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

Abstract

The application relates to a high-wear-resistance PPO / HIPS / SPS alloy material and a preparation method thereof, and the high-wear-resistance PPO / HIPS / SPS alloy material comprises the following components in mass fractions: 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 the reaction of polyphenyl ether, a bisphenol compound, methyl methacrylate, fluorine-containing acrylic ester, a silane coupling agent and glass fiber. The application not only enhances the solvent resistance, stability and wear resistance of the product, but also improves the affinity and compatibility among the components, effectively improves the strength of the composite material, solves the problems in the prior art, and has important significance for the development and popularization of the PPO / HIPS / SPS alloy material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a high wear-resistant PPO / HIPS / SPS alloy material and a preparation method thereof. BACKGROUND

[0002] PPO (polyphenylene oxide) material has the characteristics of heat resistance, insulation, waterproofness and good stability, and has excellent comprehensive performance, and is one of the world's five general engineering plastics. The PPO material applied on the market is mostly MPPO, i.e. PPO / HIPS alloy. Since PPO and HIPS (high impact polystyrene) are both non-crystalline materials, the wear resistance of the materials is not ideal, and when the materials are applied to structural parts or appearance parts that require wear resistance, wear resistance modification is often needed. The commonly used modification methods include: reinforcement by glass fiber, carbon fiber, whisker, etc.; filling by adding minerals with high hardness; adding metal oxides; adding fluorides; and making alloys with high-wear-resistant polymer materials.

[0003] However, the above technical means still has many defects: the wear resistance of the material can be improved by glass fiber reinforcement, but the surface is easy to float fiber due to the addition of glass fiber, and the appearance is poor, which is not suitable for some applications. The wear resistance of the system is improved by adding minerals with high hardness, which often needs to add a large fraction, has a large influence on the physical properties of the material, and is not worth the cost. By adding metal oxides, a large number of parts are also needed, and some metal oxides with good effect are not only expensive, but also have a large influence on the color of the material. Fluoride improves the wear resistance of the material, also needs to add a large fraction, and has an influence on the physical properties of the material. High-wear-resistant polymer materials, such as POK and PA66, often have compatibility problems with PPO, and the corresponding compatibilizer not only has a large amount of addition, but also has a relatively high cost. In addition, the addition of PPO has a great influence on the crystallinity of these materials, and often needs to be assisted by the above-mentioned methods to improve the wear resistance, otherwise it is difficult to achieve the ideal effect.

[0004] In summary, there is an urgent need to develop a new technical solution to improve the performance of the composite material to solve the problems in the prior art and meet the needs of the market and industry. SUMMARY

[0005] Based on this, the application provides a high wear-resistant PPO / HIPS / SPS alloy material and a preparation method thereof.

[0006] An object of the application is to provide a high wear-resistant PPO / HIPS / SPS alloy material, which comprises the following components in mass fraction:

[0007] PPO resin 35-50 parts

[0008] HIPS resin 10-25 parts

[0009] SPS resin 5-15 parts

[0010] Compatibility toughening agent 2-8 parts

[0011] Wear-resistant aid 1-15 parts

[0012] Modified glass fiber 5-10 parts

[0013] Other aids 0.1-5.0 parts

[0014] Among them,

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

[0016] Polystyrene (SPS) has the advantages of high strength, high hardness and fast crystallization rate, and the introduction of SPS in the PPO / HIPS system can improve the wear resistance of the material to a certain extent. The side benzene ring of SPS is arranged in an alternating order, which is rigid and brittle. However, after being combined with PPO / HIPS, the random styrene in HIPS has good affinity with SPS, and the rubber in HIPS has a toughening effect on SPS. In addition, HIPS and PPO also have good compatibility, and even without the addition of a compatibilizer, a material with excellent performance can be obtained.

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

[0018] Further, the melt index of the HIPS resin is 5-15 g / 10min, preferably 6-10 g / 10min.

[0019] Further, the density of the SPS resin is 1.01-1.05 g / cm 3 , and the melting point is about 270℃.

[0020] Further, 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] Further, the wear-resistant auxiliary agent includes a siloxane derivative and a fluororesin.

