WO2023061425A1 - 一种稳定的阻燃聚碳酸酯合金组合物及其制备方法和应用 - Google Patents

一种稳定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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WO2023061425A1
WO2023061425A1 PCT/CN2022/125026 CN2022125026W WO2023061425A1 WO 2023061425 A1 WO2023061425 A1 WO 2023061425A1 CN 2022125026 W CN2022125026 W CN 2022125026W WO 2023061425 A1 WO2023061425 A1 WO 2023061425A1
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alloy composition
flame
polycarbonate alloy
retardant polycarbonate
retardant
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PCT/CN2022/125026
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English (en)
French (fr)
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梁惠强
岑茵
黄险波
艾军伟
张志铭
彭明乐
杨志军
丁超
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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
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the invention belongs to the field of engineering plastics, and in particular relates to a stable flame-retardant polycarbonate alloy composition and a preparation method and application thereof.
  • Halogen-free flame-retardant polycarbonate ABS alloy composition is a general-purpose alloy with balanced comprehensive properties. It is a material widely used in various industries. The material should have long-term stable humidity and heat aging stability, and ensure sufficient mechanical properties during the working service period.
  • adding any conventional components to polycarbonate will lead to a decrease in the stability of wet heat aging, such as some residues in the resin, small molecules such as tougheners, and the addition of conventional flame retardants will also lead to heat resistance and The decline of environmental tolerance will further deteriorate the humidity and heat stability, and increasing the content of tougheners and flame retardants to ensure the retention rate of flame retardancy and impact strength will further deteriorate the humidity and heat aging phenomenon and accelerate the degradation of polycarbonate resin. Provide guarantee for the service safety of mechanical performance.
  • the purpose of the present invention is to overcome the lack of halogen-free flame-retardant polycarbonate ABS alloy material with excellent humidity and heat aging stability and better mechanical properties and flame-retardant properties in the prior art, and to provide a stable flame-retardant polycarbonate alloy composition.
  • the flame-retardant polycarbonate alloy composition provided by the invention has higher flame-retardant grade, better mechanical properties and humidity-heat aging stability.
  • Another object of the present invention is to provide a method for preparing the above-mentioned stable flame-retardant polycarbonate alloy composition.
  • Another object of the present invention is to provide the application of the above stable flame retardant polycarbonate alloy composition in the preparation of electrical and electronic products, transportation or communication electronic products.
  • a stable flame-retardant polycarbonate alloy composition comprising the following components in parts by weight:
  • the damp heat stabilizer is a mixture of substances containing epoxy functional groups and mercaptans; in the damp heat stabilizer, the weight ratio of substances containing epoxy functional groups to mercaptans is (1 ⁇ 4):(1 ⁇ 3);
  • the metal ash content in the flame retardant polycarbonate alloy composition is not higher than 0.5%.
  • the flame retardant polycarbonate alloy composition provided by the present invention improves the flame retardant performance by the flame retardant, improves the mechanical performance by the toughening agent; Humid heat stabilizer is added to obtain better damp heat aging stability. Specifically, by adjusting the content of metal ash in the flame-retardant polycarbonate alloy composition, the degradation and degradation by heat and humidity can be reduced. On the other hand, by adding a specific moisture-heat stabilizer, the introduction of epoxy functional groups can carry out ring-opening reactions in a certain acid-base environment, reducing the erosion of acid-base on alloy materials, especially for the hydrolysis and alcoholysis of PC.
  • the epoxy functional group can also act on the end group connection of PC to increase the stability of the end group, and at the same time, the weak bond of polycarbonate can be better protected in the presence of a certain ratio of thiols , increasing stability.
  • the flame retardant grade of the flame retardant polycarbonate alloy composition obtained in the present invention is 1.0mm, V-0, ASTM room temperature notched impact greater than 600J/m, damp heat After aging for 500 hours, the retention rate of notched impact strength is more than 50%; it has a high flame retardant grade, good mechanical properties and humidity and heat aging stability.
  • the stable flame-retardant polycarbonate alloy composition includes the following components in parts by weight:
  • the weight ratio of the epoxy functional group-containing substance to the thiol substance is (1-3):1.
  • the weight ratio of substances containing epoxy functional groups and mercaptans will affect the inhibitory effect of acid-base corrosion of alloy materials and the inhibitory effect of hydrolysis and alcoholysis of PC; it also affects the stability and stability of PC end groups. Protection against weak bonds of polycarbonate. By optimizing the mass ratio of the two, the moisture-heat aging stability of the flame-retardant polycarbonate alloy composition can be further improved.
