Wear-resistant alloy composition and wear-resistant alloy material and method of making and use thereof

Abstract

The present application relates to the field of polymer alloy material, and more particularly to a kind of wear-resistant alloy composition and wear-resistant alloy material and its preparation method and application, the composition includes: polycarbonate 40-60 parts by weight, acrylonitrile-styrene-acrylate copolymer 10-30 parts by weight, styrene-acrylonitrile copolymer 30-50 parts by weight, compatilizer 0.5-4 parts by weight, toughening agent 2-5 parts by weight, antioxidant 0.1-0.5 parts by weight, lubricant 0.2-0.5 parts by weight, ultraviolet absorber 0.1-0.3 parts by weight;The polycarbonate is isosorbide carbonate.The wear-resistant alloy material prepared by the composition has excellent wear resistance, weather resistance and impact resistance.

Description

Technical Field

[0001] This invention relates to the field of polymer alloy materials, specifically to a wear-resistant alloy composition and wear-resistant alloy material, its preparation method, and its application. Background Technology

[0002] Polycarbonate is an engineering plastic with excellent overall performance and a wide range of market applications, commonly used in the manufacture of automotive products, electronic and electrical products, and medical products. However, polycarbonate has a significant drawback: its surface has poor scratch and abrasion resistance, leaving noticeable scratches during use and severely affecting the product's appearance. Therefore, scientists hope to obtain polycarbonate with better abrasion resistance by modifying the polymerization raw materials.

[0003] Isosorbide polycarbonate is an improved product. Compared with traditional bisphenol A polycarbonate, it has a wide range of raw material sources, which can be obtained through straw processing, meeting the requirements of green and environmentally friendly raw material sources. However, due to its structural problems, isosorbide polycarbonate has poor impact resistance.

[0004] ASA alloy is a terpolymer of styrene, acrylonitrile, and acrylate. Polycarbonate and ASA are partially compatible. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor scratch resistance and wear resistance of polycarbonate products in the prior art, and to provide a wear-resistant alloy composition and wear-resistant alloy material, as well as their preparation method and application. The wear-resistant alloy material prepared by this wear-resistant alloy composition has good wear resistance and weather resistance.

[0006] To achieve the above objectives, a first aspect of the present invention provides a wear-resistant alloy composition, the composition comprising:

[0007] Polycarbonate (PC) 40-60 parts by weight, acrylonitrile-styrene-acrylate copolymer (ASA) 10-30 parts by weight, styrene-acrylonitrile copolymer (SAN) 30-50 parts by weight, compatibilizer 0.5-4 parts by weight, toughening agent 2-5 parts by weight, antioxidant 0.1-0.5 parts by weight, lubricant 0.2-0.5 parts by weight, ultraviolet absorber 0.1-0.3 parts by weight;

[0008] The polycarbonate is isosorbide-based polycarbonate.

[0009] A second aspect of the present invention provides a wear-resistant alloy material, which is formed by heating, melting and extruding the composition described in the present invention into granules.

[0010] A third aspect of this invention provides a method for preparing a wear-resistant alloy, the method comprising:

[0011] (1) Mix the composition of the present invention according to the specified proportions;

[0012] (2) The mixed material is put into a twin-screw extruder for extrusion granulation. The length-to-diameter ratio of the screw is 32-40, and the temperature of each section of the screw is 180-260℃.

[0013] The fourth aspect of the present invention provides an application of the wear-resistant alloy material described herein in sheet materials that come into frequent contact with the human body.