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

[0023] The physically modified siloxane is fumed silica dispersed siloxane, and the chemically modified siloxane is polyester grafted siloxane.

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

[0025] Further, the other auxiliary agent includes a modifier, an antioxidant, and a lubricant.

[0026] Further, the modifier is a poly-alpha-methylstyrene resin.

[0027] Further, the antioxidant is a 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 compound in a mass ratio of 1:1.

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

[0029] Further, the silane coupling agent is an acryloyloxysilane coupling agent.

[0030] Another object of the present application is to provide a preparation method of the high-wear-resistant PPO / HIPS / SPS alloy material.

[0031] S1, blending glass fibers and a silane coupling agent, and obtaining an intermediate product 1 after heating and reaction;

[0032] S2, polyphenyl ether and bisphenol compound are blended, heated and stirred under inert gas protection, then mixed with methyl methacrylate, catalyst, heated and reacted to obtain intermediate product 2;

[0033] S3, the intermediate product 1, the intermediate product 2, the fluorine-containing propylene acrylate and the initiator are blended, heated and stirred under inert gas protection to obtain modified glass fiber;

[0034] S4, the modified glass fiber and other components are blended and added into an extruder, and then melt extrusion granulation is carried out to obtain high wear-resistant PPO / HIPS / SPS alloy material.

[0035] Further, in step S1, the temperature of the heated and stirred reaction is 50-90℃.

[0036] Further, in step S2, the temperature of the heated and stirred reaction is 80-100℃, and the temperature of the heated reaction is 60-90℃.

[0037] Further, in step S3, the temperature of the heated reaction is 60-100℃.

[0038] Further, the mass ratio of the intermediate product 1, the intermediate product 2 and the fluorine-containing propylene acrylate is (5-10):(1-3):(1-2).

[0039] Further, the setting process conditions of the extruder are as follows: the first zone temperature is 220-240℃; the second zone temperature is 245-265℃; the third zone temperature is 245-265℃; the fourth zone temperature is 245-265℃; the fifth zone temperature is 245-265℃; the sixth zone temperature is 240-250℃; the seventh zone temperature is 240-250℃; the eighth zone temperature is 240-250℃; the ninth zone temperature is 240-250℃; the die temperature is 240-260℃. The main machine speed is 300-450 RPM / minute, the feeding speed is 80-150 RPM / minute, and the vacuum degree is ≤-0.05MPa.

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

[0041] The high wear-resistant PPO / HIPS / SPS alloy material provided by the present application uses PPO, HIPS and SPS resin as the main components, and a small amount of siloxane derivatives and fluororesin and the like are compounded, which not only improves the wear resistance, but also makes the product not limited to dark or black color, and can realize rich color matching, and meets the requirements of high appearance of the parts.

[0042] And, the application also uses modified glass fiber as a component, which is first treated with acryloxy silane coupling agent to obtain intermediate product 1 with active double bond, and then PPO is reacted with bisphenol compound to introduce terminal hydroxyl group, and further reacted with methacrylic anhydride to obtain intermediate product 2 with double bond as terminal group, and then the two intermediate products and fluorine-containing acrylate are polymerized to obtain modified glass fiber. On the one hand, the surface of the modified glass fiber is coated with PPO structure, which greatly improves the poor compatibility of glass fiber with polyphenyl ether, polystyrene and other matrix resins, avoids the defects of uneven distribution and floating fiber, fully plays the toughening effect of glass fiber, and the segments of polyphenyl ether and the like can also be combined through intermolecular forces, thereby greatly enhancing the strength of the composite material. On the other hand, the introduced fluorine-containing group also improves the compatibility of glass fiber with fluororesin, thereby playing a compatibilizing effect, so that various components can improve the stability and wear resistance of the alloy material. Therefore, the application also has the advantages of good processability, avoids the wear of the processing screw, is more friendly to the equipment, and the production efficiency is also improved due to less friction and wear between the material and the processing machinery. DETAILED DESCRIPTION

[0043] In order to more clearly illustrate the technical solutions of the present application, the following examples are listed. The raw materials, reactions and post-treatment means appearing in the examples are all common raw materials on the market and technical means familiar to those skilled in the art, unless otherwise stated.

