CN108774317B - Super-tough nylon resin and preparation method thereof - Google Patents
Super-tough nylon resin and preparation method thereof Download PDFInfo
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- CN108774317B CN108774317B CN201810644111.4A CN201810644111A CN108774317B CN 108774317 B CN108774317 B CN 108774317B CN 201810644111 A CN201810644111 A CN 201810644111A CN 108774317 B CN108774317 B CN 108774317B
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The invention provides super-tough nylon resin which is prepared by polymerizing a component A, a component B and a catalyst, wherein the component A is prepared by polymerizing lactam, organic diacid and diamine m, and the component B is prepared by polymerizing diamine n and carboxyl-terminated polybutadiene according to the molar ratio of 1:1, polymerization in proportion; the diamine n is branched diamine and/or alicyclic diamine. The invention also provides a preparation method of the super-tough nylon resin, which comprises the following steps: adding A, B components and a catalyst into a reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously, controlling the temperature in the reaction kettle to be 200-300 ℃ and the pressure to be 0.5-1.2 MPa, maintaining the pressure for 0.5-4 h, then exhausting and reducing the pressure to discharge water in the system, and obtaining the super-tough nylon resin by vacuumizing, pressurizing, discharging, cooling and granulating. The nylon resin prepared by the method has excellent toughness, low temperature resistance and low water absorption rate, and shows higher transparency.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to super-tough nylon resin and a preparation method thereof.
Background
Polyamide, also called nylon, is a high molecular material containing amido bonds in macromolecular chains, has excellent mechanical property, self-lubricating property and self-extinguishing property, and is widely applied to the fields of automobiles, power electronics, smart phones, industrial robots and the like. Common nylons are mainly aliphatic, aromatic and semi-aromatic nylons, such as PA6, PA66, and the like. However, due to the characteristics of large polarity, high crystallinity, high hydrogen bond density and the like of nylon macromolecules, the nylon has high water absorption rate and low toughness, and particularly, the nylon 6 and the nylon 66 have low impact toughness in a dry state and at a low temperature, and have obvious notch sensitivity.
People carry out a great deal of modification research on polyamide, and improve the arrangement regularity of a nylon macromolecular chain by technical means such as toughening modification, random copolymerization, block/short block copolymerization, graft copolymerization, alternate copolymerization and the like so as to achieve the aim of improving the toughness of nylon. Chinese patent CN201310275847.6 discloses a preparation method of a block polymer for nylon toughening, which is characterized in that a macromolecule reversible addition fragmentation chain transfer reagent, styrene and a cosolvent are uniformly mixed, then slowly added into a solution system of alkali and water, added into a reactor after ultrasonic emulsification, and heated to raise temperature for polymerization reaction under the conditions of stirring and nitrogen gas introduction; then adding a second monomer and a third monomer, carrying out polymerization reaction, demulsifying and drying to obtain a block polymer for nylon toughening; the toughness of the nylon material is improved by a physical modification method, and the conditions of uneven distribution of the toughening agent, easy breakage of molecular chains and the like exist in the blending process. Chinese patent CN201410218162.2 discloses a preparation method of a super-tough wear-resistant MC nylon composite material, wherein the MC nylon prepared by the method is embedded with polyol and isocyanate units, so that the MC nylon composite material has good toughness and wear resistance, but because the polymerization mechanism involved in preparing common nylon 6 is different from the anionic polymerization mechanism involved in preparing MC nylon in the method, and nylon 6 slices need to be prepared at high temperature and high pressure, the method can not be applied to the preparation of nylon 6 resin, and the application of the method is greatly limited.
Disclosure of Invention
The invention aims to solve the technical problems that the defects and shortcomings in the background technology are overcome, the super-tough nylon resin with low temperature resistance and low water absorption rate is provided, and meanwhile, the high-efficiency, energy-saving and environment-friendly preparation method of the nylon resin is also provided.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by lactam, organic diacid and diamine m, and the component B is polymerized by diamine n and carboxyl-terminated polybutadiene according to the mol ratio of 1: 1-1.02 proportion; the diamine n is branched diamine and/or alicyclic diamine.
