WO2025130619A1 - 一种高cti无卤阻燃聚酰胺复合物及其制备方法和应用 - Google Patents

一种高cti无卤阻燃聚酰胺复合物及其制备方法和应用 Download PDF

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WO2025130619A1
WO2025130619A1 PCT/CN2024/136863 CN2024136863W WO2025130619A1 WO 2025130619 A1 WO2025130619 A1 WO 2025130619A1 CN 2024136863 W CN2024136863 W CN 2024136863W WO 2025130619 A1 WO2025130619 A1 WO 2025130619A1
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hypophosphite
polyamide composite
polyamide
glass fiber
parts
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张亚军
陈平绪
叶南飚
吴长波
丁超
欧阳齐
金雪峰
杨志坚
郑一泉
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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
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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

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  • the invention relates to the technical field of polymer materials, and in particular to a high CTI halogen-free flame-retardant polyamide composite and a preparation method and application thereof.
  • Comparison tracking is an important parameter that characterizes the electrical properties of materials. The higher the CTI of a material, the shorter the creepage distance, and the higher the degree of freedom in structural design of the material under high voltage.
  • the CTI of halogen-free flame retardant polyamide is generally between 600-700V.
  • the present invention provides a high CTI halogen-free flame retardant polyamide composite and a preparation method and application thereof.
  • the present invention provides a high CTI halogen-free flame retardant polyamide composite, which comprises the following components by weight: 40-70 parts of polyamide resin, such as 40, 43, 45, 50, 55, 60, 65, 70 parts, 20-40 parts of reinforcing filler, such as 20, 23, 25, 28, 30, 35, 38, 40 parts, 8-18 parts of hypophosphite, such as 8, 10, 12, 14, 16, 18 parts, 1-6 parts of melamine derivative, such as 1, 2, 3, 4, 5, 6 parts;
  • the polyamide resin is a composite of PA66 and PA6, and the mass ratio of PA66 to PA6 is (1.5-9):1;
  • the iron content of the hypophosphite is ⁇ 70ppm, preferably 30-70ppm, such as 30, 35, 38, 40, 42, 45, 50, 55, 58, 60, 65, 70ppm;
  • the pH of the hypophosphite is 4-5, such as 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5;
  • the terminal amino content of the PA66 resin is 50-82ppm, such as 50, 52, 55, 60, 62, 65, 68, 70, 75, 78, 80, 82ppm, and the viscosity number of the PA6 resin is 2.0-2.5, such as 2.0, 2.1, 2.2, 2.3, 2.4, 2.5;
  • test method for the terminal amino group content is as follows: take 0.5g of polymer, add 45mL of phenol and 3mL of anhydrous methanol, heat to reflux, observe that the sample is completely dissolved, cool to room temperature, titrate the terminal amino group content with a calibrated hydrochloric acid standard solution, and titrate with a Metrohm 848Titrino plus fully automatic potentiometric titrator;
  • the viscosity number test method is: the test is carried out according to the standard IS0 307: 2007.
  • the relative viscosity of polyamide with a concentration of 0.25 g/dL is measured in 98% concentrated sulfuric acid at 25 ⁇ 0.01°C, and the measurement is carried out using the NCY-2 automatic viscometer produced by Shanghai Star Scientific Instrument Co., Ltd.
  • the amount of the polyamide resin in the composition is not less than 46%; the mass percentage of PA66 in the composition is not less than 32%.
  • PA66 has a better carbon-forming effect than PA6. Therefore, the appropriate introduction of low-molecular-weight PA6 resin can undergo amide exchange with PA66 during the discharge process, destroying the structural regularity of PA66, thereby reducing its carbon-forming effect and improving its CTI.
  • PA66 resin with high amino content can have a good binding force with halogen-free flame retardants, promote the dispersion of halogen-free flame retardants in the composite system, and the amino group of PA66 resin has a certain alkalinity, which can neutralize the acidity of halogen-free flame retardants and reduce the carbon-forming effect of halogen-free flame retardants during the discharge process, thereby improving the CTI of halogen-free flame retardant polyamide composites.
