WO2014201859A1 - 一种高流动性pa10t聚酰胺树脂及由其组成的聚酰胺组合物 - Google Patents

一种高流动性pa10t聚酰胺树脂及由其组成的聚酰胺组合物 Download PDF

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WO2014201859A1
WO2014201859A1 PCT/CN2014/070036 CN2014070036W WO2014201859A1 WO 2014201859 A1 WO2014201859 A1 WO 2014201859A1 CN 2014070036 W CN2014070036 W CN 2014070036W WO 2014201859 A1 WO2014201859 A1 WO 2014201859A1
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polyamide resin
pa10t
mol
pa10t polyamide
group value
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French (fr)
Inventor
张传辉
袁志敏
蔡彤旻
吉继亮
曾祥斌
曹民
夏世勇
叶南飚
陈大华
殷年伟
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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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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

Definitions

  • the present invention relates to the field of polymer materials, and more particularly to a high flow PA10T polyamide resin and a polyamide composition composed thereof.
  • Polyamide has a wide range of properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricating properties, low friction coefficient, certain flame retardancy, easy processing, etc. Suitable for filling reinforcement with glass fiber and other fillers to improve performance and expand application range.
  • semi-aromatic polyamides have been developed with emphasis on their heat resistance and mechanical properties.
  • the PA10T polyamide resin obtained by polymerizing a diamine and terephthalic acid has a low water absorption rate and a high melting point, and is currently developing rapidly.
  • the PA10T polyamide resin has a higher melt viscosity than the PA6T polyamide resin.
  • high melt viscosity is disadvantageous and needs to be increased by mold temperature or back pressure.
  • the above-mentioned operation means unavoidably bring about the problem of resin degradation, which limits the application of PA10T polyamide resin in many fields. Therefore, there is a need in the industry for a highly fluid PA10T polyamide resin and a polyamide composition composed thereof.
  • the PA10T polyamide resin A has a relative viscosity of 1.4-1.6 at 25 ° C, 98% concentrated sulfuric acid; the PA10T polyamide resin A has a terminal amino group value of 30-50 mol/t, and the terminal carboxyl value is 80-110 mol/t; in the PA10T polyamide resin A, the ratio of benzoic acid to the repeating unit is 4-20 mol%.
  • a polyamide composition comprising the high flow PA10T polyamide resin A, by weight The score, including the following components:
  • PA10T polyamide resin B 50-94%; mineral filler 0.8-40%; other additives 0.2-1%; wherein, the relative viscosity of the PA10T polyamide resin B at 25 ° C, 98% concentrated sulfuric acid is 2.0- 2.4;
  • the PA10T polyamide resin B has a terminal amino group value of 20-60 mol/t and a terminal carboxyl group value of 70-130 mol/t; in the PA10T polyamide resin B, the ratio of benzoic acid to the repeating unit is 0.5-4 mol. %.
  • the PA10T polyamide resin B has a relative viscosity of 2.1-2.3 at 25 ° C, 98% concentrated sulfuric acid; the PA10T polyamide resin B has a terminal amino group value of 30-50 mol/t, and the terminal carboxyl value is 80 to 11 Omol/t; in the PAl 0T polyamide resin B, the ratio of benzoic acid to the repeating unit is from 1 to 3.5 mol%.
  • the amount of the PA10T polyamide resin is less than 5% by weight, it is difficult to improve the fluidity; and since the PA10T polyamide resin A has a relatively low molecular weight, when it is used in an amount of more than 29.8 wt%, the resin property is inevitably lowered.
  • the mineral filler is selected from one or a mixture of titanium dioxide, nano zinc oxide, talc.
  • the titanium dioxide has a particle diameter selected from the group consisting of 0.2 to 0.3 um ; the nano zinc oxide has a purity of ⁇ 98%, and the particle diameter is selected from the group consisting of 20 to 80 nm; and the talc has a particle diameter selected from the group consisting of 500 to 2000 mesh.
