WO2023020413A1 - 一种高韧性的阻燃聚碳酸酯合金组合物及其制备方法和应用 - Google Patents

一种高韧性的阻燃聚碳酸酯合金组合物及其制备方法和应用 Download PDF

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WO2023020413A1
WO2023020413A1 PCT/CN2022/112402 CN2022112402W WO2023020413A1 WO 2023020413 A1 WO2023020413 A1 WO 2023020413A1 CN 2022112402 W CN2022112402 W CN 2022112402W WO 2023020413 A1 WO2023020413 A1 WO 2023020413A1
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flame
polycarbonate
alloy composition
retardant
parts
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PCT/CN2022/112402
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English (en)
French (fr)
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岑茵
黄险波
陈平绪
梁惠强
艾军伟
丁超
王培涛
田征宇
董相茂
陈勇文
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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
    • 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
    • C08L2201/02—Flame or fire retardant/resistant
    • 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

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  • the invention belongs to the field of recycled plastics, and in particular relates to a high-toughness flame-retardant polycarbonate alloy composition and a preparation method and application thereof.
  • Polycarbonate plastic products are widely used in various fields due to their high rigidity, high toughness, good dimensional stability, stable electrical performance, and good service resistance. question. Recycling and modifying polycarbonate can not only solve the pollution problem, but also bring certain economic benefits, which has attracted widespread attention from all walks of life. However, high-performance recovery and modification technology is a difficult problem to be solved urgently. Especially for plastics recovered by physical methods, due to the unavoidable existence of some impurities, their purity is not high, which will reduce the consistency of polycarbonate resin and the guarantee of molecular weight distribution during processing. Therefore, although it is convenient to use directly, it will make changes The stability of non-toxic products brings unnecessary degradation, the toughness of materials decreases, and the stability of flame retardancy decreases. The lack of comprehensive performance limits the widespread application in the fields of consumer electronics and household appliances.
  • Patent CN101003677 discloses a PC/ABS alloy using recycled PC. It uses ABS and recycled PC as a base resin system, and at the same time uses specific compatibilizer SM70 and epoxy resin for modification to improve its mechanical properties. (impact strength, tensile strength, and flexural strength); but there is still a lot of room for improvement in the improvement of mechanical properties, and it does not modify low-temperature toughness, nor does it pay attention to flame retardancy, and still has a large Application limitations.
  • the purpose of the present invention is to overcome the defects or deficiencies in the prior art that the mechanical properties and flame-retardant properties of PC materials obtained by recycling PC technology are not improved well, and provide a high-toughness flame-retardant polycarbonate alloy composition.
  • the flame-retardant polycarbonate alloy composition provided by the invention has high normal-temperature and low-temperature toughness and good flame-retardant performance, and can be widely used in the fields of personal consumer electronics and household appliances.
  • Another object of the present invention is to provide a method for preparing the above-mentioned high-toughness flame-retardant polycarbonate alloy composition.
  • Another object of the present invention is to provide the application of the above-mentioned high-toughness flame-retardant polycarbonate alloy composition in the preparation of personal consumer electronic products and household appliances.
  • a high-toughness flame-retardant polycarbonate alloy composition comprising the following components in parts by weight:
  • the toughening agent is a silicon-based toughening agent with a core-shell structure, and active groups are grafted on the shell;
  • the composite stabilizer is a mixture of EBA and a phosphite stabilizer, and the weight fraction of the phosphite stabilizer in the composite stabilizer is 5-30%.
  • the high-toughness flame-retardant polycarbonate alloy composition provided by the invention is compounded with polycarbonate and ABS to obtain a basic resin system, which can meet the requirements for mechanical properties in industrial applications and the promotion of low-carbon technology; adding flame retardants Can improve flame retardant performance.
  • adding flame retardants Can improve flame retardant performance.
  • specific tougheners and composite stabilizers for toughening and stabilization can significantly improve the toughness and flame-retardant stability. Comprehensive utilization of esters.
  • the high-toughness flame-retardant polycarbonate alloy composition includes the following components in parts by weight:
  • the weight fraction of recycled polycarbonate in the polycarbonate is not less than 60%.
  • the weight fraction of recycled polycarbonate in the polycarbonate is 70-90%.
  • recycled polycarbonate refers to recycled materials obtained by classifying and collecting waste polycarbonate according to conventional physical recycling methods in this field.
  • Virgin polycarbonate refers to polycarbonate resin that is directly used without injection molding or used after polymerization.
  • the silicon-based toughening agent grafted with active groups on the shell can refine the phase state of the ABS alloy, while providing better melt stability and reducing the negative impact of recycled PC and flame retardants on toughness.
  • EBA ethylene butyl acrylate
  • the impurities in the system are stabilized by virtue of the slight acidity brought by the acrylic acid segment.
  • the low Tg temperature of EBA itself it is a good toughening system; and in BA
  • the hydrolysis performance of phosphite stabilizers is improved, and its thermal stability can be better exerted.
  • the flame retardant in this stable system the resin flame retardant can be realized within the safe addition range. and impurities at the same time to achieve products with excellent comprehensive performance and expand applications.