  • hypophosphite of the present invention can be commercially available or synthesized by itself.
  • the synthesis process of hypophosphite is very mature, and any process in the prior art is applicable to the present invention, such as "Synthesis and flame retardant application of new halogen-free flame retardant diethyl aluminum hypophosphite, Wang Yingzhou et al., Journal of Nanjing Normal University (Natural Science Edition), Vol. 39, No. 2", which mentions various preparation methods.
  • the present invention finds that controlling the Fe element content and pH value in the hypophosphite within a suitable range can promote the gas phase arc extinguishing effect of the hypophosphite, reduce its condensed phase catalytic carbonization effect, and thus improve the CTI of the halogen-free flame retardant polyamide.
  • the iron content of the hypophosphite is tested using an inductively coupled plasma spectrometer (ICP) according to GB T 27598-2011; hypophosphite can promote the degradation of polyamide into carbon, and the lower the pH value and the higher the Fe ion content, the more obvious the catalytic degradation into carbonization effect, resulting in a lower CTI of the halogen-free flame retardant polyamide composite.
  • ICP inductively coupled plasma spectrometer
  • the iron content and pH value in the hypophosphite can be regulated by controlling the number of washings of the hypophosphite flame retardant and the content of the acid and alkali reagents in the synthesis process. For example, when the iron content is lower than the required value, the number of washings is reduced, and when the pH is lower than the required value, the acid reagent content can be reduced.
  • the process for synthesizing the hypophosphite flame retardant of the present invention is as follows: In a reactor, the sodium salt corresponding to the hypophosphite used is dissolved in water and fully stirred and dissolved to obtain a sodium salt solution.
  • Aluminum sulfate is dissolved in water in a beaker, and then a certain concentration of 98wt% of concentrated sulfuric acid is added to the aluminum sulfate solution, and the mixture is stirred and mixed evenly, and transferred to a dropping funnel. Heat the reactor, increase the temperature, and then drip the aluminum sulfate solution containing sulfuric acid, and then keep the temperature to continue the reaction. Filter while hot, and wash the precipitate several times, and control the number of washings as needed. Transfer the material to an oven for drying, cool it to room temperature after drying, and discharge the material to obtain the hypophosphite flame retardant of the present invention.
  • the raw materials for synthesizing hypophosphite such as aluminum sulfate or aluminum hydroxide, usually contain a certain amount of iron
  • the final synthesized hypophosphite contains iron in ionic state, which changes the degree to which hypophosphite catalyzes the degradation of polyamide into carbon, thus affecting the CTI value of the material.
  • polyamide composite comprises the following components in parts by weight:
  • hypophosphite is one or more of aluminum hypophosphite, diethyl aluminum hypophosphite, and isopropyl aluminum hypophosphite, preferably diethyl aluminum hypophosphite.
  • the reinforcing filler is glass fiber
  • the glass fiber is selected from one of E glass fiber, H glass fiber, S glass fiber, D glass fiber and C glass fiber, preferably E glass fiber.
  • the melamine derivative is melamine polyphosphate.
  • Melamine polyphosphate can be degraded to produce non-flammable gases such as ammonia and water, and can synergize with hypophosphite to catalyze polyamide into carbon.
  • the present invention also provides a method for preparing the polyamide composite, comprising the following steps:
  • the components are weighed in parts by weight, and the components are put into a mixer for mixing until uniform to obtain a premix, and then the obtained premix is put into a screw extruder for melt mixing, and extruded into granules to obtain the high CTI halogen-free flame retardant polyamide composite.
  • the screw speed of the screw extruder is 250 rpm-350 rpm
  • the aspect ratio is 40:1-48:1
  • the barrel temperature is 200°C-280°C.
  • the present invention also provides the application of the polyamide composite in the electrical and electronic and new energy industries, specifically in high-voltage connectors, new energy battery end plates and brackets, etc.
  • the polyamide composite of the present invention successfully improves the CTI value of the halogen-free flame retardant polyamide.
