WO2020151553A1 - 一种聚碳酸酯合金及其制备方法 - Google Patents

一种聚碳酸酯合金及其制备方法 Download PDF

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WO2020151553A1
WO2020151553A1 PCT/CN2020/072290 CN2020072290W WO2020151553A1 WO 2020151553 A1 WO2020151553 A1 WO 2020151553A1 CN 2020072290 W CN2020072290 W CN 2020072290W WO 2020151553 A1 WO2020151553 A1 WO 2020151553A1
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flame retardant
polycarbonate
polycarbonate alloy
hypophosphite
acid
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French (fr)
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艾军伟
岑茵
黄险波
叶南飚
董相茂
王培涛
陈勇文
丁超
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Kingfa Science and Technology Co Ltd
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    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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

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  • the invention relates to the technical field of polymer composite materials, in particular to a polycarbonate alloy and a preparation method thereof.
  • PC polycarbonate
  • PC and ABS are very sensitive to metals, especially heavy metals such as silver.
  • the presence of heavy metals can greatly accelerate the degradation of ABS and PC.
  • effective antibacterial agents mainly contain silver ions, and silver ions are subject to shear, heat, and environmental factors during processing and use.
  • the effective components of silver ion antibacterial agents are easily converted to more alkaline ones. Its oxide not only loses antibacterial properties and the alloy color turns gray, but also further deteriorates the alloy.
  • ABS/PC flame retardant alloys are prepared, and the addition of flame retardants will affect the stability of the alloy, and if the alloy system is in an unstable state, it will also affect the flame retardant performance.
  • flame retardants will affect the stability of the alloy, and if the alloy system is in an unstable state, it will also affect the flame retardant performance.
  • bromine-antimony flame retardant systems cannot be added to PC, because the free bromine and alkaline antimony compounds can degrade the stability of the alloy, and the high temperature during processing will aggravate the deterioration of the alloy. The processing window is shorter.
  • Chinese patent 201611189108.5 discloses a PC/ABS alloy with excellent thermal aging properties, in which 0.1-2 parts of phosphate ester is used to adjust the pH value of the alloy to 6.6-8.2, and epoxy resin is used to cap the PC.
  • the PC/ABS alloy obtained after auxiliary use meets the long-term thermal aging requirements of 100 degrees and 1000 hours.
  • the core of the invention is to use epoxy resin to cap the PC, so that the alloy can still obtain good thermal stability when the pH is alkaline, especially When the pH value of Example 3 is 8.2, good heat aging resistance can still be obtained.
  • the pH adjuster used is phosphoric acid ester (triphenyl phosphite, sodium dihydrogen phosphate, sodium dihydrogen phosphite).
  • Phosphate esters include triphenyl phosphate used as a flame retardant, etc., triphenyl phosphite Usually exists as a heat stabilizer. Sodium dihydrogen phosphate and sodium dihydrogen phosphite are mainly used to improve the stability of the ester group in the melt during processing. Therefore, it can be seen that the "phosphate ester" added by the patent cannot function alone in this system. On the other hand, using epoxy resin to cap the PC will increase the alkalinity of the alloy.
  • this patent mainly uses epoxy resin to cap the PC to increase the thermal stability of the system.
  • the pH regulator used in this patent is a weak Lewis acid, and the added amount is large, which easily affects other properties (such as impact strength and stress cracking properties).
  • Triphenyl phosphite, sodium dihydrogen phosphate, and sodium dihydrogen phosphite are in the form of solid powders or fine particles. Due to the small amount used, it is difficult to uniformly disperse in the alloy, causing difficulties in processing.
  • the purpose of the present invention is to provide a polycarbonate alloy which has the advantages of moist heat stability, a wider processing window and the like.
  • Another object of the present invention is to provide a method for preparing the above polycarbonate alloy.
  • a polycarbonate alloy in parts by weight, including the following components:
  • the pH value of the polycarbonate alloy is 6.3-6.9, and the pH value is adjusted by liquid acid.
  • the liquid acid is selected from at least one of phosphoric acid and acetic acid.
  • the main function of the liquid acid is to stably mix into the polycarbonate alloy in the melt state and stabilize the acid-base balance of the alloy melt during processing.
  • Phosphoric acid and acetic acid are more commonly used acid regulators.
  • the present invention uses liquid acid to adjust the pH value of the polycarbonate alloy. Because the acidity is stronger than that of Lewis acids, it only needs one part per thousand or less of the actual content to reach the target pH value. These acids will Evenly dispersed in the alloy, it will not affect other properties of the alloy.
  • the acidity of liquid acid is relatively strong, so the actual amount of liquid acid added during alloy pH adjustment is difficult to calculate based on the target pH value, and the high temperature in the screw can easily volatilize the liquid acid quickly, making the liquid acid entering the alloy Can not get expectations and control. Therefore, if the liquid acid is effectively incorporated into the alloy, it is a technical difficulty that plagues the present invention.
