WO2023020398A1 - 一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物及其制备方法和应用 - Google Patents

一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物及其制备方法和应用 Download PDF

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WO2023020398A1
WO2023020398A1 PCT/CN2022/112215 CN2022112215W WO2023020398A1 WO 2023020398 A1 WO2023020398 A1 WO 2023020398A1 CN 2022112215 W CN2022112215 W CN 2022112215W WO 2023020398 A1 WO2023020398 A1 WO 2023020398A1
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polycarbonate
alloy composition
long
polyester
polyester alloy
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PCT/CN2022/112215
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English (en)
French (fr)
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杨志军
陈平绪
黄险波
岑茵
艾军伟
丁超
李明昆
彭民乐
杨燕
李红刚
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金发科技股份有限公司
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Publication of WO2023020398A1 publication Critical patent/WO2023020398A1/zh

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    • 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

Definitions

  • the invention belongs to the technical field of engineering plastics, and in particular relates to a polycarbonate/polyester alloy composition with long-term thermal oxygen stability, a preparation method and application thereof.
  • Polycarbonate/polyester alloy is a high-performance alloy material, which has the advantages of good toughness, high surface gloss, and good processing fluidity.
  • the addition of polyester can significantly improve the chemical resistance of polycarbonate and further expand Its application fields, such as electrical and electronic, kitchen and bathroom, audio-visual equipment, transportation and other fields.
  • Adding antioxidants is a conventionally known method to improve the processing thermal stability of polycarbonate/polyester alloys, and an antioxidant system compounded with hindered phenol and phosphite is usually used; however, conventional hindered phenol and phosphorous acid
  • the ester-combined antioxidant system cannot meet its long-term thermo-oxidative stability requirements, resulting in the decline or loss of mechanical properties of polycarbonate/polyester alloy products after long-term use, which limits the application of the material to a certain extent .
  • Patent CN102093673A discloses a polyester with heat aging resistance, using a compound antioxidant system and a specific heat stabilizer DSTDP to improve long-term heat aging performance, but there are very few related studies, which limits the polycarbonate/polyester alloy application.
  • the purpose of the present invention is to overcome the polycarbonate/polyester alloy material in the prior art can not meet the requirement of its long-term thermo-oxidative stability, limit the defective or deficiency of its application, provide a kind of polycarbonate with long-term thermo-oxidative stability Ester/polyester alloy compositions.
  • the polycarbonate/polyester alloy composition provided by the present invention uses antimony-containing compounds to cooperate with the antioxidant system, which can inhibit the migration and precipitation of antioxidants in polycarbonate/polyester alloys, and slow down the degradation of polycarbonate/polyester alloys.
  • the obtained polycarbonate/polyester alloy composition has good mechanical properties and significantly improved long-term thermo-oxidative stability.
  • Another object of the present invention is to provide a preparation method of the above-mentioned polycarbonate/polyester alloy composition having long-term thermo-oxidative stability.
  • Another object of the present invention is to provide the application of the above-mentioned polycarbonate/polyester alloy composition with long-term thermo-oxidative stability in the preparation of electrical and electronic products, kitchen and bathroom products, audio-visual equipment or transportation products.
  • a polycarbonate/polyester alloy composition with long-term thermo-oxidative stability comprising the following components in parts by weight:
  • the antioxidant is a mixture of a main antioxidant and a secondary antioxidant, and the weight ratio of the primary antioxidant to the secondary antioxidant is 1.0:(0.5-1.0).
  • the polycarbonate/polyester alloy composition provided by the invention has a retention rate of not less than 80% in tensile strength and tensile impact strength after high-temperature aging, and can be widely used in electronic appliances, kitchen and bathroom products, audio-visual equipment or transportation products middle.
  • the polycarbonate/polyester alloy composition with long-term thermo-oxidative stability comprises the following components in parts by weight:
  • the polycarbonate is one or more of aromatic polycarbonate or siloxane copolycarbonate.
  • the aromatic polycarbonate is bisphenol A polycarbonate
  • the siloxane copolycarbonate is polydimethylsiloxane-bisphenol A polycarbonate
  • the polycarbonate is an aromatic polycarbonate.