  • PA66#1 brand PA66 EP-158, terminal amino content 50ppm, Huafeng Group;
  • PA66#2 brand PA66 EP-158N, amino end content 82ppm, Huafeng Group;
  • PA66#3 PA66 EPR27, amino group content 40ppm, Shenma Group;
  • PA66#4 brand PA66 EP1106, terminal amino content 68ppm, Huafeng Group;
  • PA6#1 brand PA6 HY-2800A, viscosity number 2.8, Haiyang Chemical Fiber;
  • PA6#2 brand PA6 HY-2500A, viscosity number 2.4, Haiyang Chemical Fiber;
  • PA6#3 brand PA6 M2400, viscosity number 2.5, Xinhui Meida;
  • PA6#4 brand PA6 M2000, viscosity number 2.0, Xinhui Meida;
  • Glass fiber #1 E glass fiber, grade ECS10-3.0-568H, China Jushi Co., Ltd.
  • Glass fiber #2 S glass fiber, grade S-1HM435TM-10-3.0, Taishan Glass Fiber Co., Ltd.;
  • Hypophosphite #1 diethylaluminum hypophosphite, brand OP1230, iron content 172 ppm, pH 4.1, Klein Co., Ltd.
  • Hypophosphite #2 diethylaluminum hypophosphite, homemade, 50 ppm iron, pH 4.2;
  • Hypophosphite #3 diethylaluminum hypophosphite, homemade, 70 ppm iron, pH 4.1;
  • Hypophosphite #4 Isopropyl aluminum hypophosphite, homemade, 62 ppm iron, pH 4.1;
  • Hypophosphite #5 diethylaluminum hypophosphite, homemade, 70 ppm iron, pH 5.0;
  • hypophosphite #6 diethylaluminum hypophosphite, homemade, 90 ppm iron, pH 3.7;
  • hypophosphite #7 diethylaluminum hypophosphite, homemade, 68 ppm iron, pH 3.6;
  • Preparation method of diethyl aluminum hypophosphite Dissolve 144g of diethyl sodium hypophosphite in 381.7g of water in a 2L reactor, stir and dissolve thoroughly to obtain a diethyl sodium hypophosphite solution. Dissolve 57g of aluminum sulfate in 133g of water in a 500mL beaker, add 4.0-4.1g of concentrated sulfuric acid with a concentration of 98wt% to the aluminum sulfate solution, stir and mix thoroughly, and transfer to a dropping funnel. Heat the reactor to 90°C, start dripping the aluminum sulfate solution containing sulfuric acid, complete the dripping within 2 hours, and keep warm to continue the reaction for 1 hour.
  • the preparation method of isopropyl aluminum hypophosphite refers to the preparation process of diethyl aluminum hypophosphite, and 172g of isopropyl sodium hypophosphite is used to replace 144g of diethyl sodium hypophosphite.
  • Flame retardant performance test The flame retardant performance of the sample strip is tested according to the relevant standards of UL94-2016, and the sample thickness is 0.8mm. Flame retardant performance is of great significance to electrical safety. The UL94 flame retardant grade needs to reach V-0 to meet application requirements.
  • CTI Comparative tracking index
  • Comparative Examples 1-12 are all single variables with Example 4, Comparative Example 1 does not add melamine polyphosphate, and Comparative Example 2 adds excessive melamine polyphosphate. It can be seen from Example 4, Comparative Example 1 and Comparative Example 2 that when the melamine content is low, the carbon layer structure formed at high temperature is loose, the flame retardant efficiency is low, and in the discharge process, inert gas cannot be generated to quench the arc, resulting in a low CTI of the halogen-free flame retardant polyamide composite; when the melamine content is high, the high temperature generated by the arc discharge promotes the carbonization of the halogen-free flame retardant polyamide composite, which also results in a low CTI.
  • PA66 can undergo amide exchange with PA66, destroying the structural regularity of PA66, thereby reducing its carbon-forming effect.
  • PA66 can have a good binding force with the halogen-free flame retardant through its high content of amino groups, promoting the dispersion of the halogen-free flame retardant in the composite system.
