R-996 (D50 of 0.376 microns) is mixed and coated, it is placed in a constant temperature forced-air drying oven at 80°C for 1 hour (stirred manually once every 10 minutes). Then, it is added to a high-speed mixer at room temperature and mixed evenly for 30 minutes to obtain material A.

[0059] Step 2: Add 20 parts by weight of low-melting-point phosphate glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 17 parts by weight of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), 6 parts by weight of halloysite powder (Lingshou City, Hebei Province), and 0.2 parts by weight of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 65℃ and the time to 30 minutes. After mixing, immediately place the mixture in a constant temperature forced-air drying oven at 110℃ for 2 hours (stir manually once every 10 minutes). After cooling, material B is obtained.

[0060] Step 3: Add all components A and B, 10 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 20 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), 4 parts ethylene-vinyl acetate (Yuyao Changying Plastics Co., Ltd., model 7470M), and 6 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain the polyolefin composite material. The mixture of polyolefin composite materials was transferred to a twin-screw extruder. The processing temperatures of each section of the extruder were 130°C for the feeding section, 150°C for the conveying section, 175°C for the plasticizing section, and 165°C for the die section. The material was extruded and granulated, and then the particles were dried at 60°C for 3 hours. The dried particles were then placed into an injection molding machine with temperatures of 170°C, 175°C, 175°C, and 170°C for each part. After injection molding, ceramicized polyolefin material samples were taken out for testing.

[0061] Example 3

[0062] Step 1: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. The resulting spray is then passed through 13 parts of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., model rutile) under stirring.

[0063] After R-996 (D50 of 0.378 microns) is mixed and coated, it is placed in a constant temperature forced-air drying oven at 75°C for 1 hour (stirred manually once every 10 minutes). Then, it is added to a high-speed mixer at room temperature and mixed evenly for 30 minutes to obtain material A.

[0064] Step 2: According to the weight ratio, add 20 parts of low melting point phosphate glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 20 parts of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), 7 parts of silica (Changzhou Lehuan Trading Co., Ltd.), and 0.2 parts of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 60℃ and the time to 30 minutes. After removing the mixture, immediately place it in a drying oven at 110℃ for 2 hours (stir manually once every 10 minutes). After cooling, material B is obtained.

[0065] Step 3: Add all A and B components, 8 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 18 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), 4 parts low-density polyethylene (Shanghai Yesu International Trade Co., Ltd.), and 10 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain a polyolefin composite material mixture. Transfer the polyolefin composite material mixture to a twin-screw extruder. The processing temperatures of each section of the extruder are as follows: feeding section 120℃, conveying section 140℃, plasticizing section 170℃, and die section 165℃. Extrusion granulation is performed, and then the particles are dried at 65℃ for 3 hours. The dried particles are then placed into an injection molding machine with temperatures of 170℃, 180℃, 180℃, and 170℃ for each part. After injection molding, ceramicized polyolefin material samples are taken out for testing.

[0066] Example 4

[0067] Step 1: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. The resulting spray is then passed through 15 parts of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., model rutile) under stirring.

[0068] After R-996 (D50 of 0.412 microns) is mixed and coated, it is placed in a constant temperature forced-air drying oven at 80°C for 1 hour (stirred manually once every 10 minutes). Then, it is added to a high-speed mixer at room temperature and mixed evenly for 30 minutes to obtain material A.

[0069] Step 2: Add 20 parts by weight of low-melting-point phosphate glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 15 parts by weight of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), 10 parts by weight of montmorillonite (Aladdin Biochemical Technology Co., Ltd.), and 0.2 parts by weight of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 80℃ and the time to 30 minutes. After removing the mixture, immediately place it in a constant temperature forced-air drying oven at 110℃ for 2 hours (stir manually once every 10 minutes). After cooling, material B is obtained.

[0070] Step 3: Add all A and B components, 13 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 17 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), and 10 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain a polyolefin composite material mixture. Transfer the polyolefin composite material mixture to a twin-screw extruder. The processing temperatures of each section of the extruder are as follows: feeding section 120℃, conveying section 140℃, plasticizing section 170℃, and die section 165℃. Extrusion granulation is performed, and then the particles are dried at 65℃ for 3 hours. The dried particles are then placed into an injection molding machine with temperatures of 170℃, 180℃, 180℃, and 170℃ for each part. After injection molding, ceramicized polyolefin material samples are taken out for testing.