  • the present invention effectively improves the flame retardant performance by adding an appropriate amount of flame retardant; effectively improves the toughness of the flame retardant polycarbonate alloy composition by adding a specific toughening agent, and overcomes the negative impact of the flame retardant on toughness at the same time ;
  • the stability of the system is effectively improved through the specific composite stabilizer, so that the flame-retardant polycarbonate alloy composition has better toughness and flame-retardant properties, and the notched impact strength at room temperature is greater than 600J/m, and the notched impact strength at low temperature is greater than 350J/m m, the flame retardant grade is at V-0 level (1.0mm), and it remains at V-0 level after heat treatment.
  • the recycled polycarbonate has a melt index MI not higher than 10g/10min under the condition of 300°C/1.2kg, and a polycarbonate whose MI heat retention rises not higher than 40%. 2.0mm thickness, light transmittance at 500nm wavelength not less than 75%, metal ash content not higher than 1%.
  • the recycled polycarbonate has a melt index MI of 6-10g/10min at 300°C/1.2kg, and a polycarbonate with a MI heat retention increase of 20-40%.
  • the reclaimed polycarbonate has a thickness of 2.0mm and a light transmittance of 75-89% at a wavelength of 500nm; the metal ash content is 0.01-0.97%.
  • the light transmittance can be obtained by testing a sample with a thickness of 2mm at a wavelength of 500nm using a colorimeter.
  • the method for measuring the metal ash content is as follows: weigh the composition particles with a fixed weight, put them into a muffle furnace with a preset temperature of 700°C for 4 hours, take them out and weigh the metal ash content, and then measure the content of metal elements by ICP.
  • the weight average molecular weight of the recycled polycarbonate is 32000-62000.
  • the recycled polycarbonate is obtained through the following process: the waste polycarbonate is classified by physical machinery and then polished-cleaned-dried-crushed-granulated-sieved and magnetically sieved.
  • the weight-average molecular weight of the virgin polycarbonate is 38,000-65,000, the content of terminal hydroxyl groups is less than 100 ppm, and the content of BPA (bisphenol propane) is less than 20 ppm.
  • the terminal hydroxyl content is determined according to the GB12008.3-1989 standard.
  • the content of BPA is determined by the following process: pass through a C18 chromatographic column and fix the column temperature at 40°C, the mobile phase acetonitrile:methanol is 9:1 (volume ratio), the flow rate is fixed at 1mL/min, and the detection wavelength is 280nm through o-cresol
  • the internal standard method was used to determine the content.
  • the rubber content of the ABS is 10-25%, and the metal ash content is not higher than 0.5%.
  • the ABS has a metal ash content of 0.01-0.35%.
  • the phosphorus flame retardant is one or more of phosphoric acid ester, phosphorus nitrogen flame retardant or phosphorus silicon flame retardant.
  • the reactive group is one or more of epoxy group, vinyl group or maleic anhydride group.
  • the toughening agent uses acrylate as the shell layer and rubber as the core, the rubber particle size D50 is 100-400nm, the silica gel content is 5-40%, and the metal ash content is not higher than 3%.
  • the rubber particle size D50 in the toughening agent is 250-400 nm
  • the silica gel content is 6-20%
  • the metal ash content is 0.8-2.6%.
  • the weight fraction of the phosphite stabilizer in the composite stabilizer is 8-15%.
  • the phosphite stabilizer is one or more of 168, 626, 9228 or PEPQ.
  • the anti-dripping agent is a fluoropolymer, including fibrillated or non-fibrillated fluoropolymers, such as fibrillated or non-fibrillated polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the other additives are one or more of antioxidants, lubricants or fillers.
  • the antioxidant is one or more of aromatic amine antioxidants, hindered phenolic antioxidants or phosphite antioxidants.
  • the weight part of the antioxidant is 0.01-1 part.
  • the lubricant is one or more of saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax, 1-olefin polymer, organosilicon compound, fluorine compound, paraffin wax or beeswax.
  • the parts by weight of the lubricant are 0.05-3 parts.
  • the filler is one or more of silica, magnesium hydroxide, aluminum hydroxide, kaolinite or zeolite.
  • the weight part of the filler is 0.1-20 parts.
  • the preparation method of the above-mentioned high-toughness flame-retardant polycarbonate alloy composition comprises the steps of: mixing polycarbonate, ABS, flame retardant, toughening agent, composite stabilizer, anti-dripping agent and other additives, melting Extrude and granulate to obtain the high-toughness flame-retardant polycarbonate alloy composition.
  • the preparation method of the above-mentioned high-toughness flame-retardant polycarbonate alloy composition includes the following steps: polycarbonate, ABS, flame retardant, toughening agent, composite stabilizer, anti-dripping agent and other auxiliary agents Stirring and mixing in a high mixer, and then melting and extruding in a twin-screw extruder, and granulating to obtain the high-toughness flame-retardant polycarbonate alloy composition.
  • the stirring and mixing speed is 20-50 rpm; the aspect ratio of the twin-screw extruder is 38-52:1, the temperature of the screw barrel is 220-260°C, and the screw speed is 300 ⁇ 600 rpm/min.