  • the molecular weight of PA6 is higher (the viscosity is higher), the PA6 content on the surface of the halogen-free flame retardant polyamide composite is low (the mass ratio of PA66 to PA6 is greater than 9:1), and the carbon-forming effect cannot be inhibited.
  • the halogen-free flame retardant polyamide When the PA6 content is too high (the mass ratio of PA66 to PA6 is less than 1.5:1), the halogen-free flame retardant polyamide will be damaged by corrosion, resulting in a lower CTI. In addition, a high PA6 content will also reduce the flame retardant properties of the halogen-free flame retardant polyamide.
  • Example 4 and comparative examples 8-9 that the hypophosphite content has an important influence on the CTI of the halogen-free flame retardant polyamide.
  • Hypophosphite can promote the degradation of polyamide into carbon. When the hypophosphite content is high, the catalytic degradation into carbon is more obvious, resulting in a lower CTI of the halogen-free flame retardant polyamide composite; but hypophosphite can generate PO free radicals, quench arcs and flames. Therefore, when the hypophosphite content is low, it will also lead to poor CTI and flame retardant properties of the halogen-free flame retardant polyamide.
  • the iron content of the hypophosphite in Comparative Example 10 is too high, which affects its ability to promote the degradation of polyamide into carbon, resulting in a lower CTI value.
  • the pH value of the hypophosphite in Comparative Example 12 is not in the range of 4-5, resulting in a smaller CTI value of the composite.
  • the iron content of the hypophosphite in Comparative Example 11 is too high and the pH value is not in the range of 4-5, which seriously affects the CTI value of the halogen-free flame retardant polyamide composite.
