CN109265678B - Polyamide resin, preparation method thereof and molded product - Google Patents
Polyamide resin, preparation method thereof and molded product Download PDFInfo
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- CN109265678B CN109265678B CN201811090896.1A CN201811090896A CN109265678B CN 109265678 B CN109265678 B CN 109265678B CN 201811090896 A CN201811090896 A CN 201811090896A CN 109265678 B CN109265678 B CN 109265678B
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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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
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Abstract
The invention relates to a polyamide resin and a preparation method and application thereof, wherein the polyamide is prepared by copolymerization and solid phase polycondensation of (A) and (B), wherein the (A) is a prepolymer obtained by polymerization of 100 parts by weight of caprolactam, 1-2.5 parts by weight of m-xylylenediamine, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid; (B) is a prepolymer obtained by polymerization reaction of 100 weight portions of caprolactam, 2 to 3 weight portions of sebacic acid, 1.5 to 2.5 weight portions of deionized water and 0.05 to 0.15 weight portion of terephthalic acid. The polyamide resin prepared by copolymerization and solid phase polycondensation of the prepolymer (A) and the prepolymer (B) has the advantages of high light transmittance, high strength and impact resistance.
Description
Technical Field
The invention relates to a polyamide preparation technology, in particular to a polyamide resin, a preparation method thereof and a molded product.
Background
Nylon 6 (polyamide-6) is a kind of engineering plastics with wide application range. The nylon 6 has good toughness and wear resistance, good mechanical comprehensive performance and good forming performance, and has strong seawater corrosion resistance, so that the nylon 6 is one of ideal monofilament materials and is also one of main application materials of fishing net wires in the current market, in particular to high-end fishing net products.
The main using conditions of the fishing net comprise severer using conditions such as seawater with higher salt content, airing conditions with higher temperature and the like, so that the requirement on the comprehensive performance of the fishing net wire is higher. Specifically, it is required to have good transparency, heat resistance, chemical resistance, strength index, elongation, and the like. The nylon 6 fishing net wire has good comprehensive performance, but has obvious aging phenomenon caused by stress, light, heat and other environments in the using process, and has the problems of strength reduction, water absorption increase, cracks, obvious reduction of mechanical property and the like along with the increase of the using time.
In order to improve the service performance of the PA6 fishing net, the material is generally required to be modified, and common modification directions comprise ultraviolet resistance, toughening, transparency improvement and the like.
Common modification methods include both chemical and physical modification methods. The chemical modification method is to modify the molecular structure of the PA6 macromolecule by methods such as process control, copolymerization, grafting and the like, so that the use performance of the PA6 macromolecule is more suitable for the use conditions of fishing net wires; the physical modification method is carried out by a physical filling method, and comprises blending or processing by using an anti-ultraviolet agent, a toughening agent, a softening agent and the like to improve the relevant properties of the material. The material can also be modified by a physical and chemical combination method to obtain better modification effect. At the present stage, a plurality of physical modification methods are used, the comprehensive performance of the method is poor, and the physical performance of other aspects can be greatly influenced while the performance of one aspect is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polyamide resin, a preparation method and a molded product thereof.
The polyamide resin is prepared by copolymerization and solid phase polycondensation of the following (A) and (B): (A) a prepolymer is obtained by polymerization reaction of 100 weight parts of caprolactam, 1 to 2.5 weight parts of m-xylylenediamine, 1.5 to 2.5 weight parts of deionized water and 0.05 to 0.15 weight part of terephthalic acid; (B) a prepolymer is obtained by polymerization reaction of 100 weight parts of caprolactam, 2 to 3 weight parts of sebacic acid, 1.5 to 2.5 weight parts of deionized water and 0.05 to 0.15 weight part of terephthalic acid; wherein the component (A) accounts for 40-60% of the total weight of the polyamide resin. Preferably, the component (A) is a prepolymer obtained by polymerization reaction of 100 parts by weight of caprolactam, 1.5-2 parts by weight of m-xylylenediamine, 2-2.5 parts by weight of deionized water and 0.1-0.15 part by weight of terephthalic acid; the polyamide resin composition is characterized in that the component (B) is a prepolymer obtained by polymerization reaction of 100 parts by weight of caprolactam, 2-3 parts by weight of sebacic acid, 2-2.5 parts by weight of deionized water and 0.1-0.15 part by weight of terephthalic acid, and the component (A) accounts for 50% of the total weight of the polyamide resin.
