CN107446129B - Preparation method of anti-aging semi-aromatic nylon resin - Google Patents
Preparation method of anti-aging semi-aromatic nylon resin Download PDFInfo
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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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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
A preparation method of anti-aging semi-aromatic nylon resin comprises the following steps: under the protection of nitrogen, adding polyimide composite salt, semi-aromatic nylon composite salt, polyhydric alcohol and an auxiliary agent into a polymerization reaction kettle, adding one or two of aliphatic nylon salt and lactam, and adjusting the temperature and pressure of the polymerization reaction kettle to prepare the anti-aging semi-aromatic nylon resin; the auxiliary agent comprises an organic stabilizer, and the organic stabilizer is one of phenolic group, amido group, phosphorus group and thioether group stabilizer. The preparation method is simple and suitable for large-scale production, and the prepared semi-aromatic nylon resin has excellent mechanical property and excellent ageing resistance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of nylon resin.
Background
The semi-aromatic nylon is obtained by polycondensation of aromatic diacid or diamine and aliphatic diamine or diacid, an aromatic ring is introduced into a nylon molecular main chain, so that the heat resistance and the mechanical property of the material are improved, the water absorption is reduced, the dimensional stability is improved, and the blank between general engineering plastics (such as aliphatic nylon and polyester) and ultrahigh-performance materials (such as PEEK, polysulfone and LCP) is filled.
The semi-aromatic nylon has excellent chemical resistance, processability and thermal stability, so that the semi-aromatic nylon is particularly suitable for being applied to the fields of automobiles, electronics and electricity. Semi-aromatic nylon is often used in high temperature resistant structural parts of automobiles, and is usually used continuously at 150 ℃ and even 200 ℃, but mechanical properties tend to be reduced due to heat aging. The thermal aging performance of the semi-aromatic nylon is improved, high mechanical property retention rate is shown under the aging condition, and the semi-aromatic nylon is more beneficial to being applied in a thermal oxidation environment. Chinese patents CN102112549B and CN102597114B disclose that polyamide is premixed with a modification auxiliary agent and then subjected to a physical modification method to improve the thermal aging performance of a nylon material, but the tensile property retention rate of the composite material is only considered, and comprehensive evaluation is lacked.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, and provide a preparation method of an anti-aging semi-aromatic nylon resin with high mechanical property retention rate. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of anti-aging semi-aromatic nylon resin comprises the following steps: under the protection of nitrogen, adding polyimide composite salt, semi-aromatic nylon composite salt, polyhydric alcohol and an auxiliary agent into a polymerization reaction kettle, adding one or two of aliphatic nylon salt and lactam, and adjusting the temperature and pressure of the polymerization reaction kettle to prepare the anti-aging semi-aromatic nylon resin;
the auxiliary agent comprises an organic stabilizer, and the organic stabilizer is one of phenolic group, amido group, phosphorus group and thioether group stabilizer.
In the above preparation method, it is preferable that the reaction system is always under nitrogen protection, otherwise the materials are easily oxidized after the post-polymerization.
In the above preparation method, preferably, the polyimide composite salt is prepared by equimolar reaction of an amino-terminated polyimide prepolymer and a dibasic acid, the semi-aromatic nylon composite salt is prepared by reaction of an aromatic dibasic acid and an aliphatic diamine, and the aliphatic nylon salt is prepared by reaction of an aliphatic dibasic acid and an aliphatic diamine.
When the polyimide composite salt is prepared, the preparation method of the amino-terminated polyimide prepolymer comprises the following steps: firstly, under the protection of nitrogen, diamine is dissolved in an organic solvent, dianhydride is added into the organic solvent for three times under the condition of ice-water bath, the mixture is stirred and reacted to obtain an organic solvent solution of polyamide acid, then a mixed solvent of m-xylene and pyridine is added into the organic solvent solution of polyamide acid, the mixture is refluxed and reacted for 12-20 hours at the temperature of 60 +/-5 ℃, and after cooling, the mixture is sequentially subjected to absolute ethyl alcohol precipitation, suction filtration, acetone extraction for 18-24 hours, deionized water washing for 3-5 times, and vacuum drying for 16-24 hours at the temperature of 100-120 ℃ to obtain a powdery amino-terminated polyimide prepolymer.
In the above preparation method of the polyimide composite salt, preferably, the organic solvent is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The structural formula of the dianhydride is as follows:
the diamine has the following structural formula:
The diamine may also be one or more of 1, 4-butanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 2-methyl-1, 5-pentanediamine, 2, 4-trimethyl-1, 6-hexanediamine and 2-methyl-1, 8-octanediamine.
