WO2024088104A1 - 一种长碳链聚酰胺组合物及其制备方法和应用 - Google Patents

一种长碳链聚酰胺组合物及其制备方法和应用 Download PDF

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WO2024088104A1
WO2024088104A1 PCT/CN2023/124872 CN2023124872W WO2024088104A1 WO 2024088104 A1 WO2024088104 A1 WO 2024088104A1 CN 2023124872 W CN2023124872 W CN 2023124872W WO 2024088104 A1 WO2024088104 A1 WO 2024088104A1
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carbon chain
long carbon
chain polyamide
polyamide composition
long
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PCT/CN2023/124872
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English (en)
French (fr)
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林立
张超
叶士兵
肖军华
王飞
刘纪庆
付大炯
安朋
方冲
张永
杨霄云
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江苏金发科技新材料有限公司
上海金发科技发展有限公司
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Publication of WO2024088104A1 publication Critical patent/WO2024088104A1/zh

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01P—COOLING OF MACHINES OR ENGINES IN GENERAL; COOLING OF INTERNAL-COMBUSTION ENGINES
    • F01P11/00—Component parts, details, or accessories not provided for in, or of interest apart from, groups F01P1/00 - F01P9/00
    • F01P11/02—Liquid-coolant filling, overflow, venting, or draining devices

