CN115044033B - Semi-aromatic polyamide resin and preparation method thereof - Google Patents
Semi-aromatic polyamide resin and preparation method thereof Download PDFInfo
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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 high polymer synthesis. The molecular chain of the polyamide resin provided by the invention contains benzene rings, and the sum of the number n and the number m of the structural units is controlled to account for 25-75% of the total number of the structural units (the sum of n, m and k), so that the benzene rings among the polyamide molecular chain are orderly distributed, and the polyamide resin has good barrier property. The results of the examples show that the oxygen permeability of the polyamide resin provided by the invention is 0.050 cm to 0.054cm 3 ·mm(m 2 ·d·MPa) ‑1 Has good barrier property.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a semi-aromatic polyamide resin and a preparation method thereof.
Background
A polyamide resin having barrier properties is one of important raw materials for manufacturing packaging materials, and for example, patent CN1508008A discloses a gas barrier multilayer structure in which a gas barrier layer is described that includes a semiaromatic polyamide resin having barrier properties. Part of the structural units in this polyamide resin react with meta-xylylenediamine and a dibasic acid. In addition, a polyamide resin having an aromatic ring structure in other structural units is also provided with barrier properties, and for example, patent CN103328574a discloses a semiaromatic polyamide resin composition in which a polyamide resin is reacted from terephthalic acid or naphthalene dicarboxylic acid and a diamine. However, the gas barrier properties of the polyamide resins described above are still poor.
Disclosure of Invention
The invention aims to provide a semi-aromatic polyamide resin and a preparation method thereof, and the semi-aromatic polyamide resin provided by the invention has excellent gas barrier property.
The invention provides a semi-aromatic polyamide resin, which has a structure shown in a formula I or a formula II:
in the formulas I and 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 to 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 the monomer A, the monomer B, the molecular weight regulator and water to obtain a prepolymer;
(2) Performing second polycondensation on the prepolymer to obtain the semi-aromatic polyamide resin with the structure shown in the formula I or the 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-aminomethylbenzoic acid and/or 3-aminomethylbenzoic acid;
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 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 structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) y -COOH; and 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 water is used in an amount of 5.0 to 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 polyamide resin and a preparation method thereof, wherein the molecular chain of the semi-aromatic polyamide resin contains benzene rings, and the sum of the number n and the number m of structural units is controlled to be 25-75% of the total number of structural units (the sum of n, m and k), so that the benzene rings among the polyamide molecular chains are regularly distributed, and the semi-aromatic polyamide resin has good gas barrier property. The results of the examples show thatThe oxygen permeability of the polyamide resin provided by the invention is 0.050 cm to 0.054cm 3 ·mm(m 2 ·d·MPa) -1 Has good gas barrier property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a chart showing the nuclear magnetic resonance hydrogen spectrum 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 formulas I and 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 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 percent, preferably 45-60 percent, of the sum of n, m and k; preferably, n is 0 or an integer of 50 to 150; m is preferably 0 or an integer from 50 to 150; k is preferably an integer of 30 to 117. In the present invention, n, m and k refer to the corresponding polymerization degrees.
In the formula I of the invention, the 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 embodiments of the present invention, the structural formulae of embodiments 1 to 4 are:
the molecular chain of the polyamide resin provided by the invention contains benzene rings, and the sum of the number n and the number m of the structural units is controlled to be 25-75% of the total number of the structural units (the sum of n, m and k), so that the benzene rings among the polyamide molecular chain are orderly arranged, and further, 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 property is excellent. When the sum of n and m is 50-80% of the sum of n, m and k, the alloy also has excellent high temperature resistance.
The invention also provides a preparation method of the semi-aromatic polyamide resin, which comprises the following steps:
(1) Carrying out first polycondensation on the monomer A, the monomer B, the 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-aminomethylbenzoic acid and/or 3-aminomethylbenzoic acid;
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 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 structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) y -COOH；
And y is an integer of 2-11, and z is an integer of 5-12.
