WO2023279984A1 - 一种力学性能稳定的pbt/pc合金及其制备方法和制品 - Google Patents

一种力学性能稳定的pbt/pc合金及其制备方法和制品 Download PDF

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WO2023279984A1
WO2023279984A1 PCT/CN2022/101019 CN2022101019W WO2023279984A1 WO 2023279984 A1 WO2023279984 A1 WO 2023279984A1 CN 2022101019 W CN2022101019 W CN 2022101019W WO 2023279984 A1 WO2023279984 A1 WO 2023279984A1
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pbt
alloy
parts
injection molding
toughening agent
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PCT/CN2022/101019
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English (en)
French (fr)
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陈伟
陈平绪
叶南飚
莫文杰
龚德君
冯健
付学俊
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金发科技股份有限公司
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a PBT/PC alloy with stable mechanical properties, a preparation method and a product thereof.
  • PC Polycarbonate
  • PBT Polybutylene terephthalate
  • PC polycarbonate
  • PBT polybutylene terephthalate
  • the blending modification of PC and PBT can not only make up for the shortcomings of high melt viscosity, poor fluidity, and poor solvent resistance of PC, but also improve the defects of PBT's low impact resistance. It can be widely used in automotive engineering, electrical and electronic engineering , Sports and leisure products.
  • PC and PBT are prone to side reactions such as transesterification and alcoholysis and acidolysis during melt blending. Make the mechanical properties of PBT/PC alloy unstable.
  • the retention rate of mechanical properties of PBT/PC alloy is generally below 75% of the properties of the new material; after three injection molding, the retention rate of mechanical properties further drops to below 50%, which has been achieved in most cases. Unable to meet the application requirements of the product.
  • the nozzle material of the PBT/PC alloy is recycled, and the nozzle material is usually mixed into the new material in a certain proportion by blending new and old materials.
  • the nozzle material cannot be used directly, and the reuse efficiency is poor.
  • the present invention provides a PBT/PC alloy with stable mechanical properties in order to overcome the defects of poor mechanical properties after multiple injection moldings described in the above-mentioned prior art.
  • the retention rate of mechanical properties after three injections is ⁇ 90%.
  • Another object of the present invention is to provide a method for preparing the above-mentioned PBT/PC alloy with stable mechanical properties.
  • Another object of the present invention is to provide a PBT/PC alloy product made from the nozzle material of the above-mentioned PBT/PC alloy.
  • a PBT/PC alloy with stable mechanical properties comprising the following components by weight:
  • trimethallyl isocyanate (TMAIC)
  • the weight ratio of PBT and PC in the PBT/PC mixture is (2 ⁇ 6): 1,
  • the toughening agent is a silicone-acrylate core-shell structure toughening agent.
  • the inventors have found that since the molecular structures of PBT and PC contain ester groups, in the process of multiple injection molding, due to the high injection temperature and high shear force, transesterification reaction between PBT and PC is very easy to occur. , resulting in a substantial decrease in the crystallization ability of the PBT/PC system, resulting in a decrease in the mechanical properties of the PBT/PC alloy material.
  • TMAIC Trimethallyl isocyanate
  • C 15 H 21 N 3 O 3 is a polymer crosslinking aid suitable for use at relatively high processing temperatures.
  • TMAIC can quickly initiate the cross-linking reaction between molecular chains in the PBT/PC system, and make up for the decrease in the mechanical properties of the alloy caused by the transesterification between PBT and PC molecules, thereby greatly improving The performance retention rate of the alloy material in the multiple injection molding process was determined.
  • cross-linking aids for polymer materials such as organic peroxides and acrylate cross-linking agents, cannot provide the same excellent cross-linking promotion effect as TMAIC in the PBT/PC system.
  • the toughening agent is a silicone-acrylate core-shell structure toughening agent
  • the shell part provides good dispersion and compatibility with the matrix resin
  • the core part can absorb and disperse impact energy.
  • the core-shell toughening agent has a more excellent toughening effect in the PBT/PC alloy system of the present invention.
