WO2022095360A1 - 一种自组装网络聚酰胺组合物及其制备方法和应用 - Google Patents

一种自组装网络聚酰胺组合物及其制备方法和应用 Download PDF

Info

Publication number
WO2022095360A1
WO2022095360A1 PCT/CN2021/090741 CN2021090741W WO2022095360A1 WO 2022095360 A1 WO2022095360 A1 WO 2022095360A1 CN 2021090741 W CN2021090741 W CN 2021090741W WO 2022095360 A1 WO2022095360 A1 WO 2022095360A1
Authority
WO
WIPO (PCT)
Prior art keywords
self
montmorillonite
polyamide composition
water absorption
assembled network
Prior art date
Application number
PCT/CN2021/090741
Other languages
English (en)
French (fr)
Inventor
郭唐华
黄险波
叶南飚
钱志军
唐宇航
Original Assignee
金发科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Publication of WO2022095360A1 publication Critical patent/WO2022095360A1/zh

Links

Classifications

    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

Definitions

  • the present invention relates to the technical field of engineering plastics, and more particularly, to a self-assembled network polyamide composition and a preparation method and application thereof.
  • Polyamide (PA) is an engineering plastic with excellent comprehensive properties, translucent or opaque milky white crystalline polymer with plasticity. It is resistant to corrosion by acids, alkalis, most inorganic salt solutions, halogenated alkanes, hydrocarbons, esters, ketones, etc., and is easily soluble in polar solvents such as phenol and formic acid. It has excellent wear resistance, self-lubrication, heat resistance, oil resistance and high mechanical strength, and is widely used in automobile, construction, electronic appliances and home appliances and other industries.
  • polyamide contains polar -NH-CO- bonds, which are easy to form hydrogen bonds with water molecules, which leads to the high water absorption of PA, resulting in poor dimensional stability of the product.
  • Chinese patent (CN107474529A) discloses a glass fiber reinforced montmorillonite modified nylon composite material with low water absorption and high dimensional stability and a preparation method thereof, and specifically discloses montmorillonite modified nylon composite, glass fiber, antioxidant and lubricants, in which montmorillonite reduces the water absorption rate of the composite, but the water absorption rate of single use of montmorillonite is still relatively high, and cannot be applied to products that require higher water absorption rate and dimensional stability.
  • the purpose of the present invention is to overcome the above-mentioned defects of low water absorption rate and low performance retention rate after water absorption in the prior art, and to provide a self-assembled network polyamide composition.
  • Another object of the present invention is to provide a preparation method of the self-assembled network polyamide composition.
  • Another object of the present invention is to provide the application of the self-assembled network polyamide composition.
  • a self-assembled network polyamide composition comprising the following components calculated in parts by weight:
  • the invention utilizes the negatively charged silicate sheet on the surface of the montmorillonite and the cationic polymer to self-assemble to form a three-dimensional network structure through the interaction of charge electrostatic force; wherein the silicate sheet structure of the montmorillonite provides a super large surface area that can interact with The super-large film structure formed by the cationic polymer effectively prevents the penetration of water vapor and reduces the water absorption rate of the polyamide, thereby improving the dimensional stability, with little influence on the initial mechanical properties, and improved performance retention after water absorption.
  • the mass ratio of the cationic polymer to the montmorillonite is (1-10): 1. If the mass ratio of the two is lower than 1:1, the ratio of the montmorillonite is too high, although the water absorption can be However, the toughness of the composition will decrease; if the mass ratio of the two is higher than 10:1, the content of montmorillonite will decrease, resulting in a small surface area for forming a three-dimensional network structure, which will affect the water absorption rate, but its water absorption rate remains at Within 2%, when the mass ratio of the two is higher than 20:1, the water absorption rate will drop significantly.
  • the mass ratio of the cationic polymer to the montmorillonite is preferably (2-6):1.
  • the cationic polymer refers to a polymer with cationic groups on the main chain, including but not limited to polydiallyldimethylammonium chloride, polyamidine, polyvinylamine, and cationic polyacrylamide.
  • Cationic polyacrylamide is a general term for polymers obtained from acrylamide homopolymers or copolymers with other monomers. Due to the amide bond contained in the cationic polyacrylamide structural unit, it is easy to form a hydrogen bond, which makes it have good water solubility and high chemical activity. .
  • the cationic polymer is preferably a cationic polyacrylamide.
  • the polyamide resin refers to a polymer having an amide bond (-NHCO-) in the main chain.
  • polyamide resins include but not limited to the following types of polyamide resins: polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid with aliphatic or cycloaliphatic or arylaliphatic diamines, such as PA66, PA610 , PA612, PA1010, PA106, PA1212, PA46, MXD6, PA92, PA102; polyamides obtained by polycondensation between at least one aromatic dicarboxylic acid and aliphatic or aromatic diamines, such as the following types of polyisophthalamides, such as PA9T, PA10T, PA11T, PA12T, PA13T or PA6T/MT, PA6T/6I, PA6T/66, PA66/6T, the following types of polyisophthalamides, such as PA6I, PA6I/6T, the following types of polynaphthalene m
  • the polyamide resin of the present invention can also be selected from polyamides obtained by polycondensing at least one amino acid or lactam with itself, and for this amino acid it is possible to open the lactam ring by hydrolysis, such as PA6, PA7, PA11, PA12 or PA13 or blends thereof and their (co)polyamide resins, types of copolyamide resins include polyamide 6/66, polyamide 6/11, polyamide 6/12 and polyamide 11/12 .
  • the montmorillonite is a natural mineral of silicate, and is the main mineral component of bentonite.
  • Montmorillonite generally contains Al 2 O 3 16.54%; MgO 4.65%; SiO 2 50.95%, and the structural formula is (Al, Mg) 2 [SiO 10 ](OH) 2 ⁇ nH 2 O.
  • Monoclinic crystal system, multi-bit crystallites, aggregates are earthy, spherical, etc.
  • Montmorillonite including calcium-based, sodium-based, sodium-calcium-based, magnesium-based montmorillonite
  • silicic acid with an average wafer thickness of less than 25 nm and a negatively charged surface. Salt flakes.
  • the montmorillonite is one of calcium-based montmorillonite, sodium-based montmorillonite, magnesium-based montmorillonite or sodium-calcium-based montmorillonite.
  • the reinforcing material is preferably one of fibrous fillers, nano-fillers or particulate fillers.
