WO2022083061A1 - 一种长期稳定的聚碳酸酯组合物及其制备方法 - Google Patents

一种长期稳定的聚碳酸酯组合物及其制备方法 Download PDF

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WO2022083061A1
WO2022083061A1 PCT/CN2021/082804 CN2021082804W WO2022083061A1 WO 2022083061 A1 WO2022083061 A1 WO 2022083061A1 CN 2021082804 W CN2021082804 W CN 2021082804W WO 2022083061 A1 WO2022083061 A1 WO 2022083061A1
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long
term stable
polycarbonate composition
stabilizer
polycarbonate
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French (fr)
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岑茵
黄险波
叶南飚
艾军伟
陈勇文
李明昆
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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to the field of polycarbonate materials, and more particularly, to a long-term stable polycarbonate composition and a preparation method thereof.
  • Polycarbonate is a widely used material, but the ester group of the molecular chain of polycarbonate is easily hydrolyzed, thereby destroying the structure of polycarbonate. Under the action of water and heat, small molecules and other impurities outside and inside Either the residue will accelerate the ester hydrolysis reaction or trigger the transesterification reaction to occur. Therefore, how to maintain high toughness and thin-wall flame retardancy while maintaining damp heat aging performance is worthy of further study.
  • Ci109021534A discloses a high temperature and high humidity polycarbonate composition and its preparation method, wherein polycarbonate, flame retardant, anti-dripping agent, toughening agent and chain extender oxazoline are disclosed.
  • the patent achieves high temperature and high humidity resistance through the synergistic effect of toughening agent and chain extender, but the strength of flame retardant grade and low temperature impact strength is unknown.
  • polycarbonate compositions do not have high low-temperature impact strength and thin-wall flame retardancy under high temperature and high humidity environment. Low temperature impact strength.
  • the purpose of the present invention is to overcome the defects that the thin-walled flame retardant and the low-temperature impact strength cannot be satisfied under the high temperature and high humidity environment, and provide a long-term stable polycarbonate composition.
  • Another object of the present invention is to provide a method for preparing the long-term stable polycarbonate composition.
  • Another object of the present invention is to provide the polycarbonate product for high temperature and high humidity environment.
  • a long-term stable polycarbonate composition comprising the following components in parts by weight:
  • the moist heat stabilizer is a block copolymer of epoxy or acid anhydride functional groups, and the low temperature toughening stabilizer is a metal oxide with hydrophobized surface treatment.
  • Block copolymers using epoxy or acid anhydride functional groups not only add less amount to maintain the performance of the matrix itself, but also improve the toughness of polycarbonate.
  • inorganic treatment is performed first, and silica or aluminum oxide is used to coat the surface; and then organic treatment is performed, and a non-polar siloxane polyolefin is sprayed onto the surface of the metal oxide.
  • the weight-average molecular weight of the polycarbonate is 22,000-30,000, the content of terminal hydroxyl groups is less than 100 ppm, and the content of BPA is less than 50 ppm, and the polycarbonate is prepared by a phosgene method and a transesterification method.
  • the weight average molecular weight of the polycarbonates was determined using gel permeation chromatography using a cross-linked styrene-divinylbenzene column and calibrated to polycarbonate standards using a UV-Vis detector set at 264 nm. Samples were prepared at a concentration of 1 mg/mL and eluted at a flow rate of 1 mL/min.
  • the two By adding a moist heat stabilizer and a low temperature toughening stabilizer, the two have synergistic effect, so that the polycarbonate composition not only has the properties of high toughness, thin-walled flame retardant, but also has anti-moisture heat aging performance, wherein the moist heat stabilizer is in the polymer.
  • the terminal hydroxyl group can be captured, and the polycarbonate can be end-capped to prevent the molecular weight of the polycarbonate from decreasing due to hydrolysis or alcoholysis, and the performance will be greatly weakened; the addition of non-polar low temperature toughening stabilizer can make the polymer
  • the carbonate system is microphase-separated to realize the dimensional voids of the matrix resin.
