High-wear-resistance PPO / HIPS / SPS alloy material and preparation method thereof

Abstract

The invention relates to a high-wear-resistance PPO / HIPS / SPS alloy material and a preparation method thereof. The high-wear-resistance PPO / HIPS / SPS alloy material comprises the following components in parts by mass: 35-50 parts of PPO resin, 10-25 parts of HIPS resin, 5-15 parts of SPS resin, 2-8 parts of a compatible toughening agent, 1-15 parts of a wear-resistant auxiliary agent, 5-10 parts of modified glass fiber and 0.1-5.0 parts of other auxiliary agents, wherein the modified glass fiber is obtained by reacting polyphenyl ether, a bisphenol compound, methacrylic anhydride, fluorinated acrylate, a silane coupling agent and glass fiber. The solvent resistance, the stability and the wear resistance of the product are enhanced, the affinity and the compatibility among the components are improved, the strength of the composite material is effectively improved, the problems in the prior art are solved, and the PPO / HIPS / SPS alloy material has important significance in development and popularization of PPO / HIPS / SPS alloy materials.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a highly wear-resistant PPO / HIPS / SPS alloy material and a preparation method thereof. Background Art

[0002] PPO (polyphenylene ether) material has the characteristics of heat resistance, insulation, waterproofness, good stability, etc., and has excellent comprehensive performance. It is one of the world's top five general engineering plastics. Most of the PPO materials used in the market are MPPO, that is, PPO / HIPS alloy. Since PPO and HIPS (high-impact polystyrene) are both non-crystalline materials, their wear resistance is not ideal. When they are used as structural parts or appearance parts that require wear resistance, wear-resistant modification is often required. Currently, the commonly used modification methods include: reinforcement through glass fiber, carbon fiber, whisker, etc.; by adding mineral fillers with higher hardness; by adding metal oxides; by adding fluorides; by making alloys with high-wear-resistant polymer materials, etc.

[0003] However, the above technical means still have many disadvantages: glass fiber reinforcement can improve the wear resistance of the material, but due to the addition of glass fiber, the surface is often prone to floating fibers and poor appearance, which is not suitable for some applications. Mineral fillers with higher hardness often need to add more fractions to improve the wear resistance of the system, which has a greater impact on the physical properties of the material, and the gains do not outweigh the losses. By adding metal oxides, more parts are also required, and some metal oxides with good effects are expensive and have a greater impact on the color of the material. Fluorides improve the wear resistance of materials, and also need to be added in a larger proportion, which has an impact on the physical properties of the materials. Polymer materials with good wear resistance, such as POK, PA66 and other materials, often have compatibility issues with PPO, and the corresponding compatibilizers are not only added in large quantities, but also relatively expensive. In addition, the addition of PPO has a greater impact on the crystallinity of such materials, and often requires the above-mentioned methods to enhance the improvement of wear resistance, otherwise it is difficult to achieve the desired effect.

[0004] In summary, there is an urgent need to develop a new technical solution to improve the various properties of composite materials in order to solve the deficiencies in existing technologies and meet the needs of the market and industry. Summary of the invention

[0005] Based on this, the present invention provides a highly wear-resistant PPO / HIPS / SPS alloy material and a preparation method thereof. The present invention adopts PPO resin, HIPS resin, SPS resin and other materials as the main components, and compounded with modified glass fiber and wear-resistant additives, which not only enhances the solvent resistance, stability and wear resistance of the product, but also improves the affinity and compatibility between the components, effectively improves the strength of the composite material, solves the problems existing in the prior art, and is of great significance to the development and promotion of PPO / HIPS / SPS alloy materials.

[0006] One object of the present invention is to provide a highly wear-resistant PPO / HIPS / SPS alloy material, wherein the highly wear-resistant PPO / HIPS / SPS alloy material comprises the following components in fractions by weight:

[0007] PPO resin 35-50 parts

[0008] HIPS resin 10-25 parts

[0009] SPS resin 5-15 parts

[0010] Compatible toughening agent 2-8 parts

[0011] 1-15 parts of wear-resistant additive

[0012] Modified glass fiber 5-10 parts

[0013] Other additives 0.1-5.0 parts;

[0014] in,

[0015] The modified glass fiber is obtained by reacting polyphenylene ether, bisphenol compound, methacrylic anhydride, fluorine-containing acrylate, silane coupling agent and glass fiber.