  • the fiber filler is glass fiber, carbon fiber or organic fiber.
  • the particulate filler a filler with a particle size of more than 1000 nm, such as iron phosphate, kaolin, calcium carbonate, diatom, graphite, mica, carbon black, zeolite, talc, wollastonite.
  • the nano-filler nano-copper oxide, silver nanoparticles, silicon dioxide, titanium dioxide, carbon nanotubes.
  • the reinforcing material is glass fiber; including chopped strand A-, chopped strand E-, chopped strand C-, chopped strand D-, chopped strand S- or chopped strand R-glass fiber.
  • the processing aid further includes at least one of antioxidants or lubricants.
  • the antioxidants refer to a class of auxiliary agents that can improve the thermal stability of polyamides, and are more representative of hindered phenol compounds and phosphite compounds.
  • hindered phenolic compound is used according to its conventional meaning in the art, and is generally intended to denote derivatives of para-substituted phenols well known in the art, especially (but not limited to) di-tert-butylphenol derivatives.
  • a "phosphite compound” can be represented by the formula P(OR) 3
  • a phosphinate can be represented by the formula P(OR) 2
  • each R can be the same or different and is typically independently selected from the group consisting of The group consists of the following: C1-20 alkyl, C3-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene , aryl, alkaryl or aralkyl moieties.
  • the lubricant is a type of higher fatty acid ester.
  • the higher fatty acid ester refers to an esterified product of higher fatty acid and alcohol. Among them, esters of aliphatic carboxylic acids having 8 to 40 carbon atoms and aliphatic alcohols having 8 to 40 carbon atoms are preferred from the viewpoint of suppressing gas generation during melt processing and suppressing mold deposits in molds during molding. .
  • the higher fatty acid the above-mentioned fatty acids can be used.
  • the aliphatic alcohol is not limited to the following, for example, stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like.
  • the higher fatty acid ester is not limited to the following, for example, stearic acid stearate, behenic acid behenate, and the like.
  • the present invention also provides a method for preparing the self-assembled network polyamide composition, comprising the following steps:
  • step S2 Add the premix prepared in step S1 into an extruder for melt extrusion and post-processing, and finally obtain composition particles.
  • the melt extrusion process includes melt plasticization of the composition, intensive shear dispersion, vacuum degassing, cooling and setting.
  • the invention provides a self-assembled network polyamide composition.
  • the compatibility of montmorillonite and cationic polymer reduces the water absorption rate of the composition and improves the dimensional stability.
  • the negatively charged silicate sheet on the surface of the montmorillonite interacts with the cationic polymer through the electrostatic force of the charge, and self-assembles to form a three-dimensional network structure, preventing the penetration of water vapor.
  • the water absorption rate of the composition is not higher than 2%, the initial mechanical properties are little affected, the performance retention rate after water absorption is not lower than 80%, and can be used in the preparation of parts and components for electronic, electrical or electrical products.
  • reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • PA66 EP-158, Huafon Group
  • Cationic polymer A cationic polyacrylamide
  • Cationic polymer B polydiallyl dimethyl ammonium chloride
  • Cationic polymer C polyamidine
  • Cationic polymer D polyvinylamine, all cationic polymers are commercially available;
  • Montmorillonite A sodium-based montmorillonite, grade AZ-180, Jiangxi Weipu Technology
  • Montmorillonite B calcium-based montmorillonite, grade Nanolin DK1, Hangzhou Xihe Chemical Co., Ltd.;
  • Reinforcement material glass fiber, ECS10-03-568H, Jushi Group;
  • Examples and comparative examples all prepare polyamide compositions by the following methods, and weigh each component according to the weight ratio of Tables 1 to 4; the specific steps are as follows:
  • step S2 Add the premix prepared in step S1 to the twin-screw extruder for melt extrusion, and set the extruder temperature section 1 to 8: 180/190/210/220/220/220/220 /230°C, post-processing, and finally obtained composition particles.
  • Example 1 Example 2
  • Example 3 Example 4
  • Polyamide 30 50 60 70 90
  • Cationic polymer A 10 10 10 10 10 10 10 Montmorillonite 2 2 2 2 2 2 Reinforcing material 30 30 30 30 30 lubricant 1 1 1 1 1 1
  • Example 6 Example 7
  • Example 8 Example 9
  • Tensile strength retention rate after water absorption tensile strength after water absorption/tensile strength before water absorption*100%
  • Water absorption dimensional change rate Do the water absorption test as above, and measure the side length of the fixed side of the front and rear panels before and after water absorption.
  • Examples 1 to 5 of the present invention with the increase of polyamide resins, the water absorption rate of them showed a downward trend. This is because the polyamide resin itself absorbs water. Since montmorillonite and cationic polymers are added in Examples 1 to 5, The self-assembly of the two to form a three-dimensional network structure can effectively reduce the water absorption rate, the water absorption rate remains low, and the tensile strength retention rate after water absorption is high.
  • Example 2 and Examples 6 to 9 that the water absorption rate of Examples 2 and 6 is lower than that of Examples 7 to 9, because the cationic polymers of Examples 2 and 6 are sufficiently close to montmorillonite.
  • the optimal self-assembled network structure is formed to minimize the water absorption of the polyamide resin.
  • Example 10 From Examples 10 to 13, the mass fraction of montmorillonite in Example 10 is 1 part, which cannot fully self-assemble with the cationic polymer to form a three-dimensional network structure, but the water absorption rate is still low, and the water absorption rate is 1.8%. As the content of montmorillonite increases, montmorillonite can fully self-assemble with cationic polymers to form a three-dimensional network structure, preventing most water vapor penetration, and the water absorption rate remains unchanged at 1.1%.
  • Examples 16 and 20 when the mass ratio of cationic polymer to montmorillonite is 20:1, the mass of montmorillonite is relatively small, and it cannot fully self-assemble with cationic polymer to form a three-dimensional network structure, and its water absorption rate is higher than that of montmorillonite. It is higher than the mass ratio of cationic polymer to montmorillonite in the range of (1-10):1, but its water absorption rate is still maintained at 2%, and the retention rate of tensile strength after water absorption is high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