  • the non-polar low temperature toughening stabilizer also has hydrophobic properties. Achieving a uniform distribution in the medium will exclude the intrusion of water, further stabilize and strengthen the stability of the material under damp-heat aging, and the long-term performance retention rate of its damp-heat aging performance is greater than 50%; it can also improve the flame retardant stability. Stable, no burning time or dripping due to resin deterioration.
  • the composition comprises the following components in parts by weight:
  • the weight average molecular weight of the polysiloxane-polycarbonate composition is 22,000-30,000, and the silicon content is 6-20%.
  • the average particle size of the low temperature toughening stabilizer is 100-500 nm.
  • the hydrophobized surface-treated metal oxide is titanium dioxide or zinc oxide.
  • the flame retardant is a sulfonate flame retardant, including perfluorinated C1-C16 alkyl sulfonate, such as potassium perfluorobutanesulfonate (Rimar salt), perfluorooctanesulfonate Potassium, tetraethylammonium perfluorohexanesulfonate, potassium diphenylsulfonesulfonate (KSS), sodium benzenesulfonate, sodium toluenesulfonate (NATS).
  • perfluorinated C1-C16 alkyl sulfonate such as potassium perfluorobutanesulfonate (Rimar salt), perfluorooctanesulfonate Potassium, tetraethylammonium perfluorohexanesulfonate, potassium diphenylsulfonesulfonate (KSS), sodium benzenesulfonate,
  • the flame retardant is a phosphorus-based flame retardant, an organic phosphate containing phosphorus-nitrogen bonds and an organic compound.
  • bifunctional or polyfunctional aromatic phosphorus-containing compounds include resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl)phosphate of hydroquinone, and bis(diphenyl) of bisphenol-A, respectively.
  • phosphorus-containing flame retardants include chlorinated phosphazenes, phosphoesteramides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris(aziridinyl) phosphine oxides, polyorganophosphazenes, and polyorganophosphazenes Phosphonates.
  • the sulfonate flame retardant is potassium diphenylsulfone sulfonate.
  • the anti-drip agent is at least one of a fibrillated fluoropolymer or a non-fibrillated fluoropolymer, such as polytetrafluoroethylene (PTFE), more preferably, the anti-drip agent may be encapsulated In rigid copolymers, such as styrene-acrylonitrile (SAN), polytetrafluoroethylene encapsulated in styrene acrylonitrile (TSAN) allows easier composition than unencapsulated polytetrafluoroethylene (PTFE) dispersion.
  • SAN styrene-acrylonitrile
  • TSAN polytetrafluoroethylene encapsulated in styrene acrylonitrile
  • the present invention also provides a preparation method of a long-term stable polycarbonate composition, comprising the following steps:
  • step S2 Add the premix prepared in step S1 into an extruder for melting, extrusion, and post-processing, and finally obtain composition particles.
  • the post-processing includes drawing, cooling, air-drying, and dicing.
  • a polycarbonate product for high temperature and high humidity environment comprising the long-term stable polycarbonate composition.
  • the polycarbonate products for high-temperature and high-humidity environments include but are not limited to outdoor equipment, car casings, lighting shades, and the like.
  • the invention provides a long-term stable polycarbonate composition.
  • the polycarbonate composition By adding a low-temperature toughening stabilizer and a moist-heat stabilizer, the polycarbonate composition not only has the properties of high toughness and thin-walled flame retardancy, but also has anti-moisture-heat aging properties.
  • the ASTM room temperature notched impact strength of the polycarbonate composition is greater than 600 J/m, the -50° C. notched impact strength is greater than 300 J/m, and the flame retardant level of the 1.0 mm thickness spline reaches the UL94-V0 level.
  • the long-term property retention rate of the wet heat aging property of the polycarbonate composition is greater than 50%. It can be used in high temperature and high humidity occasions.
  • reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • Polysiloxane-polycarbonate Silicon content 9%, weight average molecular weight 30000, ST009, Samyang, Korea
  • Titanium dioxide R104 DuPont
  • Titanium dioxide S-100 South China University of Technology
  • Titanium dioxide S-500 South China University of Technology
  • Titanium dioxide S-700 South China University of Technology
  • Hydrophobized Titanium Dioxide A R104 Surface-treated siloxane polyolefin on titanium dioxide by air spray method to obtain hydrophobized titanium dioxide, and the prepared hydrophobized R104 has an average particle size of 200 nm
  • Hydrophobized Titanium Dioxide B S-100 Surface Treatment of Siloxane Polyolefin on Titanium Dioxide by Air-Jet Method
  • Hydrophobized Titanium Dioxide C S-500 Surface Treatment of Siloxane Polyolefin on Titanium Dioxide by Air Spray
  • Zinc Oxide Zinc Oxide Aladdin Company
  • Hydrophobized zinc oxide first perform inorganic treatment, and coat the surface with silicon dioxide or aluminum oxide; then perform organic treatment, spray non-polar siloxane polyolefin onto the surface of zinc oxide, and prepare the hydrophobized zinc oxide.
  • the average particle size of zinc oxide is 200nm
  • Moisture heat stabilizer A P1901 epoxy block copolymer, Japan Mitsubishi Liyang
  • Moisture heat stabilizer B A560 anhydride block copolymer, DuPont
  • Damp heat stabilizer C MA4215 anhydride graft copolymer, Clariant
  • Anti-drip agent POLYTE30X fibrillated fluoropolymer, Korea Pacific
  • step S2 The premix prepared in step S1 is added to an extruder with a preset temperature of 230°C to 260°C and a main engine speed of 450 rpm for melt extrusion, drawing, cooling, air-drying, and pelletizing, and finally a combination is obtained. matter particles.
  • Example 8 Example 9
  • Example 10 Example 11
  • Flammability testing was carried out in accordance with the procedures of "Flammability Testing of Plastic Materials, UL94".
  • the flammability rating is calculated based on the rate of burn, the time to extinguish, the ability to resist the dip, and whether the dip is burning.
  • Samples used for testing 125mm in length and 13mm in width, and the thickness of the present invention is 1.0mm when testing.
  • materials can be classified as (UL94-HB) flame retardant grades: V0, V1, V2, 5VA and/or 5VB;
  • ASTM notched impact strength test 3.0mm IZOD notched impact strength according to ASTM D256-2010 standard; the notch type is injection notch, where the higher the impact strength, the better the toughness of the material.
  • the -50°C impact strength is also tested according to the ASTM D256-2010 standard for 3.0mm IZOD notched impact strength; the notch type is injection notch, put the specimen into the -50°C freezer for more than 4 hours and then take it out for testing.
  • the test results obtained are: Low temperature impact strength, where the higher the impact strength, the better the low temperature toughness of the material.
  • Damp heat performance test method According to ASTM D527-2008 tensile splines and ASTM D256-2010 impact splines, put them into a constant temperature and humidity test box with a preset temperature of 85°C and a humidity of 85% for damp heat aging, according to the sampling plan After 1000h aging time, take out the test sample, put it in an environment with room temperature of 25°C and humidity of 50% for more than 48h, then test and record the results. , the higher the performance retention rate, the better the damp-heat stability.
  • Table 6 shows the test results of physical properties and flame retardant properties of the long-term stable polycarbonate compositions of Examples 1-27 and Comparative Examples 1-5.
  • Example 7 It can be seen from Example 7 that the above effects can also be achieved when the hydrophobized zinc oxide is used instead of the hydrophobized titanium dioxide in the system.
  • Example 24 when the acid anhydride functional group block copolymer was used to replace the epoxy functional group block copolymer, the effect changed little, and the toughness, flame retardancy and damp-heat aging performance retention rate of the polycarbonate could still be guaranteed.
  • Comparative Example 1 when the moist heat stabilizer and polysiloxane-polycarbonate were not added, the impact strength at room temperature was less affected, but brittle fracture appeared in the low temperature environment, and the impact strength at low temperature decreased because of the addition of low temperature toughening stability.