  • the metal ash content in the flame-retardant polycarbonate alloy composition is 0.01-0.1%.
  • the weight average molecular weight of the polycarbonate is 22000-30000, the content of terminal hydroxyl groups is less than 100 ppm, and the content of bisphenol A is less than 20 ppm.
  • the terminal hydroxyl content is determined according to the GB12008.3-1989 standard.
  • Bisphenol A is determined by the following process: through a C18 chromatographic column with a fixed column temperature of 40°C, a mobile phase of acetonitrile:methanol at 9:1 (volume ratio), a fixed flow rate of 1m L/min, and a detection wavelength of 280nm The content was determined by the o-cresol internal standard method.
  • the glue content in the ABS is 10-25%, and the metal ash content is not higher than 0.1%.
  • ABS is one of the main sources of metal ash.
  • the content of metal ash in the flame-retardant polycarbonate alloy composition can be conveniently controlled.
  • the metal ash content is obtained through the following process test: Weigh the composition particles with a fixed weight, put them in a muffle furnace with a preset temperature of 700°C for 6 hours, take them out and weigh the metal ash content, and then measure the metal ash content by ICP. Unless otherwise mentioned, the metal ash content in the present invention is all measured by this method.
  • the flame retardant is a phosphorus-based flame retardant.
  • the phosphorus-based flame retardant is one or more of triphenylphosphate TPP, resorcinol bis(diphenylphosphate) RDP, bisphenol A BDP or PX200.
  • the flame retardant is bisphenol A bis(diphenyl phosphate) BDP.
  • the phenol content in the flame retardant is 1-100 ppm, the dimer content is less than 10%, and the acid value is 0.01-0.2.
  • the phenol content is obtained through the following process test: a fixed weight of the flame retardant is dissolved in toluene, diluted to 0.01mol/L, and then passed through a high-performance liquid chromatograph, and the outflow peak area formed at the outflow time t ⁇ 5min is normalized Then get the phenol content.
  • the dimer content is obtained through the following process test: a fixed weight of the flame retardant is dissolved in toluene, diluted to 0.01mol/L, and then passed through a high performance liquid chromatography, and the area of the effluent peak formed at the effluent time t ⁇ 18min is normalized The dimer content was obtained after chemical treatment.
  • the toughening agent is a silicon-based toughening agent, and the content of silica gel in the silicon-based toughening agent is 5-40%; more preferably, it is S2030, SX005, MR-01 and the like.
  • the metal ash content in the toughening agent is less than 3%.
  • the toughening agent is one of the main sources of metal ash, and the content of metal ash in the flame-retardant polycarbonate alloy composition can be conveniently controlled by controlling the content of metal ash in the toughening agent.
  • the anti-dripping agent is a fluoropolymer, which may include fibrillation forming or non-fibrillating fluoropolymers, such as polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the substance containing epoxy functional group is one or more of polyolefin grafted with epoxy functional group, SAN grafted with epoxy functional group, or a copolymer of epoxy and polyester; more preferably epoxy Grafted PP, epoxy grafted PE, epoxy grafted SAN, GMA copolymer, etc.
  • the thiol substance is a compound with a mercapto functional group (-SH); more preferably, it is one or more of dialkyl thiodipropionate or pentaerythritol thioester.
  • -SH mercapto functional group
  • the preparation method of the above-mentioned stable flame-retardant polycarbonate alloy composition comprises the steps of: mixing polycarbonate, ABS, flame retardant, toughening agent, damp heat stabilizer and anti-dripping agent, extruding, granulating, That is, the stable flame-retardant polycarbonate alloy composition is obtained.
  • the preparation method of the stable flame-retardant polycarbonate alloy composition comprises the steps of stirring and mixing polycarbonate, ABS, toughening agent, heat and humidity stabilizer and anti-dripping agent in a high mixer, Then it is melt-extruded in a twin-screw extruder and granulated to obtain the stable 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 stable flame-retardant polycarbonate alloy composition is used in the preparation of electronic and electrical housings, security system parts, and 5G outdoor communication structures.
  • the present invention has the following beneficial effects:
  • the flame-retardant polycarbonate alloy composition provided by the invention has a higher flame-retardant grade, better mechanical properties and moisture-heat aging stability.
