CN108383996B - High-crystallization-rate polyamide and preparation method and application thereof - Google Patents
High-crystallization-rate polyamide and preparation method and application thereof Download PDFInfo
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- CN108383996B CN108383996B CN201810021677.1A CN201810021677A CN108383996B CN 108383996 B CN108383996 B CN 108383996B CN 201810021677 A CN201810021677 A CN 201810021677A CN 108383996 B CN108383996 B CN 108383996B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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Abstract
The present invention provides a high crystalRate polyamide, its crystallization peak half width delta T1/2Is 6-12 ℃. The high crystallization rate polyamide is composed of a repeating unit of dicarboxylic acid and diamine. It is composed of recurring units derived from: (a) aromatic diacids and aliphatic diacids; (b) 1, 10-decamethylenediamine and an aliphatic diamine having 2 to 13 carbon atoms other than 1, 10-decamethylenediamine; wherein the aromatic diacid accounts for 70 to 100mol percent of (a), and the 1, 10-decamethylene diamine accounts for 70 to 100mol percent of (b). The polyamide with high crystallization rate has high crystallization rate, shortens the injection molding period of materials and improves the production efficiency. The invention also provides a preparation method of the polyamide, which is simple to operate, cheap and easily available in raw materials and suitable for large-scale production; the additive for improving the crystallization rate of the polyamide, such as a nucleating agent, is not added, and the influence on the basic properties of the polyamide is small.
Description
Technical Field
The invention relates to the technical field of high polymers, in particular to polyamide with high crystallization rate and a preparation method and application thereof.
Background
Due to the characteristics of excellent mechanical property, heat resistance, abrasion resistance, chemical resistance, self-lubricating property and the like, the polyamide is widely applied to the fields of electronics, electrics, automobiles, household appliances, sports goods and the like, and is engineering plastic with the largest use amount at present. The high-temperature resistant polyamide mainly comprising semi-aromatic polyamide has high heat-resistant temperature and dimensional stability, so that the polyamide has wide application prospect in the fields of electrical and electronic industries. The trend of electrical equipment miniaturization requires that the high-temperature resistant polyamide has a higher crystallization rate so as to achieve the purposes of shortening the molding period and reducing the molding defects.
At present, "prepolymerization + solid-phase tackifying" is the predominant method for preparing polyamides. In the prior art, the prepolymer is usually pelletized and then subjected to a solid-phase tackifying reaction. The particle morphology of the polyamide prepolymer has a significant effect on the structure of the product of the solid phase tackifying reaction. For example, japanese patents JP2000044677 and JP2008239908 indicate that too large polymer particles result in large differences in the degree of polymerization between the surface and the interior, uneven molecular weight distribution, and gel generation on the particle surface. The uneven structure of polyamide molecular chain leads to slow crystallization rate and affects the injection molding process. In order to increase the crystallization rate of polyamide, 0.1% -5% of nucleating agent is added in the blending extrusion process, however, if the addition amount of the nucleating agent exceeds 0.2%, the mechanical property and the yellowing resistance of the material are adversely affected, and the nucleating agent has limited help to increase the crystallization rate of the material, so that the problem of slow crystallization rate of the material cannot be fundamentally solved.
Disclosure of Invention
The object of the present invention is to overcome the above drawbacks and to provide a polyamide having a high crystallization rate. Another object of the present invention is to provide a process for producing the polyamide.
The invention is realized by the following technical scheme:
polyamide with high crystallization rate and half-peak width Delta T of crystallization peak thereof1/2Is 6-12 ℃.
The content of the nucleating agent in the polyamide with the high crystallization rate is 0.
The nucleating agent is a substance capable of increasing the crystallization rate of the polyamide, wherein the nucleating agent can be inorganic nucleating agent and organic nucleating agent.
The inorganic nucleating agent is at least one of kaolin, talcum powder, montmorillonite, graphite, glass fiber, magnesium oxide, aluminum oxide, zinc oxide, silicon dioxide, titanium dioxide, zirconium dioxide, neodymium oxide, calcium carbonate, calcium fluoride and magnesium sulfate.