提供了一种自组装网络聚酰胺组合物及其制备方法和应用，所述组合物包括如下按重量份计算的组分：聚酰胺树脂30～90份；阳离子聚合物5～20份；蒙脱土1～5份；增强材料0～40份；加工助剂0.1～1份。上述聚酰胺组合物具有超低吸水率以及吸水后性能保持率高，可以应用在制备电子、电器或电工产品的零部件制品中。

Description

一种自组装网络聚酰胺组合物及其制备方法和应用 技术领域
本发明涉及工程塑料技术领域，更具体地，涉及一种自组装网络聚酰胺组合物及其制备方法和应用。
背景技术
聚酰胺(PA)是一种综合性能优良的工程塑料，半透明或不透明乳白色结晶形聚合物，具有可塑性。能耐酸、碱、大多数无机盐水溶液、卤代烷、烃类、酯类、酮类等腐蚀，易溶于苯酚、甲酸等极性溶剂。具有优良的耐磨性、自润滑性，耐热性，耐油性、机械强度较高，广泛应用于汽车、建筑、电子电器和家电等行业。
但是聚酰胺中含有极性的-NH-CO-键，容易与水分子形成氢键，这就导致了PA吸水率较大，导致制品的尺寸稳定性较差。
中国专利(CN107474529A)公开了一种吸水率低、尺寸稳定性高的玻纤增强蒙脱土改性尼龙复合材料及其制备方法，具体公开了蒙脱土改性尼龙复合物、玻璃纤维、抗氧剂和润滑剂，其中蒙脱土是降低复合物的吸水率，但是单一使用蒙脱土的吸水率还是比较高，不能应用于对吸水率和尺寸稳定性要求更高的产品。
因此，目前聚酰胺吸水率高的问题依然没有得到很好的解决，急需开发一种吸水率低的聚酰胺组合物尤为迫切。
发明内容
本发明的目的在于克服上述现有技术吸水率低、吸水后性能保持率低的缺陷，提供一种自组装网络聚酰胺组合物。
本发明的另一目的在于提供所述自组装网络聚酰胺组合物的制备方法。
本发明的另一目的在于提供所述自组装网络聚酰胺组合物的应用。
本发明的上述目的通过以下技术方案实现：
一种自组装网络聚酰胺组合物，包括如下按重量份计算的组分：
Figure PCTCN2021090741-appb-000001
Figure PCTCN2021090741-appb-000002
本发明利用蒙脱土表面带负电的硅酸盐片层与阳离子聚合物能够通过电荷静电力相互作用自组装形成三维网络结构；其中蒙脱土的硅酸盐片层结构提供了超大表面积能够与阳离子聚合物形成的超大薄膜结构有效阻止水汽渗透，降低了聚酰胺的吸水率，从而提高了尺寸稳定性，初始机械性能影响小，吸水后性能保持率提高。
优选地，所述阳离子聚合物与所述蒙脱土的质量比优选为(1～10)：1，如果两者质量比低于1:1，蒙脱土的比例太高，虽然吸水率能够降低，但是其组合物的韧性会下降；如果两者质量比高于10:1，蒙脱土的含量变少，导致形成三维网络结构的表面积小，影响吸水率，但是其吸水率依然保持在2％以内，当两者质量比高于20:1，吸水率会明显下降。
优选地，所述阳离子聚合物与所述蒙脱土的质量比优选为(2～6):1。
所述阳离子聚合物是指主链上有阳离子基团的聚合物，包括但不限于聚二烯丙基二甲基氯化铵、聚脒，聚乙烯胺、阳离子聚丙烯酰胺。阳离子聚丙烯酰胺是丙烯酰胺均聚物或与其他单体共聚而得聚合物的统称。由于阳离子聚丙烯酰胺结构单元中含有酰胺键易形成氢键、使其具有良好的水溶性和很高的化学活性，易通过接枝或交联得到支链或网状结构的多种改性物。
优选地，所述阳离子聚合物优选为阳离子聚丙烯酰胺。
所述聚酰胺树脂是指作为主链中具有酰胺键(－NHCO－)的聚合物。包括但不限于如下种类的聚酰胺树脂：通过至少一种脂肪族二元羧酸与脂肪族或环或脂环族或芳基脂肪族的二元胺缩聚作用获得的聚酰胺，例如PA66、PA610、PA612、PA1010、PA106、PA1212、PA46、MXD6、PA92、PA102；至少一种芳香族的二元羧酸与脂肪族或芳香族的二元胺之间的缩聚作用获得的聚酰胺，例如以下类型的聚对苯二甲酰胺类，如PA9T、PA10T、PA11T、PA12T、PA13T或PA6T/MT、PA6T/6I、PA6T/66、PA66/6T，以下类型的聚间苯二甲酰胺类，如PA6I、PA6I/6T，以下类型的聚萘亚甲基酰胺类，如PA10N、PA11N、PA12N。本发明的聚酰胺树脂还可以选自通过将至少一种氨基酸或内酰胺与其本身进行缩聚而获得的聚酰胺，对于这种氨基酸有可能的是通过内酰胺环的水解打开而产生，如PA6、PA7、 PA11、PA12或PA13或者其共混物以及其(共)聚酰胺树脂，共聚酰胺树脂的类型包括聚酰胺6/66、聚酰胺6/11、聚酰胺6/12以及聚酰胺11/12。