  • ABS 1#, 275, Shanghai Gaoqiao the glue content is 15%, the metal ash content is 0.08%;
  • ABS 2#, PA757, Chimei the glue content is 20%, the metal ash content is 0.15%;
  • BDP-1 bisphenol A bis(diphenyl phosphate)
  • Wansheng-1 phenol content is 80ppm
  • dimer TPP content 1.2%
  • acid value 0.02;
  • Toughening agent 1# S-2030 (silicon-based toughening agent), Mitsubishi Rayon, the content of silica gel is 30%, and the content of metal ash is 0.008%;
  • Toughener 2# S-2001 (non-silicon-based toughener), Mitsubishi Rayon, the metal ash content is 0.5%;
  • Anti-dripping agent TS-30X, Pacific Ocean
  • Moist heat stabilizer 1# self-made, is obtained by compounding epoxy functional group-containing substance 1# and mercaptan substance 1# in a weight ratio of 2:1;
  • Moist heat stabilizer 2# self-made, is obtained by compounding epoxy functional group-containing substance 1# and thiol-containing substance 1# in a weight ratio of 4:1;
  • Moist heat stabilizer 3# self-made, is obtained by compounding epoxy functional group-containing substance 1# and mercaptan substance 1# in a weight ratio of 1:2;
  • Damp heat stabilizer 4# self-made, is obtained by compounding epoxy functional group-containing substance 1# and mercaptan substance 1# in a weight ratio of 3:1;
  • Moist heat stabilizer 5# self-made, is obtained by compounding epoxy functional group-containing substance 1# and mercaptan substance 1# in a weight ratio of 1:1;
  • Humid heat stabilizer 6# self-made, is obtained by compounding epoxy functional group-containing substance 2# and mercaptan substance 1# in a weight ratio of 2:1;
  • Damp heat stabilizer 7# self-made, is obtained by compounding epoxy functional group-containing substance 1# and mercaptan substance 2# in a weight ratio of 2:1;
  • Moist heat stabilizer 8# which is material 1# containing epoxy functional group
  • Moisture and heat stabilizer 9# which is mercaptan substance 1#;
  • Mercaptans 1# pentaerythritol tetrakis (3-mothyl thiopropionate), 412S, BASF;
  • Zinc sulfide commercially available.
  • 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 ash weight, and then measure the content of metal elements by ICP.
  • Impact strength According to the standard of ASTM D256-2010, the 3.0mm IZOD notched impact strength is tested; the notch type is injection notch, and the sample is measured at the same time after the humidity heat aging treatment with the temperature set at 85°C and the humidity at 85% for 500 hours , placed in an environment with a room temperature of 25°C and a humidity of 50% for more than 48 hours, then tested and recorded the results, and compared the performance retention rate before and after aging as the judgment of the damp heat performance. The higher the performance retention rate, the damp heat stability Sex is better.
  • 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. 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 into (UL94-HB): V0, V1, V2, 5VA and/or or 5VB. At the same time, after the sample is subjected to a humid heat aging treatment with a temperature of 85°C and a humidity of 85% in a constant temperature and humidity box for 500 hours, its flame retardancy level is determined according to the same conditions;
  • the preparation process of the stable flame retardant polycarbonate alloy composition of each embodiment of the present invention and comparative example is as follows: weigh polycarbonate, ABS, flame retardant, toughening agent, moisture heat stabilizer and anti-dripping After dropping the agent, stir and blend in a high mixer at 40 rpm to obtain a premix, then extrude, and obtain a stable flame-retardant polycarbonate alloy composition after the granulation process; the twin-screw extruder The length-to-diameter ratio is 40:1, the barrel temperature is 240°C, and the screw speed is 350 rpm.
  • This embodiment provides a series of stable flame-retardant polycarbonate alloy compositions, the formulations of which are shown in Table 1.
  • This comparative example provides a series of flame-retardant polycarbonate alloy compositions, the formulations of which are shown in Table 3.
  • Table 4 The performance test results of the flame-retardant polycarbonate alloy composition of each embodiment and comparative examples
  • the stable flame-retardant polycarbonate alloy composition provided by each embodiment of the present invention has a higher flame-retardant grade, better mechanical properties and humidity and heat aging stability, and wherein the comprehensive performance of Example 1 is the best ;
  • comparative example 1 although no damp heat stabilizer was added, although it had little effect on the initial mechanical properties, its damp heat aging stability was obviously deteriorated.

