阅读说明：本技术 一种聚酰胺合金材料的制备方法 (Preparation method of polyamide alloy material ) 是由 梁寅 孙茂银 吴健 吴泽宏 于 2020-08-19 设计创作，主要内容包括：本发明公开了一种聚酰胺合金材料的制备方法,属于聚合物材料制备、改性领域,其包括如下步骤：将两种或多种聚酰胺材料溶于合适的卤代试剂溶液中,超声搅拌,并加入适宜的催化剂,使聚酰胺端羧基得到活化,生成酰卤,酰卤与其他聚酰胺的—NH2反应,生成酰胺合金桥,链接基体材料合金组分；50～100℃回流1～2h,反应结束后将混合溶液加热至80～150℃,蒸发掉反应剩余的卤代试剂；然后加入纳米形核剂并使其均匀分散在溶液中,控制适宜的降温速率使合金材料析出球形或类球形粉体并干燥,制备得到完全相容的多功能、高性能聚酰胺合金材料。本发明克服了传统方法中改性剂不能与基体材料完全相容的局限性。(The invention discloses a preparation method of a polyamide alloy material, belonging to the field of preparation and modification of polymer materials and comprising the following steps: dissolving two or more polyamide materials in a proper halogenated reagent solution, ultrasonically stirring, adding a proper catalyst to activate carboxyl at the end of polyamide to generate acyl halide, and reacting the acyl halide with-NH 2 of other polyamide to generate an amide alloy bridge to link alloy components of the base material; refluxing for 1-2 h at 50-100 ℃, heating the mixed solution to 80-150 ℃ after the reaction is finished, and evaporating the residual halogenated reagent in the reaction; then adding a nano nucleating agent and uniformly dispersing the nano nucleating agent in the solution, controlling a proper cooling rate to separate out spherical or spheroidal powder from the alloy material and drying the spherical or spheroidal powder to prepare the completely compatible multifunctional and high-performance polyamide alloy material. The invention overcomes the limitation that the modifier can not be completely compatible with the matrix material in the traditional method.)

1. The preparation method of the polyamide alloy material is characterized by comprising the following steps of:

(1) dissolving two or more polyamide materials in a halogenated reagent solution, ultrasonically stirring, adding a catalyst to activate carboxyl at the end of the polyamide to generate acyl halide, and reacting the acyl halide with-NH 2 of other polyamide to generate an amide alloy bridge to link the alloy components of the base material;

(2) refluxing the mixture at 50-100 ℃ for 1-2 h, heating the mixed solution to 80-150 ℃ after the reaction is finished, and evaporating the residual halogenated reagent in the reaction;

(3) and (3) adding a nano nucleating agent into the solution for removing the excessive halogenated reagent, uniformly dispersing the nano nucleating agent into the solution, controlling a proper cooling rate to separate out spherical or spheroidal powder from the alloy material, and drying to prepare the polyamide alloy material.

2. The method for preparing a polyamide alloy material as claimed in claim 1, wherein the polyamide material comprises one of PA12, PA11, PA13, PA6, PA66, PA610, PA1010, PA1012, PA1013, PA6T, PA12T, and it is required that terminal carboxyl groups are present.

3. The method of claim 2, wherein the halogenating agent comprises one or more of phosphorus tribromide, phosphorus pentabromide, hydrobromic acid, phosphorus trichloride, phosphorus pentachloride, thionyl chloride and oxalyl chloride.

4. The method of claim 3, wherein the catalyst comprises one or more of N, N-dimethylformamide, N-methylacetamide, N-phenylmethylacetamide, 1-hydroxybenzotriazole, 4-dimethylaminopyridine, and 4-pyrrolidinopyridine.

5. The method for preparing polyamide alloy material as claimed in claim 4, wherein the nano nucleating agent comprises one or more of nano zinc oxide, nano silicon dioxide, nano titanium dioxide and nano silicone powder treated by coupling agent.

6. The method as claimed in claim 5, wherein the coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, aluminate coupling agents, and titanate coupling agents.

Technical Field

The invention relates to a preparation method of a polyamide alloy material, belonging to the field of preparation and modification of polymer materials.

Background

The polyamide is a general name of a high-molecular polymer containing amide groups, and is commonly called nylon. The polyamide is a multi-variety of high polymer materials, and mainly comprises aliphatic polyamide, aromatic polyamide and semi-aromatic polyamide. Polyamide is an excellent engineering plastic and is widely used in the fields of machinery industry, household appliances, artificial fibers and the like. The single type of polyamide material only has single mechanical property, forming property, corrosion resistance and the like, and with the rapid development of various fields of automobile industry, mechanical industry, aerospace and the like in China, the single-property material cannot meet the application requirement, so that the development of the material with excellent comprehensive performance is needed. At present, in practical application, the widely used polyamide modification method is added with a compatibilizer, a coupling agent, a binder and the like to improve the compatibility of the modification aid and the matrix polyamide material, so that certain properties of the matrix material are improved. These methods can achieve a certain modification effect, but because of the defects in the modification site, the modifier is not completely compatible with the matrix material, and the modification effect has a certain limitation.

Disclosure of Invention

The invention provides a preparation method of a polyamide alloy material with complete compatibility, multiple functions and high performance aiming at the limitations of the prior polyamide alloying modification technology.

The preparation method of the polyamide alloy material comprises the following steps:

(1) dissolving two or more polyamide materials in a halogenated reagent solution, ultrasonically stirring, adding a catalyst to activate carboxyl at the end of the polyamide to generate acyl halide, and reacting the acyl halide with-NH 2 of other polyamide to generate an amide alloy bridge to link the alloy components of the base material;

(2) refluxing the mixture at 50-100 ℃ for 1-2 h, heating the mixed solution to 80-150 ℃ after the reaction is finished, and evaporating the residual halogenated reagent in the reaction;

(3) and (3) adding a nano nucleating agent into the solution for removing the excessive halogenated reagent, uniformly dispersing the nano nucleating agent into the solution, controlling a proper cooling rate to separate out spherical or spheroidal powder from the alloy material, and drying to prepare the polyamide alloy material.

The preparation method of the polyamide alloy material comprises the following steps: the polyamide material comprises one of PA12, PA11, PA13, PA6, PA66, PA610, PA1010, PA1012, PA1013, PA6T, PA12T, and requires the presence of terminal carboxyl groups thereof.

The preparation method of the polyamide alloy material comprises the following steps: the halogenating agent comprises one or more of phosphorus tribromide, phosphorus pentabromide, hydrobromic acid, phosphorus trichloride, phosphorus pentachloride, thionyl chloride and oxalyl chloride.

The preparation method of the polyamide alloy material comprises the following steps: the catalyst comprises one or more of N, N-dimethylformamide, N-methylacetamide, N-phenylmethylacetamide, 1-hydroxybenzotriazole, 4-dimethylaminopyridine and 4-pyrrolidinylpyridine.

The preparation method of the polyamide alloy material comprises the following steps: the nano nucleating agent comprises one or more of nano zinc oxide, nano silicon dioxide, nano titanium dioxide and nano silicone powder which are treated by a coupling agent.

The preparation method of the polyamide alloy material comprises the following steps: the coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, an aluminate coupling agent and a titanate coupling agent.

The preparation method of the polyamide alloy material disclosed by the invention utilizes a halogenating reagent to activate carboxyl to generate acyl halide, utilizes condensation reaction of the acyl halide and terminal amino, utilizes the formed amide alloy bridge to link two or more polyamide chain segments, and fully modifies the effect from a molecular level to prepare the completely compatible integrated multifunctional polyamide alloy.

Detailed Description