CN109851780B - Preparation method of semi-aromatic polyamide - Google Patents
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Abstract
The invention discloses a preparation method of semi-aromatic polyamide, which comprises the following steps: 1) putting the raw materials into reaction equipment for salt forming reaction; the raw materials comprise dibasic acid, aliphatic diamine, a catalyst, deionized water, an antioxidant and a blocking agent; 2) performing prepolymerization on the product prepared in the step 1) to obtain a semi-aromatic polyamide prepolymer; 3) carrying out solid-phase polymerization reaction on the semi-aromatic polyamide prepolymer prepared in the step 2) to obtain semi-aromatic polyamide. The preparation method provided by the invention has simple reaction steps, and the prepolymerization and the solid-phase polymerization can be carried out in the same reaction equipment, so that continuous production can be realized; the invention improves the molecular weight of the polymer by a solid-phase polymerization method to obtain the semi-aromatic polyamide, has low production cost, and the quality of the product is easier to control by the solid-phase polymerization condition.
Description
Technical Field
The invention relates to the technical field of polymer synthesis. More particularly, it relates to a process for preparing semi-aromatic polyamides.
Background
The semi-aromatic polyamide is prepared by polycondensation of aromatic diacid or diamine and aliphatic diamine or diacid. As the aromatic ring is introduced into the molecular chain, compared with common aliphatic polyamide, the semi-aromatic polyamide has the advantages that the mechanical property and the heat resistance are obviously improved, the high-melting-point polyamide has the high melting point of 290-320 ℃, and the semi-aromatic polyamide is a special engineering plastic between general engineering plastic and high-temperature-resistant polyether-ether-ketone. In addition, the semi-aromatic polyamide has excellent dimensional stability, abrasion resistance, corrosion resistance and aging resistance. In recent years, with rapid development in the fields of the automobile industry, aerospace, electronics and electrical, military industry, and the like, the market demand for semi-aromatic polyamides has been increasing.
In general, semi-aromatic polyamide is industrially produced by a high-temperature high-pressure polymerization method using water as a medium. Because the semi-aromatic polyamide has a higher melting point, the product must be heated to above the melting point if the product is melted and discharged in the discharging process, so that the temperature of the product is too high during discharging, the oxidation and decomposition phenomena are serious, the product is yellow or even black, and the performance and the normal use of the product are influenced. In addition, the phenomenon of product sticking to the kettle is serious due to melt discharge, and the yield of the product is reduced.
In the patent CN101759853B, water is used as a reaction medium, a nitrogen pressurization method is adopted to prepare semi-aromatic polyamide, a prepolymer with the intrinsic viscosity of 0.06-0.3 dL/g is prepared, and solid-phase tackifying or melt tackifying is adopted after discharging to obtain a final product. The prepolymer obtained by the method can be subjected to the next step only by discharging, crushing, drying and other treatments, and the process is complex.
Patents US5516882 and US962628 use high temperature melt polymerization to prepare semi-aromatic polyamides. Because the reaction temperature is above the melting point of the polymer, the reaction energy consumption is high, and side reactions are easy to occur in the reaction process, the product performance stability is poor. In addition, some semi-aromatic polyamides having melting points above their decomposition temperature (e.g., PA6T) cannot be melt discharged, which limits the application of high temperature melt polymerization processes.
In patent CN101768266B, semi-aromatic nylon salt is prepared first, then methanol, ethanol or acetone is used as solvent, and the problem of difficult discharging is solved by adopting a method for preparing semi-aromatic nylon powder by a solvothermal method. However, the method adopts an organic solvent for reaction, has high cost and is not beneficial to environmental protection.
Patent CN103102486 utilizes the low viscosity of the primary polymerization product and the high pressure in the kettle to easily realize pressure spraying to prepare dry nylon polymer powder, and then further polycondenses the low polymerization degree nylon by melting condensation to prepare the final product. However, the steam pressure of 1.5MPa or more by water is always present in the kettle before the polymer is atomized and sprayed, so that the intrinsic viscosity of the prepolymer is inevitably low, which increases the difficulty of further thickening in the later stage.
The patent US6355769 uses a low-temperature solution polycondensation method for preparing polyamide, but the method needs a large amount of organic solvent, has high cost and high requirements on reaction equipment, and cannot be operated continuously, so the low-temperature solution polycondensation method is not suitable for industrial mass production.
