CN118325075B - Bio-based crosslinked polyamide capable of being repeatedly processed and preparation method thereof - Google Patents
Bio-based crosslinked polyamide capable of being repeatedly processed and preparation method thereof Download PDFInfo
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Abstract
The invention provides a bio-based cross-linked polyamide capable of being repeatedly processed and a preparation method thereof, and belongs to the technical field of high molecular polymers. The preparation method provided by the invention has the advantages that the linear diamine and the benzaldehyde are subjected to the prepolymerization reaction to obtain the prepolymer with the end capped by the amino group, and then the prepolymer is subjected to the polymerization reaction with the trimethyl citrate, so that the reaction is fully completed, the imine bond is introduced into the polymer, the crosslinked polyamide has the reworkability, the self-repairing property and the degradability, the method is simple to operate, the organic solvent and the catalyst with higher toxicity are not required to be added, and the process cost is low and the environment is protected. The results of the examples show that the polyamide prepared by the invention has tensile strength of >18MPa, elongation at break of >10%, melting temperature of >98.6 ℃, 20 ℃ and glass transition temperature of <60 ℃, thermal decomposition 5% temperature of >260 ℃ and retention rate of repeated processing mechanical properties of >85%.
Description
Technical Field
The invention relates to the technical field of high molecular polymers, in particular to a bio-based cross-linked polyamide capable of being repeatedly processed and a preparation method thereof.
Background
The polyamide elastomer has excellent wear resistance, chemical resistance and good impact resistance due to the unique three-dimensional network structure, and is widely applied to the fields of electronic appliances, new energy automobiles, LED optics and the like. However, the conventional crosslinked polyamide elastomer polymer material is only formed once, and is limited in terms of reprocessing and reuse due to the stability and irreversibility of the crosslinked structure, so that how to prepare the crosslinked polymer material capable of being processed repeatedly is an urgent technical problem in the art under the current sustainable development environment.
In addition, the conventional polyamide elastomer is generally synthesized from petrochemical resource monomers, and as petrochemical resources are gradually exhausted, the research and development of a polyamide material which is based on a biological base, has high efficiency and can be continuously developed becomes a research and development hotspot of industry. Biomass has unique advantages as a renewable resource, such as extremely short life cycle, low carbon emissions, and relatively low cost. The existing renewable and degradable cross-linked polymer is mainly concentrated on polyurethane, polyimide and other materials, for example, chinese patent CN202211581234.0 discloses a bio-based polyamideimide Vitrimer material taking absolute ethyl alcohol as a basic solvent and a preparation method, but the method has the advantages of low ratio of bio-based raw materials, addition of organic solvent and complex process. For another example, chinese patent CN202210546302.3 discloses a preparation method and application of a high biomass-based polyimide self-repairing polymer, the preparation process of the patent is complex, and p-toluenesulfonic acid needs to be added as a catalyst, so that toxicity is high.
Accordingly, there is a need to provide a method for producing a bio-based crosslinked polyamide material which is reproducible without adding an organic solvent or a highly toxic catalyst.
Disclosure of Invention
The invention aims to provide a bio-based crosslinked polyamide material which can be repeatedly processed without adding an organic solvent or a catalyst with high toxicity, and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of bio-based cross-linked polyamide capable of being repeatedly processed, which comprises the following steps:
(1) Mixing linear diamine and phthalaldehyde, and performing a prepolymerization reaction in an inert atmosphere to obtain an amino-terminated prepolymer;
(2) Mixing the amino-terminated prepolymer obtained in the step (1) with trimethyl citrate, and carrying out polymerization reaction to obtain the bio-based cross-linked polyamide capable of being repeatedly processed;
The ratio of the amount of trimethyl citrate-COOCH 3 to the amount of amino-terminated prepolymer-NH 2 in step (2) is (0.9-1.1): 1.
Preferably, the linear diamine in step (1) comprises one or more of butanediamine, pentanediamine, and decanediamine.
Preferably, the ratio of the amounts of the substances of the linear diamine and the phthalaldehyde in the step (1) is (3-6): 2-5.
Preferably, the temperature of the prepolymerization reaction in the step (1) is 100-150 ℃, and the time of the prepolymerization reaction is 10-200 min.
