CN110746596B - Copolymerized transparent polyamide and preparation method thereof - Google Patents
Copolymerized transparent polyamide and preparation method thereof 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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- 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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
Abstract
The invention discloses transparent polyamide which is prepared from three diamines and three dibasic acids through melt copolymerization. The invention respectively copolymerizes three diamines and dibasic acids, wherein 4,4' -diamino dicyclohexyl methane can ensure that the main chain has higher density of fatty rings, so that the obtained copolymer has higher glass transition temperature and excellent heat resistance, the dibasic acid with an asymmetric structure and the dibasic acid with a large-volume side group can destroy the regularity of a molecular chain to a certain extent, thereby reducing the crystallization capacity of the polymer, increasing the light transmittance, and matching aliphatic chain segments with different molecular weights in the main chain to fully disperse the three substances, further reducing the regularity, and enabling the polyamide to have low crystallinity and good transparency. The transparent copolymerized polyamide has excellent thermal and mechanical properties, and the polymerization process is simple and controllable, and the preparation cost is low.
Description
Technical Field
The invention relates to preparation of polyamide, in particular to transparent copolymerized polyamide and a preparation method thereof.
Background
Polyamide (PA) is a generic term for resins having recurring amide groups in the molecular chain. The polyamide is the basic resin with the maximum yield, the maximum variety, the widest application and excellent comprehensive performance in five general engineering plastics. The transparent polyamide is a novel special polyamide product, has the advantages of high light transmittance, low water absorption, good dimensional stability and the like compared with the common polyamide, and not only can be used for packaging beverages and foods, but also can be used as a packaging material for precise instruments, instruments and pharmaceutical chemicals.
At present, transparent polyamide on the market mainly comprises two main types of semi-aromatic transparent polyamide and alicyclic transparent polyamide, the semi-aromatic transparent polyamide is wide in raw material source and good in heat resistance of products, and the overall mechanical property and the processing property of the alicyclic transparent polyamide are superior to those of the semi-aromatic transparent polyamide, but the price of the raw material is high, so that the application of the alicyclic transparent polyamide is limited to a certain extent.
Chinese patent 20151083753.8 discloses a transparent polyamide and a preparation method thereof. The prepared transparent polyamide contains branched chain alkyl diamine units and oxalic acid units, and the preparation method comprises the following steps: under the condition of inert gas flow and the temperature of 30-120 ℃, diamine is slowly added into oxalic acid diester or oxalic acid diester is added into diamine, and prepolymer is obtained after reaction for 2-6 hours; and carrying out melt polymerization on the prepolymer for 2-5 hours under reduced pressure to obtain a transparent polyamide product. The patent refers to a reaction in which an amine transesterification reaction occurs and the transparent polyamide obtained has a low glass transition temperature.
Disclosure of Invention
The invention provides a copolymerized transparent polyamide and a preparation method thereof, aiming at the problem of low glass transition temperature of the existing transparent polyamide.
The technical scheme for solving the technical problems is as follows: a transparent polyamide is obtained by copolymerizing diamines of formulae A1, A2 and A3 and diacids of formulae B1, B2 and B3,
wherein, the diamine is respectively:
NH2-(CH2)a-NH2 A2，
NH2-(CH2)b-NH2 A3，
the dibasic acids are respectively:
COOH-(CH2)c-COOH B1，
COOH-R1-COOH B2，
COOH-R2-COOH B3，
a and b are each independently selected from 6, 9 or 10, c is 4, 8, 10 or 11;
R1comprises the following steps:
R2comprises the following steps:
R3the aromatic compound containing 1-3 benzene rings specifically comprises the following components:
the ratio of the sum of the amounts of the three diamine substances to the sum of the amounts of the three diacid substances in the transparent polyamide is 1 (0.97-1).
Furthermore, the molar fraction of the diamine is 60-70% of A1, 20-25% of A2, 5-20% of A3, 60-70% of B1, 20-25% of B2 and 5-20% of B3. Namely, the ratio of A1 aliphatic ring diamine to B1 linear diacid in the molecular chain of the transparent polyamide is the largest, and B2 and B3 play a role in further reducing the regularity of the molecular chain.
The relative viscosity of the transparent polyamide is 2.0-2.8, and the proper relative viscosity can have enough mechanical property and better processability. In practice, the relative viscosity can be suitably selected in accordance with the particular conditions of use.