  • the other auxiliary agent is selected from one or a mixture of an antioxidant, a light stabilizer, and a flow modifier; the antioxidant is selected from the group consisting of a hindered phenol antioxidant and/or a phosphite antioxidant;
  • the hindered phenolic antioxidant is selected from the group consisting of 1, 3-benzenediamide-N, N'-bis(2, 2, 6, 6-tetramethyl-4-piperidinyl), ⁇ -( Pentaerythritol 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl alcohol ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, N, N '-Bis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-1,6-hexanediamine, 1,3,5-tris(3,5-di-tert-butyl -4-mercaptopurine) 2,4,6-trimethylbenzene, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylindenyl) 1,3 One or a mixture of 5-triazine-2,4,6-
  • the light stabilizer is selected from the group consisting of a benzophenone compound, a salicylate compound, a benzotriazole compound, or a mixture thereof;
  • the flow modifier is selected from the group consisting of wax, EBS, sodium montanate, One or several mixtures of hyperbranched polymers.
  • a method for preparing the above polyamide composition comprising the steps of: adding PA10T polyamide resin A, PA10T polyamide resin B, mineral filler, and other auxiliary agents in a high-mixing machine, uniformly mixing, and then adding through a main feeding port.
  • the reinforcing filler is fed side by side feeding scale, extruded at 310 ° C ⁇ 330 ° C, cooled by water, granulated and dried to obtain a product.
  • the invention has the following beneficial effects:
  • the PA10T polyamide resin A of the present invention has a low apparent viscosity under molten conditions and has high fluidity.
  • a certain proportion of PA10T polyamide resin A is added to a semi-aromatic polyamide, the obtained polyamide is prepared.
  • the composition has high fluidity and substantially equivalent mechanical properties and can be used in applications where the size of the injection molded article is high.
  • the raw materials used in the examples and comparative examples are as follows, but are not limited to these materials:
  • the titanium dioxide used is DuPont's rutile type titanium dioxide R103 having a particle size of 0.2-0.3 ⁇ ;
  • the antioxidant used is the amine-based nylon high-efficiency yellowing agent antioxidant of Double Bond Chemical Company 1098;
  • the flow modifier used was a partially substituted sodium montanate salt of Clariant.
  • Licowax OP o Examples and performance tests of the comparative examples were carried out according to the following standards or methods:
  • Test method for relative viscosity of polyamide obtained Refer to GB12006.1-89, method for determination of polyamide viscosity number; specific test method is: measuring concentration of 0.25g/dl in 98% concentrated sulfuric acid at 25 ⁇ 0.01 °C The relative viscosity of the amide is nr; the test method for the amino group content of the obtained polyamide: the amino group content of the sample is titrated by a fully automatic potentiometric titrator; 0.5 g of the polymer, 45 mL of phenol and 3 mL of anhydrous methanol are added, and the mixture is heated under reflux to observe the sample completely. After dissolution, it is cooled to room temperature, and the terminal amino group content is titrated with the calibrated hydrochloric acid standard solution;
  • Test method for the carboxyl group content of the obtained polyamide the carboxyl group content of the sample is titrated by a fully automatic potentiometric titrator; 0.5 g of the polymer is added, 50 mL of o-cresol is added, and the solution is refluxed, and after cooling, 400 ⁇ of the formaldehyde solution is quickly added, and the calibration is performed. ⁇ -ethanol solution titration end carboxyl group content;
  • the test method for the apparent viscosity of the obtained polyamide was carried out using a Dynisco LCR-7000 capillary rheometer using a CZ394-20 die with a shear rate of 1000, a test temperature of 330 ° C, and a melting time of 5 min.
  • Tensile strength measured according to ISO 527-2, test conditions are 23 ° C and lOmm / min;
  • Elongation at break measured according to ISO 527-2, test conditions are 23 ° C and lOmm / min;
  • Flexural strength and flexural modulus measured according to ISO 178, test conditions are 23 ° C and 2 mm / min ; Notched impact strength: measured according to ISO 180/1A, the test condition is 23 ° C, and the notch type is type A. Notched impact strength: The test conditions were 23 ° C according to ISO 180/1A.