[0071] Example 5

[0072] Step 1: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. The resulting spray is then passed through 15 parts of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., model rutile) under stirring.

[0073] After R-996 (D50 of 0.377 microns) is mixed and coated, it is placed in a constant temperature forced-air drying oven at 80°C for 1 hour (stirred manually once every 10 minutes). Then, it is added to a high-speed mixer at room temperature and mixed evenly for 30 minutes to obtain material A.

[0074] Step 2: According to the weight ratio, add 20 parts of phosphate low melting point glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 22 parts of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), 3 parts of mica powder (Lingshou County Huayuan Mica Co., Ltd.), and 0.2 parts of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 60℃ and the time to 30 minutes. After removing the mixture, immediately place it in a constant temperature forced-air drying oven at 115℃ for 2 hours (stir manually once every 10 minutes). After cooling, material B is obtained.

[0075] Step 3: Add all A and B components, 8 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 25 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), and 7 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain a polyolefin composite material mixture. Transfer the polyolefin composite material mixture to a twin-screw extruder. The processing temperatures of each section of the extruder are as follows: feeding section 130℃, conveying section 150℃, plasticizing section 175℃, and die section 160℃. Extrusion granulation is performed, and then the particles are dried at 70℃ for 4 hours. The dried particles are then placed into an injection molding machine with temperatures of 175℃, 175℃, 175℃, and 170℃ for each part. After injection molding, ceramicized polyolefin material samples are taken out for testing.

[0076] Comparative Example 1

[0077] The only difference between this comparative example and Example 1 is that vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) was not used. The prepared material B, titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., rutile type R-996, D50 of 0.382 microns), and polyolefin resin were directly added to a high-speed mixer and mixed evenly to obtain a mixture of polyolefin composite materials. The polyolefin composite mixture was transferred to a twin-screw extruder. The processing temperatures of each section of the extruder were 120°C for the feeding section, 150°C for the conveying section, 175°C for the plasticizing section, and 165°C for the die section. The mixture was extruded and granulated, and then the particles were dried at 65°C for 3 hours. The dried particles were then placed into an injection molding machine, where the temperatures of each part of the injection molding machine were 170°C, 170°C, 170°C, and 170°C, respectively. After injection molding, ceramicized polyolefin material samples were taken out for testing.

[0078] Comparative Example 2

[0079] The only difference between this comparative example and Example 1 is the absence of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., rutile type R-996). 17 parts by weight of phosphate low-melting-point glass powder (Anmi Micro-Nano New Materials Co., Ltd., FR0135), 20 parts by weight of wollastonite powder, 8 parts by weight of mica powder (Lingshou County Huayuan Mica Co., Ltd.), and 0.2 parts by weight of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., DL-411) were added to a high-speed mixer and mixed thoroughly. The mixing temperature was set at 75°C for 30 minutes. Immediately after mixing, the mixture was placed in a constant-temperature drying oven at 110°C for 2 hours (with manual stirring every 10 minutes). After cooling, polyolefin resin was added and mixed. After homogenization, a mixture of polyolefin composite materials is obtained. The mixture is then transferred to a twin-screw extruder. The processing temperatures of each section of the extruder are as follows: feeding section 120℃, conveying section 150℃, plasticizing section 175℃, and die section 165℃. Extrusion granulation is performed, and then the particles are dried at 65℃ for 3 hours. The dried particles are then placed into an injection molding machine with temperatures of 170℃, 170℃, 170℃, and 170℃ for each part. After injection molding, ceramicized polyolefin material samples are taken out for testing.

[0080] Comparative Example 3

[0081] The only difference between this comparative example and Example 2 is that the sample was not placed in a constant temperature drying oven after high-speed stirring in step two.

[0082] Comparative Example 4

[0083] Step 1: Add 15 parts by weight of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., rutile type R-996, D50 is 0.412 microns) and 0.2 parts by weight of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 80℃ and the time to 30 minutes. After removing the mixture, immediately place it in a constant temperature forced-air drying oven at 110℃ for 2 hours (stir manually once every 10 minutes). After cooling, material A is obtained.