At present, the yield of the domestic semi-aromatic polyamide is far behind that of foreign enterprises. In order to advance the progress of industrialization of semi-aromatic polyamides, it is important to develop a method for producing semi-aromatic polyamides.
Therefore, the invention provides a simple, low-cost, continuous production, high-molecular-weight and easily-controlled preparation method of the semi-aromatic polyamide.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a semi-aromatic polyamide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of semi-aromatic polyamide comprises the following steps:
1) putting the raw materials into reaction equipment for salt forming reaction; the raw materials comprise dibasic acid, aliphatic diamine, a catalyst, deionized water, an antioxidant and a blocking agent;
2) performing prepolymerization on the product prepared in the step 1) to obtain a semi-aromatic polyamide prepolymer;
3) carrying out solid-phase polymerization reaction on the semi-aromatic polyamide prepolymer prepared in the step 2) to obtain semi-aromatic polyamide.
Preferably, in step 1), the conditions of the salt-forming reaction are as follows: under the protection of inert gas and the stirring condition of 50-80 rpm, heating from normal temperature to 70-100 ℃ within 0.5-1 h, and carrying out salt forming reaction at constant temperature for 0.5-2 h; wherein the inert gas is preferably nitrogen or carbon dioxide.
Preferably, in step 2), the conditions of the prepolymerization are as follows: under the stirring condition of 50-150 rpm, raising the temperature to 200-220 ℃ from the salt forming reaction temperature within 1-3 h, controlling the pressure to be 1.0-3.3 MPa, and carrying out prepolymerization reaction at constant temperature for no more than 2 h. According to the invention, through the accurate control of reaction parameters, a brittle semi-aromatic polyamide prepolymer with the intrinsic viscosity of 0.05-0.5 dL/g is obtained in the prepolymerization process.
Preferably, in step 2), after the prepolymerization reaction is completed, the method further comprises the following steps: keeping the stirring speed at 50-150 rpm, and uniformly discharging gas to normal pressure within 0.5-1 h to obtain the semi-aromatic polyamide prepolymer, wherein the semi-aromatic polyamide prepolymer is powdery. In the pressure relief process, the semi-aromatic polyamide prepolymer is crushed into powder before being agglomerated through high-speed mechanical stirring at 50-150 rpm.
Preferably, in step 3), the solid-phase polymerization conditions are: and controlling the temperature to be 180-260 ℃, vacuumizing to 5-30 Pa under the temperature condition, and carrying out solid-phase polymerization reaction for 4-48 h to obtain the semi-aromatic polyamide.
Preferably, in step 3), the solid-phase polymerization conditions are: and (3) moving the semi-aromatic polyamide prepolymer to solid-phase polycondensation equipment, controlling the temperature of the solid-phase polycondensation equipment to be 180-260 ℃, vacuumizing to 5-30 Pa under the temperature condition, and carrying out solid-phase polymerization for 4-48 h to obtain the semi-aromatic polyamide. Because the semi-aromatic polyamide prepolymer obtained in the step 2) is powdery, the semi-aromatic polyamide prepolymer can be directly subjected to solid-phase tackifying operation in reaction equipment and then discharged to obtain the semi-aromatic polyamide, or the semi-aromatic polyamide prepolymer is transferred to solid-phase polycondensation equipment for solid-phase tackifying, so that the problem of difficult discharge of the semi-aromatic polyamide is effectively solved.
Preferably, the intrinsic viscosity of the semi-aromatic polyamide prepared in the step 3) is 1.0-2.4 dL/g.
Preferably, the reaction equipment in the step 1) is a high-temperature high-pressure polymerization reaction kettle. Preferably, in step 1), the dibasic acid may be terephthalic acid alone or a plurality of dibasic acids, and in this case, at least terephthalic acid is included; further, the dibasic acid in step 1) further comprises one or more of isophthalic acid, 4' -biphenyldicarboxylic acid, 2, 5-furandicarboxylic acid, sebacic acid, and dodecanedioic acid.
Preferably, the terephthalic acid accounts for 70 to 100 mol% of the total molar amount of the dibasic acid.
Preferably, in the step 1), the aliphatic diamine is one or more selected from aliphatic diamines containing 8-14 carbon atoms.
Preferably, in step 1), the catalyst is selected from one or more of sodium hypophosphite, sodium phosphite, potassium phosphite and potassium hypophosphite.
