WO2023174069A1 - 一种透明pc/pbt合金及其制备方法和应用 - Google Patents

一种透明pc/pbt合金及其制备方法和应用 Download PDF

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WO2023174069A1
WO2023174069A1 PCT/CN2023/079323 CN2023079323W WO2023174069A1 WO 2023174069 A1 WO2023174069 A1 WO 2023174069A1 CN 2023079323 W CN2023079323 W CN 2023079323W WO 2023174069 A1 WO2023174069 A1 WO 2023174069A1
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resin
pbt
transparent
average molecular
molecular weight
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PCT/CN2023/079323
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English (en)
French (fr)
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吴俊�
陈平绪
叶南飚
岑茵
董相茂
艾军伟
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
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention relates to the technical field of polymer materials, and in particular to a transparent PC/PBT alloy and its preparation method and application.
  • PC Polycarbonate
  • PMMA polymethyl methacrylate
  • PC has significant advantages in toughness, flame retardant properties, etc., so it is most promising to be used in the preparation of products that require high transparency, such as home appliance panels, visual electronic control boxes, personal care products, water tanks, and ink cartridges wait.
  • the amorphous nature of PC also brings some disadvantages: the molecular chains in the amorphous region are loosely arranged and are easily invaded by small molecules, so PC products are prone to cracking when exposed to chemicals.
  • siloxane copolycarbonate can improve the solvent resistance and improve the toughness.
  • siloxane copolycarbonate is opaque, its addition causes a further decrease in the transparency of the alloy.
  • the PC/siloxane copolycarbonate composition in the prior art can only achieve a translucent effect.
  • Citride CN11076175A discloses a toughened PC/SI-PC/PBT alloy, which contains 5-40 parts of polycarbonate, 5-40 parts of SI-PC, 5-40 parts of PBT resin, and 3-7 parts of toughening agent. , 15-40 parts of short glass fiber, 8-15 parts of flame retardant; the melt index of polycarbonate is 8-20g/10min (12g/10min is used in the embodiment), and the melting index of polybutylene terephthalate The index is 5-130g/10min (preferably used with PBT resin with melting index of 20g/10min and 120g/10min). It can be seen that the toughened PC/SI-PC/PBT alloy does not have a transparent effect.
  • Chinese patent application CN112029252A discloses a weather-resistant, halogen-free, flame-retardant light-diffusion PC/PBT material for charging pile panels, which mainly includes 77-85 parts of PC, 8-12 parts of PBT, and bisphenol A bis (diphenyl phosphate) 7-11 parts, 0.3-0.7 parts of methylphenylsiloxane, 0.3-1 parts of transparent toughening agent, etc.
  • the material has a light transmittance of more than 90% with a thickness of 1mm.
  • this technical solution cannot further increase the content of PBT.
  • the object of the present invention is to provide a PC/PBT alloy with the advantages of good solvent resistance and high transparency.
  • Another object of the present invention is to provide a preparation method and application of the above-mentioned PC/PBT alloy.
  • a transparent PC/PBT alloy including the following components in parts by weight:
  • the weight average molecular weight of the PC resin ranges from 24,000 to 33,000, and the weight average molecular weight of the PBT resin is 0.9 to 1.6 times that of the PC resin; the transparent PC/PBT alloy has a thickness of 2 mm Below, the transparency is greater than 60% and the haze is less than 40%.
  • Transparency and haze Use an injection molding machine to inject the prepared transparent PC/PBT alloy particles into samples with a thickness of 2mm. Use a transmittance meter to measure the transmittance and haze. The higher the transmittance, the better. The lower the degree, the better.
  • the weight average molecular weight of the PBT resin is 1-1.55 times the weight average molecular weight of the PC resin.
  • the weight average molecular weight of the PBT resin is 1.3-1.5 times the weight average molecular weight of the PC resin.
  • the weight average molecular weight test method of PC resin and PBT resin in the transparent PC/PBT alloy resin matrix can be: use tetrahydrofuran to dissolve the PC/PBT alloy at room temperature for 24 hours, and then filter and separate the solution.
  • PC resin is dissolved in the supernatant solution (solution 1).
  • solution 1 Dissolve the insoluble matter in tetrahydrofuran, heat to 50°C to dissolve for 2 hours, filter the supernatant, and repeat this operation three times to ensure that the PC resin is completely removed.
  • the dissolution time was 24 hours to obtain solution 2.
  • Solution 1 and solution 2 were introduced into gel permeation chromatography (GPC) for molecular weight testing.
  • the PC resin of the present invention is bisphenol A polycarbonate.