所述蒙脱土是一种硅酸盐的天然矿物，为膨润土矿的主要矿物组分。蒙脱土一般含Al 2O 3 16.54％；MgO 4.65％；SiO 2 50.95％，结构式为(Al，Mg) 2〔SiO 10〕(OH) 2·nH 2O。单斜晶系，多位微晶，集合体呈土状、球粒等状。白色微带浅灰色，含杂质时呈浅黄、浅绿、浅蓝色，土状光泽或无光泽，有滑感。加水后其体积可膨胀数倍，并变成糊状物，受热脱水后体积收缩。具有很强的吸附能力和阳离子交换性能，主要产于火山凝灰岩的风化壳中。蒙脱土(包括钙基、钠基、钠-钙基、镁基蒙脱土)经剥片分散、提纯改型、超细分级、特殊有机复合得到平均晶片厚度小于25nm，表面带负电的硅酸盐片层。
优选地，所述蒙脱土为钙基蒙脱土、钠基蒙脱土、镁基蒙脱土或钠-钙基蒙脱土中一种。
优选地，所述增强材料优选为纤维填充剂、纳米填充剂或微粒填充剂中一种。
所述纤维填充剂为玻璃纤维、碳纤维或有机纤维。
所述微粒填充剂：粒径为1000nm以上的填充剂，如磷酸铁、高岭土、碳酸钙、硅藻、石墨、云母、碳黑、沸石、滑石、硅灰石。
所述纳米填充剂：纳米氧化铜、银纳米颗粒、二氧化硅、二氧化钛、碳纳米管。
优选地，所述增强材料为玻璃纤维；包括短切原丝A-、短切原丝E-、短切原丝C-、短切原丝D-、短切原丝S-或短切原丝R-玻璃纤维。
优选地，所述加工助剂还包括抗氧剂或润滑剂中至少一种。
所述抗氧剂是指能够提高聚酰胺热稳定性的一类助剂，比较有代表性的是受阻酚化合物和亚磷酸酯化合物。术语“受阻酚化合物”根据其在领域中的惯用含义使用，并且通常旨在表示本领域熟知的临位取代苯酚的衍生物，尤其是(但不限于)二-叔丁基苯酚衍生物。“亚磷酸酯化合物”可以用式P(OR) 3表示，而亚膦酸酯可以用式P(OR) 2表示，其中每个R可以相同或不同并且典型地独立地选自下组，该组由以下各项组成：C 1-20烷基、C 3-22烯基、C 6-40环烷基、C 7-40亚环烷基、芳基、烷芳基或芳烷基部分。
所述润滑剂是一类高级脂肪酸酯。所述高级脂肪酸酯是指高级脂肪酸与醇的酯化物。其中，从抑制熔融加工时的气体产生、抑制成型加工时在模具中的模垢 的观点考虑，优选碳原子数8～40的脂肪族羧酸与碳原子数8～40的脂肪族醇的酯。在此，作为高级脂肪酸，可以使用上述脂肪酸。作为脂肪族醇，不限于以下物质，例如：硬脂醇、山萮醇、月桂醇等。作为高级脂肪酸酯，不限于以下物质，例如：硬脂酸硬脂酯、山萮酸山萮酯等。
本发明还提供了所述自组装网络聚酰胺组合物的制备方法，包括如下步骤：
S1.称取聚酰胺树脂、阳离子聚合物、蒙脱土、增强材料、加工助剂，将上述材料投入混合机中混匀，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。
所述熔融挤出过程包括组合物的熔融塑化、强烈的剪切分散、真空脱气、冷却定型。
所述自组装网络聚酰胺组合物在制备电子、电器、电工产品的零部件制品中的应用。
与现有技术相比，本发明的有益效果是：
本发明提供一种自组装网络聚酰胺组合物，蒙脱土与阳离子聚合物配伍降低了所述组合物的吸水率，提高了尺寸稳定性。其中蒙脱土表面带负电的硅酸盐片层与阳离子聚合物通过电荷静电力相互作用，自组装形成三维网络结构，阻止水汽渗透。所述组合物的吸水率不高于2％，初始机械性能影响小，吸水后性能保持率不低于80％，可以应用在制备电子、电器或电工产品的零部件制品中。