Definitions

  • the invention belongs to the technical field of engineering plastic modification, and particularly relates to a long carbon chain polyamide composition and a preparation method and application thereof.
  • Long-chain polyamide is a polyamide with a carbon chain length of more than 10 between two amide groups in the molecule.
  • ordinary polyamides such as high strength, heat resistance, wear resistance, oil resistance, good weather resistance and easy molding and processing, it also has the advantages of low water absorption, good dimensional stability, good toughness and excellent electrical properties. It is widely used in the automotive, electronic and electrical, machinery and military industries.
  • polyamide products are basically made from petroleum derivatives as raw materials. The general synthesis process is complicated, and there is certain pollution and a large amount of carbon emissions, which can easily cause a greenhouse effect. With the increasing depletion of fossil resources and the improvement of environmental protection requirements, driven by the policies of carbon peak and carbon neutrality, completely bio-based polyamides are gradually gaining market attention.
  • the expansion kettle is an important part of the automobile cooling system. Its main function is to participate in the cooling process to compensate for the liquid lost in the system, return the gas generated in the system to the water tank, and discharge it through the pressure relief port to keep the system pressure stable and prevent the occurrence of water pump cavitation. Before driving, the driver usually needs to check the liquid level of the expansion kettle to determine whether it is suitable for driving. Because the liquid level is too high, there will be no expansion space for the coolant, and the liquid level is too low, which will cause gas to enter the engine. Therefore, the material of the expansion kettle can be selected as translucent polyamide PA66, and the current liquid level can be determined by directly observing the water level.
  • the technical problem to be solved by the present invention is to provide a long-chain polyamide composition with good resistance to Fanta coloring and alcoholysis and aging, as well as a preparation method and application thereof.
  • the long carbon chain polyamide composition of the present invention comprises the following components in parts by weight:
  • the anti-coloring agents are polyvinyl pyrrolidone and perfluoroalkyl sulfonate.
  • the long carbon chain polyamide resin is a nylon in which the length of the methylene group between two amide groups is greater than 10.
  • the number of methylene groups in all or one of the condensation monomers in the long carbon chain polyamide resin is an odd number.
  • the asymmetry increases, which reduces the intermolecular force and reduces the crystallinity compared to other monomers with an even number of methylene groups, thereby improving the visible light transmittance.
  • the long carbon chain polyamide resin is a long carbon chain bio-based nylon mainly composed of pentamethylenediamine; the long carbon chain bio-based nylon mainly composed of pentamethylenediamine is one or more of PA510, PA512, PA513, PA514, PA515, PA516, and PA518.
  • the amine stabilizer is at least one of N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)-oxalamide, dimethylglyoxime, 1,10-phenanthroline, 1,2-diaminocyclohexane, and 4.4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine.
  • the general formula of the perfluoroalkyl sulfonate is RfSO 3 ⁇ M, wherein Rf is a perfluoroalkyl group having 1 to 8 carbon atoms, and M is any one of Li, Na and K.
  • the perfluoroalkyl sulfonate is at least one of lithium perfluorobutyl sulfonate, sodium perfluorobutyl sulfonate, potassium perfluorohexyl sulfonate and potassium perfluorooctane sulfonate.
  • the mass ratio of polyvinyl pyrrolidone to perfluoroalkyl sulfonate is (2-6):1.
  • the mass ratio of the polyvinyl pyrrolidone to the perfluoroalkyl sulfonate is (3-4):1.
  • the other auxiliary agent is one or more of a lubricant, an antioxidant, and a toughening agent.
  • the lubricant includes but is not limited to any one or more of stearate, modified ethylene bis fatty acid amide, hyperbranched polyester, aliphatic fatty acid ester or ethylene-acrylic acid copolymer.
  • the antioxidant includes but is not limited to any one or more of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (antioxidant 1098), tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), pentaerythritol tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1010), bis(2,4-dicumylphenyl)pentaerythritol diphosphite (antioxidant S9228) or phosphite antioxidants.
  • antioxidant 1098 N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine
  • antioxidant 168 tris[2,4-di-tert-butylphen
  • the toughening agent includes but is not limited to any one or more of ethylene-octene copolymer, EPDM/propylene- ⁇ -olefin copolymer, propylene- ⁇ -olefin copolymer, ethylene-acrylate copolymer or ethylene-acrylate-glycidyl methacrylate copolymer.
  • the components include:
  • a method for preparing the long carbon chain polyamide composition of the present invention comprises:
  • the components are weighed according to weight proportions, and the long-chain polyamide resin, amine stabilizer, anti-coloring agent and other additives are premixed and plasticized by a twin-screw extruder.
  • Flat glass fiber is added from a side feed port. After traction, cooling, pelletizing and drying, a long-chain polyamide composition is obtained.
  • the invention discloses an application of the long carbon chain polyamide composition in an expansion kettle.
