CN111217996B - 4-arm star-shaped nylon and preparation method thereof - Google Patents
4-arm star-shaped nylon and preparation method thereof Download PDFInfo
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- CN111217996B CN111217996B CN202010181399.3A CN202010181399A CN111217996B CN 111217996 B CN111217996 B CN 111217996B CN 202010181399 A CN202010181399 A CN 202010181399A CN 111217996 B CN111217996 B CN 111217996B
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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 a 4-arm star-shaped nylon and a preparation method thereof, wherein the 4-arm star-shaped nylon has a simple molecular structure as follows:
(ii) a Wherein R =
、
、
、
、
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to 4-arm star nylon and a preparation method thereof.
Background
Star-shaped nylon polymers are the simplest class of nonlinear polymers and are structurally characterized by a branched core from which a plurality of polymeric branches or arms extend. Compared with the corresponding linear polymer, the generation of the branched structure leads to the reduction of the hydrodynamic volume and the reduction of the molecular size of the star-shaped polymer, thereby reducing the melt viscosity and the solution viscosity of the polymer and leading the polymer to be subjected to molding processing at lower temperature. In particular, the low melt viscosity is very advantageous for thin-walled articles or articles with complex structures.
However, the core of star-shaped nylon is difficult to slide between molecular chains, and causes stress concentration to lower the fracture productivity and the notch impact strength of the star-shaped nylon, that is, lower the toughness. (Parapeng, jingqiong, etc.. Four-arm star nylon 6 synthesis and characterization [ J ] polymer material science and engineering, 2002,27 (9): 33-35.).
Disclosure of Invention
In order to overcome the disadvantages or shortcomings of the prior art, the present invention is primarily directed to a 4-arm star-shaped nylon containing diphenyl ether tetracarboxylic acid as a core of the star-shaped nylon, which has not only significantly improved mobile phase but also significantly improved toughness as compared to a corresponding linear nylon.
The invention also aims to provide a preparation method of the 4-arm star-shaped nylon.
The invention is realized by the following technical scheme:
a4-arm star-shaped nylon has a molecular structure simple formula as follows:
wherein R =
、
、
、
、
A heterocyclic aromatic group or a polycyclic aromatic group.
The preparation method of the 4-arm star-shaped nylon comprises the following steps:
1) Prepolymerization: adding diacid, diamine and deionized water into a reaction kettle in proportion, replacing air in the kettle with inert gas, filling 0.05-0.2 MPa of inert gas, heating to 110-180 ℃, stabilizing the pressure at 0.1-1.1 MPa, discharging after reacting for a period of time, centrifuging, and drying a product to obtain a nylon prepolymer;
2) Polymerization reaction: adding the obtained nylon prepolymer or lactam or amino acid and tetracarboxylic acid compound into a reaction kettle, adding deionized water and a reaction auxiliary agent, replacing air in the kettle with inert gas, filling 0.05-0.2 MPa of inert gas, heating to 160-300 ℃, maintaining the pressure in the kettle to be 0.6-3.0 MPa, reacting for a period of time, slowly reducing the pressure in the kettle to normal pressure within a period of time, continuing to react for a period of time, slowly increasing the temperature in the kettle to 230-330 ℃ in the pressure reduction process, vacuumizing, continuing to react for a period of time, discharging, and drying to obtain the 4-arm star nylon.
Wherein in the step 1), the diacid is selected from one or more of terephthalic acid, isophthalic acid or aliphatic diacid with 4 to 14 carbon atoms; the diamine is selected from one or more of butanediamine, pentanediamine and hexanediamine; the molar ratio of the dibasic acid to the diamine is 1 to 1.08, preferably 1.01 to 1.
In the step 2), the lactam is one or more of lactams with 5 to 14 carbon atoms, preferably one or more of caprolactam, decanolactam and dodecanolactam; the amino acid is one or more of amino acids with 4 to 14 carbon atoms, preferably one or more of aminocaproic acid and aminocaproic acid.
Wherein in the step 1), the addition amount of the deionized water is 30-100% of the total mass of the diacid and the diamine; the inert gas is selected from one of nitrogen, carbon dioxide and argon; the drying is carried out by a vacuum oven at the temperature of 80-145 ℃ for 12-24 h.
The reaction time in the step 1) can be set in a relatively wide range, and the same effect as that of the patent can be achieved by prolonging the reaction time, but the longer the reaction time is, the lower the efficiency is, and the reaction time is preferably 1 to 5h.