The light transmittance of the polyamide resin is greater than or equal to 67%, and preferably, the light transmittance is greater than or equal to 70%.
The preparation method of the polyamide resin provided by the invention comprises the following steps of 1: adding 100 parts by weight of caprolactam, 1-2.5 parts by weight of m-xylylenediamine, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid into a high-pressure polymerization reactor 1, filling inert gas to replace air, heating to a first temperature for heat preservation reaction, then heating to a second temperature while stirring, maintaining the pressure in the kettle at 0.1 +/-0.02 MPa, and maintaining the second temperature for reaction for 3-5 hours to obtain a prepolymer (A). In the above steps, the use amount of each raw material is preferably: 100 weight portions of caprolactam, 1.5 to 2 weight portions of m-xylylenediamine, 2 to 2.5 weight portions of deionized water and 0.1 to 0.15 weight portion of terephthalic acid are polymerized. The heating to the first temperature is primarily a heating melt mixing to mix the materials uniformly, preferably the first temperature is 80-120 c, more preferably 90-110 c, for example 100 c. The carboxyl and amino are added to the second temperature to perform the polycondensation reaction, preferably, the second temperature is 230-240 ℃, more preferably 232-238 ℃, for example 235 ℃. The inert gas is another gas not participating in the reaction in the present invention, and is intended to exhaust air from the system, and a high-purity nitrogen gas may be selected as the inert gas.
The preparation method of the polyamide resin provided by the invention comprises the following steps of 2: adding 100 parts by weight of caprolactam, 2-3 parts by weight of sebacic acid, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid into a high-pressure polymerization reactor 2, filling inert gas to replace air, heating to a first temperature for heat preservation reaction, then heating to a second temperature while stirring, maintaining the pressure in the kettle at 0.1 +/-0.02 MPa, and maintaining the second temperature for reaction for 3-5 hours to obtain a prepolymer (B). In the above steps, the use amount of each raw material is preferably: 100 weight portions of caprolactam, 2 to 3 weight portions of sebacic acid, 2 to 2.5 weight portions of deionized water and 0.1 to 0.15 weight portion of terephthalic acid are polymerized. The heating to the first temperature is primarily a heating melt mixing to mix the materials uniformly, preferably the first temperature is 80-120 c, more preferably 90-110 c, for example 100 c. The carboxyl and amino are added to the second temperature to perform the polycondensation reaction, preferably, the second temperature is 230-240 ℃, more preferably 232-238 ℃, for example 235 ℃.
The preparation method of the polyamide resin provided by the invention comprises the following steps of 3: adding the prepolymer (A) prepared in the step 1 and the prepolymer (B) prepared in the step 2 into a polymerization reactor 3 which is preheated after the air is replaced by the introduced inert gas according to the mass ratio of 2:3-3:2, starting stirring, heating to 250-270 ℃, controlling the pressure in the reactor to be 0.04-0.06 MPa, and reacting for 1.5-3 hours; then reducing the pressure to-0.03 to-0.05 MPa, continuously reacting for 1.5 to 3 hours at the pressure and the temperature of 250 to 270 ℃, and then discharging and pelletizing; and carrying out extraction drying and solid-phase polycondensation reaction on the slices obtained by cutting the particles for 6-8 hours to obtain the polyamide resin. In the above step, the mixing ratio of the prepolymer (A) to the prepolymer (B) is preferably 1: 1. The purpose of preheating the polymerization reactor 3 is to prevent an unstable reaction state in which the temperatures of A and B are rapidly decreased when they enter the reactor 3, and for example, the temperature of the polymerization reactor 3 may be preheated to 220 to 240 ℃. The heating temperature in the polymerization reactor 3 is 250-270 ℃, preferably 255-. Firstly, controlling the pressure in the kettle to be 0.04-0.06 MPa, then reducing the pressure to-0.03-0.05 MPa, and firstly carrying out a pressure reaction to ensure that the reaction process is more uniform and mild; then, the pressure is reduced, and the water generated by the polycondensation reaction is removed, so that the reaction balance is moved to the product direction, and the molecular weight of the molecular chain is increased.
