CN110982063A - Semi-aromatic polyamide resin and preparation method thereof - Google Patents
Semi-aromatic polyamide resin and preparation method thereof Download PDFInfo
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- CN110982063A CN110982063A CN201911238123.8A CN201911238123A CN110982063A CN 110982063 A CN110982063 A CN 110982063A CN 201911238123 A CN201911238123 A CN 201911238123A CN 110982063 A CN110982063 A CN 110982063A
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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
- 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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- 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
- C08G69/28—Preparatory processes
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Abstract
The invention discloses a semi-aromatic polyamide resin and a preparation method thereof. The semi-aromatic polyamide resin comprises 20-80 parts of aromatic/aliphatic dibasic acid; 20-80 parts of aliphatic diamine; 0.05-1 part of hindered phenol or hindered amine; 0.01-0.06 parts of catalyst; 30-160 parts of deionized water (all parts by weight); in the aromatic/aliphatic dibasic acid, the mass ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1: (0 to 9). According to the invention, the hindered phenol or hindered amine chemical group is chemically bonded to the tail end of the polyamide molecular chain, so that the loss of the hindered phenol or hindered amine chemical group in a low-temperature environment is reduced, and the addition of the processing aid in the later modification processing process does not cause the phenomenon of agglomeration or uneven dispersion of a heat stabilizer during modification, so that the production cost is reduced, the product has better thermal stability at higher temperature and for longer time, and the mechanical property and the quality of the product are improved.
Description
Technical Field
The invention relates to the technical field of synthesis of high polymer materials, and particularly relates to semi-aromatic polyamide resin and a preparation method thereof.
Background
Polyamide, commonly known as nylon and known by the English name Polyamide, is a generic name for polymers containing amide groups in the repeating units of the macromolecular main chain. Can be prepared by ring-opening polymerization of lactam or polycondensation of diamine and dibasic acid. The polyamide has high impact strength, excellent wear resistance, heat resistance, chemical resistance, lubricity, dyeing property and the like, and particularly the strength, product precision, dimensional stability and the like of the polyamide are greatly improved after the polyamide is enhanced or alloy modified, so that the polyamide is widely applied to the fields of machinery, automobiles, electric appliances, textile equipment, chemical equipment, aviation, metallurgy and the like.
The polyamide is in various varieties, such as common nylon, e.g. PA6 and PA66, long carbon chain nylon, e.g. PA11, PA12, PA610, PA612 and PA PAl010, high temperature nylon, e.g. PA46, semi-aromatic nylon, wholly aromatic nylon and the like. The most widely used of the materials are ordinary nylon PA6 and PA66, which have very large dosage in the fields of spinning, engineering plastics, films and the like due to excellent comprehensive performance and lower raw material cost. However, in places where heat resistance is required, such as Surface Mount Technology (SMT) and fuel systems, exhaust systems, cooling systems, etc. near engines in the automobile industry, the processing temperature or the use temperature exceeds the long-term use temperature or even the melting point of ordinary nylon, and thus the use requirements of these applications cannot be met, and nylon varieties with higher temperature resistance are required.
The carboxyl end group, amine end group and amide functional group of the polyamide have high reactivity, and aging, amide bond breakage and cyclopentanone, CO and CO generation are caused by factors such as heat, ultraviolet rays, oxygen, moisture in the atmosphere and the like in the processing and using processes2And the main chain is cut off, the molecular weight is reduced, various properties of the product are reduced, and the product quality and the later use process are greatly influenced.
The conventional solution is to improve the thermal stability of the product by blending various heat stabilizers such as hindered phenol, hindered amine and the like in the plastic processing modification process, for example, CN101735609A, CN106751794A and CN110437612A are polyamide resins obtained by polymerizing dibasic acid and diamine, and then hindered phenol and hindered amine are added for physical blending. However, in the actual production process, the addition amount of the heat stabilizer is small, so that the dispersion is easy to be uneven, and in order to ensure that products produced in different periods have good heat stability, the addition amount of the heat stabilizer needs to be increased, and the operation of the operation with higher cost of the heat stabilizer undoubtedly increases the production cost of the products. The low molecular weight of the heat stabilizer can lead the product to become brittle and the mechanical property to be reduced, and the reduction degree is in direct proportion to the addition amount of the heat stabilizer. In addition, the low molecular weight of the heat stabilizer reduces the heat resistance of the heat stabilizer, i.e., the heat stabilizer starts oxidative decomposition at a relatively low temperature, and cannot achieve the effect of heat stabilization of the polymer product at a high temperature. And the heat stabilizer added by the blending mode has weak bonding force with the polymer, is easy to precipitate in the later use process, and cannot play a long-term heat stabilization effect.