The invention carries out first polycondensation on the monomer A, the monomer B, the molecular weight regulator and water to obtain prepolymer. In the present invention, the monomer A is 4-aminomethylbenzoic acid and/or 3-aminomethylbenzoic acid. When the monomer A is 4-aminomethylbenzoic acid and 3-aminomethylbenzoic acid, the invention has no special requirement on the values of n and m of the structural formula I and the structural formula II, and only the sum of n and m is 25-75% of the sum of n, m and k. When the monomer A is 4-aminomethylbenzoic acid, n in the structures of the corresponding formulas I and II is 0; when the monomer A is 3-aminomethylbenzoic acid, m in the structures of the corresponding formulas I and 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 is preferably 30-50%. The amino group and the benzene ring in the monomer A are not directly connected, and the activity of the reaction of the amino group and 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 polyamide molecular main chain contains a certain amount of benzene ring structures, the molecular chain is distributed regularly, the good barrier property is shown, 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 polyamide molecular main chain is further increased, the heat resistance is improved, and the high-temperature resistance is macroscopically excellent.
In the present invention, when preparing the semiaromatic 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 formula C x+1 H 2x+1 NO, wherein x is an integer of 5 to 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, the 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 formula of the monomer B is preferably C 12 H 23 NO, i.e. monomer B is laurolactam.
Preparation of a half of the Structure shown in IIWhen the aromatic polyamide resin is prepared, the monomer B is aliphatic diamine and aliphatic nylon salt synthesized by aliphatic dibasic acid; the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) z -NH 2 . The structural formula of the aliphatic dibasic acid is 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 y is 2, the structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) 2 -COOH, i.e. 1, 4-butanedioic 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 structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) 8 -COOH, i.e. 1, 10-sebacic acid; when y is 10, the aliphatic dibasic acid has a formula of 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-hexamethylenediamine; when z is 10, the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) 10 -NH 2 I.e., 1, 10-decanediamine; when z is 12, the structural formula of the aliphatic diamine is NH 2 -(CH 2 ) 12 -NH 2 I.e., 1, 12-dodecanediamine. The preparation method of the nylon salt is not particularly limited, and the operation of synthesizing the dibasic acid and the diamine, which are well known to those skilled in the art, is adopted.
In the present invention, the molecular weight regulator preferably includes benzoic acid and/or terephthalic acid. The molecular weight regulator is preferably 0.5 to 1%, more preferably 0.6 to 0.8% of the total mass of the monomer A, the monomer B and the molecular weight regulator.
In the present invention, the water is preferably deionized water. The amount of water to be used is preferably 5.0 to 8.0% by mass, more preferably 6 to 7% by mass, based on the total mass of the monomer A, the monomer B and the molecular weight regulator. The source of the water is not particularly limited in the present invention, and commercially available products 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, the monomer A, the monomer B, the molecular weight regulator and water are preferably uniformly mixed before the monomer A, the monomer B, the molecular weight regulator and water are subjected to the first polycondensation. The mixing mode is not particularly limited, and the invention can be carried out by adopting technical schemes well known to those skilled in the art.
In the present invention, the absolute pressure of the first polycondensation is preferably 2.0 to 4.0MPa, more preferably 2.5 to 3MPa; the temperature is 220 to 260 ℃, more preferably 230 to 250 ℃, and the time is 1 to 6 hours, more preferably 2 to 4 hours. In the present invention, the first polycondensation is preferably performed in a closed vessel; the first polycondensation is preferably carried out in an inert gas atmosphere; the inert gas is preferably nitrogen. After the first polycondensation, a low molecular weight polyamide resin is produced. The method of forming the inert gas atmosphere in the present invention is not particularly limited, and may be any method known to those skilled in the art. Specifically, in the embodiment of the present invention: vacuumizing and 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 of 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 semiaromatic polyamide resin. The operation of discharging the water vapor is not particularly limited in the present invention, as long as 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 present invention, the absolute pressure of the second polycondensation is preferably < 1000Pa, and the temperature of the second polycondensation is preferably 280 to 330 ℃; the time for the second polycondensation is preferably 0.5 to 3 hours, more preferably 1.5 to 2.5 hours. The invention preferably draws a vacuum slowly so that the absolute pressure of the second polycondensation is < 1000Pa. The present invention controls the reaction pressure below 1000Pa, and can pump away the water generated by the second polymerization, thereby promoting the reaction to proceed in the forward direction and obtaining the polyamide resin with high molecular weight. And the synergistic effect of the reaction pressure and time can increase the viscosity of the polyamide resin.