  • the present invention uses porous foamed polycarbonate or porous foamed ABS, which contains liquid acid, which can effectively make the liquid acid into the alloy in the screw, and the effective liquid acid will be evenly dispersed. In the alloy resin, excess liquid acid will volatilize.
  • the pH value points obtained by testing the addition amount of n liquid acid are drawn into a pH-liquid acid addition amount curve.
  • the more test points n the more accurate the curve, and the drawn curve obtains the addition amount of the liquid acid at the target pH value. After a few attempts to obtain the alloy product of the target pH.
  • the polycarbonate resin of the present invention may be a branched thermoplastic polymer or copolymer obtained by the reaction of a dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester.
  • the production method of the polycarbonate resin is not particularly limited, and the polycarbonate resin produced by the hitherto known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used.
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • tetramethylbisphenol A bis(4-hydroxyphenyl) )-P-diisopropylbenzene
  • hydroquinone resorcinol
  • 4,4-dihydroxydiphenyl etc.
  • a compound in which at least one tetraalkylphosphonium sulfonate is bonded to the aforementioned aromatic dihydroxy compound can also be used.
  • the polycarbonate resin is preferably an aromatic polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane, or from 2,2-bis(4-hydroxyphenyl)propane and other aromatics.
  • the polycarbonate resin may also be a copolymer in which the main composition is an aromatic polycarbonate resin, for example, a copolymer with a siloxane structure-containing polymer or oligomer.
  • a mixture of two or more of the aforementioned polycarbonate resins may be used.
  • Monovalent aromatic hydroxy compounds can be used to adjust the molecular weight of polycarbonate resins, for example, m-cresol, p-cresol, m-propyl phenol, p-propyl phenol, p-tert-butyl phenol and p-(long chain alkyl )-Substituted phenol.
  • the present invention has no particular limitation on the production method of the polycarbonate resin, and the polycarbonate resin produced by the phosgene method (interfacial polymerization method) or the melting method (transesterification method) can be used.
  • the polycarbonate resin is also provided by subjecting a polycarbonate resin produced by a melt method to a post-treatment for adjusting the amount of terminal hydroxyl groups.
  • ABS acrylonitrile-butadiene-styrene copolymer refers to acrylonitrile which can be a blend of acrylonitrile-butadiene-styrene terpolymer or styrene-butadiene rubber and styrene-acrylonitrile copolymer -Butadiene-styrene polymer.
  • the present invention has no special requirements for the content of each section, and the content of acrylonitrile can be 11-36%, the content of butadiene is 8-36%, and the content of styrene is 28-80%.
  • the pH of the polycarbonate prepared according to different raw materials, different preparation processes, synthesis residues, and different end-capping groups is between 6.2 and 7.3.
  • polycarbonate is mixed with ABS, other additives, and fillers to prepare an alloy, it will further change the pH of the alloy. If the final pH of the alloy (especially mineral filling, antibacterial silver ion filling, and the addition of a large amount of flame retardant) is not in the weak acid range of 6.3-6.9, it will seriously affect the stability of the alloy, especially the shear during melt extrusion. Make the degradation of molecules serious.
  • the silver ion antibacterial agent alloy is prepared, based on the total weight of the polycarbonate alloy, and also includes silver ions with a content of 100-1200 ppm.
  • Silver ions are derived from silver ion antibacterial agents. At this time, it is not only necessary to consider the destabilization effect of the residual substances in ABS, but also the stability of silver ions. Within the range of 6.3-6.9, the stability of silver ions is strong and the remaining impurities in ABS are effectively suppressed, making the alloy It has good antibacterial performance and good humidity and heat stability. These stability are not only reflected in the range of daily use, but also in the stability of the processing process, thus providing a wider processing window.
  • flame-retardant polycarbonate alloy If it is necessary to prepare a flame-retardant polycarbonate alloy, it also includes 0-15 parts by weight of flame retardant.
