WO2019137301A1 - 一种聚酰胺树脂组合物及其制备方法 - Google Patents

一种聚酰胺树脂组合物及其制备方法 Download PDF

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WO2019137301A1
WO2019137301A1 PCT/CN2019/070353 CN2019070353W WO2019137301A1 WO 2019137301 A1 WO2019137301 A1 WO 2019137301A1 CN 2019070353 W CN2019070353 W CN 2019070353W WO 2019137301 A1 WO2019137301 A1 WO 2019137301A1
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polyamide resin
resin composition
ion
group
parts
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French (fr)
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罗忠富
黄险波
叶南飚
王大中
杨波
丁正亚
林洁龙
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金发科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • the invention relates to the technical field of polymer chemistry, and in particular to a polyamide resin composition and a preparation method thereof.
  • polyamides Due to their excellent mechanical properties, chemical resistance, processability and heat-resistant oxygen aging properties, polyamides are often used in the electrical and electronic and automotive industries where the working environment is more demanding. Especially common.
  • the demand for high temperature resistance of materials in the field of motor vehicles is becoming more and more obvious. This is based on the temperature of the surrounding area of the automobile engine, which is usually higher than 150 ° C, especially the engine with turbocharged intake, the temperature is even higher than 180 ° C or even High temperature above 200 °C. Since polyamide compositions are often used at this temperature of use, the mechanical properties after prolonged exposure are generally reduced, a phenomenon known as heat aging.
  • heat stabilizers also known as antioxidants
  • a phosphite, a thioester or the like enhances the thermo-oxidative aging properties of the polyamide composition.
  • Chinese patent CN105440646 A discloses a heat-resistant oxygen-aged polyamide resin composition which uses a ketone carbonyl polymer and a polyol as main functional components, has good thermal stability, and has a relative humidity of 85 ° C and 85%. After 7 days of treatment, no whitening occurred. However, the amount of polyol added is large and the cost is high. Moreover, after being treated under more severe test conditions (85 ° C and 90% relative humidity) for 14 days, its heat-resistant oxygen aging performance will gradually decrease, extending to 21 days, and it is found that its heat-resistant oxygen aging performance will be greatly reduced. Because of its poor long-term heat and humidity aging resistance under this condition. Therefore, its scope of application is limited.
  • the polyamide resin composition by weight, comprises the following components:
  • Ketone carbonyl polymer 0.5-35 parts.
  • Ketone carbonyl polymer 0.5-35 parts.
  • the ketone carbonyl polymer is selected from the group consisting of a compound derived from an olefinic comonomer repeating unit and a ketone unit derived from an alternating structure of carbon monoxide repeating units; the olefinic comonomer is selected from the group consisting of ethylene, propylene, butene, and One or more of aene, octene, decene, dodecene, tetradecene, hexadecene, octadecene; preferably ethylene and/or propylene.
  • the ketone carbonyl polymer has a ketone carbonyl content of from 15% by weight to 80% by weight, preferably from 30% by weight to 80% by weight based on the total weight of the ketone carbonyl polymer.
  • the elemental analysis method for measuring the ketone carbonyl content of a ketone carbonyl polymer is as follows:
  • the proportion of carbon, oxygen and hydrogen can be measured by elemental analysis.
  • the oxygen element is derived from carbonyl oxygen, and the ratio is ⁇ oxygen .
  • the ketone carbonyl content of the ketone carbonyl polymer can be calculated according to formula I:
  • the ketone carbonyl polymer has a number average molecular weight of 1 ⁇ 10 4 or more and has a number average molecular weight of 3 ⁇ 10 5 or less.
  • the number average molecular weight of the ketone carbonyl polymer is less than 1 ⁇ 10 4 , the mechanical properties of the composition, particularly tensile strength, tensile modulus, flexural strength, flexural modulus and the like, are affected.
  • the number average molecular weight of the ketone carbonyl polymer is more than 3 ⁇ 10 5 , the ultrahigh molecular weight makes the viscosity of the process too high, which is disadvantageous for improving the mixing effect.
  • the metal element of the metal salt compound is selected from the group consisting of a main group I-II, at least one of the subgroups I-II, and an anion paired with a metal ion is selected from a halogen ion, a hydroxide ion, a carbonate ion, At least one of a nitrate ion, a sulfate ion, a hydrogen sulfate ion, and an acetate ion; preferably, the metal ion is selected from the group consisting of lithium ion, sodium ion, potassium ion, calcium ion, zinc ion, and copper ion.