  • the present invention has the following beneficial effects:
  • the invention effectively improves the flame retardant performance through the addition of an appropriate amount of flame retardant; through the addition of a specific toughening agent, the toughness of the flame retardant polycarbonate alloy composition is effectively improved, and at the same time, the negative impact of the flame retardant on the toughness is overcome;
  • the stability of the system is effectively improved through a specific composite stabilizer, so that the flame-retardant polycarbonate alloy composition has better toughness and flame-retardant properties, and the notched impact strength at room temperature is greater than 600J/m, and the notched impact strength at low temperature is greater than 350J/m , the flame retardant grade is V-0 (1.0mm), and it remains V-0 after heat treatment; it can be widely used in personal consumer electronics and household appliances.
  • Recycled polycarbonate 1# is recovered from post-consumer drinking water barrels, and is processed as follows: after physical and mechanical classification, it is recovered after physical recovery processes such as grinding-cleaning-drying-crushing-granulation-sieving and magnetic PC resin particles; according to the ISO1133-2011 standard, the melt index MI at 300°C/1.2kg is 6.7g/10min, and the thermal retention of MI is increased to 25% of the physical recycling resin grade, at a thickness of 2.0mm and a wavelength of 500nm The light transmittance is 81.7%, the metal ash content is 0.132%; the weight average molecular weight is 56000.
  • Recycled polycarbonate 2# is obtained from the recycling of post-consumer boards, and is processed as follows: after physical and mechanical classification, grinding-cleaning-drying-crushing-granulation-sieving and magnetic recovery are performed to obtain recycled PC resin Particles; under the condition of 300°C/1.2kg, the melt index MI is 24.6g/10min, the thermal retention of MI is increased to 20.8% of the physical recovery resin grade, and the light transmittance at 2.0mm thickness and 500nm wavelength is 76.3%.
  • the metal ash content is 0.89%, and the weight average molecular weight is 48000;
  • Polycarbonate 1# (new material), S-2000F, Shanghai Mitsubishi, weight average molecular weight 58000, terminal hydroxyl content 13ppm, BP70 content 8ppm;
  • Polycarbonate 2# (new material), CH8215, Dahua, Cangzhou, with a weight average molecular weight of 48500, a terminal hydroxyl content of 289ppm, and a BP70 content of 23ppm;
  • ABS1#, 3325, Shanghai Gaoqiao the rubber content is 17%, the metal ash content is 0.25%;
  • ABS2#, 747S, Taiwan Chimei rubber content is 25%, metal ash content is 1.4%;
  • Toughening agent 1#, S2200 a silicon-based toughening agent with a core-shell structure grafted with epoxy groups, Mitsubishi Rayon, the rubber particle size is 385nm, the silica gel content is 10%, and the metal ash content is 1.28%;
  • Toughening agent 2# KS-N (silicon-based toughening agent with core-shell structure grafted with epoxy groups), NOF, rubber particle size D50 is 250nm, silica gel content is 10%, metal ash content is 2.5% ;
  • Toughening agent 3# KS-E (silicon-based toughening agent with vinyl grafted core-shell structure), NOF, rubber particle size D50 is 320nm, silica gel content is 10%, metal ash content is 1.8%;
  • Toughener 4# S-2001 (silicon-based toughener with core-shell structure), Mitsubishi Rayon, rubber particle size D50 is 350nm, silica gel content is 8%, metal ash content is 2.7%;
  • Composite stabilizer 1# is a mixture of EBA1# and phosphite stabilizer 1#, and the weight fraction of phosphite stabilizer 1# is 8%;
  • Composite stabilizer 2# is a mixture of EBA1# and phosphite stabilizer 1#, and the weight fraction of phosphite stabilizer 1# is 12%;
  • Composite stabilizer 3# is a mixture of EBA1# and phosphite stabilizer 1#, and the weight fraction of phosphite stabilizer 1# is 30%;
  • Composite stabilizer 4# is a mixture of EBA1# and phosphite stabilizer 2#, and the weight fraction of phosphite stabilizer 2# is 8%;
  • Composite stabilizer 5# is a mixture of EBA2# and phosphite stabilizer 1#, and the weight fraction of phosphite stabilizer 1# is 8%;
  • Composite stabilizer 6# is a mixture of EBA1# and mercaptan stabilizers, and the weight fraction of mercaptan stabilizers is 8%;
  • Anti-dripping agent TS30X, Korean Pacific Chemical
  • antioxidant 1076 antioxidant 1076
  • BASF BASF
  • Determination of metal ash content Weigh the composition particles with a fixed weight, put them into a muffle furnace with a preset temperature of 700°C for 4 hours, take them out and weigh the metal ash, and then measure the content of metal elements by ICP.
  • the terminal hydroxyl content is determined according to the GB12008.3-1989 standard.
  • the BPA content was determined by the following process: pass through a C18 chromatographic column and fix the column temperature at 40°C, the mobile phase acetonitrile:methanol is 9:1 (volume ratio), the flow rate is fixed at 1mL/min, and the detection wavelength is 280nm. Determination of content by standard method.
  • ASTM room temperature notched impact strength according to ASTM D256-2010 standard, test 3.0mm IZOD notched impact strength; the type of notch is injection notched, and the higher the impact strength, the better the toughness of the material.
  • ASTM Low Temperature Notched Impact Strength Prepare 3.0mm IZOD notched impact strength specimens according to ASTM D256-2010 standard, place them in minus 30°C freezer for at least 4 hours and take them out for testing. The test results obtained are low temperature impact strength, where the impact strength The higher the value, the better the low temperature toughness of the material.
