CN115044033A - Semi-aromatic polyamide resin and preparation method thereof - Google Patents
Semi-aromatic polyamide resin and preparation method thereof Download PDFInfo
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- CN115044033A CN115044033A CN202210718337.0A CN202210718337A CN115044033A CN 115044033 A CN115044033 A CN 115044033A CN 202210718337 A CN202210718337 A CN 202210718337A CN 115044033 A CN115044033 A CN 115044033A
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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
- 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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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Abstract
The invention provides a polyamide resin and a preparation method thereof, belonging to the technical field of polymer synthesis. The molecular chain of the polyamide resin provided by the invention contains benzene rings, and the benzene rings among the polyamide molecular chains are regularly arranged by controlling the sum of the structural unit number n and m to account for 25-75% of the total structural unit number (sum of n, m and k), so that the polyamide resin has good barrier property. The example results show that the oxygen transmission rate of the polyamide resin provided by the invention is 0.050-0.054 cm 3 ·mm(m 2 ·d·MPa) ‑1 And has good barrier property.
Description
Technical Field
The invention belongs 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 resins with barrier properties are one of the important raw materials for producing packaging materials, and for example, patent CN1508008A discloses a gas barrier multilayer structure, in which a gas barrier layer described therein contains a semi-aromatic polyamide resin with barrier properties. Part of the structural units in this polyamide resin are reacted from m-xylylenediamine and a dibasic acid. In addition to this, polyamide resins having an aromatic ring structure in other structural units also have barrier properties, and for example, patent CN103328574A discloses a semi-aromatic polyamide resin composition in which a polyamide resin is reacted from terephthalic acid or naphthalenedicarboxylic acid and a diamine. However, the gas barrier properties of the above polyamide resins are still poor.
Disclosure of Invention
The invention aims to provide a semi-aromatic polyamide resin and a preparation method thereof.
The invention provides a semi-aromatic polyamide resin, which has a structure shown in a formula I or a formula II:
in the formula I and the formula II, n is an integer more than or equal to 0, m is an integer more than or equal to 0, and the sum of n and m is 25-75% of the sum of n, m and k;
in the formula I, x is an integer of 5-11;
in the formula II, y is an integer of 2-11, and z is an integer of 5-12.
Preferably, in formula I, x is 5, 10 or 11; in formula II, y is 2, 3, 4, 8, 10 or 11, and z is 5, 6, 10 or 12.
Preferably, n is 0 or an integer of 50-150; m is 0 or an integer of 50 to 150; k is an integer of 30 to 117.
The invention also provides a preparation method of the semi-aromatic polyamide resin, which comprises the following steps:
(1) carrying out first polycondensation on a monomer A, a monomer B, a molecular weight regulator and water to obtain a prepolymer;
(2) carrying out second polycondensation on the prepolymer to obtain a semi-aromatic polyamide resin with a structure shown in formula I or formula II;
the mass of the monomer A accounts for 30-80% of the total mass of the monomer A and the monomer B;
the monomer A is 4-aminomethyl benzoic acid and/or 3-aminomethyl benzoic acid;
when the semi-aromatic polyamide resin with the structure shown in the formula I is prepared, the monomer B is amino acid or aliphatic lactam, and the structural formula of the amino acid is NH 2 -(CH 2 ) x -COOH, said aliphatic lactam having the formula C x+1 H 2x+1 NO, wherein x is an integer of 5-11;
when the semi-aromatic polyamide resin with the structure shown in the formula II is prepared, the monomer B is aliphatic nylon salt;
the aliphatic nylon salt is synthesized by aliphatic diamine and aliphatic dibasic acid;
the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) z -NH 2 The aliphatic dibasic acid has a structural formula of COOH- (CH) 2 ) y -COOH; y is an integer of 2-11, and z is an integer of 5-12.
Preferably, the mass of the monomer A accounts for 30-50% of the total mass of the monomer A and the monomer B.
Preferably, the molecular weight regulator comprises benzoic acid and/or terephthalic acid.
Preferably, the molecular weight regulator is 0.5-1% of the total mass of the monomer A, the monomer B and the molecular weight regulator.