  • At least one of the anions selected from at least one of a halide ion and an acetate ion; more preferably, the metal ion is selected from at least one of a lithium ion and a zinc ion, and the anion is selected from the group consisting of chloride ion and acetate. At least one of the ions.
  • the polyamide resin is formed by gradually polycondensing a diamine and a dibasic acid, or by ring-opening polymerization of a lactam, or gradually polycondensing from an amino acid, or by a diamine, a dibasic acid, a lactam, or an amino acid.
  • the components are copolymerized; selected from the group consisting of PA46, PA66, PA6, PA11, PA12, PA610, PA612, PA1010, PA1012, PA1212, PA4T, PA6T, PA9T, PA10T, PA6I, PAMXD6, PA6I, PA66/6, PA6/ 66.
  • PA6T/6I and PA6T/66 preferably one or more of PA66, PA6, PA610, PA612, PA1010, PA11, PA12, PA66/6; more preferably PA66, PA6 , PA610, PA612, PA1010.
  • the polyamide resin composition further comprises 0 to 60 parts by weight of a filler; the filler is selected from at least one of a fibrous filler and a non-fibrous filler; and the fibrous filler is selected from the group consisting of glass At least one of fiber, carbon fiber, organic fiber, basalt fiber, bamboo fiber, hemp fiber, cellulose fiber, aramid fiber; the non-fibrous filler is selected from the group consisting of alumina, carbon black, clay, zirconium phosphate, kaolin At least one of calcium carbonate, copper, diatomaceous earth, graphite, mica, silica, titania, zeolite, talc, wollastonite, glass beads, and glass powder.
  • the filler is selected from at least one of glass chopped fibers having a diameter of from 7 ⁇ m to 20 ⁇ m and glass long fibers having a diameter of from 7 ⁇ m to 20 ⁇ m.
  • the polyamide resin composition further comprises 0-10 parts by weight of an additive; the additive is selected from the group consisting of a heat stabilizer, an antioxidant, a nucleating agent, an antistatic agent, a foaming agent, a lubricant, a plasticizer, At least one of the pigments.
  • an additive is selected from the group consisting of a heat stabilizer, an antioxidant, a nucleating agent, an antistatic agent, a foaming agent, a lubricant, a plasticizer, At least one of the pigments.
  • the heat stabilizer is a copper-containing composite, and more preferably, the copper-containing composite is a composite of a monovalent and/or divalent copper halide and/or an organic chelate with potassium halide, most preferably,
  • the copper complex is a complex of monovalent copper iodide and potassium iodide.
  • the secondary aromatic amine is 4,4'-bis(phenylisopropyl)diphenylamine (CAS: 10081-67-1).
  • the hindered amine is poly ⁇ [6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-dual [ (2,2,6,6,-Tetramethyl-piperidinyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl) Amino] ⁇ (CAS: 70624-18-9).
  • the hindered phenol is 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (CAS: 1843-03-4), 1, 3, 5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid (CAS: 27676-62-6), 4,4'-butylene bis(6-tert-butylm-cresol) (CAS: 85-60-9), n-octadecanol ester of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (CAS: 2082-79-3), four [ ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester (CAS: 6683-19-8), 3,9-bis[1,1-dimethyl-2-[(3) -tert-Butyl-4-hydroxy-5-methylphenyl)propanoyl
  • the phosphite is dioctadecyl pentaerythritol diphosphite (CAS: 3806-34-6), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol II Phosphate (CAS: 80693-00-1), 2-2'-methylenebis(4,6-dibutyl-benzyl)-2-ethylhexylphosphite (CAS: 126050-54-2 ), tris(2,4-di-tert-butylphenyl) phosphite (CAS: 31570-04-4), tridecyl phenyl phosphite (CAS: 26523-78-4) and 4, 4'- At least one of isopropyl diphenyl C12-15-ol phosphite (CAS: 96152-48-6);
  • the thioester compound is pentaerythritol tetrakis(3-laurylthiopropionate) (CAS: 29598-76-3).
  • the preparation method of the polyamide resin composition comprises the following steps:
  • the above polyamide resin composition is under the engine hood, charge air cooler, oil sump, thermostat, cylinder head, resonator, muffler, intake manifold, catalytic converter housing, intercooler intake Applications in automotive components such as end, engine cooling systems, water chamber end slots, intercoolers, fans, and windshields.