  • the present invention uses amine stabilizers to replace copper salts to inhibit the defect of poor transmittance of the refrigerant after alcoholysis and aging, and unexpectedly finds that perfluorosulfonates can improve the visible light transmittance of the material.
  • the long carbon chain polyamide combined with a specific ratio of perfluorosulfonates and polyvinyl pyrrolidone improves the material's anti-Fanta coloring.
  • the present invention uses long carbon chain bio-based nylon as the matrix raw material, gets rid of the dependence on petroleum resources, can effectively reduce carbon emissions, has good renewability, and will gradually replace the existing polyamide materials using petroleum resources as raw materials in the future.
  • the present invention uses a long carbon chain bio-based nylon with an odd number of methylene groups in the polycondensation monomer and a flat glass fiber to improve the visible light transmittance of the material.
  • the long carbon chain polyamide composition of the present invention can simultaneously meet the requirements of good resistance to Fanta coloring and a visible light transmittance greater than 40% after alcoholysis and aging.
  • the composition is particularly suitable for preparing an expansion kettle.
  • Long carbon chain polyamide resin-1 PA510 E3100 Shanghai Cathay Biotechnology R&D Center Co., Ltd.;
  • Long carbon chain polyamide resin-2 PA610 F150 Shandong Guangyin New Materials Co., Ltd.;
  • PA66 PA66 EP-158, Huafeng Group
  • Round glass fiber ECS-301HP, Chongqing International Composite Materials Co., Ltd.;
  • Amine stabilizer-1 NAUGARD 445 4.4-Bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, American Artifact Company;
  • Amine stabilizer-2 N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)-oxalamide Clariant
  • Copper Stabilizer PolyAD Services
  • Perfluoroalkyl sulfonate-1 potassium perfluorobutyl sulfonate: Sigma-Aldrich, Merck;
  • Perfluoroalkyl sulfonate-2 Potassium perfluorooctane sulfonate, Shanghai Hansi Chemical Co., Ltd.;
  • Anti-coloring agent-1 polyvinyl pyrrolidone and potassium perfluorobutanesulfonate in a mass ratio of 3:1;
  • Anti-coloring agent-2 polyvinyl pyrrolidone and potassium perfluorobutanesulfonate in a mass ratio of 4:1;
  • Anti-coloring agent-3 polyvinyl pyrrolidone and potassium perfluorobutanesulfonate in a mass ratio of 2:1;
  • Anti-coloring agent-4 the mass ratio of polyvinyl pyrrolidone and potassium perfluorobutanesulfonate is 6:1;
  • Anti-coloring agent-5 the mass ratio of polyvinyl pyrrolidone and potassium perfluorooctane sulfonate is 3:1;
  • Anti-coloring agent-6 polyvinyl pyrrolidone and potassium perfluorobutanesulfonate in a mass ratio of 1:1;
  • Anti-coloring agent-7 the mass ratio of polyvinyl pyrrolidone and potassium perfluorobutanesulfonate is 8:1;
  • Anti-coloring agent-8 polyvinyl pyrrolidone
  • Anti-coloring agent-9 potassium perfluorobutanesulfonate
  • the anti-coloring agent is prepared by directly mixing polyvinyl pyrrolidone and potassium perfluorobutyl sulfonate or potassium perfluorooctane sulfonate according to a certain ratio.
  • antioxidant 1098 antioxidant 1098, antioxidant S-9228 and lubricant TAF, mixed in a mass ratio of 1:1:1.
  • the antioxidant and lubricant used in the balance examples and comparative examples are the same commercially available products.
  • the components are weighed according to weight proportions, and the long-chain polyamide resin, amine stabilizer, anti-coloring agent and other additives are premixed and plasticized by a twin-screw extruder.
  • Flat glass fiber is added from a side feed port. After traction, cooling, pelletizing and drying, a long-chain polyamide composition is obtained.
  • Comparative Example 3 the amine stabilizer was replaced by a copper stabilizer, and the other conditions were the same.
  • the uncolored samples were used as references. Before being colored, the L, a, and b values of the references were measured using a colorimeter X-rite 7000A according to ASTM E 308-2008.
  • the coloration tendency in the coloration test is quantified by the value of the color difference ⁇ E.
  • the coloring trends can be categorized as follows:
  • Visible light transmittance test method Use X-rite 7000A to test visible light transmittance in accordance with GB2680-1994 standard.
  • the thickness of the color plate is 2mm. The greater the visible light transmittance, the better the visibility of the liquid surface.
  • Table 1 is the ratio of the embodiment (parts by weight)
  • Table 4 is the performance data of the embodiment
  • Table 5 is the performance data of the embodiment
  • Table 6 is the performance data of the comparative example
  • Examples 1-2 and Comparative Example 1 that the visible light transmittance of long-chain polyamide is much better than that of polyamide PA66, and the visible light transmittance of PA510 is better than that of long-chain nylon PA610. After the alcoholysis resistance test, the above rules are still met. It can be seen from Example 1 and Comparative Example 2 that the visible light transmittance of flat glass fiber is better than that of round glass fiber. It can be seen from Example 1 and Comparative Example 3 that the visible light transmittance levels of amine stabilizers and copper salt stabilizers are equivalent in dry state, but after the alcoholysis resistance test, the visible light transmittance of copper salt decreases significantly. In summary, only long-chain polyamide compounded with flat glass fiber and amine antioxidant can meet the daily observation of the liquid level of the expansion kettle.
  • the long-chain polyamide compositions can simultaneously meet the requirements of good Fanta resistance (S1 grade) and a visible light transmittance greater than 40% after alcoholysis and aging, while Comparative Examples 2-3 have good Fanta resistance, but the light transmittance after alcoholysis is less than 35%.