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：
PA66：EP-158，华峰集团；
阳离子聚合物A：阳离子聚丙烯酰胺；
阳离子聚合物B：聚二烯丙基二甲基氯化铵；
阳离子聚合物C：聚脒；
阳离子聚合物D：聚乙烯胺，阳离子聚合物均为市售；
蒙脱土A：钠基蒙脱土，牌号AZ-180，江西伟普科技；
蒙脱土B：钙基蒙脱土，牌号Nanolin DK1，杭州西河化工有限公司；
增强材料：玻璃纤维，ECS10-03-568H，巨石集团；
加工助剂：润滑剂，TR044W，STRUKTOL Co.；
高岭土：TRANSLINK445，巴斯夫股份有限公司；
黏土：市售。
下面结合实施例来详细说明本发明的技术方案。
实施例和对比例均通过以下方法制备聚酰胺组合物，按照表1～4的重量比称取各组分；具体步骤如下：
S1.分别称取聚酰胺树脂、阳离子聚合物、蒙脱土、增强材料、加工助剂，将上述材料依次按照比例投入混合机中混匀，得到预混物；
S2.将步骤S1中制备所得的预混物加入到双螺杆挤出机中进行熔融挤出，设定挤出机温度段1～8区：180/190/210/220/220/220/220/230℃、后加工，最后得到组合物粒子。
表1实施例1～5的聚酰胺组合物组分含量
组分 实施例1 实施例2 实施例3 实施例4 实施例5
聚酰胺 30 50 60 70 90
阳离子聚合物A 10 10 10 10 10
蒙脱土 2 2 2 2 2
增强材料 30 30 30 30 30
润滑剂 1 1 1 1 1
表2实施例6～10的聚酰胺组合物组分含量
组分 实施例6 实施例7 实施例8 实施例9 实施例10
聚酰胺 50 50 50 50 50
阳离子聚合物A 5 16 20 5 10
蒙脱土 2 2 2 5 1
增强材料 30 30 30 30 30
润滑剂 1 1 1 1 1
表3实施例11～20的聚酰胺组合物组分含量
Figure PCTCN2021090741-appb-000003
表4对比例1～7的聚酰胺组合物组分含量
Figure PCTCN2021090741-appb-000004
Figure PCTCN2021090741-appb-000005
材料性能测试方法：
吸水率：按照ISO 62-1999标准准备100*100*2mm方板样品并在23℃，100％R.H.的条件下做吸水测试，吸水率＝(吸水后重量-吸水前重量)/吸水前重量*100％；
拉伸强度：按照ISO 527-2-2012标准制备拉伸测试样条并测试；
吸水后拉伸强度保持率：吸水后拉伸强度/吸水前拉伸强度*100％
吸水尺寸变化率：按照上述做吸水实验，并测量吸水前后方板固定一边的边长尺寸，吸水尺寸变化率＝(吸水后尺寸-吸水前尺寸)/吸水前尺寸*100％。
表5性能测试结果
Figure PCTCN2021090741-appb-000006
Figure PCTCN2021090741-appb-000007
本发明实施例1～5，随着聚酰胺树脂的增多，其吸水率呈下降趋势，这是因为聚酰胺树脂本身就吸水，由于实施例1～5中加入了蒙脱土和阳离子聚合物，两者自组装形成三维网络结构能够有效减低吸水率，其吸水率依然保持较低水平，吸水后拉伸强度保持率高。
从实施例2和实施例6～9可知，实施例2和实施例6的吸水率要低于实施例7～9，这是因为实施例2和实施例6的阳离子聚合物与蒙脱土够形成最佳的自组装网络结构，最大限度的降低聚酰胺树脂的吸水率。
从实施例10～13看，实施例10中蒙脱土的质量份数为1份，不能充分和阳离子聚合物自组装形成网络三维结构，但是吸水率依然保持较低，吸水率为1.8％，随着蒙脱土的含量增加，蒙脱土能够充分与阳离子聚合物自组装形成三维网络结构，阻止大部分水汽渗透，吸水率为1.1％且维持不变。