  • siloxane copolycarbonate In order to further improve solvent resistance and toughness, 5-35 parts by weight of siloxane copolycarbonate are also included.
  • the degree of polymerization of siloxane copolycarbonate ranges from 40 to 80, and the silicon content The range is 5.6-7.9wt%.
  • the polycarbonate segment is bisphenol A-type polycarbonate.
  • the polymerization degree of the siloxane copolycarbonate ranges from 50 to 60, and the silicon element content ranges from 6.4 to 7.2 wt%.
  • the weight average molecular weight test method of PC resin and PBT resin in the transparent PC/PBT alloy resin matrix can be: use tetrahydrofuran to dissolve the PC/PBT alloy at room temperature for 24 hours, and then filter and separate the solution.
  • PC resin is dissolved in the supernatant solution (solution 1).
  • solution 1 Dissolve the insoluble matter in tetrahydrofuran, heat to 50°C to dissolve for 2 hours, filter the supernatant, and repeat this operation three times to ensure that the PC resin is completely removed.
  • the dissolution time was 24 hours to obtain solution 2.
  • Solution 1 and solution 2 were introduced into gel permeation chromatography (GPC) for molecular weight testing.
  • the transparent PC/PBT alloy has an inorganic filler content of less than 1 part, a reinforcing fiber content of less than 1 part, a toughening agent content of less than 1 part, a flame retardant content of less than 2 parts, and an antistatic agent content of less than 2 parts.
  • the wear-resistant agent content is less than 1 part
  • the inorganic coloring matter is less than 0.5 parts.
  • Inorganic fillers such as talc, mica, etc.
  • Reinforcement fibers such as glass fiber, carbon fiber, etc.
  • Toughening agents such as POE, EPDM, etc.
  • Flame retardants such as brominated flame retardants, halogen-free flame retardants, inorganic flame retardants, etc.;
  • Antistatic agents such as polyether amide, ethoxylated aliphatic alkyl amine, ethoxylated alkyl amine, sodium alkyl sulfonate, etc.;
  • Wear-resistant agents such as polytetrafluoroethylene, molybdenum disulfide, silica microspheres, etc.;
  • Inorganic colorants such as carbon black, inorganic metal pigments and other granular types.
  • auxiliary agents are selected from at least one of antioxidants, lubricants, and light stabilizers.
  • organic pigments can also be added, such as phthalocyanines, quinocyanines, pyrroles, quinacridones, anthraquinones, thioindigos, azos, biphenyls, Pyrene, perylene, etc.
  • the antioxidant can be: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 2,5-di-tert-butyl Diethyl-4-hydroxybenzyldimethylamine; Diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphate; Stearyl-3,5-di-tert-butyl-4-hydroxy Benzyl phosphate; 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearyl-thiotriazolylamine; 2,6-di-tert-butyl-4-hydroxy Methylphenol; 2,4-di-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylglyceryl allyl ether)-1,3,5-triazine; N,N'-hexamethylene bis(3,5-di-tert-
  • the lubricant can be: at least one of stearate lubricants, fatty acid lubricants, and stearate lubricants; the stearate lubricant is selected from calcium stearate, stearin At least one of magnesium acid and zinc stearate; the fatty acid lubricant is selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; the stearate lubricant is selected from pentaerythritol At least one stearic acid ester.
  • Light stabilizers can be: hydroxybenzoate UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, HALS UV absorbers;
  • the hydroxybenzoate UV absorber can be selected from the group consisting of 3,5-diisobutyl-4-hydroxybenzoate cetyl alcohol ester, 3,5-diisobutyl-4-hydroxybenzoic acid cetyl alcohol ester, 2,4-di-tert-butylphenyl tert-butyl-4-hydroxybenzoate, n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate;
  • the benzophenone ultraviolet absorber can be selected from 2,4-dihydroxybenzophenone; 2-hydroxy-4-alkoxybenzophenone, 1,3-bis(methoxy-3-hydroxy- 4-benzophenone) benzene, 2-hydroxy-4-phenylalkoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methyl methacrylate Benzophenone.
  • the benzotriazole ultraviolet absorber can be selected from 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-(2'-hydroxy-5'-methyl)-benzo Triazole, 2-(3',5'-di-tert-butyl-2'-hydroxy)-benzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-tert-butyl) -Benzotriazole, 2-(2'-hydroxy-3',5'-bis(1,1-dimethylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-tert.