  • Spiral flow line length The self-made Archimedes spiral flow line mold is used, and the flow groove is 5mm wide and 2.5mm high.
  • reaction raw materials were added in the proportions shown in Table 1, and then benzoic acid, sodium hypophosphite and deionized water were added; sodium hypophosphite weight In order to remove 0.1% of the weight of other feeds other than ionized water, the weight of deionized water is 30% of the total weight of the feed; vacuum is filled with high-purity nitrogen as a shielding gas, and the temperature is raised to 220 ° C within 2 hours under stirring. Stir at 220 ° C for 1 hour, then raise the temperature of the reactants to 230 ° C with stirring ;
  • the temperature was maintained at a constant temperature of 230 ° C and a constant pressure of 2.2 MPa for 2 hours.
  • the pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours to obtain a pre-preparation.
  • the poly-product, the pre-polymerized product was solid-phase-bonded at 250 ° C, 50 Pa vacuum for 10 hours to obtain PA10T polyamide resin A; the performance test is shown in Table 1.
  • Examples B1 to B4 Preparation of PA10T Polyamide Resin B In the autoclave equipped with a magnetic coupling stirring, a condenser, a gas phase port, a feeding port and a pressure explosion port, the reaction raw materials were added in the proportions shown in Table 2, and then benzoic acid, sodium hypophosphite and deionized water were added; sodium hypophosphite weight In order to remove 0.1% of the weight of other feeds other than ionized water, the weight of deionized water is 30% of the total weight of the feed; vacuum is filled with high-purity nitrogen as a shielding gas, and the temperature is raised to 220 ° C within 2 hours under stirring.