In the preparation method of the polyimide composite salt, the dibasic acid is preferably aliphatic dicarboxylic acid or alicyclic dicarboxylic acid, such as one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimethylmalonic acid, 3-diethylsuccinic acid, 2-methyladipic acid, 2-dimethylglutaric acid, 1, 3-cyclopentanedicarboxylic acid, and 1, 4-cyclohexanedicarboxylic acid. The dibasic acid can also be selected from aromatic dibasic acid, such as one or more of terephthalic acid, isophthalic acid, 2-methyl terephthalic acid, 2, 5-dichloro terephthalic acid, 2, 6-naphthalene diacid, 2, 7-naphthalene diacid, 1, 4-naphthalene diacid, 4 ' -biphenyl dicarboxylic acid, diphenylmethane-4, 4 ' -dicarboxylic acid, and diphenylsulfone-4, 4 ' -dicarboxylic acid.
The preparation method of the semi-aromatic nylon composite salt comprises the following specific operation steps: fully and uniformly mixing aromatic dibasic acid in deionized water, heating to 50-80 ℃, adding an aliphatic diamine aqueous solution under a strong stirring condition, adjusting the pH value to 7.0-8.0, continuously stirring for 0.5-2 hours, fully cooling, filtering, and drying in vacuum to obtain white powder semi-aromatic nylon composite salt.
In the preparation of the semi-aromatic nylon composite salt, preferably, the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid, 2-methyl terephthalic acid, 2, 5-dichloro terephthalic acid, 2, 6-naphthalene diacid, 2, 7-naphthalene diacid, 1, 4-naphthalene diacid, 4 ' -biphenyl dicarboxylic acid, diphenylmethane-4, 4 ' -dicarboxylic acid, phthalic acid and diphenyl sulfone-4, 4 ' -dicarboxylic acid, and more preferably, the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid.
In the preparation of the semi-aromatic nylon complex salt, the aliphatic diamine is preferably one or more selected from 1, 4-butanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 2-methyl-1, 5-pentanediamine, 2, 4-trimethyl-1, 6-hexanediamine and 2-methyl-1, 8-octanediamine, more preferably the aliphatic diamine is one or more selected from 1, 6-hexanediamine, decanediamine, 1, 12-dodecanediamine and 1, 13-tridecanediamine, further preferably, the aliphatic diamine is 1, 6-hexamethylene diamine.
When the aliphatic nylon salt is prepared, preferably, the aliphatic dibasic acid is one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimethylmalonic acid, 3-diethylsuccinic acid, 2-methyladipic acid and 2, 2-dimethylglutaric acid; the aliphatic diamine is one or more of 1, 4-butanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 2-methyl-1, 5-pentanediamine, 2, 4-trimethyl-1, 6-hexanediamine and 2-methyl-1, 8-octanediamine.
In the above preparation method, preferably, the polyhydric alcohol is one or more of ethylene-vinyl alcohol copolymer, polyvinyl alcohol and dipentaerythritol.
In the above preparation method, preferably, the lactam is one or more of caprolactam, undecanolactam and laurolactam.
In the preparation method, the auxiliary agent further comprises a catalyst, the catalyst is one of phosphoric acid, phosphorous acid, hypophosphorous acid and derivatives of salts and esters thereof, the mass ratio of the catalyst to the organic stabilizer is 1: 0.5-1: 2, and the mass ratio of the catalyst to the organic stabilizer is 1: 1.
In the above preparation method, preferably, the polyimide composite salt, the semi-aromatic nylon composite salt, the polyhydric alcohol, the aliphatic nylon salt, the lactam and the auxiliary are added in parts by weight: 0.01-8 parts of polyimide composite salt, 30-70 parts of semi-aromatic nylon composite salt, 0.01-10 parts of polyhydric alcohol, 30-70 parts of aliphatic nylon salt, 30-70 parts of lactam and 0.05-2 parts of auxiliary agent. More preferably, the polyimide composite salt, the polyhydric alcohol and the auxiliary are added in parts by weight as follows: 0.1 to 4 parts of polyimide composite salt, 0.5 to 6 parts of polyhydric alcohol and 0.1 to 0.5 part of auxiliary agent. Further preferably, the polyimide composite salt and the polyhydroxy alcohol are added in the following weight portions: 0.5 to 3 parts of polyimide complex salt and 1 to 4 parts of polyhydric alcohol. The weight parts of the above substances do not include water contained in the substances. The properties of the anti-aging semi-aromatic nylon resin obtained by the preparation method are directly related to the weight parts of the components, and the inventor finds out that the anti-aging semi-aromatic nylon resin prepared by the components with the weight parts has the most excellent performance based on a large amount of experimental research.
