CN113136030A - Polyamide derived from monomer containing single six-membered alicyclic structure and preparation method thereof - Google Patents
Polyamide derived from monomer containing single six-membered alicyclic structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses novel polyamide derived from a monomer containing single-six-membered alicyclic structure and a preparation method thereof, belonging to the field of synthesis of high polymer materials. The polyamide is prepared by polymerizing diamine or diacid containing a single hexatomic alicyclic structure and corresponding diacid or diamine (aliphatic or aromatic monomer of C3-C18) serving as raw materials through a one-step method, and the preparation method is simple, convenient and easy to implement, and convenient for industrial popularization and application. Meanwhile, the alicyclic polyamide has high temperature resistance, ultraviolet aging resistance, excellent melt flow melt processability and the like, and can be widely used in the fields of electronic appliances, automobile industry, aerospace and the like.
Description
Technical Field
The invention belongs to the technical field of compounds and preparation thereof, and particularly relates to polyamide derived from a monomer containing single six-membered alicyclic structure and a preparation method thereof.
Technical Field
Polyamide (PA), the first engineering plastic variety developed, has remained a vigorous development since its industrial production in the thirties of the last century. With the rapid development of economy and technology, especially the rapid and rapid technological innovation in the fields of aerospace, automobiles, electronic appliances and the like, urgent needs are generated for special engineering plastic varieties with high-temperature resistant engineering plastics capable of being molded and formed and the long-term use temperature of more than 150 ℃. Therefore, polyamide materials having excellent thermal stability, better solvent resistance and product stability are receiving wide attention.
The hexatomic alicyclic polyamide is obtained by condensation polymerization of diamine or diacid containing a hexatomic alicyclic structure and aliphatic/aromatic diamine or diacid. The six-membered alicyclic polyamide has excellent heat resistance and lower water absorption compared with aliphatic polyamides, and has excellent properties such as chemical stability and melt flowability due to the saturated structure of the six-membered alicyclic compared with aromatic polyamides. Patents CN 111403307B, CN105330847A and CN 102918080 a, etc. propose the preparation of bis-alicyclic polyamides. The method is characterized in that a bi-alicyclic polyamide with certain excellent transparency or gas barrier property and other properties is prepared by using bi-alicyclic diamine monomers such as 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM), 4' -diaminodicyclohexylmethane (PACM), 2-bis (4-aminocyclohexane) propane (PACP) and the like, but the bi-alicyclic polyamide cannot be used in a high-temperature environment for a long time, and a stabilizer and a catalyst are required to be added in the reaction process, so that the synthesis cost of the bi-alicyclic polyamide is increased, and the application field of the obtained product is limited.
For the high temperature resistant polymer aromatic polyamide, patents CN 101768266A, CN 101456949A, CN 103923313A, CN 105722891A, CN 109851780a and the like adopt aromatic monomers to prepare the aromatic polyamide, and it is noted that a two-step preparation method of the aromatic polyamide by adopting solution prepolymerization-solid phase post polymerization is proposed in the patents. Firstly, preparing a low-molecular-weight polyamide prepolymer in a certain solvent, cooling, separating the prepolymer from the solvent, drying, and then improving the molecular weight of the prepolymer through a solid-phase post-polymerization process. The polymerization process has long polymerization time, complex process, high production cost, low yield, waste liquid generation and other disadvantages. Meanwhile, the unsaturated structure of the aromatic polyamide is easy to yellow and age in the using process, so that the using time and the appearance of the material are influenced.
The application of literature engineering plastics, 2020, 48(8), 10-15, reports a copolyamide PA10T/10C containing a single six-membered alicyclic structure, the one-step feeding solution prepolymerization-solid phase tackifying synthesis process is adopted, the polymerization reaction temperature is high, the time is long, the energy consumption is high, the production efficiency is low, the product is easy to form gel and yellow, even black spots are generated, the product performance and the appearance are influenced, and the one-step feeding solution prepolymerization-solid phase tackifying synthesis process is not suitable for industrial production processes.
Disclosure of Invention
The invention aims to provide a polyamide derived from a monomer containing a single six-membered alicyclic structure, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
polyamide derived from a monomer containing a single six-membered alicyclic structure, and having a structural general formula:
in the formula, wherein R1、R2Is one or more of independent cycloalkyl, C3-C18 alkyl, aryl and derivatives thereof, and R1And R2Wherein there is only one hydrocarbon-based unit containing a single six-membered alicyclic structure, n>20 and ensures that the molecular weight of the polymer is not less than 1 ten thousand.