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Abstract

本发明涉及一种稳定的阻燃聚碳酸酯合金组合物及其制备方法和应用。该阻燃聚碳酸酯合金组合物包括聚碳酸酯、ABS、阻燃剂、增韧剂、湿热稳定剂和抗滴落剂。本发明提供的阻燃聚碳酸酯合金组合物具有较高的阻燃等级，较佳的机械性能，且通过金属灰分含量的优化和特定的湿热稳定剂的协同配合，可大大提升湿热老化稳定性。

Description

一种稳定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
本发明属于工程塑料领域，具体涉及一种稳定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
无卤阻燃聚碳酸酯ABS合金组合物是具备均衡的综合性能的通用型合金，在各个行业中具有广泛应用的材料，为了满足这种材料在应用中的技术更新升级需求，聚碳酸酯组合物应具备长期稳定的湿热老化稳定性，以及保证在工作服役期间中有足够的机械性能。但是，在聚碳酸酯中加入任何常规的组分均会导致湿热老化稳定性的降低，如树脂中的一些残留、增韧剂等小分子，常规阻燃剂的加入也会导致耐热性能和环境耐受性的下降，进一步劣化湿热稳定性，并且增加增韧剂和阻燃剂的含量来保证阻燃和冲击强度的保持率将进一步劣化湿热老化现象，加速聚碳酸酯树脂的降解，不能为机械性能的服役安全性提供保证。
现在的阻燃和增韧技术均具有一定的局限性，因此在一定程度上限制了材料的应用，尤其是服役安全薄壁化的行业发展趋势下，湿热老化后阻燃性不稳定，韧性下降，外观劣化等等问题一直困扰着材料的高性能化发展，限制了其应用。特别是在电子电气、交通运输、通讯电子等高端应用领域，对材料服役环境的要求越来越苛刻，如高温高湿下要保持较高的性能保持率、阻燃等级等。目前无卤阻燃PCABS合金难以达到这一苛刻要求，如湿热老化一段时间后机械性能保持率往往低于30％，对材料的服役安全性有较大的危害。
目前，已有报道利用特定含量的钾元素(例如CN106589881A)来提升耐湿热老化性能。但类似的研究还非常少。因此，开发一种具有优异湿热老化稳定性及较佳的机械性能和阻燃性能的无卤阻燃聚碳酸酯ABS合金材料以扩大其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具有优异湿热老化稳定性及较佳的机械性能和阻燃性能的无卤阻燃聚碳酸酯ABS合金材料的缺乏，提供一种稳定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阻燃 等级，较佳的机械性能和湿热老化稳定性。
本发明的另一目的在于提供上述稳定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稳定的阻燃聚碳酸酯合金组合物在制备电子电气、交通运输或通讯电子产品中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种稳定的阻燃聚碳酸酯合金组合物，包括如下重量份数的组分：
Figure PCTCN2022125026-appb-000001
所述湿热稳定剂为含环氧官能团的物质和硫醇类物质的混合物；所述湿热稳定剂中，含环氧官能团的物质和硫醇类物质的重量比为(1～4):(1～3)；
所述阻燃聚碳酸酯合金组合物中金属灰分含量不高于0.5％。
本发明提供的阻燃聚碳酸酯合金组合物通过阻燃剂来提升阻燃性能，通过增韧剂来提升机械性能；并在此基础上通过优化体系中金属灰分(例如Na、Zn)含量及添加湿热稳定剂来获得较佳的湿热老化稳定性。具体地，通过调控阻燃聚碳酸酯合金组合物中金属灰分含量，可降低湿热降解劣化。另一方面，通过加入特定的湿热稳定剂，环氧官能团的引入可在一定酸碱性的环境下进行开环反应，降低酸碱对合金材料的侵蚀，尤其针对PC的水解醇解具有较好的抑制作用；另外，环氧官能团还可以作用于PC的端基连接，增加端基的稳定性，同时再一定配比的硫醇类物质的存在下可以更好的保护聚碳酸酯的弱键，增加稳定性。
即通过金属灰分含量的优化和特定的湿热稳定剂的协同配合，本发明得到的阻燃聚碳酸酯合金组合物阻燃等级为1.0mm，V-0，ASTM常温缺口冲击大于600J/m，湿热老化500h后缺口冲击强度保持率＞50％；具有较高的阻燃等级，较佳的机械性能和湿热老化稳定性。