  • the flame retardant is selected from bromine flame retardants, C1-C16 alkyl sulfonate flame retardants, carbonate flame retardants, fluorine-silver ion composites, phosphorus flame retardants, metal hydroxides 1. At least one of antimony-containing compound flame retardant synergist and borate flame retardant;
  • the brominated flame retardant is selected from tetrabromobisphenol A, brominated triazine, brominated epoxy, decabromodiphenyl ethane, decabromodiphenyl ether, brominated polyimide, brominated polyphenylene At least one of ethylene, polybrominated styrene, brominated polycarbonate, and brominated polyacrylate;
  • the C1-C16 alkyl sulfonate flame retardant is selected from potassium perfluorobutane sulfonate, potassium perfluorooctane sulfonate, tetraethyl ammonium perfluoroethane sulfonate, potassium diphenylsulfone sulfonate At least one of
  • the carbonic acid flame retardant is selected from at least one of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, and barium carbonate;
  • the phosphorus flame retardant is selected from phosphine flame retardant, hypophosphite flame retardant, hypophosphite flame retardant, phosphonite flame retardant, phosphonite flame retardant, phosphite Flame retardant, phosphite flame retardant, phosphine oxide flame retardant, hypophosphite flame retardant, hypophosphite flame retardant, phosphonate flame retardant, phosphonate flame retardant, phosphate flame retardant , At least one of polyphosphate flame retardants;
  • the metal hydroxide flame retardant is selected from at least one of magnesium hydroxide and aluminum hydroxide;
  • the borate flame retardant is selected from at least one of anhydrous zinc borate, 3.5 water zinc borate, alkali metal salts of boric acid, and alkaline earth metal salts of boric acid.
  • the hypophosphite flame retardant is selected from at least one of aluminum hypophosphite, calcium hypophosphite, dimethyl aluminum hypophosphite, diethyl aluminum hypophosphite, and methyl ethyl aluminum hypophosphite;
  • the flame retardant is selected from bisphenol A bis (diphenyl phosphate), phenoxy phosphazene, resorcinol (diphenyl phosphate), triphenyl phosphate, melamine polyphosphate, and melamine cyanurate
  • the polyphosphate flame retardant is selected from at least one of ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate.
  • the flame retardant is selected from phosphorus flame retardants
  • the phosphorus flame retardant is selected from phosphate flame retardants
  • the phosphate ester flame retardant is selected from phenoxyphosphazene.
  • it also includes 0-5 parts of at least one of antioxidants, weathering agents, and pigments.
  • the lubricant is selected from at least one of stearate lubricants, fatty acid lubricants, and stearate lubricants;
  • the stearate lubricant is selected from at least one of calcium stearate, magnesium stearate, and zinc stearate;
  • the fatty acid lubricant is selected from fatty acids, fatty acid derivatives, and fatty acid esters At least one;
  • the stearate lubricant is selected from at least one of pentaerythritol stearate.
  • the above-mentioned preparation method of polycarbonate alloy includes the following steps: adding polycarbonate, ABS resin, porous foamed polycarbonate with liquid acid or porous foamed ABS to a high-speed mixer, and then add to In a twin-screw extruder, melt and mix at a temperature of 230-250°C, then pelletize, cool, and dry to obtain a polycarbonate alloy.
  • the present invention inhibits the cracking effect of residual impurities in the ABS resin, especially residual emulsifiers, ensures the stability of the alloy, and also improves the extrusion and melting process.
  • the stability of the machine broadens the processing window.
  • the silver ion antibacterial polycarbonate alloy system is prepared, and the pH adjustment by using liquid acid not only improves the stability of the alloy, but also improves the stability of the silver ion.
  • a stable alloy system can promote the stability of silver ions (reflected by a good antibacterial effect and good color stability), and the stability of silver ions also promotes the improvement of the stability of the alloy system. Therefore, the obtained silver ion antibacterial polycarbonate alloy has good antibacterial effect and stability, and also widens the processing window.
  • Figure 1 Schematic diagram of the zodiac grid evaluation method.
  • the sources of the raw materials used in the present invention are as follows, but are not limited by the following raw materials.
  • Silver ion source silver ion antibacterial agent, IKM50G, Japan Zeomic;
  • Liquid acid phosphoric acid
  • Flame retardant B bisphenol A bis (diphenyl phosphate);
  • Flame retardant C melamine polyphosphate
  • Lubricant stearate lubricant, PETS;
  • Example Preparation method of polycarbonate alloy Add polycarbonate, ABS resin, silver ion antibacterial agent, porous foamed polycarbonate with liquid acid or porous foamed ABS, and flame retardant to high-speed mixing according to the ratio.
  • the material is evenly mixed in the feeder, then added to the twin-screw extruder, melted and mixed at a temperature of 230-250°C, then pelletized, cooled and dried to obtain a polycarbonate alloy.
  • Alloy pH Dissolve the composition in a methylene chloride solvent, filter the solution, and perform acid-base titration of the organic phase to test the pH.
  • Processing window using the twelve grid evaluation method, under the condition of fixed injection pressure and back pressure, the injection temperature is divided into 250°C, 280°C, 300°C, 320°C, and the injection speed is divided into high and medium , Low speed, so the formation of different injection molding processing window areas, evaluate the appearance quality, mechanical performance stability, and processing screw rotation state of injection molded parts under different area windows. If the above properties can be combined, it means the processing The window is satisfied, and the more the number of regions is satisfied, the wider the processing window, the best is 12, and the worst is 0; the zodiac grid is shown in Figure 1.