The material obtained by copolymerization is extracted and dried to remove moisture, and the extraction method can be adopted to extract in hot water at 95-110 ℃ and dry at 120-150 ℃ in nitrogen atmosphere. Then, a solid phase polycondensation reaction is performed, i.e., a drying process is performed at a higher temperature, generally 160-190 ℃, for example, 175 ℃ in a nitrogen atmosphere, and the polycondensation is performed for 8 hours.
The specific scheme is as follows:
a polyamide resin is prepared by copolymerization and solid phase polycondensation of the following (A) and (B):
(A) a prepolymer is obtained by polymerization reaction of 100 weight parts of caprolactam, 1 to 2.5 weight parts of m-xylylenediamine, 1.5 to 2.5 weight parts of deionized water and 0.05 to 0.15 weight part of terephthalic acid;
(B) a prepolymer is obtained by polymerization reaction of 100 weight parts of caprolactam, 2 to 3 weight parts of sebacic acid, 1.5 to 2.5 weight parts of deionized water and 0.05 to 0.15 weight part of terephthalic acid;
wherein the component (A) accounts for 40-60% of the total weight of the polyamide resin.
Further, the prepolymer is obtained by polymerization reaction of 100 parts by weight of caprolactam, 1.5-2 parts by weight of m-xylylenediamine, 2-2.5 parts by weight of deionized water and 0.1-0.15 part by weight of terephthalic acid; the prepolymer is obtained by polymerization reaction of 100 weight parts of caprolactam, 2-3 weight parts of sebacic acid, 2-2.5 weight parts of deionized water and 0.1-0.15 weight part of terephthalic acid.
Further, the component (A) accounts for 50% of the total weight of the polyamide resin.
Further, the polyamide resin has a light transmittance of 67% or more.
The invention also provides a preparation method of the polyamide resin, which comprises the following steps:
step 1: adding 100 parts by weight of caprolactam, 1-2.5 parts by weight of m-xylylenediamine, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid into a high-pressure polymerization reactor 1, filling inert gas to replace air, heating to a first temperature for heat preservation reaction, then heating to a second temperature while stirring, maintaining the pressure in the kettle at 0.1 +/-0.02 MPa, and maintaining the second temperature for reaction for 3-5 hours to obtain a prepolymer (A);
step 2: adding 100 parts by weight of caprolactam, 2-3 parts by weight of sebacic acid, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid into a high-pressure polymerization reactor 2, filling inert gas to replace air, heating to a first temperature for heat preservation reaction, then heating to a second temperature while stirring, maintaining the pressure in the kettle at 0.1 +/-0.02 MPa, and maintaining the second temperature for reaction for 3-5 hours to obtain a prepolymer (B);
and step 3: adding the prepolymer (A) prepared in the step 1 and the prepolymer (B) prepared in the step 2 into a polymerization reactor 3 which is preheated after the air is replaced by the introduced inert gas according to the mass ratio of 2:3-3:2, starting stirring, heating to 250-270 ℃, controlling the pressure in the reactor to be 0.04-0.06 MPa, and reacting for 1.5-3 hours; then reducing the pressure to-0.03 to-0.05 MPa, continuously reacting for 1.5 to 3 hours at the pressure and the temperature of 250 to 270 ℃, and then discharging and pelletizing; and carrying out extraction drying and solid-phase polycondensation reaction on the slices obtained by cutting the particles for 6-8 hours to obtain the polyamide resin.
Further, in the step 1 or the step 2, the first temperature is 80-120 ℃, and the second temperature is 230-240 ℃.
Further, the extraction drying in the step 3 is extracting in hot water at 95-110 ℃, and drying at 120-150 ℃ in nitrogen atmosphere.
Further, the solid phase polycondensation reaction in the step 3 is carried out at a temperature of 160-190 ℃.