[0016] Polyisostyrene (SPS) has the advantages of high strength, high hardness, and fast crystallization rate. Introducing SPS into the PPO / HIPS system can improve the wear resistance of the material to a certain extent. The side benzene rings of SPS itself are arranged in an orderly manner, and it has high rigidity and brittleness. However, after being compounded with PPO / HIPS, the random styrene part in HIPS has a good affinity with SPS, and at the same time, the rubber in it has a toughening effect on SPS. HIPS also has good compatibility with PPO, and even without adding a compatibilizer, a material with excellent performance can be obtained.

[0017] Furthermore, the intrinsic viscosity of the PPO resin is 0.35 to 0.50 dl / g, preferably 0.40 dl / g.

[0018] Furthermore, the HIPS resin has a melt index of 5 to 15 g / 10 min, preferably 6 to 10 g / 10 min.

[0019] Furthermore, the density of the SPS resin is 1.01 to 1.05 g / cm 3 , the melting point is around 270℃.

[0020] Furthermore, the compatible toughening agent is one or more of styrene-butadiene-styrene block copolymer (SBS), hydrogenated SBS (SEBS), styrene-isoprene-styrene block copolymer (SIS), hydrogenated SIS (SEPS), SBS grafted maleic anhydride, SEBS grafted maleic anhydride, POE grafted maleic anhydride, EPDM grafted maleic anhydride, and PS grafted maleic anhydride.

[0021] Furthermore, the anti-wear additive includes silicone derivatives and fluororesins.

[0022] Preferably, the siloxane derivative comprises physically modified siloxane and chemically modified siloxane in a mass ratio of 2:1;

[0023] The physically modified siloxane is white carbon black dispersed siloxane, and the chemically modified siloxane is polyester grafted siloxane.

[0024] Preferably, the fluororesin comprises polytetrafluoroethylene and polyvinylidene fluoride in a mass ratio of 5:1.

[0025] Furthermore, the other additives include modifiers, antioxidants and lubricants.

[0026] Furthermore, the modifier is poly-α-methylstyrene resin.

[0027] Furthermore, the antioxidant is a compound of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and bis(2,4-di-tert-butylphenyl)pentaerythritol bis diphosphite in a mass ratio of 1:1.

[0028] Furthermore, the lubricant is selected from one or more of cyclohexane oil, high melting point paraffin, pentaerythritol stearate, ethylene bis fatty acid amide, and modified ethylene bis fatty acid amide.

[0029] Furthermore, the silane coupling agent is an acryloxysilane coupling agent.

[0030] Another object of the present invention is to provide a method for preparing the above-mentioned highly wear-resistant PPO / HIPS / SPS alloy material, the method for preparing the highly wear-resistant PPO / HIPS / SPS alloy material comprising the following steps:

[0031] S1, mixing glass fiber and silane coupling agent, heating and reacting to obtain intermediate product 1;

[0032] S2, blending polyphenylene ether and bisphenol compound, heating and stirring under inert gas protection to react, then mixing with methacrylic anhydride and a catalyst, heating and reacting to obtain intermediate product 2;

[0033] S3, blending the intermediate product 1, the intermediate product 2, the fluorinated acrylate and the initiator, heating and stirring the mixture under the protection of an inert gas to obtain a modified glass fiber;

[0034] S4. Blending the modified glass fiber with other components, adding the mixture into an extruder, and granulating the mixture by melt extrusion to obtain a highly wear-resistant PPO / HIPS / SPS alloy material.

[0035] Furthermore, in step S1, the temperature of the heating and stirring reaction is 50-90°C.

[0036] Furthermore, in step S2, the temperature of the heating and stirring reaction is 80-100°C, and the temperature of the heating reaction is 60-90°C.

[0037] Furthermore, in step S3, the temperature of the heating reaction is 60-100°C.

[0038] Furthermore, the mass ratio of the intermediate product 1, the intermediate product 2 and the fluorinated acrylate is (5-10):(1-3):(1-2).

[0039] Further, the set process conditions of the extruder are as follows: temperature of the first zone: 220-240°C; temperature of the second zone: 245-265°C; temperature of the third zone: 245-265°C; temperature of the fourth zone: 245-265°C; temperature of the fifth zone: 245-265°C; temperature of the sixth zone: 240-250°C; temperature of the seventh zone: 240-250°C; temperature of the eighth zone: 240-250°C; temperature of the ninth zone: 240-250°C; head temperature: 240-260°C. The main engine speed is 300-450RPM / min, the feed speed is 80-150RPM / min, and the vacuum degree is ≤-0.05MPa.