  • the polyamide composites prepared by Examples 1 to 25 can maintain the flame retardant grade (V-0 grade) to meet the application requirements while achieving a high CTI value (higher than 750V). Compared with the comparative example, it has obvious advantages and can effectively meet the high standard requirements of customers and the market.

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Abstract

本发明公开了一种高CTI无卤阻燃聚酰胺复合物及其制备方法和应用。所述聚酰胺复合物，以重量份计，包括如下组分：聚酰胺树脂40-70份、玻璃纤维20-40份、次磷酸盐8-18份、三聚氰胺衍生物1-6份，所述聚酰胺树脂为PA66和PA6的复合物，PA66与PA6的质量比为(1.5-9)：1，所述次磷酸盐的铁元素含量≤70ppm，所述次磷酸盐的pH为4-5，所述PA66树脂的端氨基含量为50-82ppm，所述PA6树脂的粘数为2.0-2.5，本发明的聚酰胺复合物成功提高了材料的CTI值并且阻燃性能满足应用要求，为新能源电压平台从400V往800V及以上发展提供更多可能。

Description

一种高CTI无卤阻燃聚酰胺复合物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，特别涉及一种高CTI无卤阻燃聚酰胺复合物及其制备方法和应用。
背景技术
阻燃聚酰胺由于优异的阻燃性能、力学性能、电性能和耐热性能等，被广泛应用于电子电器、汽车和轨道交通等领域。相比漏电起痕(CTI)是指表征材料电性能的一个重要参数，材料CTI越高，爬电距离越短，材料在高电压下结构设计自由度更高，无卤阻燃聚酰胺的CTI一般在600-700V之间。
但随着新能源电压平台从400V往800V及以上发展，市场对阻燃尼龙的电性能提出了更高的要求，为了更好地匹配材料在800V及以上电压平台的广泛应用，提高材料的安全性能，目前需要进一步提高无卤阻燃聚酰胺的CTI，以满足电子电器、汽车和轨道交通等行业的需求。
发明内容
针对现有技术中的缺陷，本发明提出了一种高CTI无卤阻燃聚酰胺复合物及其制备方法和应用。
本发明提供一种高CTI无卤阻燃聚酰胺复合物，按重量份计，包括如下组分：40-70份聚酰胺树脂，如40、43、45、50、55、60、65、70份，20-40份增强填料，如20、23、25、28、30、35、38、40份，8-18份次磷酸盐，如8、10、12、14、16、18份，1-6份三聚氰胺衍生物，如1、2、3、4、5、6份；
其中，所述聚酰胺树脂为PA66和PA6的复合物，PA66与PA6的质量比为(1.5-9)：1；
所述次磷酸盐的铁元素含量≤70ppm，优选30-70ppm，如30、35、38、40、42、45、50、55、58、60、65、70ppm；
所述次磷酸盐的pH为4-5，如4、4.1、4.2、4.3、4.4、4.5、4.6、4.7、4.8、4.9、5；
所述PA66树脂的端氨基含量为50-82ppm，如50、52、55、60、62、65、68、70、75、78、80、82ppm，所述PA6树脂的粘数为2.0-2.5,如2.0、2.1、2.2、2.3、2.4、2.5；
其中，端氨基含量的测试方法为：取0.5g聚合物，加45mL苯酚及3mL无水甲醇，加热回流，观察试样完全溶解后，冷却至室温，用已标定的盐酸标准溶液滴定端氨基含量，用Metrohm 848Titrino plus全自动电位滴定仪滴定进行滴定；
粘数测试方法为：根据标准IS0 307：2007进行测试。在25±0.01℃的98％的浓硫酸中测量浓度为0.25g/dL的聚酰胺的相对粘度，采用上海思尔达科学仪器有限公司生产的NCY-2自动粘度计进行测量。