Preferably, the mass of the component A accounts for 90-95% of the total mass of the component A and the component B, and the mass of the component B accounts for 5-10% of the total mass of the component A and the component B. The applicant proves through a large number of experiments that the copolymerized nylon with good mechanical property and ultrahigh toughness can be obtained by controlling the content of the A, B component within the range of the invention; when the content of the component is not matched according to the range, for example, when the content of the component A is lower and the content of the component B is higher, carboxyl-terminated polysuccinic acid in the component B contains a considerable amount of double bonds, is easy to break and recombine under the high-temperature and high-pressure polymerization condition, and has a crosslinking reaction with amido bonds, so that the material cannot be discharged, and when the content of the component A is higher and the content of the component B is lower, the obtained copolymerized nylon has insufficient toughness.
Preferably, the molecular weight of the carboxyl-terminated polybutadiene is 1000-5200. In the invention, carboxyl-terminated polybutadiene can be embedded into a molecular chain of a nylon product, and the molecular weight is controlled within the range of the invention, so that the interaction among macromolecules can be greatly reduced, the regularity of the molecular chain is damaged, and various performances of the nylon product are finally improved.
In the super tough nylon resin, the lactam is preferably at least one of caprolactam, enantholactam, undecanolactam and dodecanolactam; the mass of the lactam accounts for 60-80% of the mass of the component A. The lactam can be subjected to polymerization reaction with other components, the quality of the lactam is controlled within the range of the invention, the randomness of the copolymerized nylon can be improved, and the copolymerized nylon with the advantages of higher toughness, melting point, good mechanical property and the like is obtained.
Preferably, the diamine m is aliphatic diamine, specifically at least one of hexamethylene diamine, decamethylene diamine, and dodecane diamine; the diamine n is at least one of 2-methyl pentanediamine, 4-diaminodicyclohexylmethane (PACM), 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM) and Isophoronediamine (IPDA).
In the super tough nylon resin, the organic dibasic acid is preferably at least one of adipic acid, sebacic acid, and dodecanedioic acid.
More preferably, the diamine m is hexamethylene diamine, and the organic diacid is adipic acid.
Preferably, the catalyst is at least one of water, inorganic acid and aminocaproic acid, and the ratio of the mass of the catalyst to the total mass of the component A and the component B is (0.1-10): 100. the catalyst selected by the invention is cheap and easy to obtain, economic and environment-friendly, and has high catalytic efficiency, the dosage of the catalyst needs to be controlled within the range of the invention, the dosage of the catalyst is lower than the range of the invention, so that the reaction rate of ring opening and further reaction of lactam cannot be met, and the dosage of the catalyst exceeds the range of the invention, so that the reaction rate is high, the pressure of a reaction system is high, and the operation safety is reduced.
As a general inventive concept, the present invention also provides a preparation method of the above super tough nylon resin, comprising the steps of:
adding the component A, the component B and a catalyst into a reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the reaction system to be in an anaerobic state, controlling the temperature in the reaction kettle to be 200-300 ℃, the pressure to be 0.5-1.2 MPa, maintaining the pressure for 0.5-4 h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge water in the system, then carrying out vacuumizing treatment to obtain a super-tough nylon melt, finally pressurizing to discharge the obtained super-tough nylon melt, and cooling and pelletizing to obtain the super-tough nylon resin.
In the preparation method, preferably, the preparation method of the component B comprises the following specific operation steps: adding diamine n and carboxyl-terminated polybutadiene into a reaction kettle in a nitrogen atmosphere, controlling the reaction temperature to be 80-85 ℃, the pressure to be 1-1.5 bar, and the reaction time to be 1-1.5 h, and obtaining a component B after the reaction is finished. The parameters of the preparation process of the component B need to be controlled within the scope of the invention, otherwise the reaction is incomplete or the nylon salt of the component B is oxidized.
According to the preparation method, raw materials for preparing A, B components are not directly mixed, the A component and the B component of the amide salt are respectively prepared firstly, and then the A, B component is mixed, so that the molar ratio of two synthetic nylon salt monomers can be accurately controlled, excessive acid or excessive amine is avoided during polymerization, the polymerization reaction is promoted, the end blocking of a polymerization molecular chain is avoided, the polymerization degree is prevented from being reduced, and the nylon resin with higher molecular weight is formed.
