WO2022110666A1 - 一种红磷阻燃聚酰胺组合物及其制备方法和应用 - Google Patents

一种红磷阻燃聚酰胺组合物及其制备方法和应用 Download PDF

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WO2022110666A1
WO2022110666A1 PCT/CN2021/092778 CN2021092778W WO2022110666A1 WO 2022110666 A1 WO2022110666 A1 WO 2022110666A1 CN 2021092778 W CN2021092778 W CN 2021092778W WO 2022110666 A1 WO2022110666 A1 WO 2022110666A1
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red phosphorus
flame retardant
phosphorus flame
polyamide composition
retardant polyamide
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French (fr)
Inventor
王丰
黄险波
叶南飚
丁超
金雪峰
胡泽宇
张亚军
张永
易新
吴长波
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Kingfa Science and Technology Co Ltd
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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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to the technical field of engineering plastics, and more particularly, to a red phosphorus flame retardant polyamide composition and a preparation method and application thereof.
  • Polyamide has excellent mechanical properties, wear resistance, heat resistance, solvent resistance, etc., and is widely used in machinery manufacturing, power tools, electronic appliances, transportation and other fields.
  • Polyamide 66 (PA66) is a common polyamide that can form hydrogen bonds between molecular chains, so it has better heat resistance, mechanical properties and wear resistance.
  • Red phosphorus is modified to improve its flame retardant performance.
  • red phosphorus has little effect on mechanical properties, light density, high cost performance, and is also better than halogenated flame retardant systems in electrical properties and smoke density.
  • Red phosphorus is easy to generate phosphine under the action of heat, oxygen and water. If it is further transformed into oxo acid, it will corrode the metal, affect the conduction performance of the product, affect the quality of the product, and shorten the service life of the product.
  • red phosphorus materials One of the main reasons why the industry bans red phosphorus materials.
  • Chinese patent CN104059358A discloses a flame retardant thermoplastic polyamide composition, which includes thermoplastic polyamide, microcapsule red phosphorus flame retardant masterbatch, aniline black, reinforcing materials and other processing aids.
  • thermoplastic polyamide thermoplastic polyamide
  • microcapsule red phosphorus flame retardant masterbatch thermoplastic polyamide
  • aniline black aniline black
  • reinforcing materials other processing aids.
  • the generation of phosphine but most parts in electronic appliances, especially the body parts of photovoltaic connectors, not only require low phosphine release from red phosphorus flame retardant polyamide materials, but also high toughness (Izod notched impact strength). greater than 17kJ/m 2 ) to meet the more severe drop test in the product test (-35°C*3h, 6.78J impact without cracking).
  • the existing red phosphorus flame retardant polyamide compositions cannot meet the requirements of low phosphine release and high toughness at the same time.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies that the existing red phosphorus flame retardant polyamide composition cannot have high toughness and low phosphine release amount at the same time, and provide a red phosphorus flame retardant polyamide composition, which can be used in It can reduce the generation of phosphine and has high toughness at the same time.
  • Another object of the present invention is to provide a preparation method of a red phosphorus flame retardant polyamide composition.
  • Another object of the present invention is to provide the application of a red phosphorus flame retardant polyamide composition.
  • a red phosphorus flame retardant polyamide composition comprising the following components calculated in parts by mass:
  • polyamide 66 PA66
  • long carbon chain polyamide Due to the low polarity of the long carbon chain polyamide and the low density of amide groups, the water absorption rate of the composition is significantly reduced, and the water absorption rate of the composition is greatly reduced. The lower it is, the more beneficial it is to reduce the generation of oxoacids, thereby reducing the corrosion of oxoacids to metals at the source; the addition of toughening agents improves the toughness of the material, but the viscosity of the system also increases, resulting in shear and heat.
  • the red phosphorus flame retardant polyamide composition obtained by compounding in the present invention has both Features high toughness, low phosphine release, low metal corrosion, and high CTI value.
  • the number average molecular weight of the polyamide 66 is 15,000-40,000.
  • the relative viscosity of the polyamide 66 is 1.8-3.5
  • the terminal amino group concentration is 50-200 mmol/Kg
  • the ratio of the terminal amino group to the terminal carboxyl group is 1.5-2.5.