  • Flame retardant grade The flammability test is carried out in accordance with the regulations of "Tests for Flammability of Plastic Materials, UL94". The flammability rating is based on the burning rate, time to extinguish, ability to resist dips, and whether the dips are burning.
  • the sample used for testing 125mm length and 13mm width, the thickness of the present invention is selected as 1.0mm when testing, according to the UL94 regulations, the flame retardant grade of the material can be classified as UL94-HB, V0, V1, V2, 5V70 and/or 5VB As the judgment of the initial flame retardant level; the flame retardant level of the conditioning treatment is to put the test sample in a 70°C oven for 168 hours, and then adjust it at 25°C and 50% humidity for 48 hours. According to the UL94 regulations, it can Classify the flame retardant grade of the material as UL94-HB, V0, V1, V2, 5V70 and/or 5VB as the judgment of the adjusted flame retardant grade.
  • the preparation process of the polycarbonate alloy composition of each embodiment of the present invention and the comparative example is as follows: After weighing each component according to the proportion, add it into a high mixer for stirring and blending to obtain a premix, and then extrude it in a twin-screw extruder Extruding in the machine, and the polycarbonate alloy composition is obtained after the melt granulation process.
  • the rotational speed of stirring is 40 rpm
  • the aspect ratio of the twin-screw extruder is 40:1
  • the temperature of the screw barrel is 240° C.
  • the rotational speed of the screw is 350 rpm.
  • This embodiment provides a series of high-toughness flame-retardant polycarbonate alloy compositions, the formula of which is shown in Table 1.
  • This comparative example provides a series of flame-retardant polycarbonate alloy compositions, the formulations of which are shown in Table 2.
  • the recycled polycarbonate has a very high proportion in the flame-retardant polycarbonate alloy composition provided by each embodiment of the present invention, accounting for 60% or more of the amount of polycarbonate, and has excellent toughness and flame retardancy Performance:
  • the notched impact strength at room temperature is greater than 600J/m
  • the notched impact strength at low temperature is greater than 350J/m
  • the flame retardant grade is at V-0 level (1.0mm), and it remains at V-0 level after heat treatment.