  • Octyl)-benzotriazole 2-(2'-hydroxy-3'-(1,1-dimethylphenyl)-5'-[1,1,3,3-tetramethylbutyl] -At least one of benzotriazole and 2,2'methylene-(6-(2H-benzotriazole)-4-tert-octyl)phenol;
  • the HALS ultraviolet absorber can be selected from bis-2,2,6,6-tetramethylpiperidinol sebacate, N,N'-(2,2,6,6-tetramethyl,4-amino Piperidine)-isophthalamide, bis-1-octyloxy-2,2,6,6-tetramethylpiperidinol sebacate, methacrylic acid (1,2,2,6,6-penta At least one of methyl piperidinol) esters.
  • the PC/PBT alloy of the present invention has a transparency of more than 60% and a haze of less than 40% at a thickness of 2 mm.
  • the preparation method of the transparent PC/PBT alloy of the present invention includes the following steps: mix each component evenly according to the proportion, and then extrude and granulate through a twin-screw extruder to obtain a transparent PC/PBT alloy; wherein, when the PC resin When the weight average molecular weight range of the raw material is 30001-34000, the screw temperature range is 240-270°C, and the rotation speed range is 450-600 rpm; when the weight average molecular weight range of the PC resin raw material is 24000-30000, the screw temperature range is 200 -240°C, the speed range is 300-450rpm.
  • the factors that affect the weight average molecular weight of PC resin and PBT resin in the resin matrix are mainly heat and shear. Of course, they also include the types of other added components (such as whether to add granular hard materials), each component content, etc., but these factors are auxiliary factors and their influence is significantly less than the heat and shear of the screw.
  • the application of the PC/PBT alloy of the present invention is used to prepare at least one of home appliance panels, visual electronic control boxes, personal care product packaging, water tanks, and ink cartridges.
  • the present invention has the following beneficial effects:
  • the present invention utilizes the different reduction ranges of the weight average molecular weight of PC resin and PBT resin between "strong processing conditions” and “weak processing conditions” in the blending/shearing process to examine the weight average of the PC resin in the PC/PBT alloy resin matrix.
  • Molecular weight, PBT The distribution of the weight average molecular weight of the resin can increase the content of PBT resin while maintaining high transparency to improve solvent resistance.
  • adding a specific amount of siloxane copolycarbonate with a specific structure can also achieve high transparency while maintaining high transparency. Improved solvent properties.
  • the raw materials used in the examples and comparative examples of the present invention are as follows:
  • PC resin-A weight average molecular weight about 25,000, bisphenol A type, manufacturer LG Company;
  • PC resin-B weight average molecular weight about 26,000, bisphenol A type, manufacturer LG Company;
  • PC resin-C weight average molecular weight about 27,000, bisphenol A type, manufacturer: Taiwan Chemical Idemitsu Co., Ltd.;
  • PC resin-D weight average molecular weight about 30,000, bisphenol A type, manufacturer Mitsubishi Corporation;
  • PC resin-E weight average molecular weight about 32,000, bisphenol A type, manufacturer Wanhua Chemical Company;
  • PC resin-F weight average molecular weight about 33,000, bisphenol A type, manufacturer Luxi Chemical Company;
  • PC resin-G weight average molecular weight about 34,000, bisphenol A type, manufacturer Luxi Chemical Company;
  • PC resin-H weight average molecular weight about 23,000, bisphenol A type, manufacturer: Taiwan Chemical Idemitsu Co., Ltd.;
  • PC resin-I weight average molecular weight about 35,000, bisphenol A type, manufacturer Mitsubishi Corporation;
  • PBT resin-A weight average molecular weight is about 32,000, manufacturer Lanshan Tunhe Company;
  • PBT resin-B weight average molecular weight is about 33,000, manufacturer Yizheng Chemical Fiber Company;
  • PBT resin-C weight average molecular weight is about 34,000, manufacturer Changchun Chemical Company;
  • PBT resin-D weight average molecular weight is about 38,000, manufacturer Yizheng Chemical Fiber Company;
  • PBT resin-E weight average molecular weight is about 39,000, manufacturer Changchun Chemical Company;
  • PBT resin-F weight average molecular weight is about 40,000, manufacturer Yizheng Chemical Fiber Company;
  • PBT resin-G weight average molecular weight is about 30,000, manufacturer Yizheng Chemical Fiber Company;
  • PBT resin-H weight average molecular weight is about 41,000, manufacturer Lanshan Tunhe Company;
  • Silicone copolymerized polycarbonate A degree of polymerization range is 40, silicon content range is 5.6wt%, manufacturer Sumitomo Corporation;
  • Silicone copolymer polycarbonate B degree of polymerization range is 50, silicon content range is 6.4wt%, manufacturer Cangzhou Dahua Company;
  • Silicone copolymerized polycarbonate C degree of polymerization range is 60, silicon content range is 7.2wt%, manufacturer Cangzhou Dahua Company;
  • Silicone copolymerized polycarbonate D degree of polymerization range is 80, silicon content range is 7.9wt%, manufacturer Cangzhou Dahua Company;
  • Silicone copolycarbonate E degree of polymerization range is 35, silicon content range is 5wt%, manufacturer Wanhua Chemical Company;
  • Siloxane copolycarbonate F degree of polymerization range is 85, silicon content range is 8.5wt%, manufacturer Wanhua Chemical Company;
  • Lubricant pentaerythritol stearate, commercially available.