In the preparation method, preferably, the temperature and the pressure of the polymerization reaction kettle are adjusted to firstly maintain the pressure and the temperature in the kettle at 210-220 ℃ and 1.8-2.0 MPa for 1-4 h, then exhaust is carried out to gradually reduce the pressure in the kettle to normal pressure, gradually increase the temperature in the kettle to 300-350 ℃, and finally, the reaction is continued for 10-30 min under the conditions that the pressure in the kettle is-0.1-0.04 MPa and the temperature is 300-350 ℃.
The main chemical reaction formulas of the method of the invention are shown in the following formula (1), formula (2), formula (3), formula (4), formula (5) and formula (6), wherein formula (1) represents a synthesis equation of a polyimide prepolymer, formula (2) represents a synthesis equation of a polyimide composite salt, formula (3) represents a synthesis equation of a semi-aromatic nylon composite salt, formula (4) represents a synthesis equation of polyimide modified nylon (aliphatic nylon salt), formula (5) represents a synthesis equation of polyimide modified nylon (lactam), and formula (6) represents a synthesis equation of copolymerized nylon.
H2N-PI-NH2+HOOC-R1-COOH→H3N-PI-NH3OOC-R1-COO
Formula (2)
Compared with the prior art, the invention has the advantages that:
1. according to the invention, a polyamide-imide structure is introduced into a semi-aromatic nylon molecular chain, polyimide contains aromatic heterocyclic rings, and the aromatic heterocyclic rings are randomly distributed in a semi-aromatic nylon main chain, so that the rigidity and heat resistance of the material can be improved, and the prepared semi-aromatic nylon resin has excellent mechanical properties and excellent ageing resistance.
2. According to the invention, the polyhydroxy alcohol is added in the polymerization process, so that the anti-aging efficiency of the organic stabilizer can be improved, the polyhydroxy alcohol and the organic stabilizer can generate a synergistic effect at high temperature, the polyhydroxy alcohol and the organic stabilizer can rapidly capture free radicals generated in the decomposition process of the polymer at high temperature to carry out termination reaction, the aging of the polymer at high temperature is effectively inhibited, and the prepared semi-aromatic nylon resin has excellent anti-aging performance.
3. The preparation method is simple and suitable for large-scale production.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of anti-aging semi-aromatic nylon resin comprises the following steps:
the method comprises the following steps:
(1) under the protection of nitrogen, 4,4 '-diaminodiphenyl ether is dissolved in an N, N-dimethylformamide solvent, 4, 4' -oxydiphthalic anhydride is added in three times under the condition of ice-water bath and stirred for reaction to obtain an N, N-dimethylformamide solution of polyamic acid, wherein the molar ratio of 4,4 '-diaminodiphenyl ether to 3, 3', 4,4 '-diphenylether tetracarboxylic dianhydride is 1.5:1, 4, 4' -diaminodiphenyl ether and 3,3 ', 4, 4' -diphenylether tetracarboxylic dianhydride account for 15 percent of the total mass of the system (diamine, dianhydride and solvent);
(2) adding m-xylene/pyridine mixed solvent (volume ratio is 2:1) into the N, N-dimethylformamide solution of the polyamic acid prepared in the step (1), refluxing for 18h at 60 +/-5 ℃ to obtain the N, N-dimethylformamide solvent of the thermoplastic polyimide, cooling, precipitating with absolute ethyl alcohol, filtering, extracting with acetone for 20h, washing with deionized water for 3 times, and vacuum drying at 100 ℃ for 20h to finally obtain a powdery amino-terminated thermoplastic polyimide prepolymer;
(3) under the protection of nitrogen, uniformly mixing the polyimide prepolymer and dimethylformamide, starting stirring and heating to 120 ℃ to obtain a dimethylformamide solution of the polyimide prepolymer; uniformly mixing adipic acid (with the molar number equal to that of the polyimide prepolymer) and dimethylformamide, starting stirring, and heating to 100 ℃ to obtain a dimethylformamide solution of the adipic acid; uniformly mixing a dimethylformamide solution of a polyimide prepolymer and a dimethylformamide solution of adipic acid, fully reacting, centrifugally washing, and drying in vacuum to obtain a polyimide composite salt;
step two:
uniformly mixing phthalic acid and a proper amount of deionized water, heating to 70 ℃, starting stirring, adding a 1, 6-hexanediamine aqueous solution, adjusting the pH to 7.5-7.7, continuously stirring for 1 hour, cooling to room temperature, filtering and drying to obtain white powder PA6T salt (semi-aromatic nylon composite salt);
step three:
80g of polyimide composite salt, 1918g of PA6T salt, 1918g of PA66 salt, 80g of ethylene-vinyl alcohol copolymer, 4g of sodium hypophosphite and 4g of sodium hypophosphite
Adding 1000g of water and an organic stabilizer into a 10L high-temperature high-pressure polymerization kettle, replacing nitrogen for three times, starting stirring, heating the temperature in the kettle to 215 ℃, increasing the pressure in the kettle to 1.9MPa, and maintaining the pressure for 2 hours; then exhausting to gradually reduce the pressure in the kettle to normal pressure and gradually increase the temperature in the kettle to 320 ℃; and finally, continuously reacting for 15min under the conditions that the pressure in the kettle is-0.06 MPa and the temperature is 320 ℃, then opening a bottom valve, drawing strips, granulating, and vacuum drying for 10h to obtain the modified semi-aromatic nylon resin, wherein the melting point of the modified semi-aromatic nylon resin is 300 ℃, the intrinsic viscosity of the modified semi-aromatic nylon resin is 1.35dl/g, and carrying out aging performance test.
Comparative example 1:
the procedure of this comparative example was the same as in example 1 except that the polyimide complex salt and the ethylene-vinyl alcohol copolymer were not added in step three.
Example 2:
a preparation method of anti-aging semi-aromatic nylon resin comprises the following steps:
the procedure was as in example 1;
the second step is the same as the example 1;
step three:
80g of polyimide composite salt, 2877g of PA6T salt, 959g of caprolactam, 80g of ethylene-vinyl alcohol copolymer, 4g of sodium hypophosphite and 4g of sodium hypochlorite
Adding 1000g of water into a 10L high-temperature high-pressure polymerization kettle, replacing nitrogen for three times, starting stirring, heating the temperature in the kettle to 215 ℃, increasing the pressure in the kettle to 1.9MPa, and maintaining the pressure for 4 hours; then exhausting to gradually reduce the pressure in the kettle to normal pressure and gradually increase the temperature in the kettle to 320 ℃; and finally, continuously reacting for 15min under the conditions that the pressure in the kettle is-0.06 MPa and the temperature is 320 ℃, then opening a bottom valve, drawing strips, granulating, and vacuum drying for 10h to obtain the modified semi-aromatic nylon resin, wherein the melting point of the modified semi-aromatic nylon resin is 300 ℃, and the intrinsic viscosity of the modified semi-aromatic nylon resin is 1.25 dl/g.
Comparative example 2:
the procedure of this comparative example was the same as in example 2 except that the polyimide complex salt and the ethylene-vinyl alcohol copolymer were not added in step three.
Example 3:
a preparation method of anti-aging semi-aromatic nylon resin comprises the following steps:
the procedure was as in example 1;
the second step is the same as the example 1;
step three:
80g of polyimide composite salt, 2302g of PA6T salt, 1150g of PA66 salt, 384g of caprolactam, 80g of ethylene-vinyl alcohol copolymer, 4g of sodium hypophosphite and 4g of sodium hypophosphite
Adding 1000g of water into a 10L high-temperature high-pressure polymerization kettle, replacing nitrogen for three times, starting stirring, heating the temperature in the kettle to 215 ℃, increasing the pressure in the kettle to 1.9MPa, and maintaining the pressure for 4 hours; then exhausting to gradually reduce the pressure in the kettle to normal pressure and gradually increase the temperature in the kettle to 320 ℃; and finally, continuously reacting for 15min under the conditions that the pressure in the kettle is-0.06 MPa and the temperature is 320 ℃, then opening a bottom valve, drawing strips, granulating, and vacuum drying for 10h to obtain the modified semi-aromatic nylon resin, wherein the melting point of the modified semi-aromatic nylon resin is 302 ℃, and the intrinsic viscosity of the modified semi-aromatic nylon resin is 1.3 dl/g.
Comparative example 3:
the procedure of this comparative example was the same as in example 3 except that the polyimide complex salt and the ethylene-vinyl alcohol copolymer were not added in step three.