Disclosure of Invention
One of the purposes of the invention is to prepare a semi-aromatic polyamide resin with excellent thermal stability, wherein a hindered phenol or hindered amine chemical group is chemically bonded to the tail end of a polyamide molecular chain, so that the loss of the hindered phenol or hindered amine chemical group in a low-temperature environment is reduced, the addition of processing aids such as antioxidants and heat stabilizers in the later modification processing process is reduced, the phenomenon of thermal stabilizer agglomeration or uneven dispersion in the modification process is avoided, the production cost is reduced, the product has better thermal stability at higher temperature and in longer time, and the mechanical property and the product quality of the product are improved.
In order to achieve the above object, the present invention provides a semi-aromatic polyamide resin, comprising the following components in parts by weight:
in the aromatic/aliphatic dibasic acid, the mass ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1: (0 to 9); preferably, the mass ratio is 1: (0-5).
Further, the paint comprises the following components in parts by weight:
further, the aromatic dibasic acid is one or a mixture of more of terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; preferably, the aromatic dibasic acid is one or more of terephthalic acid and isophthalic acid.
Further, the aliphatic dibasic acid is one or a mixture of more of succinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid or tridecanedioic acid; preferably, the aliphatic dibasic acid is one or more of adipic acid and sebacic acid.
Further, the aliphatic diamine is one or a mixture of more of butanediamine, pentanediamine, 2-methylpentanediamine, hexanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine or tridecanediamine; preferably, the aliphatic diamine is at least one of butanediamine, hexanediamine and decanediamine.
Further, the hindered phenol is one or a mixture of more of 2-methyl-6-tert-butyl-4-aminophenol, 2, 6-dimethyl-4-aminophenol, 2, 6-diethyl-4-aminophenol, 2, 6-di-tert-butyl-4-aminophenol and 4- (2-aminoethyl) -2, 6-dimethoxyphenol; preferably, the hindered phenol is one or more of 2, 6-di-tert-butyl-4-aminophenol and 4- (2-aminoethyl) -2, 6-dimethoxyphenol.
Further, the hindered amine is one or a mixture of several of N, N '-diisopropyl-4-amino aniline, N' -diphenyl-4-amino aniline, N '-di (2-naphthyl) -4-amino aniline, N-phenyl-N' -isopropyl-4-amino aniline, 2,6, 6-tetramethyl piperidine amine, 2,6, 6-tetra-tert-butyl piperidine amine and 2, 6-di-tert-butyl pyridine amine; preferably, the hindered amine is one or more of N, N' -diisopropyl-4-amino aniline, 2,6, 6-tetramethyl piperidine amine, and 2, 6-di-tert-butyl pyridine amine.
Further, the catalyst is one or a mixture of more of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite; preferably, the catalyst is more than one of sodium phosphite and sodium hypophosphite.
Further, the preparation method comprises the following steps of,
s1: weighing required aromatic/aliphatic dibasic acid, aliphatic diamine, hindered phenol or hindered amine, a catalyst and deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle to remove residual air in the reaction kettle, and keeping micro-positive pressure in the high-pressure reaction kettle after replacement is finished; preferably, the micro-positive pressure is 10-50 kPa;
s2: heating the high-pressure reaction kettle under the stirring condition, carrying out constant-temperature reaction, then continuously heating, continuously heating when the pressure reaches 1.2-5MPa, starting to release water vapor in the high-pressure reaction kettle to enable the interior of the high-pressure reaction kettle to be in a constant-pressure state, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure when the temperature is raised to 340 ℃;
preferably, the step S2 is that the high-pressure reaction kettle is heated to 60-150 ℃ under the stirring condition of 30-300r/min, the constant-temperature reaction is carried out for 1-3h, then the temperature is continuously raised to 250 ℃ under 200-5 MPa, the temperature is continuously raised while the high-pressure reaction kettle is in a constant-pressure state by a method of releasing water vapor in the high-pressure reaction kettle, and the pressure is slowly released to the normal pressure after the temperature is raised to 340 ℃ under 240-2 h;
s3: filling nitrogen into the high-pressure reaction kettle; preferably, nitrogen is filled to the pressure of 0.2-2.5MPa, and the material is extruded from a die head, pulled into strips and cut into granules to obtain the semi-aromatic polyamide resin granules.