[0044] The words "preferred", "preferably", "more preferred" and the like in the present application refer to the embodiments of the present application which can provide certain beneficial effects in certain cases. However, other embodiments can also be preferred in the same or other cases. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not usable, nor is it intended to exclude other embodiments from the scope of the present application.

[0045] It should be understood that, except in any operational example or otherwise indicated, the use of amounts or all numbers expressing, for example, amounts of ingredients in the specification and claims are to be understood as being modified in all instances by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending on the desired properties to be obtained by the present application.

[0046] The PPO resin (polyphenyl ether) in the embodiments of the present application is LXN040 with intrinsic viscosity of 0.40 dl / g, Nantong Xingchen Synthetic Material Co., Ltd. Ruicheng Branch.

[0047] The HIPS resin in the embodiments of the present application is PH88 with melt index of 6.0 g / 10 min, Quaker Chemical Co., Ltd.

[0048] The SPS resin in the embodiment of the application is XAREC S105, with a density of 1.02 g / cm 3 , Nichigo.

[0049] The compatible toughening agent in the embodiment of the application is SEBS-g-MAH, W1G-2, with a maleic anhydride content of 0.4-0.8 wt%, from Kao Sichem Co., Ltd.

[0050] The white carbon black dispersion silicone in the embodiment of the application is SiC 6000S, with a silicone content of 50%, from SLOCHEM Co., Ltd.

[0051] The polyester grafted silicone in the embodiment of the application is 5140, from Chengdu Silike Technology Co., Ltd.

[0052] The polytetrafluoroethylene in the embodiment of the application 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 application is Kynar SL, from Arkema Fluorinated Chemical Co., Ltd.

[0054] The modifier in the embodiment of the application is poly-alpha-methylstyrene resin, AMS-100.

[0055] The antioxidant and lubricant in the embodiment of the application are common commercially available materials.

[0056] The glass fiber in the embodiment of the application is Giant Stone 540H.

[0057] The "parts" in the embodiment of the application all refer to mass parts.

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

[0059] Table 1 Components and mass parts of high wear-resistant PPO / HIPS / SPS alloy material

[0060] Component 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 Kynar SL 0.6 0.6 0.6 0.6 1 1 AMS-100 1 1 1 1 1 1 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 Lubricant 0.5 0.5 0.5 0.5 0.5 0.5

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

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

[0063] S2, mixing polyphenyl ether and bisphenol A with toluene as solvent, stirring at 90℃ for 30min under nitrogen atmosphere, then adding benzoyl peroxide, continuing to react for 4h, precipitating with methanol after cooling, and then filtering, washing and drying to obtain solid product;

[0064] The mass ratio of polyphenyl ether, bisphenol A and benzoyl peroxide is 10:1:0.8.

[0065] Then, the solid product, methyl acrylate and triethylamine are mixed with toluene as solvent, and reacted at 80℃ for 5h, precipitated with methanol after cooling, and then filtered, washed and dried to obtain intermediate product 2.

[0066] The mass ratio of the solid product, methyl acrylate and triethylamine is 5:2:1.

[0067] S3, mixing the intermediate product 1, intermediate product 2, trifluoromethyl acrylate and benzoyl peroxide with a mass ratio of 8:2:1:0.5 with water as solvent, stirring and reacting at 80℃ under nitrogen atmosphere for 12h to obtain modified glass fiber.

[0068] S4, the modified glass fiber and other components are put into a high-speed mixer and mixed for 2-3min, and then put into the main feeding hopper of the twin-screw extruder, and extruded according to the set process, plasticized, melted, extruded, cooled, air-dried and granulated by the twin-screw extruder to obtain the high-wear-resistant PPO / HIPS / SPS alloy material.

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

[0070] Comparative Example 1

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

[0072] Comparative Example 2

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

[0074] Test example

[0075] The PPO / HIPS / SPS alloy materials prepared in examples 1-6 and comparative examples 1-2 are subjected to performance testing.