  • the initial performance is high, resulting in a significant reduction in the impact strength retention rate and a reduction in the flame retardant grade after 1000h of damp heat aging.

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Abstract

本发明提供了一种长期稳定的聚碳酸酯组合物，包括如下重量份的组分：聚碳酸酯10～99.9份；聚硅氧烷-聚碳酸酯0.01～30份；湿热稳定剂0.01～1份；低温增韧稳定剂0.1～2份；抗滴落剂0.1～5份；阻燃剂0.01～10份；所述湿热稳定剂为环氧或酸酐官能团的嵌段共聚物，所述低温增韧稳定剂为疏水化表面处理的金属氧化物。本发明所述长期稳定的聚碳酸酯组合物具有韧性高、薄壁阻燃的条件下，湿热老化性能长期性能保持率大于50％，因此，本发明开发的一种长期稳定的聚碳酸酯组合物，能够满足在高温高湿的场合使用。

Description

一种长期稳定的聚碳酸酯组合物及其制备方法 技术领域
本发明涉及聚碳酸酯材料领域，更具体地，涉及一种长期稳定的聚碳酸酯组合物及其制备方法。
背景技术
随着行业的发展，各界对安全隐患的重视度提升。电子电气，交通运输，建筑和航空航天等行业对材料的性能的要求越来越严格。不仅要具有高韧性和薄壁阻燃，还要能够不受热、氧、水、紫外线灯不同工况影响，因此，在高温高湿的环境下能保持长期稳定的性能显得尤为重要。
聚碳酸酯是应用非常广泛的材料，但是聚碳酸酯的分子链的酯基基团容易水解，从而破坏聚碳酸酯的结构，在水和热的作用下，外界和内部的小分子和其它杂质或者残留会加速酯类水解反应或者触发酯交换反应的发生。因此，如何在保证高韧性和薄壁阻燃的前提下，同时保持湿热老化性能是值得进一步研究的。
中国专利(CN109021534A)公开了一种耐高温高湿聚碳酸酯组合物及其制备方法，其中公开了聚碳酸酯、阻燃剂、抗滴落剂、增韧剂和扩链剂噁唑啉。该专利通过增韧剂和扩链剂的协同作用达到了耐高温高湿，但是阻燃等级和低温冲击强度的强弱并未可知。
因此，目前聚碳酸酯组合物在高温高湿环境下不具有较高的低温冲击强度和薄壁阻燃，急需开发一种聚碳酸酯组合物在高温高湿环境下，依然具有薄壁阻燃和较高的低温冲击强度。
发明内容
本发明的目的在于克服在高温高湿环境下，不能满足薄壁阻燃和低温冲击强度的缺陷，提供一种长期稳定的聚碳酸酯组合物。
本发明的另一目的是提供所述长期稳定的聚碳酸酯组合物的制备方法。
本发明的另一目的是提供所述高温高湿环境用聚碳酸酯制品。
本发明的目的是通过以下技术方案实现的；
一种长期稳定的聚碳酸酯组合物，包括如下重量份的组分：
Figure PCTCN2021082804-appb-000001
Figure PCTCN2021082804-appb-000002
所述湿热稳定剂为环氧或酸酐官能团的嵌段共聚物，所述低温增韧稳定剂为疏水化表面处理的金属氧化物。
采用环氧或酸酐官能团的嵌段共聚物不仅添加量少，最大程度保持基体本身的性能，而且嵌段共聚物能够提高聚碳酸酯的韧性。
所述疏水化表面处理首先进行无机处理，采用二氧化硅或者三氧化二铝涂覆表面；再进行有机处理，用非极性的硅氧烷化聚烯烃喷涂到金属氧化物表面。
所述聚碳酸酯的重均分子量为22000～30000，端羟基含量小于100ppm，BPA含量小于50ppm，通过光气法和酯交换法制备聚碳酸酯。