  • the present invention prepares a polyamide resin composition by adding a ketone carbonyl polymer having a specific ketone carbonyl content and a metal salt compound, and the prepared polyamide resin composition has excellent long-term thermo-oxidative aging resistance, 85 ° C and 90 Excellent long-term humidity and heat aging resistance under low humidity conditions and low cost, can adapt to more harsh environments.
  • the raw materials used in the examples and comparative experiments were the following raw materials, but were not limited to the following raw materials:
  • Lithium chloride purchased from Sigma-Aldrich;
  • Lithium acetate purchased from Sigma-Aldrich;
  • Zinc acetate purchased from Sigma-Aldrich;
  • Glass fiber EC11-3.0, diameter 10um, produced by Taiwan Bicheng Company;
  • Cu Complex a copper-containing composite, a mixture of 8 parts potassium iodide and 1 part copper iodide; black pigment A: carbon black, HIBLACK 600L, available from Orion; black pigment B: nigrosine, L0080, purchased from BASF;
  • Dipentaerythritol purchased from Sigma-Aldrich;
  • Example 1-21 and Comparative Example 1-6 are identical to Example 1-21 and Comparative Example 1-6:
  • the dried polyamide resin, metal salt compound, ketone carbonyl polymer, filler and additives are blended, and then extruded, cooled and granulated at a temperature of 220 ° C to 280 ° C through a twin-screw extruder.
  • a polyamide resin composition is obtained.
  • ketone carbonyl polymer selected from the group consisting of toluene, xylene, formic acid, acetic acid, methanol, n-butanol, chloroform, tetrahydrofuran, N,N-dimethylformamide a chromatographic solvent of one or more of dimethyl sulfoxide, a ketone carbonyl polymer solution of 2 mg/ml to 10 mg/ml, which is to be fully dissolved, filtered, and ultrasonically removes bubbles from the solution and the mobile phase, and Make sure that the instrument configuration such as the syringe and flush valve does not contain air bubbles, inject the solution, and measure the number average molecular weight of the ketone carbonyl polymer by gel permeation chromatography.
  • Tensile strength retention rate Test method 1 (TS retention rate 1): Test rods of thickness 4 mm and width 10 mm prepared by molding according to ISO 527-2/1A, test speed 5 mm/min, test 23 ° C
  • Tensile strength (TS) before aging and after aging gives tensile strength T initial before aging.
  • the hot air aging is carried out using a heat aging tank, and the temperature is adjusted to 150 ° C. After the aging time is 1000 h, the sample is taken out from the aging tank, cooled to room temperature, and then sealed with an aluminum foil bag to prevent any moisture from being absorbed before the evaluation of the mechanical properties.
  • T aging and T initial are tensile strengths after aging and before aging, respectively.
  • Tensile strength retention rate Test method 2 (TS retention rate 2): According to ISO 527-2/1A, a test rod having a thickness of 4 mm and a width of 10 mm prepared by molding, a test speed of 5 mm/min, and a test of 23 ° C
  • Tensile strength (TS) before aging in air gives tensile strength T initial before aging. Place the test rod in an environmental chamber at 85% relative humidity and 90 °C. After 21 days, remove the test rod from the chamber, and then use a heat aging chamber to adjust the temperature to 150 °C. After the aging time is 1000 hours, the sample is taken.
  • T aging and T initial are tensile strengths after aging and before aging, respectively.
  • ketone carbonyl polymer selected from the group consisting of toluene, xylene, formic acid, acetic acid, methanol, n-butanol, chloroform, tetrahydrofuran, N,N-dimethylformamide a chromatographic solvent of one or more of dimethyl sulfoxide, a ketone carbonyl polymer solution of 2 mg/ml to 10 mg/ml, which is to be fully dissolved, filtered, and ultrasonically removes bubbles from the solution and the mobile phase; Performing the elemental analysis test on the configured solution;
  • the proportion of carbon, oxygen and hydrogen can be measured by elemental analysis.
  • the oxygen element is derived from carbonyl oxygen, and the ratio is ⁇ oxygen .
  • the ketone carbonyl content of the ketone carbonyl polymer can be calculated according to formula I:
  • the TS retention ratio of the polyamide resin composition is in the range of 5-60 parts of the polyamide resin; 0.1-5 parts of the metal salt compound; and 0.5-35 parts of the ketone carbonyl polymer. 1 reached 78-90%; moreover, TS retention rate 2 decreased by up to 2% with respect to TS retention rate 1. In contrast, the TS retention ratio 2 of Comparative Example 4 decreased by 26% with respect to the TS retention ratio 1. Therefore, the ketone carbonyl polymer combined with the metal salt compound has high heat-resistant oxygen aging and long-term heat and humidity resistance at 85 ° C and 90% relative humidity, and can be used in more complicated and severe environments.