优选地，所述稳定的阻燃聚碳酸酯合金组合物包括如下重量份数的组分：
Figure PCTCN2022125026-appb-000002
优选地，所述湿热稳定剂中，含环氧官能团的物质和硫醇类物质的重量比为(1～3):1。
含环氧官能团的物质和硫醇类物质的重量比将影响含环氧官能团物质酸碱对合金材料的侵蚀的抑制效果及PC的水解醇解抑制效果；同时也影响PC端基的稳定性及对聚碳酸酯的弱键的保护作用。通过优化两者的质量比，可进一步提升阻燃聚碳酸酯合金组合物的湿热老化稳定性。
优选地，所述阻燃聚碳酸酯合金组合物中金属灰分含量为0.01～0.1％。
本领域常规的聚碳酸酯、ABS(丙烯腈-丁二烯-苯乙烯共聚物)、阻燃剂、增韧剂和抗滴落剂均可用于本发明中，其制备方法也为常规的方法。
优选地，所述聚碳酸酯的重均分子量为22000～30000，端羟基含量小于100ppm，双酚A含量小于20ppm。
端羟基含量按照GB12008.3-1989标准测定得到。
双酚A(BPA)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中胶含量为10～25％，金属灰分含量不高于0.1％。
ABS是金属灰分的主要来源之一，通过控制ABS中金属灰分含量，可便利地控制阻燃聚碳酸酯合金组合物中的金属灰分含量。
金属灰分含量通过如下过程测试得到：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6h后取出并称量金属灰分重量后，通过ICP测定金属灰分含量。如未提别提及，本发明中金属灰分含量均按此方法测得。
优选地，所述阻燃剂为磷系阻燃剂。
更为优选地，所述磷系阻燃剂为三苯磷酸酯TPP、间苯二酚双(二苯磷酸酯) RDP、双酚A BDP或PX200中的一种或几种。
更为优选地，所述阻燃剂为双酚A双(二苯基磷酸酯)BDP。
更为优选地，所述阻燃剂中苯酚含量为1～100ppm，二聚体含量小于10％，酸值为0.01～0.2。
苯酚含量通过如下过程测试得到：将固定重量的阻燃剂溶解到甲苯中后稀释成0.01mol/L后通过高效液相色谱仪，在流出时间t≤5min形成的流出峰面积进行归一化处理后得到苯酚含量。
二聚体含量通过如下过程测试得到：将固定重量的阻燃剂溶解到甲苯中后稀释成0.01mol/L后通过高效液相色谱仪，在流出时间t≥18min形成的流出峰面积进行归一化处理后得到二聚体含量。
优选地，所述增韧剂为硅系增韧剂，硅系增韧剂中硅胶含量为5～40％；进一步优选为S2030、SX005、MR-01等。
优选地，所述增韧剂中金属灰分含量小于3％。
增韧剂是金属灰分的主要来源之一，通过控制增韧剂中金属灰分含量，可便利地控制阻燃聚碳酸酯合金组合物中的金属灰分含量。
优选地，所述抗滴落剂为含氟聚合物，该含氟聚合物可包括原纤化形成或非原纤化的含氟聚合物，比如聚四氟乙烯(PTFE)。
优选地，所述含环氧官能团的物质为环氧官能团接枝的聚烯烃、环氧官能团接枝的SAN或环氧与聚酯的共聚物中的一种或几种；进一步优选为环氧接枝PP、环氧接枝PE、环氧接枝SAN、GMA共聚物等。
优选地，所述硫醇类物质为巯基官能团(-SH)的化合物；进一步优选为硫代二丙酸二烷基酯类或季戊四醇硫代酯类中的一种或几种。
上述稳定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、湿热稳定剂和抗滴落剂混合，挤出，造粒，即得所述稳定的阻燃聚碳酸酯合金组合物。
优选地，所述稳定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、增韧剂、湿热稳定剂和抗滴落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，即得所述稳定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。
上述稳定的阻燃聚碳酸酯合金组合物在制备电子电气、交通运输或通讯电子产品中的应用也在本发明的保护范围内。
优选地，所述稳定的阻燃聚碳酸酯合金组合物在制备电子电气外壳、安防系统制件、5G户外通信结构中的应用。
与现有技术相比，本发明具有如下有益效果：
通过体系中金属灰分含量的优化和湿热稳定剂等的添加，本发明提供的阻燃聚碳酸酯合金组合物具有较高的阻燃等级，较佳的机械性能和湿热老化稳定性。
