CN113929902B - Coordination high-temperature-resistant polyamide material containing star-shaped crosslinking and preparation method thereof - Google Patents
Coordination high-temperature-resistant polyamide material containing star-shaped crosslinking and preparation method thereof Download PDFInfo
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- CN113929902B CN113929902B CN202111280041.7A CN202111280041A CN113929902B CN 113929902 B CN113929902 B CN 113929902B CN 202111280041 A CN202111280041 A CN 202111280041A CN 113929902 B CN113929902 B CN 113929902B
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- 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
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- 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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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Abstract
The invention discloses a coordination high-temperature resistant polyamide material containing star-shaped coordination crosslinking and a preparation method thereof.
Description
Technical Field
The invention relates to a coordination high-temperature-resistant polyamide material containing star-shaped cross-linking and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
With the development of industries such as 5G communication devices, electronic welding, surface mounting technology, automobile turbocharged engines and the like, higher requirements are continuously provided for the high temperature resistance and the mechanical property of polyamide (nylon), and the great development of the research on high-temperature nylon products is promoted. The melting temperature of the general aliphatic polyamide is lower than 260 ℃, and the requirements of the fields cannot be met. Wholly aromatic polyamides have excellent thermal properties and mechanical strength, but their high glass transition and melting temperatures make them impossible to process by low-cost melting, thereby limiting their wide-range applications. In recent years, semi-aromatic polyamides have attracted much attention due to their excellent processability in aliphatic polyamides and their excellent heat resistance in wholly aromatic polyamides, and for example, a common semi-aromatic polyamide is a copolymer of polyhexamethylene terephthalamide (PA 6T, melting temperature 370 ℃) and polyhexamethylene adipamide (PA 66), and such a high temperature resistant nylon material has improved high temperature resistance and is easy to process.
The coordination polymer is formed by embedding non-covalent interactions such as hydrogen bonds, coordination bonds, polyion bonds and the like in a polymer network structure. Non-covalent interaction is introduced into a macromolecular structure, which is beneficial to improving the mechanical property and widening the application range. The polymer network structure containing coordination bonds contains hydrogen bonds and coordination bonds, and after being stretched or compressed by an external force, the coordination bonds are firstly broken and slipped, so that the energy dissipation effect is achieved, and the important effect is achieved on the improvement of the mechanical strength of the polymer. Therefore, the coordination bond is introduced into the high-temperature-resistant nylon material, so that the mechanical property is improved.
The star-shaped polymer is a special structure of the polymer by connecting a plurality of linear branches to the same central core through chemical bonds. The branched polymer is also the simplest branched polymer, has smaller dynamic mechanical size in solution, has the characteristic of low viscosity of solution and bulk, and has important significance for processing the polymer. The star-shaped core is introduced into the coordination polyamide, so that the high temperature resistance, the mechanical property, the processing property and the like are improved, and the star-shaped coordination high temperature resistant polyamide material is constructed from the aspects of a network structure, a preparation material, a process and the like.
Disclosure of Invention
The prepared polyamide material simultaneously contains a star-shaped coordination cross-linked aromatic polyamide component and a star-shaped coordination cross-linked fatty polyamide component, has high temperature resistance and easy processability, and can be applied to aspects of engine accessories, reflow soldering and the like.
A preparation method of a coordination high-temperature resistant polyamide material containing star-shaped crosslinking comprises the following steps:
1) Taking 0.1-0.3 mass part of star-shaped nuclear polyacrylic acid, 0.8-1.2 mass part of aliphatic diamine, 0.4-0.7 mass part of aliphatic dibasic acid, 0.5-0.9 mass part of aromatic dibasic acid, 0.1-1 mass part of aromatic diamine, 0.01-0.1 mass part of coordination salt and 1.5-3.5 mass parts of solvent, dissolving the coordination salt, the aliphatic diamine, the aliphatic dibasic acid, the aromatic diamine and the aromatic dibasic acid in the solvent, heating to form a transparent coordination salt solution, adding the star-shaped nuclear polyacrylic acid into the transparent coordination salt solution, heating and dissolving to obtain a transparent salt liquid, namely solution A;
2) Adding the solution A into a polymerization kettle, and carrying out prepolymerization for 1-3 hours at 180-250 ℃; the temperature is increased to 280-300 ℃ for the second prepolymerization for 60-90 minutes; the temperature is increased to 300-335 ℃ for the third polymerization for 15-90 minutes;
3) The temperature is increased to 325 to 335 ℃, when the viscosity is between 1.8 to 2.3, nitrogen is injected under pressure, the pressure in the polymerization kettle is increased, the materials are extruded and discharged, and the materials are cut into particles, thus obtaining the star-shaped crosslinked coordination high-temperature resistant polyamide.
