CN111234207A - Transparent bio-based polyamide and preparation method thereof - Google Patents
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Abstract
The invention relates to a transparent bio-based polyamide and a preparation method thereof, wherein the preparation method comprises the following steps: performing melt polycondensation reaction on dimethyl furandicarboxylate and diamine which are used as main raw materials to prepare transparent bio-based polyamide, wherein the diamine is alicyclic diamine and/or branched alkyl diamine; the finally obtained transparent bio-based polyamide main chain is formed by alternately bonding furan dicarboxylic acid dimethyl ester units and diamine units, wherein the diamine units are alicyclic diamine units or branched alkyl-containing diamine units. The preparation method disclosed by the invention is simple to operate and easy to industrially popularize, the diamine monomer volatilization can be effectively reduced by adopting two-step synthesis, and the oligomer is obtained after prepolymerization, so that the thermal stability is improved, and the yellowing is reduced; the finally prepared transparent bio-based polyamide has higher glass transition temperature, higher transparency and good heat resistance, is easy for industrial production, and the monomer is derived from biomass resources and can be regenerated.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to transparent bio-based polyamide and a preparation method thereof.
Background
The polyamide material refers to high polymer containing amide groups in macromolecular repeating unitsAs a material, conventional polyamide materials are generally prepared by using petrochemical resources as raw materials, such as polycondensation of diacid/diamine monomers, polycondensation of amino acids, ring-opening polymerization of lactam monomers, and the like, but the prepared polyamide materials have poor transparency and low glass transition temperature (generally, T is T) due to molecular structure designg<90 c) and has limited application in the fields of beverages, food, packaging and the like.
Therefore, the patents (CN106916294A, CN109265677A and CN109970972A) disclose the design and preparation method of transparent polyamide molecular structure, the light transmittance is 85-90.4%, and T isgThe temperature is 130-162 ℃, however, the synthesis of polyamide is a polycondensation reaction, the equilibrium constant is small, the reaction is carried out in the forward direction, the small molecular byproducts in the reaction system need to be removed by high temperature and vacuum pumping, but the dicarboxylic acid in the reaction system is easy to decarboxylate and the diamine is easy to volatilize under the conditions of high temperature and vacuum pumping, which has high requirements on reaction equipment and control precision thereof, and meanwhile, the polyamide based on petrochemical resources needs to consume a large amount of non-renewable petroleum raw materials, which may bring about potential environmental crisis and energy crisis; the patent (CN105367785B) utilizes oxalic acid diester, straight-chain aliphatic diamine and branched-chain alkyl-containing diamine to polymerize and prepare transparent nylon, the transparent nylon has certain crystallinity, the transparency is not high, and the glass transition temperature is only 65 ℃; the patent (CN110172147A) also discloses a copolymerized transparent nylon which has certain crystallinity, lower transparency, light transmittance of only 70 percent and glass transition temperature of the nylon reinforced and modified by glass fiber of 120 ℃ and is prepared by adding lactam, hexamethylene diamine and terephthalic acid or isophthalic acid, aliphatic dibasic acid and aliphatic diamine into a reaction kettle, heating and stirring, molding by a pressure casting belt, cooling and pelletizing.
In the prior art, pentabasic heterocyclic diacid furan dicarboxylic acid (FDCA) is a bio-based compound prepared by taking a biomass material as a raw material through a chemical or biological method, has less carbon atoms than benzene rings and weaker aromaticity than the benzene rings, and can be used for synthesizing polyester and polyamide; polymers made from five-membered heterocyclic diacid furandicarboxylic acid (FDCA), such as furandicarboxylic polyesters and furandicarboxylic polyamides, have even better thermal and mechanical properties than polymers made from terephthalic acid, phthalic acid, which makes five-membered heterocyclic diacid furandicarboxylic acid (FDCA) one of the 12 most valuable bio-based platform compounds as evaluated by the U.S. department of energy.
Patent CN109721716A discloses a preparation method of five-membered heterocyclic diacid furan dicarboxylic acid (FDCA) copolyester, the obtained copolyester has excellent heat resistance, transparency and mechanical properties, but the wear resistance and hydrophilicity of the polyester material are far inferior to those of the polyamide material; meanwhile, patent CN106191145A discloses a method for preparing polyamide by catalyzing dimethyl furandicarboxylate and aliphatic diamine with lipase in a solvent system, and although polymerization conditions are mild and have certain transparency, the use of a large amount of solvent is not suitable for industrial production.