  • the polyamide 66 has a relatively high content of terminal amino groups, which is beneficial to improve hydrolysis resistance and aging resistance.
  • the long carbon chain polyamide is obtained by condensation polymerization of diamine and dicarboxylic acid; the diamine is hexamethylenediamine and/or decanediamine, and the diacid is sebacic acid and/or dodecanedioic acid.
  • the long carbon chain polyamide is one or more of polyamide 610, polyamide 612, polyamide 1010 and polyamide 1012.
  • the long carbon chain polyamide is polyamide 1010.
  • the red phosphorus master batch is a microcapsule red phosphorus master batch.
  • the mass content of red phosphorus in the red phosphorus master batch is 40% to 60%.
  • the hyperbranched polyester has a molecular weight of 2000-8000 and a branching degree of 0.4-1.2.
  • the hyperbranched polyester is one or more of hyperbranched polyester CYD-P218, hyperbranched polyester CYD816A, hyperbranched polyester CYD-5300, and hyperbranched polyester CYD701C.
  • the chromium complex is one or more of Solvent Black 28, Solvent Black 27, and Solvent Black 29.
  • the chromium complex is Solvent Black 28.
  • the reinforcing material is one or more of glass fibers, carbon fibers, aramid fibers, and ceramic fibers.
  • the toughening agent is a graft-modified polyethylene (PE), POE, ethylene-propylene-diene rubber in maleic anhydride (MAH), acrylic acid (AA) or glycidyl acrylate (GMA). (EPDM) or one or more of ethylene-methyl acrylate copolymer (EMA).
  • the processing aids include at least one of antioxidants and lubricants.
  • the antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 1098), triethyl Glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245), tetrakis[beta-(3,5-di-tert-butyl-4-hydroxy Phenyl) propionate] pentaerythritol ester (antioxidant 1010), tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168), phosphite antioxidant P-EPQ, copper salt antioxidant
  • One or more of the oxygen agents the compound of potassium iodide, cuprous iodide and zinc stearate whose mass ratio is 8:1:1).
  • the lubricant of the present invention includes, but is not limited to, one or more of calcium stearate, modified ethylene bis-fatty acid amide, aliphatic fatty acid ester, and ethylene-acrylic acid copolymer.
  • the present invention also protects the preparation method of the above-mentioned red phosphorus flame retardant polyamide composition, comprising the following steps:
  • Polyamide 66 long carbon chain polyamide, toughening agent, hyperbranched polyester, chromium complex, and processing aid are mixed uniformly to obtain a mixed material, and then red phosphorus masterbatch and reinforcing material are added, and after melt blending, After cooling, drying and granulation, the red phosphorus flame retardant polyamide composition is prepared.
  • the step of melt blending is to select a twin-screw extruder with double-side feeding, feed the mixed material from the main feeding port, and feed the red phosphorus masterbatch proportionally from the feeding port on one side. Into, the reinforcing material is fed from the feeding port on the other side for melt blending.
  • the temperature of the melt blending is 180-280°C.
  • the present invention also protects the application of the above-mentioned red phosphorus flame retardant polyamide composition in the manufacture of polyamide products for electronic and electrical products.
  • the red phosphorus flame retardant polyamide composition is used in the manufacture of high toughness polyamide products for electrical and electronic products.
  • the compound of polyamide 66 and long carbon chain polyamide is used as the matrix material of the red phosphorus flame retardant polyamide composition, and the toughness is improved by adding a certain proportion of toughening agent, hyperbranched polyester and chromium complex.
  • the amount of phosphine released from the red phosphorus flame retardant polyamide composition is reduced, and the red phosphorus flame retardant polyamide composition prepared by the invention can also reduce the corrosion to metals, has a high CTI value, and can be widely used in manufacturing In electronic and electrical products, such as the body parts of photovoltaic connectors.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • PA66 The model is EPR27, the relative viscosity is 2.7, the concentration of terminal amino groups is 50 mmol/Kg, the ratio of terminal amino groups to terminal carboxyl groups is 1.9:1; the number average molecular weight is 15600; purchased from Pingdingshan Shenma Engineering Plastics Co., Ltd.
