WO2022110667A1 - Kaolin-reinforced polyphenylene ether composition, preparation method thereof and use thereof - Google Patents
Kaolin-reinforced polyphenylene ether composition, preparation method thereof and use thereof Download PDFInfo
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- WO2022110667A1 WO2022110667A1 PCT/CN2021/092795 CN2021092795W WO2022110667A1 WO 2022110667 A1 WO2022110667 A1 WO 2022110667A1 CN 2021092795 W CN2021092795 W CN 2021092795W WO 2022110667 A1 WO2022110667 A1 WO 2022110667A1
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- Prior art keywords
- kaolin
- polyphenylene ether
- parts
- ether composition
- composition according
- Prior art date
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- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 3
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 47
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 47
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 229920005669 high impact polystyrene Polymers 0.000 claims description 5
- 239000004797 high-impact polystyrene Substances 0.000 claims description 5
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 5
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 5
- 229920006132 styrene block copolymer Polymers 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 claims description 4
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 239000013022 formulation composition Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- RLRINNKRRPQIGW-UHFFFAOYSA-N 1-ethenyl-2-[4-(2-ethenylphenyl)butyl]benzene Chemical compound C=CC1=CC=CC=C1CCCCC1=CC=CC=C1C=C RLRINNKRRPQIGW-UHFFFAOYSA-N 0.000 description 2
- 241001247482 Amsonia Species 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- -1 ethylene-ethylene Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the invention relates to the technical field of engineering plastics, in particular to a kaolin reinforced polyphenylene ether composition and a preparation method and application thereof.
- Polyphenylene ether reinforced material (referred to as PPE) has been widely used in the field of electrical appliances, OA and other fields due to its excellent insulating properties, high rigidity and heat resistance.
- PPE Polyphenylene ether reinforced material
- the infiltration effect of the resin on the filler is poor, resulting in poor surface appearance of the reinforced material of PPE.
- the toughness of PPE materials is very poor.
- the appearance and toughness of polyphenylene ether reinforced materials limit its demand for exterior parts, especially exterior parts used outdoors.
- the purpose of the present invention is to overcome the shortcomings of the prior art and provide a kaolin reinforced polyphenylene ether composition.
- the composition has excellent appearance and normal low temperature toughness while maintaining the high rigidity of the reinforcing material.
- a kaolin reinforced polyphenylene ether composition comprising the following components by weight: 45-80 parts of polyphenylene ether, 0-20 parts of polystyrene resin, kaolin clay 5-30 parts, toughening agent 3-10 parts and lubricant 0.1-3 parts.
- the kaolin reinforced polyphenylene ether composition includes the following components by weight: 55-75 parts of polyphenylene ether, 2-10 parts of polystyrene resin, 15-25 parts of kaolin, and 4- 8 parts and 1-2 parts lubricant.
- the particle size D50 of the kaolin is 0.1-1.0 ⁇ m.
- adding kaolin can well improve the rigidity of the material; the selection of the particle size of kaolin has a great influence on this reinforcement effect. Small is not easy to machine and provides limited rigidity.
- the particle size D50 of the kaolin is 0.2-0.4 ⁇ m.
- the intrinsic viscosity of the polyphenylene ether measured by an Ubbelohde viscometer in chloroform at 25°C is 0.2-0.8 dl/g; more preferably, the polyphenylene ether is measured by an Ubbelohde viscometer in chloroform at 25°C.
- the polyphenylene ether can use a single polyphenylene ether resin with intrinsic viscosity, or a compound of several polyphenylene ether resins with different intrinsic viscosity can be selected.
- the above-mentioned preferred polyphenylene ether resin in the present application has more excellent fluidity and comprehensive properties.
- the polystyrene-based resin is a polymer of styrene-based monomer, a copolymer of styrene-based monomer and other comonomers, a styrene-based graft copolymer, and a styrene-based copolymer elastomer. at least one of.
- the polystyrene resin can reduce the viscosity of the PPE resin, further improve the infiltration of the filler of the material during the injection molding process, and improve the apparent quality.
- the polystyrene-based resin is high impact polystyrene (HIPS).
- the toughening agent is ethylene propylene rubber, nitrile rubber, butadiene rubber, ethylene vinyl acetate copolymer, polyolefin elastomer, styrene-butadiene-styrene block copolymer, styrene-ethylene At least one of /butylene-styrene block copolymer and styrene-ethylene/propylene-styrene block copolymer; more preferably, the toughening agent is styrene-ethylene/butylene-styrene block copolymer.
- the lubricant is one of olefin-based lubricants and silicone-based lubricants.