  • PA10T polyamide resin A, B, titanium dioxide, talc, and other additives are uniformly mixed in a high-mixer, and then added to the twin-screw extruder through the main feed port to enhance the passage of the filler.
  • the side feed scale was fed side by side, extruded, water cooled, granulated and dried to obtain the polyamide composition; wherein the extrusion temperature was 330 °C.

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  • 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

本发明公开了一种高流动性PA10T聚酰胺树脂A，所述PA10T聚酰胺树脂A在25°C，98%浓硫酸中的相对粘度为1.2-1.8；所述PA10T聚酰胺树脂A的端氨基值为20-60mol/t，端羧基值为70-130mol/t；所述PA10T聚酰胺树脂A中，苯甲酸占重复单元的比例为2-20mol%；一种聚酰胺组合物，包括如下组分：5~29.8wt%PA10T聚酰胺树脂A；50~94wt%PA10T聚酰胺树脂B；0.8~40wt%矿物填料；0.2~1wt%其他助剂；本发明的PA10T聚酰胺树脂A，在熔融条件下的表观粘度较低，具有较高的流动性，当在半芳香族聚酰胺中添加一定比例的PA10T聚酰胺树脂A，制备所得的聚酰胺组合物具有高的流动性和基本相当的力学性能，可用于对注塑制品尺寸要求较高的场合。

Description

一种高流动性 PA10T聚酰胺树脂及由其组成的聚酰胺组合物
技术领域
本发明涉及高分子材料领域， 特别涉及一种高流动性 PA10T聚酰胺树脂及 由其组成的聚酰胺组合物。
背景技术
聚酰胺因具有良好的综合性能， 包括力学性能、 耐热性、 耐磨损性、 耐化学 药品性和自润滑性， 且摩擦系数低， 有一定的阻燃性， 易于加工等， 其被广泛适 于用玻璃纤维和其它填料填充增强改性， 提高性能和扩大应用范围。近几年来半 芳香族聚酰胺由于其耐热性能和力学性能更优而被重点开发。
由癸二胺和对苯二甲酸聚合而成的 PA10T聚酰胺树脂，吸水率低，熔点高， 目前发展迅速。 然而， 相对于 PA6T聚酰胺树脂， PA10T聚酰胺树脂的熔体粘度 较高。 当需要注塑大件或复杂制品的时候， 高的熔体粘度是很不利的， 需要提高 模温或背压来实现。 上述操作手段不可避免的带来树脂降解的问题， 限制了 PA10T 聚酰胺树脂在很多领域的应用。 因此， 业界亟需一种高流动性的 PA10T 聚酰胺树脂和由其组成的聚酰胺组合物。 发明内容 为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种具有高流 动性的 PA10T聚酰胺树脂。
本发明是通过以下技术方案实现的；
一种高流动性 PA10T聚酰胺树脂 A， 在 25°C， 98%浓硫酸中的相对粘度为 1.2-1.8； 所述 PA10T 聚酰胺树脂 A 的端氨基值为 20-60mol/t， 端羧基值为 70-130mol/t;所述 PA10T聚酰胺树脂 A中，苯甲酸占重复单元的比例为 2-20mol%。
优选地， 所述 PA10T聚酰胺树脂 A在 25°C， 98%浓硫酸中的相对粘度为 1.4-1.6； 所述 PA10T 聚酰胺树脂 A 的端氨基值为 30-50mol/t， 端羧基值为 80-110mol/t;所述 PA10T聚酰胺树脂 A中，苯甲酸占重复单元的比例为 4-20mol%。
一种包含所述的高流动性 PA10T聚酰胺树脂 A的聚酰胺组合物， 按重量百 分数计， 包括如下组分:
PA10T聚酰胺树脂 A 5-29.8%；
PA10T聚酰胺树脂 B 50-94%； 矿物填料 0.8-40%； 其他助剂 0.2-1%； 其中，所述 PA10T聚酰胺树脂 B 在 25°C， 98%浓硫酸中的相对粘度为 2.0-2.4; 所述 PA10T聚酰胺树脂 B的端氨基值为 20-60mol/t， 端羧基值为 70-130mol/t; 所述 PA10T聚酰胺树脂 B中， 苯甲酸占重复单元的比例为 0.5-4mol%。