所述聚碳酸酯的重均分子量使用凝胶渗透色谱，采用交联的苯乙烯-二乙烯基苯柱并且使用设定在264nm的紫外可见检测器进行校准至聚碳酸酯标样而测定。在1mg/mL的浓度下制备样品，并且在1mL/min的流速下洗脱。
发明人通过加入湿热稳定剂和低温增韧稳定剂，二者经过协同作用，使得聚碳酸酯组合物不仅具有韧性高、薄壁阻燃的性能，而且还具有抗湿热老化性能，其中湿热稳定剂在聚碳酸脂老化过程中可以捕捉端羟基，并对聚碳酸酯进行封端，防止聚碳酸酯由于水解或醇解引起分子量下降导致性能大幅度衰减；非极性低温增韧稳定剂的加入能够使聚碳酸酯体系微相分离，实现基体树脂的尺寸空隙，若材料受到外力会产生银纹和剪切，能够吸收能量，进而提高韧性；非极性低温增韧稳定剂还具有疏水性能，因此在体系中实现均匀分布会排除水的浸入，进一步稳定加强湿热老化下材料的稳定，其湿热老化性能长期性能保持率大于50％；还能够提高阻燃稳定性，由于在老化过程中对树脂体系进行了稳定，不会因为树脂劣化导致燃烧时间过长或者产生滴落现象。
优选地，所述组合物包括如下重量份的组分：
Figure PCTCN2021082804-appb-000003
Figure PCTCN2021082804-appb-000004
优选地，所述聚硅氧烷-聚碳酸酯组合物的重均分子量是22000～30000，硅含量是6～20％。
优选地，所述低温增韧稳定剂的平均粒径为100～500nm。
优选地，所述疏水化表面处理的金属氧化物为二氧化钛或氧化锌。
优选地，所述阻燃剂为磺酸盐类阻燃剂，包括全氟化的C1-C16烷基磺酸盐，例如全氟丁基磺酸钾(Rimar盐)、全氟辛烷磺酸钾、全氟己烷磺酸四乙铵、二苯砜磺酸钾(KSS)、苯磺酸钠、甲苯磺酸钠(NATS)。
优选地，所述阻燃剂为磷系阻燃剂，包含磷-氮键的有机磷酸酯和有机化合物。例如双官能或多官能芳族含磷化合物分别包括间苯二酚四苯基二磷酸酯(RDP)、对苯二酚的双(二苯基)磷酸酯和双酚-A的双(二苯基)磷酸酯；其他含磷阻燃剂包括氯化磷腈、磷酯酰胺、磷酸酰胺、膦酸酰胺、次膦酸酰胺、三(氮丙啶基)氧化膦、聚有机膦腈和聚有机膦酸酯。
更优选地，所述磺酸酯类阻燃剂为二苯砜磺酸钾。
优选地，所述抗滴落剂为原纤化氟聚合物或非原纤化含氟聚合物的至少一种，如聚四氟乙烯(PTFE)，更优选地，抗滴落剂可以被封装在刚性共聚物内，例如苯乙烯-丙烯腈共聚物(SAN)，封装在苯乙烯丙烯腈(TSAN)中的聚四氟乙烯比未被封装的聚四氟乙烯(PTFE)更容易让组合物分散。
本发明还提供了一种长期稳定的聚碳酸酯组合物的制备方法，包括以下步骤：
S1.称取聚碳酸酯、聚硅氧烷-聚碳酸酯、湿热稳定剂、低温增韧稳定剂、抗滴落剂后，将上述原料投入混合机中共混至均匀，得到预混物；
S2.将步骤S1中制备所得的预混物加入到挤出机中进行熔融、挤出、后加工，最后得到组合物粒子。
所述后加工包括拉条、冷却、风干、切粒。
一种高温高湿环境用聚碳酸酯制品，含有所述长期稳定的聚碳酸酯组合物。
作为一种具体的实施方案，所述高温高湿环境用聚碳酸酯制品包括但不限于户外器材、汽车外壳、照明灯罩等。
与现有技术相比，本发明的有益效果是：
本发明提供一种长期稳定的聚碳酸酯组合物，通过加入低温增韧稳定剂和湿热稳定剂配伍使得聚碳酸酯组合物不仅具有韧性高、薄壁阻燃的性能，而且还具有抗湿热老化性能。所述聚碳酸酯组合物的ASTM常温缺口冲击强度大于600J/m，-50℃缺口冲击强度大于300J/m，1.0mm厚度样条阻燃级别达到UL94-V0级。所述聚碳酸酯组合物的湿热老化性能长期性能保持率大于50％。能够满足在高温高湿的场合使用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，但本发明的实施方式不限于此。