  • ICP standard curve extrapolation method The Ag content in the composition is determined by optical emission spectroscopy with inductively coupled plasma (ICP-OES). In order to determine the total Ag content, weigh 2g. The composition was measured, treated with 5ml of nitric acid and stirred for trial production to dissolve, and the solution was supplemented to 100ml, and the total Ag content was calculated by the ICP standard curve extrapolation method.
  • ICP-OES inductively coupled plasma
  • Flame-retardant stability Put the composition into an aging box with a temperature of 85°C and a humidity of 85% for accelerated aging for 500 hours, and then test the flame-retardant performance according to the UL-94 standard at 1.5mm; flame-retardant stability The better, the better the stability of the alloy.
  • Example 1-4 and Comparative Example 1-2 each group distribution ratio (weight parts) and various performance test results
  • the pH value of the polycarbonate alloys of Examples 1-4 and Comparative Example 1-2 without adjusting the pH is 7.1
  • the pH value of the alloys of Examples 1-4 and Comparative Example 2 in Table 1 is obtained by adding Liquid acid regulator is adjusted.
  • Table 2 The distribution ratio (weight parts) of each group of Examples 5-8 and Comparative Examples 3-4 and the results of each performance test
  • Table 3 The distribution ratio (parts by weight) of each group of Examples 9-11 and Comparative Examples 5-6 and the results of each performance test
  • the pH of the polycarbonate alloys of the Examples and Comparative Examples under the premise of not adjusting the pH is 7.0, and the pH values of the alloys of the Examples and Comparative Examples in Table 3 are adjusted by adding a liquid acid regulator .

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Abstract

本发明公开了一种聚碳酸酯合金，其特征在于，按重量份计，包括以下组分：聚碳酸酯70份；ABS树脂1-60份；聚碳酸酯合金的pH值为6.3-6.9,pH值是通过液体酸调节的。本发明通过调节聚碳酸酯合金的pH值，来保证本发明的聚碳酸酯合金具有较好的湿热稳定性，以及较宽的加工窗口等优点。