  • PA1010 The model is RILSAN TMFO F POL, the relative viscosity is 2.7, purchased from Shandong Guangyin New Materials Co., Ltd.
  • PA612 Model A150, purchased from Shandong Guangyin New Material Co., Ltd.
  • Red phosphorus masterbatch microcapsule red phosphorus masterbatch, model FR9950KF, in which the mass content of red phosphorus is 50%, purchased from Tongcheng Xinde New Materials Co., Ltd.
  • Reinforcing material glass fiber (glass fiber), the grade is ECS10-03-568H, purchased from Jushi Group Co., Ltd.
  • Toughening agent maleic anhydride grafted ethylene-octene copolymer POE-g-MAH, model FUSABONDN493, purchased from Dow DuPont Co., Ltd.;
  • Hyperbranched polyester model CYD-5300, CYD-816A, purchased from Weihai Chenyuan Molecular New Material Co., Ltd.
  • Chromium complex Solvent Black 28, model BASF Orasol X45, CAS No. 12237-23-9, purchased from BASF; Solvent Black 29, model BASF Orasol X55, CAS No. 126-86-3, purchased from BASF Corporation.
  • Carbon black Model M717, purchased from Cabot Corporation of the United States.
  • Nigrosine Model TN-870, Oriental Chemical Industry Company.
  • Antioxidant 1098 N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, purchased from BASF.
  • Lubricant A-C540A; ethylene acrylic acid copolymer (EAA) with 5% acrylic acid content, purchased from Honeywell.
  • a red phosphorus flame retardant polyamide composition comprising the following components calculated in parts by mass:
  • the preparation method of the above-mentioned red phosphorus flame retardant polyamide composition comprises the following steps:
  • red phosphorus flame retardant polyamide compositions of Examples 2 to 16 include the components calculated in parts by mass as shown in Table 1 below:
  • the preparation method of the above-mentioned red phosphorus flame retardant polyamide composition is the same as that of Example 1, except that the components are replaced.
  • Flame retardant performance Tested according to UL 94, the spline size is 125 ⁇ 13 ⁇ 1.6mm; the flame retardant performance is evaluated by the flame retardant grade, and the flame retardant grade is ranked from low to high as HB, V-2, V-1 , V-0, 5VB, 5VA.
  • test tube into a jar, seal it well, then place the jar at 85°C for 3 days, take out the copper sheet, and then soak the corroded copper sheet in 30 mL of 5 parts of HCl solution for 1 hour, and use the ICP test to shower
  • the phosphorus content in the solution after washing the higher the phosphorus content, the more serious the corrosion of the copper sheet.
  • the red phosphorus flame retardant polyamide composition prepared by the embodiment of the present invention has the advantages of good flame retardant performance, high CTI, low phosphine release, and low corrosion to metals, which can be It is widely used in electronic and electrical products with high performance requirements, such as the body of photovoltaic connectors.
  • the amount of hyperbranched polyester in Example 4 is lower than that of the other examples.
  • the amount of phosphine released is slightly higher, the corrosion of the copper sheet is not serious, and the toughness is still high.
  • Comparative Example 1 since no long carbon chain polyamide was added, the generation of oxyacids could not be reduced from the source, and the copper sheet was seriously corroded.
  • Comparative Example 2 does not contain hyperbranched polyester, the coating layer of the red phosphorus masterbatch is seriously damaged, the amount of phosphine released increases significantly, and the copper sheet is still seriously corroded.
  • the CTI value is 600V, and the CTI value of the system after adding the chromium complex does not change, indicating that the chromium complex does not affect the CTI value of the material, while in Comparative Example 3, the chromium complex does not affect the CTI value of the material.
  • Replacing it with carbon black M717 resulted in a decrease in CTI value, a high amount of phosphine released, and severe corrosion of copper sheets.
  • Comparative Example 4 the chromium complex was replaced by nigrosine TN-870, although the amount of phosphine released was reduced, but the copper sheet was severely corroded. In Comparative Example 5, the amount of long carbon chain polyamide was increased, the toughness decreased seriously, and the flame retardant performance also decreased.