Preferably, the amount of the water is 5.0-8.0% of the total mass of the monomer A, the monomer B and the molecular weight regulator.
Preferably, the absolute pressure of the first polycondensation is 2.0-4.0 MPa, the temperature is 220-260 ℃, and the time is 1-6 h.
Preferably, the absolute pressure of the second polycondensation is less than 1000Pa, the temperature is 280-330 ℃, and the time is 0.5-3 h.
The invention provides a polymerThe semi-aromatic polyamide resin provided by the invention contains benzene rings on the molecular chain, and the benzene rings among the polyamide molecular chains are regularly arranged by controlling the sum of the number n and m of the structural units to be 25-75% of the total number (sum of n, m and k) of the structural units, so that the semi-aromatic polyamide resin has good gas barrier property. The example results show that the oxygen transmission rate of the polyamide resin provided by the invention is 0.050-0.054 cm 3 ·mm(m 2 ·d·MPa) -1 And has good gas barrier property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a nuclear magnetic resonance hydrogen spectrum curve of the semi-aromatic polyamide resin of example 1.
Detailed Description
The invention provides a semi-aromatic polyamide resin, which has a structure shown in a formula I or a formula II:
in the formula I and the formula II, n is an integer more than or equal to 0, m is an integer more than or equal to 0, and the sum of n and m is 25-75% of the sum of n, m and k;
in the formula I, x is an integer of 5-11;
in the formula II, y is an integer of 2-11, and z is an integer of 5-12.
In the formula I and the formula II, n is an integer not less than 0, m is an integer not less than 0, and the sum of n and m is 25-75% of the sum of n, m and k, preferably 45-60%; n is preferably 0 or an integer of 50-150; m is preferably 0 or an integer of 50 to 150; k is preferably an integer of 30 to 117. In the present invention, n, m and k refer to the respective degrees of polymerization.
In formula I of the present invention, x is preferably 5, 10 or 11; in formula II, y is preferably 2, 3, 4, 8, 10 or 11, and z is 5, 6, 10 or 12.
In the embodiment of the present invention, the structural formulas of embodiments 1 to 4 are as follows:
the molecular chain of the polyamide resin provided by the invention contains benzene rings, and the benzene rings among the polyamide molecular chains are regularly arranged by controlling the sum of the structural unit number n and m to account for 25-75% of the total structural unit number (sum of n, m and k), so that the polyamide resin has good gas barrier property.
When the sum of n and m is 25-75% of the sum of n, m and k, the gas barrier material has excellent gas barrier property. And when the sum of n and m is 50-80% of the sum of n, m and k, the high-temperature-resistant steel also has excellent high-temperature-resistant performance.
The invention also provides a preparation method of the semi-aromatic polyamide resin, which comprises the following steps:
(1) carrying out first polycondensation on a monomer A, a monomer B, a molecular weight regulator and water to obtain a prepolymer;
(2) performing second polycondensation on the prepolymer to obtain semi-aromatic polyamide resin;
the mass of the monomer A accounts for 30-80% of the total mass of the monomer A and the monomer B;
the monomer A is 4-aminomethyl benzoic acid and/or 3-aminomethyl benzoic acid;
when the semi-aromatic polyamide resin with the structure shown in the formula I is prepared, the monomer B is amino acid or aliphatic lactam, and the structural formula of the amino acid is NH 2 -(CH 2 ) x -COOH, said aliphatic lactam having the formula C x+1 H 2x+1 NO, wherein x is an integer of 5-11;
when the semi-aromatic polyamide resin with the structure shown in the formula II is prepared, the monomer B is aliphatic nylon salt;
the aliphatic nylon salt is synthesized by aliphatic diamine and aliphatic dibasic acid;
the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) z -NH 2 The aliphatic dibasic acid has a structural formula of COOH- (CH) 2 ) y -COOH；
Y is an integer of 2-11, and z is an integer of 5-12.
