WO2021227201A1 - Use of multi-element random copolymer in improving phase state structure and phase state stability of polyester/styrenic resin alloy - Google Patents

Use of multi-element random copolymer in improving phase state structure and phase state stability of polyester/styrenic resin alloy Download PDF

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WO2021227201A1
WO2021227201A1 PCT/CN2020/097305 CN2020097305W WO2021227201A1 WO 2021227201 A1 WO2021227201 A1 WO 2021227201A1 CN 2020097305 W CN2020097305 W CN 2020097305W WO 2021227201 A1 WO2021227201 A1 WO 2021227201A1
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monomer
polyester
styrene resin
acrylonitrile
aromatic vinyl
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PCT/CN2020/097305
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French (fr)
Chinese (zh)
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段浩
朱从山
司胜仁
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佳易容聚合物(上海)有限公司
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Priority to KR1020227043721A priority Critical patent/KR20230009980A/en
Publication of WO2021227201A1 publication Critical patent/WO2021227201A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to a special compatibilizer for improving the phase distribution and stability of a polyester/styrene resin alloy and its application.
  • PC/ABS alloys because they have the comprehensive characteristics of both PC and ABS, they have improved fluidity compared to PC. It improves the processing performance and reduces the sensitivity of the product to stress. Compared with ABS, it has better thermal stability. Therefore, it can be used in many fields such as household appliances, office equipment, communication equipment, photographic equipment, medical equipment, construction and lighting appliances, aerospace, electronic computers, optical fiber and so on. In particular, it has been widely used in high-strength and high-heat-resistant parts such as automotive interiors, exteriors, and lights.
  • PET polyethylene terephthalate
  • R-PET PET recycled material
  • ABS and PET can produce alloys with excellent performance, which has the advantages of both ABS and PET, which not only broadens the application field of recycled materials, but also overcomes some inherent performance defects of ABS and reduces the price. It is a very promising one. Such materials have been widely used in home appliances such as televisions, and OA products such as printers and copiers.
  • polyester/styrene resin alloys are relatively high, and the solubility parameters of polyester and styrene resins are quite different, which is prone to phase separation.
  • compatibility of PC/ABS is good, the ester group of PC is also easy to be degraded by the attack of active groups such as hydroxyl under the condition of long thermal history or strong shear, so it can be degraded during processing or recycling. It is easy to re-aggregate the dispersed phase; currently, to solve the compatibility problem of polyester/styrene resin is generally to add a compatibilizer.
  • Common and reported in the literature are: isocyanate, oxazoline, epoxy and acid anhydride compatibilizers.
  • the purpose of the present invention is and its preparation method. Compared with the prior art, the method has the advantages of simplicity and effectiveness, convenient use, low cost and the like.
  • the polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer.
  • the preparation method of the above-mentioned polyester/styrene resin alloy with phase distribution structure and phase stability is to put the polyester, styrene resin, compatibilizer, and auxiliary agent into a high-mixer, and then discharge the material. , And then extrude and pelletize with a screw extruder to obtain a polyester/styrene resin alloy with phase distribution structure and phase stability.
  • the processing temperature is 220-260°C
  • the screw speed is 180-600 rpm
  • the speed of the high mixer is 2000 rpm
  • the aspect ratio of the twin-screw extruder is between 34-40.
  • the multi-element random copolymer is used as a compatibilizer to prepare the polyester/styrene resin alloy; or used to improve the phase structure and phase stability of the polyester/styrene resin alloy.
  • the multi-element random copolymer as a compatibilizer is made by the copolymerization of aromatic vinyl monomers, acrylonitrile-based monomers and methacrylate monomers; among the aromatic vinyl monomers and acrylonitrile-based monomers, aromatic The weight percentage of vinyl monomer is 50wt% ⁇ 90wt%, the balance is acrylonitrile monomer; the amount of methacrylate monomer is 0.1% ⁇ of the total weight of aromatic vinyl monomer and acrylonitrile monomer. 15%.
  • the weight percentage of the aromatic vinyl monomer is 60 wt% to 80 wt%, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer It is 0.1% to 10% of the total weight of the aromatic vinyl monomer and acrylonitrile monomer, preferably 0.2% to 2%.
  • the multi-element random copolymer of the present invention is added as a compatibilizer to the polyester/styrene resin alloy to improve the phase distribution and phase stability of the alloy.
  • the weight percentage of the compatibilizer is 0.5-15% of the total weight of polyester, styrene resin, and compatibilizer.
  • the special compatibilizer for polyester/styrene resin alloy of the present invention can be prepared by blending with other raw materials and extruding granulation during the preparation process to achieve simple, effective, convenient use, and low-cost preparation. In addition to its mechanical properties, it also has a polyester/styrene resin alloy with excellent phase distribution structure and phase stability.
  • the auxiliary agent is a conventional choice.
  • the auxiliary agent is an antioxidant and/or a lubricant.
  • the auxiliary agent does not include a compatibilizer and a conductive agent.
  • the amount of the auxiliary agent is added according to the actual situation, such as an antioxidant 0.1-1wt. %, the lubricant is 0.1-0.5wt%, based on the weight sum of polyester, styrene resin and compatibilizer.
  • the weight percentage of the polyester is 30-90%
  • the weight percentage of the compatibilizer is 0.5-15%
  • the balance is styrene resin.
  • the polyester may be one of polycarbonate, polyethylene terephthalate, and polybutylene terephthalate; the styrenic resin is ABS, SAN, ASA One or more of AES can be either the bulk method or the emulsion method.
  • the weight average molecular weight of the multi-element random copolymer is 20000-100000, and the melt index at 235°C/2.16kg is 30-120g/10min.
  • the aromatic vinyl monomer includes styrenic monomers, such as styrene monomer, ⁇ -methylstyrene monomer, ⁇ -chlorostyrene monomer or p-methylstyrene monomer
  • the acrylonitrile monomer includes acrylonitrile monomer or ⁇ -methacrylonitrile monomer; the methacrylate may be one or more of methyl methacrylate and glycidyl methacrylate.
  • a multi-element random copolymer is used as a compatibilizer, in which the GMA content is 0.1wt%-10wt%, preferably 0.2wt%-2wt%, which can maximize the mechanical properties of polyester/styrene resin materials , Improve the phase structure and phase stability of polyester/styrene resin.
  • the present invention has the following beneficial effects.
  • the compatibilizer of the present invention has good thermal stability in co-extrusion with polymer, does not cause problems such as precipitation or difficulty in migrating to the interface to reduce the reactivity, the content of reactive functional groups is appropriate, and it is easy to control the occurrence of black spots or gel phenomena; and Styrene resins are completely thermodynamically compatible, and there is no problem of phase separation. Moreover, it is convenient to use, does not require masterbatch, and there is no secondary pollution; the multi-element random copolymer of the present invention has high reactivity, high use efficiency, and the use cost is one-third to two-half lower than similar products on the market First, it has an excellent price/performance ratio. Wide range of uses: It also provides a suitable simple method for improving the phase structure and taking into account the mechanical properties of the recycled polyester/styrene resin.
  • Figure 1 is a comparison of scanning electron micrographs of the alloys prepared in Examples 5-8.