- the lubricant is linear low density polyethylene, which can well enhance the appearance gloss of the material and improve the appearance of the product.
- polyphenylene ether composition of the present invention may further contain other additives, such as plasticizers, stabilizers, mold release agents, flame retardants, dyes, pigments and other resins that impart other properties, as long as the present invention is not damaged.
- additives such as plasticizers, stabilizers, mold release agents, flame retardants, dyes, pigments and other resins that impart other properties, as long as the present invention is not damaged. The effect of the invention is sufficient, and those skilled in the art can make routine selections according to actual needs.
- the present invention also provides a method for preparing the kaolin reinforced polyphenylene ether composition.
- the method is as follows: after mixing and dispersing the components through a high-speed mixer, a mixture is obtained, and then the mixture is extruded through a twin-screw.
- the kaolin reinforced polyphenylene ether composition is obtained by extruding and granulating from the machine.
- the present invention also discloses the application of the kaolin reinforced polyphenylene ether composition in appearance parts.
- the obtained polyphenylene ether composition has excellent appearance and normal low temperature toughness while maintaining the high rigidity of the reinforcing material. , very suitable for use in appearance parts.
- the preparation method of the kaolin reinforced polyphenylene ether composition of the present invention comprises the following steps: firstly dispersing the polyphenylene ether resin, styrene resin, toughening agent, kaolin, and lubricant in a high-speed mixer according to the formula proportion, and then dispersing them through a twin screw Extrusion and granulation; wherein, the extrusion process is: the rotation speed is 400rpm, the feeding is 450kg/h; the extrusion temperature is about 265°C.
- Appearance evaluation It is mainly judged by injection molding into a sample plate and observing the gloss of the surface of the sample and the precipitation of filler; it is divided into three grades according to the following standards, and the classification is as follows:
- Polyphenylene ether resin 1 PPE LXR050, the intrinsic viscosity measured by Ubbelohde viscometer in chloroform at 25°C is 0.50-0.51dl/g, Bluestar;
- Polyphenylene ether resin 2 PPE LXR035, the intrinsic viscosity measured by Ubbelohde viscometer in chloroform at 25°C is 0.35-0.36dl/g, Bluestar;
- Polyphenylene ether resin 3 SA9000, the intrinsic viscosity measured by Ubbelohde viscometer in chloroform at 25°C is 0.09-0.12dl/g, Sabic;
- Styrene resin 1 HIPS, PS 350K, commercially available;
- Styrene resin 2 GP1441, commercially available
- Toughening agent 1 ethylene-ethylene/butylene-styrene block copolymer, SEBS 6151, commercially available;
- Toughening agent 2 Polyolefin elastomer, POE DF605, Mitsui Japan;
- Kaolin 1 particle size D50 is 0.2 ⁇ m, commercially available
- Kaolin 2 particle size D50 is 0.4 ⁇ m, commercially available
- Kaolin 3 particle size D50 is 2.0 ⁇ m, commercially available
- Kaolin 4 particle size D50 is 0.15 ⁇ m, commercially available
- Lubricant 1 Linear low density polyethylene, LLDPE DFDA-7042, commercially available;
- Lubricant 2 Silicone lubricant, MB50-002, commercially available;
- the application sets Examples 1 to 13 and Comparative Examples 1 to 3.
- the components, contents and performance data of Examples 1 to 9 are shown in Table 1; the components and contents of Examples 10 to 13 and Comparative Examples 1 to 3 are shown in Table 1. and performance data as shown in Table 2;
- Examples 1 to 4 Comparing Examples 1 to 4, it can be seen that in Examples 1 to 4, except for the different particle sizes of kaolin, the others are the same; wherein, the particle size of kaolin in Example 1 is 0.2 ⁇ m, and the particle size of kaolin in Example 2 is 0.2 ⁇ m. is 0.4 ⁇ m, the particle size of kaolin in Example 3 is 2.0 ⁇ m, and the particle size of kaolin in Example 4 is 0.15 ⁇ m, and the room temperature toughness, -40 °C toughness and appearance evaluation of Examples 1, 2, and 4 are all better than those of the implementation. Example 3, and the performances of Examples 1 and 2 are better;
- Examples 1, 5, and 6 Comparing Examples 1, 5, and 6, it can be seen that in Examples 1, 5, and 6, except for the intrinsic viscosity of the polyphenylene ether resin, the others are the same; wherein, the characteristics of the polyphenylene ether resin in Examples 1, 5 The viscosity is in the range of 0.2-0.8dl/g, the polyphenylene ether resin in Example 6 is not in the above range, and the flexural modulus, normal temperature toughness, -40 °C toughness, and appearance evaluation in Examples 1 and 5 are better than those of the implementation.