  • the aromatic polycarbonate has an average molecular weight of 15,000-30,000; still more preferably, an aromatic polycarbonate with an average molecular weight of 20,000-28,000.
  • the average molecular weight is within the above range, the mechanical strength is good and good moldability can be secured.
  • the average molecular weight is tested by gel permeation chromatography.
  • the polyester is a copolyester obtained by polymerization of a diol monomer and a diacid monomer;
  • the diol monomer is ethylene glycol, hexanediol, propylene glycol, butanediol, 1.4-cyclohexane
  • dimethanol, neopentyl glycol or terephthalic acid the diacid monomer is terephthalic acid, isophthalic acid, glutaric acid, adipic acid or suberic acid one or several.
  • the polyester is one or more of polybutylene terephthalate (PBT) or polyethylene terephthalate; more preferably polybutylene terephthalate alcohol esters.
  • PBT polybutylene terephthalate
  • polyethylene terephthalate more preferably polybutylene terephthalate alcohol esters.
  • the viscosity of the polyester is not lower than 0.7 dl/g.
  • the viscosity of the present invention is measured by the Ubbelohde viscometer method according to the standard GB/T 14190, and the test temperature is 25°C.
  • the polyester has a viscosity of 0.7-1.5 dl/g.
  • the toughening agent is methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, One or more of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-vinyl acetate copolymer grafted with maleic anhydride, acrylic toughener or acrylic-silicone rubber toughener .
  • the antimony-containing compound is one or more of antimony oxides, antimonates or antimony halides.
  • the antimony oxide is one or both of antimony trioxide or antimony pentoxide.
  • the antimonate is one or both of sodium antimonate or zinc antimonate.
  • the antimony halide is antimony bromide.
  • the antimony-containing compound is one or more of antimony pentoxide, zinc antimonate or antimony bromide.
  • antimony-containing compounds are selected, they have more excellent long-term thermo-oxidative stability.
  • the weight fraction of the antimony-containing compound in the polycarbonate/polyester alloy composition is 0.5-2.5%.
  • the primary antioxidant is a hindered phenolic antioxidant.
  • the hindered phenolic antioxidant is n-octadecyl ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
  • the secondary antioxidant is one or more of phosphorus-based secondary antioxidants or sulfur-based secondary antioxidants.
  • the phosphorus-based secondary antioxidant is tris(2,4-di-tert-butylphenyl)phosphite.
  • the sulfur-based secondary antioxidant is pentaerythritol tetrakis(3-laurylthiopropionate).
  • the other additives are one or more of lubricants, anti-dripping agents or flame retardants.
  • the lubricant is pentaerythritol stearate.
  • the anti-dripping agent is polytetrafluoroethylene.
  • the flame retardant is a bromine antimony system flame retardant.
  • the preparation method of the above-mentioned polycarbonate/polyester alloy composition with long-term thermo-oxidative stability comprises the steps of: polycarbonate, polyester, toughening agent, antimony-containing compound, antioxidant and other auxiliary agents (such as Yes) mixing uniformly, melting, extruding, and granulating to obtain the polycarbonate/polyester alloy composition with long-term thermo-oxygen stability.
  • the preparation method of the polycarbonate/polyester alloy composition with long-term thermo-oxidative stability comprises the steps:
  • step (1) Put the premixed material in step (1) into twin-screw extruder and extrude and granulate to obtain the polycarbonate/polyester alloy composition with long-term thermo-oxidative stability.
  • the mixing speed, melting temperature and extrusion temperature in the present invention are not particularly limited, and these parameters can be selected by those skilled in the art based on their own experience, so that the alloy composition can be extruded.
  • the mixing speed is 300-2000 rpm.
  • the aspect ratio of the screw in the twin-screw extruder is 40-45:1
  • the temperature of the screw barrel is 210-250° C.
  • the screw speed is 500-600 rpm.
  • the present invention has the following beneficial effects:
  • the polycarbonate/polyester alloy composition provided by the present invention utilizes antimony-containing compounds to cooperate with the antioxidant system, which can inhibit the migration and precipitation of antioxidants in polycarbonate/polyester alloys, and slow down the development of polycarbonate/polyester alloys.