Example 4:
a preparation method of anti-aging semi-aromatic nylon resin comprises the following steps:
the procedure was as in example 1;
the second step is the same as the example 1;
in step three, the ethylene/vinyl alcohol copolymer of example 1 was replaced with polyvinyl alcohol, and the procedure was the same as in example 1.
Comparative example 4:
the procedure of this comparative example was the same as in example 4 except that the polyimide complex salt and polyvinyl alcohol were not added in step three.
Example 5:
a preparation method of anti-aging semi-aromatic nylon resin comprises the following steps:
the procedure was as in example 1;
the second step is the same as the example 1;
in step three, dipentaerythritol is used to replace the ethylene/vinyl alcohol copolymer of example 1, and the rest of the procedure is the same as in example 1.
Comparative example 5-1:
the procedure of this comparative example was the same as in example 5 except that the polyimide complex salt and dipentaerythritol were not added in step three.
Comparative example 5-2:
the comparative example was conducted in the same manner as in example 5 except that no organic stabilizer was added in step three
Comparative examples 5 to 3:
the procedure of this comparative example is the same as example 5 except that dipentaerythritol is not added in step three.
Comparative examples 5 to 4:
the procedure of this comparative example was the same as in example 5 except that no polyimide complex salt was added in step three.
The resins obtained in examples 1 to 5 and comparative examples 1 to 5 were subjected to performance tests, and the results are shown in tables 1 and 2.
Table 1: performance test data for examples 1-5
Table 2: comparative examples 1-5 Performance test data
From the above table, no matter aging is carried out at 150 ℃ for 800h or at 180 ℃ for 800h, the performance retention rate of the resin obtained in the embodiment is obviously superior to that of the comparative example, the polyimide composite salt, the organic stabilizer and the polyhydroxy alcohol lack any component, the performance retention rate is reduced, and the aging resistance efficiency of the resin can be improved by the polyimide composite salt, the organic stabilizer and the polyhydroxy alcohol. The test method of the above experimental results is as follows:
1. intrinsic viscosity [ η ]
The semi-aromatic copolymerized nylon tested was dissolved in concentrated sulfuric acid to give concentrations of 1g/dl, 0.8g/dl, 0.6g/dl, 0.4g/dl, 0.2g/dl, respectively, and the logarithmic viscosity of the solution was measured at 25 ℃ as ηinh：
ηinh＝[ln(t1/t0)]/C
Wherein t is0Indicates the time(s), t) at which the solvent flowed out1Denotes the time(s) at which the sample solution flowed out, C denotes the concentration (g/dl) of the sample solution, ηinhRepresents logarithmic viscosity (dl/g);
η will be mixedinhThe data of (a) was extrapolated to a concentration of 0, and the intrinsic viscosity of the sample was obtained [ η ]]。
2. Melting Point
The melting point of the sample was measured using a Mettler-Toriledo DSC1 apparatus, and the temperature was raised from room temperature to 330 ℃ at 10 ℃/min under nitrogen atmosphere for 5min, then cooled at 10 ℃/min to room temperature, and then raised at 10 ℃/min to 330 ℃ at which the endothermic peak temperature was the polymer melting point.
3. Mechanical properties
The prepared semi-aromatic copolymerized nylon injection molding test sample bar is tested for tensile strength according to the GB/T1040.2 standard, for bending strength and bending modulus according to the GB/T9341-2008 standard, and for impact strength of a simple beam according to the GB/T1043.1 standard.
4. Anti-aging performance
The prepared nylon injection molding test sample strip is subjected to a heat aging test in an air heat aging test box (model GT-7017-EMU) according to GB/T7141-2008, and the aging test conditions are 150 ℃, 800h, 180 ℃ and 800h respectively. Testing the tensile strength of the sample subjected to the aging test according to the GB/T1040.2 standard, testing the bending strength and the bending modulus according to the GB/T9341-2008 standard, and testing the impact strength of the simply supported beam according to the GB/T1043.1 standard; the aging resistance of the sample is evaluated by the mechanical property retention rate of the sample after the aging test.