Description

一种聚碳酸酯合金及其制备方法 技术领域
本发明涉及高分子复合材料技术领域，特别是涉及一种聚碳酸酯合金及其制备方法。
背景技术
目前，聚碳酸酯(PC)被广泛用于生产各种工业、民用制件(如各种透明制件、灯罩、仪表盘等)。随着，生活水平的提高，人们对健康的关注度越来越高，为了避免塑料材质的制件繁殖细菌，提高产品的安全性，对塑料抑制细菌繁殖的要求日益严苛。
PC/ABS合金中避免不了原材料带来的聚合残留杂质，残留杂质会对合金的稳定性也会有较大的劣化，由其是ABS树脂中会残留生产过程添加的乳化剂对体系产生的裂化作用，降低合金的稳定性。
PC及其ABS对金属十分敏感，特别是重金属如银，重金属的存在能够极大加速ABS和PC的劣化。而，有效的抗菌剂主要是含有银离子类的，银离子在加工和使用过程中受到剪切、热、以及环境等因素银离子抗菌剂中的有效成分银离子容易转化为碱性更强的其氧化物，不仅失去抗菌性能、合金颜色变灰，还会进一步劣化合金。
一般制备ABS/PC阻燃合金，阻燃剂的加入会影响合金的稳定性，而如果合金体系处于不稳定的状态，也会影响阻燃性能。特别是，一般来说PC中是不能加入溴锑阻燃体系的，因为溴素的游离以及碱性的含锑化合物都能劣化合金的稳定性，加工时的高温更会加重合金的劣化，因此加工窗口较短。
中国专利201611189108.5公开了一种热老化性能优异的PC/ABS合金，其中，使用了磷酸酯0.1-2份调节合金的pH值为6.6-8.2，同时使用环氧树脂对PC进行封端，两者辅配使用后得到的PC/ABS合金满足长期100度1000h热老化要求。但是，根据该专利实施例1-8的实验数据得知其发明的核心为使用环氧树脂对PC进行封端，以达到该合金在pH为碱性时候仍能得到良好的热稳定性尤其是实施例3的pH值为8.2时仍能得到好的耐热老化性能。并且，其使用的pH调节剂为磷酸酯(亚磷酸三苯酯、磷酸二氢钠、亚磷酸二氢钠)，磷酸酯类有用作阻燃剂的磷酸三苯酯等，亚磷酸三苯酯通常是作为热稳定剂存在，磷酸二氢钠、亚磷酸二氢钠主要用于提升加工过程中熔体的酯基的稳定性。因此，可以看出该专利添加的“磷酸酯”在该体系中是不能单独起到作用的。另一方面，使用环氧树脂对PC进行封端反而会提升合金的碱性。综上所述，该专利主要是通过环氧树脂对PC封端来增加体系的热稳定性。从其他性能出发，该专利所用的pH调节剂为很弱的路易斯酸类，加入量较大，容易影响其他性能(比如冲击强度和应力开裂等性能)。亚磷酸三苯酯、磷酸二氢钠、亚磷酸二氢钠为固体粉末或者细小颗粒状，由于用量很少，很难均匀分散在合金中，给加工带来困难。
发明内容
本发明的目的在于，提供一种聚碳酸酯合金，具有湿热稳定性，较宽的加工窗口等优点。
本发明的另一目的在于，提供上述聚碳酸酯合金的制备方法。
本发明是通过以下技术方案实现的：
一种聚碳酸酯合金，按重量份计，包括以下组分：
聚碳酸酯            70份；
ABS树脂             1-60份；
聚碳酸酯合金的pH值为6.3-6.9，pH值是通过液体酸调节的。
所述的液体酸选自磷酸、醋酸中的至少一种。
液体酸的主要功能是在熔体状态下稳定的混合进聚碳酸酯合金中，在加工过程中稳定合金熔体的酸碱平衡。磷酸、醋酸为较常用到的酸性调节剂。
本发明使用液体酸对聚碳酸酯合金的pH值进行调节，由于酸性较路易斯酸类强，因此， 只需要千分之一份甚至更少的实际含量即可达到目标的pH值，这些酸会均匀分散在合金中，不会对合金带来其他性能的影响。
进一步的，液体酸的酸性较强，因此合金pH调解时所加入实际液体酸的量难以根据目标pH值计算得到，并且在螺杆中的高温容易使液体酸快速的挥发，使进入合金的液体酸得不到预期和控制。因此，如果让液体酸有效融入合金中是困扰本发明的技术困难。为了解决该技术难题，本发明通过使用使用多孔发泡聚碳酸酯、或者多孔发泡ABS，其中存有液体酸，可以在螺杆中有效的使液体酸进入合金中，有效的液体酸会均匀分散在合金树脂中，多余的液体酸会挥发出。本发明通过测试n个液体酸添加量得到的pH值点绘制成pH-液体酸加入量曲线，测试点n越多，曲线越精准，再通过绘制的曲线得到目标pH值的液体酸的加入量的范围值，再通过少数尝试得到目标pH的合金产品。
聚碳酸酯树脂：本发明的聚碳酸酯树脂可为由二羟基化合物或其和少量的多羟基化合物与光气(phosgene)或碳酸二酯的反应获得的支化热塑性聚合物或共聚物。不特别限制聚碳酸酯树脂的生产方法，并且可使用由迄今为止已知的光气法(界面聚合法)或熔融法(酯交换法)生产的聚碳酸酯树脂。优选芳族二羟基化合物为原料二羟基化合物，且可示例为2,2-双(4-羟苯基)丙烷(＝双酚A)、四甲基双酚A、双(4-羟苯基)-对-二异丙基苯、对苯二酚、间苯二酚、4,4-二羟基二苯等，其中优选双酚A。还可使用其中至少一个四烷基磺酸膦(tetraalkylphosphonium sulfonate)结合至前述芳族二羟基化合物的化合物。