[0040] The present invention has the following beneficial effects:

[0041] The high wear-resistant PPO / HIPS / SPS alloy material provided by the present invention adopts PPO, HIPS, and SPS resins as main components, and is compounded with a small amount of siloxane derivatives, fluororesins and other substances, which not only improves the wear resistance, but also the product is not limited to dark or black, and can achieve rich color matching, meeting the demand for parts with high requirements on appearance.

[0042] In addition, the present invention also uses modified glass fiber as a component, which first treats the glass fiber with an acryloxysilane coupling agent to obtain an intermediate product 1 with an active double bond introduced, and reacts PPO with a bisphenol compound to introduce a terminal hydroxyl group, and then further reacts with methacrylic anhydride to obtain an intermediate product 2 with a double bond as the terminal group, and then polymerizes the two intermediate products and fluorine-containing acrylate to obtain a modified glass fiber. On the one hand, the surface of the modified glass fiber is coated with a PPO structure, which greatly improves the problem of poor compatibility between the glass fiber and matrix resins such as polyphenylene ether and polystyrene, avoids the defects of uneven distribution and floating fibers, and gives full play to the toughening effect of the glass fiber. The segments such as polyphenylene ether can also be combined through intermolecular forces, which greatly enhances the strength of the composite material; on the other hand, the introduced fluorine-containing group also improves the compatibility of the glass fiber with the fluororesin, thereby playing a capacity-enhancing role, so that multiple components can jointly improve the stability and wear resistance of the alloy material. Therefore, the present invention also achieves the advantage of good processability, avoids wear on the processing screw, is more friendly to equipment, and because the friction and wear between the material and the processing machinery is small, the production efficiency is also improved. DETAILED DESCRIPTION

[0043] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0044] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0045] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0046] The PPO resin (polyphenylene ether) in the embodiment of the present invention is LXN040, with an intrinsic viscosity of 0.40 dl / g, from Ruicheng Branch of Nantong Xingchen Synthetic Materials Co., Ltd.

[0047] The HIPS resin in the embodiment of the present invention is PH88, with a melt index of 6.0 g / 10 min, produced by Chi Mei Industrial Co., Ltd.

[0048] The SPS resin in the embodiment of the present invention is XAREC S105, with a density of 1.02 g / cm 3 , Idemitsu Kosan Co., Ltd.

[0049] The compatible toughening agent in the embodiment of the present invention is SEBS-g-MAH, W1G-2, maleic anhydride content 0.4-0.8wt%, Coase Chemical Co., Ltd.

[0050] The white carbon black dispersed siloxane in the embodiment of the present invention is SiC 6000S, with a siloxane content of 50%, produced by Siloko New Materials Co., Ltd.

[0051] The polyester grafted siloxane in the embodiment of the present invention is 5140, produced by Chengdu Silike Technology Co., Ltd.

[0052] The polytetrafluoroethylene in the embodiment of the present invention is JTW-9957, with a D50 particle size of 10-12 μm, from Zhejiang Quzhou Wannengda Technology Co., Ltd.

[0053] The polyvinylidene fluoride in the embodiment of the present invention is Kynar SL, produced by Arkema Fluorochemicals Co., Ltd.

[0054] The modifier in the embodiment of the present invention is poly-α-methylstyrene resin, AMS-100.

[0055] The antioxidant and lubricant in the embodiments of the present invention are common commercially available materials.

[0056] The glass fiber in the embodiment of the present invention is Jushi 540H.

[0057] The "parts" in the embodiments of the present invention refer to parts by mass.

[0058] The components and mass fractions of the high wear-resistant PPO / HIPS / SPS alloy materials of Examples 1-6 are shown in Table 1.