  • PC/PBT alloy Mix each component evenly, and then extrude and granulate through a twin-screw extruder to obtain a transparent PC/PBT alloy; the processing strength is as follows:
  • Weak 1 The temperature of each section of the screw is set to 200-220°C, and the speed is 300 rpm;
  • Weak 2 The temperature of each section of the screw is set to 210-230°C, and the speed is 350 rpm;
  • Weak 3 The temperature of each section of the screw is set to 220-240°C, and the speed is 450 rpm;
  • Transparency Use an injection molding machine to injection mold the prepared transparent PC/PBT alloy particles into a sample piece with a thickness of 2mm, and use a transmittance meter to measure its transmittance and haze. The higher the transmittance, the better. The lower the haze, the better.
  • the preferred range of polymerization degree of siloxane copolymerized polycarbonate is 50-60, and the silicon element content range is 6.4-7.2wt%, which has higher transparency.
  • Comparative Example 1 It can be seen from Comparative Example 1 that the retained weight average molecular weight of the PC resin is too low, the transparency is not high, and especially the solvent resistance is insufficient.

Abstract

本发明公开了一种透明PC/PBT合金，按重量份计，包括以下组分：PC树脂40份；PBT树脂25-35份；所述的透明PC/PBT合金在2mm厚度下，透明度大于60％，雾度小于40％。本发明通过多种手段考察熔融共混后的透明PC/PBT合金中PC树脂与PBT树脂的重均分子量范围，实现了高PBT含量的PC/PBT合金条件下高透明度，解决了PBT含量上升后导致PC树脂透明度大幅下降的技术难题。

Description

一种透明PC/PBT合金及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种透明PC/PBT合金及其制备方法和应用。
背景技术
聚碳酸酯(PC)是一种无定形的高分子材料，具有良好的透明性，透光率可达88～90％，雾度小于0.3，虽然透明性上略低于聚甲基丙烯酸甲酯(PMMA)，但PC在韧性、阻燃性能等方面具有显著优势，因此最有希望应用于制备一些对透明度要求较高的产品，如家电面板、可视化电控盒、个人护理产品、水箱、墨盒等。但PC的非结晶性同时也带来一些缺点：无定形区的分子链排列松散，容易被小分子侵入，因此PC产品在接触化学品时容易出现开裂。
为了提高PC树脂的耐溶剂性，现有技术为在PC中加入高结晶度的PBT，耐溶剂性提升明显。但是，当PBT超过某临界含量后，高结晶下使得透明度快速下降至不透明。
在PC/PBT合金中加入硅氧烷共聚聚碳酸酯，对耐溶剂性有一定提升，也能够提升韧性。但是，由于硅氧烷共聚聚碳酸酯是不透明的，因此其加入会导致合金透明度进一步下降。另外，现有技术中PC/硅氧烷共聚聚碳酸酯的组合物也只能达到半透明效果。