In the preparation method, the vacuumizing time is preferably 0.5-2 h, and the vacuum degree is-0.05 to-0.09 MPa. The condition parameters of the vacuum pumping treatment are controlled within the range of the invention, so that water and other small molecular substances generated by the polymerization reaction can be pumped away more easily, the polymerization reaction is facilitated, and the molecular weight and the viscosity of the product are improved; if the time and the degree of vacuum are below the range of the present invention, the reaction may be incomplete, and if the time and the degree of vacuum are above the range of the present invention, the resin may be yellowed and the requirement for equipment may be high.
Compared with the prior art, the invention has the advantages that:
according to the method, branched or alicyclic diamine and carboxyl-terminated polybutadiene are added into raw materials, a carboxyl-terminated double bond structure, a branching unit and alicyclic are introduced into nylon macromolecules through a polymerization reaction, the regularity of the nylon macromolecules is damaged, and a copolymerized nylon product has a large amorphous area, so that various performances of a nylon material are improved on a molecular chain level.
The polybutadiene molecular structure containing double bonds is introduced into a nylon macromolecular chain, so that the impact toughness and water absorption performance of nylon can be improved, and the mechanical property of the nylon can be improved; can greatly improve the molecular chain regularity of the nylon and reduce the density of hydrogen bonds, so that the nylon material has the toughness of rubber materials and the excellent processability and mechanical property of the nylon.
The method adopts a chemical copolymerization reaction form, avoids nylon macromolecules from being degraded due to physical action in a physical modification process, simultaneously avoids the use of various processing aids in the reaction process, keeps the mechanical property and the processing property of the resin, adopts water as a reaction medium in the process, and is safe, pollution-free and simple to operate.
The super-tough nylon resin prepared by the method has excellent toughness, low temperature resistance and low water absorption rate, and has low polymer crystallinity, amorphous state and high transparency due to the fact that the super-tough nylon resin contains irregular macromolecular chain structures (cyclic and branched units).
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by caprolactam, adipic acid and hexamethylene diamine, the mass of the caprolactam accounts for 70% of that of the component A, and the component B is polymerized by 2-methylpentamethylene diamine and carboxyl-terminated polybutadiene with the molecular weight of 2000 according to the mol ratio of 1:1 proportion is polymerized. The mass of the component A accounts for 90% of the total mass of the component A and the component B, and the mass of the component B accounts for 10% of the total mass of the component A and the component B. The catalyst is water, and the mass of the catalyst is 2% of the total mass of the component A and the component B.
The preparation method of the super-tough nylon resin comprises the following steps:
(1) under the nitrogen atmosphere, putting carboxyl-terminated polybutadiene and 2-methylpentamethylenediamine in a molar ratio of 1:1 into an automatic control polymerization kettle with a stirrer, controlling the reaction temperature to be 80 ℃, the pressure to be 1bar and the reaction time to be 1.5h, and obtaining a component B after the reaction is finished;
(2) putting the component A, the component B and catalyst water into a 10L stainless steel high-pressure reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the whole system to be in an oxygen-free state, controlling the temperature in the reaction kettle to be 250 ℃, controlling the pressure to be 1.0MPa, maintaining the pressure for 1.5h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge moisture in the system, then carrying out vacuumizing treatment for 1.5h, controlling the vacuum degree to be-0.08 MPa to obtain super-tough nylon melt, finally filling nitrogen gas to remove the remaining moisture, then pressurizing and discharging the obtained super-tough nylon melt, and carrying out die head casting belt molding on the melt, cooling and pelletizing to obtain the super-tough nylon resin.
Example 2:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by caprolactam, adipic acid and hexamethylene diamine, the mass of the caprolactam accounts for 70% of that of the component A, and the component B is polymerized by 2-methylpentamethylene diamine and carboxyl-terminated polybutadiene with the molecular weight of 2000 according to the mol ratio of 1:1 proportion is polymerized. The mass of the component A accounts for 91% of the total mass of the component A and the component B, and the mass of the component B accounts for 9% of the total mass of the component A and the component B. The catalyst is water, and the mass of the catalyst is 2% of the total mass of the component A and the component B.