  • Fig. 2 is a comparison of multi-axis impact of Example 5 and Example 8.
  • Figure 3 is a comparison of the phase stability (TEM) between the near gate and the far gate of the injection molded parts of Example 5 and Example 6.
  • Figure 4 is a comparison of the impact performance of the injection molded parts of Example 5 and Example 6 between the near gate and the far gate.
  • Figure 5 is a comparison of the phase stability of Example 5 and Example 3 after multiple extrusions.
  • Fig. 6 is a comparison diagram of the microscopic appearance diagrams of Examples 9-13.
  • the invention discloses a multi-element random copolymer as a compatibilizer by copolymerization of aromatic vinyl monomers, acrylonitrile monomers and methacrylate monomers; the specific preparation method can be selected according to the prior art, as follows.
  • the preparation of the compatibilizer in the following examples can be carried out according to this, and the addition of raw materials can be adjusted in proportion.
  • the polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer.
  • the auxiliary agent is a conventional choice, for example, the auxiliary agent is an antioxidant and/or a lubricant.
  • Example 1-4 According to the raw material composition ratio in Table 1, a special compatibilizer for improving the phase distribution and stability of polyester/styrene resin alloy was prepared. Examples 1-4, 14 and Comparative Example 1 -2 (The preparation method is the same as the embodiment, and the addition is adjusted regularly). And these compatibilizers are used to prepare polyester/styrene resin alloys to study the improvement of the phase state and phase stability of such alloys.
  • Example 5-9 PC resin is selected from Teijin Corporation’s PCI250WP (relative number average molecular weight is 22000g/mol, glass transition temperature is 140°C); ABS resin is selected from Korea’s Kumho Petrochemical’s P/D190 (relative weight average molecular weight is 120,000 g/mol, wherein the butadiene weight percentage content is 50%, the acrylonitrile weight percentage content is 15%, and the styrene weight percentage content is 35%.
  • the processing temperature is 220 ⁇ 260°C, and the screw speed is 300 rpm; high-mixer
  • the speed of the twin-screw extruder is 2000rpm, and the aspect ratio of the twin-screw extruder is 36.
  • Example 2 and Comparative Examples 1 and 2 are relatively blank samples without compatibilizer can improve the phase structure, but in comparison, in the case of the same composition, the PC/ABS with Example 2 as the compatibilizer has A finer dispersed phase structure. Combined with the mechanical properties data in Table 3, a better phase structure also means better mechanical properties, especially impact strength. Although the components of Examples 7 and 8 have higher rubber components, the results show that Example 5 The impact performance is better, which is mainly due to the optimization of the phase structure.
  • Example 3 was used to replace Example 2 in Example 5, and the rest remained unchanged.
  • the resulting sheet material (Example 15) had a cantilever beam impact strength of 748J/m;
  • Example 1 was used to replace Example 2 in Example 5.
  • the rest remains unchanged, and the obtained sheet cantilever beam impact strength is 808J/m, which has decreased.
  • the optimization of the phase state of the present invention in addition to showing advantages in conventional mechanical properties, can also have special effects in some special applications.
  • Figure 2 The results of multi-axis impact show the destructiveness of impact, which is more specific. The conventional impact performance is high, but the multi-axis impact performance is not necessarily good. It can be seen that the performance advantages of the present invention are obvious.
  • ASTM In D1709 due to the change of the phase structure, there is an essential difference.
  • the sample of Example 5 using Example 2 as a compatibilizer shows better passability, while Examples 6-8 respectively show A certain degree of failure occurs.
  • Example 8 the total energy of Example 8 is 52.2J, all brittleness, the total energy of Example 7 is 55.3J, 50% toughness, the total energy of Example 6 is 54.8J, 70% toughness, and the total energy of Example 5 is 56.4 J. 100% toughness; this difference allows PC/ABS alloy to be used in higher-level safety protection materials.
  • Example 5 and 6 are different. Combined with the scanning electron microscope of Figure 3, the injection molded parts of Example 5 and Example 6 were sampled at the near gate position and the far gate position, respectively, and then subjected to transmission electron microscopy analysis after slicing. Phase structure to observe its phase stability. In order to illustrate the influence of the compatibilizer of the present invention on the stability of the alloy phase distribution, conventional injection molding with a large mold was used to prepare injection molded parts with a length of 30 cm and a width of the standard width of the notched impact spline.
  • the special compatibilizer for improving the phase distribution and stability of the polyester/styrene resin alloy disclosed in the present invention has a more efficient performance.
  • the phase stability is compared with repeated extrusion and granulation. That is, after the first extruding and granulating with the screw extruder, the particles are put into the extruder again, and the granulation is continued, which is a secondary extrusion. Such a cycle. The particles obtained from different extrusion times are injected according to the same conventional method as mentioned above. The transmission electron microscope TEM of the alloy sheet can be seen from the figure.
  • Example 3 After multiple extrusion processing, due to multiple heat-shearing history, the phase state of Example 3 has a certain degree of disperse phase aggregation, while that of Example 5 It still maintains a better phase structure, and therefore performs better in terms of mechanical properties. See Table 4, which is the sheet test after the particles are conventionally injected. The test method is as above.
  • Embodiment 9 ⁇ 12 PET resin selected commercial embodiment Bottle regrind (intrinsic viscosity 0.65); ABS resin selected Korea Kumho Petrochemical P / D190 (a relative weight average molecular weight of 120000g / mol, wherein the percentage by weight of butadiene 50%, 15% by weight of acrylonitrile and 35% by weight of styrene) and Taiwan Chemical’s SAN resin NF2200 (relative weight average molecular weight is about 120,000g/mol, of which 24% by weight of acrylonitrile, benzene The ethylene weight percentage content is 76%).
  • the processing temperature is 220 ⁇ 260°C, and the screw speed is 500 rpm; high-mixer
  • the speed of the twin-screw extruder is 2000rpm, and the aspect ratio of the twin-screw extruder is 36.
  • the particles prepared according to Examples 9 to 13 were conventionally injection molded into sheets and then subjected to microscopic morphology observation and mechanical property testing.
  • the cross-sectional SEM morphology is shown in Figure 6. It can be seen from Figure 6 that the phase state of Examples 9-11 is better than that of Examples 12 and 13, which is related to the structure of the selected compatibilizer, and compares the two of Example 2 and Comparative Example 1 in the PC/ABS system. The results of a compatibilizer are similar.
  • Example 13 is the worst.
  • the uniformity of the phase state of Example 12 is acceptable, but the particle size of the dispersed phase is too large, and the compatibilizer used also has GMA functional groups. This result may be related to the MMA in the structure.
  • the existence of MMA affects GMA The reaction activity, which leads to the difference in phase state.
  • Table 6 shows the mechanical performance test data, and the test method is as above.
  • the obtained sheet notched impact strength (1/8 inch) is 178J/m; replace Example 2 in Example 10 of the present invention with the compatibilizer prepared in Example 4 of the existing CN105462149A, and the rest remain unchanged, the resulting sheet notched impact strength (1/8 inch) is 141J/m; replacing Example 2 in Example 10 of the present invention with the existing ADR-4370 compatibilizer, and the rest remain unchanged, the obtained sheet notched impact strength (1/8 inch) is 152J/m.