Therefore, a preparation method of transparent bio-based polyamide with high transparency, high glass transition temperature and easy industrial production is urgently needed to be researched.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of transparent bio-based polyamide, which has high transparency and glass transition temperature and is easy for industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing transparent bio-based polyamide comprises the step of carrying out melt polycondensation reaction on dimethyl furandicarboxylate and diamine which are used as main raw materials to prepare the transparent bio-based polyamide, wherein the diamine is alicyclic diamine and/or diamine containing branched alkyl.
The molecular structure is regular, the crystallinity is high, and the transparency is reduced; and vice versa. Transparent polyamides are generally amorphous or microcrystalline polymers, and are classified by molecular chain structure: one is a (semi) aromatic transparent polyamide and the other is an aliphatic transparent polyamide. The (semi) aromatic transparent polyamide has high softening point and high melting temperature due to the existence of a benzene ring structure, and is not beneficial to processing and production; the aliphatic transparent polyamide comprises straight-chain aliphatic transparent polyamide and aliphatic transparent polyamide containing a ring structure, wherein a straight-chain aliphatic monomer in the straight-chain aliphatic transparent polyamide has limited damage to the sequence regularity of a product, the crystallization rate is high, and the process is difficult to control, so that the application of the polyamide in industrial production is limited, and the ring structure is introduced into a polyamide molecular chain, so that the structural regularity can be damaged, the crystallinity is reduced and the transparency is improved on the premise of hardly influencing the mechanical property and the thermal property.
The branched alkyl diamine contains asymmetric carbon atoms, and the regularity of the molecular structure is damaged due to the asymmetric carbon atoms, so that the crystallinity of a polyamide molecular chain is reduced, and the transparency of the polyamide molecular chain is ensured. In the prior art, branched alkyl group-containing diamine is used for preparing aliphatic transparent polyamide, polyoxamide is prepared by reacting the branched alkyl group-containing diamine with oxalic acid diester, and the polyoxamide has high crystallinity and poor transparency because adjacent amide bonds are arranged in opposite directions to form double hydrogen bonds.
In the prior art, alicyclic diamine is used for preparing aliphatic transparent polyamide, but the alicyclic diamine does not react with ester much, and mostly reacts with dicarboxylic acid, the dicarboxylic acid is easy to generate decarboxylation reaction under the conditions of high temperature and vacuum pumping, the decarboxylation of the dicarboxylic acid can cause the imbalance of the proportion of functional groups, and a high molecular weight polymer is difficult to obtain.
In addition, the transparent bio-based polyamide prepared by the invention adopts melt polycondensation reaction, and does not adopt a solvent, so that the method is easy for industrial production.
As a preferred technical scheme:
in the above method for preparing a transparent bio-based polyamide, the alicyclic diamine is 1, 3-cyclohexyldimethylamine, 4 '-diaminodicyclohexylmethane or 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane.
In the above method for preparing a transparent bio-based polyamide, the alicyclic diamine is 1, 3-cyclohexyldimethylamine. The molecular formula of the 1, 3-cyclohexyldimethylamine contains a cyclohexane structure, and the cyclohexane has two conformations of boehrland and chaehrland, so that the 1, 3-cyclohexyldimethylamine is a cis-trans isomer mixture, which shows that the structural symmetry is broken, and the crystallization capacity of a product prepared from the 1, 3-cyclohexyldimethylamine can be effectively reduced, thereby improving the transparency of the product. In addition, 1, 3-cyclohexyldimethylamine has a rigid molecular chain (cyclohexane structure), so that the glass transition temperature of a product produced therefrom can be effectively increased.
A method for preparing transparent bio-based polyamide as described above, the branched alkyl-containing diamine is trimethyl hexamethylene diamine or 2-methyl-1, 5-pentanediamine, and the trimethyl hexamethylene diamine is a mixture of 2,2, 4-trimethyl hexamethylene diamine and 2,4, 4-trimethyl hexamethylene diamine.
The preparation method of the transparent bio-based polyamide is characterized in that the branched alkyl-containing diamine is trimethyl hexamethylene diamine. Trimethylhexamethylenediamine (a mixture of 2,2, 4-trimethylhexamethylenediamine and 2,4, 4-trimethylhexamethylenediamine) contains three methyl branches and asymmetric carbon atoms, which can reduce the crystallinity of a polyamide molecular chain and ensure the transparency of the polyamide molecular chain, and the structure of the diamine (containing the asymmetric carbon atoms) is the main reason for causing the product to be amorphous, good in transparency and high in glass transition temperature.