The preparation method of the super-tough nylon resin comprises the following steps:
(1) under the nitrogen atmosphere, putting carboxyl-terminated polybutadiene and 2-methylpentamethylenediamine in a molar ratio of 1:1 into an automatic control polymerization kettle with a stirrer, controlling the reaction temperature to be 80 ℃, the pressure to be 1bar and the reaction time to be 1.5h, and obtaining a component B after the reaction is finished;
(2) putting the component A, the component B and catalyst water into a 10L stainless steel high-pressure reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the whole system to be in an oxygen-free state, controlling the temperature in the reaction kettle to be 250 ℃, controlling the pressure to be 1.0MPa, maintaining the pressure for 1.5h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge moisture in the system, then carrying out vacuumizing treatment for 1.5h, controlling the vacuum degree to be-0.08 MPa to obtain super-tough nylon melt, finally filling nitrogen gas to remove the remaining moisture, then pressurizing and discharging the obtained super-tough nylon melt, and carrying out die head casting belt molding on the melt, cooling and pelletizing to obtain the super-tough nylon resin.
Example 3:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by caprolactam, adipic acid and hexamethylene diamine, the mass of the caprolactam accounts for 70% of that of the component A, and the component B is polymerized by 2-methylpentamethylene diamine and carboxyl-terminated polybutadiene with the molecular weight of 2000 according to the mol ratio of 1:1 proportion is polymerized. The mass of the component A accounts for 92% of the total mass of the component A and the component B, and the mass of the component B accounts for 8% of the total mass of the component A and the component B. The catalyst is water, and the mass of the catalyst is 2% of the total mass of the component A and the component B.
The preparation method of the super-tough nylon resin comprises the following steps:
(1) under the nitrogen atmosphere, putting carboxyl-terminated polybutadiene and 2-methylpentamethylenediamine in a molar ratio of 1:1 into an automatic control polymerization kettle with a stirrer, controlling the reaction temperature to be 80 ℃, the pressure to be 1bar and the reaction time to be 1.5h, and obtaining a component B after the reaction is finished;
(2) putting the component A, the component B and catalyst water into a 10L stainless steel high-pressure reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the whole system to be in an oxygen-free state, controlling the temperature in the reaction kettle to be 250 ℃, controlling the pressure to be 1.0MPa, maintaining the pressure for 1.5h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge moisture in the system, then carrying out vacuumizing treatment for 1.5h, controlling the vacuum degree to be-0.08 MPa to obtain super-tough nylon melt, finally filling nitrogen gas to remove the remaining moisture, then pressurizing and discharging the obtained super-tough nylon melt, and carrying out die head casting belt molding on the melt, cooling and pelletizing to obtain the super-tough nylon resin.
Example 4:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by caprolactam, adipic acid and hexamethylene diamine, the mass of the caprolactam accounts for 70% of that of the component A, and the component B is polymerized by 2-methylpentamethylene diamine and carboxyl-terminated polybutadiene with the molecular weight of 2000 according to the mol ratio of 1:1 proportion is polymerized. The mass of the component A accounts for 93 percent of the total mass of the component A and the component B, and the mass of the component B accounts for 7 percent of the total mass of the component A and the component B. The catalyst is water, and the mass of the catalyst is 2% of the total mass of the component A and the component B.
The preparation method of the super-tough nylon resin comprises the following steps:
(1) under the nitrogen atmosphere, putting carboxyl-terminated polybutadiene and 2-methylpentamethylenediamine in a molar ratio of 1:1 into an automatic control polymerization kettle with a stirrer, controlling the reaction temperature to be 80 ℃, the pressure to be 1bar and the reaction time to be 1.5h, and obtaining a component B after the reaction is finished;
(2) putting the component A, the component B and catalyst water into a 10L stainless steel high-pressure reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the whole system to be in an oxygen-free state, controlling the temperature in the reaction kettle to be 250 ℃, controlling the pressure to be 1.0MPa, maintaining the pressure for 1.5h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge moisture in the system, then carrying out vacuumizing treatment for 1.5h, controlling the vacuum degree to be-0.08 MPa to obtain super-tough nylon melt, finally filling nitrogen gas to remove the remaining moisture, then pressurizing and discharging the obtained super-tough nylon melt, and carrying out die head casting belt molding on the melt, cooling and pelletizing to obtain the super-tough nylon resin.