  • the initial mechanical properties of the PBT/PC alloy are improved, on the other hand, the performance degradation of the alloy during multiple injection molding processes is reduced, and a good performance retention rate is obtained.
  • the acid value of the TMAIC is ⁇ 1 mgKOH/g.
  • the acid value test method is based on GB/T 264-1983.
  • the toughening agent uses methyl methacrylate or grafted polymethyl methacrylate as the shell and a cross-linked acrylate-silicone copolymer as the core.
  • the toughening agent can be S-2501, S-2001, S-2006 from Mitsubishi Rayon Co., Ltd., MR-502 from Zhongyuan Chemical Industry, DONGEM S-203, or BSMCMX-520S/550S.
  • the PC is one or more of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branched polycarbonate or siloxane copolycarbonate.
  • the PC is aromatic polycarbonate.
  • the viscosity average molecular weight of the aromatic polycarbonate is 13000-40000.
  • the viscosity average molecular weight of the aromatic polycarbonate is 18000-28000.
  • the detection method of the viscosity-average molecular weight of the PC is as follows: using dichloromethane as a solvent, and calculating it by Ubbelohde viscosity at a test temperature of 25°C.
  • PC within the above viscosity-average molecular weight range, as the matrix resin of the PBT/PC alloy, can bring more excellent mechanical strength retention to the alloy.
  • the intrinsic viscosity of the PBT at 25°C is 0.7 ⁇ 1.1 dL/g.
  • the intrinsic viscosity test method of PBT is based on GB/T 14190-2017.
  • the glass fibers are treated with a coupling agent.
  • the coupling agent is N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, isopropyl di( A blend of methacryl) isostearyl titanate.
  • the blending weight ratio of isostearyl titanate is 2:1:3.
  • the glass fiber treated with coupling agent has more excellent interfacial properties with PBT and PC components. Better performance retention can be maintained during overmolding or overmolding.
  • the optimal ratio of the glass fiber can have the best interfacial bonding force between the phases of the PBT resin and the PC resin.
  • the epoxy resin is bisphenol A glycidyl ether, and the epoxy equivalent is less than 600g/eq.
  • the epoxy equivalent of the epoxy resin is 450-500 g/eq.
  • test method of described epoxy equivalent is based on GB/T 4612-2008.
  • the retention rate of mechanical properties of the PBT/PC alloy described in the present invention can be maintained at a good level during multiple cycles of injection molding.
  • a large number of creative experimental data show that when a certain component or two components are missing, the PBT/PC alloy cannot achieve the effect of maintaining the mechanical properties described in the present invention.
  • the antioxidant is a hindered phenolic antioxidant.
  • the antioxidant is ⁇ (3,5 di-tert-butyl-4-hydroxyphenyl) octadecyl propionate (antioxidant 1076) and/or 1,3,5-tri(4 -tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.
  • the present invention also protects the preparation method of the above-mentioned PBT/PC alloy, comprising the following steps:
  • Epoxy resin, antioxidant, toughener and TMAIC are mixed to obtain a premix
  • PBT, PC, glass fiber and the premix are mixed and fed into an extruder, melted, extruded and granulated to obtain the PBT/PC alloy.
  • the extruder is a twin-screw extruder.
  • the temperature of the first zone of the twin-screw extruder from the feeding port to the machine head is 200-230°C
  • the temperature of the second zone is 240-260°C
  • the temperature of the third zone is 235-255°C
  • the temperature of the fourth zone is 235 ⁇ 255°C
  • the temperature in the fifth zone is 235 ⁇ 255°C
  • the temperature in the sixth zone is 240 ⁇ 260°C
  • the temperature in the seventh zone is 240 ⁇ 260°C
  • the temperature in the eighth zone is 220 ⁇ 240°C
  • the temperature in the ninth zone is 220 ⁇ 240°C
  • the temperature in the tenth zone is 240-260° C.
  • the screw speed of the twin-screw extruder is 200-450 rpm.
  • the invention also protects a PBT/PC alloy product, which is directly processed from the nozzle material of the above-mentioned PBT/PC alloy.