  • the obtained polycarbonate/polyester alloy composition has good mechanical properties and significantly improved long-term thermo-oxidative stability.
  • PC Polycarbonate 1: 1300 10NP (aromatic polycarbonate), LG Chemicals, the average molecular weight is 25000, prepared by phosgene method;
  • PC 2 7030 (aromatic polycarbonate), Mitsubishi, Japan, the average molecular weight is 36000, prepared by phosgene method;
  • Polyester (PBT) 1 GL236, Yizheng Chemical, viscosity 1.3dl/g;
  • Polyester (PET) 2 CR-7702, China Resources Chemical, viscosity is 0.52dl/g;
  • Acrylic-silicone rubber toughening agent S-2130, Mitsubishi, Japan;
  • Antimony-containing compound 1 antimony pentoxide, McLean Reagent Company;
  • Antimony-containing compound 2 antimony trioxide, McLean Reagent Company;
  • Antimony-containing compound 3 sodium antimonate, McLean Reagent Company
  • Antimony-containing compound 4 zinc antimonate, McLean Reagent Company
  • Antimony-containing compound 5 antimony bromide, McLean Reagent Company;
  • Primary antioxidant 1 ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, Sanfeng Chemical Co., Ltd.;
  • Primary antioxidant 2 tetrakis [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, Sanfeng Chemical Co., Ltd.;
  • Secondary antioxidant 1 three (2,4-di-tert-butylphenyl) phosphite, Sanfeng Chemical Co., Ltd.;
  • the polycarbonate/polyester alloy composition in the embodiment of the present invention and comparative example is prepared through the following process:
  • each component is weighed according to the formula, premixed in a high mixer to obtain a premix, the above premix is put into a twin-screw extruder, melted and mixed in a twin-screw extruder, extruded and granulated, and obtained Polycarbonate/polyester alloy composition wherein the screw length-to-diameter ratio is 45:1, the screw barrel temperature is 250° C., and the screw speed is 550 rpm.
  • the screw length-to-diameter ratio is 45:1
  • the screw barrel temperature is 250° C.
  • the screw speed is 550 rpm.
  • Each raw material enumerated in the present invention, and the upper and lower limits of each raw material of the present invention, the interval value, and the upper and lower limits of process parameters (such as temperature, time, etc.), the interval value can realize the present invention, do not enumerate one by one here .
  • test methods of each performance of each embodiment of the present invention and comparative example polycarbonate/polyester alloy composition are as follows:
  • Tensile strength test the tensile strength of the tensile sample according to ASTM D638-2014 standard; at the same time, the tensile sample is subjected to thermal oxygen aging in a constant temperature test box with a preset temperature of 130°C, and the aging time is 3000h according to the sampling plan Finally, after taking out the test sample, put it in an environment with a room temperature of 23 ⁇ 2°C and a humidity of 50% for adjustment for more than 48 hours, then perform a tensile strength test and record the results, and compare the retention rate of tensile strength properties before and after aging as the long-term The judgment of thermal oxygen stability is good or bad, the higher the performance retention rate, the better the long-term thermal oxygen stability.
  • Impact strength According to ASTM D1822-2013 standard, test the tensile impact strength of 3.0mm splines; the type of splines is Type c, and heat the tensile impact splines in a constant temperature test box with a preset temperature of 130°C Oxygen aging, take out the test sample after 3000h aging time according to the sampling plan, put it in an environment with a room temperature of 23 ⁇ 2°C and a humidity of 50% for adjustment for more than 48h, then perform a tensile strength test and record the results, by comparing before and after aging
  • the performance retention rate is used as the judgment of long-term thermal oxygen stability. The higher the performance retention rate, the better the long-term thermal oxygen stability.
  • This embodiment provides a series of polycarbonate/polyester alloy compositions, the formulations of which are shown in Table 1 and Table 2.
  • This comparative example provides a series of polycarbonate/polyester alloy compositions, the formulations of which are shown in Table 3.
  • the polycarbonate/polyester alloy composition provided by each embodiment has good mechanical properties and significantly improved long-term thermo-oxidative stability.