  • the overall performance is the best; the comparative example 1 does not carry out toughening and stabilizing modification treatment on the resin system, the initial toughness is poor, and the flame retardancy cannot be realized; the comparative example 2 does not add a toughening agent, the initial toughness is also poor, and the same cannot be realized Flame retardant properties; the toughening agent added in Comparative Example 3 is not grafted with active groups, because the molecular weight distribution is not controlled, the low temperature toughness of the material cannot be guaranteed, and the flame retardant stability degradation after adjustment treatment cannot guarantee V0 safe flame retardant; Proportion 4 does not add composite stabilizers, low-temperature toughness is low, and the initial flame retardancy is reduced to V1 grade, and the flame-retardant grade is further reduced after adjustment; in comparative example 5, the composite stabilizer added is compounded with mercaptan stabilizers, and the low-temperature toughness low and poor flame retardant stability; comparative example 6 only added EBA as a stabilizer, although the toughness was good, but the low temperature

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Abstract

本发明涉及一种高韧性的阻燃聚碳酸酯合金组合物及其制备方法和应用。该高韧性的阻燃聚碳酸酯合金组合物，包括聚碳酸酯、ABS、阻燃剂、增韧剂、复合稳定剂、抗滴落剂和其它助剂。本发明提供的阻燃聚碳酸酯合金组合物具有较高的韧性和较佳的阻燃性能，可广泛应用于个人消费电子产品和家用电器等领域。

Description

一种高韧性的阻燃聚碳酸酯合金组合物及其制备方法和应用 技术领域
本发明属于回收塑料领域，具体涉及一种高韧性的阻燃聚碳酸酯合金组合物及其制备方法和应用。
背景技术
聚碳酸酯塑料制品由于其高刚性高韧性，尺寸稳定性好，电气性能稳定，耐服役性能好的优点被广泛的应用于各个领域，与之而来的是大量的废弃塑料所带来的环境问题。对聚碳酸酯进行回收改性利用不但可解决该污染问题，还可带来一定的经济效益，受到了各界的广泛关注。但是高性能的回收改性技术是目前亟待解决的难题。特别是通过物理方法回收的塑料，由于不可避免存在一些杂质导致其纯度不高，将降低聚碳酸酯树脂的一致性性以及加工过程中的分子量分布保证，因此直接使用虽然方便，但会给改性产品的稳定性带来不必要的劣化，对材料的韧性下降，且阻燃稳定性降低，其综合性能的不足在消费电子和家用电器领域无法广泛推广应用受到限制。
专利CN101003677公开了一种利用回收PC的PC/ABS合金，其利用ABS与回收PC复配作为基础树脂体系，同时利用特定的相容剂SM70和环氧树脂等进行改性，提高了其机械性能(冲击强度、拉伸强度和弯曲强度)；但其对机械性能的提升还有较大的进步空间，且其并未对低温韧性进行改性，也未关注阻燃性能，仍具有较大的应用局限。
因此，开发一种较佳的回收利用PC的技术以有效提升其力学性能、阻燃性能具有重要的环保经济价值。
发明内容
本发明的目的在于克服现有技术中回收PC技术得到的PC材料力学性能及阻燃性能提升不佳的缺陷或不足，提供一种高韧性的阻燃聚碳酸酯合金组合物。本发明提供的阻燃聚碳酸酯合金组合物具有较高的常温及低温韧性和较佳的阻燃性能，可广泛应用于个人消费电子产品、家用电器领域。
本发明的另一目的在于提供上述高韧性的阻燃聚碳酸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高韧性的阻燃聚碳酸酯合金组合物在制备个人消费电子产品、家用电器中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种高韧性的阻燃聚碳酸酯合金组合物，包括如下重量份数的组分：
Figure PCTCN2022112402-appb-000001
所述增韧剂为硅系增韧剂，具有核壳结构，且壳层上接枝有活性基团；
所述复合稳定剂为EBA和亚磷酸酯类稳定剂的混合物，所述复合稳定剂中亚磷酸酯类稳定剂的重量分数为5～30％。
本发明提供的高韧性的阻燃聚碳酸酯合金组合物以聚碳酸酯和ABS复配得到基础树脂体系，可满足行业应用时对机械性能的要求以及对低碳技术的推广；添加阻燃剂可提升阻燃性能。同时利用特定的增韧剂和复合稳定剂进行增韧及稳定，可显著提升韧性及阻燃稳定性，不单适应于常规的新料聚碳酸酯，还可实现对分子量分布较大的回收聚碳酸酯的综合利用。
优选地，所述高韧性的阻燃聚碳酸酯合金组合物，包括如下重量份数的组分：