The present invention also provides a method for preparing the semi-aromatic polyamide resin, comprising the steps of,
s1: weighing required aromatic/aliphatic dibasic acid, aliphatic diamine, hindered phenol or hindered amine, a catalyst and deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle to remove residual air in the reaction kettle, and keeping micro-positive pressure in the high-pressure reaction kettle after replacement is finished; preferably, the micro-positive pressure is 10-50 kPa;
s2: heating the high-pressure reaction kettle under the stirring condition, carrying out constant-temperature reaction, then continuously heating, continuously heating when the pressure reaches 1.2-5MPa, starting to release water vapor in the high-pressure reaction kettle to enable the interior of the high-pressure reaction kettle to be in a constant-pressure state, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure when the temperature is raised to 340 ℃;
preferably, the step S2 is that the high-pressure reaction kettle is heated to 60-150 ℃ under the stirring condition of 30-300r/min, the constant-temperature reaction is carried out for 1-3h, then the temperature is continuously raised to 250 ℃ under 200-5 MPa, the temperature is continuously raised while the high-pressure reaction kettle is in a constant-pressure state by a method of releasing water vapor in the high-pressure reaction kettle, and the pressure is slowly released to the normal pressure after the temperature is raised to 340 ℃ under 240-2 h;
s3: filling nitrogen into the high-pressure reaction kettle; preferably, nitrogen is filled to the pressure of 0.2-2.5MPa, and the material is extruded from a die head, pulled into strips and cut into granules to obtain the semi-aromatic polyamide resin granules.
When the aliphatic diamine is a long-carbon-chain diamine (such as decamethylene diamine, etc.), the aromatic/aliphatic dibasic acid can be only aromatic dibasic acid, but not aliphatic dibasic acid (at this time, the melting point and the heat resistance of the product are reduced by adding the aliphatic dibasic acid); when the aliphatic diamine is short-chain diamine (such as hexamethylene diamine), aliphatic dicarboxylic acid is required in the aromatic/aliphatic dicarboxylic acid (the melting point of a product obtained without adding the aliphatic dicarboxylic acid is higher than the decomposition temperature, and the product cannot be subjected to melt processing), and on the contrary, too much aliphatic dicarboxylic acid cannot be added, so that the melting point and the heat resistance of the product are reduced.
In the aromatic/aliphatic dibasic acid, the mass ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1: (0 to 9); preferably, the mass ratio is 1: (0-5). If the content of the aromatic dibasic acid is too high, the melting point of the product is too high and the processing performance is poor if the content of the aromatic dibasic acid is over the range, and if the content of the aliphatic dibasic acid is too high, the heat resistance of the product is poor if the content of the aliphatic dibasic acid is over the range, so that the use requirement cannot be met.
The amine end groups on the hindered amine or hindered phenol react with the carboxyl at the tail end of the polyamide molecular chain, the activity is high, and the amine end groups and the carboxyl form amide bonds to the tail end of the polyamide molecular chain after the reaction.
Compared with the prior art, the invention has the following advantages:
according to the invention, hindered phenol or hindered amine chemical groups are connected to the tail end of a polyamide molecular chain through chemical bonds, and due to the existence of the groups, a polyamide product has excellent thermal stability, cannot be separated out in the later use process, and has the long-term thermal stability effect.
According to the invention, the hindered phenol or hindered amine chemical group is connected to the tail end of the polyamide molecular chain through a chemical bond, and the great bond of the chemical bond can increase the thermal stability of the hindered phenol and hindered amine molecules, reduce the loss of the hindered phenol and hindered amine chemical group in a low-temperature environment, and enable the product to have better thermal stability at higher temperature and for longer time.
According to the invention, the hindered phenol and hindered amine chemical groups are connected to the tail end of the polyamide molecular chain through chemical bonds, and the phenomenon of agglomeration or uneven dispersion of the added heat stabilizer in the modification process is avoided, so that the product has stable heat resistance.
According to the invention, the hindered phenol and hindered amine chemical groups are connected to the tail end of the polyamide molecular chain through chemical bonds, the phenomenon of agglomeration or uneven dispersion of the added heat stabilizer in the modification process is avoided, the desired thermal stability can be achieved by adding a small amount of hindered amine or hindered phenol, the use amount of the hindered amine or hindered phenol is reduced, and the mechanical property of the product is improved.
According to the invention, the hindered phenol and hindered amine chemical groups are connected to the tail end of the polyamide molecular chain through chemical bonds, so that the phenomenon of agglomeration or uneven dispersion of the heat stabilizer added in the modification process is avoided, the addition of processing aids such as antioxidant and heat stabilizer in the later modification processing process is reduced, the production cost is reduced, and the product competitiveness is increased.