  • the performance retention rate of the polyester alloy composition after aging is higher than 70%; in particular, the polycarbonate/polyester alloy composition provided in Examples 1 to 4, 6 to 9, and 12 to 16 is aged at a high temperature of 3000h and 130°C After treatment, the polycarbonate/polyester alloy composition retains more than 80% of its properties after aging.
  • the performance retention rate of polycarbonate/polyester alloy composition after aging shows the trend of first increasing and then decreasing; in embodiment 2, 6 ⁇ 9, select Different antimony-containing compounds have little difference in the performance retention rate of samples after aging.
  • the examples here are only examples, such as replacing the toughening agent in Example 1 with methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-glycidyl methacrylate terpolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer or acrylic
  • the conventional toughening agents in the field such as tougheners, or when adding lubricants, anti-dripping agents, flame retardants, and other additives commonly used in the field, the resulting polycarbonate/polyethylene Compared with Example 1, the ester alloy composition has good mechanical properties similar to Example 1 and significantly improved long-term thermo-oxidative stability after 3000 hours of high-temperature aging treatment at 130°C.

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Abstract

本发明涉及一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物及其制备方法和应用。该聚碳酸酯/聚酯合金组合物包括聚碳酸酯、聚酯、增韧剂、含锑化合物、抗氧剂和其他助剂。本发明提供的聚碳酸酯/聚酯合金组合物利用含锑化合物与抗氧剂体系协同，可抑制抗氧剂在聚碳酸酯/聚酯合金的迁移、析出，减缓聚碳酸酯/聚酯合金的热氧老化，得到的聚碳酸酯/聚酯合金组合物具有良好的机械性能以及明显改善的长期热氧稳定性能。

Description

一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物及其制备方法和应用 技术领域
本发明属于工程塑料技术领域，具体涉及一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物及其制备方法和应用。
背景技术
聚碳酸酯/聚酯合金是一种高性能的合金材料，具有韧性好，表面光泽度高，加工流动性好等优点，同时聚酯的加入能够显著提高聚碳酸酯的耐化学性，进一步拓展其应用领域，如电子电气、厨卫、视听设备、交通运输等领域。
高分子材料加工及使用过程中会在热、氧等作用下发生老化，即材料性能劣化，如泛黄、表面龟裂、分子链降低并导致机械性能下降或丧失的现象。随着行业的快速发展对材料提出了越来越高的要求，尤其是在服役安全和稳定性方面，为了满足材料在实际应用中的技术变化需求，聚碳酸酯/聚酯合金应具备长期的热氧稳定性以保证其在长期服役过程中保持足够的机械性能。