Figure PCTCN2022112402-appb-000002
优选地，所述聚碳酸酯中回收聚碳酸酯的重量分数不低于60％。
更为优选地，所述聚碳酸酯中回收聚碳酸酯的重量分数为70～90％。
应当说明的是，回收聚碳酸酯是指按照本领域常规的物理回收处理方式对废弃的聚碳酸酯进行分类收集得到的回收料。
新料聚碳酸酯是指经过聚合后直接使用未经注塑或者使用的聚碳酸酯树脂。
当树脂体系中存在大比例的回收原材料——回收聚碳酸酯时，回收聚碳酸酯对性能的稳定性将带来负面的隐患；另外，阻燃剂的引入会对韧性造成伤害，且不能通过单纯的增加增韧剂进行弥补。本发明的发明人经反复研究发现，利用特定的增韧剂和复合稳定剂可克服上述的缺陷，实现较好的增韧效果。
具体地，壳层上接枝有活性基团的硅系增韧剂可细化ABS合金相态，同时提供更好的熔体稳定性，降低回收PC以及阻燃剂对韧性的负面影响。
复合稳定剂中以EBA(乙烯丙烯酸丁酯)为基体，借助丙烯酸链段带来的微酸性，稳定体系的杂质，同时由于EBA本身Tg温度低，是一种良好的增韧体系；且在BA(聚乙烯链段)的存在下亚磷酸酯类稳定剂水解性能提高，可以更好的发挥其热稳定作用，同时由于阻燃剂在此稳定体系下可以在安全添加量范围实现树脂阻燃剂和杂质的同时稳定，实现综合性能优异的产品，扩展应用。
即本发明通过阻燃剂的适量添加有效提升了阻燃性能；通过特定的增韧剂的添加有效提升了阻燃聚碳酸酯合金组合物的韧性，同时克服了阻燃剂对韧性的负面影响；通过特定的复合稳定剂有效提升了体系的稳定性，使得阻燃聚碳酸酯合金组合物具有较佳的韧性和阻燃性能，常温缺口冲击强度大于600J/m，低温缺口冲击强度大于350J/m，阻燃等级在V-0级(1.0mm)，经热处理后仍保持为V-0级。
优选地，所述回收聚碳酸酯按照ISO1133-2011标准，在300℃/1.2kg条件下的熔融指数MI不高于10g/10min，MI热滞留升高不高于40％的聚碳酸酯，在2.0mm厚度，500nm波长下的透光率不低于75％，金属灰分含量不高于1％。
更为优选地，所述回收聚碳酸酯按照ISO1133-2011标准，在300℃/1.2kg条件下的熔融指数MI为6～10g/10min，MI热滞留升高为20～40％的聚碳酸酯；所述回收聚碳酸酯在2.0mm厚度，500nm波长下的透光率为75～89％；金属灰分含量为0.01～0.97％。
透光率利用色差仪在500nm波长下，测试2mm厚度的样板即可得到。
金属灰分含量测定方法为：称量固定重量的组合物粒子，放入预设温度为 700℃的马弗炉中4h后取出并称量金属灰分重量后，通过ICP测定金属元素的含量。
优选地，所述回收聚碳酸酯的重均分子量为32000～62000。
优选地，所述回收聚碳酸酯通过如下过程得到：废弃聚碳酸酯通过物理机械分类后进行打磨-清洗-烘干-破碎-造粒-过筛过磁，即得。
本领域常规的新料聚碳酸酯、ABS、阻燃剂、抗滴落剂和其它助剂均可用于本发明中。
优选地，所述新料聚碳酸酯的重均分子量为38000～65000，端羟基含量小于100ppm，BPA(双酚基丙烷)含量小于20ppm。
端羟基含量按照GB12008.3-1989标准测定得到。
BPA含量通过如下过程测定得到：通过C18色谱柱并固定柱温为40℃，流动相位乙腈：甲醇为9：1(体积比)，流速固定为1m L/min，检测波长为280nm通过邻甲酚内标法进行含量的测定。
优选地，所述ABS的橡胶含量为10～25％，金属灰分含量不高于0.5％。
ABS的橡胶含量通过如下过程测定得到：通过FTIR红外法，通过对比C＝C特征吸收峰与CN特征吸收峰的积分面积之比可得到橡胶含量。
更为优选地，所述ABS的金属灰分含量为0.01～0.35％。
优选地，所述磷系阻燃剂为磷酸酯、磷氮系阻燃剂或磷硅系阻燃剂中的一种或几种。
优选地，所述活性基团为环氧基团、乙烯基或马来酸酐基团中的一种或几种。
优选地，所述增韧剂以丙烯酸酯类为壳层，以橡胶为核，橡胶粒径D50为100～400nm，硅胶含量为5～40％，金属灰分含量不高于3％。
更为优选地，所述增韧剂中橡胶粒径D50为250～400nm，硅胶含量为6～20％，金属灰分含量为0.8～2.6％。
优选地，所述复合稳定剂中亚磷酸酯类稳定剂的重量分数为8～15％。
优选地，所述亚磷酸酯类稳定剂为168、626、9228或PEPQ中的一种或几种。
优选地，所述抗滴落剂为含氟聚合物，该含氟聚合物包括原纤化形成或非原纤化含氟聚合物，比如原纤化形成或非原纤化的聚四氟乙烯(PTFE)。
优选地，所述其它助剂为抗氧剂、润滑剂或填料中的一种或几种。
更为优选地，所述抗氧剂为芳香胺类抗氧剂、受阻酚类抗氧剂或亚磷酸酯类抗氧剂中的一种或几种。
更为优选地，所述抗氧剂的重量份数为0.01～1份。
更为优选地，所述润滑剂为饱和脂肪酸酯、不饱和脂肪酸酯、聚烯烃系蜡、1－烯烃聚合物、有机硅化合物、氟化合物、石蜡或蜂蜡中的一种或几种。
更为优选地，所述润滑剂的重量份数为0.05～3份。
更为优选地，所述填料为二氧化硅、氢氧化镁、氢氧化铝、高岭石或沸石中的一种或几种。
更为优选地，所述填料的的重量份数为0.1～20份。
上述高韧性的阻燃聚碳酸酯合金组合物的制备方法，包括如下步骤：将聚碳酸酯、ABS、阻燃剂、增韧剂、复合稳定剂、抗滴落剂和其它助剂混合，熔融挤出，造粒，即得所述高韧性的阻燃聚碳酸酯合金组合物。
优选地，上述高韧性的阻燃聚碳酸酯合金组合物的制备方法，包括如下步骤：将聚碳酸酯、ABS、阻燃剂、增韧剂、复合稳定剂、抗滴落剂和其它助剂在高混机中搅拌混合，然后在双螺杆挤出机中熔融挤出，造粒，即得所述高韧性的阻燃聚碳酸酯合金组合物。
更为优选地，所述搅拌混合的转速为20～50转/min；所述双螺杆挤出机的长径比为38～52:1，螺筒温度为220～260℃，螺杆转速为300～600转/mim。
上述高韧性的阻燃聚碳酸酯合金组合物在制备个人消费电子产品、家用电器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：