The invention also discloses a molded product containing the polyamide resin prepared by the preparation method of the polyamide resin.
Has the advantages that:
in the invention, the polyamide resin is prepared by copolymerization and solid phase polycondensation of the prepolymer (A) and the prepolymer (B), and has the advantages of high light transmittance and meeting the strength requirement of a monofilament product. The preparation method of the polyamide resin combines a physical method and a chemical method, finishes the modification of polyamide on the basis of the original nylon 6 slice production equipment, does not need to additionally increase production equipment, and can effectively reduce the modification cost of polyamide.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The test methods used below included:
and (3) testing light transmittance: testing the light transmittance of the polyamide by using a spectrophotometer method according to GB/T2410-2008;
tensile strength: reference GB/T1040-2006;
notched impact strength: reference GB/T1843-2008;
flexural modulus: reference is made to GB 9341-.
The following main reagents were used:
caprolactam: meets GB/T13254-;
(ii) m-xylylenediamine: the content is more than or equal to 99.5 percent;
③ sebacic acid: industrial grade, meets GB/T2092-.
Fourthly, refined terephthalic acid: industrial grade, and meets GB/T32685-2016 standard.
Example 1
100g of caprolactam, 1g of m-xylylenediamine, 1.5g of deionized water, and 0.05g of terephthalic acid were charged into a high-pressure polymerization reactor 1, and then high-purity nitrogen gas was charged into the reactor to displace air. Gradually heating to 100 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 230 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 5 hours to obtain the prepolymer (A).
100g of caprolactam, 1.5g of deionized water, 2g of sebacic acid, and 0.05g of terephthalic acid were charged into a high-pressure polymerization reactor 2, and then the reactor was charged with high-purity nitrogen gas to displace air. Gradually heating to 100 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 230 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 5 hours to obtain the prepolymer (B).
Adding the prepolymer (A) and the prepolymer (B) into a polymerization reactor 3 which has been fully preheated after air displacement according to the mass ratio of 1:1, starting stirring, raising the temperature in the kettle to 250 ℃ at the speed of 10 ℃/10min, controlling the pressure to be 0.04-0.06 MPa, and reacting for 2 hours. And (3) slowly and continuously reducing the pressure by adjusting an air release valve, reducing the pressure to-0.03 to-0.05 MPa by using a vacuum pump, maintaining the temperature and the pressure, continuously reacting for 2 hours, discharging and pelletizing. And extracting, drying and performing solid phase polycondensation for 8 hours to obtain polyamide resin chips.
Example 2
100g of caprolactam, 2.5g of m-xylylenediamine, 2.5g of deionized water, and 0.15g of terephthalic acid were charged into a high-pressure polymerization reactor 1, and then high-purity nitrogen gas was charged into the reactor to displace air. Gradually heating to 90 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 240 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 3 hours to obtain the prepolymer (A).
100g of caprolactam, 2.5g of deionized water, 3g of sebacic acid, and 0.15g of terephthalic acid were charged into a high-pressure polymerization reactor 2, and then the reactor was charged with high-purity nitrogen gas to displace air. Gradually heating to 90 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 240 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 3 hours to obtain the prepolymer (B).
Adding the prepolymer (A) and the prepolymer (B) into a polymerization reactor 3 which has been fully preheated after air displacement according to the mass ratio of 2:3, starting stirring, raising the temperature in the kettle to 270 ℃ at the speed of 10 ℃/10min, controlling the pressure to be 0.04-0.06 MPa, and reacting for 2 hours. And (3) slowly and continuously reducing the pressure by adjusting an air release valve, reducing the pressure to-0.03 to-0.05 MPa by using a vacuum pump, maintaining the temperature and the pressure, continuously reacting for 2 hours, discharging and pelletizing. And extracting, drying and performing solid phase polycondensation for 6 hours to obtain polyamide resin chips.
Example 3
100g of caprolactam, 2g of m-xylylenediamine, 1.5g of deionized water and 0.10g of terephthalic acid were charged into a high-pressure polymerization reactor 1, and then high-purity nitrogen gas was charged into the reactor to displace air. Gradually heating to 110 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 235 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 4 hours to obtain the prepolymer (A).