[0059] Table 1 Composition and mass fraction of high wear-resistant PPO / HIPS / SPS alloy materials

[0060] Components Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 LXN040 50 50 50 50 50 50 XARECS105 7 12 17 17 17 17 PH88 30 25 20 20 20 20 W1G-2 5 5 5 5 5 5 Modified glass fiber 6 6 6 5 7 7 SiC6000S 2 2 2 1 1 2 5140 1 1 1 0.5 0.5 1 JTW-9957 3 3 3 3 5 5 KynarSL 0.6 0.6 0.6 0.6 1 1 AMS-100 1 1 1 1 1 1 Antioxidants 0.2 0.2 0.2 0.2 0.2 0.2 Lubricants 0.5 0.5 0.5 0.5 0.5 0.5

[0061] The preparation method of the above-mentioned highly wear-resistant PPO / HIPS / SPS alloy material comprises the following steps:

[0062] S1, using ethanol as solvent, blending glass fiber and KH-570 in a mass ratio of 1:0.3, reacting at 80°C for 6h, washing and drying to obtain intermediate product 1;

[0063] S2, using toluene as solvent, mixing polyphenylene ether and bisphenol A, stirring at 90°C for 30 minutes under a nitrogen atmosphere, then adding benzoyl peroxide, continuing the reaction for 4 hours, cooling and precipitating with methanol, filtering, washing and drying to obtain a solid product;

[0064] Wherein, the mass ratio of polyphenylene ether, bisphenol A and benzoyl peroxide is 10:1:0.8;

[0065] Then, the solid product, methacrylic anhydride and triethylamine were mixed with toluene as solvent, reacted at 80° C. for 5 h, cooled, precipitated with methanol, filtered, washed and dried to obtain intermediate product 2;

[0066] Wherein, the mass ratio of solid product, methacrylic anhydride and triethylamine is 5:2:1;

[0067] S3, using water as a solvent, mixing the intermediate product 1, the intermediate product 2, trifluoromethylacrylate and benzoyl peroxide in a mass ratio of 8:2:1:0.5, stirring and reacting at 80° C. for 12 hours under a nitrogen atmosphere to obtain a modified glass fiber;

[0068] S4. According to the above mass fractions, the modified glass fiber and other components are placed in a high-speed mixer and mixed for 2 to 3 minutes. After being evenly mixed, they are put into the main feeding hopper of a twin-screw extruder and extruded according to the set process. After plasticization, melting, extrusion, cooling, air drying and granulation by the twin-screw extruder, the highly wear-resistant PPO / HIPS / SPS alloy material is obtained.

[0069] The set process conditions of the twin-screw extruder are as follows: temperature of the first zone: 220-240°C; temperature of the second zone: 245-265°C; temperature of the third zone: 245-265°C; temperature of the fourth zone: 245-265°C; temperature of the fifth zone: 245-265°C; temperature of the sixth zone: 240-250°C; temperature of the seventh zone: 240-250°C; temperature of the eighth zone: 240-250°C; temperature of the ninth zone: 240-250°C; head temperature: 240-260°C. The main engine speed is 300-450RPM / min, the feed speed is 80-150RPM / min, and the vacuum degree is ≤-0.05MPa.

[0070] Comparative Example 1

[0071] A PPO / HIPS / SPS alloy material. The difference between this comparative example and Example 1 is that steps S2 and S3 are deleted, intermediate product 1 is used as the modified glass fiber, and other components and preparation methods are the same as those in Example 1.

[0072] Comparative Example 2

[0073] A PPO / HIPS / SPS alloy material. The difference between this comparative example and Example 1 is that step S2 is deleted, and in step S3, methyl methacrylate is used to replace intermediate product 2. Other components and preparation methods are the same as those in Example 1.

[0074] Test Case

[0075] The performance of the PPO / HIPS / SPS alloy materials prepared in Examples 1-6 and Comparative Examples 1-2 was tested.

[0076] The test method is as follows:

[0077] The materials obtained in the examples and comparative examples were dried at 100° C. for 4 to 6 hours, injection molded into standard specimens by an injection molding machine, and tested according to the corresponding national standards.

[0078] The tensile strength and elongation at break are tested according to GB / T 1040-2018, the flexural properties and flexural modulus are tested according to GB / T9341-2008, and the notched impact strength is tested according to GB / T 1843-2008.

[0079] Wear rate and friction coefficient were tested in accordance with GB / T 3960-2016, at room temperature (23±2)℃, relative humidity (50±5)%, and without lubrication. The test ring rotation speed was 0.42m / s, the test time was 120min, and the load was 100N. Five pieces of each formula material were tested, and the specific wear rate was calculated as K=△m / (ρ·F·v·t) (△m is the wear mass, kg; ρ is the sample density, kg / m 3 ; v is the sliding speed, m / s; t is the sliding time, s; F is the load, N), and the results are averaged. The friction coefficient is calculated according to μ = M / (r·F) (M is the moment, N.cm; r is the radius of the ring, cm; F is the test load, N), and the results are averaged.