The preparation method of the transparent bio-based polyamide comprises the following specific steps:
(1) mixing dimethyl furandicarboxylate and diamine, and reacting for 0.5-3 h under the protection of nitrogen or inert gas at the temperature of 120-210 ℃ to obtain a prepolymer; the reaction time is not limited to this, and may be adjusted appropriately, but it is not too long, and too short reaction time results in low reaction degree of prepolymerization, and the monomer is removed under the subsequent conditions of high temperature and high vacuum; the reaction time is too long, which increases the cost; similarly, the reaction temperature is not limited to this, and can be adjusted appropriately, but it is not too high, and the diamine may volatilize due to too high reaction temperature; the reaction temperature is too low, the molecular weight of the polymer produced by prepolymerization is too low, and further, the rate of subsequent polymerization reaction is also reduced;
(2) heating to 230-270 ℃, reducing the pressure to below 1kPa, and continuing to react for 20-600 min to obtain transparent bio-based polyamide; the reaction time is not limited to the above range and can be properly adjusted, but the reaction time is not too long, the reaction time is too short, the polymerization is insufficient, and the molecular weight of the prepared transparent bio-based polyamide is low; the reaction time is too long, the transparent bio-based polyamide obtained by polymerization can be degraded, and the color of the polyamide is further influenced; similarly, the reaction temperature is not limited to this, and can be adjusted properly, but should not be too high, and the polymerization process will generate more side reactions, which will affect the quality and color of the polyamide; the reaction temperature is too low, and the molecular weight of the prepared polyamide is too low.
The invention adopts a two-step method to synthesize the transparent bio-based polyamide, and the transparent bio-based polyamide is firstly prepolymerized at low temperature and then polycondensed at high temperature, so that the oligomer can be obtained by prepolymerization, the thermal stability is improved, and the volatilization of diamine monomers under the conditions of high temperature and vacuum is effectively reduced.
According to the preparation method of the transparent bio-based polyamide, the molar ratio of the dimethyl furandicarboxylate to the diamine is 1: 0.9-1.2, the diamine is volatile at high temperature, a methylation side reaction may occur between the dimethyl furandicarboxylate and the diamine, the dimethyl furandicarboxylate can remove methanol to generate the furan dicarboxylic acid, the furan dicarboxylic acid is easy to decarboxylate, the ratio of functional groups is not adjusted, and the molar ratio of the dimethyl furandicarboxylate to the diamine is set in the range to ensure that the reaction is sufficient.
The invention also provides the transparent bio-based polyamide prepared by the preparation method of the transparent bio-based polyamide, the main chain is formed by alternately bonding dimethyl furandicarboxylate units and diamine units, and the diamine units are alicyclic diamine units or branched alkyl-containing diamine units.
The transparent polyamide is usually an amorphous or microcrystalline polymer, the selected alicyclic diamine has an asymmetric structure, the structural regularity is damaged, the crystallization performance is reduced, the cyclohexane structure can provide rigidity for the polymer, and the glass transition temperature of the polyamide is improved; the selected branched chain alkyl-containing diamine has an asymmetric branched chain structure, so that the crystallinity can be reduced, and the transparency can be improved; the dimethyl furandicarboxylate used provides a rigid group, thus ensuring that the resulting product is amorphous.
As a preferred technical scheme:
the transparent biobased polyamide has the glass transition temperature of 100-300 ℃, the thermal degradation temperature (namely the temperature of the substance with the fastest mass loss by adopting a TGA test) of 300-500 ℃ and the light transmittance of 85-92%.
Has the advantages that:
(1) according to the preparation method of the transparent bio-based polyamide, the two-step synthesis is adopted, so that the volatilization of diamine monomers can be effectively reduced, the ratio of functional groups is maintained at 1:1 as much as possible, the molecular weight is improved, and the oligomer is obtained after prepolymerization, so that the thermal stability is improved, and the yellowing is reduced;
(2) the transparent bio-based polyamide prepared by the preparation method of the transparent bio-based polyamide is amorphous, has good transparency, high glass transition temperature and good heat resistance, but the processing temperature is not too high and does not exceed 300 ℃ at most, is convenient to process, and the monomer is derived from biomass resources and can be regenerated.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Glass transition temperature test method: about 7mg of sample was taken using a TADSC-Q100 analyzer under the following test conditions: heating the obtained transparent bio-based polyamide from 30 ℃ to 240 ℃ under the nitrogen atmosphere; keeping the temperature at 240 ℃ for 2 minutes, and then reducing the temperature to 30 ℃ at a cooling rate of 20 ℃/min; after keeping the temperature at 30 ℃ for 2 minutes, the temperature was again raised to 240 ℃ at a temperature rise rate of 20 ℃/min, and the glass transition temperature was determined from the DSC second temperature rise curve.