Preferably, in the step 1), the antioxidant is one or more of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, tris [2, 4-di-tert-butylphenyl ] phosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Preferably, in step 1), the blocking agent is a monoacid and/or a monoamine.
Preferably, in the step 1), the total molar amount of the aliphatic diamine is 1 to 1.03 times of the total molar amount of the dibasic acid; the mass of the catalyst is 0.1-0.5 wt% of the total mass of the dibasic acid and the aliphatic diamine; the mass of the antioxidant is 0.02-0.5 wt% of the total mass of the dibasic acid and the aliphatic diamine; the mole number of the end capping agent is 0.5-3 mol% of the total mole number of the dibasic acid; the mass of the deionized water is 0.5-1.5 times of the total mass of the raw materials except the deionized water.
Unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
(1) the preparation method provided by the invention has simple reaction steps, and the prepolymerization and the solid-phase polymerization can be carried out in the same reaction equipment, so that the continuous production can be realized.
(2) According to the invention, the powdery semi-aromatic polyamide prepolymer is directly prepared by accurately controlling the prepolymerization reaction conditions, the discharge is easy, and the problem of difficult discharge of the semi-aromatic polyamide is effectively solved.
(3) The particle size of the semi-aromatic polyamide prepolymer in the present invention can be adjusted by the reaction time, temperature and stirring conditions.
(4) The invention improves the molecular weight of the polymer by a solid-phase polymerization method to obtain the semi-aromatic polyamide, has low production cost, and the quality of the product is easier to control by the solid-phase polymerization condition.
(5) The medium used in the invention is deionized water, which is green and environment-friendly, has low cost and is easy to recycle.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows an appearance of a powdery semi-aromatic polyamide PA10T prepolymer obtained in example 1 of the present invention.
Fig. 2 shows an external view of powdery semi-aromatic polyamide PA10T obtained in example 1 of the present invention.
Fig. 3 shows a nuclear magnetic resonance hydrogen spectrum of powdery semi-aromatic polyamide PA10T obtained in example 1 of the present invention.
FIG. 4 is a photograph showing the appearance of powdery semi-aromatic polyamide PA10T/1012 obtained in example 1 of the present invention.
FIG. 5 shows an infrared spectrum of a powdery semi-aromatic polyamide PA10T/1012 obtained in example 1 of the present invention.
Fig. 6 shows an appearance of the block-shaped semi-aromatic polyamide PA10T prepolymer prepared in comparative example 1.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the present invention, the production method is a conventional method unless otherwise specified, and the raw materials used are commercially available from public sources unless otherwise specified, and the percentages are mass percentages unless otherwise specified.
Example 1
The preparation method of the semi-aromatic polyamide comprises the following steps:
adding 1mol (166.13 g) of terephthalic acid, 1.01mol (174.05 g) of decamethylene diamine, 0.01mol (1.22 g) of benzoic acid, 0.34g of sodium hypophosphite, 1.00g N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine and 510g of deionized water into a high-temperature high-pressure polymerization reaction kettle, replacing air in the kettle with nitrogen for 10 times, starting stirring, heating to 80 ℃ within 0.5h at the rotating speed of 100rpm, and carrying out salt forming reaction at constant temperature for 1 h; after the salt forming reaction is finished, heating to 220 ℃ within 2h, controlling the pressure to be not more than 2.8MPa by discharging gas in the kettle during the period, carrying out prepolymerization at constant temperature for 0.5h, and uniformly discharging gas to normal pressure within 1h after the prepolymerization reaction is finished to obtain powdery semi-aromatic polyamide prepolymer; and closing the air release valve, vacuumizing the kettle to 3-10 Pa, maintaining the temperature at 230 ℃ for solid phase polymerization reaction for 10 hours, and discharging after the solid phase polymerization reaction is finished to obtain the white powdery semi-aromatic polyamide.
As can be seen from fig. 1 and 2, the semi-aromatic polyamide is already in powder form after the pre-polymerization is completed, and a white final product is obtained after further tackifying. The chemical structure of the product was confirmed by nmr hydrogen spectroscopy (fig. 3). The product performance test results are shown in table 1.
Example 2
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1 except that the rotation speed of the stirrer was changed to 120 rpm. The product performance test results are shown in table 1.