According to the invention, the hindered phenol and hindered amine chemical groups are connected to the tail end of the polyamide molecular chain through chemical bonds, so that the phenomenon of agglomeration or uneven dispersion of the heat stabilizer added in the modification process is avoided, the addition of processing aids such as antioxidant and heat stabilizer in the later modification processing process is reduced, the addition of powder filler is reduced, and the improvement of the workshop environment in the processing process is facilitated.
The hindered phenol and hindered amine added in the invention replace aliphatic diamine to react with carboxyl at the tail end of a polyamide molecular chain to generate a chemical bond, so that the amino content at the tail end of the original molecular chain is reduced, the aging performance of the product is improved, and the thermal stability is improved.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The invention provides a semi-aromatic polyamide resin which is characterized by comprising the following components in parts by weight:
in the aromatic/aliphatic dibasic acid, the mass ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1: (0 to 9); preferably, the mass ratio is 1: (0-5).
Further, the paint comprises the following components in parts by weight:
further, the aromatic dibasic acid is one or a mixture of more of terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; preferably, the aromatic dibasic acid is one or more of terephthalic acid and isophthalic acid.
Further, the aliphatic dibasic acid is one or a mixture of more of succinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid or tridecanedioic acid; preferably, the aliphatic dibasic acid is one or more of adipic acid and sebacic acid.
Further, the aliphatic diamine is one or a mixture of more of butanediamine, pentanediamine, 2-methylpentanediamine, hexanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine or tridecanediamine; preferably, the aliphatic diamine is at least one of butanediamine, hexanediamine and decanediamine.
Further, the hindered phenol is one or a mixture of more of 2-methyl-6-tert-butyl-4-aminophenol, 2, 6-dimethyl-4-aminophenol, 2, 6-diethyl-4-aminophenol, 2, 6-di-tert-butyl-4-aminophenol and 4- (2-aminoethyl) -2, 6-dimethoxyphenol; preferably, the hindered phenol is one or more of 2, 6-di-tert-butyl-4-aminophenol and 4- (2-aminoethyl) -2, 6-dimethoxyphenol.
Further, the hindered amine is one or a mixture of several of N, N '-diisopropyl-4-amino aniline, N' -diphenyl-4-amino aniline, N '-di (2-naphthyl) -4-amino aniline, N-phenyl-N' -isopropyl-4-amino aniline, 2,6, 6-tetramethyl piperidine amine, 2,6, 6-tetra-tert-butyl piperidine amine and 2, 6-di-tert-butyl pyridine amine; preferably, the hindered amine is one or more of N, N' -diisopropyl-4-amino aniline, 2,6, 6-tetramethyl piperidine amine, and 2, 6-di-tert-butyl pyridine amine.
Further, the catalyst is one or a mixture of more of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite; preferably, the catalyst is more than one of sodium phosphite and sodium hypophosphite.
Further, the preparation method comprises the following steps of,
s1: weighing required aromatic/aliphatic dibasic acid, aliphatic diamine, hindered phenol or hindered amine, a catalyst and deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle to remove residual air in the reaction kettle, and keeping micro-positive pressure in the high-pressure reaction kettle after replacement is finished; preferably, the micro-positive pressure is 10-50 kPa;
s2: heating the high-pressure reaction kettle under the stirring condition, carrying out constant-temperature reaction, then continuously heating, continuously heating when the pressure reaches 1.2-5MPa, starting to release water vapor in the high-pressure reaction kettle to enable the interior of the high-pressure reaction kettle to be in a constant-pressure state, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure when the temperature is raised to 340 ℃;
preferably, the step S2 is that the high-pressure reaction kettle is heated to 60-150 ℃ under the stirring condition of 30-300r/min, the constant-temperature reaction is carried out for 1-3h, then the temperature is continuously raised to 250 ℃ under 200-5 MPa, the temperature is continuously raised while the high-pressure reaction kettle is in a constant-pressure state by a method of releasing water vapor in the high-pressure reaction kettle, and the pressure is slowly released to the normal pressure after the temperature is raised to 340 ℃ under 240-2 h;
s3: filling nitrogen into the high-pressure reaction kettle; preferably, nitrogen is filled to the pressure of 0.2-2.5MPa, and the material is extruded from a die head, pulled into strips and cut into granules to obtain the semi-aromatic polyamide resin granules.