The organic nucleating agent is at least one of adipamide dimer, polyarylethersulfone, polyphenylene sulfide, phthalocyanine blue, phenyl hypophosphite, acetate and carbon fiber.
The polyamide with high crystallization rate does not contain any additive such as nucleating agent and the like which can improve the crystallization rate of the polyamide. The high crystallization rate polyamide is composed of a repeating unit of dicarboxylic acid and diamine.
The dicarboxylic acid is selected from at least one of aromatic diacid or aliphatic diacid; the diamine is at least one selected from aliphatic diamine with 2-13 carbon atoms.
The high crystallization rate polyamide is composed of repeating units derived from:
(a) aromatic diacids and aliphatic diacids;
(b) 1, 10-decamethylenediamine and an aliphatic diamine having 2 to 13 carbon atoms other than 1, 10-decamethylenediamine;
wherein the aromatic diacid accounts for 70 to 100mol percent of (a), and the 1, 10-decamethylene diamine accounts for 70 to 100mol percent of (b).
The aliphatic diacid is selected from at least one of oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 2-methylsuberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid and 1, 14-tetradecanedioic acid; at least one of 1, 6-adipic acid and 1, 10-sebacic acid is preferable.
The aliphatic diamine with the carbon number of 2-13 is selected from at least one of ethylenediamine, propylenediamine, putrescine, cadaverine, 2-methylpentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 2-methyloctanediamine, 2,4, 4-trimethylhexamethylenediamine, 5-methyl-nonanediamine, 1, 9-nonanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine and 1, 13-tridecanediamine; at least one of 1, 6-hexanediamine, 1, 8-octanediamine, 1, 12-dodecanediamine, and 1, 13-tridecanediamine is preferable.
The aromatic diacid is terephthalic acid.
A method for preparing polyamide with high crystallization rate comprises the following steps:
(A) a prepolymerization step: adding dicarboxylic acid, diamine and a reaction auxiliary agent into a reaction kettle, heating the reaction kettle, carrying out prepolymerization reaction, and discharging the prepolymer in a spray state by using the pressure in the reaction kettle after the reaction is finished;
(B) and (3) crushing the prepolymer: crushing the cooled prepolymer, wherein the crushed prepolymer is powder granular prepolymer, and the powder granular prepolymer with the grain diameter of less than 80 mu m accounts for not less than 70 percent of the total powder granular prepolymer by weight;
(C) and (3) tackifying reaction: and performing tackifying reaction on the powdery and granular prepolymer to obtain the polyamide.
Preferably, in the prepolymer pulverization step, the powdery granular prepolymer having a particle size of more than 500 μm is contained in an amount of not more than 5% by weight based on the whole powdery granular prepolymer.
The dicarboxylic acid is selected from at least one of aromatic diacid or aliphatic diacid; the diamine is at least one selected from aliphatic diamine with 2-13 carbon atoms.
The high crystallization rate polyamide is composed of repeating units derived from:
(a) aromatic diacids and aliphatic diacids;
(b) 1, 10-decamethylenediamine and an aliphatic diamine having 2 to 13 carbon atoms other than 1, 10-decamethylenediamine;
wherein the aromatic diacid accounts for 70 to 100mol percent of (a), and the 1, 10-decamethylene diamine accounts for 70 to 100mol percent of (b).
The aliphatic diacid is at least one selected from oxalic acid, malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 2-methylsuberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, 1, 12-dodecanedioic acid, 1, 13-tridecanedioic acid and 1, 14-tetradecanedioic acid.
The aliphatic diamine with the carbon number of 2-13 is at least one selected from ethylenediamine, propylenediamine, putrescine, cadaverine, 2-methylpentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 2-methyloctanediamine, 2, 4-trimethylhexamethylenediamine, 5-methyl-nonanediamine, 1, 9-nonanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine and 1, 13-tridecanediamine.
The aromatic diacid is terephthalic acid.