  • the processing method of described PBT/PC alloy product can be:
  • the nozzle material of the above-mentioned PBT/PC alloy is added to an injection molding machine, and injection molding is performed at 220-270°C.
  • the present invention effectively improves the retention rate of the mechanical properties of the PBT/PC alloy after multiple injections through the synergistic effect of trimethallyl isocyanate, a silicone-acrylate toughening agent with a core-shell structure and epoxy resin,
  • the stability of mechanical properties of PBT/PC alloy is improved.
  • TMAIC can quickly trigger the crosslinking reaction between molecular chains, effectively preventing the breakage of PBT and PC molecular chains, thereby reducing the degradation of PBT/PC alloys in the multiple injection molding process;
  • the effect further improves the mechanical property retention rate of PBT/PC alloy.
  • the PBT/PC alloy of the invention has a mechanical property retention rate of ⁇ 95% after secondary injection molding, and a mechanical property retention rate of ⁇ 90% after three injection moldings, and is suitable for multiple cycle injection molding.
  • the raw material in embodiment and comparative example all can be obtained by commercially available;
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • the temperature of the first zone from the feed port to the head of the twin-screw extruder is 200-230°C
  • the temperature of the second zone is 240-260°C
  • the temperature of the third zone is 235-255°C
  • the temperature of the fourth zone is 235-255°C
  • the temperature of the fifth zone is 235-255°C.
  • the temperature in the zone is 235-255°C
  • the temperature in the sixth zone is 240-260°C
  • the temperature in the seventh zone is 240-260°C
  • the temperature in the eighth zone is 220-240°C
  • the temperature in the ninth zone is 220-240°C
  • the temperature in the tenth zone is 240-240°C 260°C
  • the screw speed of the twin-screw extruder is 200-450 rpm.
  • the temperature of the first zone from the feed port to the head of the twin-screw extruder is 200-230°C
  • the temperature of the second zone is 240-260°C
  • the temperature of the third zone is 235-255°C
  • the temperature of the fourth zone is 235-255°C
  • the temperature of the fifth zone is 235-255°C.
  • the temperature in the zone is 235-255°C
  • the temperature in the sixth zone is 240-260°C
  • the temperature in the seventh zone is 240-260°C
  • the temperature in the eighth zone is 220-240°C
  • the temperature in the ninth zone is 220-240°C
  • the temperature in the tenth zone is 240-240°C 260°C
  • the screw speed of the twin-screw extruder is 200-450 rpm.
  • PBT/PC alloy is subjected to primary injection molding, secondary injection molding, and tertiary injection molding, and the specific methods are as follows:
  • Initial injection molding Dry the extruded and granulated PBT/PC alloy pellets in a blast drying oven at 120°C for 6 hours, and then inject them into ISO standard mechanical splines through an injection molding machine, which is the initial injection molding mechanical splines;
  • Secondary injection molding crush the mechanical splines obtained by the primary injection molding with a crusher, dry the crushed particles in a blast drying oven at 120°C for 6 hours, and then inject them into ISO standard mechanical splines through an injection molding machine, which is the secondary injection molding.
  • Injection Molding Mechanics Splines
  • Three-time injection molding crush the mechanical splines obtained by secondary injection molding with a crusher, dry the crushed particles in a blast drying oven at 120°C for 6 hours, and then inject them into ISO standard mechanical splines through an injection molding machine, which is three-time injection molding Mechanics splines.
  • Notched impact strength tested according to the ISO180-2000 standard method, the unit is kJ/m 2 ;
  • Retention rate (detection value of secondary injection molding or tertiary injection molding/corresponding detection value of primary injection molding)*100%.
  • the PBT/PC alloys of Examples 1 to 19 are through secondary injection molding, compared with the initial injection molding, the mechanical property retention rate is ⁇ 95%, and the PBT/PC alloy is through three injection moldings, compared with the initial injection molding, The retention rate of mechanical properties is ⁇ 90%. This shows that the PBT/PC alloy of the present invention has very little loss of mechanical properties after repeated injection molding, and still maintains high rigidity and toughness.