中国专利CN11076175A公开了一种增韧PC/SI-PC/PBT合金，其中包含聚碳酸酯5-40份、SI-PC 5-40份、PBT树脂5-40份、增韧剂3-7份、短玻纤15-40份、阻燃剂8-15份；其中聚碳酸酯的熔融指数为8～20g/10min(实施例采用12g/10min)、聚对苯二甲酸丁二醇酯的熔融指数为5～130g/10min(优选为熔指20g/10min和120g/10min的PBT树脂搭配使用)。可见，该增韧PC/SI-PC/PBT合金不具有透明的效果。
中国专利申请CN112029252A公开了一种充电桩面板用耐候无卤阻燃光扩散PC/PBT材料，其中主要包括77-85份PC、8-12份PBT、双酚A双(二苯基磷酸酯)7-11份、甲基苯基硅氧烷0.3-0.7份、透明增韧剂0.3-1份等。其材料具有1mm厚度90％以上的透光率，但是，由于PBT的结晶性，该技术方案也无法将PBT的含量进一步提升。
发明内容
本发明的目的在于，提供一种PC/PBT合金，具有耐溶剂性能好、透明度高的优点。
本发明的另一目的在于，提供上述PC/PBT合金的制备方法和应用。
本发明是通过以下技术方案实现的：
一种透明PC/PBT合金，按重量份计，包括以下组分：
PC树脂    40份；
PBT树脂    25-35份；
透明PC/PBT合金树脂基体中，PC树脂的重均分子量范围是24000-33000，PBT树脂的重均分子量是PC树脂的重均分子量的0.9-1.6倍；所述透明PC/PBT合金在2mm厚度下，透明度大于60％，雾度小于40％。
透明度与雾度使用注塑机将制备得到的透明PC/PBT合金粒子注塑成厚度为2mm的样片，使用透光率仪对其透光率和雾度进行测量，透光率越高越好，雾度越低越好。优选的，透明PC/PBT合金树脂基体中，PBT树脂的重均分子量是PC树脂的重均分子量的1-1.55倍。
更优选的，透明PC/PBT合金树脂基体中，PBT树脂的重均分子量是PC树脂的重均分子量的1.3-1.5倍。
透明PC/PBT合金树脂基体中PC树脂和PBT树脂的重均分子量测试方法可以是：在室温环境下，使用四氢呋喃对PC/PBT合金进行溶解24h，对溶液进行过滤分离。上清溶液(溶液1)中溶有PC树脂。将不溶物至于四氢呋喃中，加热至50℃溶解2小时后，滤去上清液，重复此操作3次以确保PC树脂被完全除去。将得到的不溶物在室温下溶解于邻氯苯酚与三氯甲烷的混合溶剂中，(二者体积比为邻氯苯酚：三氯甲烷＝1:3)，溶解时间24h，得到溶液2。将溶液1和溶液2导入凝胶渗透色谱(GPC)中，进行分子量测试。
本发明的PC树脂为双酚A型聚碳酸酯。
为了进一步提升耐溶剂性、韧性的提升，按重量份计，还包括5-35份硅氧烷共聚聚碳酸酯，其中硅氧烷共聚聚碳酸酯的聚合度范围是40-80，硅元素含量范围是5.6-7.9wt％。
硅氧烷共聚聚碳酸酯中，聚碳酸酯链段为双酚A型聚碳酸酯。
优选的，硅氧烷共聚聚碳酸酯的聚合度范围是50-60，硅元素含量范围是6.4-7.2wt％。
透明PC/PBT合金树脂基体中PC树脂和PBT树脂的重均分子量测试方法可以是：在室温环境下，使用四氢呋喃对PC/PBT合金进行溶解24h，对溶液进行过滤分离。上清溶液(溶液1)中溶有PC树脂。将不溶物至于四氢呋喃中，加热至50℃溶解2小时后，滤去上清液，重复此操作3次以确保PC树脂被完全除去。将得到的不溶物在室温下溶解于邻氯苯酚与三氯甲烷的混合溶剂中，(二者体积比为邻氯苯酚：三氯甲烷＝1:3)，溶解时间24h，得到溶液2。将溶液1和溶液2导入凝胶渗透色谱(GPC)中，进行分子量测试。
在塑料容器中使用氢氟酸将样品消解，所得溶液根据情况进行稀释后，使用电感耦合等离子体质谱仪(ICP)测试稀释液中Si元素含量，并根据稀释比例换算得出样品中硅元素含量。
为了使PC/PBT合金保持高透明度，列举的，以下物质的含量分别不能够超过2份，总含量不能超过4份，否则会对透明度带来严重的负面影响。按重量份计，所述的透明PC/PBT合金无机填料含量小于1份，增强纤维含量小于1份，增韧剂含量小于1份，阻燃剂含量小于2份，抗静电剂含量小于2份，耐磨剂含量小于1份、无机着色物小于0.5份。
无机填料如滑石粉、云母等；
增强纤维如玻璃纤维、碳纤维等；
增韧剂如POE、EPDM等；
阻燃剂如溴系阻燃剂、无卤阻燃剂、无机阻燃剂等；
抗静电剂如聚醚酰胺、乙氧基化脂肪族烷基胺、乙氧基化烷基酸胺、烷基磺酸钠等等；
耐磨剂如聚四氟乙烯、二硫化钼、二氧化硅微球等；
无机着色物如炭黑、无机金属颜料等颗粒型。