[0084] Step 2: Add 20 parts by weight of low-melting-point phosphate glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 15 parts by weight of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), 10 parts by weight of montmorillonite (Aladdin Biochemical Technology Co., Ltd.), and 0.2 parts by weight of aluminate coupling agent (Shijiazhuang Tengchi Chemical Co., Ltd., model DL-411) to a high-speed mixer and mix evenly. Set the mixing temperature to 80℃ and the time to 30 minutes. After removing the mixture, immediately place it in a constant temperature forced-air drying oven at 110℃ for 2 hours (stir manually once every 10 minutes). After cooling, material B is obtained.

[0085] Step 3: Add all A and B components, 13 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 17 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), and 10 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain a polyolefin composite material mixture. Transfer the polyolefin composite material mixture to a twin-screw extruder. The processing temperatures of each section of the extruder are as follows: feeding section 120℃, conveying section 140℃, plasticizing section 170℃, and die section 165℃. Extrusion granulation is performed, and then the particles are dried at 65℃ for 3 hours. The dried particles are then placed into an injection molding machine with temperatures of 170℃, 180℃, 180℃, and 170℃ for each part. After injection molding, ceramicized polyolefin material samples are taken out for testing.

[0086] Comparative Example 5

[0087] Step 1: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. The resulting spray is then passed through 15 parts of titanium dioxide (Sichuan Longmang Titanium Industry Co., Ltd., model rutile) under stirring.

[0088] After R-996 (D50 of 0.377 microns) is mixed and coated, it is placed in a constant temperature forced-air drying oven at 80°C for 1 hour (stirred manually once every 10 minutes). Then, it is added to a high-speed mixer at room temperature and mixed evenly for 30 minutes to obtain material A.

[0089] Step 2: Add 0.2 parts of vinyltris(β-methoxyethoxy)silane (Guangzhou Zhongjie New Materials Co., Ltd., model A-172, molecular formula CH2=CHSi(OC2H4OCH3)3) and anhydrous ethanol (1:1) (C2H6O, Sinopharm Chemical Reagent Co., Ltd.) to the atomizer. After atomization, the resulting spray is passed into 20 parts of low-melting-point phosphate glass powder (Anmi Micro-Nano New Materials Co., Ltd., model FR0135), 22 parts of wollastonite powder (Changzhou Rongao Chemical New Materials Co., Ltd.), and 3 parts of mica powder (Lingshou County Huayuan Mica Co., Ltd.) under stirring to achieve mixing and coating. Then, place it in a constant temperature forced-air drying oven at 80℃ for 1 hour (stir manually once every 10 minutes). At room temperature, add it to a high-speed mixer and mix evenly for 30 minutes to obtain material B.

[0090] Step 3: Add all A and B components, 8 parts polypropylene (China Petroleum & Chemical Corporation, model PPH-T03), 25 parts linear low-density polyethylene (Yuyao Qihong Plastics Co., Ltd., model DFDA-7042), and 7 parts polyolefin elastomer (Dow Chemical Company, model 8100) to a high-speed mixer and mix evenly at room temperature to obtain a polyolefin composite material mixture. Transfer the polyolefin composite material mixture to a twin-screw extruder. The processing temperatures of each section of the extruder are as follows: feeding section 130℃, conveying section 150℃, plasticizing section 175℃, and die section 160℃. Extrusion granulation is performed, and then the particles are dried at 70℃ for 4 hours. The dried particles are then placed into an injection molding machine with temperatures of 175℃, 175℃, 175℃, and 170℃ for each part. After injection molding, ceramicized polyolefin material samples are taken out for testing.

[0091] Various testing methods:

[0092] (1) Mechanical property test: The test specimen is a standard dumbbell-shaped specimen produced by injection molding, and its tensile strength and elongation at break are tested on a high and low temperature double column tester in accordance with the national standard GB / T 528-2009.

[0093] (2) Thermal insulation: The composite material was pressed into a 100mm×100mm×2mm square plate. Then, three samples were placed on a 45-degree inclined exposure plate and fixed. The front of the exposure plate faced the sunlight. Under the condition of noon when the weather was sunny and there was plenty of sunshine, the plates were placed outdoors to receive sunlight. Four hours later, the surface temperature of the square plate was tested with an infrared thermometer and recorded. The average surface temperature of the three plates was taken as the surface temperature.