Further, the star-shaped core polyacrylic acid in the step 1) is one of low molecular weight polyacrylic acid, low molecular weight polyacrylic acid-co-acrylate, polyacrylic acid-coated nano silicon dioxide and polyacrylic acid-co-acrylate-coated nano silicon dioxide.
Further, the molecular weight of the low molecular weight polyacrylic acid in the step 1) is 500-3000; the diameter of the polyacrylic acid coated nano silicon dioxide is 50-150 nanometers; the diameter of the polyacrylic acid-co-acrylate coated nano silicon dioxide is 50-150 nanometers.
Further, the complex salt in the step 1) is one of zinc acetate, magnesium acetate and barium acetate.
Further, the aliphatic diamine in the step 1) is one of butanediamine, pentanediamine, hexanediamine, decanediamine and 2-methyl-hexanediamine.
Further, the aliphatic dibasic acid in the step 1) is one of succinic acid, glutaric acid, adipic acid, sebacic acid and 2-methyl-adipic acid.
Further, the aromatic diamine in the step 1) is one of p-xylylenediamine, o-xylylenediamine, and m-xylylenediamine.
Further, the aromatic dibasic acid in the step 1) is one of terephthalic acid, phthalic acid and isophthalic acid.
Further, the solvent in the step 1) is water.
Further, the heating temperature in the step 1) is 40-70 ℃, and the heating time is 0.5-1.5h.
Further, the pressure in the polymerizer described in the above step 3) was increased to 0.6 to 0.7MPa.
The application also protects a coordination high-temperature-resistant polyamide material containing star-shaped crosslinking prepared according to the preparation method.
The coordination high-temperature resistant polyamide material containing star-shaped crosslinking is prepared by a salifying-prepolymerization-dehydration condensation-adhesion method through processes of coordination salt monomers, star-shaped nuclei, prepolymerization and solid-phase adhesion, the prepared coordination high-temperature resistant polyamide material containing the star-shaped crosslinking comprises a star-shaped coordination aromatic polyamide component and a star-shaped coordination aliphatic polyamide component, the star-shaped coordination aromatic polyamide component in the coordination high-temperature resistant polyamide material containing the star-shaped crosslinking is grafted with the star-shaped coordination aliphatic polyamide component, and the opposite star-shaped coordination aliphatic polyamide component is grafted with the star-shaped coordination aromatic polyamide component to form the coordination crosslinking semi-crystalline high-temperature resistant polyamide material containing the star-shaped crosslinking.
Has the advantages that:
(1) The invention creatively utilizes the star-shaped core, the coordination salt, the aliphatic diamine, the aliphatic dibasic acid, the aromatic dibasic acid and the aromatic diamine to prepare the coordinate type high-temperature resistant polyamide material, and the viscosity of the high-temperature resistant polyamide can be controlled by adjusting the content of the salt, the pH value of the salt, the polymerization process and the tackifying process. The coordination type high-temperature-resistant polyamide material comprises coordination type aromatic polyamide and coordination type aliphatic polyamide, wherein a network component containing coordination aliphatic polyamide is grafted in the component structure of the coordination type aromatic polyamide to form a coordination crosslinking and crystallization type high-temperature-resistant polyamide material.
(2) The coordination type high-temperature-resistant polyamide prepared by the method has high-temperature resistance and easy processability, and can be applied to aspects such as engine accessories, reflow soldering and the like.