所述聚酰胺树脂在组合物中的用量不低于46％；所述组合物中PA66的质量百分含量不低于32％。
在高温下，PA66比PA6具有较好的成碳作用。因此，适当引入低分子量的PA6树脂，在放电过程中，可以与PA66发生酰胺交换，破坏PA66结构规整性，从而降低其成碳作用，提高其CTI。而高氨基含量PA66树脂可以与无卤阻燃剂有较好的结合力，促进无卤阻燃剂在复合物体系中的分散，且PA66树脂的氨基具有一定碱性，可以中和无卤阻燃剂的酸性，降低无卤阻燃剂在放电过程中的成碳作用，从而提高无卤阻燃聚酰胺复合物的CTI，由于漏电起痕破坏主要发生在表面，而PA6分子量越高(粘数高)，无卤阻燃聚酰胺复合物表面PA6含量低，无法发挥抑制成碳的作用。
本发明的次磷酸盐可来自市售或自身合成。次磷酸盐的合成工艺十分成熟，现有技术中任何工艺均适用于本发明，如“新型无卤阻燃剂二乙基次磷酸铝的合成及阻燃应用，王影洲等，《南京师大学报(自然科学版)》，第39卷第2期”中提到了各种制备方法。本发明发现，控制次磷酸盐中Fe元素含量和pH值在合适范围内可以促进次磷酸盐的气相灭弧作用，降低其凝聚相催化成碳作用，从而提高无卤阻燃聚酰胺的CTI。所述次磷酸盐铁元素含量采用电感耦合等离子光谱发生仪(ICP)根据GB T 27598-2011进行测试；次磷酸盐可以促进聚酰胺降解成碳，pH值越低和Fe离子含量越高，催化降解成碳作用越明显，导致无卤阻燃聚酰胺复合物CTI较低。次磷酸盐中的铁元素含量与pH值可通过控制次磷酸盐阻燃剂洗涤的次数与合成过程中酸碱试剂的含量进行调控，如，当铁元素含量低于所需值时，则减少洗涤次数，当pH低于所需值时，则可降低酸试剂含量。示例性地，本发明合成次磷酸盐阻燃剂的工艺如下：在反应釜中将与所使用次磷酸盐相对应的钠盐溶于水中充分搅拌溶解，得到钠盐溶液。在烧杯中将硫酸铝溶于水中，再在硫酸铝溶液中加入一定浓度为98wt％的浓硫酸充分搅拌混合均匀，转移到滴液漏斗中。加热反应釜，升温，再滴加含硫酸的硫酸铝溶液，而后保温继续反应。趁热过滤，并多次洗涤沉淀物，根据需要控制洗涤次数。转移物料至烘箱进行干燥，干燥完成后降温至常温，出料，即得本发明的次磷酸盐阻燃剂。
由于合成次磷酸盐的原料，如硫酸铝或氢氧化铝等中通常会含有一定量的铁元素，最终合成的次磷酸盐中含有以离子状态出现的铁元素，这使得次磷酸盐催化聚酰胺降解成碳的程度发生变化，因此影响材料的CTI值。
进一步地，所述聚酰胺复合物，按重量份计，包括以下组分：
进一步地，所述次磷酸盐为次磷酸铝、二乙基次磷酸铝、异丙基次磷酸铝中的一种或几种，优选为二乙基次磷酸铝。
进一步地，所述增强填料为玻璃纤维，所述玻璃纤维选自E玻璃纤维、H玻璃纤维、S玻璃纤维、D玻璃纤维和C玻璃纤维中的一种，优选为E玻璃纤维。
进一步地，所述三聚氰胺衍生物为三聚氰胺多聚磷酸盐。三聚氰胺多聚磷酸盐一方面可以降解产生氨气和水等不可燃气体，另一方面可与次磷酸盐协效，催化聚酰胺成碳。
本发明还提供所述的聚酰胺复合物的制备方法，包括如下步骤：
按重量份称取各组分，将所述各组分投入混合机中进行混合直至均匀，得到预混物，然后将所得预混物投入螺杆挤出机中进行熔融混合，并挤出造粒，得到所述高CTI无卤阻燃聚酰胺复合物。
进一步的，所述螺杆挤出机的螺杆转速为250rpm-350rpm，长径比为40:1-48:1，螺筒温度为200℃-280℃。
本发明还提供所述的聚酰胺复合物在电子电气和新能源行业中的应用，具体为在高压连接器、新能源电池端板和支架等中的应用。
综上，与现有技术相比，本发明达到了以下技术效果：
(1)本发明的聚酰胺复合物成功提高了无卤阻燃聚酰胺的CTI值。
(2)本发明的聚酰胺复合物的阻燃性能满足应用要求，垂直燃烧性能达到V-0等级。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，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，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
实施例