可以根据实际需要决定是否加入0-2份的助剂；所述的助剂选自抗氧剂、润滑剂、光稳定剂中的至少一种。为了实现透明彩色复合材料，还可以添加适量的有机颜料，如酞菁类、喹酞酮类、吡咯类、喹吖啶酮类、蒽醌类、硫靛类、偶氮类、联苯类、芘类、苝类等。
抗氧剂可以是：1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯；2,5-二-叔丁基-4-羟基苄基二甲胺；二乙基-3,5-二-叔丁基-4-羟基苄基磷酸酯；硬脂基-3,5-二-叔丁基-4-羟基苄基磷酸酯；3,5-二-叔丁基-4-羟基苯基-3,5-二硬脂基-硫代三唑基胺；2,6-二-叔丁基-4-羟基甲基苯酚；2,4-二-(正辛硫基)-6-(4-羟基-3,5-二-叔丁基甘油烯丙基醚基)-1,3,5-三嗪；N,N’-六亚甲基二(3,5-二-叔丁基-4-羟基-氢化肉桂酰胺)；N,N’-双-(3-(3,5-二-叔丁基-4-羟基苯基)丙酰基)己二胺；十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯；季戊四醇基-四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]；三甘醇-二[3-(3,5-二甲基-4-羟基苯基)丙酸酯]；二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]；2,2’-硫代二乙基-二[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯，等。
润滑剂可以是：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。
光稳定剂可以是：羟基苯甲酸酯类紫外线吸收剂、二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂、HALS类紫外线吸收剂；
羟基苯甲酸酯类紫外线吸收剂可以选自3，5-二异丁基-4-羟基苯甲酸十六醇酯、3,5-二 叔丁基-4-羟基苯甲酸-2,4-二叔丁基苯酯、3,5-二叔丁基-4-羟基苯甲酸正十六酯；
二苯甲酮类紫外线吸收剂可以选自2,4-二羟基二苯甲酮；2-羟基-4-烷氧基二苯甲酮、1，3-二(甲氧基-3-羟基-4二苯甲酮)苯、2-羟基-4-苯烷氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-羟基-4-甲基丙烯酸甲酯基二苯甲酮。
苯并三唑类紫外线吸收剂可以选自2-(2’-羟基-5’-甲基苯基)苯并三氮唑、2-(2’-羟基-5’-甲基)-苯并三唑、2-(3’,5’-二叔丁基-2’-羟基)-苯并三唑、2-(2’-羟基-3’-异丁基-5’-叔丁基)-苯并三唑、2-(2’-羟基-3’,5’-双(1,1-二甲基苯基)-苯并三唑、2-(2’-羟基-5’-叔辛基)-苯并三唑、2-(2’-羟基-3’-(1,1-二甲基苯基)-5’-[1,1,3,3-四甲基丁基]-苯并三唑、2,2’亚甲基-(6-(2H-苯并三唑)-4-叔辛基)苯酚中的至少一种；
HALS类紫外线吸收剂可以选自癸二酸双2,2,6,6-四甲基哌啶醇酯、N,N’-(2,2,6,6-四甲基,4-胺基哌啶)-间苯二酰胺、癸二酸双1-辛氧基-2,2,6,6-四甲基哌啶醇酯、甲基丙烯酸(1,2,2,6,6-五甲基哌啶醇)酯中的至少一种。
本发明的PC/PBT合金在2mm厚度下的透明度大于60％，雾度小于40％。
本发明透明PC/PBT合金的制备方法，包括以下步骤：按照配比，将各组分混合均匀，再通过双螺杆挤出机挤出造粒，得到透明PC/PBT合金；其中，当PC树脂原料的重均分子量范围是30001-34000时，螺杆的温度范围是240-270℃，转速范围是450-600rpm；当PC树脂原料的重均分子量范围是24000-30000时，螺杆的温度范围是200-240℃，转速范围是300-450rpm。
当螺筒温度范围是240-270℃、转速范围是450-600rpm时，属于强加工，在此加工工艺条件下PC树脂、PBT树脂的重均分子量在熔融剪切的过程中下降幅度较大。
当螺筒温度范围是200-240℃、转速范围是300-450rpm时，属于弱加工，在此加工工艺条件下PC树脂、PBT树脂的重均分子量在熔融剪切的过程中下降幅度较小。