In order to further illustrate the present invention, a semiaromatic polyamide resin and a method for preparing the same, which are provided by the present invention, are described in detail below with reference to the accompanying drawings and examples, but they are not to be construed as limiting the scope of the present invention.
Example 1
1.5kg of 4-aminomethylbenzoic acid, 3.5kg of caprolactam, 30g of benzoic acid and 260g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen introducing for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 220 ℃, and the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 280 ℃, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is 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 spectrometry, and the results are shown in fig. 1. As is clear from FIG. 1, the peaks at chemical shifts of 7 to 8ppm correspond to the benzene ring hydrogen atoms in the 4-aminomethylbenzoic acid structure, and the peaks at chemical shifts of 1 to 4ppm correspond to the methylene hydrogen atoms in the 4-aminomethylbenzoic acid structure and the methylene hydrogen atoms after ring opening of caprolactam, which proves that the copolymerization of 4-aminomethylbenzoic acid and caprolactam is successful.
Example 2
2.52kg of 4-aminomethylbenzoic acid, 2.53kg of caprolactam, 30g of benzoic acid and 300g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen introducing for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 220 ℃, and the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 320 ℃, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 60 and k is 60.
Example 3
2.5kg of 4-aminomethylbenzoic acid, 2.5kg of 11-aminoundecanoic acid, 30g of terephthalic acid and 280g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen gas for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 280 ℃, and the absolute pressure in the kettle is 2MPa. And (3) after heat preservation 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, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 58 and k is 60.
Example 4
2.5kg of 4-aminomethylbenzoic acid, 2.5kg of hexamethylenediamine adipate, 30g of terephthalic acid and 350g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen introducing for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 220 ℃, and the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation 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, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 60 and k is 60.
Example 5
4.0kg of 4-aminomethylbenzoic acid, 1.7kg of hexamethylenediamine adipate, 30g of terephthalic acid and 350g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen introducing for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 220 ℃, and the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation 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, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 120 and k is 53.
Example 6
4.0kg of 4-aminomethylbenzoic acid, 1.0kg of hexamethylenediamine adipate, 30g of terephthalic acid and 350g of deionized water are weighed and added into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen introducing for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 220 ℃, and the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation 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, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
where n is 124 and k is 32.
Comparative example 1
0.5kg of 4-aminomethylbenzoic acid, 4.5kg of caprolactam, 30g of benzoic acid and 300g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen introducing for 3 times, then stirring is started, the reaction kettle is heated to the internal temperature of 220 ℃, and the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 280 ℃, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 10 and k is 98.
Comparative example 2
1kg of 4-aminomethylbenzoic acid, 4kg of caprolactam, 30g of benzoic acid and 280g of deionized water are weighed into a 10L high-pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times through vacuumizing, stirring is started, and the reaction kettle is heated to the internal temperature of 220 ℃ until the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation for 2 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, heating to 280 ℃, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 20 and k is 82.
Comparative example 3
2.41kg of p-xylylenediamine, 2.59kg of adipic acid, 30g of terephthalic acid and 350g of deionized water are weighed and added into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen gas for 3 times, stirring is started, salt formation reaction is carried out for 2 hours at 100 ℃, and then the temperature is raised to 220 ℃, wherein the absolute pressure in the kettle is 2.4MPa. And (3) after heat preservation 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, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is as follows:
wherein n is 50 and k is 52.