本发明所采用的试剂、方法和设备，如无特殊说明，均为本技术领域常规试剂、方法和设备。
以下实施例及对比例中采用的原料如下：
聚碳酸酯：1300-10NP LG化学
聚硅氧烷-聚碳酸酯：硅含量9％，重均分子量30000，ST009，韩国三养
二氧化钛：R104杜邦公司
二氧化钛：S-100华南理工大学
二氧化钛：S-500华南理工大学
二氧化钛：S-700华南理工大学
疏水化二氧化钛A：R104通过气喷法将硅氧烷化聚烯烃对二氧化钛进行表面处理得到疏水化的二氧化钛，制备得到的疏水化R104平均粒径为200nm
疏水化二氧化钛B：S-100通过气喷法将硅氧烷化聚烯烃对二氧化钛进行表面处理得到疏水化的二氧化钛，制备得到的疏水化疏水化S-100的平均粒径为100nm
疏水化二氧化钛C：S-500通过气喷法将硅氧烷化聚烯烃对二氧化钛进行表面处理得到疏水化的二氧化钛，制备得到的疏水化S-500的平均粒径为500nm
疏水化二氧化钛D：S-700通过气喷法将硅氧烷化聚烯烃对二氧化钛进行表面处理得到疏水化的二氧化钛，制备得到的疏水化S-700的平均粒径为700nm
氧化锌：氧化锌 阿拉丁公司
疏水化氧化锌：首先进行无机处理，采用二氧化硅或者三氧化二铝涂覆表面； 再进行有机处理，用非极性的硅氧烷化聚烯烃喷涂到氧化锌表面，制备得到的疏水化氧化锌的平均粒径为200nm
湿热稳定剂A：P1901环氧嵌段共聚物，日本三菱立阳
湿热稳定剂B：A560酸酐嵌段共聚物，杜邦
湿热稳定剂C：MA4215酸酐接枝共聚物，科莱恩
抗滴落剂：POLYTE30X原纤化氟聚合物，韩国太平洋
阻燃剂：NATS二苯砜磺酸钾，美国ARICHEM
下面结合实施例和对比例来详细说明本发明。
下面实施例1～24和对比例1～7均通过以下方法制备聚碳酸酯组合物，按照表1～5的重量比称取各组分；具体步骤如下：
S1.分别称取聚碳酸酯、聚硅氧烷-聚碳酸酯、湿热稳定剂、低温增韧稳定剂、抗滴落剂后，将上述原料投入预设温度为50℃转速为200rpm的混合机中共混至均匀，得到预混物；
S2.将步骤S1中制备所得的预混物加入到预设温度为230℃～260℃主机转速为450rpm的挤出机中进行熔融挤出、拉条、冷却、风干、切粒，最后得到组合物粒子。
表1实施例1～7各组分的含量
Figure PCTCN2021082804-appb-000005
表2实施例8～12各组分的含量
组分(份数) 实施例8 实施例9 实施例10 实施例11 实施例12
聚碳酸酯 70 70 70 70 70
聚硅氧烷-聚碳酸酯 0.01 0.1 1 10 20
疏水化二氧化钛A 0.2 0.2 0.2 0.2 0.2
湿热稳定剂A 0.3 0.3 0.3 0.3 0.3
抗滴落剂 0.5 0.5 0.5 0.5 0.5
阻燃剂 0.3 0.3 0.3 0.3 0.3
表3实施例13～19各组分的含量
Figure PCTCN2021082804-appb-000006
表4实施例20～27各组分的含量
Figure PCTCN2021082804-appb-000007
表5对比例1～7各组分比例含量表
Figure PCTCN2021082804-appb-000008
Figure PCTCN2021082804-appb-000009
将上述实施例1～27和对比例1～5制备得到的长期稳定的聚碳酸酯组合物，进行以下性能测试，测试所参照标准和方法如下：