The invention also discloses a preparation method of the transparent polyamide, which specifically comprises the following steps: converting the components into specific mass according to the molar fraction, respectively weighing the components, salifying, uniformly mixing, adding the components into a reaction kettle, adding a catalyst and water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 190-plus-210 ℃, adjusting the pressure in the kettle to be 1.5-2.5MPa, continuously heating to 280-plus-305 ℃, adjusting the pressure in the kettle to be 1.5-2MPa, maintaining the pressure for 1-2h, then discharging the air to the normal pressure, discharging the water in the system, gradually vacuumizing to reduce the pressure of the system to-0.03-0.07 MPa, and discharging to obtain the transparent polyamide resin.
Wherein, the catalyst is one of phosphoric acid, phosphorous acid or sodium hypophosphite, and the dosage of the catalyst is 0.1 to 0.5 percent of the total weight of the reactants; the amount of water is 2-5% of the total weight of the reactants.
The invention has the beneficial effects that: the three diamines and the dibasic acids are copolymerized respectively, wherein A14,4' -diamino dicyclohexyl methane can ensure that the main chain has higher density of aliphatic rings, so that the obtained copolymer has higher glass transition temperature and excellent heat resistance, the dibasic acid B2 with an asymmetric structure and the dibasic acid B3 with a large-volume side group can destroy the regularity of a molecular chain to a certain extent, the crystallization capacity of the polymer is reduced, the light transmittance is increased, and the main chain is matched with aliphatic chain segments with different molecular weights, so that the three substances are fully dispersed, the regularity is further reduced, and the polyamide has low crystallinity and good transparency. The transparent copolymerized polyamide has excellent thermal and mechanical properties, and the polymerization process is simple and controllable, and the preparation cost is low.
Drawings
FIG. 1 is an infrared image of the transparent polyamide obtained in example 1; FIG. 2 is a DSC second temperature rise curve of the transparent polyamide obtained in example 1.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
The diamines used in examples 1-6 of the present invention are selected from:
NH2-(CH2)6-NH2 A2-1，NH2-(CH2)9-NH2 A2-2，NH2-(CH2)10-NH2 A2-3；
NH2-(CH2)6-NH2 A3-1，NH2-(CH2)9-NH2 A3-2，NH2-(CH2)10-NH2 A3-3；
the dibasic acid used is selected from:
COOH-(CH2)4-COOH B1-1，COOH-(CH2)8-COOH B1-2，
COOH-(CH2)10-COOH B1-3，COOH-(CH2)11-COOH B1-4；
the reactants and mole fractions of examples 1-6 are shown in Table 1.
TABLE 1 EXAMPLES 1-6 reactants and mole fractions
Example 1
A preparation method of transparent polyamide comprises the following steps: converting the mole fraction shown in the table 1 into mass fraction, respectively weighing each reactant, controlling the sum of the diamine substance and the diacid substance to be 1:0.97, respectively salifying each reactant, uniformly mixing, adding 100kg of the reactants into a reaction kettle, adding 0.1kg of catalyst phosphoric acid and 5kg of water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 190 ℃, adjusting the pressure in the kettle to be 1.5MPa, continuously heating to 305 ℃, adjusting the pressure in the kettle to be 2MPa, maintaining the pressure for 2h, then discharging the water in the system to be normal pressure, gradually vacuumizing to reduce the pressure of the system to-0.03 MPa, discharging to obtain the transparent polyamide resin, wherein the relative viscosity of the obtained transparent polyamide resin is 2.3.
Example 2
A preparation method of transparent polyamide comprises the following steps: converting the mole fraction shown in the table 1 into mass fraction, respectively weighing each reactant, controlling the sum of the diamine substance and the diacid substance to be 1:0.98, respectively salifying each reactant, uniformly mixing, adding 100kg of the reactants into a reaction kettle, adding 0.2kg of catalyst phosphorous acid and 4kg of water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 210 ℃, adjusting the pressure in the kettle to be 2.5MPa, continuously heating to 280 ℃, adjusting the pressure in the kettle to be 2MPa, maintaining the pressure for 1h, then discharging the water in the system, gradually vacuumizing to reduce the pressure of the system to-0.07 MPa, discharging to obtain the transparent polyamide resin, wherein the relative viscosity of the obtained transparent polyamide resin is 2.7.