A method for producing the semi-aromatic polyamide resin, characterized by comprising the steps of,
s1: weighing required aromatic/aliphatic dibasic acid, aliphatic diamine, hindered phenol or hindered amine, a catalyst and deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle to remove residual air in the reaction kettle, and keeping micro-positive pressure in the high-pressure reaction kettle after replacement is finished; preferably, the micro-positive pressure is 10-50 kPa;
s2: heating the high-pressure reaction kettle under the stirring condition, carrying out constant-temperature reaction, then continuously heating, continuously heating when the pressure reaches 1.2-5MPa, starting to release water vapor in the high-pressure reaction kettle to enable the interior of the high-pressure reaction kettle to be in a constant-pressure state, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure when the temperature is raised to 340 ℃;
preferably, the step S2 is that the high-pressure reaction kettle is heated to 60-150 ℃ under the stirring condition of 30-300r/min, the constant-temperature reaction is carried out for 1-3h, then the temperature is continuously raised to 250 ℃ under 200-5 MPa, the temperature is continuously raised while the high-pressure reaction kettle is in a constant-pressure state by a method of releasing water vapor in the high-pressure reaction kettle, and the pressure is slowly released to the normal pressure after the temperature is raised to 340 ℃ under 240-2 h;
s3: filling nitrogen into the high-pressure reaction kettle; preferably, nitrogen is filled to the pressure of 0.2-2.5MPa, and the material is extruded from a die head, pulled into strips and cut into granules to obtain the semi-aromatic polyamide resin granules.
In the following examples:
and (3) testing the content of the terminal amino group: titrating the content of the terminal amino group of the polyamide resin by using a full-automatic potentiometric titrator, taking 0.5g of polymer, adding 50mL of m-cresol, heating and stirring for 1h at the temperature of 65 ℃ to completely dissolve the sample, adding 33mL of isopropanol into the dissolved sample, and titrating the content of the terminal amino group by using a perchloric acid-ethanol standard titration solution.
And (3) yellowing resistance test: the polyamide resin to be tested was dried in a forced air oven at 180 ℃ for 2h and then tested for b value using a yellowness index colorimeter.
Comparative example 1
(1) 830.7g of terephthalic acid, 730.7g of adipic acid, 1138.9g of hexamethylenediamine, 1g of catalyst sodium hypophosphite and 1200g of deionized water are weighed and added into a high-pressure reaction kettle, the high-pressure reaction kettle is vacuumized and filled with nitrogen, residual air in the reaction kettle is removed by repeating the steps for three times, and the high-pressure reaction kettle keeps micro-positive pressure of 25kPa after replacement is completed;
(2) heating the high-pressure reaction kettle to 100 ℃ under the stirring condition of 100r/min, reacting at a constant temperature for 1.5h, then continuously heating to 235 ℃, continuously increasing the temperature and starting to make the interior of the high-pressure reaction kettle in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle after the pressure reaches 2.5MPa, and slowly releasing the pressure of the high-pressure reaction kettle to the normal pressure within 1h when the temperature is increased to 300 ℃;
(3) and (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.8MPa, extruding, bracing and cutting the materials from a die head to obtain PA6T/66 polyamide resin particles.
Example 1
(1) Weighing 830.7g of terephthalic acid, 730.7g of adipic acid, 1137.7g of hexamethylenediamine, 2.5g of hindered phenol 2, 6-di-tert-butyl-4-aminophenol, 1g of catalyst sodium hypophosphite and 1200g of deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle, repeating the steps for three times to remove residual air in the reaction kettle, and keeping the micro-positive pressure of the high-pressure reaction kettle at 25kPa after replacement is completed;
(2) heating the high-pressure reaction kettle to 100 ℃ under the stirring condition of 100r/min, reacting at a constant temperature for 1.5h, then continuously heating to 235 ℃, continuously increasing the temperature and starting to make the interior of the high-pressure reaction kettle in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle after the pressure reaches 2.5MPa, and slowly releasing the pressure of the high-pressure reaction kettle to the normal pressure within 1h when the temperature is increased to 300 ℃;
(3) and (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.8MPa, extruding, bracing and cutting the materials from a die head to obtain PA6T/66 polyamide resin particles with excellent thermal stability.