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Abstract

本发明公开了一种聚酰胺树脂组合物及其制备方法。聚酰胺树脂组合物，按重量份计，包括以下组分：5-60份聚酰胺树脂；0.1-5份金属盐化合物；0.5-35份酮羰基聚合物。本发明选自含有衍生自烯属共聚单体重复单元和衍生自一氧化碳重复单元交替结构的酮单元的化合物，酮羰基聚合物的酮羰基含量为15wt％-80wt％，优选为30wt％-80wt％，数均分子量大于等于1×104，小于等于3×105。金属盐化合物的金属元素选自第I-II主族，第I-II副族中的至少一种，其中与金属离子配对的阴离子选自卤素离子、醋酸根离子中的至少一种。本发明制备得到的聚酰胺树脂组合物具有优良的耐长期热氧老化性能、85℃和90％相对湿度条件下优良的长期耐湿热老化性能以及成本低廉等优点。

Description

一种聚酰胺树脂组合物及其制备方法 技术领域
本发明涉及高分子化学技术领域，尤其是涉及一种聚酰胺树脂组合物及其制备方法。
背景技术
聚酰胺由于具有优异的机械性能、耐化学品性、可加工性、耐热氧老化性能，使它们常用于对工作环境要求比较苛刻的电子电器、机动车行业，其中以机动车发动机周边的应用尤为常见。在机动车领域出现的对材料的耐高温需求越来越明显，这是基于汽车发动机周边区域的温度通常高于150℃，尤其是涡轮增压进气方式的发动机，温度甚至高于180℃乃至200℃以上的高温。由于聚酰胺组合物常用于该使用温度下，在长时间暴露之后的机械性能通常会降低，该现象称为热老化。为业内所共知的，通过添加热稳定剂也称为抗氧剂可提高聚酰胺组合物的耐热氧老化性能，包括单独添加或复配添加铜盐、受阻酚、多芳香胺、受阻胺、亚磷酸酯、硫酯等提高聚酰胺组合物的热氧老化性能。
中国专利CN105440646 A公开了一种耐热氧老化的聚酰胺树脂组合物，其使用了酮羰基聚合物和多元醇为主要功能性成分，具有良好的热稳定性能，经85℃和85％相对湿度的条件下处理7天，没有出现析出泛白现象。但是多元醇添加量大，成本高。并且，其在更严苛的测试条件(85℃和90％相对湿度)下处理14天，其耐热氧老化性能就会逐渐下降，延长至21天，发现其耐热氧老化性能会大幅下降，是因为其在该条件下的长期耐湿热老化性能较差。因此，限制了其应用范围。
发明内容
为了克服现有技术缺陷，本发明的首要目的是提供一种具有优良的耐长期热氧老化性能、优良的85℃和90％相对湿度条件下的长期耐湿热老化性能以及成本低廉的聚酰胺树脂组合物及其制备方法。
本发明是通过以下技术方案实现的：
所述的聚酰胺树脂组合物，按重量份计，包括以下组分：
聚酰胺树脂     5-60份；
金属盐化合物   0.1-5份；
酮羰基聚合物   0.5-35份。
优选的，按重量份计，包括以下组分：
聚酰胺树脂     15-60份；
金属盐化合物   0.5-5份；
酮羰基聚合物   0.5-35份。
所述的酮羰基聚合物选自含有衍生自烯属共聚单体重复单元和衍生自一氧化碳重复单元交替结构的酮单元的化合物；所述烯属共聚单体选自乙烯、丙烯、丁烯、己烯、辛烯、癸烯、十二烯、十四烯、十六烯、十八烯中的一种或几种；优选为乙烯和/或丙烯。
基于酮羰基聚合物的总重量，根据元素分析法测得酮羰基聚合物的酮羰基含量为15wt％-80wt％，优选为30wt％-80wt％。
所述的元素分析法测得酮羰基聚合物的酮羰基含量的测试方法：
使用合适的溶剂将酮羰基聚合物从聚酰胺树脂组合物中分离提取，合适的溶剂选自甲苯、二甲苯、甲酸、乙酸、甲醇、正丁醇、氯仿、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种，将聚酰胺树脂组合物溶解或溶胀，得到酮羰基聚合物的溶液或沉淀物，将得到的溶液或沉淀物进行多次溶解并选择减压旋转蒸馏，获得酮羰基聚合物精提物；
酮羰基聚合物精提物，使用选自甲苯、二甲苯、甲酸、乙酸、甲醇、正丁醇、氯仿、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种的色谱级溶剂，配置2mg/ml-10mg/ml的酮羰基聚合物溶液，待充分溶解后过滤，超声波对溶液及流动相脱除气泡；再将配置好的溶液进行元素分析法测试；通过元素分析法可以测得碳元素、氧元素和氢元素所占比例，其中氧元素来源于羰基氧，其测得比例为ω oxygen，酮羰基聚合物的酮羰基含量根据式I计算可得：