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1#，S-2000F，上海三菱工程，平均分子量为23000，端羟基含量为47ppm，BPA含量为12ppm；
聚碳酸酯2#，CZ-1211E，沧州大化，平均分子量为22300，端羟基含量为385ppm，BPA含量为97ppm；
ABS 1#，275，上海高桥，胶含量为15％，金属灰分含量为0.08％；
ABS 2#，PA757，奇美，胶含量为20％，金属灰分含量为0.15％；
阻燃剂1#，BDP-1(双酚A双(二苯基磷酸酯))，万盛-1，苯酚含量为80ppm，二聚体TPP含量为1.2％，酸值为0.02；
阻燃剂2#，BDP-2(双酚A双(二苯基磷酸酯))，万盛，苯酚含量为260ppm，二聚体TPP含量为3.7％，酸值为0.13；
增韧剂1#，S-2030(硅系增韧剂)，三菱丽阳，硅胶含量为30％，金属灰分含量为0.008％；
增韧剂2#，S-2001(非硅系增韧剂)，三菱丽阳，金属灰分含量为0.5％；
抗滴落剂，TS-30X，太平洋；
湿热稳定剂1#，自制，将含环氧官能团的物质1#和硫醇类物质1#按重量比2:1复配得到；
湿热稳定剂2#，自制，将含环氧官能团的物质1#和含硫醇类物质1#按重量比4:1复配得到；
湿热稳定剂3#，自制，将含环氧官能团的物质1#和硫醇类物质1#按重量比1:2复配得到；
湿热稳定剂4#，自制，将含环氧官能团的物质1#和硫醇类物质1#按重量比3:1复配得到；
湿热稳定剂5#，自制，将含环氧官能团的物质1#和硫醇类物质1#按重量比1:1复配得到；
湿热稳定剂6#，自制，将含环氧官能团的物质2#和硫醇类物质1#按重量比2:1复配得到；
湿热稳定剂7#，自制，将含环氧官能团的物质1#和硫醇类物质2#按重量比2:1复配得到；
湿热稳定剂8#，为含环氧官能团的物质1#；
湿热稳定剂9#，为硫醇类物质1#；
其中，含环氧官能团的物质1#，环氧与聚酯的共聚物，P1901，三菱丽阳；
含环氧官能团的物质2#，环氧接枝SAN，SAG-002，日之升；
硫醇类物质1#，季戊四醇四(3-月季基硫代丙酸酯)，412S，BASF；
硫醇类物质2#，硫代二丙酸二月桂酯|，DLSDP，利安隆；
硫化锌，市售。
本发明各实施例及对比例的稳定的阻燃聚碳酸酯合金组合物的各项性能的测试方法如下：
金属灰分含量：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后取出并称量灰分重量后，通过ICP测定金属元素的含量。
冲击强度：根据ASTM D256-2010标准下测试3.0mm IZOD缺口冲击强度；缺口类型为注塑缺口，同时测定样品经在恒温恒湿箱中设定温度为85℃湿度为85％的湿热老化处理500h后，放在室温为25℃湿度为50％的环境下进行调节48h以上，然后进行测试并记录结果，通过对比老化前后的性能保持率作为湿热性能 好坏的判定，性能保持率越高，湿热稳定性越好。
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、5VA和/或5VB。同时测定样品经在恒温恒湿箱中设定温度为85℃湿度为85％的湿热老化处理500h后，按照相同的条件测定其阻燃等级；
本发明的各实施例及对比例的稳定的阻燃聚碳酸酯合金组合物的制备工艺如下：按照配比称取聚碳酸酯、ABS、阻燃剂、增韧剂、湿热稳定剂和抗滴落剂后在高混机中在40转/min下搅拌共混，得到预混料，然后进行挤出，造粒工序后即得稳定的阻燃聚碳酸酯合金组合物；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/mim。
实施例1～15
本实施例提供一系列的稳定的阻燃聚碳酸酯合金组合物，其配方如表1。
表1 实施例1～9提供的稳定的阻燃聚碳酸酯合金组合物的配方(份)
Figure PCTCN2022125026-appb-000003
表2 实施例10～15提供的稳定的阻燃聚碳酸酯合金组合物的配方(份)
Figure PCTCN2022125026-appb-000004
Figure PCTCN2022125026-appb-000005
对比例1～4
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3。
表3 对比例1～4提供的阻燃聚碳酸酯合金组合物的组分(份)