Preparing raw materials:
dimethyl furan dicarboxylate: purity 98%, available from TCI;
1, 3-cyclohexyldimethylamine: purity 98%, available from TCI;
trimethylhexamethylenediamine: purity 99%, available from TCI;
4,4' -diaminodicyclohexylmethane: purity 98%, available from TCI;
3,3' -dimethyl-4, 4-diaminodicyclohexylmethane: purity 98%, available from TCI;
2-methyl-1, 5-pentanediamine: purity 98% was obtained from TCI company.
Example 1
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 4.267g of 1, 3-cyclohexyldimethylamine are added into a test tube, and the temperature is raised to 120 ℃ in a nitrogen atmosphere to react for 0.5 hour to obtain a prepolymer;
(2) the temperature is increased to 230 ℃, the pressure is reduced to 730Pa, and the reaction is continued for 60min to obtain 7.872g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 181 ℃, the thermal degradation temperature of the polyamide is 389 ℃, and the light transmittance of the polyamide is 86% through testing.
Example 2
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 4.267g of 1, 3-cyclohexyldimethylamine are added into a test tube, and the temperature is raised to 120 ℃ in a nitrogen atmosphere to react for 0.5 hour to obtain a prepolymer;
(2) and continuously heating to 240 ℃, reducing the pressure to 620Pa, and continuously reacting for 60min to obtain 7.754g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding furan dicarboxylic acid dimethyl ester units and diamine units, and the glass transition temperature Tg of the polyamide is 178 ℃, the thermal degradation temperature of the polyamide is 395 ℃, and the light transmittance of the polyamide is 87% after testing.
Example 3
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 4.267g of 1, 3-cyclohexyldimethylamine are added into a test tube, and the temperature is raised to 120 ℃ in a nitrogen atmosphere to react for 0.5 hour to obtain a prepolymer;
(2) and continuously heating to 250 ℃, decompressing to 550Pa, and continuously reacting for 60min to obtain 7.518g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 167 ℃, the thermal degradation temperature of the polyamide is 405 ℃, and the light transmittance of the polyamide is 88% through testing.
Example 4
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 3.84g of 1, 3-cyclohexyldimethylamine are added into a test tube, and the temperature is raised to 120 ℃ under the atmosphere of helium to react for 3 hours, so as to obtain a prepolymer;
(2) the temperature is continuously increased to 230 ℃, the pressure is reduced to 460Pa, and the reaction is continuously carried out for 600min to obtain 5.956g of yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 300 ℃, the thermal degradation temperature of the polyamide is 489 ℃, and the light transmittance of the polyamide is 90% through testing.
Example 5
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 4.694g of 1, 3-cyclohexyldimethylamine are added into a branched test tube, and the temperature is raised to 160 ℃ under the atmosphere of neon gas, so that the reaction is carried out for 1.75 hours, and a prepolymer is obtained;
(2) and continuously heating to 250 ℃, decompressing to 330Pa, and continuously reacting for 300min to obtain 6.888g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 261 ℃, the thermal degradation temperature of the polyamide is 500 ℃, and the light transmittance of the polyamide is 90% through testing.
Example 6
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 5.121g of 1, 3-cyclohexyldimethylamine are added into a test tube, and the temperature is raised to 210 ℃ in a nitrogen atmosphere to react for 0.5 hour to obtain a prepolymer;
(2) and continuously heating to 270 ℃, reducing the pressure to 570Pa, and continuously reacting for 60min to obtain 6.806g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 143 ℃, the thermal degradation temperature is 406 ℃, and the light transmittance is 88% through testing.
Example 7
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 4.749g of trimethyl hexamethylene diamine are added into a test tube, and the temperature is raised to 120 ℃ under the nitrogen atmosphere to react for 0.5 hour to obtain a prepolymer;
(2) and continuously heating to 240 ℃, decompressing to 480Pa, and continuously reacting for 180min to obtain 7.769g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 200 ℃, the thermal degradation temperature of the polyamide is 423 ℃ and the light transmittance of the polyamide is 92% through testing.
Example 8
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 3.48g of 2-methyl-1, 5-pentanediamine are added into a test tube with a support, and the temperature is raised to 120 ℃ under the nitrogen atmosphere to react for 0.5 hour to obtain a prepolymer;
(2) and continuously heating to 240 ℃, reducing the pressure to 750Pa, and continuously reacting for 180min to obtain 6.660g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 126 ℃, the thermal degradation temperature of the polyamide is 300 ℃, and the light transmittance of the polyamide is 89% through testing.