(3) The preparation process is simple, easy to control and convenient to operate, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a high temperature nylon melt diagram.
Detailed Description
In order to make the technical solutions in the present application better understood, the present invention is further illustrated with reference to the following examples, which are only a part of the examples of the present application, but not all of them, and the present invention is not limited by the following examples.
Example 1
1. Experimental procedure
1. Preparation of coordination high-temperature-resistant polyamide material containing star-shaped crosslinking
(1) Accurately weighing 1.1 parts by mass of hexamethylenediamine, 0.8 part by mass of adipic acid, 0.8 part by mass of terephthalic acid, 0.8 part by mass of p-xylylenediamine and 0.05 part by mass of zinc acetate, sequentially adding the materials into 1.5 parts by mass of aqueous solution at the temperature of 50 ℃, adjusting the pH of the solution to be =7.0, and heating the solution for 1 hour to form a transparent coordination salt solution;
(2) Heating and mixing the transparent coordination salt solution prepared in the step (1) and 0.1 part by mass (with the molecular weight of 1000) of star-shaped nuclear polyacrylic acid to form a colorless transparent salt solution A, adding the solution A into a polymerization kettle, and carrying out prepolymerization at 220 ℃ for 3 hours to prepolymerize to form polyamide with small molecular weight; carrying out secondary prepolymerization at 280-300 ℃ for 60 minutes; prepolymerizing at 300-335 ℃ for 15 minutes. And (3) flushing nitrogen, pressurizing, drawing strips, and cutting into granules to form the star-shaped cross-linked coordination type high-temperature resistant polyamide resin.
(3) Solid-phase tackifying: the resin was placed in a vacuum oven and polymerized for 6 hours under-0.1 MPa to further increase the molecular weight and the final viscosity was 2.4.
2. Preparation of nylon without aromatic monomer
Accurately weighing 1.1 parts by mass of hexamethylenediamine, 0.8 parts by mass of adipic acid and 0.05 parts by mass of zinc acetate, sequentially adding into 1.5 parts by mass of an aqueous solution at the temperature of 50 ℃, adjusting the pH of the solution to =7.0, heating for 1 hour to form a transparent coordination salt solution, and carrying out the same polymerization process as described above.
2. Analysis of results
The melting point of the polyamide is about 305 ℃ (figure 1), the heat resistance of the polyamide can be improved by introducing aromatic monomers, and the melting point of the nylon without introducing aromatic monomers is about 260 ℃. This polyamide strip was tested according to the national standard (GB/T1043-2008): the tensile strength is about 45MPa, the bending strength is about 48MPa, and the notch impact strength (23 ℃) is more than or equal to 10KJ per square meter. The coordination salt and the star-shaped core can improve the crosslinking performance of the polyamide and improve the mechanical property of the polyamide compared with the polyamide without the addition of the coordination salt and the star-shaped core.
Example 2
1. Resin for preparing star-shaped cross-linked coordination type high-temperature-resistant polyamide
(1) Accurately weighing 0.5 part by mass of hexamethylene diamine, 0.8 part by mass of terephthalic acid, 0.5 part by mass of p-xylylenediamine, 1.5 parts by mass of water and 0.05 part by mass of zinc acetate, sequentially adding the materials into 1.5 parts by mass of aqueous solution, adjusting the pH of the solution to be =7.0, and heating the solution for 1.5 hours to form a transparent coordination salt solution.
(2) Heating and mixing the transparent coordination salt solution prepared in the step (1) and 0.1 part (with the molecular weight of 1000) of star-shaped nuclear polyacrylic acid-co-acrylic ester to form a transparent solution B, adding the solution B into a polymerization kettle, and carrying out prepolymerization at 220 ℃ for 3 hours to prepolymerize to form polyamide with small molecular weight; carrying out secondary prepolymerization for 60 minutes at 280-300 ℃; prepolymerizing at 300-335 deg.C for 15 min. And (3) flushing nitrogen, pressurizing, drawing strips, and cutting into granules to form the star-shaped cross-linked coordination type high-temperature resistant polyamide resin.