优选地， 所述 PA10T 聚酰胺树脂 B在 25°C， 98%浓硫酸中的相对粘度为 2.1-2.3； 所述 PA10T 聚酰胺树脂 B 的端氨基值为 30-50mol/t， 端羧基值为 80- 11 Omol/t;所述 PAl 0T聚酰胺树脂 B中，苯甲酸占重复单元的比例为 1 -3.5mol%。
当 PA10T聚酰胺树脂用量小于 5wt%时， 难以起到流动性改善的效果； 而由 于 PA10T聚酰胺树脂 A分子量较低， 当其用量大于 29.8wt%时， 必然引起树脂 性能的下降。
所述矿物填料选自二氧化钛、 纳米氧化锌、 滑石粉的一种或几种混合物。 所述二氧化钛的粒径选自 0.2-0.3um; 所述纳米氧化锌的纯度≥98%， 粒径选 自 20-80 nm; 所述滑石粉的粒径选自 500-2000目。
所述其它助剂选自抗氧化剂、 光稳定剂、 流动改性剂的一种或几种混合物； 所述抗氧化剂选自受阻酚类抗氧剂和 /或亚磷酸酯类抗氧剂；
优选地， 所述受阻酚类抗氧剂选自 1， 3-苯二酰胺 -N， N' -双 (2， 2， 6， 6- 四甲基 -4-哌啶基)、 β -(3， 5-二叔丁基 -4-羟基苯基)丙酸季戊四醇酯、 β -(3， 5- 二叔丁基 -4-羟基苯基)丙酸十八垸基醇酯、 N， N' -双 [ β -(3， 5-二叔丁基 -4-羟基 苯基)丙酰] -1， 6-己二胺、 1,3,5-三 (3,5-二叔丁基 -4-痉基卞基) 2,4,6-三甲基苯、 1,3,5- 三 (4-叔丁基 -3-羟基 -2， 6-二甲基卞基) 1,3,5-三嗪 -2， 4， 6-(1Η,3Η,5Η)三酮的一种 或几种混合物；所述亚磷酸酯类抗氧剂选自三 (2,4-二叔丁基苯酚)亚磷酸酯、双 (3， 5-二叔丁基苯基)季戊四醇二亚磷酸酯的一种或几种混合物。
所述光稳定剂选自二苯甲酮化合物、水杨酸酯化合物、苯丙三唑化合物的一 种或几种混合物； 所述流动改性剂选自 Ε蜡、 EBS、 褐煤酸钠盐、 超支化聚合物 的一种或几种混合物。 一种上述聚酰胺组合物的制备方法， 包括如下步骤： 将 PA10T聚酰胺树脂 A、 PA10T聚酰胺树脂 B、 矿物填料、 其他助剂置于高混机中混合均匀后， 通过 主喂料口加入双螺杆挤出机中，增强填料通过侧喂料秤侧喂，在 310°C~330°C下， 挤出， 过水冷却， 造粒并干燥后得到产品。
本发明与现有技术相比， 具有如下有益效果：
本发明的 PA10T聚酰胺树脂 A， 在熔融条件下的表观粘度较低， 具有较高 的流动性， 当在半芳香族聚酰胺中添加一定比例的 PA10T聚酰胺树脂 A， 制备 所得的聚酰胺组合物具有高的流动性和基本相当的力学性能，可用于对注塑制品 尺寸要求较高的场合。
具体实施方式
现对实施例及对比例所用的原材料做如下说明， 但不限于这些材料： 所用钛白粉是杜邦公司的粒径 0.2-0.3μηι的金红石型二氧化钛 R103;
所用抗氧剂是双键化工公司的胺类尼龙高效耐黄变剂抗氧剂 1098;
所用流动改性剂是科莱恩公司的部分取代的褐煤酸钠盐 Licowax OP o 实施例及对比例的性能测试按如下标准或方法进行：
所得聚酰胺相对粘度的测试方法： 参照 GB12006.1-89, 聚酰胺粘数测定方 法； 具体测试方法为： 在 25 ±0.01°C的 98%的浓硫酸中测量浓度为 0.25g/dl的 聚酰胺的相对粘度 n r; 所得聚酰胺端氨基含量的测试方法：用全自动电位滴定仪滴定样品端氨基含 量； 取 0.5g聚合物， 加苯酚 45mL及无水甲醇 3mL， 加热回流， 观察试样完全 溶解后， 冷至室温， 用已标定的盐酸标准溶液滴定端氨基含量；
所得聚酰胺端羧基含量的测试方法：用全自动电位滴定仪滴定样品端羧基含 量； 取 0.5g聚合物， 加邻甲酚 50mL， 回流溶解， 放冷后迅速加入 400μί甲醛溶 液， 用已标定的 ΚΟΗ-乙醇溶液滴定端羧基含量；
所得聚酰胺表观粘度的测试方法： 用 Dynisco公司 LCR-7000型毛细管流变 仪进行， 采用 CZ394-20型口模， 剪切速率为 1000 ， 测试温度为 330°C， 熔融 时间为 5min。
拉伸强度： 根据 ISO 527-2测定， 测试条件为 23°C和 lOmm/min;
断裂伸长率： 根据 ISO 527-2测定， 测试条件为 23°C和 lOmm/min;