Example 3
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1, except that the prepolymerization temperature was changed to 210 ℃. The product performance test results are shown in table 1.
Example 4
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1 except that the prepolymerization time was changed to 1 hour. The product performance test results are shown in table 1.
Example 5
Preparation of a semi-aromatic polyamide, the procedure is as in example 1, except that the prepolymerization pressure is changed to not more than 2 MPa. The product performance test results are shown in table 1.
Example 6
Semi-aromatic polyamide was prepared according to the same procedure as in example 1, except that the gas was uniformly vented to atmospheric pressure within 0.5h after completion of the prepolymerization. The product performance test results are shown in table 1.
Example 7
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1 except that the solid-phase polymerization temperature was changed to 260 ℃. The product performance test results are shown in table 1.
Example 8
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1 except that the solid-phase polymerization time was changed to 20 hours. The product performance test results are shown in table 1.
Example 9
The procedure of the semi-aromatic polyamide preparation was the same as in example 1, except that the prepolymer was transferred to a solid phase polymerizer to be subjected to solid phase polymerization after the completion of the prepolymerization process. The product performance test results are shown in table 1.
Example 10
Preparation of a semi-aromatic polyamide, the process steps are identical to example 1, except that 1mol (i.e. 166.13g) of terephthalic acid is changed to 0.9mol (i.e. 149.52g) of terephthalic acid and 0.1mol (i.e. 23.03g) of dodecanedioic acid. The product performance test results are shown in table 1. The product appearance is shown in fig. 4.
Some comparative examples
In order to ensure that the obtained product is powdery in the process of carrying out the method for producing a semi-aromatic polyamide, it is necessary to control the degree of the preliminary polymerization reaction, that is, the intrinsic viscosity of the prepolymer, within a suitable range by precisely controlling the reaction conditions. If the intrinsic viscosity of the prepolymer is too high, it is difficult to break the prepolymer into a powder, and if the intrinsic viscosity of the prepolymer is too low, it is difficult to perform solid-phase polymerization. Comparative examples 1 to 5 are to further examine the influence of the stirrer rotation speed, the prepolymerization temperature, the prepolymerization time, the prepolymerization gas release time and other factors on the product performance.
Comparative example 1
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1 except that the rotation speed of the stirrer was changed to 20 rpm.
The results show that: due to the over-slow rotating speed, the product has wide particle size distribution, and more massive products exist in the product, so that powdery products cannot be completely obtained. The product appearance is shown in fig. 6.
Comparative example 2
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1, except that the prepolymerization temperature was changed to 250 ℃.
The results show that: due to the high temperature, the inherent viscosity of the prepolymer is high, and a powdery product cannot be formed. The resulting product is shown in FIG. 6.
Comparative example 3
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1, except that the prepolymerization temperature was changed to 190 ℃. The product performance test results are shown in table 1.
The results show that: since the temperature is too low, the intrinsic viscosity of the obtained prepolymer is too low, and under the solid-phase polymerization conditions, a powdery product with high intrinsic viscosity cannot be obtained, resulting in poor product properties.
Comparative example 4
The procedure for the preparation of the semi-aromatic polyamide was the same as in example 1 except that the prepolymerization time was changed to 3 hours.
The results show that: because the prepolymerization reaction time is longer, the reaction degree is higher, the inherent viscosity of the prepolymer is higher, and a powdery product cannot be formed.
Comparative example 5
Semi-aromatic polyamide was prepared according to the same procedure as in example 1, except that the gas was uniformly vented to atmospheric pressure within 2 hours after completion of the prepolymerization.
The results show that: water is produced during the polycondensation of polyamide, and the polycondensation is promoted due to the reduction of the amount of water in the kettle during the degassing. When the degassing time of the prepolymerization is longer, the reaction degree is higher, the intrinsic viscosity of the prepolymer is higher, and a powdery product cannot be formed.