  • the method of the present invention is simple and easy to implement.
  • a multi-element random copolymer of the present invention as a compatibilizer, adding a suitable ratio and selecting a suitable functional group content, the polyester/styrene resin can be effectively improved.
  • the mechanical properties of the material increase the phase structure of the polyester/styrene resin and the phase stability during processing. This is because the multi-element random copolymer of the present invention makes the dispersed phase particle size finer, smaller shape change, and more evenly distributed through chemical reaction, so that the alloy material can absorb more energy when subjected to external force, showing In order to increase the impact strength, the sensitivity to the notch decreases and other performance advantages.
  • Multi-element random copolymers can be directly mixed with polyester and styrene resins without masterbatch, easy to use, and low addition. It is a method to obtain high-performance polyester/styrene resin alloys.

Abstract

The use of a multi-element random copolymer in improving the phase state structure and phase state stability of a polyester/styrene resin alloy or the use of the multi-element random copolymer in preparing the polyester/styrene resin alloy. The multi-element random copolymer is formed by copolymerizing an aromatic vinyl monomer, an acrylonitrile monomer and a glycidyl methacrylate. As a special compatibilizer for polyester/styrene resin alloys, the copolymer can be blended with other raw materials, and extruded and granulated, such that a polyester/styrene resin alloy with an excellent phase state structure and phase state stability can be prepared simply, effectively, conveniently and cost-effectively. While maintaining excellent mechanical properties, such an alloy has special effects such as repeatable processing, an excellent multiaxial impact resistance, and a low notch sensitivity, which are all due to the phase state stability, and the application fields of such an alloy can thus be broadened.

Description

多元无规共聚物在改善聚酯/苯乙烯类树脂合金相态结构及相态稳定性中的应用Application of Multi-element Random Copolymer in Improving the Phase Structure and Phase Stability of Polyester/Styrenic Resin Alloy 技术领域Technical field
本发明涉及一种改善聚酯/苯乙烯类树脂合金相态分布及稳定性的专用相容剂及其应用。The invention relates to a special compatibilizer for improving the phase distribution and stability of a polyester/styrene resin alloy and its application.
背景技术Background technique
聚合物合金材料由于兼具了两种聚合物的优点，而越来越受到研究人员的关注，比如PC/ABS合金，由于兼具了PC和ABS两者的综合特性，较之PC提高了流动性，改善了加工性能，减少了制品对应力的敏感性，而较之ABS则具有更为优异的热稳定性。因而可以应用在在家用电器、办公设备、通讯设备、照像器材、医疗器械、建筑和照明用具以及航空航天、电子计算机、光纤等诸多领域。特别是在汽车内饰，外饰，车灯等高强度，高耐热零件方面更获得了广泛应用。Polymer alloy materials have attracted more and more attention from researchers because they have the advantages of both polymers. For example, PC/ABS alloys, because they have the comprehensive characteristics of both PC and ABS, they have improved fluidity compared to PC. It improves the processing performance and reduces the sensitivity of the product to stress. Compared with ABS, it has better thermal stability. Therefore, it can be used in many fields such as household appliances, office equipment, communication equipment, photographic equipment, medical equipment, construction and lighting appliances, aerospace, electronic computers, optical fiber and so on. In particular, it has been widely used in high-strength and high-heat-resistant parts such as automotive interiors, exteriors, and lights.
近年来，PC/ABS的市场一直保持着10%以上的增长幅度，随着汽车、家电等行业的发展，人们对更为美观、更高性能的聚酯/苯乙烯类树脂需求不断增长，新一代高性能的聚酯/苯乙烯类树脂合金系列材料，不仅需要具有优异的力学性能，更需要包括相态分布结构及相态稳定性、免喷涂、超低先泽、耐化学品性等系列新的特性。In recent years, the PC/ABS market has maintained a growth rate of more than 10%. With the development of industries such as automobiles and home appliances, people’s demand for more beautiful and higher-performance polyester/styrene resins continues to grow. The new generation of high-performance polyester/styrene resin alloy series materials not only need to have excellent mechanical properties, but also need to include phase distribution structure and phase stability, spray-free, ultra-low first ze, chemical resistance, etc. New features.
此外，随着塑料制品在各行业领域得到广泛的应用，伴随而来的塑料废弃物也日益增多，造成了能源的巨大浪费和因塑料不可生物降解性带来的严重污染。因此，废旧塑料的回收利用越来越受到人们的重视。其中聚对苯二甲酸乙二醇酯（PET）就是一种被广泛回收使用的材料。目前，PET回料（R-PET）主要来源于瓶片料的回收，回收料的性能较差，主要是用在合金、聚酯短纤维的填料、聚酯增强木塑复合材料等。国家“十二五”规划的《意见》中，明确指出要大力提升聚酯料的回收再利用。In addition, as plastic products are widely used in various industries, the accompanying plastic waste is also increasing, resulting in a huge waste of energy and serious pollution caused by the non-biodegradability of plastics. Therefore, the recycling of waste plastics has attracted more and more attention. Among them, polyethylene terephthalate (PET) is a widely recycled material. At present, PET recycled material (R-PET) mainly comes from the recycling of bottle flakes, and the performance of recycled materials is poor, mainly used in alloys, polyester staple fiber fillers, and polyester-reinforced wood-plastic composite materials. In the "Opinions" of the national "Twelfth Five-Year Plan", it is clearly pointed out that the recycling and reuse of polyester materials should be vigorously promoted.
ABS与PET共混可以制得性能优异的合金，兼具ABS与PET的优点，既拓宽了回收材料的应用领域，又可克服ABS的一些固有的性能缺陷并降低价格，是非常有前景的一类材料，在电视机等家电，打印机、复印机等OA产品上都得到了广发应用。The blending of ABS and PET can produce alloys with excellent performance, which has the advantages of both ABS and PET, which not only broadens the application field of recycled materials, but also overcomes some inherent performance defects of ABS and reduces the price. It is a very promising one. Such materials have been widely used in home appliances such as televisions, and OA products such as printers and copiers.
一般来说，聚酯/苯乙烯类树脂合金的加工温度较高，而且聚酯与苯乙烯类树脂的溶解度参数差异较大，容易发生相分离。PC/ABS虽然相容性还不错，但是由于PC的酯基也易在热历史较长或强剪切的条件下受到羟基等活性基团的进攻而降解，因此在加工过程中或者回收使用过程中容易发生分散相的重新聚集；目前解决聚酯/苯乙烯类树脂的相容性问题一般是添加相容剂。常见与文献报道的有：异氰酸酯类、噁唑啉类、环氧类以及酸酐类相容剂。已工业化生产的为酸酐类与环氧类产品居多，但都是以扩链、增韧等用途居多，如BASF的ADR-4370，阿科玛公司的AX8900，杜邦的PTW等，但还没有相关相容剂在改善相态及相态稳定性方面的报道。Generally speaking, the processing temperature of polyester/styrene resin alloys is relatively high, and the solubility parameters of polyester and styrene resins are quite different, which is prone to phase separation. Although the compatibility of PC/ABS is good, the ester group of PC is also easy to be degraded by the attack of active groups such as hydroxyl under the condition of long thermal history or strong shear, so it can be degraded during processing or recycling. It is easy to re-aggregate the dispersed phase; currently, to solve the compatibility problem of polyester/styrene resin is generally to add a compatibilizer. Common and reported in the literature are: isocyanate, oxazoline, epoxy and acid anhydride compatibilizers. Most of the products that have been industrially produced are acid anhydrides and epoxy products, but they are mostly used for chain extension and toughening, such as BASF's ADR-4370, Arkema's AX8900, DuPont's PTW, etc., but there is no relevant Reports on compatibilizers in improving phase state and phase state stability.