- Example 6 wherein the intrinsic viscosity of the polyphenylene ether resin of Example 1 is in the range of 0.4-0.6dl/g, and its various properties are better;
- Example 7 is the same as Example 1 except for the choice of polystyrene resin, and the polystyrene resin in Example 1 is high-impact polystyrene, Its normal temperature toughness and -40 °C toughness are better than Example 7;
- Example 8 is the same as Example 1 except for the selection of the toughening agent, and the toughening agent in Example 1 is styrene-ethylene/butylene-styrene
- the block copolymer, its flexural modulus and -40 °C toughness are better than Example 8;
- Example 9 is the same as Example 1 except for the choice of lubricant.
- the lubricant in Example 1 is linear low density polyethylene, and its flexural modulus, normal temperature
- the toughness, -40°C toughness and appearance evaluation are all better than those of Example 9;
- Comparative Example 10 Comparing Example 10 with Comparative Examples 1 and 2, it can be seen that Comparative Example 1 does not contain kaolin, and Comparative Example 2 does not contain lubricant.
- the toughness of Example 10 is comparable to that of the non-reinforced material in Comparative Example 1, but the flexural modulus is much higher than that of Comparative Example 1.
- the room temperature toughness, -40°C toughness and appearance evaluation of Comparative Example 2 are all worse than those of Example 10;
- Comparing Example 11 with Comparative Example 3 the kaolin content in Comparative Example 3 is not within the scope of the present application, and the room temperature toughness, -40°C toughness, and appearance evaluation in Comparative Example 3 are all inferior to Example 11;
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kaolin-reinforced polyphenylene ether composition, comprising the following components, in parts by weight: 45-80 parts of polyphenylene ether, 0-20 parts of a polystyrene resin, 5-30 parts of kaolin, 3-10 parts of a toughening agent and 0.1-3 parts of a lubricating agent. In the polyphenylene ether composition, by adding the kaolin and the lubricating agent and optimizing the formulation composition and content, the resulting polyphenylene ether composition has an excellent appearance and excellent room- and low-temperature toughness while maintaining the high rigidity of a reinforced material, and is very suited for being used in exterior parts.
Description
本发明涉及工程塑料技术领域，尤其涉及一种高岭土增强聚苯醚组合物及其制备方法与应用。The invention relates to the technical field of engineering plastics, in particular to a kaolin reinforced polyphenylene ether composition and a preparation method and application thereof.
聚苯醚增强材料(简称PPE)由于具有优异的绝缘性能、高刚性和耐热性能，在电器领域、OA等领域得到了广泛使用。但是在聚苯醚加入填料后，由于PPE熔体粘度较高的影响，树脂对填料的浸润效果差，导致PPE的增强类材料表面外观很差。同时由于增强材料的引入，导致PPE材料韧性，尤其是低温韧性很差。聚苯醚增强材料的外观和韧性问题，限制了其在外观制件尤其是户外使用的外观制件的需求。Polyphenylene ether reinforced material (referred to as PPE) has been widely used in the field of electrical appliances, OA and other fields due to its excellent insulating properties, high rigidity and heat resistance. However, after the polyphenylene ether is added to the filler, due to the influence of the high melt viscosity of the PPE, the infiltration effect of the resin on the filler is poor, resulting in poor surface appearance of the reinforced material of PPE. At the same time, due to the introduction of reinforcing materials, the toughness of PPE materials, especially the low temperature toughness, is very poor. The appearance and toughness of polyphenylene ether reinforced materials limit its demand for exterior parts, especially exterior parts used outdoors.
发明内容SUMMARY OF THE INVENTION
基于此，本发明的目的在于克服上述现有技术的不足之处而提供一种高岭土增强聚苯醚组合物。所述组合物在维持增强材料的高刚性的同时，具有优异的外观和常低温韧性。Based on this, the purpose of the present invention is to overcome the shortcomings of the prior art and provide a kaolin reinforced polyphenylene ether composition. The composition has excellent appearance and normal low temperature toughness while maintaining the high rigidity of the reinforcing material.
为实现上述目的，本发明所采取的技术方案为：一种高岭土增强聚苯醚组合物，包括如下重量份的成分：聚苯醚45-80份、聚苯乙烯类树脂0-20份、高岭土5-30份、增韧剂3-10份和润滑剂0.1-3份。In order to achieve the above purpose, the technical scheme adopted in the present invention is: a kaolin reinforced polyphenylene ether composition, comprising the following components by weight: 45-80 parts of polyphenylene ether, 0-20 parts of polystyrene resin, kaolin clay 5-30 parts, toughening agent 3-10 parts and lubricant 0.1-3 parts.