Example 5:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by caprolactam, adipic acid and hexamethylene diamine, the mass of the caprolactam accounts for 70% of that of the component A, and the component B is polymerized by 2-methylpentamethylene diamine and carboxyl-terminated polybutadiene with the molecular weight of 2000 according to the mol ratio of 1:1 proportion is polymerized. The mass of the component A accounts for 94% of the total mass of the component A and the component B, and the mass of the component B accounts for 6% of the total mass of the component A and the component B. The catalyst is water, and the mass of the catalyst is 2% of the total mass of the component A and the component B.
The preparation method of the super-tough nylon resin comprises the following steps:
(1) under the nitrogen atmosphere, putting carboxyl-terminated polybutadiene and 2-methylpentamethylenediamine in a molar ratio of 1:1 into an automatic control polymerization kettle with a stirrer, controlling the reaction temperature to be 80 ℃, the pressure to be 1bar and the reaction time to be 1.5h, and obtaining a component B after the reaction is finished;
(2) putting the component A, the component B and catalyst water into a 10L stainless steel high-pressure reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the whole system to be in an oxygen-free state, controlling the temperature in the reaction kettle to be 250 ℃, controlling the pressure to be 1.0MPa, maintaining the pressure for 1.5h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge moisture in the system, then carrying out vacuumizing treatment for 1.0h and controlling the vacuum degree to be-0.08 MPa to obtain super-tough nylon melt, finally filling nitrogen gas to remove the remaining moisture, then pressurizing and discharging the obtained super-tough nylon melt, and carrying out die head casting belt molding on the melt, cooling and dicing to obtain the super-tough nylon resin.
Example 6:
the super-tough nylon resin is prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by caprolactam, adipic acid and hexamethylene diamine, the mass of the caprolactam accounts for 70% of that of the component A, and the component B is polymerized by 2-methylpentamethylene diamine and carboxyl-terminated polybutadiene with the molecular weight of 2000 according to the mol ratio of 1:1 proportion is polymerized. The mass of the component A accounts for 95% of the total mass of the component A and the component B, and the mass of the component B accounts for 5% of the total mass of the component A and the component B. The catalyst is water, and the mass of the catalyst is 2% of the total mass of the component A and the component B.
The preparation method of the super-tough nylon resin comprises the following steps:
(1) under the nitrogen atmosphere, putting carboxyl-terminated polybutadiene and 2-methylpentamethylenediamine in a molar ratio of 1:1 into an automatic control polymerization kettle with a stirrer, controlling the reaction temperature to be 80 ℃, the pressure to be 1bar and the reaction time to be 1.5h, and obtaining a component B after the reaction is finished;
(2) putting the component A, the component B and catalyst water into a 10L stainless steel high-pressure reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously to enable the whole system to be in an oxygen-free state, controlling the temperature in the reaction kettle to be 250 ℃, controlling the pressure to be 1.0MPa, maintaining the pressure for 1.5h, then exhausting to enable the pressure in the reaction kettle to be reduced to normal pressure to discharge moisture in the system, then carrying out vacuumizing treatment for 1.5h, controlling the vacuum degree to be-0.08 MPa to obtain super-tough nylon melt, finally filling nitrogen gas to remove the remaining moisture, then pressurizing and discharging the obtained super-tough nylon melt, and carrying out die head casting belt molding on the melt, cooling and pelletizing to obtain the super-tough nylon resin.
Comparative example 1:
a nylon resin is prepared by polymerizing lactam, adipic acid, hexamethylene diamine and catalyst water, wherein the mass of the water accounts for 2% of the total mass of the lactam, the adipic acid and the hexamethylene diamine.