技术问题technical problem
如何获得一种能够改善聚酯/苯乙烯类树脂合金相态分布及稳定性的相容剂成为一个重要的问题，同时利用该种相容剂稳定、简单、有效地改善聚酯/苯乙烯类树脂的相态结构及相态的稳定性，并能提高合金的力学性能，更是制备高性能聚酯/苯乙烯类树脂合金的关键。How to obtain a compatibilizer that can improve the phase distribution and stability of the polyester/styrene resin alloy has become an important issue. At the same time, the use of this compatibilizer to stabilize, simply and effectively improve the polyester/styrene resin alloy The phase structure and phase stability of the resin, and can improve the mechanical properties of the alloy, are the key to the preparation of high-performance polyester/styrene resin alloys.
本发明的目的在于及其制备方法，该方法与现有技术相比，具有简单有效、使用方便、成本低廉等优点。The purpose of the present invention is and its preparation method. Compared with the prior art, the method has the advantages of simplicity and effectiveness, convenient use, low cost and the like.
技术解决方案Technical solutions
本发明的目的可以通过以下技术方案来实现。The purpose of the present invention can be achieved by the following technical solutions.
多元无规共聚物在制备聚酯/苯乙烯类树脂合金中的应用。The application of multi-element random copolymers in the preparation of polyester/styrene resin alloys.
多元无规共聚物在改善聚酯/苯乙烯类树脂合金的相态结构及相态稳定性中的应用。The application of multiple random copolymers in improving the phase structure and phase stability of polyester/styrene resin alloys.
具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金，由聚酯、苯乙烯类树脂、相容剂、助剂制备；所述相容剂为多元无规共聚物。The polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer.
上述具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金的制备方法为，将聚酯、苯乙烯类树脂、相容剂、助剂放入高混机中混合后出料，然后用螺杆挤出机挤出造粒，得到具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金。比如将聚酯、苯乙烯类树脂、相容剂、助剂放入高混机中在25℃～90℃下混合1～5分钟，出料，然后用螺杆挤出机挤出造粒，挤出加工温度在220～260℃，螺杆转数在180～600转/分，所述高混机的转速为2000rpm，所述双螺杆挤出机的长径比介于34-40之间，得到具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金。The preparation method of the above-mentioned polyester/styrene resin alloy with phase distribution structure and phase stability is to put the polyester, styrene resin, compatibilizer, and auxiliary agent into a high-mixer, and then discharge the material. , And then extrude and pelletize with a screw extruder to obtain a polyester/styrene resin alloy with phase distribution structure and phase stability. For example, put polyester, styrenic resin, compatibilizer, and auxiliary agent into a high-mixer and mix for 1 to 5 minutes at 25°C to 90°C, discharge the material, and then extrude and pelletize with a screw extruder. The processing temperature is 220-260°C, the screw speed is 180-600 rpm, the speed of the high mixer is 2000 rpm, and the aspect ratio of the twin-screw extruder is between 34-40. Polyester/styrene resin alloy with phase distribution structure and phase stability.
本发明中，多元无规共聚物作为相容剂应用在制备聚酯/苯乙烯类树脂合金中；或者应用在改善聚酯/苯乙烯类树脂合金的相态结构及相态稳定性中。作为相容剂的多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成；芳香族乙烯基单体、丙烯腈系单体中，芳香族乙烯基单体的重量百分数为50wt％～90wt％，余量为丙烯腈系单体；甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1％～15％。进一步的，芳香族乙烯基单体、丙烯腈系单体中，芳香族乙烯基单体的重量百分数为60wt％～80wt％，余量为丙烯腈系单体；甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1％～10％，优选0.2％～2％。本发明涉及的多元无规共聚物作为相容剂添加到聚酯/苯乙烯类树脂合金中，用于改善合金的相态分布及相态稳定性。In the present invention, the multi-element random copolymer is used as a compatibilizer to prepare the polyester/styrene resin alloy; or used to improve the phase structure and phase stability of the polyester/styrene resin alloy. The multi-element random copolymer as a compatibilizer is made by the copolymerization of aromatic vinyl monomers, acrylonitrile-based monomers and methacrylate monomers; among the aromatic vinyl monomers and acrylonitrile-based monomers, aromatic The weight percentage of vinyl monomer is 50wt%～90wt%, the balance is acrylonitrile monomer; the amount of methacrylate monomer is 0.1%～of the total weight of aromatic vinyl monomer and acrylonitrile monomer. 15%. Further, among the aromatic vinyl monomers and acrylonitrile monomers, the weight percentage of the aromatic vinyl monomer is 60 wt% to 80 wt%, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer It is 0.1% to 10% of the total weight of the aromatic vinyl monomer and acrylonitrile monomer, preferably 0.2% to 2%. The multi-element random copolymer of the present invention is added as a compatibilizer to the polyester/styrene resin alloy to improve the phase distribution and phase stability of the alloy.
本发明中，所述相容剂的重量百分数为聚酯、苯乙烯类树脂、相容剂重量和的0.5～15%。本发明的聚酯/苯乙烯类树脂合金专用相容剂，通过在制备过程中，与其它原料共混、挤出造粒，即可实现简单有效、使用方便、成本低廉地制备得到在维持优良的力学性能的同时，还具有优异的相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金。In the present invention, the weight percentage of the compatibilizer is 0.5-15% of the total weight of polyester, styrene resin, and compatibilizer. The special compatibilizer for polyester/styrene resin alloy of the present invention can be prepared by blending with other raw materials and extruding granulation during the preparation process to achieve simple, effective, convenient use, and low-cost preparation. In addition to its mechanical properties, it also has a polyester/styrene resin alloy with excellent phase distribution structure and phase stability.
本发明中，助剂为常规选择，比如助剂为抗氧剂和/或润滑剂，助剂不包括相容剂、导电剂，助剂的用量根据实际情况添加，比如抗氧剂0.1～1wt％，润滑剂0.1～0.5wt％，以聚酯、苯乙烯类树脂、相容剂的重量和为基数。In the present invention, the auxiliary agent is a conventional choice. For example, the auxiliary agent is an antioxidant and/or a lubricant. The auxiliary agent does not include a compatibilizer and a conductive agent. The amount of the auxiliary agent is added according to the actual situation, such as an antioxidant 0.1-1wt. %, the lubricant is 0.1-0.5wt%, based on the weight sum of polyester, styrene resin and compatibilizer.