Example 2
(1) 1661.3g of terephthalic acid, 1686.9g of decamethylene diamine, 2.5g of hindered amine 2,2,6, 6-tetramethyl piperidine amine, 1.3g of catalyst sodium phosphite and 2000g of deionized water are weighed and added into a high-pressure reaction kettle, the high-pressure reaction kettle is vacuumized and filled with nitrogen, the residual air in the reaction kettle is removed by repeating three times, and the high-pressure reaction kettle keeps micro-positive pressure of 40kPa after replacement is completed;
(2) heating the high-pressure reaction kettle to 150 ℃ under the stirring condition of 200r/min, reacting at a constant temperature for 2h, then continuously heating to 240 ℃, continuously heating while starting to enable the interior of the high-pressure reaction kettle to be in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle after the pressure reaches 3MPa, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure within 1.5h when the temperature is increased to 315 ℃;
(3) and (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.3MPa, extruding, bracing and cutting the materials from a die head to obtain PA10T polyamide resin particles with excellent thermal stability.
Example 3
(1) Weighing 332.3g of isophthalic acid, 1169.1g of adipic acid, 1130.7g of hexamethylenediamine, 15g of hindered phenol 4- (2-aminoethyl) -2, 6-dimethoxyphenol, 1.8g of catalyst calcium phosphate and 1000g of deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle, repeating the steps for three times to remove residual air in the reaction kettle, and keeping the micro-positive pressure of the high-pressure reaction kettle at 10kPa after replacement is completed;
(2) heating the high-pressure reaction kettle to 65 ℃ under the stirring condition of 40r/min, reacting at a constant temperature for 1h, then continuously heating to 200 ℃, continuously increasing the temperature and starting to enable the interior of the high-pressure reaction kettle to be in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle when the pressure reaches 1.5MPa, and slowly releasing the pressure of the high-pressure reaction kettle to the normal pressure within 0.5h when the temperature is increased to 270 ℃;
(3) and (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 1.2MPa, extruding, bracing and cutting the materials from a die head to obtain PA66/6I polyamide resin particles with excellent thermal stability.
Example 4
(1) Weighing 166.1g of terephthalic acid, 1820.3g of sebacic acid, 1688.4g of decanediamine, 0.3g of hindered phenol 2-methyl-6-tert-butyl-4-aminophenol, 0.3g of hindered amine N-phenyl-N' -isopropyl-4-amino aniline, 0.5g of catalyst zinc phosphite and 4000g of deionized water, adding the mixture into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle, repeating the steps for three times to remove residual air in the reaction kettle, and keeping the micro-positive pressure of the high-pressure reaction kettle at 50kPa after the replacement is finished;
(2) heating the high-pressure reaction kettle to 120 ℃ under the stirring condition of 300r/min, reacting at a constant temperature for 3 hours, then continuously heating to 180 ℃, continuously heating while starting to enable the interior of the high-pressure reaction kettle to be in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle after the pressure reaches 1MPa, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure within 2 hours when the temperature is raised to 220 ℃;
(3) and (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 2.5MPa, extruding, bracing and cutting the material from a die head to obtain PA1010/10T polyamide resin particles with excellent thermal stability.
Example 5
(1) Weighing 1246g of terephthalic acid, 415.3g of isophthalic acid, 1133g of hexamethylenediamine, 10g of hindered amine 2, 6-di-tert-butylpyridine amine, 1.5g of catalyst magnesium phosphate and 3000g of deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle, repeating the steps for three times to remove residual air in the reaction kettle, and keeping the micro-positive pressure of the high-pressure reaction kettle at 20kPa after the replacement is finished;
(2) heating the high-pressure reaction kettle to 80 ℃ under the stirring condition of 150r/min, reacting at a constant temperature for 2.5h, then continuously heating to 250 ℃, continuously increasing the temperature and starting to enable the interior of the high-pressure reaction kettle to be in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle when the pressure reaches 5MPa, and slowly releasing the pressure of the high-pressure reaction kettle to the normal pressure within 1.5h when the temperature is increased to 340 ℃;
(3) and (3) filling nitrogen into the high-pressure reaction kettle to a pressure of 2MPa, extruding, bracing and cutting the materials from a die head to obtain PA6T/6I polyamide resin particles with excellent thermal stability.
The performance test data for examples 1-5 and comparative example 1 are shown in table 1.
TABLE 1
By comparing the polymerization process and the test data of comparative example 1 and example 1, it can be shown that the hindered phenol is not added in comparative example 1, the rest components, the use amount and the polymerization process are completely the same, and the obtained product has a similar structure. Comparative example 1 a PA6T/66 copolyamide resin particle was directly polymerized, and example 1 a hindered phenol thermal stabilizing group was attached to the end of the PA6T/66 molecular chain by adding a hindered phenol having an amino group to react with the carboxyl group at the end of the PA6T/66 molecular chain to form an amide bond. The PA6T/66 copolymerized polyamide resin in the comparative example 1 and the PA6T/66 copolymerized polyamide resin connected with the hindered phenol heat-stable group in the example 1 are subjected to amino-terminal content and yellowing resistance tests, so that the content of the amino-terminal group after the PA6T/66 copolymerized polyamide resin connected with the hindered phenol heat-stable group in the example 1 is obviously reduced, and the PA6T/66 copolymerized polyamide resin connected with the hindered phenol heat-stable group is also obviously improved in yellowing resistance and greatly reduced in b value after being baked at 180 ℃.