Comparative example 4
2.55kg of decanediamine, 2.45kg of terephthalic acid, 30g of benzoic acid and 350g of deionized water are weighed and added into a 10L high-pressure reaction kettle, the air in the kettle is replaced by vacuum pumping and nitrogen gas for 3 times, stirring is started, salt forming reaction is carried out for 2 hours at 100 ℃, and then the temperature is raised to 235 ℃, wherein the absolute pressure in the kettle is 4MPa. And (3) after heat preservation for 3 hours, slowly exhausting until the pressure in the kettle is consistent with the external atmospheric pressure, gradually heating to 340 ℃, performing constant-temperature polycondensation, and then starting vacuumizing to ensure that the absolute pressure in the kettle is less than 1000Pa, and keeping for 2 hours to obtain the semi-aromatic polyamide resin. The structural formula is 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 test, and the results are shown in tables 1 and 2, wherein the test criteria are as follows:
relative viscosity test conditions and methods: and (3) preparing polyamide/concentrated sulfuric acid solution with the concentration of 0.01g/mL by using concentrated sulfuric acid as a solvent, and respectively recording the time required by the polyamide/concentrated sulfuric acid solution and the concentrated sulfuric acid solution to flow from the scale above the Ubbelohde viscometer to the scale below the Ubbelohde viscometer in a constant-temperature water bath environment with the temperature of 20+/-0.05 ℃, wherein the ratio is the relative viscosity of the corresponding polyamide resin.
Melting point test conditions and methods: 5-8 mg of a sample is weighed, the sample is heated to 270 ℃ to be melted for 3min under the protection of nitrogen, the liquid nitrogen is used for quenching, then the quenched sample is heated to 350 ℃, cooled to normal temperature, and heated to 350 ℃ at the heating rate of 10 ℃/min.
Tensile strength test conditions and methods: the tensile bars are placed in a constant temperature and humidity box for 24 hours and tested by a testing machine, and the testing standard is GB/T1040.2-2006.
Flexural strength test conditions and methods: the bent bars were placed in a constant temperature and humidity cabinet for 24 hours and tested using a testing machine with the test standard GB/T9341-2008.
Oxygen permeability test standard and method: the test was performed using the GB/T19789 packaging material plastic film and sheet oxygen permeability test coulometer test method.
TABLE 1 results of Performance test of semi-aromatic Polyamide resins prepared in examples 1 to 4
TABLE 2 Performance test results of semi-aromatic polyamide resins prepared in comparative examples 1 to 4
As can be seen 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 the content of benzene ring structure on the main chain of the polyamide resin is further increased along with the increase of the n proportion in the molecular chain of the polyamide resin, so that the heat resistance is improved.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. A semiaromatic polyamide resin characterized by having a structure represented by formula I or formula II:
in the formulas I and 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 the total structural unit numbers 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;
k is an integer of 30 to 117.
2. The semiaromatic polyamide resin according to claim 1, wherein 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 semiaromatic 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.
4. A process for producing a semiaromatic polyamide resin according to any of claims 1 to 3, characterized by comprising the steps of:
(1) Carrying out first polycondensation on the monomer A, the monomer B, the molecular weight regulator and water to obtain a prepolymer;
(2) Performing second polycondensation on the prepolymer to obtain the semi-aromatic polyamide resin with the structure shown in the formula I or the 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-aminomethylbenzoic acid and/or 3-aminomethylbenzoic acid;
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 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 structural formula of the aliphatic dibasic acid is COOH- (CH) 2 ) y -COOH; and y is an integer of 2-11, and z is an integer of 5-12.
5. The preparation method according to claim 4, wherein the mass of the monomer A is 30-50% of the total mass of the monomer A and the monomer B.
6. The process of claim 4, wherein the molecular weight regulator 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 water is used in an amount of 5.0 to 8.0% based on the total mass of the monomer A, the monomer B and the molecular weight regulator.
9. The process according to claim 4, wherein the absolute pressure of the first polycondensation is 2.0 to 4.0MPa, the temperature is 220 to 260℃and the time is 1 to 6 hours.
10. The process according to claim 4, wherein the absolute pressure of the second polycondensation is less than 1000Pa, the temperature is 280 to 330℃and the time is 0.5 to 3 hours.
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