UL94阻燃性的测定方法：
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，计算阻燃等级。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；
ASTM缺口冲击强度的测定方法：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，其中冲击强度越高，材料韧性越好。-50℃冲击强度也是根据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，将样条放入-50℃冷冻箱调节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。
湿热性能测试方法：根据ASTM D527-2008拉伸样条和ASTM D256-2010冲击样条放入在预设好温度为85℃湿度为85％的恒温恒湿实验箱中进行湿热老化，按照取样计划1000h老化时间后取出测试样条后，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。
实施例1～27和对比例1～5的长期稳定的聚碳酸酯组合物的物理性能和阻燃性能测试结果见表6。
表6性能测试结果
Figure PCTCN2021082804-appb-000010
Figure PCTCN2021082804-appb-000011
从实施例1～6看，体系中随着聚碳酸酯组分的增加，因为PC分子链之间的作用力增加，湿热老化中拉伸性能保持率略有增加，湿热老化的冲击性能保持率略微下降，低温冲击强度会略微降低，这是因为整体的硅共聚成分含量下降，组分的分散均一性会下降，由于低温增韧剂和湿热稳定剂的存在，下降幅度不大，阻燃等级不变。
从实施例7看，当体系中采用疏水化的氧化锌替代疏水化的二氧化钛也能达到上述效果。
从实施例8～12看，聚硅氧烷-聚碳酸酯的含量越高，低温缺口冲击强度也越高。随着聚硅氧烷-聚碳酸酯共聚物的含量增加，湿热老化的冲击保持率会增加，这是因为共聚的硅成分的存在降低了PC分子链之间的缠结，同时因为一定含量的硅氧烷存在改善了低温增韧剂和湿热稳定剂的分散均一性，随着含量的增加，低温冲击改善明显，阻燃等级维持不变，另外由于硅氧烷具有一定的疏水性，可以阻挡水分的侵入对韧性的损伤。
从实施例13～17看，随着低温增韧剂含量的增加，在湿热稳定剂的存在下，常温冲击强度和低温冲击强度会随着添加量的增加而有所上升，但上升到最佳值后呈现下降的趋势，这是因为低温增韧剂在体系中形成均一的分散后，相互之间存在有效的树脂层距离，随着添加量的增加树脂层的距离降低，降低到一定程度 后反而对韧性造成不良影响。低温增韧剂的存在对湿热老化性能保持率的提高有稳定作用。
从实施例18～23看，随着湿热稳定剂的增加，常温缺口冲击强度会随之降低，但基本维持在同一水平，低温缺口冲击强度随着湿热稳定剂的增加先增加后降低，而湿热老化性保持率随着湿热稳定剂的增加而升高，同时低温增韧稳定剂的存在进一步保持湿热老化过程中材料的湿热性能和韧性。
实施例24，当采用酸酐官能团嵌段共聚物替换环氧官能团的嵌段共聚物，其效果变化不大，依然能够保证聚碳酸酯的韧性、阻燃性能和湿热老化性能保持率。
从实施例4和实施例25～27看，采用不同粒径的疏水化二氧化钛对聚碳酸酯的数据有影响，其中当粒径从100nm增长到500nm时，常温冲击强度和低温冲击强度先增大后减小，湿热老化性能保持率较高；当选用疏水化二氧化钛的粒径为700nm时，冲击强度的湿热老化性能保持率只有50％。