[0080] The test results are shown in Table 2.

[0081] Table 2 Performance test results

[0082]

[0083]

[0084] According to Table 1, it can be concluded that the high wear-resistant PPO / HIPS / SPS alloy material prepared in the embodiment of the present invention can effectively improve the mechanical strength of the material, has low surface friction, and excellent wear resistance. However, comparative examples 1 and 2 replace the modified glass fiber, resulting in a significant decrease in the compatibility between the components, and defects such as floating fibers are prone to occur, which not only reduces the mechanical properties of the material, but also reduces the wear resistance to varying degrees. Compared with the embodiment, there are more shortcomings and the performance improvement is not ideal.

[0085] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0086] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A highly wear-resistant PPO / HIPS / SPS alloy material, characterized in that: The highly wear-resistant PPO / HIPS / SPS alloy material comprises the following components in parts by mass: PPO resin 35-50 parts HIPS resin 10-25 parts SPS resin 5-15 parts Compatible toughening agent 2-8 parts Wear-resistant additive 1-15 parts Modified glass fiber 5-10 parts Other additives 0.1-5.0 parts; in, The modified glass fiber is obtained by reacting polyphenylene ether, bisphenol compound, methacrylic anhydride, fluorine-containing acrylate, silane coupling agent and glass fiber.

2. The highly wear-resistant PPO / HIPS / SPS alloy material according to claim 1, characterized in that: The compatible toughening agent is selected from one or more of styrene-butadiene-styrene block copolymer, hydrogenated SBS, styrene-isoprene-styrene block copolymer, hydrogenated SIS, SBS grafted maleic anhydride, SEBS grafted maleic anhydride, POE grafted maleic anhydride, EPDM grafted maleic anhydride, and PS grafted maleic anhydride.

3. The highly wear-resistant PPO / HIPS / SPS alloy material according to claim 1, characterized in that: The anti-wear aids include silicone derivatives and fluororesins.

4. The highly wear-resistant PPO / HIPS / SPS alloy material according to claim 1, characterized in that: The other additives include modifiers, antioxidants and lubricants.

5. The highly wear-resistant PPO / HIPS / SPS alloy material according to claim 4, characterized in that: The modifier is poly-alpha-methylstyrene resin.

6. The method for preparing the highly wear-resistant PPO / HIPS / SPS alloy material according to any one of claims 1 to 5, characterized in that: The preparation method of the highly wear-resistant PPO / HIPS / SPS alloy material comprises the following steps: S1, mixing glass fiber and silane coupling agent, heating and reacting to obtain intermediate product 1; S2, blending polyphenylene ether and bisphenol compound, heating and stirring under inert gas protection to react, then mixing with methacrylic anhydride and a catalyst, heating and reacting to obtain intermediate product 2; S3, blending the intermediate product 1, the intermediate product 2, the fluorinated acrylate and the initiator, heating and stirring the mixture under the protection of an inert gas to obtain a modified glass fiber; S4. Blending the modified glass fiber with other components, adding the mixture into an extruder, and granulating the mixture by melt extrusion to obtain a highly wear-resistant PPO / HIPS / SPS alloy material.

7. The method for preparing the highly wear-resistant PPO / HIPS / SPS alloy material according to claim 6, characterized in that: In step S1, the temperature of the heating and stirring reaction is 50-90°C.

8. The method for preparing the highly wear-resistant PPO / HIPS / SPS alloy material according to claim 6, characterized in that: In step S2, the temperature of the heating and stirring reaction is 80-100°C, and the temperature of the heating reaction is 60-90°C.

9. The method for preparing the highly wear-resistant PPO / HIPS / SPS alloy material according to claim 6, characterized in that: In step S3, the temperature of the heating reaction is 60-100°C.

10. The method for preparing the highly wear-resistant PPO / HIPS / SPS alloy material according to claim 6, characterized in that: The mass ratio of the intermediate product 1, the intermediate product 2 and the fluorine-containing acrylate is (5-10):(1-3):(1-2).

Images