从实施例14～16看，当聚酰胺组合物中不加入玻璃纤维组分，其吸水率依然能保持2％以内，阳离子聚合物和蒙脱土自组装形成的三维网络结构依然能够有效降低吸水率，且吸水后拉伸强度保持率不低于80％。
实施例16和20，当阳离子聚合物与蒙脱土的质量比为20:1时，蒙脱土的质 量相对较少，不能够充分和阳离子聚合物自组装形成三维网络结构，其吸水率要比阳离子聚合物与蒙脱土的质量比为(1～10)：1范围内的要高，但是其吸水率依然保持在2％，且吸水后拉伸强度保持率较高。
实施例17～19，在这三个实施例中分别采用聚二烯丙基二甲基氯化铵、聚脒和聚乙烯胺替代阳离子聚丙烯酰胺，结果发现，其吸水率依然保持1.2％，吸水后拉伸强度保持率高。
从对比例1～3可以看出，在组合物中不加入蒙脱土、不加入阳离子聚合物或两者都不加，其吸水率都不能保持在2％以下，且吸水后拉伸强度保持率大幅度降低。
对比例4虽然加入了蒙脱土和阳离子聚合物，但是蒙脱土的含量极低，不能和阳离子聚合物形成有效的自组装三维网络结构，不能够有效降低吸水率，吸水后力学性能下降。
对比例5中虽然都加入了蒙脱土和阳离子聚合物，但是蒙脱土的含量过高，导致蒙脱土和聚酰胺树脂界面强度大大降低，使得水分进入树脂后拉伸强度降低，吸水后拉伸强度保持率下降。
对比例6和7中，采用高岭土或黏土替换蒙脱土，其吸水率分别达到了3.1％和3％，且吸水后力学性能下降很大，也不能满足要求。
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. 一种自组装网络聚酰胺组合物，其特征在于，包括如下按重量份计算的组分：
    Figure PCTCN2021090741-appb-100001
  2. 如权利要求1所述自组装网络聚酰胺组合物，其特征在于，所述阳离子聚合物与所述蒙脱土的质量比为(1～10)：1。
  3. 如权利要求2所述自组装网络聚酰胺组合物，其特征在于，所述阳离子聚合物与所述蒙脱土的质量比为(2～6)：1。
  4. 如权利要求1所述自组装网络聚酰胺组合物，其特征在于，所述阳离子聚合物为聚二烯丙基二甲基氯化铵、聚脒、聚乙烯胺或阳离子聚丙烯酰胺中一种。
  5. 如权利要求4所述自组装网络聚酰胺组合物，其特征在于，所述阳离子聚合物为阳离子聚丙烯酰胺。
  6. 如权利要求1所述自组装网络聚酰胺组合物，其特征在于，所述蒙脱土为钙基蒙脱土、钠基蒙脱土、镁基蒙脱土或钠-钙基蒙脱土中一种。
  7. 如权利要求1所述自组装网络聚酰胺组合物，其特征在于，所述增强材料为纤维填充剂、纳米填充剂或微粒填充剂中一种。
  8. 如权利要求1所述自组装网络聚酰胺组合物，其特征在于，所述加工助剂还包括抗氧剂或润滑剂中至少一种。
  9. 如权利要求1～8任一项所述自组装网络聚酰胺组合物的制备方法，其特征在于，包括如下步骤：
    S1.称取聚酰胺树脂、阳离子聚合物、蒙脱土、增强材料、加工助剂，将上述材料投入混合机中混匀，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. 权利要求1～8任一项所述自组装网络聚酰胺组合物在制备电子、电器或电工产品的零部件制品中的应用。
PCT/CN2021/090741 2020-11-05 2021-04-28 一种自组装网络聚酰胺组合物及其制备方法和应用 WO2022095360A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011225211.7 2020-11-05
CN202011225211.7A CN112341812B (zh) 2020-11-05 2020-11-05 一种自组装网络聚酰胺组合物及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2022095360A1 true WO2022095360A1 (zh) 2022-05-12