100g of caprolactam, 2g of deionized water, 2.5g of sebacic acid, and 0.15g of terephthalic acid were charged into a high-pressure polymerization reactor 2, and then the reactor was charged with high-purity nitrogen gas to displace air. Gradually heating to 110 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 235 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 4 hours to obtain the prepolymer (B).
Adding the prepolymer (A) and the prepolymer (B) into a polymerization reactor 3 which has been fully preheated after air displacement according to the mass ratio of 3:2, starting stirring, raising the temperature in the kettle to 260 ℃ at the speed of 10 ℃/10min, controlling the pressure to be 0.04-0.06 MPa, and reacting for 2 hours. And (3) slowly and continuously reducing the pressure by adjusting an air release valve, reducing the pressure to-0.03 to-0.05 MPa by using a vacuum pump, maintaining the temperature and the pressure, continuously reacting for 2 hours, discharging and pelletizing. After extraction, drying and solid phase polycondensation for 7 hours, polyamide resin chips are obtained.
Example 4
100g of caprolactam, 2g of m-xylylenediamine, 1g of deionized water, and 0.05g of terephthalic acid were charged into a high-pressure polymerization reactor 1, and then high-purity nitrogen gas was charged into the reactor to displace air. Gradually heating to 80 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 232 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 3-5 hours to obtain the prepolymer (A).
100g of caprolactam, 1.5g of deionized water, 2g of sebacic acid, and 0.15g of terephthalic acid were charged into a high-pressure polymerization reactor 2, and then the reactor was charged with high-purity nitrogen gas to displace air. Gradually heating to 80 deg.C, maintaining the temperature for 30min, and stirring. And slowly raising the temperature to 232 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 3-5 hours to obtain the prepolymer (B).
Adding the prepolymer (A) and the prepolymer (B) into a polymerization reactor 3 which has been fully preheated after air displacement according to the mass ratio of 1:1, starting stirring, raising the temperature in the kettle to 265 ℃ at the speed of 10 ℃/10min, controlling the pressure to be 0.04-0.06 MPa, and reacting for 2 hours. And (3) slowly and continuously reducing the pressure by adjusting an air release valve, reducing the pressure to-0.03 to-0.05 MPa by using a vacuum pump, maintaining the temperature and the pressure, continuously reacting for 2 hours, discharging and pelletizing. And extracting, drying and performing solid phase polycondensation for 6 hours to obtain polyamide resin chips.
Example 5
100g of caprolactam, 2g of m-xylylenediamine, 1g of deionized water, and 0.05g of terephthalic acid were charged into a high-pressure polymerization reactor 1, and then high-purity nitrogen gas was charged into the reactor to displace air. Gradually heating to 120 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 238 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 4 hours to obtain the prepolymer (A).
100g of caprolactam, 1.5g of deionized water, 2g of sebacic acid, and 0.15g of terephthalic acid were charged into a high-pressure polymerization reactor 2, and then the reactor was charged with high-purity nitrogen gas to displace air. Gradually heating to 120 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 238 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 4 hours to obtain the prepolymer (B).
Adding the prepolymer (A) and the prepolymer (B) into a polymerization reactor 3 which has been fully preheated after air displacement according to the mass ratio of 1:1, starting stirring, raising the temperature in the kettle to 255 ℃ at the speed of 10 ℃/10min, controlling the pressure to be 0.04-0.06 MPa, and reacting for 2 hours. And (3) slowly and continuously reducing the pressure by adjusting an air release valve, reducing the pressure to-0.03 to-0.05 MPa by using a vacuum pump, maintaining the temperature and the pressure, continuously reacting for 2 hours, discharging and pelletizing. And extracting, drying and performing solid phase polycondensation for 8 hours to obtain polyamide resin chips.