(3) Solid-phase tackifying: the resin was placed in a vacuum oven and polymerized for 6 hours under-0.1 MPa to further increase the molecular weight and the final viscosity was 2.6.
2. Analysis of Material Properties
This polyamide strip was tested according to the national standard (GB/T1043-2008): the tensile strength is about 47MPa, the bending strength is about 49MPa, and the notch impact strength (23 ℃) is more than or equal to 10KJ per square meter. The coordination salt and the star-shaped core can improve the crosslinking performance of the polyamide and improve the mechanical property of the polyamide compared with the polyamide without the addition of the coordination salt and the star-shaped core.
The melting point analysis was carried out in the same manner as in example 1, and the melting point was measured at 306 ℃.
Claims (7)
1. A preparation method of a coordination high-temperature resistant polyamide material containing star-shaped crosslinking is characterized by comprising the following steps:
1) Taking 0.1 to 0.3 mass part of star-shaped nuclear polyacrylic acid, 0.8 to 1.2 mass parts of aliphatic diamine, 0.4 to 0.7 mass part of aliphatic dibasic acid, 0.5 to 0.9 mass part of aromatic dibasic acid, 0.1 to 1 mass part of aromatic diamine, 0.01 to 0.1 mass part of coordination salt and 1.5 to 3.5 mass parts of solvent, dissolving the coordination salt, the aliphatic diamine, the aliphatic dibasic acid, the aromatic diamine and the aromatic dibasic acid in water, heating to form a transparent coordination salt solution, adding the star-shaped nuclear polyacrylic acid into the transparent coordination salt solution, and heating to dissolve to obtain a transparent salt liquid, namely a solution A;
the star-shaped nuclear polyacrylic acid is one of low-molecular-weight polyacrylic acid, low-molecular-weight polyacrylic acid-co-acrylate, polyacrylic acid-coated nano silicon dioxide and polyacrylic acid-co-acrylate-coated nano silicon dioxide; the molecular weight of the low molecular weight polyacrylic acid is 500 to 3000; the diameter of the polyacrylic acid-coated nano silicon dioxide is 50 to 150 nanometers; the diameter of the polyacrylic acid-co-acrylate coated nano silicon dioxide is 50 to 150 nanometers;
the coordination salt is one of zinc acetate, magnesium acetate and barium acetate;
2) Adding the solution A into a polymerization kettle, and carrying out prepolymerization for 1-3 hours at 180-250 ℃; raising the temperature to 280-300 ℃ for second prepolymerization for 60-90 minutes; the temperature is increased to 300 to 335 ℃, and polymerization is carried out for the third time for 15 to 90 minutes;
3) Increasing the temperature to 325 to 335 ℃, when the viscosity is between 1.8 to 2.3, pressurizing and charging nitrogen, increasing the pressure in the polymerization kettle to 0.6 to 0.7MPa, extruding and discharging, and pelletizing to obtain the star-shaped crosslinked coordination high-temperature resistant polyamide.
2. The method of claim 1, wherein the aliphatic diamine in step 1) is one of butanediamine, pentanediamine, hexanediamine, decanediamine, and 2-methyl-hexanediamine.
3. The method according to claim 1, wherein the aliphatic dibasic acid in step 1) is one of succinic acid, glutaric acid, adipic acid, sebacic acid, and 2-methyl-adipic acid.
4. The method according to claim 1, wherein the aromatic diamine in the step 1) is one of p-xylylenediamine, o-xylylenediamine, and m-xylylenediamine.
5. The method according to claim 1, wherein the aromatic dibasic acid in the step 1) is one of terephthalic acid, phthalic acid and isophthalic acid.
6. The method of claim 1, wherein the heating in step 1) is carried out at a temperature of 40 to 70 ℃ for a time of 0.5 to 1.5 hours.
7. A coordinated high temperature resistant polyamide material containing "star" crosslinks prepared according to the preparation method of claim 1.
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