优选地，所述的高岭土增强聚苯醚组合物，包括如下重量份的成分：聚苯醚55-75份、聚苯乙烯类树脂2-10份、高岭土15-25份、增韧剂4-8份和润滑剂1-2份。Preferably, the kaolin reinforced polyphenylene ether composition includes the following components by weight: 55-75 parts of polyphenylene ether, 2-10 parts of polystyrene resin, 15-25 parts of kaolin, and 4- 8 parts and 1-2 parts lubricant.
优选地，所述高岭土的粒径D50为0.1-1.0μm。在本申请增强聚苯醚组合物中，加入高岭土可以很好的提高材料的刚性；高岭土的粒径选择对这一增强效果影响很大，粒径过大会造成外观不良和韧性下降，粒径过小不易加工，且刚性提供有限。Preferably, the particle size D50 of the kaolin is 0.1-1.0 μm. In the reinforced polyphenylene ether composition of the present application, adding kaolin can well improve the rigidity of the material; the selection of the particle size of kaolin has a great influence on this reinforcement effect. Small is not easy to machine and provides limited rigidity.
更优选地，所述高岭土的粒径D50为0.2-0.4μm。More preferably, the particle size D50 of the kaolin is 0.2-0.4 μm.
优选地，所述聚苯醚在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.2-0.8dl/g；更优选地，所述聚苯醚在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.4-0.6dl/g。Preferably, the intrinsic viscosity of the polyphenylene ether measured by an Ubbelohde viscometer in chloroform at 25°C is 0.2-0.8 dl/g; more preferably, the polyphenylene ether is measured by an Ubbelohde viscometer in chloroform at 25°C. The intrinsic viscosity of 0.4-0.6dl/g.
所述聚苯醚可以使用一种单独特性粘度的聚苯醚树脂，也可以选用几种不同特性粘度聚苯醚树脂的复合物。本申请上述优选的聚苯醚树脂具有更加优异的流动性与综合性能。The polyphenylene ether can use a single polyphenylene ether resin with intrinsic viscosity, or a compound of several polyphenylene ether resins with different intrinsic viscosity can be selected. The above-mentioned preferred polyphenylene ether resin in the present application has more excellent fluidity and comprehensive properties.
优选地，所述聚苯乙烯类树脂为苯乙烯类单体的聚合物、苯乙烯类单体与其他共聚单体的共聚物、苯乙烯类接枝共聚物、苯乙烯类共聚物弹性体中的至少一种。聚苯乙烯类树脂可以降低PPE树脂的粘度，进一步提高注塑过程中材料的填料的浸润，提高表观质量。Preferably, the polystyrene-based resin is a polymer of styrene-based monomer, a copolymer of styrene-based monomer and other comonomers, a styrene-based graft copolymer, and a styrene-based copolymer elastomer. at least one of. The polystyrene resin can reduce the viscosity of the PPE resin, further improve the infiltration of the filler of the material during the injection molding process, and improve the apparent quality.
更优选地，所述聚苯乙烯类树脂为高抗冲聚苯乙烯(HIPS)。More preferably, the polystyrene-based resin is high impact polystyrene (HIPS).
优选地，所述增韧剂为乙丙橡胶、丁腈橡胶、顺丁橡胶、乙烯醋酸乙烯共聚物、聚烯烃弹性体、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物、苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物中的至少一种；更优选地，所述增韧剂为苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。Preferably, the toughening agent is ethylene propylene rubber, nitrile rubber, butadiene rubber, ethylene vinyl acetate copolymer, polyolefin elastomer, styrene-butadiene-styrene block copolymer, styrene-ethylene At least one of /butylene-styrene block copolymer and styrene-ethylene/propylene-styrene block copolymer; more preferably, the toughening agent is styrene-ethylene/butylene-styrene block copolymer.
优选地，所述润滑剂为烯烃类润滑剂、硅酮类润滑剂中的一种。Preferably, the lubricant is one of olefin-based lubricants and silicone-based lubricants.
更优选地，所述润滑剂为线性低密度聚乙烯，其可以很好地增强材料的外观光泽度，提高产品外观。More preferably, the lubricant is linear low density polyethylene, which can well enhance the appearance gloss of the material and improve the appearance of the product.
此外，本发明的聚苯醚组合物中还可以进一步含有其它的添加剂，如增塑剂、稳定剂、脱模剂、阻燃剂、染料、颜料和其它赋予其它特性的树脂，只要不损害本发明的效果即可，具体本领域技术人员可以根据实际需要进行常规选择。In addition, the polyphenylene ether composition of the present invention may further contain other additives, such as plasticizers, stabilizers, mold release agents, flame retardants, dyes, pigments and other resins that impart other properties, as long as the present invention is not damaged. The effect of the invention is sufficient, and those skilled in the art can make routine selections according to actual needs.