Example 3
A preparation method of transparent polyamide comprises the following steps: converting the mole fraction shown in the table 1 into mass fraction, respectively weighing each reactant, controlling the sum of the diamine substance and the diacid substance to be 1:0.99, respectively salifying each reactant, uniformly mixing, adding 100kg of the reactants into a reaction kettle, adding 0.3kg of catalyst sodium hypophosphite and 3.5kg of water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 200 ℃, adjusting the pressure in the kettle to be 2MPa, continuously heating to 300 ℃, adjusting the pressure in the kettle to be 1.5-2MPa, maintaining the pressure for 1.5h, then discharging to normal pressure, discharging water in the system, gradually vacuumizing to reduce the pressure of the system to-0.04 MPa, discharging to obtain transparent polyamide resin, wherein the relative viscosity of the obtained transparent polyamide resin is 2.8.
Example 4
A preparation method of transparent polyamide comprises the following steps: converting the mole fraction shown in the table 1 into mass fraction, respectively weighing each reactant, controlling the sum of the diamine substance and the diacid substance to be 1:1, respectively salifying each reactant, uniformly mixing, adding 100kg of the reactants into a reaction kettle, adding 0.4kg of catalyst sodium hypophosphite and 3kg of water, replacing air in the reaction kettle for 3-4 times by high-purity nitrogen, heating to 210 ℃, adjusting the pressure in the kettle to be 2.3MPa, continuously heating to 280 ℃, adjusting the pressure in the kettle to be 1.5MPa, maintaining the pressure for 2h, then discharging to normal pressure, discharging water in the system, gradually vacuumizing to reduce the pressure of the system to-0.05 MPa, discharging to obtain transparent polyamide resin, wherein the relative viscosity of the obtained transparent polyamide resin is 2.5.
Example 5
A preparation method of transparent polyamide comprises the following steps: converting the mole fraction shown in the table 1 into mass fraction, respectively weighing each reactant, controlling the sum of the diamine substance and the diacid substance to be 1:0.97, respectively salifying each reactant, uniformly mixing, adding 100kg of the reactants into a reaction kettle, adding 0.5kg of catalyst phosphoric acid and 2kg of water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 190 ℃ and 210 ℃, adjusting the pressure in the kettle to be 2MPa, continuously heating to 305 ℃, maintaining the pressure in the kettle to be 2MPa, maintaining the pressure for 1.5h, then discharging to normal pressure, discharging water in the system, gradually vacuumizing to reduce the pressure of the system to-0.06 MPa, discharging to obtain the transparent polyamide resin, wherein the relative viscosity of the obtained transparent polyamide resin is 2.0.
Example 6
A preparation method of transparent polyamide comprises the following steps: converting the mole fraction shown in the table 1 into mass fraction, respectively weighing each reactant, controlling the sum of the diamine substance and the diacid substance to be 1:1, respectively salifying each reactant, uniformly mixing, adding 100kg of the reactants into a reaction kettle, adding 3kg of catalyst phosphorous acid and 2.5kg of water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 210 ℃, adjusting the pressure in the kettle to be 2MPa, continuously heating to 280 ℃, adjusting the pressure in the kettle to be 1.5MPa, maintaining the pressure for 2h, then discharging the water in the system, gradually vacuumizing to reduce the pressure of the system to-0.03 MPa, discharging to obtain the transparent polyamide resin, wherein the relative viscosity of the obtained transparent polyamide resin is 2.6.
Comparative example 1
A preparation method of polyamide comprises the following steps: salifying terephthalic acid and hexamethylene diamine in water to obtain a component A; salifying m-phthalic acid and hexamethylene diamine in water to obtain a component B; putting A, B components into a reaction kettle according to a mass ratio of 70:30 and 100kg, adding 250g of sodium hypophosphite and 250g of deionized water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 200 ℃, keeping the pressure in the kettle at 2.5MPa, continuously heating to 295 ℃, keeping the pressure in the kettle at 2.0MPa, maintaining the pressure for 2 hours, discharging to normal pressure, discharging water in a system, gradually vacuumizing to reduce the pressure of the system to-0.03 MPa, and discharging to obtain the sodium hypophosphite.
The transparent polyamides obtained in examples 1 to 6 and the polyamide obtained in comparative example 1 were examined, and the results are shown in Table 2.
