Weather-resistant and cold-resistant alloy material and preparation method and application thereof

Abstract

The application discloses a weather-resistant and cold-resistant alloy material and a preparation method and application thereof, and relates to the technical field of high polymer composite materials. According to weight parts, raw materials of the alloy material include 60-100 parts of polyketone (POK), 10-50 parts of ASA resin, 3-15 parts of a toughening agent and 0.5-2 parts of an auxiliary agent. The weather resistance, impact performance, toughness and low-temperature resistance of the alloy material are remarkably improved by optimizing the components and the proportioning of the alloy material, and the application of the alloy material in more fields is expanded.

Description

Technical Field

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

[0002] Polyketone (POK) resin, a highly crystalline polymer, is a novel green polymer material synthesized from carbon monoxide and olefins (such as ethylene and propylene). Its molecular backbone, composed of hydrocarbons, forms a compact crystalline structure through high crystallinity, endowing POK with excellent comprehensive properties, including high abrasion resistance, outstanding hydrolysis resistance, excellent chemical resistance, and good flowability and molding processability, demonstrating potential application value in numerous fields. However, under sunlight exposure, the molecular chains of POK are prone to cyclization reactions, leading to yellowing of the material. This defect severely limits its application in areas such as cosmetic parts where high color stability is required.

[0003] ASA resin is a terpolymer graft copolymer composed of acrylonitrile (A), styrene (S), and acrylate (A). Compared to ABS resin, ASA resin has significantly improved weather resistance due to the introduction of acrylate rubber without double bonds to replace butadiene rubber, with weather resistance approximately 10 times that of ABS resin. Simultaneously, ASA resin is similar to ABS resin in terms of mechanical properties such as processing performance, electrical insulation, and chemical resistance, possessing excellent weather resistance, good processing performance, chemical resistance, and balanced mechanical properties. However, ASA resin also has significant performance shortcomings, such as lower heat resistance, poor abrasion resistance, insufficient cold resistance, and poor flame retardancy. These drawbacks limit the application of ASA resin in many fields with specific material performance requirements.

[0004] Given the respective performance advantages and disadvantages of POK and ASA, how to combine their advantages and overcome their respective defects through reasonable material design and formulation optimization to obtain an alloy material with better overall performance has become a technical problem that urgently needs to be solved by those skilled in the art.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a weather-resistant and cold-resistant alloy material, its preparation method, and its application.

[0007] This invention is implemented as follows: In a first aspect, embodiments of the present invention provide an alloy material, the raw materials of which, by weight, include the following components: 60-100 parts of polyketone POK, 10-50 parts of ASA resin, 3-15 parts of toughening agent and 0.5-2 parts of additives.

[0008] Secondly, embodiments of the present invention provide a method for preparing alloy materials as described in the foregoing embodiments, which includes preparing the alloy materials using the raw materials described in the foregoing embodiments.

[0009] Thirdly, the embodiments of the present invention provide the application of alloy materials as described in the foregoing embodiments or alloy materials prepared by the preparation methods described in the foregoing embodiments in the preparation of automotive parts, building components, sports equipment components, electronic components, electrical equipment, medical devices or chemical equipment.

[0010] The present invention has the following beneficial effects: This application significantly improves the weather resistance, impact resistance, toughness, and low-temperature resistance of alloy materials by optimizing their composition and proportions, thus expanding their application in more fields. Detailed Implementation

[0011] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0012] On one hand, embodiments of the present invention provide an alloy material, the raw materials of which, by weight, include the following components: 60-100 parts of polyketone POK, 10-50 parts of ASA resin, 3-15 parts of toughening agent and 0.5-2 parts of additives.

[0013] Specifically, the weight parts of polyketone (POK) can be any one or any two of the following: 60, 62, 64, 65, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, and 100 parts. The weight parts of ASA resin can be any one or any two of the following: 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, and 50 parts. The weight parts of toughening agent can be any one or any two of the following: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 parts. The weight parts of the adjuvant can be any one or any two of the following: 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8 and 2 parts.