本发明通过阻燃剂的适量添加有效提升了阻燃性能；通过特定的增韧剂的添加有效提升了阻燃聚碳酸酯合金组合物的韧性，同时克服了阻燃剂对韧性的负面影响；通过特定的复合稳定剂有效提升了体系的稳定性，使得阻燃聚碳酸酯合金组合物具有较佳的韧性和阻燃性能，常温缺口冲击强度大于600J/m，低温缺口冲击强度大于350J/m，阻燃等级在V-0级(1.0mm)，经热处理后仍保持为V-0级；可广泛应用于个人消费电子产品、家用电器领域。
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：
回收聚碳酸酯1#，由消费后饮用水桶回收得到，并进行如下处理：通过物理机械分类后进行打磨-清洗-烘干-破碎-造粒-过筛过磁等物理回收工艺后得到回收PC树脂粒子；按照ISO1133-2011标准，在300℃/1.2kg条件下的熔融指数MI为6.7g/10min，MI热滞留升高为25％的物理回收树脂等级，在2.0mm厚度，500nm波长下的透光率为81.7％，金属灰分含量为0.132％；重均分子量为56000。
回收聚碳酸酯2#，由消费后板材回收得到，并进行如下处理：通过物理机械分类后进行打磨-清洗-烘干-破碎-造粒-过筛过磁等物理回收工艺后得到回收PC树脂粒子；在300℃/1.2kg条件下的熔融指数MI为24.6g/10min，MI热滞留升高为20.8％的物理回收树脂等级，在2.0mm厚度，500nm波长下的透光率为76.3％，金属灰分含量为0.89％，重均分子量为48000；
经打磨-清洗-烘干-破碎-造粒-过筛过磁处理过后，可去除废弃聚碳酸酯中的杂质、污渍及表面氧化等缺陷，并得到柱状的颗粒，截面直径为0.8～2mm，长度为1.5～3mm。
聚碳酸酯1#(新料)，S-2000F，上海三菱，重均分子量为58000，端羟基含量为13ppm，BP70含量为8ppm；
聚碳酸酯2#(新料)，CH8215，沧州大化，重均分子量为48500，端羟基含量为289ppm，BP70含量为23ppm；
ABS1#，3325，上海高桥，橡胶含量为17％，金属灰分含量为0.25％；
ABS2#，747S，台湾奇美，橡胶含量为25％，金属灰分含量为1.4％；
磷系阻燃剂1#，BDP，艾迪科；
磷系阻燃剂2#，PX200，日本大八；
溴系阻燃剂，BC-58，大湖；
增韧剂1#，S2200，环氧基团接枝的核壳结构的硅系增韧剂，三菱丽阳，橡 胶粒径为385nm，硅胶含量为10％，金属灰分含量为1.28％；
增韧剂2#，KS-N(环氧基团接枝的核壳结构的硅系增韧剂)，日油，橡胶粒径D50为250nm，硅胶含量为10％，金属灰分含量为2.5％；
增韧剂3#，KS-E(乙烯基接枝的核壳结构的硅系增韧剂)，日油，橡胶粒径D50为320nm，硅胶含量为10％，金属灰分含量为1.8％；；
增韧剂4#，S-2001(核壳结构的硅系增韧剂)，三菱丽阳，橡胶粒径D50为350nm，硅胶含量为8％，金属灰分含量为2.7％；
复合稳定剂1#，为EBA1#和亚磷酸酯类稳定剂1#的混合物，亚磷酸酯类稳定剂1#的重量分数为8％；
复合稳定剂2#，为EBA1#和亚磷酸酯类稳定剂1#的混合物，亚磷酸酯类稳定剂1#的重量分数为12％；
复合稳定剂3#，为EBA1#和亚磷酸酯类稳定剂1#的混合物，亚磷酸酯类稳定剂1#的重量分数为30％；
复合稳定剂4#，为EBA1#和亚磷酸酯类稳定剂2#的混合物，亚磷酸酯类稳定剂2#的重量分数为8％；
复合稳定剂5#，为EBA2#和亚磷酸酯类稳定剂1#的混合物，亚磷酸酯类稳定剂1#的重量分数为8％；
复合稳定剂6#，为EBA1#和硫醇类稳定剂的混合物，硫醇类稳定剂的重量分数为8％；
EBA1#，70560，美国杜邦；
EBA2#，70C3210，美国杜邦；
亚磷酸酯类稳定剂1#，168，BASF；
亚磷酸酯类稳定剂2#，568，科莱恩；
硫醇类稳定剂，412S，天津利安隆；
抗滴落剂，TS30X，韩国太平洋化学；
其它助剂，抗氧剂1076，BASF。
本发明各实施例和对比例提供的阻燃聚碳酸酯合金组合物按如下测试方法进行性能测定：
金属灰分含量测定：称量固定重量的组合物粒子，放入预设温度为700℃的 马弗炉中4h后取出并称量金属灰分重量后，通过ICP测定金属元素的含量。
端羟基含量按照GB12008.3-1989标准测定得到。
BPA含量通过如下过程测定得到通过C18色谱柱并固定柱温为40℃，流动相位乙腈：甲醇为9：1(体积比)，流速固定为1m L/min，检测波长为280nm通过邻甲酚内标法进行含量的测定。
ASTM常温缺口冲击强度：根据ASTMD256-2010标准下测试3.0mm IZOD缺口冲击强度；缺口类型为注塑缺口，其中冲击强度越高，材料韧性越好。
ASTM低温缺口冲击强度：根据ASTMD256-2010标准下制备3.0mm IZOD缺口冲击强度样条后放置在零下30℃冷冻箱调节至少4h以上后取出进行测试，得到的测试结果为低温冲击强度，其中冲击强度越高，材料低温韧性越好。
阻燃等级：按照“塑料材料的可燃性测试，UL94”的规程进行可燃性测试。基于燃烧速率、熄灭时间、抵抗低落的能力、以及低落是否正燃烧，来得出阻燃等级。用于测试的样品：125mm长度13mm宽度，本发明在进行测试时厚度选为1.0mm，根据UL94规程，可以将材料阻燃等级分类为UL94-HB、V0、V1、V2、5V70和/或5VB作为初始阻燃等级的判断；调节处理的阻燃等级是将测试样条放在70℃烘箱中恒温烘烤168h后，在25℃以及50％湿度条件下调节48h后测试，根据UL94规程，可以将材料阻燃等级分类为UL94-HB、V0、V1、V2、5V70和/或5VB作为调节后阻燃等级的判断。
本发明的各实施例及对比例的聚碳酸酯合金组合物的制备工艺如下：按照配比称取各组分后，加入高混机中搅拌共混，得到预混料，然后在双螺杆挤出机中进行挤出，熔融造粒工序后即得聚碳酸酯合金组合物。其中，搅拌的转速为40转/min，双螺杆挤出机的长径比为40:1，螺筒温度为240℃，螺杆转速为350转/min。