In the step 2), the constant pressure reaction time can be set in a wider range, the same effect as the patent can be achieved by prolonging the constant pressure reaction time, but the efficiency is lower the longer the time is, and the constant pressure reaction time is preferably 1 to 5 hours; the time for reducing the pressure in the kettle to the normal pressure can be set in a wider range, the same effect as the patent can be achieved by prolonging the pressure reduction time, but the longer the time is, the lower the efficiency is, and the pressure reduction time is preferably 1 to 4h; the normal-pressure reaction time can be set in a wider range, the same effect as the patent can be achieved by prolonging the normal-pressure reaction time, but the efficiency is lower as the time is longer, and the normal-pressure reaction time is preferably 2 to 5 hours; the vacuum reaction time after vacuumizing can be set in a wider range, the same effect as the patent can be achieved by prolonging the vacuum reaction time, but the longer the time is, the lower the efficiency is, and the preferable vacuum reaction time is 2 to 5h; the vacuum degree after vacuum pumping is based on vacuum pumping equipment, the lower the vacuum degree is, the more favorable the reaction is, the higher the vacuum degree is, the longer the required reaction time is, and the preferable reaction time is 0 to 60Pa.
In the step 2), the addition amount of the deionized water is 10-100% of the total mass of the diacid and the diamine; the inert gas is selected from one of nitrogen, carbon dioxide and argon.
In the step 2), the general structural formula of the tetracarboxylic acid compound is:
wherein R =
、
、
、
、
One of a heterocyclic aromatic group and a polycyclic aromatic group; the tetracarboxylic acid compound is preferably one of biphenyl diphenol type diphenyl ether tetracarboxylic acid, hydroquinone type diphenyl ether tetracarboxylic acid, m-benzene type diphenyl ether tetracarboxylic acid, bisphenol A type diphenyl ether tetracarboxylic acid, bisphenol S type diphenyl ether tetracarboxylic acid heterocyclic dihydroxy type diphenyl ether tetracarboxylic acid or polycyclic diphenol type diphenyl ether tetracarboxylic acid.
In the step 2), the adding amount of the tetracarboxylic acid compound is 0-2% of the molar weight of the nylon prepolymer monomer or lactam or amino acid, and preferably 0.5-1.5%.
Wherein, in the step 2), the coating also comprises an end-capping reagent and other auxiliary agents; the end capping agent is selected from one or more of benzoic acid, acetic acid, propionic acid or phthalic anhydride, and the addition amount is 0-2% of the total mole number of the dibasic acid monomer; the other auxiliary agents are selected from one or more of catalysts, antioxidants and ultraviolet-resistant additives; wherein the catalyst is selected from one or more of sodium phosphate, calcium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, zinc phosphite, sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite and zinc hypophosphite, and the addition amount of the catalyst is 0-0.5% of the total mass of the dibasic acid and the diamine monomer; the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1098 and antioxidant 1076, and the addition amount of the antioxidant is 0-0.5 percent of the total mass of the dibasic acid and the diamine monomer; the anti-ultraviolet additive is selected from salicylic acid esters, benzophenones and benzotriazoles, and the addition amount of the anti-ultraviolet additive is 0-0.5 percent of the total mass of the dibasic acid and the diamine monomer.
Compared with the prior art, the invention has the following beneficial effects:
1) The 4-arm star-shaped nylon contains diphenyl ether tetracarboxylic acid as a core of the star-shaped nylon, has a novel structure, can ensure that the toughness of the star-shaped nylon is obviously improved and the toughness is also obviously improved compared with that of the corresponding linear nylon by introducing an ether bond into the core.
2) The invention prepares the novel 4-arm star-shaped nylon taking diphenyl ether tetracarboxylic acid as the core by adding the tetracarboxylic acid compound with specific structure and content as the core of the star-shaped nylon and reacting with the nylon prepolymer or lactam or amino acid, compared with the corresponding linear nylon, the invention obviously improves the mobile phase on the basis of ensuring other performances of the nylon; compared with the conventional star-shaped nylon, the fluidity reaches a considerable level, and the toughness is greatly improved.
Detailed Description
The present invention is further illustrated by the following specific embodiments, which are not intended to limit the scope of the invention.
The test method of each performance index is as follows:
TABLE 1
| Performance item | Test standard |
| Melt index g/10min | ISO 1133 |
| Elongation at break% | ISO 527-1/-2 |
| Notched impact strength kJ/m 2 | ISO 180/1A |
The tetracarboxylic acid compound is prepared as follows:
(1) Biphenyl diphenol type diphenyl ether tetracarboxylic acid: adding biphenyl diphenyl ether dianhydride and water into a reaction kettle, replacing gas in the kettle with nitrogen, starting stirring, heating to 120-180 ℃, maintaining the pressure in the kettle at 0.2MPa-1.0 MPa, reacting for 1-5 h, then cooling, discharging, centrifuging, and drying to obtain biphenyl diphenol diphenyl ether tetracarboxylic acid.