According to the invention, a monomer A, a monomer B, a molecular weight regulator and water are subjected to first polycondensation to obtain a prepolymer. In the present invention, the monomer A is 4-aminomethyl benzoic acid and/or 3-aminomethyl benzoic acid. When the monomer A is 4-aminomethyl benzoic acid and 3-aminomethyl benzoic acid, the invention has no special requirements on the values of n and m in the structural formula I and the structural formula II, and the sum of n and m is only 25-75% of the sum of n, m and k. When the monomer A is 4-aminomethyl benzoic acid, n in the corresponding structures of formula I and formula II is 0; when the monomer A is 3-aminomethyl benzoic acid, m in the corresponding structures of formula I and formula II is 0. The mass of the monomer A accounts for 30-80% of the total mass of the monomer A and the monomer B, and preferably 30-50%. The amino group and the benzene ring in the monomer A are not directly connected, and the activity of the reaction polycondensation reaction with the carboxylic acid group is high, so that the preparation of the semi-aromatic polyamide resin with high molecular weight is facilitated.
When the mass of the monomer A accounts for 30-50% of the total mass of the monomer A and the monomer B, the main chain of the polyamide molecule contains a certain amount of benzene ring structures, the molecular chain arrangement is regular, and good barrier property is shown, and when the mass of the monomer A accounts for 40-70% of the total mass of the monomer A and the monomer B, the content of the benzene ring structures on the main chain of the polyamide molecule is further increased, the heat resistance is improved, and the excellent high-temperature resistance is shown macroscopically.
In the invention, when preparing the semi-aromatic polyamide resin with the structure shown in the formula I, the monomer B is amino acid or aliphatic lactam, and the structural formula of the amino acid is NH 2 -(CH 2 ) x -COOH, said aliphatic lactam having the formula C x+1 H 2x+1 And NO, wherein x is an integer of 5-11. When x is 5 in formula I, the structural formula or molecular formula of the monomer B is preferably NH 2 -(CH 2 ) 5 -COOH or C 6 H 11 NO, i.e. monomer B is 6-aminocaproic acid or caprolactam; when x is 10 in formula I, theThe structural formula of the monomer B is preferably NH 2 -(CH 2 ) 10 -COOH, i.e. monomer B is 11-aminoundecanoic acid; when x is 11 in formula I, the molecular formula of the monomer B is preferably C 12 H 23 NO, i.e.monomer B, is laurolactam.
When the semi-aromatic polyamide resin with the structure shown in the formula II is prepared, the monomer B is aliphatic nylon salt synthesized by aliphatic diamine and aliphatic dibasic acid; the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) z -NH 2 . The aliphatic dibasic acid has a structural formula of COOH- (CH) 2 ) y -COOH, wherein y is an integer from 2 to 11, and z is an integer from 5 to 12. In the formula II, when the y is 2, the aliphatic dibasic acid has a structural formula of COOH- (CH) 2 ) 2 -COOH, i.e. 1, 4-succinic acid; when y is 3, the structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) 2 -COOH, i.e. 1, 5-glutaric acid; when y is 4, the structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) 4 -COOH, i.e. 1, 6-adipic acid; when y is 8, the aliphatic dibasic acid has a structural formula of COOH- (CH) 2 ) 8 -COOH, i.e. 1, 10-sebacic acid; when the y is 10, the molecular formula of the aliphatic dibasic acid is COOH- (CH) 2 ) 10 -COOH, i.e. 1, 12-dodecanedioic acid; when y is 11, the structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) 11 -COOH, i.e. 1, 13-tridecanedioic acid. When z is 5, the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) 5 -NH 2 I.e., 1, 5-pentanediamine; when z is 6, the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) 6 -NH 2 I.e., 1, 6-hexanediamine; when z is 10, the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) 10 -NH 2 I.e., 1, 10-decamethylenediamine; when z is 12, the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) 12 -NH 2 I.e., 1, 12-dodecadiamine. The preparation method of the nylon salt is not specialFor limitation, procedures for the synthesis of diacids and diamines, which are well known to those skilled in the art, may be used.
In the present invention, the molecular weight regulator preferably comprises benzoic acid and/or terephthalic acid. The molecular weight regulator is preferably 0.5-1% of the total mass of the monomer A, the monomer B and the molecular weight regulator, and more preferably 0.6-0.8%.