Preferably, the polymerization reaction in the step (2) includes a first polymerization reaction, a second polymerization reaction, and a curing reaction which are sequentially performed, the second polymerization reaction having a temperature higher than that of the first polymerization reaction.
Preferably, the temperature of the first polymerization reaction is 130-180 ℃, and the time of the first polymerization reaction is 10-200 min.
Preferably, the temperature of the second polymerization reaction is 140-200 ℃, and the time of the second polymerization reaction is 10-200 min.
Preferably, the temperature of the curing reaction is 150-200 ℃, and the curing reaction time is 1-20 h.
Preferably, the curing reaction is performed under a negative pressure, and the pressure of the negative pressure is 10-300 Pa.
The invention also provides the bio-based crosslinked polyamide which is prepared by the preparation method and can be repeatedly processed.
The invention provides a preparation method of a reproducible bio-based cross-linked polyamide, which comprises the following steps of mixing linear diamine and phthalaldehyde, carrying out a prepolymerization reaction under an inert atmosphere to obtain an amino-terminated prepolymer, mixing the amino-terminated prepolymer with trimethyl citrate, and carrying out a polymerization reaction to obtain the reproducible bio-based cross-linked polyamide, wherein the ratio of the amount of the-COOCH 3 of trimethyl citrate to the amount of the-NH 2 of the amino-terminated prepolymer is (0.9-1.1): 1. The linear diamine is derived from biomass raw materials, and trimethyl citrate is used as a bio-based cross-linking agent, so that the application of petrochemical resources can be reduced; the preparation method provided by the invention has the advantages that the linear diamine and the benzaldehyde are subjected to the prepolymerization reaction to obtain the prepolymer with the end capped by the amino group, and then the prepolymer is subjected to the polymerization reaction with the trimethyl citrate, so that the reaction is fully completed, the imine bond is introduced into the polymer, the crosslinked polyamide has the reworkability, the self-repairing property and the degradability, the method is simple to operate, the organic solvent and the catalyst with higher toxicity are not required to be added, and the process cost is low and the environment is protected. The results of the examples show that the polyamide prepared by the invention is repeatedly processed and degradable, and has tensile strength of more than 18MPa, elongation at break of more than 10%, melting temperature of more than 98.6 ℃, glass transition temperature of 20 ℃ and 60 ℃, thermal decomposition temperature of 5% of more than 260 ℃ and retention rate of mechanical properties of repeated processing of more than 85%.
Drawings
FIG. 1 is an infrared spectrum of an amino-terminated prepolymer prepared in step (1) of examples 1 to 4 of the present invention;
FIG. 2 is an infrared spectrum of a reworkable bio-based crosslinked polyamide prepared according to examples 1-4 of the present invention;
FIG. 3 is a hydrogen spectrum of an amino-terminated prepolymer prepared in step (1) of examples 1-4 of the present invention;
FIG. 4 is a carbon spectrum of an amino-terminated prepolymer prepared in step (1) of examples 1-4 of the present invention;
FIG. 5 is a DSC curve of a reworkable bio-based crosslinked polyamide prepared in examples 1-4 of the present invention;
FIG. 6 is a photograph of a sample obtained by chipping and re-pressing the reworkable bio-based crosslinked polyamide prepared in examples 1 to 4 of the present invention;
FIG. 7 is a thermogravimetric plot of reworkable bio-based crosslinked polyamides prepared in examples 1-4 of the present invention;
FIG. 8 is a photograph showing the reworkable bio-based crosslinked polyamide prepared in examples 1-4 of the present invention after standing in hydrochloric acid solution for 0 h;
FIG. 9 is a photograph showing the reworkable bio-based crosslinked polyamide prepared in examples 1-4 of the present invention after being allowed to stand in a hydrochloric acid solution for 24 hours;
FIG. 10 is a photograph of a product prepared in comparative example 1 of the present invention;
FIG. 11 is a photograph of a product prepared in comparative example 2 of the present invention.
Detailed Description
The invention provides a preparation method of bio-based cross-linked polyamide capable of being repeatedly processed, which comprises the following steps:
(1) Mixing linear diamine and phthalaldehyde, and performing a prepolymerization reaction in an inert atmosphere to obtain an amino-terminated prepolymer;
(2) Mixing the amino-terminated prepolymer obtained in the step (1) with trimethyl citrate, and carrying out polymerization reaction to obtain the bio-based cross-linked polyamide capable of being repeatedly processed;
The ratio of the amount of trimethyl citrate-COOCH 3 to the amount of amino-terminated prepolymer-NH 2 in step (2) is (0.9-1.1): 1.