(2) The process for producing hydroquinone type diphenyl ether tetracarboxylic acid, m-phenylene type diphenyl ether tetracarboxylic acid, bisphenol a type diphenyl ether tetracarboxylic acid, bisphenol S type diphenyl ether tetracarboxylic acid heterocyclic dihydroxy type diphenyl ether tetracarboxylic acid, and polycyclic diphenol type diphenyl ether tetracarboxylic acid is carried out by merely replacing the corresponding raw materials with hydroquinone type diphenyl ether dianhydride, m-phenylene type diphenyl ether dianhydride, bisphenol a type diphenyl ether dianhydride, bisphenol S type diphenyl ether dianhydride, heterocyclic dihydroxy type diphenyl ether dianhydride, and polycyclic diphenol type diphenyl ether dianhydride.
Example 1
Adding 1.97kg of laurolactam, 92.5g of biphenyldiphenol type diphenyl ether tetracarboxylic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle at 2.5MPa for reaction for 2 hours, slowly reducing the pressure in the kettle to normal pressure within 2 hours, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to 50Pa, continuing to react for 1 hour, discharging and drying to obtain the 4-arm star-shaped nylon 12. The results of testing the performance indexes such as melting point, relative viscosity, melt index, elongation at break, notched impact strength and the like of the obtained 4-arm star nylon 12 are shown in table 1.
Example 2
Adding 1.97kg of dodecalactam, 30.0g of biphenyldiphenol diphenyl ether tetracarboxylic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle to be 2.5MPa, reacting for 2 hours, maintaining the reaction temperature within 2 hours, slowly reducing the pressure in the kettle to be normal pressure, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to be 50Pa, continuing to react for 1 hour, discharging, and drying to obtain the 4-arm star nylon 12. The test results of the performance indexes of the obtained 4-arm star nylon 12, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
Example 3
Adding 1.97kg of dodecalactam, 10g of biphenyldiphenol diphenyl ether tetracarboxylic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle to be 2.5MPa, reacting for 2 hours, maintaining the reaction temperature within 2 hours, slowly reducing the pressure in the kettle to the normal pressure, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to 50Pa, continuing to react for 1 hour, discharging, and drying to obtain the 4-arm star nylon 12. The test results of the performance indexes of the obtained 4-arm star nylon 12, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
Example 4
Adding 1.97kg of laurolactam, 51.4g of biphenyldiphenol type diphenyl ether tetracarboxylic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle at 2.5MPa for reaction for 2 hours, slowly reducing the pressure in the kettle to normal pressure within 2 hours, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to 50Pa, continuing to react for 1 hour, discharging and drying to obtain the 4-arm star-shaped nylon 12. The test results of the performance indexes of the obtained 4-arm star nylon 12, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
Example 5
And (3) prepolymerization: 1.46kg of adipic acid and 1.18kg of adipic acid were added to a reaction kettle, 2600ml of deionized water was added, the reaction kettle was closed, and N was used 2 Replacing the gas in the kettle, and filling N into the kettle 2 Stirring under 0.2MPa, heating to 180 deg.C, reacting for 3 hr, cooling, discharging, centrifuging, and treating in vacuum oven at 80 deg.C for 12 hr to obtain PA66 prepolymer.