It can be seen from the comparison of the polymerization processes and the test results of the other examples that the terminal amino group content and yellowing resistance of the product are closely related to the types of nylon monomers, hindered phenols and hindered amine additives in the raw materials. The smaller the molecular weight of the nylon monomer, the higher the amido bond content in the product, the higher the terminal amino group content of the product, the poorer the yellowing resistance of the product, the higher the content of hindered phenol and hindered amine additives in the product, the lower the terminal amino group content in the product, and the better the yellowing resistance. Therefore, the hindered phenol and the hindered amine are connected to the tail end of the polyamide molecular chain through chemical bonds, the content of terminal amino groups in the product is reduced, the thermal stability of the product is improved, the hindered phenol and the hindered amine cannot be separated out in the later use process, meanwhile, the loss of the hindered phenol and the hindered amine chemical groups in a low-temperature environment can be reduced through the bonds with larger chemical bonds, and the obtained product has better thermal stability at higher temperature and in longer time. The phenomenon of thermal stabilizer agglomeration or uneven dispersion in the modification process does not exist, the desired thermal stability can be achieved by adding a small amount of hindered amine or hindered phenol, the using amount of the hindered amine or hindered phenol is reduced, the production cost is reduced, the product competitiveness is increased, the product mechanical property is improved, in addition, the addition of powder filler in the modification process is reduced, and the improvement of the workshop environment in the processing process is facilitated.
In the above examples, the same effect can be achieved by replacing one or a mixture of several of terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid with an aromatic dibasic acid.
The aliphatic dibasic acid can be replaced by one or a mixture of more of succinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid or tridecanedioic acid to achieve the same effect.
The aliphatic diamine can be replaced by one or a mixture of more of butanediamine, pentanediamine, 2-methylpentanediamine, hexanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine or tridecanediamine to achieve the same effect.
The hindered phenol is replaced by one or a mixture of more of 2-methyl-6-tert-butyl-4-aminophenol, 2, 6-dimethyl-4-aminophenol, 2, 6-diethyl-4-aminophenol, 2, 6-di-tert-butyl-4-aminophenol and 4- (2-aminoethyl) -2, 6-dimethoxyphenol, and the same effect can be achieved.
The same effect can be achieved by replacing the hindered amine with one or a mixture of more of N, N '-diisopropyl-4-amino aniline, N' -diphenyl-4-amino aniline, N '-di (2-naphthyl) -4-amino aniline, N-phenyl-N' -isopropyl-4-amino aniline, 2,6, 6-tetramethylpiperidylamine, 2,6, 6-tetra-tert-butylpiperidinamine and 2, 6-di-tert-butylpyridinamine.
The catalyst is one or a mixture of more of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite, and the same effect can be achieved.
Although embodiments of the present invention have been shown and described, it will be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that those skilled in the art can make changes, modifications, substitutions and alterations to the above embodiments without departing from the spirit and scope of the present invention.
Claims (10)
1. The semi-aromatic polyamide resin is characterized by comprising the following components in parts by weight:
in the aromatic/aliphatic dibasic acid, the mass ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1: (0 to 9); preferably, the mass ratio is 1: (0-5).
2. The semi-aromatic polyamide resin of claim 1, comprising the following components in parts by weight:
3. the semi-aromatic polyamide resin according to claim 1, wherein the aromatic dibasic acid is one or a mixture of terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; preferably, the aromatic dibasic acid is one or more of terephthalic acid and isophthalic acid.
4. The semi-aromatic polyamide resin of claim 1, wherein the aliphatic dibasic acid is one or a mixture of succinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid or tridecanedioic acid; preferably, the aliphatic dibasic acid is one or more of adipic acid and sebacic acid.
5. The semi-aromatic polyamide resin according to claim 1, wherein the aliphatic diamine is one or a mixture of butanediamine, pentanediamine, 2-methylpentanediamine, hexanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, or tridecanediamine; preferably, the aliphatic diamine is at least one of butanediamine, hexanediamine and decanediamine.