Family

ID=74429252

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/090741 WO2022095360A1 (zh) 2020-11-05 2021-04-28 一种自组装网络聚酰胺组合物及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN112341812B (zh)
WO (1) WO2022095360A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341812B (zh) * 2020-11-05 2022-04-19 金发科技股份有限公司 一种自组装网络聚酰胺组合物及其制备方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288023A (zh) * 2000-10-20 2001-03-21 中国科学院化学研究所 聚酰胺66复合材料及其制备方法
WO2007058869A2 (en) * 2005-11-10 2007-05-24 Graham Packaging Pet Technologies Inc. Methods for intercalating, exfoliating and/or dispersing clay particles and articles incorporating such clay particles
CN103254423A (zh) * 2013-05-20 2013-08-21 金发科技股份有限公司 一种聚酰胺树脂和由其组成的聚酰胺组合物
CN104710781A (zh) * 2013-12-17 2015-06-17 上海杰事杰新材料(集团)股份有限公司 一种共插层剂改性蒙脱土/尼龙610t复合材料及其制备方法
CN106334539A (zh) * 2016-10-04 2017-01-18 青岛大学 一种阳离子聚合物改性蒙脱土吸附剂及其制备方法
CN106675009A (zh) * 2015-11-05 2017-05-17 株洲时代新材料科技股份有限公司 一种轨道扣件用高强高韧尼龙复合材料及其制备方法
CN107474529A (zh) * 2017-08-22 2017-12-15 合肥会通新材料有限公司 一种吸水率低、尺寸稳定性高的玻纤增强蒙脱土改性尼龙复合材料及其制备方法
CN108192336A (zh) * 2017-12-19 2018-06-22 会通新材料股份有限公司 一种低吸水、高尺寸稳定性的pa/pp合金材料及其制备方法
CN111074548A (zh) * 2019-12-27 2020-04-28 海澜之家股份有限公司 一种阻燃织物及其制备方法
CN112341812A (zh) * 2020-11-05 2021-02-09 金发科技股份有限公司 一种自组装网络聚酰胺组合物及其制备方法和应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11059015B2 (en) * 2015-06-10 2021-07-13 Council Of Scientific And Industrial Research Microcapsules modified with nanomaterial for controlled release of active agent and process for preparation thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288023A (zh) * 2000-10-20 2001-03-21 中国科学院化学研究所 聚酰胺66复合材料及其制备方法
WO2007058869A2 (en) * 2005-11-10 2007-05-24 Graham Packaging Pet Technologies Inc. Methods for intercalating, exfoliating and/or dispersing clay particles and articles incorporating such clay particles
CN103254423A (zh) * 2013-05-20 2013-08-21 金发科技股份有限公司 一种聚酰胺树脂和由其组成的聚酰胺组合物
CN104710781A (zh) * 2013-12-17 2015-06-17 上海杰事杰新材料(集团)股份有限公司 一种共插层剂改性蒙脱土/尼龙610t复合材料及其制备方法
CN106675009A (zh) * 2015-11-05 2017-05-17 株洲时代新材料科技股份有限公司 一种轨道扣件用高强高韧尼龙复合材料及其制备方法
CN106334539A (zh) * 2016-10-04 2017-01-18 青岛大学 一种阳离子聚合物改性蒙脱土吸附剂及其制备方法
CN107474529A (zh) * 2017-08-22 2017-12-15 合肥会通新材料有限公司 一种吸水率低、尺寸稳定性高的玻纤增强蒙脱土改性尼龙复合材料及其制备方法
CN108192336A (zh) * 2017-12-19 2018-06-22 会通新材料股份有限公司 一种低吸水、高尺寸稳定性的pa/pp合金材料及其制备方法
CN111074548A (zh) * 2019-12-27 2020-04-28 海澜之家股份有限公司 一种阻燃织物及其制备方法
CN112341812A (zh) * 2020-11-05 2021-02-09 金发科技股份有限公司 一种自组装网络聚酰胺组合物及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SONIA, ZULFIQAR: "Influence of oligomerically modified reactive montmorillonite on thermal and mechanical properties of aromatic polyamide-clay nanocomposites", ACTA MATERIALIA, vol. 56, 31 December 2008 (2008-12-31), pages 4905 - 4912, XP025429225, DOI: 10.1016/j.actamat.2008.06.005 *