A method for preparing the nylon resin of this comparative example, comprising the steps of:
the lactam, the adipic acid, the hexamethylenediamine and the catalyst water are put into a 10L stainless steel high-pressure reaction kettle, the air in the kettle is replaced by nitrogen for more than 3 times continuously, the whole system is in an oxygen-free state, the temperature in the reaction kettle is controlled to be 250 ℃, the pressure is 1.0MPa, the pressure is maintained for 1.5h, then the exhaust is carried out, the pressure in the reaction kettle is reduced to normal pressure, the moisture in the system is discharged, the vacuumizing treatment is carried out, the vacuumizing treatment time is 1.5h, and the vacuum degree is-0.08 MPa, the super-tough nylon melt is obtained, finally the nitrogen is injected, the obtained nylon melt is pressurized and discharged, the melt is cast and molded through a die head, and the nylon resin of the embodiment is obtained after cooling and grain cutting.
The nylon resins prepared in examples 1 to 6 and comparative example 1 were tested for tensile strength, impact toughness, low temperature impact toughness (-40 ℃), and water absorption, and the results are shown in Table 1.
TABLE 1 detection results of the relative properties of the nylon resins of examples 1-6 and comparative example 1
As can be seen from table 1, compared with comparative example 1, the super-tough nylon prepared by the preparation method of the present invention has excellent toughness, lower water absorption and water absorption, and excellent low temperature impact resistance.
Claims (9)
1. The super-tough nylon resin is characterized by being prepared by carrying out polymerization reaction on a component A, a component B and a catalyst; the component A is polymerized by lactam, organic diacid and diamine m, and the component B is polymerized by diamine n and carboxyl-terminated polybutadiene according to the mol ratio of 1: 1-1.02 proportion; the diamine n is branched diamine and/or alicyclic diamine; the molecular weight of the carboxyl-terminated polybutadiene is 1000-5200.
2. The super tough nylon resin according to claim 1, wherein the mass of the component A is 90 to 95% of the total mass of the component A and the component B, and the mass of the component B is 5 to 10% of the total mass of the component A and the component B.
3. The super tough nylon resin according to claim 1, wherein the lactam is at least one of caprolactam, enantholactam, undecanolactam, and dodecanolactam; the mass of the lactam accounts for 60-80% of the mass of the component A.
4. The super tough nylon resin according to claim 1, wherein the diamine m is at least one selected from the group consisting of hexamethylenediamine, decamethylenediamine, and dodecanediamine; the diamine n is at least one of 2-methyl pentanediamine, 4-diaminodicyclohexyl methane, 3-dimethyl-4, 4-diaminodicyclohexyl methane and isophorone diamine.
5. The super tough nylon resin according to claim 1, wherein the organic dibasic acid is at least one of adipic acid, sebacic acid, and dodecanedioic acid.
6. The super tough nylon resin according to claim 1, wherein the catalyst is at least one of water, an inorganic acid and aminocaproic acid, and the ratio of the mass of the catalyst to the total mass of the A component and the B component is (0.1 to 10): 100.
7. a method for preparing the super tough nylon resin according to any one of claims 1 to 6, comprising the steps of:
adding the component A, the component B and a catalyst into a reaction kettle, replacing air in the kettle with nitrogen gas for more than 3 times continuously, controlling the temperature in the reaction kettle to be 200-300 ℃ and the pressure to be 0.5-1.2 MPa, maintaining the pressure for 0.5-4 h, then exhausting to reduce the pressure in the reaction kettle to normal pressure to discharge water in a system, carrying out vacuumizing treatment to obtain a super-tough nylon melt, finally, pressurizing to discharge the obtained super-tough nylon melt, cooling and pelletizing to obtain the super-tough nylon resin.
8. The preparation method according to claim 7, characterized in that the preparation method of the B component comprises the following specific operation steps: adding diamine n and carboxyl-terminated polybutadiene into a reaction kettle in a nitrogen atmosphere, controlling the reaction temperature to be 80-85 ℃, the pressure to be 1-1.5 bar, and the reaction time to be 1-1.5 h, and obtaining a component B after the reaction is finished.
9. The preparation method according to claim 7, wherein the time of the vacuuming is 0.5 to 2 hours, and the vacuum degree is-0.05 to-0.09 MPa.
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| CN111471298A (en) * | 2020-04-22 | 2020-07-31 | 建湖县兴隆尼龙有限公司 | Toughened nylon material and preparation method thereof |
| CN112920596A (en) * | 2021-01-27 | 2021-06-08 | 浙江工业大学 | Preparation method of high-transparency nylon material |
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