Preferably, in the prepolymerization step, a nylon salt can be added before the reaction kettle is heated; the nylon salt comprises at least one of hexamethylene diamine adipate, hexamethylene diamine sebacate, hexamethylene diamine dodecalaurate, hexamethylene diamine tridecanoate, hexamethylene diamine tetradecanoate and hexamethylene diamine hexadecanoate.
The reaction auxiliary agent is at least one of a catalyst and a molecular weight regulator.
The adding amount of the catalyst is 0.02-0.2wt% based on the total weight of the added dicarboxylic acid, diamine, molecular weight regulator, nylon salt and catalyst; the catalyst is selected from at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid, phosphate, phosphite, hypophosphite, phenylphosphonate, phenylphosphinate, triphenyl phosphate, triphenyl phosphite and triester phosphite;
the addition amount of the molecular weight regulator is 0.5-2.5wt% based on the total weight of the added dicarboxylic acid, diamine, nylon salt, molecular weight regulator and catalyst; the molecular weight regulator is selected from at least one of monoacid or at least one of monoamine.
The monoacid is at least one selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, cyclohexane carboxylic acid, benzoic acid, alpha-naphthalene carboxylic acid, beta-naphthalene carboxylic acid, methyl naphthalene carboxylic acid and phenyl acetic acid; preferably at least one of formic acid, acetic acid and benzoic acid.
The monoamine is at least one of methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, diphenylamine and naphthylamine; preferably decylamine and/or benzylamine.
Preferably, the reaction kettle is stirred in the prepolymerization step.
Preferably, the tackifying reaction is carried out under vacuum or nitrogen conditions.
Preferably, in the prepolymerization step, the reaction temperature is 210-260 ℃ and the reaction time is 1-3 hours.
The tackifying reaction step comprises the reaction temperature of 230 ℃ and 260 ℃, the reaction time of 6-16 hours and the vacuum degree of 50-9000 Pa.
Preferably, the tackifying reaction step has the reaction temperature of 245-255 ℃, the reaction time of 8-12 hours and the vacuum degree of 100-1000 Pa.
The polyamide with high crystallization rate is prepared by the preparation method of the polyamide with high crystallization rate;
the polyamide with high crystallization rate is applied to the fields of electric and electronic equipment, automobile parts, office supplies, household supplies and the like.
The invention has the following beneficial effects:
the polyamide of the invention has the advantage of high crystallization rate, and the half-peak width of the crystallization peak of the polyamide is delta T without adding additives such as nucleating agent for accelerating the crystallization rate of the polyamide1/26-12 ℃, shortens the injection molding cycle of the material and improves the production efficiency. The polyamide does not contain other additives for improving the crystallization rate of the polyamide such as a nucleating agent, and the like, and has no influence on the basic properties of the polyamide. The method for producing the polyamide of the present invention is a method for producing a particulate prepolymer having a powder particle diameter of less than 80 μmThe weight percentage of the prepolymer in the granules is not less than 70%, so that the heat transfer is quicker in the tackifying process, the heat on the surfaces of the granules can be quickly diffused into the granules, the polymerization degrees on the surfaces of the granules and the polymerization degrees in the granules are close to each other, and the generation of gel on the surfaces of the granules is inhibited. The method is simple to operate, the raw materials are cheap and easy to obtain, and the method is suitable for large-scale production.
The specific implementation mode is as follows:
the present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials adopted by the invention are all from commercial products;
examples 1-10 preparation of high crystallization Rate polyamides:
a prepolymerization step: according to the mixture ratio of table 1, weighed dicarboxylic acid, diamine, nylon salt, benzoic acid and sodium hypophosphite are added into a pressure kettle provided with a magnetic coupling stirring device, a condenser pipe, a gas phase port, a feeding port and a pressure explosion-proof port, and N is filled into the pressure kettle after vacuum pumping2The mixture is pumped into N after being vacuumized repeatedly until the pressure reaches normal pressure2The process is carried out three times, and finally N is added2The pressure rises to 0.3 MPa. The temperature was raised to 220 ℃ over 2 hours with stirring, the reaction mixture was stirred at 220 ℃ for 1 hour, and then the temperature of the reaction was raised to 230 ℃ with stirring. The reaction was continued at a constant temperature of 230 ℃ and a constant pressure of 2.2MPa for 2 hours, the pressure was kept constant by removing the water formed, the reaction was discharged in the form of a spray after completion of the reaction, and the prepolymer was vacuum-dried at 80 ℃ for 24 hours.