本发明中，聚酯、苯乙烯类树脂、相容剂中，聚酯的重量百分数为30～90％，相容剂的重量百分数为0.5～15%，余量为苯乙烯类树脂。通过实施例可确定，本发明的改善聚酯/苯乙烯类树脂合金相态分布及稳定性的专用相容剂，在保障聚酯/苯乙烯类树脂合金的力学性能的前提下，通过简单地添加获得具有相态分布结构优异及相态稳定性的合金；尤其是，本发明的聚酯/苯乙烯类树脂合金中，聚酯的含量可在30～90％范围内可调， 适用范围广。In the present invention, in the polyester, styrenic resin, and compatibilizer, the weight percentage of the polyester is 30-90%, the weight percentage of the compatibilizer is 0.5-15%, and the balance is styrene resin. Through the examples, it can be determined that the special compatibilizer for improving the phase distribution and stability of the polyester/styrene resin alloy of the present invention can be achieved by simply Adding to obtain an alloy with excellent phase distribution structure and phase stability; in particular, in the polyester/styrene resin alloy of the present invention, the content of polyester can be adjusted within the range of 30-90%, and the application range is wide. .
本发明中，所述聚酯可以是聚碳酸酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯中的一种；所述苯乙烯类树脂为ABS、SAN、ASA、AES中的一种或几种，可以是本体法，亦可以是乳液法。In the present invention, the polyester may be one of polycarbonate, polyethylene terephthalate, and polybutylene terephthalate; the styrenic resin is ABS, SAN, ASA One or more of AES can be either the bulk method or the emulsion method.
本发明中，所述多元无规共聚物的重均分子量为20000～100000，235℃/2.16kg 的熔体指数为30～120g/10min。In the present invention, the weight average molecular weight of the multi-element random copolymer is 20000-100000, and the melt index at 235°C/2.16kg is 30-120g/10min.
本发明中，所述芳香族乙烯基单体包括苯乙烯系单体，比如苯乙烯单体、α-甲基苯乙烯单体、α-氯苯乙烯单体或p-甲基苯乙烯单体；所述丙烯腈系单体包括丙烯腈单体或α-甲基丙烯腈单体；所述甲基丙烯酸酯可以是甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的一种或者几种。更优选的，选用多元无规共聚物作为相容剂，其中GMA含量为0.1wt％～10wt％，优选0.2wt％～2wt％，可最大限度地提高聚酯/苯乙烯类树脂材料的力学性能，改善聚酯/苯乙烯类树脂的相态结构及相态稳定性。In the present invention, the aromatic vinyl monomer includes styrenic monomers, such as styrene monomer, α-methylstyrene monomer, α-chlorostyrene monomer or p-methylstyrene monomer The acrylonitrile monomer includes acrylonitrile monomer or α-methacrylonitrile monomer; the methacrylate may be one or more of methyl methacrylate and glycidyl methacrylate. More preferably, a multi-element random copolymer is used as a compatibilizer, in which the GMA content is 0.1wt%-10wt%, preferably 0.2wt%-2wt%, which can maximize the mechanical properties of polyester/styrene resin materials , Improve the phase structure and phase stability of polyester/styrene resin.
有益效果Beneficial effect
与现有技术相比，本发明具有如下有益效果。Compared with the prior art, the present invention has the following beneficial effects.
本发明的相容剂与聚合物共挤热稳定性良好，不会发生析出或难以迁移到界面而降低反应活性等问题，反应性官能团含量合适，易于控制黑点或凝胶现象的发生；与苯乙烯类树脂完全热力学相容，不存在相分离的问题。而且使用方便，不需母粒化，也不存在二次污染；本发明的多元无规共聚物反应活性高，使用效率高，使用成本比市场上类似用途商品低三分之一到二分之一，具有极好的性价比。用途广泛：为回收利用的聚酯/苯乙烯类树脂也提供了一种适用的改善相态结构并兼顾力学性能的简单方法。The compatibilizer of the present invention has good thermal stability in co-extrusion with polymer, does not cause problems such as precipitation or difficulty in migrating to the interface to reduce the reactivity, the content of reactive functional groups is appropriate, and it is easy to control the occurrence of black spots or gel phenomena; and Styrene resins are completely thermodynamically compatible, and there is no problem of phase separation. Moreover, it is convenient to use, does not require masterbatch, and there is no secondary pollution; the multi-element random copolymer of the present invention has high reactivity, high use efficiency, and the use cost is one-third to two-half lower than similar products on the market First, it has an excellent price/performance ratio. Wide range of uses: It also provides a suitable simple method for improving the phase structure and taking into account the mechanical properties of the recycled polyester/styrene resin.
附图说明Description of the drawings
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显。By reading the detailed description of the non-limiting embodiments with reference to the following drawings, other features, purposes and advantages of the present invention will become more apparent.
图1为实施例5～8制备合金的扫描电镜图对比。Figure 1 is a comparison of scanning electron micrographs of the alloys prepared in Examples 5-8.
图2为实施例5以及实施例8的多轴冲击对比。Fig. 2 is a comparison of multi-axis impact of Example 5 and Example 8.
图3为实施例5与实施例6注塑制件近浇口与远浇口的相态稳定性对比（TEM）。Figure 3 is a comparison of the phase stability (TEM) between the near gate and the far gate of the injection molded parts of Example 5 and Example 6.
图4为实施例5与实施例6注塑制件近浇口与远浇口的冲击性能对比。Figure 4 is a comparison of the impact performance of the injection molded parts of Example 5 and Example 6 between the near gate and the far gate.
图5为实施例5与实施例3经多次挤出对比相态稳定性对比。Figure 5 is a comparison of the phase stability of Example 5 and Example 3 after multiple extrusions.
图6为实施例9-13的微观相貌图对比图。Fig. 6 is a comparison diagram of the microscopic appearance diagrams of Examples 9-13.
本发明的实施方式Embodiments of the present invention
本发明公开了作为相容剂的多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成；具体制备方法可根据现有技术选择，如下。The invention discloses a multi-element random copolymer as a compatibilizer by copolymerization of aromatic vinyl monomers, acrylonitrile monomers and methacrylate monomers; the specific preparation method can be selected according to the prior art, as follows.
以实施例2的760g芳香族乙烯基单体、240g丙烯腈系单体、10g甲基丙烯酸酯单体为例，将500g芳香族乙烯基单体、180g丙烯腈系单体、5g甲基丙烯酸酯单体与1500g去离子水混合后在70℃搅拌反应1小时，然后滴加剩余的芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体混合物，1小时滴加完成，继续反应1小时，然后升温至90℃熟化1小时，再出料、过滤、水洗、烘干，得到多元无规共聚物，作为改善聚酯/苯乙烯类树脂合金相态分布及稳定性的专用相容剂。Taking the 760g aromatic vinyl monomer, 240g acrylonitrile-based monomer, and 10g methacrylate monomer of Example 2 as an example, 500g aromatic vinyl monomer, 180g acrylonitrile-based monomer, 5g methacrylic acid The ester monomer is mixed with 1500g of deionized water and reacted at 70°C for 1 hour with stirring, and then the remaining aromatic vinyl monomer, acrylonitrile monomer and methacrylate monomer mixture are added dropwise, and the addition is completed in 1 hour. Continue the reaction for 1 hour, then heat up to 90°C for curing for 1 hour, then discharge, filter, wash, and dry to obtain a multi-element random copolymer, which is used as a special purpose for improving the phase distribution and stability of polyester/styrene resin alloys. Compatibilizer.