同时，本发明还提供一种所述的高岭土增强聚苯醚组合物的制备方法，所述方法为：将各成分经过高速混合机混合分散后，得到混合料，然后将混合料 通过双螺杆挤出机进行挤出造粒，得到所述高岭土增强聚苯醚组合物。At the same time, the present invention also provides a method for preparing the kaolin reinforced polyphenylene ether composition. The method is as follows: after mixing and dispersing the components through a high-speed mixer, a mixture is obtained, and then the mixture is extruded through a twin-screw. The kaolin reinforced polyphenylene ether composition is obtained by extruding and granulating from the machine.
进一步地，本发明还公开一种所述的高岭土增强聚苯醚组合物在外观制件中的应用。Further, the present invention also discloses the application of the kaolin reinforced polyphenylene ether composition in appearance parts.
相对于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本发明聚苯醚组合物中，通过高岭土和润滑剂的添加、配方组成及含量的优化，得到的聚苯醚组合物，在维持增强材料的高刚性的同时，具有优异的外观和常低温韧性，十分适用于在外观制件中使用。In the polyphenylene ether composition of the present invention, through the addition of kaolin and lubricant, and optimization of the formulation composition and content, the obtained polyphenylene ether composition has excellent appearance and normal low temperature toughness while maintaining the high rigidity of the reinforcing material. , very suitable for use in appearance parts.
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。以下实施例只是本发明的典型例，本发明的保护范围并不局限于此。本发明高岭土增强聚苯醚组合物的制备方法，其步骤是：先将聚苯醚树脂、苯乙烯类树脂、增韧剂、高岭土、润滑剂按照配方比例经过高速混合机分散后，通过双螺杆挤出造粒；其中，挤出工艺为：转速400rpm，喂料450kg/h；挤出温度为265℃左右。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments. The following embodiments are only typical examples of the present invention, and the protection scope of the present invention is not limited thereto. The preparation method of the kaolin reinforced polyphenylene ether composition of the present invention comprises the following steps: firstly dispersing the polyphenylene ether resin, styrene resin, toughening agent, kaolin, and lubricant in a high-speed mixer according to the formula proportion, and then dispersing them through a twin screw Extrusion and granulation; wherein, the extrusion process is: the rotation speed is 400rpm, the feeding is 450kg/h; the extrusion temperature is about 265°C.
以下实施例和对比例中，各性能测试标准及方法如下：In the following examples and comparative examples, each performance test standard and method are as follows:
弯曲模量：按照标准ISO 178:2019进行测试，弯曲速率为2mm/min；Flexural modulus: tested according to standard ISO 178:2019, the bending rate is 2mm/min;
常低温韧性评价：测试-40℃和23℃下的缺口冲击强度：按照标准GB/T1843-2006进行测试；Normal and low temperature toughness evaluation: test the notched impact strength at -40°C and 23°C: test according to the standard GB/T1843-2006;
外观评价：主要通过注塑成样板，观察样品表面的光泽度和填料析出情况来进行判断；按照如下标准分为三级，分级如下：Appearance evaluation: It is mainly judged by injection molding into a sample plate and observing the gloss of the surface of the sample and the precipitation of filler; it is divided into three grades according to the following standards, and the classification is as follows:
1级：无填料在表面、并且表面光泽度高；Level 1: No filler on the surface, and the surface gloss is high;
2级：无填料在表面，表面光泽度一般；Level 2: No filler on the surface, the surface gloss is average;
3级：有填料在表面。Grade 3: There is filler on the surface.