前述中，聚碳酸酯树脂优选源于2,2-双(4-羟苯基)丙烷的芳族聚碳酸酯树脂，或源于2,2-双(4-羟苯基)丙烷和其它芳族二羟基化合物的芳族聚碳酸酯共聚物。聚碳酸酯树脂还可为其中主要组成为芳族聚碳酸酯树脂的共聚物，例如，与含硅氧烷结构的聚合物或低聚物的共聚物。此外，可使用两种或更多种的上述聚碳酸酯树脂的混合物。一元芳族羟基化合物可用于调整聚碳酸酯树脂的分子量，例如，间甲基苯酚、对甲基苯酚、间丙基苯酚、对丙基苯酚、对叔丁基苯酚和对-(长链烷基)-取代酚。
本发明对聚碳酸酯树脂的生产方法没有特别限制，且可使用由光气法(界面聚合法)或熔融法(酯交换法)生产的聚碳酸酯树脂。聚碳酸酯树脂还通过由熔融法生产的聚碳酸酯树脂进行调节末端羟基的量的后处理来提供。
ABS(丙烯腈-丁二烯-苯乙烯共聚物)是指可以是丙烯腈-丁二烯-苯乙烯三元共聚物或丁苯橡胶和苯乙烯-丙烯腈共聚物的共混物的丙烯腈-丁二烯-苯乙烯聚合物。本发明对于各段的含量没有特殊的要求，可以是丙烯腈的含量为11-36％，丁二烯的含量为8-36％，苯乙烯的含量为28-80％。
一般的，根据不同原料、不同制备工艺、合成残留、不同的封端基团制备得到的聚碳酸酯的pH在6.2-7.3之间。当聚碳酸酯和ABS、其他添加剂、填料混合制备成合金后，还会进一步改变合金的pH。如果合金(尤其是矿物填充、抗菌银离子填充、大量阻燃剂的加入)的最终pH不在6.3-6.9的弱酸性范围内，会严重影响合金的稳定性，尤其是熔融挤出时的剪切使分子的降解严重。
制备银离子抗菌剂合金，基于聚碳酸酯合金的总重量，还包括含量为100-1200ppm的银离子。
银离子来源于银离子抗菌剂。这时不仅需要考虑抑制ABS中残留物质的不稳定作用，还需要考虑银离子的稳定性，在6.3-6.9范围内，银离子稳定性强以及ABS中残的留杂质得到了有效抑制，使合金的抗菌性能好、湿热稳定性好。这些稳定性不仅体现在日常使用范围，也体现在加工过程中的稳定性，因此提供了较宽的加工窗口。
如需要制备成为阻燃聚碳酸酯合金，按重量份计，还包括0-15份的阻燃剂。
所述的阻燃剂选自溴系阻燃剂、C1-C16烷基磺酸盐阻燃剂、碳酸盐类阻燃剂、氟-银离子复合物、磷系阻燃剂、金属氢氧化物、含锑化合物阻燃协效剂、硼酸盐阻燃剂中的至少一 种；
所述的溴系阻燃剂选自四溴双酚A、溴代三嗪、溴化环氧、十溴二苯乙烷、十溴联苯醚、溴化聚酰亚胺、溴化聚苯乙烯、聚溴化苯乙烯、溴化聚碳酸酯、溴化聚丙烯酸酯中的至少一种；
所述的C1-C16烷基磺酸盐阻燃剂选自全氟丁基磺酸钾、全氟辛烷磺酸钾、全氟乙烷磺酸四乙基铵、二苯砜磺酸钾中的至少一种；
所述的碳酸类阻燃剂选自碳酸钠、碳酸钾、碳酸镁、碳酸钙、碳酸钡中的至少一种；
所述的磷系阻燃剂选自膦阻燃剂、次亚磷酸酯阻燃剂、次亚磷酸盐阻燃剂、亚膦酸酯阻燃剂、亚膦酸盐阻燃剂、亚磷酸酯阻燃剂、亚磷酸盐阻燃剂、氧化膦阻燃剂、次磷酸酯阻燃剂、次磷酸盐阻燃剂、膦酸酯阻燃剂、膦酸盐阻燃剂、磷酸酯阻燃剂、聚磷酸盐阻燃剂中的至少一种；
所述的金属氢氧化物阻燃剂选自氢氧化镁、氢氧化铝中的至少一种；
所述的硼酸盐阻燃剂选自无水硼酸锌、3.5水硼酸锌、硼酸的碱金属盐、硼酸的碱土金属盐中的至少一种。
所述的次磷酸盐阻燃剂选自次磷酸铝、次磷酸钙、二甲基次磷酸铝、二乙基次磷酸铝、甲基乙基次磷酸铝的至少一种；所述的磷酸酯阻燃剂选自双酚A双(磷酸二苯酯)、苯氧基膦腈、间苯二酚(二苯基磷酸酯)、磷酸三苯酯、三聚氰胺聚磷酸酯、三聚氰胺氰尿酸酯中的至少一种；所述的聚磷酸盐阻燃剂选自聚磷酸铵、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐、三聚氰胺聚磷酸盐的至少一种。
优选的，所述的阻燃剂选自磷系阻燃剂；
更优选的，所述的磷系阻燃剂选自磷酸酯阻燃剂；
进一步优选的，所述的磷酸酯阻燃剂选自苯氧基膦腈。
按重量份计，还包括0-5份的抗氧剂、耐候剂、颜料中的至少一种。
按重量份计，还包括0.1-3份的润滑剂；所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑剂选自季戊四醇硬脂酸酯中的至少一种。