[0014] Through the above technical solution, the wear-resistant alloy material prepared by the present invention using a composition containing isosorbide polycarbonate, acrylonitrile-styrene-acrylate copolymer and styrene-acrylonitrile copolymer has excellent wear resistance and weather resistance. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] The first aspect of the present invention provides a wear-resistant alloy material composition, the composition comprising:

[0017] The composition includes 40-60 parts by weight of polycarbonate, 10-30 parts by weight of acrylonitrile-styrene-acrylate copolymer, 30-50 parts by weight of styrene-acrylonitrile copolymer, 0.5-4 parts by weight of compatibilizer, 2-5 parts by weight of toughening agent, 0.1-0.5 parts by weight of antioxidant, 0.2-0.5 parts by weight of lubricant, and 0.1-0.3 parts by weight of ultraviolet absorber; wherein the polycarbonate is isosorbide-based polycarbonate.

[0018] The wear-resistant alloy material prepared by the wear-resistant alloy composition provided by the present invention has excellent wear resistance and weather resistance.

[0019] According to a preferred embodiment of the present invention, the composition comprises: 50-60 parts by weight of polycarbonate, 12-18 parts by weight of acrylonitrile-styrene-acrylate copolymer, 30-38 parts by weight of styrene-acrylonitrile copolymer, 0.5-2 parts by weight of compatibilizer, 2-5 parts by weight of toughening agent, 0.1-0.5 parts by weight of antioxidant, 0.2-0.5 parts by weight of lubricant, and 0.1-0.3 parts by weight of ultraviolet absorber.

[0020] According to a preferred embodiment of the present invention, the sum of the weight parts of the polycarbonate, acrylonitrile-styrene-acrylate copolymer, and styrene-acrylonitrile copolymer is 100 parts by weight. This is beneficial for improving the wear resistance and weather resistance of the wear-resistant alloy material.

[0021] According to a preferred embodiment of the present invention, the isosorbide-based polycarbonate is obtained by copolymerization of isosorbide and diphenyl carbonate, and has a melt index of 6-15 g / 10 min at 300°C and a load of 1.2 kg. It is commercially available, for example, isosorbide-based polycarbonate manufactured by Teijin Corporation.

[0022] According to a preferred embodiment of the present invention, in the acrylonitrile-styrene-acrylate copolymer, the content of structural units from acrylate is ≥50 wt%; more preferably, based on the total amount of the acrylonitrile-styrene-acrylate copolymer, the content of structural units from acrylate is 45-70 wt%, the content of structural units from acrylonitrile is 26-28 wt%, and the content of structural units from styrene is 2-27 wt%. This is beneficial for improving the wear resistance and weather resistance of the wear-resistant alloy material. It is commercially available, for example, XC-500 from Kumho Chemical Co., Ltd. of South Korea.

[0023] According to a preferred embodiment of the present invention, preferably, the styrene-acrylonitrile copolymer has a melt index of 1.4-3.3 g / 10 min at 200°C and a 5 kg load. This is beneficial for improving the wear resistance and weather resistance of the wear-resistant alloy material. It is commercially available, for example, 80HF from LG Chem Enterprises Ltd.

[0024] In this invention, the selected compatibilizer can help improve the bonding force between the PC and ASA phases, and help improve the wear resistance and weather resistance of the wear-resistant alloy material. According to a preferred embodiment of the present invention, the compatibilizer is a styrene-maleic anhydride copolymer and / or an epoxy functional group grafted polyolefin elastomer.

[0025] According to a preferred embodiment of the present invention, the content of maleic anhydride in the styrene-maleic anhydride copolymer is 20-45 wt%. It is commercially available, for example, from Perico Polymer's SZ40005.

[0026] According to a preferred embodiment of the present invention, the epoxy-functionalized grafted polyolefin elastomer is an epoxy-functionalized grafted ethylene-acrylate graft copolymer; preferably, the epoxy-functionalized grafted polyolefin elastomer contains 1-4 wt% epoxy functional groups (GMA). It is commercially available, for example, SAG-002 from Jia Yi Rong Polymer (Shanghai) Co., Ltd.