Polymerization reaction: adding 2.26kg of PA66 prepolymer prepared by prepolymerization, 33g of bisphenol A diphenyl ether tetraacid, 11g of sodium hypophosphite and 2000ml of deionized water into a reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle at 2.5MPa for reaction for 2 hours, maintaining the reaction temperature within 2 hours, slowly reducing the pressure in the kettle to normal pressure, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to 50Pa, continuing to react for 1 hour, discharging and drying to obtain the 4-arm star-shaped nylon 66. The test results of the performance indexes of the obtained 4-arm star nylon 66, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
Comparative example 1
Adding 1.97kg of dodecalactam, 12.2g of benzoic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing the air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle to be 2.5MPa for reaction for 2 hours, maintaining the reaction temperature within 2 hours, slowly reducing the pressure in the kettle to be normal pressure, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to be 50Pa, continuing to react for 1 hour, discharging and drying to obtain the 4-arm star-shaped nylon 12. The test results of the performance indexes of the obtained 4-arm star nylon 12, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
Comparative example 2
Adding 1.97kg of laurolactam, 127.5g of biphenyldiphenol type diphenyl ether tetracarboxylic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle at 2.5MPa for reaction for 2 hours, slowly reducing the pressure in the kettle to normal pressure within 2 hours, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to 50Pa, continuing to react for 1 hour, discharging and drying to obtain the 4-arm star-shaped nylon 12. The test results of the performance indexes of the obtained 4-arm star nylon 12, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
Comparative example 3
Adding 1.97kg of dodecalactam, 15g of pyromellitic acid, 4g of sodium hypophosphite and 2000ml of deionized water into a high-pressure reaction kettle, sealing the reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 0.1MPa, starting stirring, gradually heating to 260 ℃, maintaining the pressure in the kettle at 2.5MPa for reaction for 2 hours, maintaining the reaction temperature within 2 hours, slowly reducing the pressure in the kettle to normal pressure, continuing to react for 2 hours, vacuumizing, reducing the pressure in the kettle to 50Pa, continuing to react for 1 hour, discharging and drying to obtain 4-arm star-shaped nylon 12; the test results of the performance indexes of the obtained 4-arm star nylon 12, such as melting point, relative viscosity, melt index, elongation at break, notched impact strength, are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Melting Point/. Degree.C | 177.5 | 177.3 | 177.3 | 177.4 | 262.2 | 176.8 | 177.2 | 177.6 |
| Relative viscosity | 1.47 | 1.62 | 1.82 | 1.61 | 1.58 | 1.86 | 1.35 | 1.52 |
| Melt index g/10min | 18.8 | 16.5 | 5.2 | 16.4 | 11.6 | 4.5 | 22.3 | 13.2 |
| Elongation at break% | 245 | 263 | 242 | 265 | 220 | 240 | 187 | 142 |
| Notched impact strength kJ/m 2 | 5.2 | 6.7 | 5.8 | 6.9 | 3.5 | 5.5 | 3.6 | 2.4 |
Claims (11)
1. A4-arm star-shaped nylon is characterized in that the molecular structure is as follows:
wherein R =
、
、
、
、
And a heterocyclic aromatic group;
the preparation method of the 4-arm star-shaped nylon comprises the following steps:
1) And (3) prepolymerization: adding diacid, diamine and deionized water into a reaction kettle in proportion, replacing air in the kettle with inert gas, filling 0.05-0.2 MPa of inert gas, heating to 110-180 ℃, stabilizing the pressure at 0.1-1.1 MPa, discharging after reacting for a period of time, centrifuging, and drying a product to obtain a nylon prepolymer;
2) Polymerization reaction: adding the obtained nylon prepolymer or lactam or amino acid and tetracarboxylic acid compound into a reaction kettle, adding deionized water and a reaction auxiliary agent, replacing air in the kettle with inert gas, filling 0.05-0.2 MPa of inert gas, heating to 160-300 ℃, maintaining the pressure in the kettle at 0.6-3.0 MPa, reacting for a period of time, slowly reducing the pressure in the kettle to normal pressure within a period of time, continuing to react for a period of time, slowly increasing the temperature in the kettle to 230-330 ℃ in the process of reducing the pressure, then vacuumizing, continuing to react for a period of time, discharging, and drying to obtain the 4-arm star nylon;
in the step 2), the adding amount of the tetracarboxylic acid compound is 0.5-2% of the molar weight of the nylon prepolymer monomer or lactam or amino acid.
2. The method for preparing the 4-arm star nylon according to claim 1, comprising the following steps:
1) And (3) prepolymerization: adding diacid, diamine and deionized water into a reaction kettle in proportion, replacing air in the kettle with inert gas, filling 0.05-0.2 MPa of inert gas, heating to 110-180 ℃, stabilizing the pressure at 0.1-1.1 MPa, discharging after reacting for a period of time, centrifuging, and drying a product to obtain a nylon prepolymer;
2) Polymerization reaction: adding the obtained nylon prepolymer or lactam or amino acid and tetracarboxylic acid compound into a reaction kettle, adding deionized water and a reaction auxiliary agent, replacing air in the kettle with inert gas, filling 0.05-0.2 MPa of inert gas, heating to 160-300 ℃, maintaining the pressure in the kettle to be 0.6-3.0 MPa, reacting for a period of time, slowly reducing the pressure in the kettle to normal pressure within a period of time, continuing to react for a period of time, slowly increasing the temperature in the kettle to 230-330 ℃ in the pressure reduction process, vacuumizing, continuing to react for a period of time, discharging, and drying to obtain the 4-arm star nylon;
in the step 2), the adding amount of the tetracarboxylic acid compound is 0.5-2% of the molar weight of the nylon prepolymer monomer or lactam or amino acid.