上述的聚碳酸酯合金的制备方法，包括以下步骤：将聚碳酸酯、ABS树脂、存有液体酸的多孔发泡聚碳酸酯或者多孔发泡ABS加入高速混料机中混合均匀，再加入到双螺杆挤出机中，在230-250℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯合金。
本发明具有如下有益效果：
本发明通过调节聚碳酸酯合金体系的pH值为6.3-6.9，抑制了ABS树脂中残留杂质尤其是残留乳化剂的裂化影响，保证了合金的稳定性，同时也提高了挤出熔融加工过程中的稳定性，扩宽了加工窗口。
制备银离子抗菌聚碳酸酯合金体系，通过使用液体酸调节pH不仅提高合金的稳定性，还提高了银离子的稳定性。反过来，稳定的合金体系能够促进银离子稳定(体现为抗菌效果好，颜色稳定性好)，而银离子的稳定也促进合金体系稳定性的提高。因此得到的银离子抗菌聚碳酸酯合金具有好的抗菌效果以及稳定性，也拓宽了加工窗口。
同理，通过调节了合金的pH值，缓解了阻燃剂的加入对合金加工性能的影响，也促进了阻燃效果的稳定。
附图说明
图1：十二宫格评价方法示意图。
具体实施方式
本发明通过以下实施例来进一步说明本发明，但是本发明不受以下实施例限制。
本发明所用原料来源如下，但是不受以下原料限制。
银离子来源：银离子类抗菌剂，IKM50G，日本洁而美；
液体酸：磷酸；
阻燃剂A：苯氧基磷腈；
阻燃剂B：双酚A双(磷酸二苯酯)；
阻燃剂C：三聚氰胺聚磷酸盐；
润滑剂：硬脂酸酯类润滑剂，PETS；
实施例聚碳酸酯合金的制备方法：按照配比，将聚碳酸酯、ABS树脂、银离子抗菌剂、存有液体酸的多孔发泡聚碳酸酯或者多孔发泡ABS、阻燃剂加入高速混料机中混合均匀，再加入到双螺杆挤出机中，在230-250℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯合金。
各性能测试方法：
(1)合金pH：将组合物溶解于二氯甲烷溶剂中，将溶液过滤后，进行有机相的酸碱滴定进行测试pH。
(2)湿热稳定性：将组合物放入温度设定为85℃湿度为85％的老化箱中进行加速老化500h，如果样条出现鼓泡变形等，则记录为NG，不满足评价要求；若样条不出现变形，则通过组合物的分子量进行湿热稳定性评价，分子量越高，湿热稳定性约好。
(3)加工窗口：采用十二宫格评价方法，在固定的注塑压力以及背压的情况下，将注塑温度分为250℃，280℃，300℃，320℃，注塑速度分为高，中，低速，因此形成不同注塑加工窗口的区域，评价不同区域窗口下的注塑制件外观质量，机械性能稳定性，以及加工螺杆转动状态来进行，如果以上几种性能均能复合，则说明该加工窗口满足，满足的区域数越多，则加工窗口越宽，最好的是12，最差的是0；十二宫格如图1所示。
(4)银离子含量：ICP标准曲线外推法，将组合物中Ag含量的测定通过具有感应耦合等离子体(ICP-OES)的光学发射光谱进行，为了测定总的Ag含量，称量2g待测组合物，用5ml硝酸处理并搅拌试制溶解，并将该溶液补充至100ml，进行ICP标准曲线外推法计算出总Ag含量。
(5)抗菌效果：GB 21551.2-2010(贴膜法)，实验菌种为ATCC6538P和AS1.90。
(6)颜色稳定性：组合物在300-330℃的进行注塑2.0mm的标准色板，与不添加银离子抗菌剂的颜色标样进行色板的L值，a值和b值进行对比，观察色相；L表示黑白，也有说亮暗，+表示偏白，-表示偏暗，a表示红绿，+表示偏红，-表示偏绿，b表示黄蓝，+表示偏黄，-表示偏蓝，单纯的L、a、b是绝对值，用这三个数值可以在一个三维立体图中，精确的表示出一个颜色的点，用相对值就可以得出和基准点的差异来进行修正，总色差可以通过式子△E＝[(△L) 2+(△a) 2+(△b) 2] 1/2来进行计算，ΔΕ越大表示颜色变化越大，颜色稳定性不好。
(7)阻燃等级：按照UL-94标准，1.5mm。
(8)阻燃稳定性：将组合物放入温度设定为85℃湿度为85％的老化箱中进行加速老化500h，再按照UL-94标准，1.5mm测试阻燃性能；阻燃稳定性越好，说明合金的稳定性越好。
表1：实施例1-4和对比例1-2各组分配比(重量份)及各项性能测试结果
Figure PCTCN2020072290-appb-000001
Figure PCTCN2020072290-appb-000002
表1配方中，不调节pH前提下实施例1-4和对比例1-2的聚碳酸酯合金的pH为7.1，表1中实施例1-4和对比例2的合金pH值是通过加入液体酸调节剂进行调节得到的。
从实施例1-4和对比例1-2可以看出，合金的pH值在6.3-6.9范围内，湿热稳定性和加工窗口都较好。
表2：实施例5-8和对比例3-4各组分配比(重量份)及各性能测试结果