弯曲强度和弯曲模量： 根据 ISO 178测定， 测试条件为 23°C和 2mm/min; 缺口冲击强度：根据 ISO 180/1A测定，测试条件为 23°C，缺口类型为 A型。 无缺口冲击强度： 根据 ISO 180/1A测定， 测试条件为 23°C。
螺旋流动线长度： 采用自制阿基米德螺旋流动线模具， 流动槽宽 5mm， 高 2.5mm。
挠度： 参照 GB9341-2000塑料弯曲性能试验方法。
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 A1~A4: PA10T聚酰胺树脂 A的制备
在配有磁力偶合搅拌、 冷凝管、 气相口、 加料口、 压力防爆口的压力釜中按 表 1中的比例加入反应原料， 再加入苯甲酸、 次磷酸钠和去离子水； 次磷酸钠重 量为除去离子水外其他投料重量的 0.1%， 去离子水重量为总投料重量的 30%; 抽真空充入高纯氮气作为保护气， 在搅拌下 2小时内升温到 220°C， 将反应混合 物在 220°C搅拌 1 小时， 然后在搅拌下使反应物的温度升高到 230°C; 反应在
230°C的恒温和 2.2Mpa的恒压下继续进行 2小时， 通过移去所形成的水而保持 压力恒定，反应完成后出料，预聚物于 80°C下真空干燥 24小时，得到预聚产物， 所述预聚产物在 250°C、 50Pa真空条件下固相增粘 10小时， 得到 PA10T聚酰胺 树脂 A; 性能测试见表 1。
表 1
Figure imgf000005_0001
实施例 B1~B4: PA10T聚酰胺树脂 B的制备 在配有磁力偶合搅拌、 冷凝管、 气相口、 加料口、 压力防爆口的压力釜中按 表 2中的比例加入反应原料， 再加入苯甲酸、 次磷酸钠和去离子水； 次磷酸钠重 量为除去离子水外其他投料重量的 0.1%， 去离子水重量为总投料重量的 30%; 抽真空充入高纯氮气作为保护气， 在搅拌下 2小时内升温到 220°C， 将反应混合 物在 220°C搅拌 1 小时， 然后在搅拌下使反应物的温度升高到 230°C。 反应在 230°C的恒温和 2.2Mpa的恒压下继续进行 2小时， 通过移去所形成的水而保持 压力恒定，反应完成后出料，预聚物于 80°C下真空干燥 24小时，得到预聚产物， 所述预聚产物在 250°C、 50Pa真空条件下固相增粘 10小时， 得到 PA10T聚酰胺 树脂 B; 性能测试见表 2。
表 2
Figure imgf000006_0001
实施例 C1~C8和对比例 1~3： 聚酰胺组合物的制备
按表 3-4的配方将 PA10T聚酰胺树脂 A、 B、 钛白粉、 滑石粉、 其他助剂在 高混机中混合均匀后，通过主喂料口加入双螺杆挤出机中，增强填料通过侧喂料 秤侧喂， 挤出， 过水冷却， 造粒并干燥后得到所述聚酰胺组合物； 其中， 挤出温 度为 330°C。
表 3
Figure imgf000006_0002
5 15 29.8 10 10 9.8 15 15
B1 B2 B4 B3 B2 B1 B3 B1
PAIOT聚酰胺 B/wt%
94 80 50 50 50 50 72.8 69.8 钛白粉 /wt% 0.7 4.3 10 30 30 30.2 10 10 滑石粉 /wt% 0.1 0.5 9.8 9.8 9.8 9.8 2 5 抗氧剂 1098/wt% 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1
Licowax OP/wt% 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1 表观粘度 / Pa»s 90 81 48 107 84 53 79 75 螺旋流动线长度 /mm 500 556 938 421 536 849 570 600 拉伸强度 /MPa 43 46 29 52.2 50 46 52 55 断裂伸长率 /% 2.67 2.82 1.69 2.96 2.35 2.00 2.87 2.69 弯曲强度 /MPa 79.1 82.6 53.7 105.3 95.3 80.7 110 103 弯曲模量 /MPa 4650 4479 3842 4927 4836 4568 5012 4896 缺口冲击强度 /kJ/m2 4.1 3.7 2.6 4.8 4.3 3.5 4.9 4.6 无缺口冲击强度 /kJ/m2 18 11 8 25 21 12 28 24 挠度 /mm 4.8 3.9 2.6 5.7 5.1 3.8 6.1 5.6 表 4