[0027] In this invention, the toughening agent can improve the ductility and impact resistance of wear-resistant alloy materials, thereby enhancing their wear resistance and impact resistance. According to a preferred embodiment of the invention, the toughening agent is selected from at least one of acrylate toughening agents, silicone-acrylate toughening agents, and styrene-methyl methacrylate-butadiene terpolymer toughening agents, preferably silicone-acrylate toughening agents and acrylate toughening agents. The toughening agent is commercially available, for example, from Kanekachi M-577 and M-732 in Japan and Mitsubishi Rayon S2030 in Japan.

[0028] According to a preferred embodiment of the present invention, the lubricant is selected from at least one of stearamide, hydrocarbon and fatty acid lubricants.

[0029] In this invention, the ultraviolet absorber can be used to improve the weather resistance of wear-resistant alloy materials. According to a preferred embodiment of the invention, the ultraviolet absorber is selected from at least one of salicylates, benzophenones and benzotriazoles.

[0030] According to a preferred embodiment of the present invention, the ultraviolet absorber is selected from UV-234 and / or UV-770, more preferably a composite of UV-234 and UV-770. By selecting UV-770, which has better performance against ASA, and UV-234, which has better performance against polycarbonate, the composite of UV-234 and UV-770 solves the defect of insufficient product service life caused by poor weather resistance of a single absorber, improves the weather resistance of wear-resistant alloy materials, and extends the service life of products.

[0031] According to a preferred embodiment of the present invention, in the composite of UV-234 and UV-770, the mass ratio of UV-234 to UV-770 is 1:0.5-1.5.

[0032] In this invention, the antioxidant can be used to improve the weather resistance of wear-resistant alloy materials. According to a preferred embodiment of this invention, the antioxidant is a phosphite antioxidant and / or a hindered phenolic antioxidant.

[0033] According to a preferred embodiment of the present invention, the antioxidant is at least one of antioxidant 168, antioxidant 626, and antioxidant 1076, preferably a compound of antioxidant 168, antioxidant 626, and antioxidant 1076. By selecting a compound antioxidant and utilizing the synergistic effect between the antioxidants, the amount of antioxidant used is reduced, thereby lowering the possibility of additive precipitation during product manufacturing. Preferably, in the compound, the weight ratio of antioxidant 168, antioxidant 626, and antioxidant 1076 is 2-6:0-3:0.5-1.5.

[0034] A second aspect of the present invention provides a wear-resistant alloy material, which is obtained by melt processing of the composition described in the present invention; the wear-resistant alloy material has excellent wear resistance, weather resistance and impact resistance.

[0035] A third aspect of the present invention provides a method for preparing a wear-resistant alloy material, the method comprising:

[0036] The components of the composition provided in the first aspect of the present invention are mixed, and the mixed material is put into a twin-screw extruder for extrusion granulation. The length-to-diameter ratio of the screw is 32-40, and the temperature of each section of the screw is 180-260°C.

[0037] According to a preferred embodiment of the present invention, the temperature of the feeding section of the twin-screw extruder is 180-220°C, the temperature of the melting section is 245-260°C, the temperature of the homogenization section is 245-255°C, and the temperature of the die head is 230-250°C.

[0038] The fourth aspect of the present invention provides the application of the wear-resistant alloy material described herein in articles that come into contact with the human body.

[0039] The present invention will be described in detail below through embodiments.

[0040] The following embodiments describe the material performance testing and methods:

[0041] (1) Impact strength, tested according to ASTM D256 standard.

[0042] (2) Abrasion resistance test: The pencil hardness test is conducted in accordance with GB / T 6739-2006 standard. The movement speed is controlled at 5-10cm / s and the movement distance is about 10mm. The hardness of the pencil is changed from soft to hard in turn until the scratches are visible to the naked eye.

[0043] (3) Weather resistance test: The impact strength retention rate (%) and color difference change ΔE of the wear-resistant alloy material after aging for 1000h were tested according to ASTM G155 standard.

[0044] (4) Drop ball test: A 1kg ball is dropped freely from a height of 1.3m. The breakage of the wear-resistant alloy material parts is observed. Passing is marked as P, and failing is marked as F.