螺杆的加工过程中影响树脂基体中PC树脂、PBT树脂的重均分子量的因素主要为热与剪切，当然还包括其他所添加的组分种类(如是否加入颗粒状硬物料)、各组分含量等相关，但是这些因素属于辅助因素，影响显著小于螺杆的热与剪切。
本发明的PC/PBT合金的应用，用于制备家电面板、可视化电控盒、个人护理产品包装、水箱、墨盒中的至少一种。
本发明与现有技术相比具有如下有益效果：
第一，本发明利用共混/剪切工艺中“强加工条件”与“弱加工条件”PC树脂、PBT树脂重均分子量下降的幅度不同，考察对PC/PBT合金树脂基体中PC树脂重均分子量、PBT 树脂重均分子量的分布，能够在保持高透明度的前提下增加PBT树脂的含量，以提升耐溶剂性能。
第二，在本发明PC/PBT合金树脂基体中两种树脂重均分子量分布的前提下，加入特定结构的特定量的硅氧烷共聚聚碳酸酯，也能够在保持高透明度的前提下实现耐溶剂性的提升。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明实施例和对比例所用原材料如下：
PC树脂-A：重均分子量约25000，双酚A型，厂家LG公司；
PC树脂-B：重均分子量约26000，双酚A型，厂家LG公司；
PC树脂-C：重均分子量约27000，双酚A型，厂家台化出光公司；
PC树脂-D：重均分子量约30000，双酚A型，厂家三菱公司；
PC树脂-E：重均分子量约32000，双酚A型，厂家万华化学公司；
PC树脂-F：重均分子量约33000，双酚A型，厂家鲁西化工公司；
PC树脂-G：重均分子量约34000，双酚A型，厂家鲁西化工公司；
PC树脂-H：重均分子量约23000，双酚A型，厂家台化出光公司；
PC树脂-I：重均分子量约35000，双酚A型，厂家三菱公司；
PBT树脂-A：重均分子量约32000，厂家蓝山屯河公司；
PBT树脂-B：重均分子量约33000，厂家仪征化纤公司；
PBT树脂-C：重均分子量约34000，厂家长春化工公司；
PBT树脂-D：重均分子量约38000，厂家仪征化纤公司；
PBT树脂-E：重均分子量约39000，厂家长春化工公司；
PBT树脂-F：重均分子量约40000，厂家仪征化纤公司；
PBT树脂-G：重均分子量约30000，厂家仪征化纤公司；
PBT树脂-H：重均分子量约41000，厂家蓝山屯河公司；
硅氧烷共聚聚碳酸酯A：聚合度范围是40，硅元素含量范围是5.6wt％，厂家住友公司；
硅氧烷共聚聚碳酸酯B：聚合度范围是50，硅元素含量范围是6.4wt％，厂家沧州大化公司；
硅氧烷共聚聚碳酸酯C：聚合度范围是60，硅元素含量范围是7.2wt％，厂家沧州大化公司；
硅氧烷共聚聚碳酸酯D：聚合度范围是80，硅元素含量范围是7.9wt％，厂家沧州大化公司；
硅氧烷共聚聚碳酸酯E：聚合度范围是35，硅元素含量范围是5wt％，厂家万华化学公司；
硅氧烷共聚聚碳酸酯F：聚合度范围是85，硅元素含量范围是8.5wt％，厂家万华化学公司；
润滑剂：季戊四醇硬脂酸酯，市售。
实施例和对比例PC/PBT合金的制备方法：将各组分混合均匀，再通过双螺杆挤出机挤出造粒，得到透明PC/PBT合金；加工强度如下：
弱1：螺杆各区间温度设置为200-220℃，转速300转/分；
弱2：螺杆各区间温度设置为210-230℃，转速350转/分；
弱3：螺杆各区间温度设置为220-240℃，转速450转/分；
强1：螺杆各区间温度设置为240-250℃，转速450转/分；
强2：螺杆各区间温度设置为250-265℃，转速500转/分；
强3：螺杆各区间温度设置为260-270℃，转速600转/分；
各项测试方法：
(1)透明度：使用注塑机将制备得到的透明PC/PBT合金粒子注塑成厚度为2mm的样片，使用透光率仪对其透光率和雾度进行测量，透光率越高越好，雾度越低越好。
(2)耐溶剂性：使用1.5％应变的弧面模具夹持样条，涂抹极性溶剂磷酸三丁酯，4h后样条无裂纹，则为4级；3-4h内样条出现裂纹，则为3级；2-3h内样条出现裂纹，则为2级；2h内出现裂纹，则为1级。
表1：实施例1-12PC/PBT合金各组分含量(重量份)及测试结果
由全部实施例与对比例可知，在螺杆的剪切共混加工过程中PBT树脂的重均分子量下降幅度要大于PC树脂。
续表1：
由实施例1-12可知，在本发明PC与PBT复配下能够实现3级耐溶剂性。具体的，在优选的PC树脂、PBT树脂的保留重均分子量下，透明度得到进一步提升。
表2：实施例13-18PC/PBT合金各组分含量(重量份)及测试结果
由实施例13-18可知，通过添加硅氧烷共聚聚碳酸酯能够进一步提升耐溶剂性。具体的，由实施例7和实施例15可知，通过添加硅氧烷共聚聚碳酸酯还能够进一步提升透明度。