Comparative example 1
100g of caprolactam and 0.05g of terephthalic acid were fed into a high-pressure polymerization reactor 1, and then the reactor was charged with high-purity nitrogen gas to replace air. Gradually heating to 120 deg.C, maintaining the temperature for 30min, and stirring. Slowly raising the temperature to 238 ℃ at the speed of 15 ℃/10min, simultaneously adjusting the pressure in the kettle, maintaining the pressure in the kettle within the range of 0.1 +/-0.02 MPa, and carrying out heat preservation and pressure maintaining reaction for 4 hours. And continuously heating the temperature in the kettle to 255 ℃ at the speed of 15 ℃/10min, controlling the pressure to be 0.04-0.06 MPa, and reacting for 2 hours. And (3) slowly and continuously reducing the pressure by adjusting an air release valve, reducing the pressure to-0.03 to-0.05 MPa by using a vacuum pump, maintaining the temperature and the pressure, continuously reacting for 2 hours, discharging and pelletizing. After extraction, drying and solid phase polycondensation for 8 hours, comparative polyamide resin chips were obtained.
Performance detection
The polyamides obtained in the examples and comparative examples were examined and the results of their property measurements are shown in Table 1.
Table 1 product performance test results table
As can be seen from the detection results in Table 1, the light transmittance of the polyamide prepared by the method of the invention is greater than or equal to 67%, and the light transmittance effect is better than that of the comparative product. As can be seen from the test data of notch impact strength and flexural modulus, the polyamide product prepared by the method has high strength and impact resistance, and is suitable for the application fields of fishing net wires and the like.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (5)
1. A method for preparing polyamide resin is characterized in that: the method comprises the following steps:
step 1: adding 100 parts by weight of caprolactam, 1-2.5 parts by weight of m-xylylenediamine, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid into a high-pressure polymerization reactor 1, filling inert gas to replace air, heating to a first temperature for heat preservation reaction, then heating to a second temperature while stirring, maintaining the pressure in the kettle at 0.1 +/-0.02 MPa, and maintaining the second temperature for reaction for 3-5 hours to obtain a prepolymer (A);
step 2: adding 100 parts by weight of caprolactam, 2-3 parts by weight of sebacic acid, 1.5-2.5 parts by weight of deionized water and 0.05-0.15 part by weight of terephthalic acid into a high-pressure polymerization reactor 2, filling inert gas to replace air, heating to a first temperature for heat preservation reaction, then heating to a second temperature while stirring, maintaining the pressure in the kettle at 0.1 +/-0.02 MPa, and maintaining the second temperature for reaction for 3-5 hours to obtain a prepolymer (B);
and step 3: adding the prepolymer (A) prepared in the step 1 and the prepolymer (B) prepared in the step 2 into a polymerization reactor 3 which is preheated after the air is replaced by the introduced inert gas according to the mass ratio of 2:3-3:2, starting stirring, heating to 250-270 ℃, controlling the pressure in the reactor to be 0.04-0.06 MPa, and reacting for 1.5-3 hours; then reducing the pressure to-0.03 to-0.05 MPa, continuously reacting for 1.5 to 3 hours at the pressure and the temperature of 250 to 270 ℃, and then discharging and pelletizing; and carrying out extraction drying and solid-phase polycondensation reaction on the slices obtained by cutting the particles for 6-8 hours to obtain the polyamide resin.
2. The method for producing a polyamide resin according to claim 1, characterized in that: in the step 1 or the step 2, the first temperature is 80-120 ℃, and the second temperature is 230-240 ℃.
3. The method for producing a polyamide resin according to claim 1, characterized in that: and 3, extracting and drying in hot water at the temperature of 95-110 ℃, and drying at the temperature of 120-150 ℃ in nitrogen atmosphere.
4. The method for producing a polyamide resin according to claim 1, characterized in that: and 3, drying the solid-phase polycondensation reaction at the temperature of 160-190 ℃.
5. A molded article comprising the polyamide resin produced by the method for producing a polyamide resin according to any one of claims 1 to 4.
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| CN110343244B (en) * | 2019-08-09 | 2021-12-10 | 阿喀琉斯测试科技(苏州)有限公司 | Method for producing polyamide fiber-forming polymers and use thereof |
| CN111187409B (en) * | 2020-01-09 | 2022-07-12 | 万华化学集团股份有限公司 | Method and apparatus for reduced pressure polymerization of semi-aromatic polyamide |
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