  • PC is preferably aromatic polycarbonate, more preferably aromatic polycarbonate with a viscosity average molecular weight of 18000-28000. Within this range, the retention rate of mechanical properties of PBT/PC alloy is better after secondary or tertiary injection molding.
  • the weight ratio of PBT and PC is preferably (2 ⁇ 4):1.
  • the toughening agent is preferably grafted polymethyl methacrylate as the shell and a crosslinked acrylate-organosilicon copolymer as the core.
  • Example 13 the glass fiber is not treated with a coupling agent, and the mechanical property retention rate of the prepared PBT/PC alloy is slightly poor after repeated injection molding.
  • the toughening agent is not a core-shell structure.
  • crosslinking agent 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is used to replace TMAIC to obtain
  • the mechanical property retention rate is ⁇ 88%
  • the mechanical property retention rate is ⁇ 81% after the third injection molding.
  • the weight ratio of PBT and PC is 1: 1, which exceeds the weight ratio range of PBT and PC in the technical solution of the present invention, and the obtained PBT/PC alloy is difficult to maintain excellent mechanical properties after secondary and tertiary injection molding .

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

本发明公开了一种力学性能稳定的PBT/PC合金及其制备方法。本发明的PBT/PC合金包括如下重量份的组分：PBT/PC混合物50～80份，玻璃纤维10～40份，环氧树脂2～5份，抗氧剂0.1～0.3份，增韧剂4～8份，三甲代烯丙基异氰酸酯2～4份；所述PBT/PC混合物中PBT和PC的重量比为(2～6)∶1，所述增韧剂为有机硅-丙烯酸酯类的核-壳结构增韧剂。本发明通过三甲代烯丙基异氰酸酯、具有核-壳结构的增韧剂和环氧树脂的协同作用，有效提高了PBT/PC合金的多次注塑后力学性能保持率。本发明的PBT/PC合金经过二次注塑力学性能保持率≥95％，三次注塑后力学性能保持率≥90％，耐多次循环注塑使用。

Description

一种力学性能稳定的PBT/PC合金及其制备方法和制品 技术领域
本发明涉及工程塑料技术领域，更具体的，涉及一种力学性能稳定的PBT/PC合金及其制备方法和制品。
背景技术
聚碳酸酯(PC)作为一种非结晶性的热塑性塑料，其冲击强度高、耐蠕变性能优良，聚对苯二甲酸丁二醇酯(PBT)，是一种结晶性的热塑性塑料，具有结晶速度快，刚性高、耐化学药品性优良、熔体流动性好等优点。将PC和PBT进行共混改性，既可以弥补PC熔体粘度大、流动性差、耐溶剂性能差等不足，又能改善PBT耐冲击性能低等缺陷，可以广泛应用于汽车工程、电子电气工程、运动和休闲用品领域。