TABLE 2 index test for examples 1-6 and comparative example 1
Note: test standard
Tensile strength test conditions: placing the tensile sample strip in a constant temperature and humidity box for treatment for 24h, and testing by using a testing machine, wherein the testing standard is GB/T1040.2-2006;
bending strength test conditions: placing the bent sample strip in a constant temperature and humidity box for treatment for 24h, and testing by using a testing machine, wherein the testing standard is GB/T9341-2008;
notched impact strength test conditions: placing the impact sample strip in a constant temperature and humidity box for treatment for 24h, and testing by using a testing machine, wherein the testing standard is GB/T1043.1-2008;
glass transition temperature test conditions: weighing 5-8 mg of a sample, heating the sample to 250 ℃ under the protection of nitrogen, melting for 3min, quenching with liquid nitrogen, heating the quenched sample to 250 ℃, cooling to normal temperature, heating to 250 ℃, wherein the heating rate is 10 ℃/min;
the light transmittance test conditions are as follows: the method comprises the following steps of testing the light transmittance of a 722-type visible spectrophotometer produced by Shanghai optical instrument factories, preparing a round sample by a tablet press, wherein the sample is uniform and has no bubbles, and two measuring surfaces are flat, smooth and parallel and have no scratches, foreign matters, oil stains and the like;
water absorption test conditions: the test specimens were oven dried at 100 deg.C, oven cooled, and tested according to ASTM D570-98.
As can be seen from the data in the table, compared with the existing polyamide, the transparent polyamide obtained by the invention not only has better mechanical property, higher glass transition temperature and low water absorption rate, but also has excellent light transmittance.
FIG. 1 is an infrared image of a transparent polyamide obtained in example 1, in which 3280cm-1、1633cm-1、1540cm-1And 1260cm-1The absorption peaks at the positions correspond to 1460cm of amide II band and amide III band formed by coupling N-H stretching vibration, C ═ O stretching vibration (amide I band), N-H bending vibration and C-N stretching vibration of the amide compound, respectively-1The absorption peak at (A) corresponds to-CH on cyclohexane2Stretching vibration ofAnd the peak is that the polyamide resin is successfully synthesized by random copolymerization of diamine and dibasic acid through infrared spectrum analysis. FIG. 2 is a DSC second temperature rise curve of the transparent polyamide obtained in example 1, and it can be seen that the glass transition temperature is between 145 ℃ and 150 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A transparent polyamide, characterized in that it is obtained by copolymerizing diamines of the formulae A1, A2 and A3 with diacids of the formulae B1, B2 and B3,
wherein, the diamine is respectively:
NH2-(CH2)a-NH2 A2，
NH2-(CH2)b-NH2 A3，
the dibasic acids are respectively:
COOH-(CH2)c-COOH B1，
COOH-R1-COOH B2，
COOH-R2-COOH B3，
a and b are each independently selected from 6, 9 or 10, c is 4, 8, 10 or 11;
R1comprises the following steps:
R2comprises the following steps:
R3comprises the following steps:
the mass ratio of diamine to diacid is 1 (0.97-1);
the molar fraction of diamine is 60-70% of A1, 20-25% of A2, 5-20% of A3, 60-70% of B1, 20-25% of B2 and 5-20% of B3.
2. The transparent polyamide according to claim 1, characterized in that the relative viscosity of the transparent polyamide is between 2.0 and 2.8.
3. A process for the preparation of the transparent polyamide according to claim 2, characterized in that the specific process is: converting the components into specific mass according to the molar fraction, respectively weighing the components, salifying, uniformly mixing, adding the components into a reaction kettle, adding a catalyst and water, replacing air in the reaction kettle with high-purity nitrogen for 3-4 times, heating to 190-plus-210 ℃, adjusting the pressure in the kettle to be 1.5-2.5MPa, continuously heating to 280-plus-305 ℃, adjusting the pressure in the kettle to be 1.5-2MPa, maintaining the pressure for 1-2h, then discharging the air to the normal pressure, discharging the water in the system, gradually vacuumizing to reduce the pressure of the system to-0.03-0.07 MPa, and discharging to obtain the transparent polyamide resin.
4. The method for preparing transparent polyamide as claimed in claim 3, wherein the catalyst is one of phosphoric acid, phosphorous acid or sodium hypophosphite, and is used in an amount of 0.1-0.5% by weight based on the total weight of the reactants.
5. Process for the preparation of transparent polyamides according to claim 3, characterized in that the amount of water is 2-5% by weight of the total weight of the reactants.
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| US4978733A (en) * | 1989-03-09 | 1990-12-18 | Hoechst Celanese Corp. | Polyamide-polyamide-polyimide and polybenzoxazole-polyamide-polyimide polymer having at least one fluorine-containing linking group |
| CN109265677A (en) * | 2018-09-11 | 2019-01-25 | 杭州聚合顺新材料股份有限公司 | A kind of preparation method of thermostable transparent polyamide |
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| CN109265677A (en) * | 2018-09-11 | 2019-01-25 | 杭州聚合顺新材料股份有限公司 | A kind of preparation method of thermostable transparent polyamide |
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