下面结合具体实施例和对比实施例来进一步说明本发明，以下具体实施例均为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制，特别并不局限于下述具体实施例中所使用的各组分原料的型号。
一、实施例和对比例的原料来源如下：
PA66#1：牌号PA66 EP-158，端氨基含量50ppm，华峰集团；
PA66#2：牌号PA66 EP-158N，端氨基含量82ppm，华峰集团；
PA66#3：牌号PA66 EPR27，端氨基含量40ppm，神马集团；
PA66#4：牌号PA66 EP1106，端氨基含量68ppm，华峰集团；
PA6#1：牌号PA6 HY-2800A，粘数2.8，海阳化纤；
PA6#2：牌号PA6 HY-2500A，粘数2.4，海阳化纤；
PA6#3：牌号PA6 M2400，粘数2.5，新会美达；
PA6#4：牌号PA6 M2000，粘数2.0，新会美达；
玻璃纤维#1：E玻璃纤维，牌号ECS10-3.0-568H，中国巨石股份有限公司；
玻璃纤维#2：S玻璃纤维，牌号S-1HM435TM-10-3.0，泰山玻璃纤维有限公司；
次磷酸盐#1：二乙基次磷酸铝，牌号OP1230，铁元素含量172ppm，pH为4.1，克莱恩有限公司；
次磷酸盐#2：二乙基次磷酸铝，自制，铁元素含量50ppm，pH为4.2；
次磷酸盐#3：二乙基次磷酸铝，自制，铁元素含量70ppm，pH为4.1；
次磷酸盐#4：异丙基次磷酸铝，自制，铁元素含量62ppm，pH为4.1；
次磷酸盐#5：二乙基次磷酸铝，自制，铁元素含量70ppm，pH为5.0；
次磷酸盐#6：二乙基次磷酸铝，自制，铁元素含量90ppm，pH为3.7；
次磷酸盐#7：二乙基次磷酸铝，自制，铁元素含量68ppm，pH为3.6；
三聚氰胺聚磷酸盐：牌号BUDIT 3141，德国Budenheim Iberica；
二乙基次磷酸铝的制备方法；在2L的反应釜中把144g二乙基次磷酸钠溶于381.7g的水，充分搅拌溶解，得到二乙基次磷酸钠溶液。在500mL的烧杯中把57g硫酸铝溶于133g水中，再在硫酸铝溶液中加入4.0-4.1g浓度为98wt％的浓硫酸充分搅拌混合均匀，转移到滴液漏斗中。加热反应釜，升温至90℃，开始滴加含硫酸的硫酸铝溶液，2小时内滴加完成，保温继续反应1小时。趁热过滤，并多次洗涤沉淀物，根据需要控制洗涤次数。转移物料至烘箱，升温至120℃，干燥60min，固体物水分含量为0.1wt％，再以2℃/min的速度升温至180℃，保持60min，再以1℃/min升温至320℃，保持30min，降温至常温，出料。通过控制洗涤次数和硫酸含量来控制二乙基次磷酸铝的Fe离子含量和pH值；
异丙基次磷酸铝的制备方法参照二乙基次磷酸铝的制备流程，用172g异丙基次磷酸钠替代144g二乙基次磷酸钠。
本发明实施例和对比例的聚酰胺复合物的制备方法，包括如下步骤：
按重量份称取各组分，将所述各组分投入混合机中进行混合直至均匀，得到预混物，然后将所得预混物投入双螺杆挤出机中进行熔融混合，并挤出造粒，得到所述高CTI无卤阻燃聚酰胺复合物，其中双螺杆挤出机的螺杆转速为250-350rpm，长径比为40:1-48:1，螺筒温度为200℃-280℃。
二、各项性能测试方法
(1)阻燃性能测试：根据UL94-2016的相关标准对样条进行阻燃性能测试，样品厚度为0.8mm。阻燃性能对于电气安全的意义重大，UL94阻燃等级需要达到V-0才能满足应用需求。
(2)相比耐漏电起痕指数(CTI)测试：根据IEC 60112-2020进行测试，样品尺寸100*100*3mm，仪器测试范围为0-1000V。
表1实施例技术方案和效果(单位为重量份)
表1实施例技术方案和效果(单位为重量份)
表2对比例技术方案和效果(单位为重量份)
对比例1-12均与实施例4单一变量，对比例1未加三聚氰胺聚磷酸盐，对比例2加入过量三聚氰胺聚磷酸盐。由实施例4、对比例1和对比例2可知，当三聚氰胺含量较少时，高温下形成的碳层结构松散，阻燃效率低，并且在放电过程中，不能产生惰性气体，淬灭电弧，导致无卤阻燃聚酰胺复合物CTI较低；当三聚氰胺含量较高时，在电弧放电产生的高温下，促进无卤阻燃聚酰胺复合物成碳，同样导致其CTI较低。