3. The method for preparing the 4-arm star nylon according to claim 2, wherein in the step 1), the diacid is selected from one or more of terephthalic acid, isophthalic acid or aliphatic diacid with 4 to 14 carbon atoms; the diamine is selected from one or more of aliphatic diamines with 4-14 carbon atoms; the molar ratio of the diacid to the diamine is 1 to 1.08.
4. The method for preparing a 4-arm star-shaped nylon according to claim 3, wherein the molar ratio of the diacid to the diamine is 1.01 to 1.05.
5. The preparation method according to claim 2, wherein the lactam is one or more of lactams with 5 to 14 carbon atoms; the amino acid is one or more of amino acids with 4 to 14 carbon atoms.
6. The preparation method according to claim 5, wherein the lactam is one or more of caprolactam, decanolactam and dodecanolactam.
7. The preparation method according to claim 5, wherein the amino acid is one or more of aminocaproic acid and aminocaproic acid.
8. The method for preparing the 4-arm star-shaped nylon according to claim 2, wherein in the step 1), the addition amount of the deionized water is 30-100% of the total mass of the diacid and the diamine; the inert gas is selected from one of nitrogen, carbon dioxide and argon; the drying is carried out by using a vacuum oven at the temperature of 80-145 ℃ for 12-24 h; the reaction time is preferably 1 to 5 hours.
9. The method for preparing the 4-arm star-shaped nylon according to claim 2, wherein in the step 2), the addition amount of the deionized water is 10-100% of the total mass of the diacid and the diamine; the inert gas is selected from one of nitrogen, carbon dioxide and argon.
10. The method for preparing a 4-arm star-shaped nylon according to claim 2, wherein the tetracarboxylic acid compound in the step 2) has a general structural formula:
wherein R =
、
、
、
、
And a heterocyclic aromatic group.
11. The method for preparing the 4-arm star nylon according to claim 2, wherein the method further comprises an end-capping agent and other auxiliary agents in the step 2); the end capping agent is selected from one or more of benzoic acid, acetic acid, propionic acid or phthalic anhydride, and the addition amount of the end capping agent is 0-2% of the total mole number of diacid monomers; the other auxiliary agents are selected from one or more of catalysts, antioxidants and ultraviolet-resistant additives; wherein the catalyst is selected from one or more of sodium phosphate, calcium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, zinc phosphite, sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite and zinc hypophosphite, and the addition amount of the catalyst is 0-0.5% of the total mass of the diacid and diamine monomers; the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1098 and antioxidant 1076, and the addition amount of the antioxidant is 0-0.5 percent of the total mass of the diacid and diamine monomers; the anti-ultraviolet additive is selected from salicylic acid esters, benzophenones and benzotriazoles, and the addition amount of the anti-ultraviolet additive is 0-0.5 percent of the total mass of diacid and diamine monomers.
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| CN116003782A (en) * | 2022-04-26 | 2023-04-25 | 湖南世博瑞高分子新材料有限公司 | Synthesis method and application of high-flow low-temperature-resistant PA66 resin |
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| US4395531A (en) * | 1981-03-14 | 1983-07-26 | Mitsui Toatsu Chemical Incorporated | Process for the preparation of polyamide compounds by the reaction of polycarboxylic acids with diisocyanates in the presence of at least one mono-alkali metal salt of dicarboxylic acid |
| CA2096144A1 (en) * | 1990-11-19 | 1992-05-20 | Jean M.J. Frechet | Hyperbranched polyesters and polyamides |
| JP3355612B2 (en) * | 1992-04-14 | 2002-12-09 | 株式会社豊田中央研究所 | Star-shaped nylon and its production method, and tetrasubstituted carboxylic acid and its production method |
| CN100591707C (en) * | 2007-11-02 | 2010-02-24 | 湖南大学 | Synthesis process for ultra-branching nylon 6 |
| CN102477155B (en) * | 2010-11-29 | 2014-03-19 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of multi-arm star polyamide polymer |
| CN105622928B (en) * | 2014-10-28 | 2017-12-15 | 株洲时代新材料科技股份有限公司 | Branched polyamides and preparation method thereof |
| CN109749078A (en) * | 2019-01-31 | 2019-05-14 | 珠海派锐尔新材料有限公司 | A kind of high temperature resistant nylon and preparation method thereof |
| CN110156985B (en) * | 2019-04-30 | 2021-12-21 | 珠海派锐尔新材料有限公司 | High-fluidity random copolymerization semi-aromatic nylon and preparation method thereof |
| CN110156984A (en) * | 2019-06-18 | 2019-08-23 | 北京旭阳科技有限公司 | A kind of semiaromatic branched polyamide block copolymer and preparation method thereof |
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