添加抗氧剂是常规已知的改善聚碳酸酯/聚酯合金的加工热稳定性的方法，并且通常采用受阻酚与亚磷酸酯复配的抗氧剂体系；然而常规的受阻酚与亚磷酸酯复配的抗氧剂体系无法满足其长期热氧稳定性的要求，导致聚碳酸酯/聚酯合金制品在长时间后使用后机械性能下降或丧失，这在一定程度上限制了材料的应用。
专利CN102093673A公开一种具有抗热老化性能的聚酯，利用复配的抗氧剂体系和特定的热稳定剂DSTDP来改善长期热老化性能，但相关研究非常少，限制了聚碳酸酯/聚酯合金的应用。
因此，开发一种具有长期热氧稳定性及较佳机械性能的聚碳酸酯/聚酯合金材料以提高其服役安全性、稳定性及扩大应用范围具有重要的研究意义。
发明内容
本发明的目的在于克服现有技术中聚碳酸酯/聚酯合金材料无法满足其长期热氧稳定性的要求，限制了其应用的缺陷或不足，提供一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物。本发明提供的聚碳酸酯/聚酯合金组合物利用含锑化合物与抗氧剂体系协同，可抑制抗氧剂在聚碳酸酯/聚酯合金的迁移、析出， 减缓聚碳酸酯/聚酯合金的热氧老化，得到的聚碳酸酯/聚酯合金组合物具有良好的机械性能以及明显改善的长期热氧稳定性能。
本发明的另一目的在于提供上述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物的制备方法。
本发明的另一目的在于提供上述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物在制备电子电气、厨卫产品、视听设备或交通运输产品中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，包括如下重量份数的组分：
Figure PCTCN2022112215-appb-000001
所述抗氧剂为主抗氧剂和辅抗氧剂的混合物，所述主抗氧剂和辅抗氧剂的重量比为1.0:(0.5～1.0)。
研究发现，现有抗氧剂体系(主抗氧剂和辅抗氧剂复配体系)的添加虽然可提升聚碳酸酯/聚酯合金的加工热稳定性，但在长期高温条件下，会存在抗氧剂在聚碳酸酯/聚酯合金中迁移、析出的问题，进而导致长期热氧稳定性不佳，机械性能无法较好保持。经反复试验，本发明的发明人发现，在聚碳酸酯/聚酯合金中加入少量的含锑化合物，并配合抗氧剂体系，含锑化合物和抗氧剂体系之间存在一定的相互作用可以抑制抗氧剂在聚碳酸酯/聚酯合金的迁移、析出，减缓聚碳酸酯/聚酯合金的热氧老化，从而可以使制得的聚碳酸酯/聚酯合金组合物具有良好的机械性能以及明显改善的长期热氧稳定性能。
本发明提供的聚碳酸酯/聚酯合金组合物经高温老化后拉伸强度及拉伸冲击强度保持率不低于80％，可广泛应用于电子电气、厨卫产品、视听设备或交通运输产品中。
优选地，所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，包括如下 重量份数的组分：
聚碳酸酯15～90份，
聚酯10～50份，
增韧剂1～20份，
含锑化合物0.8～2.5份，
抗氧剂0.05～1.5份，
其他助剂0.2～8份。
本领域常规的聚碳酸酯、聚酯、增韧剂均可用于本发明中，可通过商购得到。
优选地，所述聚碳酸酯为芳香族聚碳酸酯或硅氧烷共聚碳酸酯中的一种或几种。
更为优选地，所述芳香族聚碳酸酯为双酚A型聚碳酸酯；
更为优选地，所述硅氧烷共聚碳酸酯为聚二甲基硅氧烷-双酚A型聚碳酸酯；
更为优选地，所述聚碳酸酯为芳香族聚碳酸酯。
进一步优选地，所述芳香族聚碳酸酯的平均分子量为15000～30000；再进一步优选为平均分子量20000～28000的芳香族聚碳酸酯。当平均分子量在上述范围内，机械强度良好并且能保证良好的成型性。其中，平均分子量通过凝胶渗透色谱法测试。
优选地，所述聚酯为二醇单体与二酸单体聚合得到的共聚酯；所述二醇单体为乙二醇、己二醇、丙二醇、丁二醇、1.4-环己烷二甲醇、新戊二醇或对苯二甲醇中的一种或几种；所述二酸单体为对苯二甲酸、间苯二甲酸、戊二酸、己二酸或辛二酸中的一种或几种。
更为优选地，所述聚酯为聚对苯二甲酸丁二醇酯(PBT)或聚对苯二甲酸乙二醇酯中的一种或几种；进一步优选为聚对苯二甲酸丁二醇酯。
更为优选地，所述聚酯的粘度不低于0.7dl/g。
如无特殊说明，本发明的粘度根据标准GB/T 14190采用乌氏粘度计法测定得到，测试温度为25℃。
更为优选地，所述聚酯的粘度为0.7～1.5dl/g。