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  • Health & Medical Sciences (AREA)
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Abstract

本发明公开了一种红磷阻燃聚酰胺组合物及其制备方法和应用，由一定配比的聚酰胺66、长碳链聚酰胺、红磷母粒、增强材料、增韧剂、超支化聚酯、铬络合物、加工助剂制得红磷阻燃聚酰胺组合物，本发明通过聚酰胺66与长碳链聚酰胺复配，以及添加增韧剂、超支化聚酯、铬络合物，提高韧性的同时显著降低磷化氢释放量，减少对金属的腐蚀，同时提高相对耐漏电起痕指数，另外，本发明的制备方法易操作，制得的红磷阻燃聚酰胺组合物可很好的应用于制造电子电器产品中。

Description

一种红磷阻燃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，涉及一种红磷阻燃聚酰胺组合物及其制备方法和应用。
背景技术
聚酰胺具有优良的机械性能、耐磨性能、耐热性能、耐溶剂性能等，广泛应用于机械制造业、电动工具、电子电器及交通运输等领域。聚酰胺66(PA66)是一种常见的聚酰胺，分子链之间可以形成氢键，因此耐热性能、力学性能、耐磨性能更为优异。
电子电器中大多数部件要求改性聚酰胺的阻燃等级达到V-0，但是PA66的阻燃性能只有V-2，限制了其在电子电器领域的应用，目前常见的方法是在PA66中加入红磷改性以提高其阻燃性能，红磷作为无卤阻燃剂，对力学性能的影响小，密度轻，性价比高，电性能和烟密度方面也优于有卤阻燃体系，但由于红磷在热、氧、水的作用下易产生磷化氢，如果进一步转变为含氧酸，会腐蚀金属，影响产品的导通性能，影响产品质量、缩短产品的使用寿命，这也是某些行业禁用红磷材料的主要原因之一。
如中国专利CN104059358A公开了一种阻燃热塑性聚酰胺组合物，包括热塑性聚酰胺、微胶囊红磷阻燃母粒、苯胺黑、增强材料以及其他加工助剂制成，虽然能在一定程度上减少磷化氢的产生，但电子电器中大多数部件尤其是光伏连接器的本体部件不仅要求红磷阻燃聚酰胺材料的磷化氢释放量低，同时还需要有高韧性(悬臂梁缺口冲击强度大于17kJ/m 2)才能满足产品测试中比较严酷的跌落测试(-35℃*3h，6.78J的冲击不开裂)。而现有的红磷阻燃聚酰胺组合物不能同时达到低磷化氢释放量和高韧性的要求。
发明内容
本发明要解决的技术问题是克服现有红磷阻燃聚酰胺组合物不能同时具有高韧性和低磷化氢释放量的缺陷和不足，提供一种红磷阻燃聚酰胺组合物，在使用的时候能够减少磷化氢产生，同时具有高韧性。
本发明的另一目的是提供一种红磷阻燃聚酰胺组合物的制备方法。
本发明的又一目的是提供一种红磷阻燃聚酰胺组合物的应用。
本发明上述目的通过以下技术方案实现：
一种红磷阻燃聚酰胺组合物，包括如下按照质量份计算的组分制成：
Figure PCTCN2021092778-appb-000001
本发明通过聚酰胺66(PA66)与长碳链聚酰胺按一定比例复配，由于长碳链聚酰胺极性低，酰胺基密度低，显著降低了组合物的吸水率，组合物的吸水率越低，越有利于减少含氧酸的生成，从而在源头上减少含氧酸对金属的腐蚀；由于增韧剂的加入提高了材料的韧性，但是体系粘度也增加，导致剪切和热量的增加，加剧对红磷母粒包覆层的破坏，因此体系中还添加了超支化聚酯，一方面促进红磷母粒的分散，另一方面利用超支化聚酯在分子链之间的突出润滑效果，降低了分子间作用力，体系粘度下降，减少剪切生热、弱化剪切传递，减少红磷母粒包覆层在挤出加工过程中的破坏，减少磷化氢的产生；还通过加入一定配比的铬络合物，显著降低磷化氢释放量，同时提高相对耐漏电起痕指数(CTI)，因此，本发明通过复配获得的红磷阻燃聚酰胺组合物兼具高韧性、低磷化氢释放量、低金属腐蚀性、高CTI值的特点。
优选地，包括如下按照质量份计算的组分制成：