实施例和对比例中用到的材料如下：The materials used in the examples and comparative examples are as follows:
聚苯醚树脂Polyphenylene ether resin
聚苯醚树脂1：PPE LXR050，在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.50-0.51dl/g，蓝星；Polyphenylene ether resin 1: PPE LXR050, the intrinsic viscosity measured by Ubbelohde viscometer in chloroform at 25°C is 0.50-0.51dl/g, Bluestar;
聚苯醚树脂2：PPE LXR035，在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.35-0.36dl/g，蓝星；Polyphenylene ether resin 2: PPE LXR035, the intrinsic viscosity measured by Ubbelohde viscometer in chloroform at 25°C is 0.35-0.36dl/g, Bluestar;
聚苯醚树脂3：SA9000，在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.09-0.12dl/g，沙比克；Polyphenylene ether resin 3: SA9000, the intrinsic viscosity measured by Ubbelohde viscometer in chloroform at 25°C is 0.09-0.12dl/g, Sabic;
苯乙烯类树脂：Styrene resin:
苯乙烯类树脂1：HIPS，PS 350K，市售；Styrene resin 1: HIPS, PS 350K, commercially available;
苯乙烯类树脂2：GP1441，市售；Styrene resin 2: GP1441, commercially available;
增韧剂：Toughening agent:
增韧剂1：乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，SEBS 6151，市售；Toughening agent 1: ethylene-ethylene/butylene-styrene block copolymer, SEBS 6151, commercially available;
增韧剂2：聚烯烃弹性体，POE DF605，日本三井；Toughening agent 2: Polyolefin elastomer, POE DF605, Mitsui Japan;
高岭土：Kaolin:
高岭土1：粒径D50为0.2μm，市售；Kaolin 1: particle size D50 is 0.2 μm, commercially available;
高岭土2：粒径D50为0.4μm，市售；Kaolin 2: particle size D50 is 0.4 μm, commercially available;
高岭土3：粒径D50为2.0μm，市售；Kaolin 3: particle size D50 is 2.0 μm, commercially available;
高岭土4：粒径D50为0.15μm，市售；Kaolin 4: particle size D50 is 0.15 μm, commercially available;
润滑剂：Lubricant:
润滑剂1：线性低密度聚乙烯，LLDPE DFDA-7042，市售；Lubricant 1: Linear low density polyethylene, LLDPE DFDA-7042, commercially available;
润滑剂2：硅酮类润滑剂，MB50-002，市售；Lubricant 2: Silicone lubricant, MB50-002, commercially available;
本申请设置实施例1～13及对比例1～3，实施例1～9中各成分、含量及性能数据如表1所示；实施例10～13及对比例1～3的各成分、含量及性能数据如表2所示；The application sets Examples 1 to 13 and Comparative Examples 1 to 3. The components, contents and performance data of Examples 1 to 9 are shown in Table 1; the components and contents of Examples 10 to 13 and Comparative Examples 1 to 3 are shown in Table 1. and performance data as shown in Table 2;
表1实施例1～9中的成分、含量及性能数据Table 1 Composition, content and performance data in Examples 1 to 9
表2实施例10～13及对比例1～3的成分、含量及性能数据Table 2 Composition, content and performance data of Examples 10-13 and Comparative Examples 1-3
将实施例1～4进行对比可知，实施例1～4中除高岭土的粒径不同外，其他均相同；其中，实施例1中高岭土的粒径为0.2μm，实施例2中高岭土的粒径为0.4μm，实施例3中高岭土的粒径为2.0μm，实施例4中高岭土的粒径为0.15μm，实施例1、2、4的常温韧性、-40℃韧性、外观评价均优于实施例3，且实施例1、2的各项性能更好；Comparing Examples 1 to 4, it can be seen that in Examples 1 to 4, except for the different particle sizes of kaolin, the others are the same; wherein, the particle size of kaolin in Example 1 is 0.2 μm, and the particle size of kaolin in Example 2 is 0.2 μm. is 0.4 μm, the particle size of kaolin in Example 3 is 2.0 μm, and the particle size of kaolin in Example 4 is 0.15 μm, and the room temperature toughness, -40 ℃ toughness and appearance evaluation of Examples 1, 2, and 4 are all better than those of the implementation. Example 3, and the performances of Examples 1 and 2 are better;
将实施例1、5、6进行对比可知，实施例1、5、6中除聚苯醚树脂的特性粘度不同外，其他均相同；其中，实施例1、5中的聚苯醚树脂的特性粘度在0.2-0.8dl/g范围内，实施例6中的聚苯醚树脂不在上述范围内，实施例1、5中的弯曲模量、常温韧性、-40℃韧性、外观评价均优于实施例6，其中实施例1的聚苯醚树脂的特性粘度在0.4-0.6dl/g范围内，其各项性能更好；Comparing Examples 1, 5, and 6, it can be seen that in Examples 1, 5, and 6, except for the intrinsic viscosity of the polyphenylene ether resin, the others are the same; wherein, the characteristics of the polyphenylene ether resin in Examples 1, 5 The viscosity is in the range of 0.2-0.8dl/g, the polyphenylene ether resin in Example 6 is not in the above range, and the flexural modulus, normal temperature toughness, -40 ℃ toughness, and appearance evaluation in Examples 1 and 5 are better than those of the implementation. Example 6, wherein the intrinsic viscosity of the polyphenylene ether resin of Example 1 is in the range of 0.4-0.6dl/g, and its various properties are better;