由实施例15-18可知，优选硅氧烷共聚聚碳酸酯的聚合度范围是50-60，硅元素含量范围是6.4-7.2wt％透明度更高。
表3：对比例PC/PBT合金各组分含量(重量份)及测试结果
由对比例1可知，PC树脂的保留重均分子量过低，透明度不高，尤其是耐溶剂性不足。
由对比例2可知，当PC和PBT树脂的保留重均分子量低于0.9时，耐溶剂性差。
由对比例3可知，当PC和PBT树脂的保留重均分子量高于1.6时，透明度差。
由对比例2/4可知，当PC和PBT树脂的保留重均分子量低于0.9并且还加入硅氧烷共聚聚碳酸酯会进一步降低透明度。
由对比例3/5可知，当PC和PBT树脂的保留重均分子量高于1.6并且加入硅氧烷共聚聚碳酸酯也会进一步降低透明度。
由对比例6/7可知，当PBT树脂的含量过低时，耐溶剂性差；当PBT树脂的含量过高时，透明度差。

Claims (8)

  1. 一种透明PC/PBT合金，其特征在于，按重量份计，包括以下组分：
    PC树脂        40份；
    PBT树脂       25-35份；
    透明PC/PBT合金树脂基体中，PC树脂的重均分子量范围是24000-33000，PBT树脂的重均分子量是PC树脂的重均分子量的0.9-1.6倍；
    所述的透明PC/PBT合金在2mm厚度下，透明度大于60％，雾度小于40％。
  2. 根据权利要求1所述的透明PC/PBT合金，其特征在于，透明PC/PBT合金树脂基体中，PBT树脂的重均分子量是PC树脂的重均分子量的1-1.55倍。
  3. 根据权利要求2所述的透明PC/PBT合金，其特征在于，透明PC/PBT合金树脂基体中，PBT树脂的重均分子量是PC树脂的重均分子量的1.3-1.5倍。
  4. 根据权利要求1所述的透明PC/PBT合金，其特征在于，按重量份计，还包括5-35份硅氧烷共聚聚碳酸酯，其中硅氧烷共聚聚碳酸酯的聚合度范围是40-80，硅元素含量范围是5.6-7.9wt％。
  5. 根据权利要求4所述的透明PC/PBT合金，其特征在于，硅氧烷共聚聚碳酸酯的聚合度范围是50-60，硅元素含量范围是6.4-7.2wt％。
  6. 根据权利要求1所述的透明PC/PBT合金，其特征在于，按重量份计，还包括0-2份助剂；所述的助剂选自抗氧剂、润滑剂、紫外吸收剂中的至少一种。
  7. 权利要求1-6任一项所述透明PC/PBT合金的制备方法，其特征在于，包括以下步骤：按照配比，将各组分混合均匀，再通过双螺杆挤出机挤出造粒，得到透明PC/PBT合金；其中，当PC树脂原料的重均分子量范围是30001-34000时，螺杆的温度范围是240-270℃，转速范围是450-600rpm；当PC树脂原料的重均分子量范围是24000-30000时，螺杆的温度范围是200-240℃，转速范围是300-450rpm。
  8. 权利要求1-6任一项所述透明PC/PBT合金的应用，其特征在于，用于制备家电面板、可视化电控盒、个人护理产品包装、水箱、墨盒、磁卡转运盒、新能源充电桩组件中的至少一种。
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CN107312300A (zh) * 2017-06-29 2017-11-03 上海锦湖日丽塑料有限公司 流动性改善的透明树脂组合物及其制备方法
CN110760175A (zh) * 2019-11-20 2020-02-07 中广核高新核材科技（苏州）有限公司 一种增韧pc/si-pc/pbt合金材料及其制备方法
CN111635624A (zh) * 2020-06-05 2020-09-08 上海锦湖日丽塑料有限公司 一种高流动性和耐化兼优的高透明pc/pbt合金及其制备方法
CN113698751A (zh) * 2021-08-26 2021-11-26 金发科技股份有限公司 一种pc/pbt合金材料及其制备方法和应用
CN113930061A (zh) * 2021-10-26 2022-01-14 天津金发新材料有限公司 一种pc/pbt组合物及其制备方法
CN114921078A (zh) * 2022-03-16 2022-08-19 金发科技股份有限公司 一种透明pc/pbt合金及其制备方法和应用

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