And (3) crushing the prepolymer: the prepolymer was placed in a rocking granulator model YK-160. The rotation speed of the screen and the drum is adjusted to control the particle size of the prepolymer. And then, quickly transferring the prepolymer particles into a GFG high-efficiency boiling dryer, setting the drying temperature to be 90 ℃, and drying for 10min to obtain granular prepolymers, wherein the particle size distribution of the powdery granular prepolymers is shown in Table 1. The YK-160 type oscillating granulator and the GFG high-efficiency boiling dryer are manufactured by honor fine drying equipment ltd, yozhou city.
And (3) tackifying reaction: heating the pulverized prepolymer to 150 ℃ at a heating rate of 50 ℃/h; heating to 200 ℃ at a heating rate of 30 ℃/hour; then the temperature is increased to 230 ℃ at the temperature rising rate of 10 ℃/hour; finally, the temperature is raised to 250 ℃ at the temperature raising rate of 5 ℃/hour, the temperature is kept constant, the tackifying reaction is carried out under the condition that the vacuum degree is 100Pa, and the prepared polyamide has the relative viscosity, the melting point and the half-peak width of the crystallization peak, and the results are listed in Table 1.
Comparative examples 1-10 preparation of polyamides:
a prepolymerization step: according to the mixture ratio of table 1, weighed dicarboxylic acid, diamine, nylon salt, benzoic acid and sodium hypophosphite are added into a pressure kettle provided with a magnetic coupling stirring device, a condenser pipe, a gas phase port, a feeding port and a pressure explosion-proof port, and N is filled into the pressure kettle after vacuum pumping2The mixture is pumped into N after being vacuumized repeatedly until the pressure reaches normal pressure2The process is carried out three times, and finally N is added2The pressure rises to 0.3 MPa. The temperature was raised to 220 ℃ over 2 hours with stirring, the reaction mixture was stirred at 220 ℃ for 1 hour, and then the temperature of the reaction was raised to 230 ℃ with stirring. The reaction was continued at a constant temperature of 230 ℃ and a constant pressure of 2.2MPa for 2 hours, the pressure was kept constant by removing the water formed, the discharge was effected after the reaction was completed, and the prepolymer was vacuum-dried at 80 ℃ for 24 hours to give a prepolymer.
And (3) granulating the prepolymer: 600g of water were added to 3000g of prepolymer and mixed well. After discharging, the material was placed in a YK-160 rocking granulator. The particle size of the prepolymer is controlled by adjusting the rotation speed of the screen and the drum. And then, quickly transferring the prepolymer particles into a GFG efficient boiling dryer, setting the drying temperature to be 90 ℃, and drying for 10min to obtain granular prepolymers, wherein the particle size distribution of the granular prepolymers is shown in Table 1.
And (3) tackifying reaction: heating the granulated prepolymer to 150 ℃ at a heating rate of 50 ℃/hour; heating to 200 ℃ at a heating rate of 30 ℃/hour; then the temperature is increased to 230 ℃ at the temperature rising rate of 10 ℃/hour; finally, the temperature is raised to 250 ℃ at the temperature raising rate of 5 ℃/hour, the temperature is kept constant, the tackifying reaction is carried out under the condition that the vacuum degree is 100Pa, and the prepared polyamide has the relative viscosity, the melting point and the half-peak width of the crystallization peak, and the results are listed in Table 1.
And (4) testing standard:
(1) relative viscosity (. eta.)r) And (3) testing: the test is carried out according to the national standard GB12006.1-89 of the people's republic of China and the method for measuring the viscosity number of polyamide. The specific test method is to measure the relative viscosity eta of polyamide with the concentration of 0.25g/dl in 98wt% concentrated sulfuric acid at 25 +/-0.01 DEG CrThe measurement was carried out by means of an NCY-2 automatic viscometer manufactured by Shanghai Sierda scientific instruments Co.