对比例3加入端氨基含量过低的PA66，对比例4加入粘数过高的PA6，对比例5加入端氨基含量过少的PA66且粘数过高的PA6，对比例6的PA66与PA6的质量比大于9:1，对比例7的PA66与PA6的质量比小于1.5:1，由实施例4和对比例3-7可知，PA66树脂的端氨基含量、PA66与PA6的质量比及PA6的粘数均对无卤阻燃聚酰胺复合物CTI具有重要影响。由于PA66比PA6具有较好的成碳作用，因此在PA66中适当引入低分子量的PA6树脂，在放电过程中，可以与PA66发生酰胺交换，破坏PA66结构规整性，从而降低其成碳作用，而PA66通过高含量氨基可以与无卤阻燃剂有较好的结合力，促进无卤阻燃剂在复合物体系中的分散，但如果PA6分子量越高(粘数高)，无卤阻燃聚酰胺复合物表面PA6含量低(PA66与PA6的质量比大于9:1)，无法发挥抑制成碳的作用，而当PA6含量过高(PA66与PA6的质量比小于1.5:1)，会导致无卤阻燃聚酰胺发生蚀损破坏，导致其CTI较低，此外，PA6含量较高也会降低无卤阻燃聚酰胺的阻燃性能。
对比例8加入次磷酸盐过少，对比例9加入过量次磷酸盐，由实施例4、对比例8-9可知，次磷酸盐含量对无卤阻燃聚酰胺CTI具有重要影响，次磷酸盐可以促进聚酰胺降解成碳，当次磷酸盐含量较高时，催化降解成碳作用越明显，导致无卤阻燃聚酰胺复合物CTI较低；但次磷酸盐又可以产生PO自由基，猝灭电弧和火焰，因此，当次磷酸盐含量较低时，也会导致无卤阻燃聚酰胺CTI和阻燃性能较差。
对比例10的次磷酸盐铁元素含量过高，影响其促进聚酰胺降解成碳，使得CTI值较低，对比例12的次磷酸盐的pH值不在4-5范围，导致复合物的CTI值较小，对比例11的次磷酸盐铁元素含量过高且pH值不在4-5范围，严重影响无卤阻燃聚酰胺复合物CTI值。
基于表1和表2中垂直燃烧性能和CTI值的测试数据说明，通过实施例1～25制备得到的聚酰胺复合物，其在达到高CTI值(高于750V)的前提下，能够保持阻燃等级(V-0等级)达到应用要求。相比于对比例具有明显优势，可有效满足客户与市场高标准需求。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种聚酰胺复合物，其特征在于，按重量份计，包括如下组分：
    其中，所述聚酰胺树脂为PA66和PA6的复合物，PA66与PA6的质量比为(1.5-9)：1；
    所述次磷酸盐的铁元素含量≤70ppm；
    所述次磷酸盐的pH为4-5；
    所述PA66树脂的端氨基含量为50-82ppm，所述PA6树脂的粘数为2.0-2.5；
    其中，端氨基含量的测试方法为：取0.5g聚合物，加45mL苯酚及3mL无水甲醇，加热回流，观察试样完全溶解后，冷却至室温，用已标定的盐酸标准溶液滴定端氨基含量，用电位滴定仪滴定进行滴定；
    粘数测试方法为：在25±0.01℃的98％的浓硫酸中测量浓度为0.25g/dL的聚酰胺的相对粘度，采用自动粘度计进行测量。
  2. 根据权利要求1所述的聚酰胺复合物，其特征在于，按重量份计；包括以下组分：
  3. 根据权利要求1或2所述的聚酰胺复合物，其特征在于，所述次磷酸盐为次磷酸铝、二乙基次磷酸铝、异丙基次磷酸铝中的一种或几种。
  4. 根据权利要求1所述的聚酰胺复合物，其特征在于，所述增强填料为玻璃纤维。
  5. 根据权利要求4所述的聚酰胺复合物，其特征在于，所述玻璃纤维选自E玻璃纤维、H玻璃纤维、S玻璃纤维、D玻璃纤维和C玻璃纤维中的任意一种。
  6. 根据权利要求1所述的聚酰胺复合物，其特征在于，所述三聚氰胺衍生物为三聚氰胺多聚磷酸盐。
  7. 权利要求1-6任意一项所述的聚酰胺复合物的制备方法，其特征在于，包括如下步骤：
    按重量份称取各组分，将所述各组分投入混合机中进行混合直至均匀，得到预混物，然后将所得预混物投入螺杆挤出机中进行熔融混合，并挤出造粒，得到所述高CTI无卤阻燃聚酰胺复合物。
  8. 根据权利要求7所述的制备方法，其特征在于，所述螺杆挤出机的螺杆转速为250rpm-350rpm，长径比为40:1-48:1，螺筒温度为200℃-280℃。
  9. 权利要求1-6任意一项所述的聚酰胺复合物在电子电气和新能源行业中的应用。
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