Claims (8)
1. The preparation method of the anti-aging semi-aromatic nylon resin is characterized by comprising the following steps: under the protection of nitrogen, adding polyimide composite salt, semi-aromatic nylon composite salt, polyhydric alcohol and an auxiliary agent into a polymerization reaction kettle, adding one or two of aliphatic nylon salt and lactam, and adjusting the temperature and pressure of the polymerization reaction kettle to prepare the anti-aging semi-aromatic nylon resin;
the auxiliary agent comprises an organic stabilizer, wherein the organic stabilizer is one of phenol-based stabilizer, amino-based stabilizer, phosphorus-based stabilizer and thioether-based stabilizer;
wherein the polyhydric alcohol is one or more of ethylene-vinyl alcohol copolymer, polyvinyl alcohol and dipentaerythritol;
the polyimide composite salt, the semi-aromatic nylon composite salt, the polyhydroxy alcohol, the aliphatic nylon salt, the lactam and the auxiliary agent are added in parts by weight: 0.01-8 parts of polyimide composite salt, 30-70 parts of semi-aromatic nylon composite salt, 0.01-10 parts of polyhydric alcohol, 30-70 parts of aliphatic nylon salt, 30-70 parts of lactam and 0.05-2 parts of auxiliary agent.
2. The method for preparing the anti-aging semi-aromatic nylon resin according to claim 1, wherein the polyimide composite salt is prepared by equimolar reaction of an amino-terminated polyimide prepolymer and a dibasic acid, the semi-aromatic nylon composite salt is prepared by reaction of an aromatic dibasic acid and an aliphatic diamine, and the aliphatic nylon salt is prepared by reaction of an aliphatic dibasic acid and an aliphatic diamine.
3. The method for preparing the anti-aging semi-aromatic nylon resin according to claim 2, wherein the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid;
the aliphatic dibasic acid is one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimethylmalonic acid, 3-diethylsuccinic acid, 2-methyladipic acid and 2, 2-dimethylglutaric acid;
the aliphatic diamine is one or more of 1, 4-butanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 2-methyl-1, 5-pentanediamine, 2, 4-trimethyl-1, 6-hexanediamine and 2-methyl-1, 8-octanediamine.
4. The method for preparing the anti-aging semi-aromatic nylon resin as claimed in claim 1, wherein the lactam is one or more of caprolactam, undecanolactam and laurolactam.
5. The preparation method of the anti-aging semi-aromatic nylon resin according to claim 1, wherein the auxiliary agent further comprises a catalyst, the catalyst is one of phosphoric acid, phosphorous acid, hypophosphorous acid and derivatives of salts and esters thereof, and the mass ratio of the catalyst to the organic stabilizer is 1: 0.5-1: 2.
6. The preparation method of the anti-aging semi-aromatic nylon resin as claimed in claim 1, wherein the polyimide composite salt, the polyhydric alcohol and the auxiliary are added in parts by weight as follows: 0.1 to 4 parts of polyimide composite salt, 0.5 to 6 parts of polyhydric alcohol and 0.1 to 0.5 part of auxiliary agent.
7. The method for preparing the anti-aging semi-aromatic nylon resin according to claim 6, wherein the polyimide composite salt and the polyhydric alcohol are added in the following weight parts: 0.5 to 3 parts of polyimide complex salt and 1 to 4 parts of polyhydric alcohol.
8. The method for preparing the anti-aging semi-aromatic nylon resin according to any one of claims 1 to 7, wherein the temperature and pressure in the polymerization reaction kettle are adjusted to maintain the pressure at 210 to 220 ℃ and 1.8 to 2.0MPa for 1 to 4 hours, then the pressure in the kettle is gradually reduced to normal pressure by exhausting, the temperature in the kettle is gradually increased to 300 to 350 ℃, and finally the reaction is continued for 10 to 30 minutes under the conditions that the pressure in the kettle is-0.1 to-0.04 MPa and the temperature is 300 to 350 ℃.
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| JP2012107217A (en) * | 2010-10-20 | 2012-06-07 | Ube Industries Ltd | Polyamide resin composition and film composed of the same |
| CN103923313A (en) * | 2014-04-30 | 2014-07-16 | 株洲时代新材料科技股份有限公司 | Method for preparing semi aromatic copolymer nylon |
| CN106336512A (en) * | 2016-08-11 | 2017-01-18 | 株洲时代新材料科技股份有限公司 | Preparation method of polyimide modified nylon resin |
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| JP2012107217A (en) * | 2010-10-20 | 2012-06-07 | Ube Industries Ltd | Polyamide resin composition and film composed of the same |
| CN103923313A (en) * | 2014-04-30 | 2014-07-16 | 株洲时代新材料科技股份有限公司 | Method for preparing semi aromatic copolymer nylon |
| CN106336512A (en) * | 2016-08-11 | 2017-01-18 | 株洲时代新材料科技股份有限公司 | Preparation method of polyimide modified nylon resin |
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