(2) Melting Point (T)m) And (3) testing: the Test was performed with reference to ASTM D3418-2003, Standard Test Method for transformation tests of Polymer by Differential Scanning calibration. The specific test method is that a Perkin Elmer Dimond DSC analyzer is adopted to test the melting point of the sample; nitrogen atmosphere, the flow rate is 40 mL/min; during the test, the temperature is firstly increased to 350 ℃ at the speed of 10 ℃/min, the temperature is kept for 5min at the speed of 350 ℃, then the temperature is cooled to 50 ℃ at the speed of 10 ℃/min, the temperature is increased to 350 ℃ at the speed of 10 ℃/min, and the endothermic peak temperature at the moment is taken as the melting point Tm.
(3) half-Width of crystalline Peak (. DELTA.T)1/2): the Test was performed with reference to ASTM D3418-2003, Standard Test Method for transformation tests of Polymer by Differential Scanning calibration. The specific test method is that a Perkin Elmer Dimond DSC analyzer is adopted to test the melting point of the sample; nitrogen atmosphere, the flow rate is 40 mL/min; during the test, the temperature is increased to 350 ℃ at the speed of 10 ℃/min, the temperature is kept for 5min at the temperature of 350 ℃, then the temperature is cooled to 50 ℃ at the speed of 10 ℃/min, the initial temperature of the exothermic peak is set as the melting point T1, the end temperature of the exothermic peak is set as the melting point T2, delta T1/2= (T1-T2)/2。
(4) And (3) testing the particle size distribution ratio: the tests were carried out according to the national standard GB/T20405.3-2006 (test method for incontinence with urine absorbent: characteristics of polymeric matrix liquid absorbing material-part 3: determination of particle size distribution by sieving).
Table 1: comparison of examples and comparative examples and test results of the samples
Continuing with Table 1:
continuing with Table 1:
as can be seen from Table 1, the polyamide of the present invention has a half width at half maximum of crystallization (. DELTA.T)1/2Has excellent crystallization rate at 6-12 ℃. While the polyamides of comparative examples 1-10, the half width of crystallization (. DELTA.T)1/212.5-23.5 ℃, and the crystallization rate is slow.
Claims (5)
1. A preparation method of polyamide with high crystallization rate is characterized by comprising the following steps:
(A) a prepolymerization step: adding dicarboxylic acid, diamine and a reaction auxiliary agent into a reaction kettle, heating the reaction kettle, carrying out prepolymerization reaction, and discharging the prepolymer in a spray state by using the pressure in the reaction kettle after the reaction is finished;
(B) and (3) crushing the prepolymer: crushing the cooled prepolymer, wherein the crushed prepolymer is powder granular prepolymer, and screening the particle size of the powder granular prepolymer to ensure that the powder granular prepolymer with the particle size of less than 80 mu m accounts for not less than 70% of the total powder granular prepolymer and the powder granular prepolymer with the particle size of more than 500 mu m accounts for not more than 5% of the total powder granular prepolymer;
(C) and (3) tackifying reaction: performing tackifying reaction on the powdery granular prepolymer to obtain polyamide;
the high crystallization rate polyamide is composed of repeating units derived from:
(a) terephthalic acid, or terephthalic acid with 1, 6-adipic acid, or terephthalic acid with 1, 10-sebacic acid;
(b) at least one of 1, 10-decamethylenediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, or at least one of 1, 10-decamethylenediamine and other diamines selected from at least one of 1, 6-hexanediamine, 1, 8-octamethylenediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine;
the half-peak width Delta T of the crystallization peak of the polyamide with high crystallization rate1/2At 6-12 deg.C, as tested according to ASTM D3418-2003 standard, the temperature is raised to 350 deg.C at 10 deg.C/min, maintained at 350 deg.C for 5min, and then cooled to 50 deg.C at 10 deg.C/min.