优选地，所述增韧剂为甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、甲基丙烯酸甲酯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯- 丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物、马来酸酐接枝的乙烯-醋酸乙烯共聚物、丙烯酸类增韧剂或丙烯酸-硅橡胶类增韧剂中的一种或几种。
优选地，所述含锑化合物为锑的氧化物、锑酸盐或卤化锑中的一种或几种。
更为优选地，所述锑的氧化物为三氧化二锑或五氧化二锑中的一种或两种。
更为优选地，所述锑酸盐为锑酸钠或锑酸锌中的一种或两种。
更为优选地，所述卤化锑为溴化锑。
更为优选地，所述含锑化合物为五氧化二锑、锑酸锌或溴化锑中的一种或几种。选用这几种含锑化合物时，具有更为优异的长期热氧稳定性。
所述含锑化合物在聚碳酸酯/聚酯合金组合物中的重量分数为0.5～2.5％。
优选地，所述主抗氧剂为受阻酚类抗氧剂。
更为优选地，所述受阻酚类抗氧剂为β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯。
优选地，所述辅抗氧剂为磷系辅抗氧剂或硫系辅抗氧剂中的一种或几种。
更为优选地，所述磷系辅抗氧剂为三(2,4-二叔丁基苯基)亚磷酸酯。
更为优选地，所述硫系辅抗氧剂为季戊四醇四(3-月桂基硫代丙酸酯)。
本领域中常规的其他助剂均可用于本发明。优选地，所述其他助剂为润滑剂、抗滴落剂或阻燃剂中的一种或几种。
更为优选地，所述润滑剂为季戊四醇硬脂酸酯。
更为优选地，所述抗滴落剂为聚四氟乙烯。
更为优选地，所述阻燃剂为溴锑体系的阻燃剂。
上述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物的制备方法，包括如下步骤：将聚碳酸酯、聚酯、增韧剂、含锑化合物、抗氧剂和其他助剂(如有)混合均匀，熔融，挤出，造粒，即得所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物。
具体地，所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物的制备方法包括如下步骤：
S1：按照配比称取聚碳酸酯、聚酯、含锑化合物、抗氧剂及其他助剂后在高混机中搅拌共混，得到预混料；
S2：将步骤(1)中的预混料投入双螺杆挤出机中挤出造粒即可得到所述的 具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物。
本发明中的混合速度、熔融温度和挤出温度等，没有特别的限定，这些参数可以由本领域技术人员根据自己经验来选择，使得合金组合物挤出即可。
优选地，所述混合的速度为300-2000rpm。
优选地，所述双螺杆挤出机中螺杆长径比为40-45:1，螺筒温度为210-250℃，螺杆转速为500-600rpm。
上述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物在制备电子电气、厨卫产品、视听设备或交通运输产品中的应用也在本发明的保护范围内。
与现有技术相比，本发明具有如下有益效果：
本发明提供的聚碳酸酯/聚酯合金组合物利用含锑化合物与抗氧剂体系协同，可抑制抗氧剂在聚碳酸酯/聚酯合金的迁移、析出，减缓聚碳酸酯/聚酯合金的热氧老化，得到的聚碳酸酯/聚酯合金组合物具有良好的机械性能以及明显改善的长期热氧稳定性能。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
聚碳酸酯(PC)1：1300 10NP(芳香族聚碳酸酯)，LG化学，平均分子量为25000，光气法制备得到；
聚碳酸酯(PC)2：7030(芳香族聚碳酸酯)，日本三菱，平均分子量为36000，光气法制备得到；
聚酯(PBT)1：GL236，仪征化学，粘度为1.3dl/g；
聚酯(PET)2：CR-7702，华润化学，粘度为0.52dl/g；
丙烯酸-硅橡胶类增韧剂：S-2130，日本三菱；
含锑化合物1：五氧化二锑，麦克林试剂公司；
含锑化合物2：三氧化二锑，麦克林试剂公司；
含锑化合物3：锑酸钠，麦克林试剂公司；
含锑化合物4：锑酸锌，麦克林试剂公司；
含锑化合物5：溴化锑，麦克林试剂公司；
主抗氧剂1：β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯，三丰化工有限公司；
主抗氧剂2：四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯，三丰化工有限公司；
辅抗氧剂1：三(2,4-二叔丁基苯基)亚磷酸酯，三丰化工有限公司；
辅抗氧剂2：Revonox 608,奇钛化工；
润滑剂：PETS，发基化学品有限公司；
本发明实施例以及对比例中聚碳酸酯/聚酯合金组合物通过如下过程制备得到：