ω＝ω oxygen×M CO/M O    式I
其中，M CO为酮羰基的摩尔质量的数值，单位为克每摩尔(g/mol)[M CO＝28.01]；
M O为氧原子的摩尔质量的数值，单位为克每摩尔(g/mol)[M O＝15.99]。
其中，酮羰基聚合物具有大于等于1×10 4的数均分子量，具有小于等于3×10 5的数均分子量。当酮羰基聚合物的数均分子量小于1×10 4，会影响组合物的机械性能，尤其是拉伸强度、拉伸模量、弯曲强度、弯曲模量等。当酮羰基聚合物的数均分子量大于3×10 5，超高的分子量使加工过程粘度过高，不利于改善混合效果。
所述的金属盐化合物的金属元素选自第I-II主族，第I-II副族中的至少一种，与金属离子配对的阴离子选自卤素离子、氢氧根离子、碳酸根离子、硝酸根离子、硫酸根离子、硫酸氢根离子、醋酸根离子中的至少一种；优选的，所述的金属离子选自锂离子、钠离子、钾离子、钙离子、锌离子、铜离子中的至少一种，所述的阴离子选自卤素离子、醋酸根离子中 的至少一种；更优选的，金属离子选自锂离子、锌离子中的至少一种，阴离子选自氯离子、醋酸根离子中的至少一种。
所述聚酰胺树脂由二元胺和二元酸逐步缩聚而成，或由内酰胺开环聚合而成，或由氨基酸逐步缩聚而成，或由二元胺、二元酸、内酰胺、氨基酸中的组分共聚而成；选自PA46、PA66、PA6、PA11、PA12、PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I、PA66/6、PA6/66、PA6T/6I、PA6T/66中的一种或几种；优选为PA66、PA6、PA610、PA612、PA1010、PA11、PA12、PA66/6中的一种或几种；更优选为PA66、PA6、PA610、PA612、PA1010。
所述的聚酰胺树脂组合物还包括0-60重量份的填充剂；所述填充剂选自纤维状填充剂、非纤维状填充剂中的至少一种；所述纤维状填充剂选自玻璃纤维、碳纤维、有机纤维、玄武岩纤维、竹纤维、麻纤维、纤维素纤维、芳纶纤维中的至少一种；所述非纤维状填充剂选自氧化铝、炭黑、粘土、磷酸锆、高岭土、碳酸钙、铜、硅藻土、石墨、云母、硅石、二氧化钛、沸石、滑石、硅灰石、玻璃珠、玻璃粉末中的至少一种。所述填充剂选自直径为7μm-20μm的玻璃短切纤维、直径为7μm-20μm玻璃长纤维中的至少一种。
所述的聚酰胺树脂组合物还包括0-10重量份的添加剂；所述添加剂选自热稳定剂、抗氧剂、成核剂、抗静电剂、发泡剂、润滑剂、增塑剂、颜料中的至少一种。
所述热稳定剂为含铜复合物，更优选地，含铜复合物为一价和/或二价铜的卤化物和/或有机螯合物与卤化钾的复合物，最优选地，含铜复合物为一价铜碘化物和碘化钾的复合物。
所述抗氧剂包括仲芳胺、受阻胺、受阻酚、亚磷酸酯、硫酯化合物及它们的混合物。
更优选地，所述仲芳胺为4,4'-二(苯基异丙基)二苯胺(CAS：10081-67-1)。
更优选地，所述的受阻胺为聚{[6-[(1,1,3,3-四甲基丁基)氨基]]-1,3,5-三嗪-2,4-双[(2,2,6,6,-四甲基-哌啶基)亚氨基]-1,6-己二撑[(2,2,6,6-四甲基-4-哌啶基)亚氨基]}(CAS：70624-18-9)。
更优选地，所述受阻酚为1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷(CAS：1843-03-4)，1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸(CAS：27676-62-6)，4,4'-亚丁基双(6-叔丁基间甲酚)(CAS：85-60-9)，β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯(CAS：2082-79-3)，四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(CAS：6683-19-8)，3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺[5.5]十一烷 (CAS：90498-90-1)和1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯(CAS：1709-70-2)中的至少一种；