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Abstract

本发明涉及一种长碳链聚酰胺组合物及其制备方法和应用，组分包括：长碳链聚酰胺树脂、扁平玻璃纤维、胺类稳定剂、抗着色剂、其他助剂。本发明的长碳链聚酰胺组合物具有较好的透光性、抗着色性和耐醇解性。

Description

一种长碳链聚酰胺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改性技术领域，特别涉及一种长碳链聚酰胺组合物及其制备方法和应用。
背景技术
长碳链聚酰胺是分子中2个酰胺基团之间的碳链长度在10以上的聚酰胺，除具有普通聚酰胺的大多数通用性如强度高、耐热性、耐磨性、耐油性、耐候性良好和易成型加工性等，还具有吸水率低、尺寸稳定性好、韧性好、电性能优异的优点，广泛应用于汽车、电子电气、机械及军工等行业。目前的聚酰胺产品基本上都是以石油的衍生物作为原料制得，一般合成工艺复杂，且存在一定污染和大量碳排放，容易造成温室效应。伴随着化石资源日益枯竭和环保要求的提高，在碳达峰和碳中和的政策驱动下，完全生物基聚酰胺逐渐受到市场重视。
膨胀水壶是汽车冷却系统中的重要组成部分，其主要功能是参与冷却过程中对系统损失的液体进行补偿，对系统中产生的气体回流到水箱中，通过泄压口排出，使系统压力保持稳定，防止水泵气蚀的发生。行车前，驾驶员通常需要查看膨胀水壶液位，以确定能否适于行车。因为液位过高会导致冷却液无膨胀空间，而液位过低又会导致气体进入发动机。因此，膨胀水壶的材质可选半透明聚酰胺PA66，通过直接观察水位液面来确定当前液位。然而这些塑料制件处于发动机周边，长期处于冷却液介质腐蚀和高温环境，一旦膨胀水壶长时间老化，或者被污渍沾污或着色(如芬达碳酸饮料)，膨胀水壶液位的观察将会非常困难，大大降低了膨胀水壶的使用寿命。
发明内容
针对现有技术的缺陷，本发明所要解决的技术问题是提供一种抗芬达着色良好且耐醇解老化的长碳链聚酰胺组合物及其制备方法和应用。
本发明的一种长碳链聚酰胺组合物，按重量份数，组分包括：
其中抗着色剂为聚乙烯吡咯烷酮和全氟烷基磺酸盐。
长碳链聚酰胺树脂为两个酰胺基之间的亚甲基长度大于10的尼龙。
优选地，所述长碳链聚酰胺树脂中的缩聚单体其全部或一种单体中亚甲基个数为奇数。
长碳链聚酰胺的缩聚单体其全部或一种单体中亚甲基个数为奇数时，其不对称性增加，降低了分子间的作用力，相较其他亚甲基为偶数的单体降低了结晶度，使得可见光透过率提升。
所述长碳链聚酰胺树脂为戊二胺为主的长碳链生物基尼龙；所述戊二胺为主的长碳链生物基尼龙为PA510、PA512、PA513、PA514、PA515、PA516、PA518中的一种或几种。
优选地，所述胺类稳定剂为N-(2-乙氧基苯基)-N'-(4-乙基苯基)-乙二酰胺、二甲基乙二肟、1,10-菲咯啉、1,2-二氨基环己烷、4.4′-双(α,α-二甲基苄基)二苯胺的至少一种。
优选地，所述全氟烷基磺酸盐其通式为RfSO3·M，其中Rf为碳原子数为1-8的全氟烷基，M是Li、Na、K中的任一种元素。
优选地，所述全氟烷基磺酸盐为全氟丁基磺酸锂、全氟丁基磺酸钠、全氟己基磺酸钾、全氟辛烷磺酸钾中的至少一种。
优选地，所述聚乙烯吡咯烷酮和全氟烷基磺酸盐的质量比(2-6)：1。
进一步优选地，所述聚乙烯吡咯烷酮和全氟烷基磺酸盐的质量比(3-4)：1。
优选地，所述其他助剂为润滑剂、抗氧剂、增韧剂中的一种或几种。
进一步，所述润滑剂包括但不限于硬脂酸盐、改性乙撑双脂肪酸酰胺、超支化聚酯、脂肪族脂肪酸酯或乙烯-丙烯酸共聚物中的任意一种或几种。
进一步，所述抗氧剂包括但不限于N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺(抗氧剂1098)、三[2.4-二叔丁基苯基]亚磷酸酯(抗氧剂168)、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯(抗氧剂S9228)或亚磷酸酯类抗氧剂中的任意一种或几种。
进一步，所述增韧剂包括但不限于乙烯-辛烯共聚物、三元乙丙橡胶/丙烯-α烯烃共聚物、丙烯-α烯烃共聚物、乙烯-丙烯酸酯共聚物或乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物中的任意一种或几种。
优选地，按重量份数，组分包括：