Figure PCTCN2021092778-appb-000002
优选地，所述聚酰胺66的数均分子量为15000～40000。
优选地，所述聚酰胺66的相对粘度为1.8～3.5，端氨基浓度为50～200mmol/Kg，端氨基与端羧基之比为1.5～2.5。所述聚酰胺66的端氨基含量较高，有利于提升耐水解能力和耐老化能力。
优选地，所述长碳链聚酰胺为二元胺与二元羧酸通过缩合聚合反应得到；所述二元胺为己二胺和/或癸二胺，所述二元酸为癸二酸和/或十二碳二元酸。
更优选地，所述长碳链聚酰胺为聚酰胺610、聚酰胺612、聚酰胺1010、聚酰胺1012的一种或多种。
进一步优选地，所述长碳链聚酰胺为聚酰胺1010。
优选地，所述红磷母粒为微胶囊红磷母粒。
优选地，所述红磷母粒中红磷的质量含量为40％～60％。
优选地，所述超支化聚酯为分子量为2000～8000，支化度为0.4～1.2。
优选地，所述超支化聚酯为超支化聚酯CYD-P218、超支化聚酯CYD816A、超支化聚酯CYD-5300、超支化聚酯CYD701C中的一种或多种。
优选地，所述铬络合物为溶剂黑28、溶剂黑27、溶剂黑29中的一种或多种。
更优选地，所述铬络合物为溶剂黑28。
优选地，所述增强材料为玻璃纤维、碳纤维、芳纶纤维、陶瓷纤维中的一种或多种。
优选地，所述增韧剂为马来酸酐(MAH)、丙烯酸(AA)或丙烯酸缩水甘油酯(GMA)中的一种接枝改性的聚乙烯(PE)、POE、三元乙丙橡胶(EPDM)或乙烯-丙烯酸甲酯共聚物(EMA)中的一种或多种。优选地，所述加工助剂包括抗氧剂、润滑剂中的至少一种。
优选地，所述抗氧剂为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)、三乙二醇醚-二(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯(抗氧剂245)、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、三[2.4-二叔丁基苯基]亚磷酸酯(抗氧剂168)、亚磷酸酯类抗氧剂P-EPQ、铜盐抗氧剂(质量比为8:1:1的碘化钾、碘化亚铜、硬脂酸锌的复配物)中的一种或多种。
本发明所述润滑剂包含但不限于硬脂酸钙、改性乙撑双脂肪酸酰胺、脂肪族脂肪酸酯、乙烯-丙烯酸共聚物中的一种或多种。
本发明还保护上述红磷阻燃聚酰胺组合物的制备方法，包括如下步骤：
将聚酰胺66、长碳链聚酰胺、增韧剂、超支化聚酯、铬络合物、加工助剂混合均匀得到混合物料，再加入红磷母粒、增强材料，进行熔融共混后，经过冷却、干燥、造粒，制得红磷阻燃聚酰胺组合物。
具体地，所述熔融共混的步骤为选用带双侧喂的双螺杆挤出机，将混合物料从主喂料口喂入，将红磷母粒从其中一侧的喂料口按比例喂入，将增强材料从另一侧的喂料口喂入，熔融共混。
优选地，所述熔融共混的温度为180～280℃。
本发明还保护上述红磷阻燃聚酰胺组合物在制造电子电器产品用聚酰胺制品中的应用。
优选地，所述红磷阻燃聚酰胺组合物在制造高韧性的电子电器产品用聚酰胺制品中的应用。
更优选地，所述红磷阻燃聚酰胺组合物在制造光伏连接器用聚酰胺制品中的应用。
与现有技术相比，本发明的有益效果是：
本发明通过聚酰胺66与长碳链聚酰胺复配作为红磷阻燃聚酰胺组合物的基体材料，再通过添加一定配比的增韧剂、超支化聚酯、铬络合物，提高韧性的同时，降低红磷阻燃聚酰胺组合物磷化氢释放量，本发明制得的红磷阻燃聚酰胺组合物同时还能减少对金属的腐蚀，CTI值较高，可广泛应用于制造电子电器产品中，如制造光伏连接器的本体部件。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例和对比例中使用的材料：
PA66：型号为EPR27，相对粘度为2.7，端氨基浓度为50mmol/Kg，端氨基与端羧基之比为1.9:1；数均分子量为15600；购于平顶山神马工程塑料有限责任公司。