更优选地，所述亚磷酸酯为双十八烷基季戊四醇双亚磷酸酯(CAS：3806-34-6)，双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯(CAS：80693-00-1)，2-2’-亚甲基双(4，6-二丁基-苄基)-2-乙基己基亚磷酸酯(CAS：126050-54-2)，亚磷酸三(2,4-二叔丁基苯基)酯(CAS：31570-04-4)，亚磷酸三壬基苯酯(CAS：26523-78-4)和4,4'-对开异丙基二苯基C12-15-醇亚磷酸酯(CAS：96152-48-6)中的至少一种；
更优选地，所述硫酯化合物为季戊四醇四(3-月桂基硫代丙酸酯)(CAS：29598-76-3)。
所述聚酰胺树脂组合物的制备方法，包括以下步骤：
1)将聚酰胺树脂干燥至水分含量低于1500ppm；
2)按照配比将干燥后的聚酰胺树脂、金属盐化合物、酮羰基聚合物、填充剂、添加剂共混，然后经过双螺杆挤出机在220℃-280℃的温度挤出、冷却、造粒即得。
上述聚酰胺树脂组合物在发动机引擎罩以下部件、增压空气冷却器、油底壳、节温器、汽缸盖、谐振器、消声器、进气歧管、触媒转换器外壳、中冷器进气端、发动机冷却系统、水室端槽、中冷器、风扇、护风圈等汽车零部件中的应用。
本发明的有益效果是：
本发明通过添加含有特定酮羰基含量的酮羰基聚合物以及金属盐化合物制备得到的聚酰胺树脂组合物，该制备得到的聚酰胺树脂组合物具有优良的耐长期热氧老化性能、85℃和90％相对湿度条件下优良的长期耐湿热老化性能以及成本低廉等优点，能适应更多的严苛环境。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例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。
实施例与对比例实验所用的原料为以下原料，但不限于以下原料：
聚酰胺树脂：PA66：商品名为PA66 27AEXX，熔点为263℃，购自罗地亚；
酮羰基聚合物：自制，共聚单体选自乙烯:丙烯＝1:1，制备方法参照专利公开号CN1035120A；
氯化锂，购自Sigma-Aldrich；
醋酸锂，购自Sigma-Aldrich；
醋酸锌，购自Sigma-Aldrich；
玻璃纤维：EC11-3.0，直径10um，产自台湾必成公司；
Cu Complex：含铜复合物，8份碘化钾和1份碘化铜的混合物；黑颜料A：炭黑，HIBLACK 600L，购自Orion；黑颜料B：苯胺黑，L0080，购自巴斯夫；
二(三羟甲基)丙烷：购自Sigma-Aldrich；
二季戊四醇：购自Sigma-Aldrich；
实施例1-21及对比例1-6：
聚酰胺树脂组合物的制备：
根据表1将干燥后的聚酰胺树脂、金属盐化合物、酮羰基聚合物、填充剂及添加剂共混，然后经过双螺杆挤出机在220℃-280℃的温度挤出、冷却、造粒即得聚酰胺树脂组合物。
各性能测试方法：
(1)酮羰基聚合物的数均分子量测试方法：酮羰基聚合物，使用选自甲苯、二甲苯、甲酸、乙酸、甲醇、正丁醇、氯仿、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种的色谱级溶剂，配置2mg/ml-10mg/ml的酮羰基聚合物溶液，待充分溶解后过滤，超声波对溶液及流动相脱除气泡，并确保注射器及冲洗阀等仪器构造不含气泡，将该溶液进样，并通过凝胶渗透色谱可以测得酮羰基聚合物的数均分子量。
(2)拉伸强度测试方法：根据ISO 527-2/1A，通过将树脂组合物模制成型，制备的4mm厚、10mm宽的测试棒，测试速度为5mm/min，测试23℃在空气中的拉伸强度(TS)(至少5个相同组成和形状样品测试结果的平均值)。