In the present invention, the water is preferably deionized water. The amount of the water is preferably 5.0-8.0% of the total mass of the monomer A, the monomer B and the molecular weight regulator, and more preferably 6-7%. The source of the water is not particularly limited in the present invention, and a commercially available product known to those skilled in the art may be used. In the present invention, water is used as a solvent for dissolving other raw materials.
In the present invention, before the first polycondensation of the monomer A, the monomer B, the molecular weight modifier and water, the monomer A, the monomer B, the molecular weight modifier and water are preferably uniformly mixed. The mixing method of the present invention is not particularly limited, and the technical solutions known to those skilled in the art may be adopted.
In the present invention, the absolute pressure of the first polycondensation is preferably 2.0 to 4.0MPa, more preferably 2.5 to 3 MPa; the temperature is 220-260 ℃, more preferably 230-250 ℃, and the time is 1-6 hours, more preferably 2-4 hours. In the present invention, the first polycondensation is preferably carried out in a closed vessel; the first polycondensation is preferably carried out in an atmosphere of an inert gas; the inert gas is preferably nitrogen. After the first polycondensation, a low molecular weight polyamide resin is produced. The manner of forming the inert gas atmosphere in the present invention is not particularly limited, and may be any manner known to those skilled in the art. Specifically, in the embodiment of the present invention: vacuumizing, introducing nitrogen to replace air in the kettle for 3 times.
After the first polycondensation is completed, the present invention preferably discharges the water vapor in the closed container, and then heats the obtained prepolymer to the temperature of the second polycondensation reaction to perform the second polycondensation reaction, thereby obtaining the semi-aromatic polyamide resin. The operation of discharging the water vapor is not particularly limited, and the air pressure of the closed container is ensured to be consistent with the external atmospheric pressure. The invention discharges the water vapor in the closed container, which is beneficial to improving the polymerization degree.
In the invention, the absolute pressure of the second polycondensation is preferably less than 1000Pa, and the temperature of the second polycondensation is preferably 280-330 ℃; the second polycondensation time is preferably 0.5 to 3 hours, and more preferably 1.5 to 2.5 hours. The invention preferably provides a slow evacuation such that the absolute pressure of the second polycondensation is < 1000 Pa. In the present invention, the reaction pressure is controlled to 1000Pa or less, and the water produced by the second polymerization can be pumped away to promote the reaction in the forward direction, thereby obtaining a polyamide resin having a high molecular weight. And the viscosity of the polyamide resin can be improved by the synergistic effect of the reaction pressure and the reaction time.
In order to further illustrate the present invention, the following will describe in detail a semi-aromatic polyamide resin and a method for preparing the same, which are provided by the present invention, with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 1.5kg of 4-aminomethyl benzoic acid, 3.5kg of caprolactam, 30g of benzoic acid and 260g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, starting stirring, and heating the reaction kettle until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) after the temperature is kept for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 280 ℃, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 50 and k is 110.
The semi-aromatic polyamide resin of example 1 was subjected to nuclear magnetic resonance hydrogen spectroscopy, and the results are shown in fig. 1. As can be seen from FIG. 1, the peak with the chemical shift of 7-8 ppm corresponds to the hydrogen atom of the benzene ring in the 4-aminomethyl benzoic acid structure, and the peak with the chemical shift of 1-4 ppm corresponds to the hydrogen atom of the methylene in the 4-aminomethyl benzoic acid structure and the hydrogen atom of the methylene after the ring opening of caprolactam, which proves that the copolymerization of 4-aminomethyl benzoic acid and caprolactam is successful.
Example 2
2.52kg of 4-aminomethyl benzoic acid, 2.53kg of caprolactam, 30g of benzoic acid and 300g of deionized water are weighed and added into a 10L high-pressure reaction kettle, the high-pressure reaction kettle is vacuumized and filled with nitrogen to replace the air in the kettle for 3 times, then the stirring is started, and the reaction kettle is heated until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) after the temperature is kept for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 320 ℃, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 60 and k is 60.
Example 3
Weighing 2.5kg of 4-aminomethyl benzoic acid, 2.5kg of 11-aminoundecanoic acid, 30g of terephthalic acid and 280g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, then starting stirring, heating the reaction kettle until the internal temperature reaches 280 ℃, and the absolute pressure in the kettle is 2 MPa. And (3) keeping the temperature for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 320 ℃, performing constant-temperature polycondensation, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 58 and k is 60.