Also Published As

Publication number Publication date
CN112341812A (zh) 2021-02-09
CN112341812B (zh) 2022-04-19

Similar Documents

Publication Publication Date Title
JP5337692B2 (ja) ポリアミドおよびセピオライト型粘土のナノ複合材料組成物
EP0605005B1 (en) Reinforced polyamide resin composition and process for producing the same
TWI391430B (zh) 熱穩定化之塑型組成物
KR100761799B1 (ko) 나노복합체 및 이를 이용한 열가소성 나노복합재 수지조성물
CN104629353B (zh) 对热和光稳定的聚酰胺组合物
US20090142585A1 (en) Nanocomposite compositions of polyamides, sepiolite-type clays and copper species and articles thereof
WO2011118441A1 (ja) 半芳香族ポリアミド、およびその製造方法
WO2022095361A1 (zh) 一种阻燃聚酰胺复合材料及其制备方法和应用
JP2013053244A (ja) ポリアミド樹脂組成物およびそれを成形してなる成形体
CN112159591B (zh) 一种空心玻璃微珠改性尼龙复合材料及其制备方法、应用
US6156838A (en) Polyamide resin composition and process for producing the same
US6255378B1 (en) Polyamide resin composition and process for producing the same
WO2022095360A1 (zh) 一种自组装网络聚酰胺组合物及其制备方法和应用
US20070004842A1 (en) Polymer nanocomposite blends
EP2644647B1 (de) Thermoplastische Formmassen mit erhöhter Hydrolyse-Beständigkeit
TW200804514A (en) Polyamide resin composition
JP2011208105A (ja) ポリアミド樹脂組成物、該ポリアミド樹脂組成物の製造方法および該ポリアミド樹脂組成物を用いてなる成形体
JP2012062335A (ja) ポリアミド樹脂組成物、該ポリアミド樹脂組成物の製造方法および該ポリアミド樹脂組成物を用いてなる成形体
JPH10168310A (ja) 滑り性の優れたポリアミドフィルム
JP2010150533A (ja) ポリアミド樹脂組成物及びその成形品
JP5730284B2 (ja) ポリアミド樹脂組成物、該ポリアミド樹脂組成物の製造方法および該ポリアミド樹脂組成物を用いてなる成形体
CN109233242B (zh) 聚苯醚树脂复合材料及其制备方法和应用
JP4761501B2 (ja) ポリアミド樹脂組成物の製造方法
CN113897038B (zh) 一种高耐热pbt组合物及其制备方法和应用
JP2011094103A (ja) 自動車用アンダーフード部品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21888064

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 28.09.2023)