Example 9
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 7.868g of 3,3' -dimethyl-4, 4-diaminodicyclohexyl methane are added into a test tube, and the temperature is raised to 120 ℃ under the atmosphere of nitrogen to react for 3 hours, so as to obtain a prepolymer;
(2) and continuously heating to 240 ℃, reducing the pressure to 400Pa, and continuously reacting for 600min to obtain 10.843g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 100 ℃, the thermal degradation temperature of the polyamide is 350 ℃, and the light transmittance of the polyamide is 87% through testing.
Example 10
A preparation method of transparent bio-based polyamide comprises the following steps:
(1) 5.525g of furan dicarboxylic acid dimethyl ester and 6.311g of 4, 4-diaminodicyclohexyl methane are added into a test tube, and the temperature is raised to 120 ℃ under the atmosphere of nitrogen to react for 0.5 hour to obtain a prepolymer;
(2) and continuously heating to 250 ℃, decompressing to 420Pa, and continuously reacting for 300min to obtain 8.230g of light yellow transparent bio-based polyamide.
The main chain of the finally prepared transparent bio-based polyamide is formed by alternately bonding a dimethyl furandicarboxylate unit and a diamine unit, and the glass transition temperature Tg of the polyamide is 136 ℃, the thermal degradation temperature of the polyamide is 366 ℃, and the light transmittance of the polyamide is 85% through testing.
Claims (9)
1. A preparation method of transparent bio-based polyamide is characterized by comprising the following steps: the method comprises the step of carrying out melt polycondensation reaction on dimethyl furandicarboxylate and diamine as main raw materials to prepare the transparent bio-based polyamide, wherein the diamine is alicyclic diamine and/or branched alkyl-containing diamine.
2. The method of claim 1, wherein the cycloaliphatic diamine is 1, 3-cyclohexyldimethylamine, 4 '-diaminodicyclohexylmethane, or 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane.
3. The method of claim 2, wherein the cycloaliphatic diamine is 1, 3-cyclohexyldimethylamine.
4. The method of claim 1, wherein the branched alkyl-containing diamine is trimethylhexamethylenediamine or 2-methyl-1, 5-pentanediamine, and the trimethylhexamethylenediamine is a mixture of 2,2, 4-trimethylhexamethylenediamine and 2,4, 4-trimethylhexamethylenediamine.
5. The method of claim 4, wherein the branched alkyl group-containing diamine is trimethylhexamethylenediamine.
6. The method for preparing the transparent bio-based polyamide according to claim 1, characterized by comprising the following steps:
(1) mixing dimethyl furandicarboxylate and diamine, and reacting for 0.5-3 h under the protection of nitrogen or inert gas at the temperature of 120-210 ℃ to obtain a prepolymer;
(2) heating to 230-270 ℃, reducing the pressure to below 1kPa, and continuing to react for 20-600 min to obtain the transparent bio-based polyamide.
7. The method of claim 6, wherein the molar ratio of dimethyl furandicarboxylate to diamine is 1: 0.9-1.2.
8. The transparent bio-based polyamide prepared by the preparation method of the transparent bio-based polyamide as claimed in any one of claims 1 to 7, which is characterized in that: the main chain is formed by alternate bonding of furan dicarboxylic acid dimethyl ester units and diamine units, and the diamine units are alicyclic diamine units or branched chain alkyl-containing diamine units.
9. The transparent biobased polyamide of claim 8, wherein the transparent biobased polyamide has a glass transition temperature of 100 to 300 ℃, a thermal degradation temperature of 300 to 500 ℃, and a light transmittance of 85 to 92%.
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| CN112745499A (en) * | 2020-08-26 | 2021-05-04 | 杭州师范大学 | Preparation method of bio-based modified transparent polyamide polymer and fiber |
| CN113429569A (en) * | 2021-07-23 | 2021-09-24 | 四川大学 | Preparation method of high molecular weight furan polyamide |
| CN114249890A (en) * | 2021-12-02 | 2022-03-29 | 南京工业大学 | Bio-based polyesteramide and preparation method thereof |
| WO2023045819A1 (en) * | 2021-09-24 | 2023-03-30 | 珠海万通特种工程塑料有限公司 | Furan diacid-based polyamide resin, preparation method therefor, and polyamide molding composition |
| CN117209751A (en) * | 2022-06-02 | 2023-12-12 | 中国科学院化学研究所 | Preparation method of all-bio-based polyamide |
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| CN114249890A (en) * | 2021-12-02 | 2022-03-29 | 南京工业大学 | Bio-based polyesteramide and preparation method thereof |
| CN114249890B (en) * | 2021-12-02 | 2023-02-21 | 南京工业大学 | Bio-based polyesteramide and preparation method thereof |
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