(3)拉伸强度保持率测试方法1(TS保持率1)：根据ISO 527-2/1A，通过模制成型制备的厚度4mm、宽度10mm测试棒，测试速度5mm/min，测试23℃在空气中的老化前及老化后拉伸强度(TS)(至少5个相同组成和形状样品测试结果的平均值)，得到老化前的拉伸强度T initial。热空气老化使用热老化箱，调节温度为150℃进行，在达到老化时间1000h后样品从老化箱取出，冷却至室温后用铝箔袋热密封，防止在评价力学性能之前吸收任何湿气，测试速度5mm/min，测试温度23℃的拉伸强度(TS)(至少5个相同组成和形状样品测试结果的平均值)，得到老化后的拉伸强度T aging。与老化前的对应力学性能比较，计算出拉伸强度的保持率，并以百分比表示，记为老化后TS保持率R1，R1的计算如下：
Figure PCTCN2019070353-appb-000001
式中T aging及T initial分别是老化后及老化前拉伸强度。
(4)拉伸强度保持率测试方法2(TS保持率2)：根据ISO 527-2/1A，通过模制成型制备的厚度4mm、宽度10mm测试棒，测试速度5mm/min，测试23℃在空气中的老化前的拉伸强度(TS)(至少5个相同组成和形状样品测试结果的平均值)，得到老化前的拉伸强 度T initial。将测试棒放置于85％相对湿度和90℃条件下的环境舱中，21天后，将测试棒从舱中取出，再使用热老化箱，调节温度为150℃进行，在达到老化时间1000h后样品从老化箱取出，冷却至室温后用铝箔袋热密封，防止在评价力学性能之前吸收任何湿气，测试速度5mm/min，测试温度23℃的拉伸强度(TS)(至少5个相同组成和形状样品测试结果的平均值)，得到老化后的拉伸强度T aging。与老化前的对应力学性能比较，计算出拉伸强度的保持率，并以百分比表示，记为老化后TS保持率R2，R2的计算如下：
Figure PCTCN2019070353-appb-000002
式中T aging及T initial分别是老化后及老化前拉伸强度。
(5)酮羰基聚合物酮羰基含量的测试方法：酮羰基聚合物，使用选自甲苯、二甲苯、甲酸、乙酸、甲醇、正丁醇、氯仿、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜中的一种或多种的色谱级溶剂，配置2mg/ml-10mg/ml的酮羰基聚合物溶液，待充分溶解后过滤，超声波对溶液及流动相脱除气泡；再将配置好的溶液进行元素分析法测试；
通过元素分析法可以测得碳元素、氧元素和氢元素所占比例，其中氧元素来源于羰基氧，其测得比例为ω oxygen，酮羰基聚合物的酮羰基含量根据式I计算可得：
ω＝ω oxygen×M CO/M O     式I
其中，M CO为酮羰基的摩尔质量的数值，单位为克每摩尔(g/mol)[M CO＝28.01]；
M O为氧原子的摩尔质量的数值，单位为克每摩尔(g/mol)[M O＝15.99]。
表1:实施例1-21聚酰胺树脂组合物配方及性能测试结果(重量份)
Figure PCTCN2019070353-appb-000003
续表1
Figure PCTCN2019070353-appb-000004
表2：对比例1-6聚酰胺树脂组合物配方及性能测试结果(重量份)
Figure PCTCN2019070353-appb-000005
从表1、表2的数据可以看出：在5-60份聚酰胺树脂；0.1-5份金属盐化合物；0.5-35份酮羰基聚合物的范围内，聚酰胺树脂组合物的TS保持率1达到78-90％；而且，TS保持率2相对于TS保持率1最多下降2％。相比之下，对比例4的TS保持率2相对于TS保持率1下降了26％。因此，酮羰基聚合物配合金属盐化合物的耐热氧老化和85℃和90％相对湿度条件下长期耐湿热老化性能强，可以在更多复杂、严苛的环境下使用。

Claims (12)

  1. 一种聚酰胺树脂组合物，其特征在于，按重量份计，包括以下组分：
    聚酰胺树脂    5-60份；
    金属盐化合物   0.1-5份；
    酮羰基聚合物   0.5-35份。