[0014] In some embodiments, the raw materials comprise, by weight, the following components: 70-90 parts of polyketone POK, 10-30 parts of ASA resin, 3-15 parts of toughening agent, and 0.5-2 parts of additives.

[0015] In some embodiments, the toughening agent comprises high-polymer powder.

[0016] By optimizing the ratio of POK and ASA and selecting high-rubber powder as a toughening agent, it is beneficial to optimize the weather resistance of alloy materials and at the same time significantly improve the impact performance, toughness and low-temperature resistance of the materials.

[0017] In some embodiments, the molecular weight of the polyketone (POK) is 10,000 to 100,000 Da, specifically any one or any two of the following: 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, and 100,000 Da.

[0018] In some embodiments, the number-average molecular weight of the polyketone POK is 60,000 to 80,000 Da.

[0019] In some embodiments, the weight-average molecular weight of the ASA resin is 80,000 to 150,000 g / mol, specifically any one or any two of the following: 80,000, 90,000, 100,000, 110,000, 120,000, 130,000, 140,000, and 150,000 g / mol.

[0020] In some embodiments, the ASA resin is a graft copolymer of propylene ester rubber, acrylonitrile, and styrene.

[0021] In some embodiments, the ASA resin contains 5% to 30% by weight of acrylate rubber, specifically within any one or any two of the following ranges: 5%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, and 30%; 10% to 30% by weight of acrylonitrile, specifically within any one or any two of the following ranges: 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, and 30%; and 40% to 70% by weight of styrene, specifically within any one or any two of the following ranges: 40%, 45%, 50%, 55%, 60%, 65%, and 70%.

[0022] In some embodiments, the additives include any one or more of antioxidants and lubricants.

[0023] In some embodiments, the antioxidant accounts for 0.4 to 1.6 parts by weight and the lubricant accounts for 0.1 to 0.4 parts in 0.5 to 2 parts by weight of the additive.

[0024] In the additives, the antioxidant can be in the range of any one or any two of the following weight parts: 0.4, 0.6, 0.8, 1.0, 1.2, 1.4 and 1.6 parts; the lubricant can be in the range of any one or any two of the following weight parts: 0.1, 0.2, 0.3 and 0.4 parts.

[0025] In some embodiments, the lubricant comprises any one or more of stearic acid and its salts, ethylene bis-stearamide, N,N-ethylene bis-stearamide (abbreviated as ethylene bis-stearamide), and pentaerythritol stearate.

[0026] In some embodiments, the antioxidant includes any one or more of hindered phenolic antioxidants and phosphite antioxidants.

[0027] In some embodiments, in 0.4 to 1.6 parts of antioxidant, the hindered phenolic antioxidant accounts for 0.2 to 1.0 parts and the phosphite antioxidant accounts for 0.2 to 0.6 parts. Specifically, the weight percentage of the hindered phenolic antioxidant can be any one or any two of 0.2, 0.4, 0.6, 0.8, and 1.0 parts. The weight percentage of the phosphite antioxidant can be any one or any two of 0.2, 0.3, 0.4, 0.5, and 0.6 parts.

[0028] In some embodiments, the hindered phenolic antioxidant includes: antioxidant 168.

[0029] In some embodiments, the phosphite antioxidant includes antioxidant 1076.

[0030] In some embodiments, the raw material further includes a compatibilizer.

[0031] In some embodiments, the raw material comprises, by weight parts: 60-100 parts of polyketone POK, 10-50 parts of ASA resin, 1-10 parts of compatibilizer, 3-15 parts of toughening agent, and 0.5-2 parts of additives. The weight parts of the compatibilizer can be any one or any two of the following: 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 parts.

[0032] In some embodiments, the compatibilizer includes any one of: styrene-acrylonitrile-maleic anhydride terpolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer, and ethylene-methyl acrylate-glycidyl methacrylate.