2. The method for preparing polyamide with high crystallization rate according to claim 1, wherein in the prepolymerization step, a nylon salt is further added before the reaction kettle is heated; the nylon salt is at least one selected from hexamethylene diamine adipate, hexamethylene diamine sebacate, hexamethylene diamine dodecalaurate, hexamethylene diamine tridecanoate, hexamethylene diamine tetradecanoate and hexamethylene diamine hexadecanoate.
3. The method for preparing polyamide with high crystallization rate according to claim 1, wherein the reaction auxiliary is at least one selected from the group consisting of a catalyst and a molecular weight modifier.
4. The method for preparing polyamide with high crystallization rate according to claim 3, wherein the catalyst is added in an amount of 0.02 to 0.2wt% based on the total weight of the dicarboxylic acid, diamine, molecular weight modifier, nylon salt and catalyst, and the catalyst is at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid, phosphate, phosphite, hypophosphite, phenylphosphonate, phenylphosphinate, triphenyl phosphate, triphenyl phosphite and triester phosphite; the addition amount of the molecular weight regulator is 0.5-2.5wt% based on the total weight of the added dicarboxylic acid, diamine, nylon salt, molecular weight regulator and catalyst, and the molecular weight regulator is selected from at least one of monoacid or at least one of monoamine.
5. The method for preparing polyamide with high crystallization rate according to claim 1, wherein the aromatic diacid accounts for 70 to 100mol% of (a) and the 1, 10-decamethylene diamine accounts for 70 to 100mol% of (b).
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| CN108383996B (en) * | 2018-01-10 | 2020-10-30 | 金发科技股份有限公司 | High-crystallization-rate polyamide and preparation method and application thereof |
| CN108795001B (en) | 2018-05-28 | 2020-04-07 | 金发科技股份有限公司 | Biodegradable polymer composition and application thereof |
| CN111019122B (en) * | 2019-12-24 | 2021-08-03 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide thermoplastic elastomer and continuous production method thereof |
| WO2021149815A1 (en) * | 2020-01-24 | 2021-07-29 | ユニチカ株式会社 | Method for producing polyamide resin film |
| CN115612095A (en) * | 2021-07-15 | 2023-01-17 | 上海凯赛生物技术股份有限公司 | High-temperature-resistant semi-aromatic copolyamide and preparation method, composition and molded product thereof |
| CN115838532B (en) * | 2021-09-18 | 2024-03-01 | 珠海万通特种工程塑料有限公司 | PA10T molding composite material and preparation method and application thereof |
| CN115819964B (en) * | 2021-09-18 | 2024-03-01 | 珠海万通特种工程塑料有限公司 | Polyamide molding composite material and preparation method and application thereof |
| CN116376011B (en) * | 2023-04-28 | 2024-08-20 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
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| FR2685700B1 (en) * | 1991-12-31 | 1995-02-24 | Atochem | NEW POLYAMIDES AND OBJECTS OBTAINED THEREFROM. |
| JP2000044677A (en) * | 1998-07-31 | 2000-02-15 | Kuraray Co Ltd | Production of polyamide by solid phase polymerization |
| JP5174921B2 (en) * | 2008-07-11 | 2013-04-03 | キンファ エスシーアイ アンド テック カンパニー リミテッド | Semi-aromatic polyamide and method for preparing semi-aromatic polyamide |
| CN102993437B (en) * | 2012-11-23 | 2014-12-24 | 金发科技股份有限公司 | Polyamide as well as preparation method and application thereof |
| CN104530421A (en) * | 2015-01-05 | 2015-04-22 | 无锡殷达尼龙有限公司 | Semi-aromatic polyamide preparation method |
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| CN108383996B (en) * | 2018-01-10 | 2020-10-30 | 金发科技股份有限公司 | High-crystallization-rate polyamide and preparation method and application thereof |
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2018
- 2018-01-10 CN CN201810021677.1A patent/CN108383996B/en active Active
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2019
- 2019-01-04 WO PCT/CN2019/070355 patent/WO2019137303A1/en active Application Filing
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| Publication number | Publication date |
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| CN108383996A (en) | 2018-08-10 |
| WO2019137303A1 (en) | 2019-07-18 |
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