实施例1～16
本实施例提供一系列的高韧性的阻燃聚碳酸酯合金组合物，其配方如表1。
表1实施例1～5提供的高韧性的阻燃聚碳酸酯合金组合物的配方(份)
Figure PCTCN2022112402-appb-000003
Figure PCTCN2022112402-appb-000004
表2实施例6～16提供的稳定的阻燃聚碳酸酯合金组合物的配方(份)
Figure PCTCN2022112402-appb-000005
对比例1～8
本对比例提供一系列的阻燃聚碳酸酯合金组合物，其配方如表2。
表3对比例1～8提供的阻燃聚碳酸酯合金组合物的组分(份)
Figure PCTCN2022112402-appb-000006
Figure PCTCN2022112402-appb-000007
按上述提及的测试方法对各实施例和对比例的阻燃聚碳酸酯合金组合物的性能进行测定，测试结果如表4。
表4各实施例和对比例的阻燃聚碳酸酯合金组合物的性能测试结果
Figure PCTCN2022112402-appb-000008
从表4可知，本发明各实施例提供的阻燃聚碳酸酯合金组合物中回收聚碳酸 酯具有非常高的比例，占聚碳酸酯用量的60％及以上，且具有优异的韧性和阻燃性能：常温缺口冲击强度大于600J/m，低温缺口冲击强度大于350J/m，阻燃等级在V-0级(1.0mm)，经热处理后仍保持为V-0级，其中以实施例1的综合性能最佳；对比例1未对树脂体系进行增韧及稳定改性处理，初始韧性差，无法实现阻燃特性；对比例2为未添加增韧剂，初始韧性也较差，同样无法实现阻燃特性；对比例3添加的增韧剂未接枝活性基团，由于分子量分布没有控制，材料在低温韧性上无法保证，且调节处理后阻燃稳定性降级无法保证V0安全阻燃；对比例4未添加复合稳定剂，低温韧性低，且初始阻燃降低至V1等级，调节处理后阻燃等级进一步下降；对比例5添加的复合稳定剂选用硫醇类稳定剂进行复配，低温韧性低且阻燃稳定性差；对比例6仅添加EBA作为稳定剂，虽然韧性较好，但低温韧性仍不足，且阻燃等级无法保持V0；对比例7仅添加亚磷酸酯类稳定剂，低温韧性无法保证，调节后阻燃V2失效；对比例8添加溴系类阻燃剂，对PC合金树脂基体韧性损伤大，溴系体系的存在会影响稳定剂的作用，导致热处理后阻燃失效。
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. 一种高韧性的阻燃聚碳酸酯合金组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯100份，
    ABS 1～35份，
    磷系阻燃剂0.001～35份，
    增韧剂0.01～25份，
    复合稳定剂0.1～2份，
    抗滴落剂0.001～5份，
    其它助剂0～30份；
    所述增韧剂为硅系增韧剂，具有核壳结构，且壳层上接枝有活性基团；
    所述复合稳定剂为EBA和亚磷酸酯类稳定剂的混合物，所述复合稳定剂中亚磷酸酯类稳定剂的重量分数为5～30％。
  2. 根据权利要求1所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯100份，
    ABS3～23份，
    磷系阻燃剂1.2～20份，
    增韧剂1.2～12份，
    复合稳定剂0.12～1份，
    抗滴落剂0.1～3份，
    其它助剂0.1～20份。
  3. 根据权利要求1所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，所述聚碳酸酯中回收聚碳酸酯的重量分数不低于60％。
  4. 根据权利要求3所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，所述聚碳酸酯中回收聚碳酸酯的重量分数为70～90％。
  5. 根据权利要求3所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，所述回收聚碳酸酯按照ISO1133-2011标准，在300℃/1.2kg条件下的熔融指数MI不高于10g/10min，MI热滞留升高不高于40％的聚碳酸酯，在2.0mm厚度，500nm波长下的透光率不低于75％，金属灰分含量不高于1％；所述新料聚 碳酸酯的重均分子量为38000～65000，端羟基含量小于100ppm，BPA含量小于20ppm。
  6. 根据权利要求1所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，所述ABS的橡胶含量为10～25％，金属灰分含量不高于0.5％；所述磷系阻燃剂为磷酸酯、磷氮系阻燃剂或磷硅系阻燃剂中的一种或几种；所述增韧剂以丙烯酸酯类为壳层，以橡胶为核，橡胶粒径D50为100～400nm，硅胶含量为5～80％，金属灰分含量不高于2.8％。
  7. 根据权利要求1所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，所述活性基团为环氧基团、乙烯基或马来酸酐基团中的一种或几种。
  8. 根据权利要求1所述高韧性的阻燃聚碳酸酯合金组合物，其特征在于，所述复合稳定剂中亚磷酸酯类稳定剂的重量分数为8～15％。
  9. 权利要求1～8任一所述高韧性的阻燃聚碳酸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、ABS、阻燃剂、增韧剂、复合稳定剂、抗滴落剂和其它助剂混合，熔融挤出，造粒，即得所述高韧性的阻燃聚碳酸酯合金组合物。
  10. 权利要求1～8任一所述高韧性的阻燃聚碳酸酯合金组合物在制备个人消费电子产品、家用电器中的应用。
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