Figure imgf000007_0001
断裂伸长率 /% 3.03 0.59 3.52 弯曲强度 /MPa 107.3 32.8 121.4 弯曲模量 /MPa 4719 2210 5638 缺口冲击强度 /kJ/m2 4.8 1.1 6.8
无缺口冲击强度 /kJ/m2 20 3 28
挠度 /mm 5.4 1.3 7.1 通过实施例和对比例的比较可以看出， 单独使用 PA10T聚酰胺树脂 B的表 观粘度为 180Pa*s，流动性不高；若在 PA10T聚酰胺 B中添加 40wt%PA10T聚酰 胺树脂 A， 添加量过多， 将导致树脂性能极大下降； 当在 PA10T聚酰胺 B中加 入 5~29.8^%的 PA10T聚酰胺树脂 A， 表观粘度能够大幅度降低， 流动性能得 到大幅度提高， 并且能基本保持与聚酰胺树脂 6T/66相当的力学性能。

Claims

权 利 要 求 书
1、 一种高流动性 PA10T聚酰胺树脂 A， 其特征在于： 所述 PA10T聚酰胺树脂 A 在 25°C， 98%浓硫酸中的相对粘度为 1.2-1.8; 所述 PA10T聚酰胺树脂 A的端氨 基值为 20-60mol/t， 端羧基值为 70-130mol/t; 所述 PA10T聚酰胺树脂 A中， 苯 甲酸占重复单元的比例为 2-20mol%。
2、根据权利要求 1所述的高流动性 PA10T聚酰胺树脂 A，其特征在于，所述 PA10T 聚酰胺树脂 A在 25°C， 98%浓硫酸中的相对粘度为 1.4-1.6; 所述 PA10T聚酰胺 树脂 A的端氨基值为 30-50mol/t， 端羧基值为 80-llOmol/t; 所述 PAIOT聚酰胺 树脂 A中， 苯甲酸占重复单元的比例为 4-20mol%。
3、一种包含权利要求 1~2任一项所述的高流动性 PA10T聚酰胺树脂 A的聚酰胺 组合物， 按重量百分数计， 包括如下组分：
PA10T聚酰胺树脂 A 5-29.8%；
PA10T聚酰胺树脂 B 50-94%； 矿物填料 0.8~40%； 其他助剂 0.2~1%； 其中，所述 PA10T聚酰胺树脂 B 在 25°C， 98%浓硫酸中的相对粘度为 2.0-2.4; 所述 PA10T聚酰胺树脂 B的端氨基值为 20-60mol/t， 端羧基值为 70-130mol/t; 所述 PA10T聚酰胺树脂 B中， 苯甲酸占重复单元的比例为 0.5-4mol%。
4、 根据权利要求 3所述的聚酰胺组合物， 其特征在于， 所述 PA10T聚酰胺树脂 B在 25°C， 98%浓硫酸中的相对粘度为 2.1-2.3; 所述 PA10T聚酰胺树脂 B的端 氨基值为 30-50mol/t， 端羧基值为 80-110mol/t; 所述 PA10T聚酰胺树脂 B中， 苯甲酸占重复单元的比例为 l-3.5mol%。
5、 根据权利要求 3所述的聚酰胺组合物， 其特征在于， 所述矿物填料选自二氧 化钛、 纳米氧化锌、 滑石粉的一种或几种混合物。
6、 根据权利要求 5所述的聚酰胺组合物， 其特征在于， 所述二氧化钛的粒径选 自 0.2-0.3um; 所述纳米氧化锌的纯度≥98%， 粒径选自 20-80 nm; 所述滑石粉的 粒径选自 500-2000目。
7、 根据权利要求 5所述的聚酰胺组合物， 其特征在于， 所述其它助剂选自抗氧 化剂、光稳定剂、流动改性剂的一种或几种混合物； 所述抗氧化剂选自受阻酚类 抗氧剂和 /或亚磷酸酯类抗氧剂； 所述光稳定剂选自二苯甲酮化合物、 水杨酸酯 化合物、苯丙三唑化合物的一种或几种混合物；所述流动改性剂选自 E蜡、 EBS、 褐煤酸钠盐、 超支化聚合物的一种或几种混合物。
8、 一种如权利要求 3所述的聚酰胺组合物的制备方法， 其特征在于， 包括如下 步骤： 将 PA10T聚酰胺树脂 A、 PA10T聚酰胺树脂 B、 矿物填料、 其他助剂置 于高混机中混合均匀后，通过主喂料口加入双螺杆挤出机中，增强填料通过侧喂 料秤侧喂， 在 310°C~330°C下， 挤出， 过水冷却， 造粒并干燥后得到产品。
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