PA1010：型号为RILSAN TMFO F POL，相对粘度为2.7，购于山东广垠新材料有限公司。
PA612：型号为A150，购于山东广垠新材料有限公司。
红磷母粒：微胶囊红磷母粒，型号为FR9950KF，其中红磷质量含量50％，购于桐城市信得新材料有限公司。
增强材料：玻璃纤维(玻纤)，牌号为ECS10-03-568H，购于巨石集团有限公司。
增韧剂：马来酸酐接枝乙烯-辛烯共聚物POE-g-MAH，型号为FUSABONDN493，购于陶氏杜邦有限责任公司；
超支化聚酯：型号为CYD-5300、CYD-816A，购于威海晨源分子新材料有限公司。
铬络合物：溶剂黑28，型号为BASF Orasol X45，CAS号为12237-23-9，购于巴斯夫公司；溶剂黑29，型号为BASF Orasol X55，CAS号为126-86-3，购于巴斯夫公司。
炭黑：型号为M717，购于美国卡博特公司。
苯胺黑：型号为TN-870，东方化学工业公司。
抗氧剂1098：N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺，购于巴斯夫公司。
润滑剂：A-C540A；乙烯丙烯酸共聚物(EAA)，丙烯酸含量为5％，购于霍尼韦尔公司。
实施例1
一种红磷阻燃聚酰胺组合物，包括如下按照质量份计算的组分：
Figure PCTCN2021092778-appb-000003
上述红磷阻燃聚酰胺组合物的制备方法，包括如下步骤：
将PA66EPR27、PA1010、POE-g-MAH、CYD-5300、抗氧剂1098、润滑剂A-C540A、BASF Orasol X45在高混机中混合均匀得混合物料，然后选用带双侧喂的双螺杆挤出机，从主喂下料；再将红磷母粒FR9950KF从第一侧喂口下料，玻纤ECS10-03-568H从第二侧喂口下料，然后在280℃下熔融共混，挤出、水冷、风干、造粒；再将材料烘干、注塑制得红磷阻燃聚酰胺组合物。
实施例2～16和对比例1～6
实施例2～16的红磷阻燃聚酰胺组合物，包括如下表1所示的按照质量份计算的组分：
表1实施例2～16和对比例1～6组分及其质量份
Figure PCTCN2021092778-appb-000004
Figure PCTCN2021092778-appb-000005
Figure PCTCN2021092778-appb-000006
Figure PCTCN2021092778-appb-000007
上述红磷阻燃聚酰胺组合物的制备方法与实施例1相同，区别在于组分的替换。
性能测试
1、测试方法
(1)悬臂梁缺口冲击强度：按照ISO 180:2000进行测试。
(2)阻燃性能：按照UL 94测试，样条规格125×13×1.6mm；阻燃性能由阻燃等级评定，阻燃等级依次由低到高排序为HB、V-2、V-1、V-0、5VB、5VA。
(3)CTI：按照IEC 60112进行测试，A溶液(0.1份氯化铵溶液)。
(4)磷化氢释放量：①设备：干燥皿(口径300mm)，德尔格公司的磷化氢测试仪，秒表；②在285℃、280℃、275℃、270℃下连续注塑，取20模，取21模的样条放入干燥皿中、密封，按下秒表计时，取5min时的读数；③磷化氢释放量＝检测仪的读数/样条质量(kg)。
(5)磷腐蚀的表征：①设备：热老化烘箱，广口瓶，直径12mm*长度100mm的试管，分析天平，电感耦合原子发射光谱仪ICP，镊子；②取50克造粒后的红磷阻燃聚酰胺组合物放置在500ml广口瓶中，然后取规格为80mm*10mm*1.0mm的紫铜片，插入粒子中，露出部分的长度是40mm，在试管中装入8mL的去离子水，将试管放入广口瓶中，密封好，然后将广口瓶在85℃下放置3天，取出铜片，然后将腐蚀后的铜片在30mL的5份HCl溶液中浸泡1h，用ICP测试淋洗后溶液中磷含量，磷含量越高则铜片腐蚀越严重。
2、测试结果