以下实施例的相容剂制备可按此进行，原料加入可按比例调整。The preparation of the compatibilizer in the following examples can be carried out according to this, and the addition of raw materials can be adjusted in proportion.
具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金，由聚酯、苯乙烯类树脂、相容剂、助剂制备；所述相容剂为多元无规共聚物。助剂为常规选择，比如助剂为抗氧剂和/或润滑剂。The polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer. The auxiliary agent is a conventional choice, for example, the auxiliary agent is an antioxidant and/or a lubricant.
下面结合实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干调整和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that for those of ordinary skill in the art, several adjustments and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例 1-4   按照表1的原料组成配比，制备了一种改善聚酯/苯乙烯类树脂合金相态分布及稳定性的专用相容剂，实施例1-4、14与对照例1-2（制备方法与实施例一致，加料常规调整）。并将这些相容剂用于制备聚酯/苯乙烯类树脂合金，用以研究其对此类合金的相态及相态稳定性的改善。 Example 1-4 According to the raw material composition ratio in Table 1, a special compatibilizer for improving the phase distribution and stability of polyester/styrene resin alloy was prepared. Examples 1-4, 14 and Comparative Example 1 -2 (The preparation method is the same as the embodiment, and the addition is adjusted regularly). And these compatibilizers are used to prepare polyester/styrene resin alloys to study the improvement of the phase state and phase stability of such alloys.
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实施例 5-9   PC 树脂选用日本帝人公司的PCI250WP( 相对数均分子量为22000g/ mol，玻璃化转变温度为140℃ ) ；ABS 树脂选用韩国锦湖石油化学的P /D190( 相对重均分子量为120000g /mol，其中丁二烯重量百分比含量为50％，丙烯腈重量百分比含量为15％，苯乙烯重量百分比含量为35％。 Example 5-9 PC resin is selected from Teijin Corporation’s PCI250WP (relative number average molecular weight is 22000g/mol, glass transition temperature is 140℃); ABS resin is selected from Korea’s Kumho Petrochemical’s P/D190 (relative weight average molecular weight is 120,000 g/mol, wherein the butadiene weight percentage content is 50%, the acrylonitrile weight percentage content is 15%, and the styrene weight percentage content is 35%.
Figure 131924dest_path_image002
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Figure 131924dest_path_image002
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将上述组分按比例放入高混机中混合3分钟，出料，然后用螺杆挤出机挤出造粒，加工温度在220～260℃，螺杆转数在300转/分；高混机的转速为2000rpm，双螺杆挤出机的长径比36。Put the above-mentioned components into a high-mixer in proportion to mix for 3 minutes, discharge the material, and then extrude and pelletize with a screw extruder. The processing temperature is 220～260℃, and the screw speed is 300 rpm; high-mixer The speed of the twin-screw extruder is 2000rpm, and the aspect ratio of the twin-screw extruder is 36.
根据实施例5～8制备的粒子经常规注塑制得片材，分别为样品1～样品4，样品经液氮冷却脆断后刻蚀橡胶相，对断面进行扫描电镜观察，结果见图1，可见，实施例2与对照例1、2相对空白无相容剂的样品可改善相态结构，但是相比而言，在同等组分情况下，以实施例2为相容剂的PC/ABS具有更为精细的分散相结构。结合表3的力学性能数据，更优异的相态结构也意味着更优异的力学性能，特别是冲击强度，虽然实施例7、8的组分中，橡胶成分更高，但结果显示实施例5的冲击性能更优异，这主要得益于相态结构的优化。以实施例3替换实施例5中的实施例2，其余不变，得到的片材（实施例15）悬臂梁冲击强度为748J/m；以实施例1替换实施例5中的实施例2，其余不变，得到的片材悬臂梁冲击强度为808J/m，有所下降。The particles prepared according to Examples 5 to 8 were conventionally injection molded into sheets, samples 1 to 4, respectively. After the samples were cooled by liquid nitrogen, the rubber phase was etched and the cross section was observed by scanning electron microscopy. The results are shown in Figure 1. , Example 2 and Comparative Examples 1 and 2 are relatively blank samples without compatibilizer can improve the phase structure, but in comparison, in the case of the same composition, the PC/ABS with Example 2 as the compatibilizer has A finer dispersed phase structure. Combined with the mechanical properties data in Table 3, a better phase structure also means better mechanical properties, especially impact strength. Although the components of Examples 7 and 8 have higher rubber components, the results show that Example 5 The impact performance is better, which is mainly due to the optimization of the phase structure. Example 3 was used to replace Example 2 in Example 5, and the rest remained unchanged. The resulting sheet material (Example 15) had a cantilever beam impact strength of 748J/m; Example 1 was used to replace Example 2 in Example 5. The rest remains unchanged, and the obtained sheet cantilever beam impact strength is 808J/m, which has decreased.
Figure 331961dest_path_image003
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Figure 331961dest_path_image003
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本发明相态的优化，除了在常规力学性能上表现出优势以外，在一些特殊应用场合也可以起到特殊的效果，请见图2，多轴冲击结果显示冲击的破坏性，比较有特殊性，常规冲击性能高，多轴冲击性能不一定好，可以看出本发明的性能优势明显。在多轴冲击的测试（ASTM D1709）中，因为相态结构的变化，表现出了本质上的差异，使用实施例2作为相容剂的实施例5的样品，表现出较好的通过性，而实施例6-8分别表现出一定程度的失效，具体的，实施例8总能量52.2J、全部脆性，实施例7总能量55.3J、50%韧性，实施例6总能量54.8J、70%韧性，实施例5总能量56.4J、100%韧性；这种差异使得PC/ABS合金可以在更高等级的安全防护材料中得以使用。The optimization of the phase state of the present invention, in addition to showing advantages in conventional mechanical properties, can also have special effects in some special applications. Please refer to Figure 2. The results of multi-axis impact show the destructiveness of impact, which is more specific. The conventional impact performance is high, but the multi-axis impact performance is not necessarily good. It can be seen that the performance advantages of the present invention are obvious. In the multiaxial impact test (ASTM In D1709), due to the change of the phase structure, there is an essential difference. The sample of Example 5 using Example 2 as a compatibilizer shows better passability, while Examples 6-8 respectively show A certain degree of failure occurs. Specifically, the total energy of Example 8 is 52.2J, all brittleness, the total energy of Example 7 is 55.3J, 50% toughness, the total energy of Example 6 is 54.8J, 70% toughness, and the total energy of Example 5 is 56.4 J. 100% toughness; this difference allows PC/ABS alloy to be used in higher-level safety protection materials.