然而，由于PC分子链端具有-OH基团，PBT分子链链端具有-OH和-COOH基团，PC和PBT在熔融共混时很容易发生酯交换反应和醇解酸解等副反应，使得PBT/PC合金的力学性能不稳定。
与此同时，由于PBT/PC合金在注塑过程中，通常会产生大量无使用价值的浇注系统凝料，即水口材料。一般而言，若将PBT/PC合金的水口材料粉碎后二次注塑成型，材料的性能会大幅劣化，因而无法多次循环注塑使用，造成巨大浪费。
一般情况下，二次注塑使用后，PBT/PC合金力学性能保持率一般在全新料性能的75％以下；三次注塑使用后，力学性能保持率进一步降至50％以下，在绝大部分场合已经无法满足制品的应用要求。现有技术中，为了避免资源浪费，回收利用PBT/PC合金的水口材料，通常以新旧料共混的方式，将水口材料以一定的比例掺进新料中。但该方法中，水口材料仍不能直接使用，再利用效率差。
因此，需要开发出一种力学性能稳定的PBT/PC合金，无需将PBT/PC合金水口材料与新料共混，而是直接循环注塑，仍保持良好的力学性能。
发明内容
本发明为克服上述现有技术所述的多次注塑后力学性能差的缺陷，提供一种力学性能稳定的PBT/PC合金，该PBT/PC合金经过二次注塑力学性能保持率 ≥95％，三次注塑后力学性能保持率≥90％。
本发明的另一目的在于提供上述力学性能稳定的PBT/PC合金的制备方法。
本发明的另一目的在于提供一种PBT/PC合金制品，由上述PBT/PC合金的水口材料制得。
为解决上述技术问题，本发明采用的技术方案是：
一种力学性能稳定的PBT/PC合金，包括如下重量份的组分：
PBT/PC混合物50～80份，
玻璃纤维10～40份，
环氧树脂2～5份，
抗氧剂0.1～0.3份，
增韧剂4～8份，
三甲代烯丙基异氰酸酯(TMAIC)2～4份；
所述PBT/PC混合物中PBT和PC的重量比为(2～6)∶1，
所述增韧剂为有机硅-丙烯酸酯类的核-壳结构增韧剂。
发明人研究发现，由于PBT和PC的分子结构中均含有酯基，在多次注塑的过程中，由于注塑温度较高，且剪切力较大，PBT和PC之间极易发生酯交换反应，从而导致PBT/PC体系的结晶能力大幅下降，使得PBT/PC合金材料的力学性能降低。
三甲代烯丙基异氰酸酯(TMAIC)，分子式为C 15H 21N 3O 3，是一种适合在较高加工温度下使用的聚合物交联助剂。在PBT/PC合金注塑的过程中，TMAIC能够在PBT/PC体系内快速引发分子链间交联反应，并最大限度地弥补PBT、PC分子间酯交换造成的合金力学性能下降，从而极大地提高了合金材料在多次注塑过程中的性能保持率。
发明人发现，其他种类的用于高分子材料的交联助剂，如有机过氧化物、丙烯酸酯类交联剂，在PBT/PC体系中，无法提供如TMAIC相当的优异促交联作用。
本发明中增韧剂为有机硅-丙烯酸酯类的核-壳结构增韧剂，壳部分提供了与基体树脂间的良好分散性和相容性，核部分可以吸收和分散冲击能量。与非核-壳结构的增韧剂相比，核壳结构增韧剂在本发明的PBT/PC合金体系中具有更为优异的增韧效果。
通过增韧剂和TMAIC的协同作用，一方面提高了PBT/PC合金的初始力学性能，另一方面降低了合金在多次注塑过程中的性能下降，获得了良好的性能保持率。
优选地，所述TMAIC的酸值≤1mgKOH/g。
所述酸值测试方法依据GB/T 264-1983。
TMAIC的酸值过高时，会使得PBT/PC体系不稳定，且对PBT、PC分子链间交联反应的引发促进作用较慢，进而影响PBT/PC合金的力学性能保持率。
优选地，所述增韧剂以甲基丙烯酸甲酯或接枝的聚甲基丙烯酸甲酯为壳，以交联的丙烯酸酯-有机硅共聚物为核。
可选的，所述增韧剂可以为日本三菱丽阳株式会社S-2501、S-2001、S-2006，钟渊化工MR-502，DONGEM S-203，或BSMCMX-520S/550S。
优选地，所述PC为芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯或硅氧烷共聚碳酸酯中的一种或几种。
更优选地，所述PC为芳香族聚碳酸酯。
优选地，所述芳香族聚碳酸酯的粘均分子量为13000～40000。
更优选地，所述芳香族聚碳酸酯的粘均分子量为18000～28000。
所述PC的粘均分子量的检测方法为：以二氯甲烷作为溶剂，在25℃测试温度下通过乌氏粘度计算得到。