[0076] The test method is as follows:

[0077] The materials obtained in the examples and comparative examples are dried at 100 DEG C for 4-6 hours, and then injected into standard sample bars 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 bending performance and bending modulus are tested according to GB / T9341-2008, and the notched impact strength is tested according to GB / T 1843-2008.

[0079] The wear rate and friction coefficient are tested according to GB / T 3960-2016, under the conditions of room temperature (23±2) DEG C, relative humidity (50±5) %, and without lubrication. The rotating speed of the experimental ring is 0.42 m / s, the test time is 120 min, and the load is 100 N. Five samples are tested for each formula, the specific wear rate is calculated as K=△m / (p·F·v·t) (△m is the wear mass, kg; p 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 as μ=M / (r·F) (M is the torque, 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 examples can effectively improve the mechanical strength of the material, has a lower surface friction, and has excellent wear resistance. The comparative examples 1 and 2 replace the modified glass fiber, which significantly reduces the compatibility between the components, and easily causes defects such as floating fibers, not only reduces the mechanical properties of the material, but also causes the wear resistance to decrease to varying degrees. Compared with the examples, the performance is not ideal.

[0085] It will be obvious to a person skilled in the art that the application is not limited to the details of the foregoing exemplary embodiments and can be implemented in other concrete forms without departing from the spirit or essential characteristics of the application. The embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

[0086] Furthermore, it should be understood that although the description is made on the basis of the embodiments, not every embodiment contains only one independent technical solution, and the description is made in this way only for the sake of clarity, and a person skilled in the art should consider the description as a whole, and the technical solutions in each embodiment can also be properly combined to form other embodiments that can be understood by a person skilled in the art.

Claims

1. A high wear resistant PPO / HIPS / SPS alloy material characterized in that, The high wear-resistant PPO / HIPS / SPS alloy material comprises components in mass fractions as follows: PPO resin 35-50 parts HIPS resin 10-25 parts SPS resin 5-15 parts Compatibility toughening agent 2-8 parts Wear-resistant aid 1-15 parts Modified glass fiber 5-10 parts Other aids 0.1-5.0 parts; Among them, The modified glass fiber is obtained by reaction of polyphenyl ether, bisphenol compound, methacrylic anhydride, fluorine-containing acrylic ester, silane coupling agent and glass fiber; The preparation method of the high wear-resistant PPO / HIPS / SPS alloy material comprises the following steps: S1, blending glass fiber and silane coupling agent, heating and reacting to obtain intermediate product 1; S2, blending polyphenyl ether and bisphenol compound, heating and stirring under inert gas protection, then mixing with methacrylic anhydride and catalyst, heating and reacting to obtain intermediate product 2; S3, blending the intermediate product 1, the intermediate product 2, fluorine-containing acrylic ester and initiator, heating and stirring under inert gas protection to obtain modified glass fiber; S4, blending the modified glass fiber and other components, adding them into an extruder, melt extruding and granulating to obtain the high wear-resistant PPO / HIPS / SPS alloy material; The silane coupling agent is acryloyloxy silane coupling agent.

2. The high wear resistant PPO / HIPS / SPS alloy material according to claim 1, characterized in that, The compatibility 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 high wear resistant PPO / HIPS / SPS alloy material according to claim 1, characterized in that, The wear-resistant aid comprises siloxane derivative and fluororesin.

4. The high wear resistant PPO / HIPS / SPS alloy material according to claim 1, characterized in that, The other aids comprise modifier, antioxidant and lubricant.

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

6. The high wear resistant PPO / HIPS / SPS alloy material of claim 1, wherein, In step S1, the heating and stirring temperature is 50-90℃.

7. The high wear resistant PPO / HIPS / SPS alloy material of claim 1, wherein, In step S2, the heating and stirring temperature is 80-100℃, and the heating reaction temperature is 60-90℃.

8. The high wear resistant PPO / HIPS / SPS alloy material of claim 1, wherein, In step S3, the heating reaction temperature is 60-100℃.

9. The high wear resistant PPO / HIPS / SPS alloy material of claim 1, wherein, The mass ratio of the intermediate product 1, the intermediate product 2 and fluorine-containing acrylic ester is (5-10):(1-3):(1-2).

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