按配方称取各组分，在高混机中进行预混合得到预混料，将上述预混物投入双螺杆挤出机中，在双螺杆挤出机中熔融混合并挤出造粒，得到聚碳酸酯/聚酯合金组合物其中，螺杆长径比为45:1，螺筒温度为250℃，螺杆转速为550rpm。本发明所列举的各原料，以及本发明各原料的上下限、区间取值，以及工艺参数(如温度、时间等)的上下限、区间取值都能实现本发明，在此不一一列举。
本发明各实施例及对比例聚碳酸酯/聚酯合金组合物的各项性能的测试方法如下：
拉伸强度：根据ASTM D638-2014标准测试拉伸样条的拉伸强度；同时将拉伸样条在预设好温度为130℃的恒温实验箱中进行热氧老化，按照取样计划3000h老化时间后取出测试样条后，放在室温为23±2℃湿度为50％的环境下进行调节48h以上，然后进行拉伸强度测试并记录结果，通过对比老化前后的拉伸强度性能保持率作为长期热氧稳定性好坏的判定，性能保持率越高，长期热氧稳定性越好。
冲击强度：根据ASTM D1822-2013标准下测试3.0mm样条的拉伸冲击强度；样条类型为Type c，同时将拉伸冲击样条在预设好温度为130℃的恒温实验箱中进行热氧老化，按照取样计划3000h老化时间后取出测试样条后，放在室温为23±2℃湿度为50％的环境下进行调节48h以上，然后进行拉伸强度测试并记 录结果，通过对比老化前后的性能保持率作为长期热氧稳定性好坏的判定，性能保持率越高，长期热氧稳定性越好。
实施例1～16
本实施例提供一系列聚碳酸酯/聚酯合金组合物，其配方如表1和表2。
表1实施例1～9的配方(份)
Figure PCTCN2022112215-appb-000002
表2实施例10～16的配方(份)
Figure PCTCN2022112215-appb-000003
对比例1～5
本对比例提供一系列聚碳酸酯/聚酯合金组合物，其配方如表3。
表3对比例1～5的配方(份)
  对比例1 对比例2 对比例3 对比例4 对比例5
聚碳酸酯1 62.5 62.5 62.5 62.5 62.5
聚酯1 30 30 30 30 30
丙烯酸-硅橡胶类增韧剂 5 5 5 5 5
含锑化合物1 / / / 2 1
主抗氧剂1 / 0.2 / / 0.2
主抗氧剂2 / / 0.2 / /
辅抗氧剂1 / 0.1 / / /
辅抗氧剂2 / / 0.1 / /
润滑剂 0.2 0.2 0.2 0.2 0.2
按前述的性能测试方法对各实施例和对比例所提供的聚碳酸酯/聚酯合金组合物的性能进行测试，结果如表4。
表4实施例1～16和对比例1～5提供的聚碳酸酯/聚酯合金组合物的性能测
试结果
Figure PCTCN2022112215-appb-000004
由上述测试结果可知，各实施例提供的聚碳酸酯/聚酯合金组合物具有良好的机械性能以及明显改善的长期热氧稳定性能，经3000h、130℃的高温老化处理后，聚碳酸酯/聚酯合金组合物老化后性能保持率高于70％；特别地，实施例1～4、6～9、12～16提供的聚碳酸酯/聚酯合金组合物经3000h、130℃的高温老化处理后，聚碳酸酯/聚酯合金组合物老化后性能保持率高于80％。实施例3、1～2和4中随着含锑化合物含量的增加，聚碳酸酯/聚酯合金组合物老化后性能保持率呈先升高后降低趋势；实施例2、6～9中选用不同的含锑化合物，样品老化后的性能保持率差异不大。对比例1中未对热氧稳定性进行改性，其老化后拉伸强度和拉伸冲击强度保持率均不足10％；对比例2和3的聚碳酸酯/聚酯合金组合物中未添加含锑化合物，其老化后拉伸强度及拉伸冲击强度保持率低于40％；其中，对比例3选用的抗氧剂体系(主抗氧剂)更易迁移和析出，其老化后拉伸强度及拉伸冲击强度保持率更低；对比例4的聚碳酸酯/聚酯合金组合物中未添加抗氧剂体系，其老化后拉伸强度和拉伸冲击强度保持率均不足20％；对比例5中的聚碳酸酯/聚酯合金组合物中未添加辅抗氧剂，导致聚碳酸酯/聚酯合金组合物耐老化性能下降，其老化后拉伸强度和拉伸冲击强度保持率均低于50％。
另外，需要说明的是，此处的实施例仅为示例，如将实施例1中增韧剂替换为甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、甲基丙烯酸甲酯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物、马来酸酐接枝的乙烯-醋酸乙烯共聚物或丙烯酸类增韧剂等本领域常规的增韧剂中的一种或几种时，或添加润滑剂、抗滴落剂、阻燃剂、等本领域常用的其他助剂时，得到的聚碳酸酯/聚酯合金组合物与实施例1相比，经3000h、130℃的高温老化处理后，具有与实施例1相近的良好的机械性能以及明显改善的长期热氧稳定性能。
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。