本发明的一种所述长碳链聚酰胺组合物的制备方法，包括：
按重量份数称取各组分，将长碳链聚酰胺树脂、胺类稳定剂、抗着色剂、其他助剂预混后，由双螺杆挤出机塑化，扁平玻璃纤维由侧喂料口加入，经过牵引、冷却、切粒、干燥后，得到长碳链聚酰胺组合物。
本发明的一种所述长碳链聚酰胺组合物在膨胀水壶中的应用。
首先，本发明中选用胺类稳定剂替代铜盐抑制冷冻液醇解老化后透过率变差的缺陷，同时意外发现全氟磺酸盐能提升材料的可见光透光性。长碳链聚酰胺结合特定比例的全氟磺酸盐和聚乙烯吡咯烷酮复配提高了材料的抗芬达着色性。
本发明采用长碳链生物基尼龙作为基体原料，摆脱了对石油资源的依赖，能够有效地降低碳排放，可再生性好，未来必将逐步替代现有的以石油资源为原料的聚酰胺材料。其次，本发明采用缩聚单体亚甲基为奇数的长碳链生物基尼龙和扁平玻璃纤维复配来提高材料的可见光透过性。
有益效果
本发明的长碳链聚酰胺组合物可同时满足抗芬达着色良好且醇解老化后可见光透过率大于40％，该组合物特别适用于制备膨胀水壶。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，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。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
一、原料来源
长碳链聚酰胺树脂-1：PA510 E3100上海凯赛生物科技研发中心有限公司；
长碳链聚酰胺树脂-2：PA610 F150山东广垠新材料有限公司；
聚酰胺PA66：PA66 EP-158，华峰集团；
扁平玻璃纤维：ECS301HP-3-M4，平均异形比4.0，重庆国际复合材料股份有限公司；
圆形玻璃纤维：ECS-301HP，重庆国际复合材料股份有限公司；
胺类稳定剂-1：NAUGARD 445 4.4-双(α,α-二甲基苄基)二苯胺美国亚蒂凡特公司；
胺类稳定剂-2：N-(2-乙氧基苯基)-N'-(4-乙基苯基)-乙二酰胺科莱恩公司
铜稳定剂：PolyAD Services公司；
聚乙烯吡咯烷酮：SIAL，默克化学；
全氟烷基磺酸盐-1：全氟丁基磺酸钾：默克Sigma-Aldrich；
全氟烷基磺酸盐-2：全氟辛烷磺酸钾，上海瀚思化工有限公司；
抗着色剂-1：聚乙烯吡咯烷酮和全氟丁基磺酸钾的质量比3：1；
抗着色剂-2：聚乙烯吡咯烷酮和全氟丁基磺酸钾的质量比4：1；
抗着色剂-3：聚乙烯吡咯烷酮和全氟丁基磺酸钾的质量比2：1；
抗着色剂-4：聚乙烯吡咯烷酮和全氟丁基磺酸钾的质量比6：1；
抗着色剂-5：聚乙烯吡咯烷酮和全氟辛烷磺酸钾的质量比为3:1；
抗着色剂-6：聚乙烯吡咯烷酮和全氟丁基磺酸钾的质量比1：1；
抗着色剂-7：聚乙烯吡咯烷酮和全氟丁基磺酸钾的质量比8：1；
抗着色剂-8：聚乙烯吡咯烷酮；
抗着色剂-9：全氟丁基磺酸钾；
抗着色剂为将聚乙烯吡咯烷酮和全氟丁基磺酸钾或全氟辛烷磺酸钾按配比直接混合。
其他助剂：抗氧剂1098、抗氧剂S-9228和润滑剂TAF，按质量比为1:1:1混合。
平衡实施例和对比例中采用的抗氧剂、润滑剂为同一市售产品。
二、制备方法
实施例和对比例4-10的制备方法：
按重量份数称取各组分，将长碳链聚酰胺树脂、胺类稳定剂、抗着色剂、其他助剂预混后，由双螺杆挤出机塑化，扁平玻璃纤维由侧喂料口加入，经过牵引、冷却、切粒、干燥后，得到长碳链聚酰胺组合物。
对比例1中将上述制备方法中的长碳链聚酰胺树脂替换为聚酰胺PA66，其他均相同。
对比例2中将扁平玻璃纤维替换为圆形玻璃纤维，其他均相同。
对比例3中将胺类稳定剂替换为铜稳定剂，其他均相同。
三、测试标准和方法
1.芬达碳酸饮料抗着色测试方法：
将未经着色的样本用作参考品。在被着色前，根据ASTM E 308-2008的测定，使用色度计爱色丽X-rite 7000A测定参考品的L、a、b值。
将5ml芬达碳酸饮料用滴管施加在组合物注塑成型的色板上，色板保持水平的方式放置4小时，用热水(50℃±2℃)清洗后晾干。根据ASTM E 30-2008的测定，通过使用色 度计爱色丽X-rite 7000A测定测试着色板的L*、a*、b*值。
根据如下公式计算参考品颜色位置(L、a、b)和着色板位置(L*、a*、b*)之间的色差ΔE
△E*＝[(L*-L)2+(a*-a)2+(b*-b)2]1/2。
通过色差ΔE的值量化所述着色测试中的着色趋势。
所述着色趋势可以如下分类：
S1：无着色或仅轻微着色(0<ΔE≤2)—良好；
S2：大量着色(2<ΔE≤4)—中等；
S3：严重染色(对应于ΔE>4)—不良；
2.可见光透视率测试方法：按照GB2680-1994标准使用爱色丽X-rite 7000A测试可见光透过率，色板厚度2mm，可见光透视率越大，液面可视性越好。
3.耐醇解测试：高压反应釜中加入乙二醇：水＝50:50(体积比)的混合溶液，将厚度2mm色板浸泡在混合溶液中，然后将反应釜放置到设定在130℃的烘箱中1000h后，取出用蒸馏水清洗晾干后测试可见光透过率。
表1为实施例的配比(重量份)
表2实施例的配比(重量份)
表3对比例的配比(重量份)
表4为实施例的性能效果数据
表5为实施例的性能效果数据
表6为对比例的性能效果数据