The monomer of the six-membered alicyclic structure is para-substituted six-membered alicyclic diacid or para-substituted six-membered alicyclic diamine, preferably one or more monomers of six-membered alicyclic dicarboxylic acid, six-membered alicyclic diacetic acid, six-membered alicyclic diamine, six-membered alicyclic dimethylamine and six-membered alicyclic diethylamine.
The preparation method of the polyamide derived from the monomer containing the single six-membered alicyclic structure comprises the following steps:
(1) mixing a mixture of 1: adding 0.98-1.02 of dicarboxylic acid and diamine into water, taking water as a solvent, wherein the mass of the water is 40-80% of the total mass of the acid amine monomers, heating to 40-100 ℃, stirring, adjusting the pH value to 7.0-7.5, continuously reacting for 20-40 min, and drying to obtain the alicyclic polyamide salt;
(2) adding alicyclic polyamide salt into a reaction kettle, polymerizing by a one-step polymerization process, raising the temperature of a system to a preset temperature at a temperature raising rate of 5-20 ℃/min under the protection of inert atmosphere, keeping the pressure of the kettle at 0.7-2.0 MPa, maintaining the pressure for 0.5-4 h, reducing the water discharge to normal pressure, ensuring that water vapor is completely discharged within 0.5-2 h, continuing raising the temperature of the system to a certain temperature, vacuumizing until the pressure in the kettle is less than 100Pa, and reducing the temperature and discharging after carrying out negative pressure polymerization for 2-5 h to obtain the hexabasic alicyclic polyamide.
The molar ratio of cis configuration to trans configuration of the six-membered alicyclic monomer in the step (1) is 100: 0 to 0: 100, obtaining the six-membered alicyclic polyamide with different cis-trans ratios. In the step (2), the temperature ranges of the pressure-maintaining polymerization and the negative-pressure polymerization are different according to different chain structures of the six-membered alicyclic polyamide. The pressure-maintaining polymerization temperature of alicyclic polyamide salt taking alkyl compounds as monomers is 180-220 ℃, and the negative pressure polymerization temperature is 210-250 ℃; and the pressure-maintaining polymerization temperature of the alicyclic polyamide salt of which the monomer is a phenyl compound is 230-260 ℃, the negative pressure polymerization temperature is 250-280 ℃, and the negative pressure polymerization temperature is not less than the pressure-maintaining polymerization temperature. The inert gas is one of carbon dioxide, argon, nitrogen or helium.
By regulating and controlling the cis-trans ratio of the six-membered alicyclic monomer in the six-membered alicyclic polyamide, the thermal property, the optical property, the mechanical property and the like of the polyamide can be controlled.
Compared with the prior art, the invention has the following positive effects:
(1) provided is a cycloaliphatic polyamide having a novel structure; the alicyclic polyamide has high temperature resistance, ultraviolet aging resistance, excellent melt flow melt processability and the like, and can be widely used in the fields of electronic appliances, automobile industry, aerospace and the like.
(2) The invention designs a method for obtaining alicyclic linear chain polyamide by one-step solid phase polycondensation based on the basic synthesis process of polyamide, the whole preparation method is simple and easy to implement, the industrial production is more convenient and practical, no melting phenomenon exists, the powdery product is discharged, and the method has the advantages of less side reaction and good controllability and is convenient for industrial popularization and application.
Drawings
FIG. 1 is a graph showing an infrared spectrum of a cycloaliphatic linear polyamide obtained in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the alicyclic linear polyamide of example 1;
FIG. 3 is a DSC spectrum of the cycloaliphatic linear polyamide obtained in example 1;
FIG. 4 is a TG spectrum of the alicyclic linear polyamide obtained in example 1;
FIG. 5 is an XRD spectrum of the cycloaliphatic linear polyamide of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples and accompanying drawings. It should be noted that these examples are presented to aid understanding of the invention and are not meant to limit the scope of the invention. The raw materials used in the present invention are all commercially available.
Example 1
An aliphatic polyamide obtained by condensation polymerization of 1, 4-cyclohexanedicarboxylic acid (172g/mol) and decamethylenediamine (172g/mol) in a cis-trans ratio of 0/100.