The materials prepared in the examples and comparative examples were subjected to the following tests:
intrinsic viscosity: according to the determination of GB/T12006.1-2009, 96% concentrated sulfuric acid is used as a solvent, the temperature is 25 +/-0.01 ℃, and the measurement is carried out in an Ubbelohde viscometer meeting the requirements of ISO 31052 type;
glass transition temperature: the test is carried out on a Mettler-Toledo DMA/SDTA861e, the size of a sample strip is 9mm multiplied by 4.5mm multiplied by 1mm, the stretching mode is adopted, the heating rate is 3 ℃/min, the tension is 5N, the frequency is 1Hz, and the amplitude is 15 μm;
thermal decomposition temperature: testing on a TA Q50V20.10built 36instrument, wherein the heating rate is 10 ℃/min, and the temperature when the weight loss is 5% is taken as the thermal decomposition temperature;
tensile property: according to GB/T1040.1-2006, the tensile rate is 5mm/min, and the test temperature is 23 ℃;
impact properties: the test temperature is 23 ℃ according to the test of GB/T1843-2008;
water absorption: the samples were left for 24h in air at a relative humidity of 50% and a temperature of 23 ℃ before testing as determined by GB/T1034 + 2008.
The results of various performance tests on the semi-aromatic transparent copolyamide materials prepared in examples 1-9 and comparative example 2 are shown in table 1. The data in the table show that the semi-aromatic polyamide prepared by the method has higher intrinsic viscosity, outstanding mechanical property and excellent thermal property.
TABLE 1 Performance test results
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (5)
1. The preparation method of the semi-aromatic polyamide is characterized by comprising the following steps:
1) putting the raw materials into reaction equipment for salt forming reaction; the raw materials comprise dibasic acid, aliphatic diamine, a catalyst, deionized water, an antioxidant and a blocking agent; the dibasic acid comprises at least terephthalic acid; the terephthalic acid accounts for 70-100 mol% of the total molar amount of the dibasic acid; the aliphatic diamine is decamethylene diamine; the catalyst is sodium hypophosphite; the antioxidant is N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; the end-capping reagent is benzoic acid;
2) performing prepolymerization on the product prepared in the step 1) to obtain a semi-aromatic polyamide prepolymer; the semi-aromatic polyamide prepolymer is powdery;
3) carrying out solid-phase polymerization reaction on the semi-aromatic polyamide prepolymer prepared in the step 2) to obtain semi-aromatic polyamide;
in the step 2), the prepolymerization reaction conditions are as follows: under the stirring condition of 50-150 rpm, heating the temperature to 200-220 ℃ from the salt forming reaction temperature within 1-3 h, controlling the pressure to be 1.0-3.3 MPa, and carrying out a prepolymerization reaction at a constant temperature, wherein the prepolymerization reaction time is not more than 2 h;
in the step 2), after the prepolymerization reaction is completed, the method further comprises the following steps: keeping the stirring speed at 50-150 rpm, and uniformly discharging the gas to the normal pressure within 0.5-1 h to obtain the semi-aromatic polyamide prepolymer.
2. The process for preparing a semi-aromatic polyamide according to claim 1, characterized in that in step 1), the conditions of the salt-forming reaction are: under the protection of inert gas and the stirring condition of 50-80 rpm, heating to 70-100 ℃ within 0.5-1 h, and carrying out salt forming reaction at constant temperature for 0.5-2 h.
3. The method for producing a semi-aromatic polyamide according to claim 1, wherein in the step 3), the solid-phase polymerization is performed under the following conditions: and controlling the temperature to be 180-260 ℃, vacuumizing to 5-30 Pa under the temperature condition, and carrying out solid-phase polymerization reaction for 4-48 h to obtain the semi-aromatic polyamide.
4. The method for producing a semi-aromatic polyamide according to claim 1, wherein in the step 3), the solid-phase polymerization is performed under the following conditions: and (3) moving the semi-aromatic polyamide prepolymer to solid-phase polycondensation equipment, controlling the temperature of the solid-phase polycondensation equipment to be 180-260 ℃, vacuumizing to 5-30 Pa under the temperature condition, and carrying out solid-phase polymerization for 4-48 h to obtain the semi-aromatic polyamide.
5. The method for producing a semi-aromatic polyamide as claimed in claim 1, wherein in step 1), the total molar amount of the aliphatic diamine is 1 to 1.03 times the total molar amount of the dibasic acid;
the mass of the catalyst is 0.1-0.5 wt% of the total mass of the dibasic acid and the aliphatic diamine;
the mass of the antioxidant is 0.02-0.5 wt% of the total mass of the dibasic acid and the aliphatic diamine;
the mole number of the end capping agent is 0.5-3 mol% of the total mole number of the dibasic acid;
the mass of the deionized water is 0.5-1.5 times of the total mass of the raw materials except the deionized water.
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