[0033] On the other hand, embodiments of the present invention provide a method for preparing alloy materials as described in any of the foregoing embodiments, which includes preparing the alloy materials as described in any of the foregoing embodiments using raw materials.

[0034] In some embodiments, the preparation steps include: mixing the raw materials according to a ratio, and then extruding, cooling, granulating and drying to obtain an alloy material.

[0035] In some embodiments, the extrusion is performed using a twin-screw extruder; In some embodiments, the temperatures of zones 1 to 11 of the twin-screw extruder are set to 90~110℃, 210~230℃, 210~230℃, 200~220℃, 200~220℃, 190~210℃, 190~210℃, 180~200℃, 180~200℃, 170~190℃, and 170~190℃, respectively.

[0036] In some embodiments, the temperatures of zones 1 to 11 of the twin-screw extruder are set to 98~102℃, 218~222℃, 218~222℃, 208~212℃, 208~212℃, 198~202℃, 198~202℃, 188~192℃, 188~192℃, 178~182℃, and 178~182℃, respectively.

[0037] Furthermore, embodiments of the present invention also provide the application of alloy materials as described in any of the foregoing embodiments or alloy materials prepared by the preparation methods described in any of the foregoing embodiments in the preparation of automotive parts, building components, sports equipment components, electronic components, electrical equipment, medical devices or chemical equipment.

[0038] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0039] Material Polyketone POK is a polymer synthesized from carbon monoxide and olefins, supplied by Hyosung Group of South Korea, model number M330F.

[0040] ASA resin is a graft copolymer of propylene ester rubber with acrylonitrile and styrene, such as PW-957 from Chi Mei Industrial Co., Ltd.

[0041] Antioxidant 1076 and Antioxidant 168 were provided by Tianjin Lianlong New Materials Co., Ltd.

[0042] The high-polymer powder, model HR181, is supplied by Shanghai Zemin Plastics Co., Ltd.

[0043] The toughening agent Vistamaxx 6202 was supplied by ExxonMobil Chemical Company.

[0044] The toughening agent PARALOID EXL-2691J was supplied by Dow Chemical Company.

[0045] The toughening agent FUSABOND N493 was supplied by Dow Chemical Company.

[0046] Ethylene bis-stearamide (EBS) was provided by Kao Corporation of Japan.

[0047] Styrene-acrylonitrile-maleic anhydride terpolymer, provided by Jiaxing Huawen Chemical Co., Ltd., model SMA-800, contains 6-10% maleic anhydride; Styrene-acrylonitrile-glycidyl methacrylate terpolymer, provided by Jiayirong Compatibilizer Jiangsu Co., Ltd., model SAG-005, contains 5-10% epoxy functional groups; Ethylene-methyl acrylate-glycidyl methacrylate, supplied by SK Group of South Korea, model number LOTADERAX8900, contains 8% glycidyl methacrylate.

[0048] Example 1 Sixteen experimental groups were set up, and alloy materials were provided for each group. The composition, proportion and performance test results of the raw materials in groups 1 to 6 are shown in Table 2, and the composition, proportion and performance test results of the raw materials in groups 7 to 16 are shown in Table 3.

[0049] Preparation method of alloy materials: According to the alloy material ratio of each experimental group, polyketone (POK), ASA resin, compatibilizer, toughening agent, and additives were mixed at high speed, then extruded, cooled, granulated, dried, and injection molded into standard test strips to obtain weather-resistant and cold-resistant POK / ASA alloy materials. During extrusion, the temperatures of zones 11 of the twin-screw extruder were set to 100℃, 220℃, 220℃, 210℃, 210℃, 200℃, 200℃, 190℃, 190℃, 180℃, and 180℃, respectively, and the main extruder speed was 220 rpm.

[0050] The evaluation methods for each performance are shown in Table 1. All performance tests were conducted after the composite material was prepared into test specimens.