Example 4
Weighing 2.5kg of 4-aminomethyl benzoic acid, 2.5kg of hexamethylene diamine adipate, 30g of terephthalic acid and 350g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, then starting stirring, and heating the reaction kettle until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) keeping the temperature for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 320 ℃, performing constant-temperature polycondensation, then starting to vacuumize until the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 60 and k is 60.
Example 5
Weighing 4.0kg of 4-aminomethyl benzoic acid, 1.7kg of hexamethylene diamine adipate, 30g of terephthalic acid and 350g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, then starting stirring, and heating the reaction kettle until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) keeping the temperature for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 320 ℃, performing constant-temperature polycondensation, then starting to vacuumize until the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 120 and k is 53.
Example 6
Weighing 4.0kg of 4-aminomethyl benzoic acid, 1.0kg of hexamethylene diamine adipate, 30g of terephthalic acid and 350g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, then starting stirring, and heating the reaction kettle until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) keeping the temperature for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 320 ℃, performing constant-temperature polycondensation, then starting to vacuumize until the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 124 and k is 32.
Comparative example 1
0.5kg of 4-aminomethyl benzoic acid, 4.5kg of caprolactam, 30g of benzoic acid and 300g of deionized water are weighed and added into a 10L high-pressure reaction kettle, the high-pressure reaction kettle is vacuumized and filled with nitrogen to replace air in the kettle for 3 times, then stirring is started, and the reaction kettle is heated until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) after the temperature is kept for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 280 ℃, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 10 and k is 98.
Comparative example 2
Weighing 1kg of 4-aminomethyl benzoic acid, 4kg of caprolactam, 30g of benzoic acid and 280g of deionized water, adding the weighed materials into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, starting stirring, and heating the reaction kettle until the internal temperature reaches 220 ℃ and the absolute pressure in the kettle is 2.4 MPa. And (3) keeping the temperature for 2 hours, slowly exhausting the gas until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 280 ℃, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 20 and k is 82.
Comparative example 3
Weighing 2.41kg of p-xylylenediamine, 2.59kg of adipic acid, 30g of terephthalic acid and 350g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, starting stirring, carrying out salt forming reaction at 100 ℃ for 2 hours, then heating to 220 ℃, wherein the absolute pressure in the kettle is 2.4 MPa. And (3) keeping the temperature for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, gradually heating to 280 ℃, performing constant-temperature polycondensation, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 50 and k is 52.
Comparative example 4
Weighing 2.55kg of decamethylenediamine, 2.45kg of terephthalic acid, 30g of benzoic acid and 350g of deionized water, adding into a 10L high-pressure reaction kettle, vacuumizing, introducing nitrogen to replace air in the kettle for 3 times, starting stirring, carrying out salt forming reaction at 100 ℃ for 2 hours, then heating to 235 ℃, and keeping the absolute pressure in the kettle at 4 MPa. And (3) keeping the temperature for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, gradually heating to 340 ℃, carrying out constant-temperature polycondensation, then starting to vacuumize to enable the absolute pressure in the kettle to be less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structure is simple as follows:
wherein n is 50 and k is 50.
The semi-aromatic polyamide resins prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to performance tests, and the results are shown in tables 1 and 2, wherein the test standards are as follows:
relative viscosity test conditions and methods: selecting concentrated sulfuric acid as a solvent, preparing a polyamide/concentrated sulfuric acid solution with the concentration of 0.01g/mL, and respectively recording the time required for the polyamide/concentrated sulfuric acid solution and the concentrated sulfuric acid solution to flow from the upper scale to the lower scale of the Ubbelohde viscometer in a constant-temperature water bath environment at the temperature of 20 +/-0.05 ℃, wherein the ratio of the time to the time is the relative viscosity of the corresponding polyamide resin.
Melting point test conditions and methods: weighing 5-8 mg of a sample, heating the sample to 270 ℃ under the protection of nitrogen, melting for 3min, quenching with liquid nitrogen, heating the quenched sample to 350 ℃, cooling to normal temperature, heating to 350 ℃, and heating at the rate of 10 ℃/min.