对比例1中在不加入湿热稳定剂和聚硅氧烷-聚碳酸酯时，常温冲击强度影响较小，但低温环境下显现的是脆性断裂，低温冲击强度降低，因为加入了低温增韧稳定剂，其初始性能高，导致经过1000h的湿热老化后，冲击强度保持率大幅度降低，阻燃等级降低。
对比例2中不加入低温增韧稳定剂和聚硅氧烷-聚碳酸酯时，对常温冲击强度降低作用明显，同时低温冲击明显呈现脆性断裂，1.0mm厚度燃烧时间延长，只能达到阻燃等级V-1水平，湿热老化后冲击强度保持率低，阻燃等级降低。
对比例3中不加入湿热稳定剂和低温增韧稳定剂时，聚硅氧烷-聚碳酸酯不能很好的发挥低温韧性的保障作用，低温冲击强度无法保持较高水平，但要依然高于对比例1和对比例2；不添加湿热稳定剂的情况下，湿热老化后的拉伸强度和冲击强度衰减大，阻燃等级降低。
对比例4采用未进行疏水化表面处理的二氧化钛替代疏水化表面处理的二氧化钛，常温缺口冲击强度和低温缺口冲击强度都下降，其湿热老化的冲击强度性能保持率只有37.2％。
对比例5中采用酸酐接枝共聚物替代酸酐嵌段共聚物，常温冲击强度和低温冲击强度均下降，湿热老化冲击强度性能保持率仅有12.4％，这可能是因为接枝共聚物本身韧性不足。
对比例6中，体系中不加入湿热稳定剂，其低温冲击强度下降，湿热老化性能下降。
对比例7，体系中不加入低温增韧稳定，低温冲击强度明显下降，1.0mm厚度燃烧时间延长，只能达到阻燃等级V-1水平，湿热老化后冲击强度保持率低，阻燃等级降低。
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. 一种长期稳定的聚碳酸酯组合物，其特征在于，包括如下重量份的组分：
    Figure PCTCN2021082804-appb-100001
    所述湿热稳定剂为环氧或酸酐官能团的嵌段共聚物，所述低温增韧稳定剂为疏水化表面处理的金属氧化物。
  2. 如权利要求1所述长期稳定的聚碳酸酯组合物，其特征在于，所述聚硅氧烷-聚碳酸酯组合物的重均分子量是22000～30000，硅含量是6～20％。
  3. 如权利要求1所述长期稳定的聚碳酸酯组合物，其特征在于，所述低温增韧稳定剂的平均粒径为100～500nm。
  4. 如权利要求1所述长期稳定的聚碳酸酯组合物，其特征在于，所述疏水化表面处理的金属氧化物为二氧化钛或氧化锌。
  5. 如权利要求1所述长期稳定的聚碳酸酯组合物，其特征在于，所述阻燃剂为磺酸酯类阻燃剂或磷系阻燃剂中的一种。
  6. 如权利要求5所述长期稳定的聚碳酸酯组合物，其特征在于，所述磺酸酯类阻燃剂为二苯砜磺酸钾。
  7. 如权利要求1所述长期稳定的聚碳酸酯组合物，其特征在于，所述抗滴落剂为原纤化氟聚合物或非原纤化含氟聚合物的一种。
  8. 如权利要求7所述长期稳定的聚碳酸酯组合物，其特征在于，所述抗滴落剂为聚四氟乙烯。
  9. 如权利要求1～8中任一项所述长期稳定的聚碳酸酯组合物的制备方法，其特征在于，包括以下步骤：
    S1.称取聚碳酸酯、聚硅氧烷-聚碳酸酯、湿热稳定剂、低温增韧稳定剂、抗滴落剂和阻燃剂后，将上述原料投入混合机中共混至均匀，得到预混物；
    S2.将步骤S1中制备所得的预混物加入到挤出机中进行熔融、挤出、后加工，得到组合物粒子。
  10. 一种高温高湿环境用聚碳酸酯制品，其特征在于，含有权利要求1～8所述长期稳定的聚碳酸酯组合物。
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