[0051] Table 1 Measurement Standards for Each Performance Item

[0052] Note: The sample size shall be made in accordance with the sample size in the implementation standard.

[0053] Table 2. Content (parts by weight) and performance test results of each component in groups 1-6.

[0054] Table 3. Content (weight percentage) and performance test results of each component in groups 7-16

[0055] As shown in Tables 2-3, the addition of ASA to POK resin significantly improves the weather resistance of POK materials, and the weather resistance is better when the POK / ASA ratio is (60-90):(10-30). The addition of compatibilizer does not significantly improve the performance of POK / ASA alloy materials. Using high-rubber powder as a toughening agent greatly improves the impact resistance and low-temperature resistance of the material.

[0056] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An alloy material, characterized in that, The raw materials comprise the following components by weight: 60-100 parts of polyketone POK, 10-50 parts of ASA resin, 3-15 parts of toughening agent, and 0.5-2 parts of additives; the toughening agent is high-polymer powder, and the molecular weight of the polyketone POK is 10,000-100,000 Da; The ASA resin is a graft copolymer of acrylate rubber, acrylonitrile and styrene; in the ASA resin, the weight percentage of acrylate rubber is 5% to 30%, the weight percentage of acrylonitrile is 10% to 30%, and the weight percentage of styrene is 40% to 70%.

2. The alloy material according to claim 1, characterized in that, The raw materials, by weight, comprise the following components: 70-90 parts of polyketone POK, 10-30 parts of ASA resin, 3-15 parts of toughening agent, and 0.5-2 parts of additives.

3. The alloy material according to claim 1, characterized in that, The weight-average molecular weight of the ASA resin is 80,000 to 150,000 g / mol.

4. The alloy material according to claim 1, characterized in that, The additives are antioxidants and lubricants; In 0.5 to 2 parts of additives, the antioxidant accounts for 0.4 to 1.6 parts, and the lubricant accounts for 0.1 to 0.4 parts; The lubricant includes any one or more of stearic acid and its salts, methyl bis-stearamide, N,N-ethylene bis-stearamide, and pentaerythritol stearate.

5. The alloy material according to claim 4, characterized in that, The antioxidants include any one or more of hindered phenolic antioxidants and phosphite antioxidants; The hindered phenolic antioxidants include: antioxidant 168; The phosphite antioxidants include: antioxidant 1076.

6. The alloy material according to claim 5, characterized in that, In 0.4 to 1.6 parts of antioxidants, the hindered phenolic antioxidant accounts for 0.2 to 1.0 parts and the phosphite antioxidant accounts for 0.2 to 0.6 parts.

7. The alloy material according to claim 1, characterized in that, The raw materials also include 1 to 10 parts of a compatibilizer; The compatibilizer is any one of ethylene-methyl acrylate-glycidyl methacrylate.

8. The method for preparing the alloy material according to any one of claims 1 to 7, characterized in that, It includes: After the raw materials are mixed according to the specified ratio, the alloy material is obtained by extrusion, cooling, granulation and drying. The extrusion is performed using a twin-screw extruder; The temperatures of zones 1 to 11 of the twin-screw extruder are set to 90~110℃, 210~230℃, 210~230℃, 200~220℃, 200~220℃, 190~210℃, 190~210℃, 180~200℃, 180~200℃, 170~190℃, and 170~190℃, respectively.

9. The preparation method according to claim 8, characterized in that, The temperatures of zones 1 to 11 of the twin-screw extruder are set to 98~102℃, 218~222℃, 218~222℃, 208~212℃, 208~212℃, 198~202℃, 198~202℃, 188~192℃, 188~192℃, 178~182℃, and 178~182℃, respectively.

10. The application of the alloy material as described in any one of claims 1 to 7 or the alloy material prepared by the preparation method as described in claim 8 or 9 in the preparation of automotive parts, building components, sports equipment components, electronic components, electrical equipment, medical devices or chemical equipment.

Images