[0045] The following raw materials are used in the following embodiments:

[0046] The PC used is isosorbide-based polycarbonate manufactured by Teijin Corporation, model H-7000, with a melt index of 10 g / 10 min at 300°C and 1.2 kg load.

[0047] The PC used is bisphenol A type polycarbonate produced by Ningbo Zhetie Dafeng Chemical Co., Ltd., model PC02-10.

[0048] Acrylonitrile-styrene-acrylate copolymer (ASA), model XC-500, with 60wt% of acrylate structural units, Kumho Corporation, South Korea.

[0049] Styrene-acrylonitrile copolymer (SAN), model 80HF, melt index of 3 g / 10 min at 200°C and 5 kg load, LG Chem Enterprises Ltd.

[0050] Compatibilizer, styrene-maleic anhydride copolymer (SMA), model SZ40005, maleic anhydride content 42% by mass, styrene content 58% by mass, Perico Polymer.

[0051] Compatibilizer, epoxy-grafted styrene-acrylonitrile copolymer, model SAG-002, GMA content 2%, manufactured by Jia Yi Rong Polymer (Shanghai) Co., Ltd.

[0052] Acrylic toughening agent (ACR), model M-577, Kanekachi, Japan.

[0053] Styrene-methyl methacrylate-butadiene terpolymer (MBS) toughening agent, M-732, Kanekachi, Japan.

[0054] Silicone-acrylate toughening agent, S2030, Mitsubishi Rayon, Japan.

[0055] The antioxidants are a complex of antioxidant 168, antioxidant 626, and antioxidant 1076 in a ratio of 4:2:1. Antioxidant 168, model Irgafos 168, purity ≥99%, is manufactured by BASF, Germany; antioxidant 626, model Irgafos626, purity ≥99%, is also manufactured by BASF, Germany; antioxidant 1076, model Irganox 1076, purity ≥99%, is also manufactured by BASF, Germany.

[0056] Lubricant, pentaerythritol stearate (PETS), model PETS-AHS, Italian brand Fagi.

[0057] The ultraviolet absorber is a composite of UV-234 and UV-770 in a 1:1 ratio; UV234, purity ≥99.9%, Tianjin Lianlong; UV-770, Tianjin Lianlong.

[0058] In the following implementation, the preparation method of wear-resistant alloy material includes the following steps:

[0059] The components of the wear-resistant alloy material composition are mixed, and the mixed material is fed into a twin-screw extruder for extrusion granulation. The length-to-diameter ratio of the screw is 32-40. The temperature of the feeding section of the twin-screw extruder is 180-220℃, the temperature of the melting section is 245-260℃, the temperature of the homogenization section is 245-255℃, and the temperature of the die head is 230-250℃.

[0060] The component contents of Examples 1-9 and Comparative Examples 1-3 are shown in Table 1. The test results are shown in Table 2.

[0061]

[0062] Table 2

[0063]

[0064] Compared with Comparative Example 4, in Example 2, isosorbide-based polycarbonate significantly improves the wear resistance and weather resistance of wear-resistant alloy materials while maintaining high impact resistance.

[0065] Compared to Example 2, in Example 6, the impact strength of the alloy material with 0.5 parts of SAG002 added was comparable to that of the alloy material with 2 parts of SMA added. This indicates that SAG002 improves compatibility better than SMA. Comparing the two, maleic anhydride-type graft copolymers are cheaper, but have lower functional group reactivity, thus requiring a larger addition amount. Epoxy group-grafted copolymers require less addition but are more expensive.

[0066] Examples 2, 8, and 9 show that adding the same proportions of the three types of toughening agents results in comparable impact strength for the alloy materials. However, weathering test results indicate that the addition of silicon-based toughening agents resulted in less color difference changes in the alloy materials before and after aging, while the addition of M-732 resulted in greater color difference changes after aging.