表2各实施例和对比例制得的红磷阻燃聚酰胺组合物性能测试结果
Figure PCTCN2021092778-appb-000008
Figure PCTCN2021092778-appb-000009
通过表2可以发现，本发明制得的产品的悬臂梁缺口冲击强度可以满足应用的要求，即加入了添加剂后对组合物的韧性没有影响。
而且通过表2还可以发现，通过本发明实施例制备的红磷阻燃聚酰胺组合物具有较好的阻燃性能、高CTI、低磷化氢释放量、对金属的腐蚀低的优点，可以 广泛用于性能要求较高的电子电器产品中，比如光伏连接器的本体。其中，实施例4的超支化聚酯用量较其他实施例的低，虽然磷化氢释放量稍高，但是铜片腐蚀不严重，且韧性仍然较高。而对比例1由于没有添加长碳链聚酰胺，不能从源头上减少含氧酸的生成，铜片腐蚀严重。对比例2不含超支化聚酯，红磷母粒包覆层破坏严重，磷化氢释放量明显增加，铜片腐蚀仍然严重。对比例6不含有黑色染料的体系，CTI值为600V，添加了铬络合物后的体系CTI值不变，说明铬络合物不影响材料的CTI值，而对比例3将铬络合物替换为炭黑M717，导致CTI值下降，且磷化氢释放量高，铜片腐蚀严重。对比例4将铬络合物替换为苯胺黑TN-870，虽然降低了磷化氢的释放量，但是铜片腐蚀严重。对比例5增加了长碳链聚酰胺的用量，韧性下降严重，阻燃性能也有所降低。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种红磷阻燃聚酰胺组合物，其特征在于，包括如下按照质量份计算的组分：
    Figure PCTCN2021092778-appb-100001
  2. 根据权利要求1所述红磷阻燃聚酰胺组合物，其特征在于，包括如下按照质量份计算的组分：
    Figure PCTCN2021092778-appb-100002
  3. 根据权利要求1或2所述红磷阻燃聚酰胺组合物，其特征在于，所述长碳链聚酰胺为二元胺与二元羧酸通过缩合聚合反应得到；所述二元胺为己二胺和/或癸二胺，所述二元酸为癸二酸和/或十二碳二元酸。
  4. 根据权利要求1所述红磷阻燃聚酰胺组合物，其特征在于，所述红磷母粒为微胶囊红磷母粒。
  5. 根据权利要求1所述红磷阻燃聚酰胺组合物，其特征在于，所述超支化聚酯的分子量为2000～8000，支化度为0.4～1.2。
  6. 根据权利要求1所述红磷阻燃聚酰胺组合物，其特征在于，所述铬络合物为溶剂黑28、溶剂黑27、溶剂黑29中的一种或多种。
  7. 根据权利要求1所述红磷阻燃聚酰胺组合物，其特征在于，所述增强材料为玻璃纤维、碳纤维、芳纶纤维、陶瓷纤维中的一种或多种。
  8. 根据权利要求1所述红磷阻燃聚酰胺组合物，其特征在于，所述加工助剂包括抗氧剂、润滑剂中的至少一种。
  9. 权利要求1～8任一项所述红磷阻燃聚酰胺组合物的制备方法，其特征在于，包括如下步骤：
    将聚酰胺66、长碳链聚酰胺、增韧剂、超支化聚酯、铬络合物、加工助剂混合均匀得到混合物料，再加入红磷母粒、增强材料，进行熔融共混后，经过冷却、干燥、造粒，制得红磷阻燃聚酰胺组合物。
  10. 权利要求1～8任一项所述红磷阻燃聚酰胺组合物在制造电子电器产品用聚酰胺制品中的应用。
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CN109111736A (zh) * 2018-07-18 2019-01-01 余姚中国塑料城塑料研究院 一种耐摩擦的抗老化增强尼龙及制备方法
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CN111117222A (zh) * 2019-12-12 2020-05-08 中广核俊尔(浙江)新材料有限公司 一种耐灼热丝不起燃的聚酰胺组合物及其制备方法和应用
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