发明人研究发现，在上述粘均分子量范围内的PC作为PBT/PC合金的基体树脂，能够为合金带来更优异的机械强度保持性。
优选地，所述PBT在25℃下的特性粘度为0.7～1.1dL/g。
PBT的特性粘度测试方法依据GB/T 14190-2017。
发明人研究发现，该粘度范围的PBT能使得本发明的PBT/PC合金具有更高的二次注塑性能保持率。
优选地，所述玻璃纤维经偶联剂处理。
更优选地，所述偶联剂为N-(β-氨基乙基)-γ-氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯的共混物。
进一步优选地，所述N-(β-氨基乙基)-γ-氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯的共 混重量比为2:1:3。
经偶联剂处理的玻璃纤维，具有与PBT、PC组分间更优异的界面性能。在二次注塑或三次注塑的过程中，能够维持更优的性能保持率。
发明人研究发现，较高比例的异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯偶联剂能赋予PC树脂与玻璃纤维间更优异的界面结合力，而2:1:3的优选比例能使得玻纤与PBT树脂和PC树脂相间均具有最佳的界面结合力。
优选地，所述环氧树脂为双酚A型缩水甘油醚，环氧当量＜600g/eq。
更优选地，所述环氧树脂的环氧当量为450～500g/eq。
所述环氧当量的测试方法依据GB/T 4612-2008。
在环氧树脂、增韧剂和TMAIC的共同作用下，本发明所述PBT/PC合金在多次循环注塑的过程中力学性能保持率才得以维持良好水平。大量的创造性实验数据表明，当缺少某一组分或某两种组分，PBT/PC合金均无法达到本发明所述的力学性能保持效果。
优选地，所述抗氧剂为受阻酚类抗氧剂。
可选的，所述抗氧剂为β(3，5二叔丁基-4-羟基苯基)丙酸十八醇酯(抗氧剂1076)和/或1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮。
本发明还保护上述PBT/PC合金的制备方法，包括如下步骤：
将环氧树脂、抗氧剂、增韧剂和TMAIC混合，得到预混物；
将PBT、PC、玻璃纤维和预混物混合后加入挤出机，经熔融挤出造粒，得到所述PBT/PC合金。
优选地，所述挤出机为双螺杆挤出机。
更优选地，所述双螺杆挤出机从喂料口到机头的一区温度为200～230℃，二区温度为240～260℃，三区温度为235～255℃，四区温度为235～255℃，五区温度为235～255℃，六区温度为240～260℃，七区温度为240～260℃，八区温度为220～240℃，九区温度为220～240℃，十区温度为240～260℃，所述双螺杆挤出机的螺杆转速为200～450转/分钟。
本发明还保护一种PBT/PC合金制品，由上述PBT/PC合金的水口材料直接加工制得。
所述PBT/PC合金制品的加工方法可以为：
将上述PBT/PC合金的水口材料加至注塑机，在220～270℃下注塑成型。
与现有技术相比，本发明的有益效果是：
本发明通过三甲代烯丙基异氰酸酯、具有核-壳结构的有机硅-丙烯酸酯类增韧剂和环氧树脂的协同作用，有效提高了PBT/PC合金的多次注塑后力学性能保持率，改善了PBT/PC合金的力学性能稳定性。在TMAIC能够快速引发分子链间交联反应，有效阻止了PBT、PC分子链的断裂，从而降低了PBT/PC合金在多次注塑过程中的降解；同时由于增韧剂和环氧树脂的协同作用，进一步提高了PBT/PC合金的力学性能保持率。本发明的PBT/PC合金经过二次注塑力学性能保持率≥95％，三次注塑后力学性能保持率≥90％，适合多次循环注塑使用。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例及对比例中的原料均可通过市售得到；
[根据细则26改正08.08.2022]　
Figure WO-DOC-FIGURE-01
Figure PCTCN2022101019-appb-000002
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1～19
实施例1～19的PBT/PC合金中各组分的含量如表1所示。
其制备方法为：将偶联剂N-(β-氨基乙基)-γ-氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯按照重量比2:1:3共混后，对玻璃纤维进行偶联处理，得到经偶联处理的玻璃纤维；