[0067] The weathering test results from Examples 2 and 5 show that the alloy material with both UV770 and UV234 added exhibits less color difference variation. The alloy material with only UV770 or UV234 added shows greater color difference variation. This indicates that UV770 and UV234 have a good synergistic effect.

[0068] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A wear-resistant alloy composition, characterized in that, The composition comprises: 40-60 parts by weight of polycarbonate, 10-30 parts by weight of acrylonitrile-styrene-acrylate copolymer, 30-50 parts by weight of styrene-acrylonitrile copolymer, 0.5-4 parts by weight of compatibilizer, 2-5 parts by weight of toughening agent, 0.1-0.5 parts by weight of antioxidant, 0.2-0.5 parts by weight of lubricant, and 0.1-0.3 parts by weight of ultraviolet absorber; The polycarbonate is isosorbide-based polycarbonate.

2. The composition according to claim 1, wherein, The isosorbide-based polycarbonate has a melt index of 6-15 g / 10 min at 300°C and a load of 1.2 kg; and / or The sum of the weight parts of the polycarbonate, acrylonitrile-styrene-acrylate copolymer and styrene-acrylonitrile copolymer is 100 parts by weight.

3. The composition according to claim 1 or 2, wherein, The melt index of the styrene-acrylonitrile copolymer at 200°C and 5 kg load is 1.4-3.3 g / 10 min.

4. The composition according to claim 1 or 2, wherein, Based on the total amount of the acrylonitrile-styrene-acrylate copolymer, the content of structural units from acrylate in the acrylonitrile-styrene-acrylate copolymer is 45-70 wt%, the content of structural units from acrylonitrile is 26-28 wt%, and the content of structural units from styrene is 2-27 wt%.

5. The composition according to claim 1 or 2, wherein, The compatibilizer is a styrene-maleic anhydride copolymer and / or an epoxy functional group grafted polyolefin elastomer. And / or, the toughening agent is selected from at least one of acrylate toughening agents, silicone-acrylate toughening agents, and styrene-methyl methacrylate-butadiene terpolymer toughening agents; And / or, the lubricant is selected from at least one of stearamide, hydrocarbon and fatty acid lubricants; And / or, the ultraviolet absorber is selected from at least one of salicylates, benzophenones and benzotriazoles; And / or, the antioxidant is a phosphite antioxidant and / or a hindered phenolic antioxidant.

6. The composition according to claim 5, wherein, In the styrene-maleic anhydride copolymer, the mass content of maleic anhydride is 20-45%; The epoxy-functionalized grafted polyolefin elastomer is an epoxy-functionalized grafted ethylene-acrylate copolymer, with an epoxy functionalized group content of 1-4% by mass. And / or, the toughening agent is a silicone-acrylate toughening agent and an acrylate toughening agent.

7. The composition according to claim 1 or 2, wherein, The antioxidant is at least one of antioxidant 168, antioxidant 626 and antioxidant 1076.

8. The composition according to claim 1 or 2, wherein, The antioxidant is a compound of antioxidant 168, antioxidant 626 and antioxidant 1076; in the compound, the weight ratio of antioxidant 168, antioxidant 626 and antioxidant 1076 is 2-6:0-3:0.5-1.

5.

9. A wear-resistant alloy material, characterized in that, The wear-resistant alloy material is obtained by melting and processing raw materials containing the composition described in any one of claims 1-8.

10. A method for preparing a wear-resistant alloy material, characterized in that, The method includes: Mix the components of the composition according to any one of claims 1-8, and put the mixed material into a twin-screw extruder for extrusion granulation, wherein the length-to-diameter ratio of the screw is 32-40, and the temperature of each section of the screw is 180-260°C.

11. The preparation method according to claim 10, wherein, The twin-screw extruder has a feeding section temperature of 180-220℃, a melting section temperature of 245-260℃, a homogenization section temperature of 245-255℃, and a die head temperature of 230-250℃.

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