  2. 根据权利要求1所述的聚酰胺树脂组合物，其特征在于，按重量份计，包括以下组分：
    聚酰胺树脂    15-60份；
    金属盐化合物   0.5-5份；
    酮羰基聚合物   0.5-35份。
  3. 根据权利要求1或2所述的一种聚酰胺树脂组合物，其特征在于，所述的酮羰基聚合物选自含有衍生自烯属共聚单体重复单元和衍生自一氧化碳重复单元交替结构的酮单元的化合物；所述烯属共聚单体选自乙烯、丙烯、丁烯、己烯、辛烯、癸烯、十二烯、十四烯、十六烯、十八烯中的一种或几种；优选为乙烯和/或丙烯。
  4. 根据权利要求1-3任一项所述的聚酰胺树脂组合物，其特征在于，所述的酮羰基聚合物，基于酮羰基聚合物的总重量，根据元素分析法测得酮羰基聚合物的酮羰基含量为15wt％-80wt％，优选为30wt％-80wt％。
  5. 根据权利要求1-4任一项所述的一种聚酰胺树脂组合物，其特征在于，所述的酮羰基聚合物的数均分子量大于等于1×10 4，小于等于3×10 5。
  6. 根据权利要求1或2所述的一种聚酰胺树脂组合物，其特征在于，所述的金属盐化合物的金属元素选自第I-II主族，第I-II副族中的至少一种，与金属离子配对的阴离子选自卤素离子、氢氧根离子、碳酸根离子、硝酸根离子、硫酸根离子、硫酸氢根离子、醋酸根离子中的至少一种；优选的，所述的金属离子选自锂离子、钠离子、钾离子、钙离子、锌离子、铜离子中的至少一种，所述的阴离子选自卤素离子、醋酸根离子中的至少一种；更优选的，金属离子选自锂离子、锌离子中的至少一种，阴离子选自氯离子、醋酸根离子中的至少一种。
  7. 根据权利要求1或2所述的聚酰胺树脂组合物，其特征在于，所述聚酰胺树脂由二元胺和二元酸逐步缩聚而成，或由内酰胺开环聚合而成，或由氨基酸逐步缩聚而成，或由二元胺、二元酸、内酰胺、氨基酸中的组分共聚而成；选自PA46、PA66、PA6、PA11、PA12、PA610、PA612、PA1010、PA1012、PA1212、PA4T、PA6T、PA9T、PA10T、PA6I、PAMXD6、PA6I、PA66/6、PA6/66、PA6T/6I、PA6T/66中的至少一种；优选为PA66、PA6、PA610、PA612、PA1010、PA11、PA12、PA66/6中的至少一种；更优选为PA66、PA6、PA610、PA612、PA1010中的至少一种。
  8. 根据权利要求1或2所述的聚酰胺树脂组合物，其特征在于，所述的聚酰胺树脂组合物还包括0-60重量份的填充剂；所述填充剂选自纤维状填充剂、非纤维状填充剂中的至少一种；所述纤维状填充剂选自玻璃纤维、碳纤维、有机纤维、玄武岩纤维、竹纤维、麻纤维、纤维素纤维、芳纶纤维中的至少一种；所述非纤维状填充剂选自氧化铝、炭黑、粘土、磷酸锆、高岭土、碳酸钙、铜、硅藻土、石墨、云母、硅石、二氧化钛、沸石、滑石、硅灰石、玻璃珠、玻璃粉末中的至少一种。
  9. 根据权利要求8所述的聚酰胺树脂组合物，其特征在于，所述填充剂选自直径为7μm-20μm的玻璃短切纤维、直径为7μm-20μm玻璃长纤维中的至少一种。
  10. 根据权利要求1或2所述的聚酰胺树脂组合物，其特征在于，所述的聚酰胺树脂组合物还包括0-10重量份的添加剂；所述添加剂选自热稳定剂、抗氧剂、成核剂、抗静电剂、发泡剂、润滑剂、增塑剂、颜料中的至少一种。
  11. 一种包含权利要求1-10任一项所述聚酰胺树脂组合物的制备方法，其特征在于，包括以下步骤：
    1)将聚酰胺树脂干燥至水分含量低于1500ppm；
    2)按照配比将干燥后的聚酰胺树脂、金属盐化合物、酮羰基聚合物、填充剂、添加剂共混；
    3)经过双螺杆挤出机在220℃-280℃的温度挤出、冷却、造粒即得。
  12. 权利要求1-11任一项所述的聚酰胺树脂组合物的应用，其特征在于，所述的聚酰胺树脂组合物在发动机引擎罩以下部件、增压空气冷却器、油底壳、节温器、汽缸盖、谐振器、消声器、进气歧管、触媒转换器外壳、中冷器进气端、发动机冷却系统、水室端槽、中冷器、风扇、护风圈等汽车零部件中的应用。
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