将实施例1与实施例7对比可知，实施例7除聚苯乙烯类树脂的选择不同外，其他均与实施例1相同，实施例1中聚苯乙烯类树脂为高抗冲聚苯乙烯，其常温韧性、-40℃韧性均优于实施例7；Comparing Example 1 with Example 7, it can be seen that Example 7 is the same as Example 1 except for the choice of polystyrene resin, and the polystyrene resin in Example 1 is high-impact polystyrene, Its normal temperature toughness and -40 ℃ toughness are better than Example 7;
将实施例1与实施例8对比可知，实施例8除增韧剂的选择不同外，其他均与实施例1相同，实施例1中的增韧剂为苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，其弯曲模量、-40℃韧性均优于实施例8；Comparing Example 1 with Example 8, it can be seen that Example 8 is the same as Example 1 except for the selection of the toughening agent, and the toughening agent in Example 1 is styrene-ethylene/butylene-styrene The block copolymer, its flexural modulus and -40 ℃ toughness are better than Example 8;
将实施例1与实施例9对比可知，实施例9除润滑剂的选择不同外，其他均与实施例1相同，实施例1中的润滑剂为线性低密度聚乙烯，其弯曲模量、常温韧性、-40℃韧性、外观评价均优于实施例9；Comparing Example 1 with Example 9, it can be seen that Example 9 is the same as Example 1 except for the choice of lubricant. The lubricant in Example 1 is linear low density polyethylene, and its flexural modulus, normal temperature The toughness, -40°C toughness and appearance evaluation are all better than those of Example 9;
将实施例10与对比例1、2对比可知，对比例1中不含有高岭土，对比例2中不含有润滑剂。实施例10的韧性和对比例1非增强材料相当，但是弯曲模量远远高于对比例1，对比例2的常温韧性、-40℃韧性、外观评价均差于实施例10；Comparing Example 10 with Comparative Examples 1 and 2, it can be seen that Comparative Example 1 does not contain kaolin, and Comparative Example 2 does not contain lubricant. The toughness of Example 10 is comparable to that of the non-reinforced material in Comparative Example 1, but the flexural modulus is much higher than that of Comparative Example 1. The room temperature toughness, -40°C toughness and appearance evaluation of Comparative Example 2 are all worse than those of Example 10;
将实施例11与对比例3相比，对比例3中的高岭土含量不在本申请范围内，对比例3中的常温韧性、-40℃韧性、外观评价均差于实施例11；Comparing Example 11 with Comparative Example 3, the kaolin content in Comparative Example 3 is not within the scope of the present application, and the room temperature toughness, -40°C toughness, and appearance evaluation in Comparative Example 3 are all inferior to Example 11;
将实施例10、11与实施例12、13对比可知，实施例10、11中满足“聚苯醚55-75份、聚苯乙烯类树脂2-10份、高岭土15-25份、增韧剂4-8份和润滑剂1-2份”，实施例10、11中的常温韧性、-40℃韧性、外观评价优于实施例12、13。Comparing Examples 10 and 11 with Examples 12 and 13, it can be seen that in Examples 10 and 11, "55-75 parts of polyphenylene ether, 2-10 parts of polystyrene resin, 15-25 parts of kaolin, and toughening agent are satisfied. 4-8 parts and 1-2 parts of lubricant", the room temperature toughness, -40°C toughness and appearance evaluation in Examples 10 and 11 are better than those in Examples 12 and 13.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的 普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.
Claims (11)
- 一种高岭土增强聚苯醚组合物，其特征在于，包括如下重量份的成分：聚苯醚45-80份、聚苯乙烯类树脂0-20份、高岭土5-30份、增韧剂3-10份和润滑剂0.1-3份。A kaolin reinforced polyphenylene ether composition, comprising the following components by weight: 45-80 parts of polyphenylene ether, 0-20 parts of polystyrene resin, 5-30 parts of kaolin, and 3-30 parts of toughening agent. 10 parts and lubricant 0.1-3 parts.
- 如权利要求1所述的高岭土增强聚苯醚组合物，其特征在于，包括如下重量份的成分：聚苯醚55-75份、聚苯乙烯类树脂2-10份、高岭土15-25份、增韧剂4-8份和润滑剂1-2份。The kaolin reinforced polyphenylene ether composition according to claim 1, characterized in that it comprises the following components by weight: 55-75 parts of polyphenylene ether, 2-10 parts of polystyrene resin, 15-25 parts of kaolin, 4-8 parts of toughening agent and 1-2 parts of lubricant.
- 如权利要求1所述的高岭土增强聚苯醚组合物，其特征在于，所述高岭土的粒径D50为0.1-1.0μm。The kaolin reinforced polyphenylene ether composition according to claim 1, wherein the particle size D50 of the kaolin is 0.1-1.0 μm.