[0094] (3) Thermal aging test: Each injection-molded standard sample was placed in hot air at 135℃ for accelerated aging for 4 days, cooled to room temperature, and then subjected to tensile test.

[0095] (4) Porcelain forming performance test: The injection-molded standard sample was placed in a muffle furnace for sintering, and the porcelain forming effect was observed after sintering at 950℃ for 3 hours.

[0096] The specific experimental procedure is recorded as follows:

[0097]

[0098]

[0099] The data in the table shows that by adding a specific proportion of modified heat insulation agent (titanium dioxide), modified flux (glass powder), and other modified mineral raw materials, the mechanical properties of ceramicized polyolefins are improved through the synergistic effect of the three. Moreover, after aging at 135℃ for 96 hours, the strength increases significantly. It has excellent heat insulation properties under strong light irradiation, which can meet the requirements of long-term outdoor use. Furthermore, when sintered at 800-900℃, it has good density, smooth surface, high hardness, and a crisp ceramic sound when tapped. It can withstand certain spraying and mechanical vibration.

Claims

1. A ceramicized polyolefin composite material, characterized in that... The ceramicized polyolefin composite material is made of the following components in parts by weight: 40 parts of polyolefin resin 15-20 parts of low-melting-point phosphate glass powder 15 to 22 parts wollastonite powder 3 to 10 parts of mineral raw materials 10-20 parts of heat insulation agent 0.15~0.3 parts of silane coupling agent Aluminate coupling agent 0.15~0.3 parts The polyolefin resin comprises the following components in parts by weight: 7 to 13 parts of polypropylene 15 to 25 parts of low-density linear polyethylene 5 to 10 parts of polyolefin elastomer The mineral raw material is one or a mixture of two or more of mica powder, halloysite powder, silica, and montmorillonite; the phosphate low-melting-point glass powder has a melting point of 300-400℃; the heat insulation agent is titanium dioxide; and the silane coupling agent is one or a mixture of two or more of silane KH-550, silane KH-570, and silane A-172. The ceramicized polyolefin composite material is prepared according to the following method: S1: Mix anhydrous ethanol and the required amount of silane coupling agent evenly, atomize the resulting mixture into the required amount of heat insulation agent under stirring, and dry to obtain material A. S2: Mix the phosphate low-melting-point glass powder, wollastonite powder, mineral raw materials and aluminate coupling agent evenly, and modify at 100-200℃ for 2-2.5 hours to obtain material B; S3: Mix all of the A material described in step S1, all of the B material described in step S2, and the total amount of polyolefin resin to obtain the ceramicized polyolefin composite material.

2. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The polyolefin resin further includes 3 to 8 parts by weight of other polyolefin resins, wherein the other polyolefin resins are one or a mixture of two or more of high-density polyethylene, nonlinear low-density polyethylene, and ethylene-vinyl acetate.

3. The ceramicized polyolefin composite material according to any one of claims 1-2, characterized in that: The ceramicized polyolefin composite material is made of the following components in parts by weight: 40 parts of polyolefin resin 20 parts of low-melting-point phosphate glass powder 22 parts of wollastonite powder 3 portions of mineral raw materials 15 parts heat insulation agent 0.2 parts of silane coupling agent 0.2 parts aluminate The polyolefin resin is based on the following components in parts by weight. composition: 8 parts of polypropylene 25 parts of low-density linear polyethylene 7 parts polyolefin elastomer The mineral raw material is mica powder; the heat insulation agent is rutile titanium dioxide; and the silane coupling agent is silane A-172.

4. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The heat insulation agent is rutile titanium dioxide.

5. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The average particle size of the heat insulation agent is 0.3~0.5 micrometers.

6. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The mass ratio of the silane coupling agent to anhydrous ethanol in step S1 is 1:1-1.

2.

7. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The modification in step S2 is performed at a temperature of 115°C for 2 hours.

8. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The mineral raw material is mica powder.

9. The ceramicized polyolefin composite material as described in claim 1, characterized in that: The silane coupling agent is silane A-172.

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