Tensile strength test conditions and methods: and (3) placing the tensile sample strips in a constant temperature and humidity box for processing for 24h, and testing by using a testing machine, wherein the testing standard is GB/T1040.2-2006.
Bending strength test conditions and methods: the bent sample strip is placed in a constant temperature and humidity box for treatment for 24h, and a testing machine is used for testing, wherein the testing standard is GB/T9341-.
Oxygen transmission rate test standard and method: the test is carried out by adopting oxygen permeability test coulometer detection method of GB/T19789 packaging material plastic film and thin sheet.
TABLE 1 results of performance test of semi-aromatic polyamide resins prepared in examples 1 to 4
TABLE 2 results of performance test of semi-aromatic polyamide resins prepared in comparative examples 1 to 4
As is clear from tables 1 and 2, the semi-aromatic polyamide resin provided by the present invention has an oxygen transmission rate of 0.050 to 0.054cm 3 ·mm(m 2 ·d·MPa) -1 The gas barrier property is improved. And with the increase of the proportion of n in the molecular chain of the polyamide resin, the content of the benzene ring structure on the main chain of the polyamide molecule is further increased, and the heat resistance is improved.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A semi-aromatic polyamide resin having a structure represented by formula I or formula II:
in the formula I and the formula II, n is an integer more than or equal to 0, m is an integer more than or equal to 0, and the sum of n and m is 25-75% of the sum of n, m and k;
in the formula I, x is an integer of 5-11;
in the formula II, y is an integer of 2-11, and z is an integer of 5-12.
2. Semi-aromatic polyamide resin according to claim 1, characterized in that in formula I, x is 5, 10 or 11; in formula II, y is 2, 3, 4, 8, 10 or 11, and z is 5, 6, 10 or 12.
3. The semi-aromatic polyamide resin according to claim 1 or 2, characterized in that n is 0 or an integer of 50 to 150; m is 0 or an integer of 50 to 150; k is an integer of 30 to 117.
4. A method for preparing a semi-aromatic polyamide resin according to any one of claims 1 to 3, comprising the steps of:
(1) carrying out first polycondensation on a monomer A, a monomer B, a molecular weight regulator and water to obtain a prepolymer;
(2) carrying out second polycondensation on the prepolymer to obtain a semi-aromatic polyamide resin with a structure shown in formula I or formula II;
the mass of the monomer A accounts for 30-80% of the total mass of the monomer A and the monomer B;
the monomer A is 4-aminomethyl benzoic acid and/or 3-aminomethyl benzoic acid;
when the semi-aromatic polyamide resin with the structure shown in the formula I is prepared, the monomer B is amino acid or aliphatic lactam, and the structural formula of the amino acid is NH 2 -(CH 2 ) x -COOH, said aliphatic lactam having the formula C x+1 H 2x+1 NO, wherein x is an integer of 5-11;
when the semi-aromatic polyamide resin with the structure shown in the formula II is prepared, the monomer B is aliphatic nylon salt;
the aliphatic nylon salt is synthesized by aliphatic diamine and aliphatic dibasic acid;
the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) z -NH 2 The aliphatic dibasic acid has a structural formula of COOH- (CH) 2 ) y -COOH; y is an integer of 2-11, and z is an integer of 5-12.
5. The method according to claim 4, wherein the mass of the monomer A is 30 to 50% of the total mass of the monomer A and the monomer B.
6. The production method according to claim 4, wherein the molecular weight modifier comprises benzoic acid and/or terephthalic acid.
7. The method according to claim 4 or 6, wherein the molecular weight modifier is 0.5 to 1% of the total mass of the monomer A, the monomer B and the molecular weight modifier.
8. The method according to claim 4, wherein the amount of water used is 5.0 to 8.0% by mass based on the total mass of the monomer A, the monomer B and the molecular weight modifier.
9. The process according to claim 4, wherein the first polycondensation has an absolute pressure of 2.0 to 4.0MPa, a temperature of 220 to 260 ℃ and a time of 1 to 6 hours.
10. The process according to claim 4, wherein the second polycondensation has an absolute pressure of < 1000Pa, a temperature of 280 to 330 ℃ and a time of 0.5 to 3 hours.
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