- 如权利要求3所述的高岭土增强聚苯醚组合物，其特征在于，所述高岭土的粒径D50为0.2-0.4μm。The kaolin reinforced polyphenylene ether composition according to claim 3, wherein the particle size D50 of the kaolin is 0.2-0.4 μm.
- 如权利要求1所述的高岭土增强聚苯醚组合物，其特征在于，所述聚苯醚在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.2-0.8dl/g；优选地，所述聚苯醚在25℃氯仿中采用乌氏粘度计测定的特性粘度为0.4-0.6dl/g。The kaolin reinforced polyphenylene ether composition according to claim 1, wherein the intrinsic viscosity of the polyphenylene ether measured by an Ubbelohde viscometer in chloroform at 25°C is 0.2-0.8 dl/g; preferably, the The intrinsic viscosity of the polyphenylene ether measured by an Ubbelohde viscometer in chloroform at 25° C. is 0.4-0.6 dl/g.
- 如权利要求1所述的高岭土增强聚苯醚组合物，其特征在于，所述聚苯乙烯类树脂为高抗冲聚苯乙烯。The kaolin reinforced polyphenylene ether composition according to claim 1, wherein the polystyrene resin is high impact polystyrene.
- 如权利要求1所述的高岭土增强聚苯醚组合物，其特征在于，所述增韧剂为乙丙橡胶、丁腈橡胶、顺丁橡胶、乙烯醋酸乙烯共聚物、聚烯烃弹性体、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物、苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物中的至少一种；优选地，所述增韧剂为苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。The kaolin reinforced polyphenylene ether composition according to claim 1, wherein the toughening agent is ethylene propylene rubber, nitrile rubber, butadiene rubber, ethylene vinyl acetate copolymer, polyolefin elastomer, styrene - at least one of butadiene-styrene block copolymer, styrene-ethylene/butylene-styrene block copolymer, and styrene-ethylene/propylene-styrene block copolymer; preferably, the The toughening agent is a styrene-ethylene/butylene-styrene block copolymer.
- 如权利要求1所述的高岭土增强聚苯醚组合物，其特征在于，所述润滑剂为烯烃类润滑剂、硅酮类润滑剂中的一种。The kaolin reinforced polyphenylene ether composition according to claim 1, wherein the lubricant is one of an olefin-based lubricant and a silicone-based lubricant.
- 如权利要求8所述的高岭土增强聚苯醚组合物，其特征在于，所述润滑剂为线性低密度聚乙烯。The kaolin reinforced polyphenylene ether composition according to claim 8, wherein the lubricant is linear low density polyethylene.
- 如权利要求1～9任一项所述的高岭土增强聚苯醚组合物的制备方法，其特征在于，所述方法为：将各成分经过高速混合机混合分散后，得到混合料，然后将混合料通过双螺杆挤出机进行挤出造粒，得到所述高岭土增强聚苯醚组合物。The method for preparing a kaolin reinforced polyphenylene ether composition according to any one of claims 1 to 9, wherein the method is as follows: after mixing and dispersing each component by a high-speed mixer, a mixture is obtained, and then mixing The material is extruded and pelletized through a twin-screw extruder to obtain the kaolin reinforced polyphenylene ether composition.
- 如权利要求1～9任一项所述的高岭土增强聚苯醚组合物在外观制件中的应用。Application of the kaolin reinforced polyphenylene ether composition according to any one of claims 1 to 9 in an appearance article.
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| US4166812A (en) * | 1977-09-30 | 1979-09-04 | General Electric Company | Filled compositions of a polyphenylene ether resin and rubber-modified alkenyl aromatic resins |
| WO2010134608A1 (en) * | 2009-05-22 | 2010-11-25 | 旭化成ケミカルズ株式会社 | Automobile lamp accessory |
| CN103709719A (en) * | 2009-05-22 | 2014-04-09 | 旭化成化学株式会社 | Automobile lamp accessory |
| CN106800740A (en) * | 2017-02-13 | 2017-06-06 | 肇庆汇展塑料科技有限公司 | A kind of preparation method of shock resistance engineering plastics |
| CN110343381A (en) * | 2019-07-09 | 2019-10-18 | 合肥邦联新材料有限责任公司 | A kind of flame-resistant polyphenylether material |
| CN112480646A (en) * | 2020-11-30 | 2021-03-12 | 金发科技股份有限公司 | Kaolin reinforced polyphenyl ether composition and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480646A (en) | 2021-03-12 |
| CN112480646B (en) | 2022-05-10 |
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