分析说明
从实施例1-2和对比例1可以看出，长碳链聚酰胺可见光透过率远优于聚酰胺PA66，PA510的可见光透过性要优于长碳链尼龙PA610，耐醇解测试后，仍满足上述规律。从实施例1和对比例2可以看出，扁平玻璃纤维的可见光透过率要优于圆形玻璃纤维。从实施例1和对比例3可以看出，胺类稳定剂和铜盐稳定剂在干态时可见光透过率水平相当，但是耐醇解测试后，铜盐可见光透过率下降明显。综上，只有长碳链聚酰胺复配扁平玻纤和胺类抗氧剂，才能满足日常对膨胀水壶液面水平的观测。
从实施例和对比例4-5可以看出，聚乙烯吡咯烷酮和全氟丁基磺酸钾才能得到较优的抗着色效果，单独添加全氟丁基磺酸钾或者聚乙烯吡咯烷酮容易使得芬达碳酸饮料的大量着色ΔE大于3。从实施例1-2和对比例1可以看出，长碳链尼龙PA610、PA510的抗芬达着色性要远优于普通的聚酰胺PA66。
从实施例1-17可知，长碳链聚酰胺组合物均达可同时满足抗芬达着色良好(S1等级)且醇解老化后可见光透过率大于40％，而对比例2-3虽然抗芬达着色良好，但是醇解后可透光率均小于35％。

Claims (10)

  1. 一种长碳链聚酰胺组合物，其特征在于，按重量份数，组分包括：
    其中抗着色剂为聚乙烯吡咯烷酮和全氟烷基磺酸盐。
  2. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，所述长碳链聚酰胺树脂中的单体其全部或一种单体中亚甲基个数为奇数。
  3. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，所述长碳链聚酰胺树脂为戊二胺为主的长碳链生物基尼龙；所述戊二胺为主的长碳链生物基尼龙为PA510、PA512、PA513、PA514、PA515、PA516、PA518中的一种或几种。
  4. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，所述胺类稳定剂为N-(2-乙氧基苯基)-N'-(4-乙基苯基)-乙二酰胺、二甲基乙二肟、1,10-菲咯啉、1,2-二氨基环己烷、4,4′-双(α,α-二甲基苄基)二苯胺的至少一种。
  5. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，所述全氟烷基磺酸盐其通式为RfSO3·M，其中Rf为碳原子数为1-8的全氟烷基，M是Li、Na、K中的任一种元素。
  6. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，所述聚乙烯吡咯烷酮和全氟烷基磺酸盐的质量比(2-6)：1。
  7. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，所述其他助剂为润滑剂、抗氧剂、增韧剂中的一种或几种。
  8. 根据权利要求1所述长碳链聚酰胺组合物，其特征在于，按重量份数，组分包括：
  9. 一种权利要求1-8任一所述长碳链聚酰胺组合物的制备方法，包括：
    按重量份数称取各组分，将长碳链聚酰胺树脂、胺类稳定剂、抗着色剂、其他助剂预 混后，由双螺杆挤出机塑化，扁平玻璃纤维由侧喂料口加入，经过牵引、冷却、切粒、干燥后，得到长碳链聚酰胺组合物。
  10. 一种权利要求1-8任一所述长碳链聚酰胺组合物在膨胀水壶中的应用。
PCT/CN2023/124872 2022-10-28 2023-10-17 一种长碳链聚酰胺组合物及其制备方法和应用 WO2024088104A1 (zh)

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