The preparation method comprises the following steps:
1) adding 172g of decamethylenediamine and 172g of 1, 4-cyclohexanedicarboxylic acid into a three-neck flask with a thermometer, adding 172g of distilled water, heating to 50 ℃, magnetically stirring for 30min until a clear transparent solution is obtained, adjusting the pH value to 7.0-7.5, continuously stirring for 30min to balance the reaction, evaporating the water by reduced pressure distillation, and drying in a vacuum oven to obtain white PA10C salt powder.
2) 100gPA10C salt was added to a 500mL kettle and 5g of distilled water was added to the kettle. Sealing the reaction kettle, and replacing the air in the reaction kettle by repeating the steps of inflating, vacuumizing and inflating with high-purity nitrogen gas for 3 timesRemoving oxygen in the system to ensure that the reaction is carried out under the inert gas atmosphere; and starting the temperature rise process of the system, raising the temperature to 220 ℃ at a speed of 10 ℃/min, carrying out heat preservation and pressure maintaining for 0.5h, releasing steam for 0.5h, raising the temperature to 250 ℃ in a vacuum state, and continuing to react for 5h to obtain the hexatomic alicyclic polyamide PA10℃. Its melting point is 353 deg.C, T5％(temperature at 5% weight loss) 428 ℃ C., intrinsic viscosity 1.27, and transparency 71%.
Example 2
An aliphatic polyamide is obtained by condensation polymerization of 1, 4-cyclohexanediacetic acid (200g/mol) and p-phenylenediamine (108g/mol) in a cis-trans ratio of 20/80.
The preparation method comprises the following steps:
1) 108g of p-phenylenediamine and 200g of 1, 4-cyclohexanediacetic acid are added into a three-neck flask with a thermometer, 154g of distilled water is added, the temperature is raised to 100 ℃, magnetic stirring is carried out for 30min until a clear transparent solution is obtained, the pH is adjusted to 7.0-7.5, stirring is continued for 20min, the reaction is balanced, water is evaporated to dryness through reduced pressure distillation, and the white PATC salt powder is obtained after the drying in a vacuum oven.
2) 100g of PATC salt was added to a 500mL reaction kettle, and 5g of distilled water was added to the reaction kettle. Sealing the reaction kettle, and repeatedly performing the operations of inflating, vacuumizing and inflating by using high-purity nitrogen gas for 3 times to replace the air in the reaction kettle so as to remove oxygen in the system and ensure that the reaction is performed under the inert gas atmosphere; and (3) starting the temperature rise process of the system, raising the temperature to 260 ℃ at the speed of 20 ℃/min, carrying out heat preservation and pressure maintaining for 1h, releasing steam for 1h, raising the temperature to 280 ℃ in a vacuum state, and continuing to react for 4h to obtain the six-membered alicyclic polyamide PATC. Its melting point is 359 ℃ and T5％(temperature at 5% weight loss) 435 ℃, intrinsic viscosity 1.21, and transparency 76%.
Example 3
An aliphatic polyamide is prepared by condensation polymerization (284g/mol) of 1, 4-cyclohexanedipropionic acid (228g/mol) with octadecylene diamine in a cis-trans ratio of 50/50.
The preparation method comprises the following steps:
1) 284g of octadecylene diamine and 228g of 1, 4-cyclohexanedipropionic acid are added into a three-neck flask with a thermometer, then 256g of distilled water is added, the temperature is raised to 40 ℃, magnetic stirring is carried out for 30min until a clear transparent solution is obtained, the pH is adjusted to 7.0-7.5, stirring is carried out for 40min continuously, the reaction is balanced, water is evaporated to dryness through reduced pressure distillation, and the solution is placed in a vacuum oven to be dried, so that PADC18 salt white powder is obtained.
2) 100g of PADC18 salt was added to a 500mL kettle and 5g of distilled water was added to the kettle. Sealing the reaction kettle, and repeatedly performing the operations of inflating, vacuumizing and inflating by using high-purity nitrogen gas for 3 times to replace the air in the reaction kettle so as to remove oxygen in the system and ensure that the reaction is performed under the inert gas atmosphere; the system begins to heat up, the temperature is raised to 180 ℃ at the speed of 5 ℃/min for heat preservation and pressure maintaining for 2h, steam is released for 0.5h, the temperature is raised to 210 ℃ in a vacuum state for continuous reaction for 2h, and the six-membered alicyclic polyamide PADC18 is obtained, the melting point is 246 ℃, and T is5％(temperature at 5% weight loss) 319 ℃, intrinsic viscosity 1.37, and transparency 84%.