实施例5、6的相态结构有区别，结合图3的扫描电镜，分别将实施例5与实施例6的注塑制件在近浇口位置与远浇口位置取样，切片后进行透射电镜分析相态结构，以观测其相态稳定性。为了说明本发明相容剂对合金相态分布稳定性的影响，采用大模具常规注塑制备长度30厘米、宽度为缺口冲击样条标准宽度的注塑件，分别取最接近浇口的样条与最远离浇口的样条，进行测试；可见在注塑模具中，由于剪切-拉伸力场的存在，实施例6相态结构是不稳定的，远浇口位置的相态结构相对近浇口而言，明显发生了一定程度的相团聚，分散相的均匀性有所下降；但是实施例5的远浇口位置的相态仍然保持非常好的相态结构。这也直接在冲击强度上有所反应，见图4，实施例5远浇口达到831J/m，而实施例6远浇口近浇口片材的性能差距较大，还发现，实施例8远浇口/近浇口片材的性能差距比实施例6还大。在此提一下，除了该段样品的制备，本发明实施例其他样品的制备大小都与标准测试样条一致。The phase structures of Examples 5 and 6 are different. Combined with the scanning electron microscope of Figure 3, the injection molded parts of Example 5 and Example 6 were sampled at the near gate position and the far gate position, respectively, and then subjected to transmission electron microscopy analysis after slicing. Phase structure to observe its phase stability. In order to illustrate the influence of the compatibilizer of the present invention on the stability of the alloy phase distribution, conventional injection molding with a large mold was used to prepare injection molded parts with a length of 30 cm and a width of the standard width of the notched impact spline. Test the spline far away from the gate; it can be seen that in the injection mold, due to the existence of the shear-tension force field, the phase structure of Example 6 is unstable, and the phase structure at the far gate position is relatively close to the gate. In other words, a certain degree of phase agglomeration has obviously occurred, and the uniformity of the dispersed phase has decreased; however, the phase state at the far gate position of Example 5 still maintains a very good phase state structure. This is also directly reflected in the impact strength, as shown in Figure 4, in Example 5, the far gate reaches 831J/m, while the performance gap of the far gate near gate sheet in Example 6 is large. It is also found that Example 8 The performance gap of the far gate/near gate sheet is larger than that of Example 6. It should be mentioned here that, except for the preparation of the samples in this section, the preparation sizes of other samples in the embodiment of the present invention are consistent with the standard test strips.
可见本发明公开的改善聚酯/苯乙烯类树脂合金相态分布及稳定性的专用相容剂具有更高效的表现，图5中，结合反复挤出造粒来对比研究其相态稳定性，即首次用螺杆挤出机挤出造粒后，将粒子再次投入挤出机，继续造粒，为二次挤出，如此循环，不同挤出次数得到的粒子根据上述同样的常规方法注塑，测试合金片材的透射电镜TEM，从图中可见，经多次挤出加工后，由于多次受热-剪切历史，实施例3的相态发生了一定程度的分散相聚集，而实施例5则依然保持较好的相态结构，因而在力学性能上，也表现更为优异，见表4，为粒子常规注塑后的片材测试，测试方法如上。It can be seen that the special compatibilizer for improving the phase distribution and stability of the polyester/styrene resin alloy disclosed in the present invention has a more efficient performance. In Figure 5, the phase stability is compared with repeated extrusion and granulation. That is, after the first extruding and granulating with the screw extruder, the particles are put into the extruder again, and the granulation is continued, which is a secondary extrusion. Such a cycle. The particles obtained from different extrusion times are injected according to the same conventional method as mentioned above. The transmission electron microscope TEM of the alloy sheet can be seen from the figure. After multiple extrusion processing, due to multiple heat-shearing history, the phase state of Example 3 has a certain degree of disperse phase aggregation, while that of Example 5 It still maintains a better phase structure, and therefore performs better in terms of mechanical properties. See Table 4, which is the sheet test after the particles are conventionally injected. The test method is as above.
Figure 59746dest_path_image004
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Figure 59746dest_path_image004
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实施例 9 ～ 12  PET 树脂选用市售瓶片回收料( 特性粘度0.65 ) ；ABS 树脂选用韩国锦湖石油化学的P /D190( 相对重均分子量为120000g /mol，其中丁二烯重量百分比含量为50％，丙烯腈重量百分比含量为15％，苯乙烯重量百分比含量为35％)以及台湾化学的SAN树脂NF2200（相对重均分子量约为120000g /mol，其中丙烯腈重量百分比含量为24％，苯乙烯重量百分比含量为76％）。 Embodiment 9 ~ 12 PET resin selected commercial embodiment Bottle regrind (intrinsic viscosity 0.65); ABS resin selected Korea Kumho Petrochemical P / D190 (a relative weight average molecular weight of 120000g / mol, wherein the percentage by weight of butadiene 50%, 15% by weight of acrylonitrile and 35% by weight of styrene) and Taiwan Chemical’s SAN resin NF2200 (relative weight average molecular weight is about 120,000g/mol, of which 24% by weight of acrylonitrile, benzene The ethylene weight percentage content is 76%).
Figure 610813dest_path_image005
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Figure 610813dest_path_image005
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将上述组分按比例放入高混机中混合3分钟，出料，然后用螺杆挤出机挤出造粒，加工温度在220～260℃，螺杆转数在500转/分；高混机的转速为2000rpm，双螺杆挤出机的长径比36。Put the above components into a high-mixer in proportion to mix for 3 minutes, discharge the material, and then extrude and pelletize with a screw extruder. The processing temperature is 220～260℃, and the screw speed is 500 rpm; high-mixer The speed of the twin-screw extruder is 2000rpm, and the aspect ratio of the twin-screw extruder is 36.
根据实施例9～13制得的粒子常规注塑成片材后分别进行微观形貌观察与力学性能测试，断面SEM形貌见图6。由图6可见，实施例9-11的相态要优于实施例12、13，这与选用的相容剂结构有关，与在PC/ABS体系中对比了实施例2与对照例1的两种相容剂结果类似。The particles prepared according to Examples 9 to 13 were conventionally injection molded into sheets and then subjected to microscopic morphology observation and mechanical property testing. The cross-sectional SEM morphology is shown in Figure 6. It can be seen from Figure 6 that the phase state of Examples 9-11 is better than that of Examples 12 and 13, which is related to the structure of the selected compatibilizer, and compares the two of Example 2 and Comparative Example 1 in the PC/ABS system. The results of a compatibilizer are similar.
在PET/ABS体系中也是如此，因此从相态结构可见，实施例13最差。实施例12的相态均匀性尚可，但是分散相粒径偏大，其所用的相容剂也是带有GMA官能团，这种结果可能与结构中的MMA有关，由于MMA的存在，影响了GMA的反应活性，从而导致了相态上的差异。表6为力学性能测试数据，测试方法如上。以CN106189167A实施例中的相容剂（数均分子量25000）替换本发明实施例10中的实施例2，其余不变，得到的片材缺口冲击强度(1/8 inch)为178J/m；以现有CN105462149A实施例4制备的相容剂替换本发明实施例10中的实施例2，其余不变，得到的片材缺口冲击强度(1/8 inch)为141J/m；以现有ADR-4370相容剂替换本发明实施例10中的实施例2，其余不变，得到的片材缺口冲击强度(1/8 inch)为152J/m。This is also true in the PET/ABS system, so from the phase structure, it can be seen that Example 13 is the worst. The uniformity of the phase state of Example 12 is acceptable, but the particle size of the dispersed phase is too large, and the compatibilizer used also has GMA functional groups. This result may be related to the MMA in the structure. The existence of MMA affects GMA The reaction activity, which leads to the difference in phase state. Table 6 shows the mechanical performance test data, and the test method is as above. Use the compatibilizer (number average molecular weight of 25000) in the example of CN106189167A to replace the example 2 in the example 10 of the present invention, and the rest remain unchanged, the obtained sheet notched impact strength (1/8 inch) is 178J/m; replace Example 2 in Example 10 of the present invention with the compatibilizer prepared in Example 4 of the existing CN105462149A, and the rest remain unchanged, the resulting sheet notched impact strength (1/8 inch) is 141J/m; replacing Example 2 in Example 10 of the present invention with the existing ADR-4370 compatibilizer, and the rest remain unchanged, the obtained sheet notched impact strength (1/8 inch) is 152J/m.