  实施例1 对比例1 对比例2 对比例3 对比例4
聚碳酸酯1# 74 74 74 74 74
ABS 1# 12 12 12 12 12
阻燃剂1# 8 8 8 8 8
增韧剂1# 5 5 5 5 5
湿热稳定剂1# 0.5 / / / 0.5
湿热稳定剂8# / / 0.5 / /
湿热稳定剂9# / / / 0.5 /
抗滴落剂 0.5 0.5 0.5 0.5 0.5
硫化锌 / / / / 0.5
金属灰分含量 0.021 0.033 0.024 0.62 0.021
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 PCTCN2022125026-appb-000006
Figure PCTCN2022125026-appb-000007
从表4可知，本发明各实施例提供的稳定的阻燃聚碳酸酯合金组合物具有较高阻燃等级，较佳的机械性能和湿热老化稳定性，其中以实施例1的综合性能最佳；对比例1由于未添加湿热稳定剂，虽然对初始的力学性能影响不大，其湿热老化稳定性明显劣化，经湿热老化处理500h后，冲击保持率仅有13％，且拉伸强度保持率也仅有33％，且阻燃等级也严重恶化；对比例2由于仅选用含环氧官能团的物质作为湿热稳定剂，对阻燃稳定有负面作用以至于1.0mm阻燃初始由于燃烧时间长导致仅可达到V1等级，不能实现薄壁阻燃的目的；对比例3由于仅选用硫醇类物质作为湿热稳定剂，湿热前性能良好可以实现薄壁阻燃高韧性，但在湿热老化后由于不能稳定PC湿热老化后分子量维持导致出现了滴落引燃的V2阻燃等级，且冲击强度和拉伸强度保持率均低；对比例4由于未优化组合物中金属灰分含量导致对初始的性能有明显的衰减尤其对冲击强度影响较大，且金属灰分含量高导致阻燃性能不稳定，且拉伸强度湿热保持率比不加湿热稳定剂体系劣化作用更明显。
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. 一种稳定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：
    Figure PCTCN2022125026-appb-100001
    所述湿热稳定剂为含环氧官能团的物质和硫醇类物质的混合物；所述湿热稳定剂中，含环氧官能团的物质和硫醇类物质的重量比为(1～4):(1～3)；
    所述阻燃聚碳酸酯合金组合物中金属灰分含量不高于0.5％。
  2. 根据权利要求1所述稳定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：
    Figure PCTCN2022125026-appb-100002
  3. 根据权利要求1所述稳定的阻燃聚碳酸酯合金组合物，其特征在于，所述湿热稳定剂中，含环氧官能团的物质和硫醇类物质的重量比为(1～3):1。
  4. 根据权利要求1所述稳定的阻燃聚碳酸酯合金组合物，其特征在于，所述阻燃聚碳酸酯合金组合物中金属灰分含量为0.01～0.1％。
  5. 根据权利要求1所述稳定的阻燃聚碳酸酯合金组合物，其特征在于，所述聚碳酸酯的平均分子量为22000～30000，端羟基含量小于100ppm，BPA含量小于20ppm。
  6. 根据权利要求1所述稳定的阻燃聚碳酸酯合金组合物，其特征在于，所述阻燃剂为磷系阻燃剂；所述增韧剂为硅系增韧剂，硅系增韧剂中硅胶含量为5～40％；所述抗滴落剂为含氟聚合物。
  7. 根据权利要求1所述稳定的阻燃聚碳酸酯合金组合物，其特征在于，所述含环氧官能团的物质为环氧官能团接枝的聚烯烃、环氧官能团接枝的SAN或环氧与聚酯的共聚物中的一种或几种。
  8. 根据权利要求1所述稳定的阻燃聚碳酸酯合金组合物，其特征在于，所述硫醇类物质为硫代二丙酸二烷基酯类或季戊四醇硫代酯类中的一种或几种。
  9. 权利要求1～8任一所述稳定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、湿热稳定剂和抗滴落剂混合，挤出，造粒，即得所述稳定的阻燃聚碳酸酯合金组合物。
  10. 权利要求1～8任一所述稳定的阻燃聚碳酸酯合金组合物在制备电子电气、交通运输或通讯电子产品中的应用。
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