Example 4
An aliphatic polyamide obtained by condensation polymerization of 1, 4-cyclohexanediamine (114g/mol) with glutaric acid (132g/mol) in a cis-trans ratio of 80/20.
The preparation method comprises the following steps:
1) adding 114g of 1, 4-cyclohexanediamine and 132g of glutaric acid into a three-neck flask with a thermometer, adding 123g of distilled water, heating to 70 ℃, magnetically stirring for 30min until a clear transparent solution is obtained, adjusting the pH value to 7.0-7.5, continuously stirring for 30min to balance the reaction, evaporating the water by reduced pressure distillation, and drying in a vacuum oven to obtain PAD5 salt white powder.
2) 100g of PAD5 salt was added, the tube was placed in a 500mL kettle, and a small amount of distilled water was added to the kettle. Sealing the reaction kettle, and repeatedly performing the operations of inflating, vacuumizing and inflating by using high-purity nitrogen gas for 3 times to replace the air in the reaction kettle so as to remove oxygen in the system and ensure that the reaction is performed under the inert gas atmosphere; starting the temperature rise process of the system, raising the temperature to 220 ℃ at a speed of 10 ℃/min, carrying out heat preservation and pressure maintaining for 4h, releasing steam for 2h, raising the temperature to 250 ℃ in a vacuum state, continuing to react for 5h to obtain the hexatomic alicyclic polyamide PAD5, and melting the hexatomic alicyclic polyamide PAD5Point 315 ℃ and T5％(temperature at 5% weight loss) was 387 ℃, intrinsic viscosity was 1.25, and transparency was 87%.
Example 5
An aliphatic polyamide is obtained by condensation polymerization of 1, 4-cyclohexanedimethylamine (142g/mol) and p-phenylenediacetic acid (194g/mol) in a cis-trans ratio of 100/0.
The preparation method comprises the following steps:
1) adding 1, 4-cyclohexanedimethanamine 142g and p-phthalic acid 194g into a three-neck flask with a thermometer, adding 169g of distilled water, heating to 60 ℃, magnetically stirring for 30min until a clear transparent solution is obtained, adjusting the pH value to 7.0-7.5, continuously stirring for 30min to balance the reaction, evaporating the water by reduced pressure distillation, and drying in a vacuum oven to obtain white PADMT salt powder.
2) 100g of PADMT salt was added, the tube was placed in a 500mL reaction kettle, and a small amount of distilled water was added to the reaction kettle. Sealing the reaction kettle, and repeatedly performing the operations of inflating, vacuumizing and inflating by using high-purity nitrogen gas for 3 times to replace the air in the reaction kettle so as to remove oxygen in the system and ensure that the reaction is performed under the inert gas atmosphere; and starting the temperature rise process of the system, raising the temperature to 230 ℃ at a speed of 10 ℃/min, carrying out heat preservation and pressure maintaining for 1h, releasing steam for 2h, raising the temperature to 250 ℃ in a vacuum state, and continuing to react for 3h to obtain the hexatomic alicyclic polyamide PADMT. Its melting point is 295 ℃ and T5％(temperature at 5% weight loss) 377 ℃, intrinsic viscosity 1.35, and transparency 92%.
Structural characterization and Performance testing
In order to show that the obtained product is the target product, the invention takes example 1 as an example, and the prepared alicyclic linear chain polyamide is subjected to structure characterization and performance test, and the results are shown in figures 1-5.
Wherein, FIG. 1 is an infrared spectrum of the alicyclic linear polyamide as the final product obtained in example 1, and FIG. 2 is a nuclear magnetic hydrogen spectrum of the alicyclic linear polyamide as the final product obtained in example 1. As can be seen from FIGS. 1 and 2, the product obtained by the present invention is the target product.
FIG. 3 is a DSC chart of the cycloaliphatic linear polyamide obtained in example 1, wherein the melting point is 342 ℃ and the melting range is 314-351 ℃.
FIG. 4 is a TGA spectrum of a nuclear magnetic resonance spectrum of the alicyclic linear polyamide as the final product obtained in example 1, wherein T is shown in the graph5％(temperature at 5% weight loss) 428 ℃ and Td,maxAt 464 ℃.