Figure PCTCN2020072290-appb-000003
表2配方中，不调节pH前提下实施例和对比例的聚碳酸酯合金的pH为7.2，表2中实施例和对比例的合金pH值都是通过加入液体酸调节剂进行调节得到的。
从实施例5-8和对比例3-4可以看出，加入银离子抗菌剂的合金，加工窗口会变窄，但是通过调节pH控制在6.3-6.9范围内综合性能好。
表3：实施例9-11和对比例5-6各组分配比(重量份)及各性能测试结果
Figure PCTCN2020072290-appb-000004
表3配方中，不调节pH前提下实施例和对比例的聚碳酸酯合金的pH为7.0，表3中实施例和对比例5的合金pH值都是通过加入液体酸调节剂进行调节得到的。
从实施例9-11和对比例5-6可以看出，加入阻燃剂，合金的加工窗口会下降、阻燃性能也差，通过调节合金pH值，能够明显提升加工窗口和阻燃性能；并且，在本发明的pH范围内，优选的阻燃剂的其综合性能更好。

Claims (10)

  1. 一种聚碳酸酯合金，其特征在于，按重量份计，包括以下组分：
    聚碳酸酯   70份；
    ABS树脂    1-60份；
    聚碳酸酯合金的pH值为6.3-6.9,pH值是通过液体酸调节的。
  2. 根据权利要求1所述的聚碳酸酯合金，其特征在于，所述的液体酸选自磷酸、醋酸中的至少一种。
  3. 根据权利要求1所述的聚碳酸酯合金，其特征在于，基于聚碳酸酯合金的总重量，还包括含量为100-1200ppm的银离子。
  4. 根据权利要求3所述的聚碳酸酯合金，其特征在于，银离子来源于银离子抗菌剂。
  5. 根据权利要求1所述的聚碳酸酯合金，其特征在于，按重量份计，还包括0-15份的阻燃剂，所述的阻燃剂选自溴系阻燃剂、C1-C16烷基磺酸盐阻燃剂、碳酸盐类阻燃剂、氟-银离子复合物、磷系阻燃剂、金属氢氧化物、含锑化合物阻燃协效剂、硼酸盐阻燃剂中的至少一种；
    所述的溴系阻燃剂选自四溴双酚A、溴代三嗪、溴化环氧、十溴二苯乙烷、十溴联苯醚、溴化聚酰亚胺、溴化聚苯乙烯、聚溴化苯乙烯、溴化聚碳酸酯、溴化聚丙烯酸酯中的至少一种；
    所述的C1-C16烷基磺酸盐阻燃剂选自全氟丁基磺酸钾、全氟辛烷磺酸钾、全氟乙烷磺酸四乙基铵、二苯砜磺酸钾中的至少一种；
    所述的碳酸类阻燃剂选自碳酸钠、碳酸钾、碳酸镁、碳酸钙、碳酸钡中的至少一种；
    所述的磷系阻燃剂选自膦阻燃剂、次亚磷酸酯阻燃剂、次亚磷酸盐阻燃剂、亚膦酸酯阻燃剂、亚膦酸盐阻燃剂、亚磷酸酯阻燃剂、亚磷酸盐阻燃剂、氧化膦阻燃剂、次磷酸酯阻燃剂、次磷酸盐阻燃剂、膦酸酯阻燃剂、膦酸盐阻燃剂、磷酸酯阻燃剂、聚磷酸盐阻燃剂中的至少一种；
    所述的金属氢氧化物阻燃剂选自氢氧化镁、氢氧化铝中的至少一种；
    所述的硼酸盐阻燃剂选自无水硼酸锌、3.5水硼酸锌、硼酸的碱金属盐、硼酸的碱土金属盐中的至少一种。
  6. 根据权利要求5所述的聚碳酸酯合金，其特征在于，所述的次磷酸盐阻燃剂选自次磷酸铝、次磷酸钙、二甲基次磷酸铝、二乙基次磷酸铝、甲基乙基次磷酸铝的至少一种；所述的磷酸酯阻燃剂选自双酚A双(磷酸二苯酯)、苯氧基膦腈、间苯二酚(二苯基磷酸酯)、磷酸三苯酯、三聚氰胺聚磷酸酯、三聚氰胺氰尿酸酯中的至少一种；所述的聚磷酸盐阻燃剂选自聚磷酸铵、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐、三聚氰胺聚磷酸盐的至少一种。
  7. 根据权利要求5所述的聚碳酸酯合金，其特征在于，所述的阻燃剂选自磷系阻燃剂；优选的，所述的磷系阻燃剂选自磷酸酯阻燃剂；更优选的，所述的磷酸酯阻燃剂选自苯氧基膦腈。
  8. 根据权利要求1所述的聚碳酸酯合金，其特征在于，按重量份计，还包括0-5份的抗氧剂、耐候剂、颜料中的至少一种。
  9. 根据权利要求1所述的聚碳酸酯合金，其特征在于，按重量份计，还包括0.1-3份的润滑剂；所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑剂选自季戊四醇硬脂酸酯中的至少一种。
  10. 根据权利要求2所述的聚碳酸酯合金的制备方法，其特征在于，包括以下步骤：将聚碳酸酯、ABS树脂、存有液体酸的多孔发泡聚碳酸酯或者多孔发泡ABS加入高速混料机中混合均匀，再加入到双螺杆挤出机中，在230-250℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯合金。
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