根据表1将环氧树脂、抗氧剂、增韧剂和TMAIC混合，得到预混物；将PBT、PC、经偶联处理的玻璃纤维或未经偶联处理的玻璃纤维和预混物混合后加入双螺杆挤出机，经熔融挤出造粒，得到PBT/PC合金。
双螺杆挤出机从喂料口到机头的一区温度为200～230℃，二区温度为240～260℃，三区温度为235～255℃，四区温度为235～255℃，五区温度为235～255℃，六区温度为240～260℃，七区温度为240～260℃，八区温度为220～240℃，九区温度为220～240℃，十区温度为240～260℃，双螺杆挤出机的螺杆转速为200～450转/分钟。
表1 实施例1～19的PBT/PC合金中各组分的含量(重量份)
  1 2 3 4 5 6 7 8 9 10
PBT-1 56 56 56 56 56   47 60 56 56
PBT-2           56        
PC-1 14         14 23 10 14 14
PC-2   14                
PC-3     14              
PC-4       14            
PC-5         14          
玻璃纤维 20 20 20 20 20 20 20 20 20 20
环氧树脂A 2 2 2 2 2 2 2 2   2
环氧树脂B                 2  
抗氧剂1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
增韧剂A 4 4 4 4 4 4 4 4 4 4
TMAIC-1 2 2 2 2 2 2 2 2 2  
TMAIC-2                   2
Figure PCTCN2022101019-appb-000003
对比例1～6
对比例1～6的PBT/PC合金中各组分的含量如表2所示。
其制备方法为：根据表2将环氧树脂、抗氧剂、增韧剂和TMAIC(如有)混合，得到预混物；将PBT、PC、玻璃纤维和预混物混合后加入双螺杆挤出机，经熔融挤出造粒，得到PBT/PC合金。
双螺杆挤出机从喂料口到机头的一区温度为200～230℃，二区温度为240～260℃，三区温度为235～255℃，四区温度为235～255℃，五区温度为235～255℃，六区温度为240～260℃，七区温度为240～260℃，八区温度为220～240℃，九区温度为220～240℃，十区温度为240～260℃，双螺杆挤出机的螺杆转速为200～450转/分钟。
表2 对比例1～6的PBT/PC合金中各组分的含量(重量份)
  1 2 3 4 5 6
PBT-1 56 56 56 56 56 35
PC-1 14 14 14 14 14 35
玻璃纤维 20 20 20 20 20 20
环氧树脂A 2 2 - 2 2 2
抗氧剂1076 0.1 0.1 0.1 0.1 0.1 0.1
增韧剂A - 4 4 - 4 4
增韧剂C       4    
TMAIC-1 2 - 2 2 - 2
有机过氧化物         2  
性能测试
对上述实施例及对比例制备的PBT/PC合金进行性能测试，测试方法如下。
对上述PBT/PC合金进行初次注塑、二次注塑、三次注塑，具体方法为：
初次注塑：将经挤出造粒的PBT/PC合金粒料在120℃鼓风干燥箱中干燥6h，然后通过注塑机注塑成ISO标准力学样条，即为初次注塑力学样条；
二次注塑：将初次注塑得到的力学样条使用破碎机进行破碎，将破碎后的颗粒在120℃鼓风干燥箱中干燥6h，然后通过注塑机注塑成ISO标准力学样条，即为二次注塑力学样条；
三次注塑：将二次注塑得到的力学样条使用破碎机进行破碎，将破碎后的颗粒在120℃鼓风干燥箱中干燥6h，然后通过注塑机注塑成ISO标准力学样条，即为三次注塑力学样条。
分别将初次/二次/三次注塑力学样条进行力学性能测试，力学性能测试的具体方法为：
拉伸强度：按照ISO527-2012标准方法检测，单位为MPa；
缺口冲击强度：按照ISO180-2000标准方法检测，单位为kJ/m 2；
保持率：(二次注塑或三次注塑的检测值/初次注塑的对应检测值)*100％。
测试结果
实施例1～19的性能测试结果见表3，对比例1～6的性能测试结果见表4。
表3 实施例1～19的性能测试结果