FIG. 5 is an XRD spectrum of alicyclic linear polyamide as a final product obtained in example 1. As can be seen from the graph, 2. theta. was 21.1 degrees, the crystallinity was 59.8%, and the interplanar spacing was 6.6 nm. The results of the other examples are consistent with the results of this example.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A polyamide derived from a monomer containing a single six-membered alicyclic structure, characterized in that: the structural general formula of the polyamide is as follows:
in the formula, R1、R2Is one or more of independent cycloalkyl, C3-C18 alkyl, aryl and derivatives thereof, and R1And R2Wherein there is only one hydrocarbon-based unit containing a single six-membered alicyclic structure, n>20 and ensures that the molecular weight of the polymer is not less than 1 ten thousand.
2. A polyamide derived from a monomer containing a single six-membered alicyclic structure according to claim 1, wherein: the monomer of the six-membered alicyclic structure is para-substituted six-membered alicyclic diacid or para-substituted six-membered alicyclic diamine, preferably one or more monomers of six-membered alicyclic dicarboxylic acid, six-membered alicyclic diacetic acid, six-membered alicyclic diamine, six-membered alicyclic dimethylamine and six-membered alicyclic diethylamine.
3. A process for the preparation of a polyamide derived from a monomer containing a single six-membered alicyclic structure according to claim 1 or 2, wherein: the method comprises the following steps:
(1) preparing an alicyclic polyamide salt, wherein the alicyclic ring is a six-membered alicyclic structure;
(2) adding alicyclic polyamide salt into a reaction kettle, polymerizing by a one-step polymerization process, under the protection of inert atmosphere, raising the temperature of a system to a preset temperature at a temperature rise rate of 5-20 ℃/min, keeping the pressure in the kettle at 0.7-2.0 MPa, maintaining pressure for polymerization for 0.5-4 h, reducing the water discharge to normal pressure, continuing raising the temperature of the system to a certain temperature, vacuumizing until the pressure in the kettle is less than 100Pa, polymerizing for 2-5 h under negative pressure, cooling and discharging to obtain the hexabasic alicyclic polyamide.
4. A process for preparing a polyamide derived from a monomer containing a single six-membered alicyclic structure according to claim 3, wherein: in the step (1), the alicyclic polyamide salt is prepared by a water solvent method, and the specific operation is as follows: adding dibasic acid and diamine corresponding to the hexa-membered alicyclic polyamide into water according to a ratio, heating to 40-100 ℃, stirring, adjusting the pH to 7.0-7.5, continuing to react for 20-40 min, and drying to obtain the polyamide salt.
5. A process for preparing a polyamide derived from a monomer containing a single six-membered alicyclic structure according to claim 3, wherein: in the step (2), the pressure-maintaining polymerization temperature of the alicyclic polyamide salt taking the alkyl compound as the monomer is 180-220 ℃, and the negative pressure polymerization temperature is 210-250 ℃; the alicyclic polyamide salt of which the monomer is a phenyl compound is polymerized at a pressure-maintaining polymerization temperature of 230 to 260 ℃ and at a negative-pressure polymerization temperature of 250 to 280 ℃.
6. The method of producing a six-membered alicyclic polyamide salt according to claim 4, wherein: the dosage ratio of the dibasic acid to the diamine is 1: 0.98-1.02 percent, and the adding amount of water is 40-80 percent of the total mass of the dicarboxylic acid and the diamine.
7. A method of producing a six-membered alicyclic polyamide according to claim 3, wherein: in the step (2), the temperature is reduced to normal pressure within 0.5-2 h, and the negative pressure polymerization temperature is not less than the pressure maintaining polymerization temperature.
8. The method for producing a six-membered alicyclic polyamide according to claim 4, wherein: in the step (1), the molar ratio of cis configuration to trans configuration of the six-membered alicyclic monomer is 100: 0 to 0: 100, obtaining the six-membered alicyclic polyamide with different cis-trans ratios.
9. A method of producing a six-membered alicyclic polyamide according to claim 3, wherein: in the step (2), the inert gas is one of carbon dioxide, argon, nitrogen or helium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116903484A (en) * | 2023-09-14 | 2023-10-20 | 西华大学 | Bialicyclic diamide hindered phenol antioxidant and preparation method and application thereof |
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| JP2017165935A (en) * | 2016-03-11 | 2017-09-21 | 旭化成株式会社 | Transparent polyamide composition, molded body and method for producing the same |
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| CN101456949A (en) * | 2007-12-14 | 2009-06-17 | 金发科技股份有限公司 | Semi-aromatic polyamide and preparation method thereof |
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| CN116903484B (en) * | 2023-09-14 | 2023-11-24 | 西华大学 | Bialicyclic diamide hindered phenol antioxidant and preparation method and application thereof |
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