6. The semi-aromatic polyamide resin according to claim 1, wherein the hindered phenol is one or a mixture of 2-methyl-6-tert-butyl-4-aminophenol, 2, 6-dimethyl-4-aminophenol, 2, 6-diethyl-4-aminophenol, 2, 6-di-tert-butyl-4-aminophenol, 4- (2-aminoethyl) -2, 6-dimethoxyphenol; preferably, the hindered phenol is one or more of 2, 6-di-tert-butyl-4-aminophenol and 4- (2-aminoethyl) -2, 6-dimethoxyphenol.
7. The semi-aromatic polyamide resin according to claim 1, wherein the hindered amine is one or a mixture of N, N '-diisopropyl-4-amino aniline, N' -diphenyl-4-amino aniline, N '-bis (2-naphthyl) -4-amino aniline, N-phenyl-N' -isopropyl-4-amino aniline, 2,6, 6-tetramethylpiperidylamine, 2,6, 6-tetra-tert-butylpiperidylamine, 2, 6-di-tert-butylpiperidylamine; preferably, the hindered amine is one or more of N, N' -diisopropyl-4-amino aniline, 2,6, 6-tetramethyl piperidine amine, and 2, 6-di-tert-butyl pyridine amine.
8. The semi-aromatic polyamide resin of claim 1, wherein the catalyst is one or a mixture of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and zinc hypophosphite; preferably, the catalyst is more than one of sodium phosphite and sodium hypophosphite.
9. The semi-aromatic polyamide resin according to claim 1, which is prepared by a process comprising,
s1: weighing required aromatic/aliphatic dibasic acid, aliphatic diamine, hindered phenol or hindered amine, a catalyst and deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle to remove residual air in the reaction kettle, and keeping micro-positive pressure in the high-pressure reaction kettle after replacement is finished; preferably, the micro-positive pressure is 10-50 kPa;
s2: heating the high-pressure reaction kettle under the stirring condition, carrying out constant-temperature reaction, then continuously heating, continuously heating when the pressure reaches 1.2-5MPa, starting to release water vapor in the high-pressure reaction kettle to enable the interior of the high-pressure reaction kettle to be in a constant-pressure state, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure when the temperature is raised to 340 ℃;
preferably, the step S2 is that the high-pressure reaction kettle is heated to 60-150 ℃ under the stirring condition of 30-300r/min, the constant-temperature reaction is carried out for 1-3h, then the temperature is continuously raised to 250 ℃ under 200-5 MPa, the temperature is continuously raised while the high-pressure reaction kettle is in a constant-pressure state by a method of releasing water vapor in the high-pressure reaction kettle, and the pressure is slowly released to the normal pressure after the temperature is raised to 340 ℃ under 240-2 h;
s3: filling nitrogen into the high-pressure reaction kettle; preferably, nitrogen is filled to the pressure of 0.2-2.5MPa, and the material is extruded from a die head, pulled into strips and cut into granules to obtain the semi-aromatic polyamide resin granules.
10. A process for producing a semi-aromatic polyamide resin according to claim 1, which comprises the steps of,
s1: weighing required aromatic/aliphatic dibasic acid, aliphatic diamine, hindered phenol or hindered amine, a catalyst and deionized water, adding into a high-pressure reaction kettle, vacuumizing and filling nitrogen into the high-pressure reaction kettle to remove residual air in the reaction kettle, and keeping micro-positive pressure in the high-pressure reaction kettle after replacement is finished; preferably, the micro-positive pressure is 10-50 kPa;
s2: heating the high-pressure reaction kettle under the stirring condition, carrying out constant-temperature reaction, then continuously heating, continuously heating when the pressure reaches 1.2-5MPa, starting to release water vapor in the high-pressure reaction kettle to enable the interior of the high-pressure reaction kettle to be in a constant-pressure state, and slowly releasing pressure of the high-pressure reaction kettle to normal pressure when the temperature is raised to 340 ℃;
preferably, the step S2 is that the high-pressure reaction kettle is heated to 60-150 ℃ under the stirring condition of 30-300r/min, the constant-temperature reaction is carried out for 1-3h, then the temperature is continuously raised to 250 ℃ under 200-5 MPa, the temperature is continuously raised while the high-pressure reaction kettle is in a constant-pressure state by a method of releasing water vapor in the high-pressure reaction kettle, and the pressure is slowly released to the normal pressure after the temperature is raised to 340 ℃ under 240-2 h;
s3: filling nitrogen into the high-pressure reaction kettle; preferably, nitrogen is filled to the pressure of 0.2-2.5MPa, and the material is extruded from a die head, pulled into strips and cut into granules to obtain the semi-aromatic polyamide resin granules.
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