Claims (10)

  1. 一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，包括如下重量份数的组分：
    Figure PCTCN2022112215-appb-100001
    所述抗氧剂为主抗氧剂和辅抗氧剂的混合物，所述主抗氧剂和辅抗氧剂的重量比为1.0:(0.5～1.0)。
  2. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯15～90份，
    聚酯10～50份，
    增韧剂1～20份，
    含锑化合物0.8～2.5份，
    抗氧剂0.05～1.5份，
    其他助剂0.2～8份。
  3. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，所述聚碳酸酯为芳香族聚碳酸酯、脂肪族聚碳酸酯、支化聚碳酸酯、芳香族-脂肪族聚碳酸酯或硅氧烷共聚碳酸酯中的一种或几种。
  4. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，所述聚酯为二醇单体与二酸单体聚合得到的共聚酯；所述二醇单体为乙二醇、己二醇、丙二醇、丁二醇、1.4-环己烷二甲醇、新戊二醇或对苯二甲醇中的一种或几种；所述二酸单体为对苯二甲酸、间苯二甲酸、戊二酸、己二酸或辛二酸中的一种或几种。
  5. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，所述增韧剂为甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、甲基丙烯酸甲酯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸丁酯共聚物、乙 烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物、马来酸酐接枝的乙烯-醋酸乙烯共聚物、丙烯酸类增韧剂或丙烯酸-硅橡胶类增韧剂中的一种或几种。
  6. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，所述含锑化合物为锑的氧化物、锑酸盐或卤化锑中的一种或几种；所述含锑化合物在聚碳酸酯/聚酯合金组合物中的重量分数为0.5～2.5％。
  7. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，所述主抗氧剂为受阻酚类抗氧剂；所述辅抗氧剂为磷系辅抗氧剂或硫系辅抗氧剂中的一种或几种。
  8. 根据权利要求1所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物，其特征在于，所述其他助剂为润滑剂、抗滴落剂或阻燃剂中的一种或几种。
  9. 权利要求1～8任一所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物的制备方法，其特征在于，包括如下步骤：将聚碳酸酯、聚酯、增韧剂、含锑化合物、抗氧剂和其他助剂混合均匀，熔融，挤出，造粒，即得所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物。
  10. 权利要求1～8任一所述具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物在制备电子电气、厨卫产品、视听设备或交通运输产品中的应用。
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KR20100133786A (ko) * 2009-06-12 2010-12-22 제일모직주식회사 폴리에스테르/폴리카보네이트 얼로이 수지 조성물　및 이를 이용한 성형품
CN104693755A (zh) * 2013-12-10 2015-06-10 青岛同创节能环保工程有限公司 一种pc/pbt阻燃改性材料及其制备方法
CN104845332A (zh) * 2014-12-12 2015-08-19 青岛佳亿阳工贸有限公司 一种阻燃性pc/ptt/碳纳米管复合材料
KR20170032672A (ko) * 2015-09-15 2017-03-23 롯데케미칼 주식회사 열안정성이 향상된 폴리카보네이트/폴리에스테르 얼로이 수지 조성물
CN113637310A (zh) * 2021-08-17 2021-11-12 金发科技股份有限公司 一种具有长期热氧稳定性的聚碳酸酯/聚酯合金组合物及其制备方法和应用

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