Figure 878983dest_path_image006
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Figure 878983dest_path_image006
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综上所述，本发明的方法简单易行，通过本发明的一种多元无规共聚物作为相容剂，添加合适的比例并选用合适的官能团含量，可有效提高聚酯/苯乙烯类树脂材料的力学性能，增加聚酯/苯乙烯类树脂的相态结构与加工过程中的相态稳定性。这是由于本发明的多元无规共聚物通过化学反应使分散相粒径更细，形变更小，分布更趋均匀，从而使合金材料在受到外力作用时，可吸收更多的能量，表现出为冲击强度的提升上升，对缺口敏感性下降等多种性能优势。多元无规共聚物可直接与聚酯以及苯乙烯类树脂混合，无需再母粒化，易于使用，添加量低，是一种获得高性能聚酯/苯乙烯树脂合金的方法。In summary, the method of the present invention is simple and easy to implement. By using a multi-element random copolymer of the present invention as a compatibilizer, adding a suitable ratio and selecting a suitable functional group content, the polyester/styrene resin can be effectively improved. The mechanical properties of the material increase the phase structure of the polyester/styrene resin and the phase stability during processing. This is because the multi-element random copolymer of the present invention makes the dispersed phase particle size finer, smaller shape change, and more evenly distributed through chemical reaction, so that the alloy material can absorb more energy when subjected to external force, showing In order to increase the impact strength, the sensitivity to the notch decreases and other performance advantages. Multi-element random copolymers can be directly mixed with polyester and styrene resins without masterbatch, easy to use, and low addition. It is a method to obtain high-performance polyester/styrene resin alloys.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which does not affect the essence of the present invention.

Claims (10)

  1. 多元无规共聚物在制备聚酯/苯乙烯类树脂合金中的应用或者多元无规共聚物在改善聚酯/苯乙烯类树脂合金的相态结构及相态稳定性中的应用，其特征在于，所述多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成。The application of multiple random copolymers in the preparation of polyester/styrene resin alloys or the application of multiple random copolymers in improving the phase structure and phase stability of polyester/styrene resin alloys is characterized by The multi-element random copolymer is formed by copolymerization of aromatic vinyl monomers, acrylonitrile monomers and methacrylate monomers.
  2. 根据权利要求1所述的应用，其特征在于，聚酯/苯乙烯类树脂合金由聚酯、苯乙烯类树脂、相容剂、助剂制备。The application according to claim 1, wherein the polyester/styrene resin alloy is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent.
  3. 根据权利要求1所述的应用，其特征在于，所述芳香族乙烯基单体包括苯乙烯系单体；所述丙烯腈系单体包括丙烯腈单体或α-甲基丙烯腈单体；所述甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的一种或者几种。The application according to claim 1, wherein the aromatic vinyl monomer comprises a styrenic monomer; the acrylonitrile monomer comprises an acrylonitrile monomer or an α-methacrylonitrile monomer; The methacrylate is one or more of methyl methacrylate and glycidyl methacrylate.
  4. 根据权利要求1所述的应用，其特征在于，芳香族乙烯基单体、丙烯腈系单体中，芳香族乙烯基单体的重量百分数为50wt％～90wt％，余量为丙烯腈系单体；甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1％～15％。The application according to claim 1, wherein in the aromatic vinyl monomers and acrylonitrile-based monomers, the weight percentage of the aromatic vinyl monomer is 50wt% to 90wt%, and the balance is the acrylonitrile-based monomer. The amount of methacrylate monomer is 0.1%-15% of the total weight of aromatic vinyl monomer and acrylonitrile monomer.
  5. 根据权利要求1所述的应用，其特征在于，所述聚酯为聚碳酸酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯中的一种；所述苯乙烯类树脂为ABS、SAN、ASA、AES中的一种或几种。The application according to claim 1, wherein the polyester is one of polycarbonate, polyethylene terephthalate, and polybutylene terephthalate; the styrene The similar resin is one or more of ABS, SAN, ASA, and AES.
  6. 具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金，由聚酯、苯乙烯类树脂、相容剂、助剂制备；所述相容剂为多元无规共聚物，其特征在于，所述多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成。The polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer, which It is characterized in that the multi-element random copolymer is formed by copolymerization of aromatic vinyl monomers, acrylonitrile-based monomers and methacrylate monomers.
  7. 根据权利要求6所述具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金，其特征在于，芳香族乙烯基单体、丙烯腈系单体中，芳香族乙烯基单体的重量百分数为50wt％～90wt％，余量为丙烯腈系单体；甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1％～15％。The polyester/styrene resin alloy having a phase distribution structure and phase stability according to claim 6, wherein among the aromatic vinyl monomers and acrylonitrile-based monomers, the aromatic vinyl monomers The weight percentage of is 50wt% to 90wt%, and the balance is acrylonitrile monomer; the amount of methacrylate monomer is 0.1% to 15% of the total weight of aromatic vinyl monomer and acrylonitrile monomer.
  8. 根据权利要求6所述具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金，其特征在于，聚酯、苯乙烯类树脂、相容剂中，聚酯的重量百分数为30～90％，相容剂的重量百分数为0.5～15%，余量为苯乙烯类树脂。The polyester/styrene resin alloy with phase distribution structure and phase stability according to claim 6, wherein the weight percentage of polyester in the polyester, styrene resin, and compatibilizer is 30 ~90%, the weight percentage of the compatibilizer is 0.5-15%, and the balance is styrene resin.
  9. 多元无规共聚物，其特征在于，所述多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成；芳香族乙烯基单体、丙烯腈系单体中，芳香族乙烯基单体的重量百分数为50wt％～90wt％，余量为丙烯腈系单体；甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1％～15％。The multi-element random copolymer is characterized in that the multi-element random copolymer is copolymerized by an aromatic vinyl monomer, an acrylonitrile-based monomer, and a methacrylate monomer; the aromatic vinyl monomer, acrylonitrile Among the monomers, the weight percentage of the aromatic vinyl monomer is 50% to 90% by weight, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer is the aromatic vinyl monomer and the acrylonitrile monomer. 0.1% to 15% of the total body weight.
  10. 根据权利要求9所述多元无规共聚物，其特征在于，所述芳香族乙烯基单体包括苯乙烯系单体；所述丙烯腈系单体包括丙烯腈单体或α-甲基丙烯腈单体；所述甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的一种或者几种。The multi-element random copolymer according to claim 9, wherein the aromatic vinyl monomer comprises a styrenic monomer; the acrylonitrile monomer comprises an acrylonitrile monomer or α-methacrylonitrile Monomer; The methacrylate is one or more of methyl methacrylate and glycidyl methacrylate.
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