Figure PCTCN2022101019-appb-000004
Figure PCTCN2022101019-appb-000005
Figure PCTCN2022101019-appb-000006
由表1的测试结果，实施例1～19的PBT/PC合金经过二次注塑，与初次注塑相比，力学性能保持率≥95％，PBT/PC合金经三次注塑，与初次注塑相比，力学性能保持率≥90％。这说明本发明的PBT/PC合金经过多次循环注塑后，力学性能损失极少，仍维持较高的刚性和韧性。
由实施例1～5，PC优选为芳香族聚碳酸酯，更优选为粘均分子量为18000～28000的芳香族聚碳酸酯。在此范围内，PBT/PC合金经过二次注塑或三次注塑后，力学性能保持率更优。由实施例1、实施例7～8，PBT与PC的重量 比优选为(2～4)∶1。根据实施例1和实施例10的测试结果，TMAIC的酸值≤1mg KOH/g时，PBT/PC合金的力学性能保持率更高。由实施例1和实施例15，增韧剂优选为以接枝的聚甲基丙烯酸甲酯作为壳，以交联的丙烯酸酯-有机硅共聚物为核。
由实施例13，玻璃纤维未经偶联剂处理，制得的PBT/PC合金经多次循环注塑后力学性能保持率稍差。
表4 对比例1～6的性能测试结果
Figure PCTCN2022101019-appb-000007
根据表4的测试结果，由对比例1～3，环氧树脂、增韧剂或TMAIC缺少某一组分时，PBT/PC合金均无法获得较高的力学性能保持率，这说明环氧树脂、增韧剂和TMAIC必须配合使用，以达到协同增效的作用。
对比例4中增韧剂并非为核-壳结构，对比例5中使用交联剂2,5-二甲基-2,5-双(叔丁基过氧基)己烷替代TMAIC，制得的PBT/PC合金二次注塑后，力学性能保持率≤88％，三次注塑后力学性能保持率≤81％。对比例4和对比例5的力学保持率虽然与对比例1～3相比有一定提升，但仍未达到本发明实施例的优异水平。
对比例6中，PBT与PC的重量比为1∶1，超出本发明技术方案中PBT与PC的重量比范围，制得的PBT/PC合金经过二次和三次注塑，难以保持优异的力学性能。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非 是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种力学性能稳定的PBT/PC合金，其特征在于，包括如下重量份的组分：
    PBT/PC混合物50～80份，玻璃纤维10～40份，环氧树脂2～5份，抗氧剂0.1～0.3份，增韧剂4～8份，三甲代烯丙基异氰酸酯2～4份；
    所述PBT/PC混合物中PBT和PC的重量比为(2～6)∶1，所述增韧剂为有机硅-丙烯酸酯类的核-壳结构增韧剂。
  2. 根据权利要求1所述PBT/PC合金，其特征在于，所述三甲代烯丙基异氰酸酯的酸值≤1mgKOH/g。
  3. 根据权利要求2所述PBT/PC合金，其特征在于，所述增韧剂以甲基丙烯酸甲酯或接枝的聚甲基丙烯酸甲酯为壳，以交联的丙烯酸酯-有机硅共聚物为核。
  4. 根据权利要求3所述PBT/PC合金，其特征在于，所述PC为芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯或硅氧烷共聚碳酸酯中的一种或几种。
  5. 根据权利要求4所述PBT/PC合金，其特征在于，所述PC为芳香族聚碳酸酯。
  6. 根据权利要求5所述PBT/PC合金，其特征在于，所述芳香族聚碳酸酯的粘均分子量为13000～40000。
  7. 根据权利要求6所述PBT/PC合金，其特征在于，PBT在25℃下的特性粘度为0.7～1.1dL/g。
  8. 根据权利要求7所述PBT/PC合金，其特征在于，所述环氧树脂为双酚A型缩水甘油醚，环氧当量＜600g/eq。
  9. 权利要求1～8任一项所述PBT/PC合金的制备方法，其特征在于，包括如下步骤：
    将环氧树脂、抗氧剂、增韧剂和三甲代烯丙基异氰酸酯混合，得到预混物；
    将PBT、PC、玻璃纤维和预混物混合后加入挤出机，经熔融挤出造粒，得到所述PBT/PC合金。
  10. 一种PBT/PC合金制品，其特征在于，由权利要求1～8任一项所述PBT/PC合金的水口材料直接加工制得。
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