In the present invention, unless otherwise specified, the chemical reagents used in the present invention are all from commercially available products conventional in the art.
The invention mixes linear diamine and benzene dicarboxaldehyde, and carries out prepolymerization reaction under inert atmosphere to obtain amino end capped prepolymer.
In the present invention, the linear diamine preferably includes one or more of butanediamine, pentanediamine, and decanediamine, and more preferably decanediamine. The invention adopts the linear diamine with the two end groups of amino groups, which is more beneficial to forming the prepolymer containing imine bonds, and the decanediamine is derived from bio-based castor oil, and the pentanediamine and butanediamine can be prepared by a biological fermentation method, belong to bio-based raw materials, and can reduce the application of petrochemical resources.
In the present invention, the terephthalaldehyde preferably includes isophthalaldehyde or terephthalaldehyde, and more preferably terephthalaldehyde. The invention adopts the benzene dicarboxaldehyde as a monomer, and can react with linear diamine to form prepolymer containing imine bond.
In the present invention, the ratio of the amounts of the linear diamine and the phthalaldehyde is preferably (3 to 6): 2 to 5, more preferably (4 to 6): 3 to 5. The present invention can form an amino-terminated prepolymer by controlling the amounts of both in the above-mentioned ranges and by allowing the linear diamine to be excessive.
The method for mixing the linear diamine and the benzaldehyde is not particularly limited, and the linear diamine and the benzaldehyde can be uniformly mixed by adopting a conventional mixing method.
In the present invention, the inert atmosphere is preferably nitrogen. The invention can prevent side reaction when the reaction is carried out in inert atmosphere.
In the invention, the temperature of the prepolymerization reaction is preferably 100-150 ℃, more preferably 120-140 ℃, and the time of the prepolymerization reaction is preferably 10-200 min, more preferably 30-180 min. The present invention controls the temperature and time of the prepolymerization reaction within the above-mentioned ranges, and enables the prepolymerization reaction to proceed sufficiently.
The apparatus for the prepolymerization reaction is not particularly limited, and a conventional polymerization reaction apparatus may be used. In the present invention, the apparatus for the prepolymerization is preferably a reaction vessel.
In the invention, the pressure in the reaction kettle is preferably controlled to be 300-1000 Pa, more preferably 300-500 Pa, during the prepolymerization reaction. The invention can promote the discharge of the product water and prevent the imine bond from being decomposed when meeting water by controlling the pressure intensity to be in the range.
After the amino-terminated prepolymer is obtained, the amino-terminated prepolymer and trimethyl citrate are mixed for polymerization reaction, and the bio-based cross-linked polyamide capable of being repeatedly processed is obtained.
In the invention, the trimethyl citrate is used as a bio-based cross-linking agent, so that the application of petrochemical resources can be reduced.
In the present invention, the ratio of the amounts of-COOCH 3 of trimethyl citrate to-NH 2 of the amino-terminated prepolymer is (0.9 to 1.1): 1, preferably (0.95 to 1.05): 1. In the present invention, the ratio of the amounts of-COOCH 3 of trimethyl citrate to-NH 2 of amino-terminated prepolymer is abbreviated as the ratio of the amounts of-COOCH 3/-NH2, and the ratio of the amounts of-COOCH 3/-NH2 is in the above range, whereby the system can be sufficiently crosslinked.
The method for mixing the amino-terminated prepolymer and the trimethyl citrate is not particularly limited, and the amino-terminated prepolymer and the trimethyl citrate are uniformly mixed by adopting a conventional mixing method.
In the present invention, the polymerization reaction preferably includes a first polymerization reaction, a second polymerization reaction, and a curing reaction which are sequentially performed, the second polymerization reaction having a temperature higher than that of the first polymerization reaction.
In the invention, the temperature of the first polymerization reaction is preferably 130-180 ℃, more preferably 140-160 ℃, and the time of the first polymerization reaction is preferably 10-200 min, more preferably 30-180 min. In the invention, the temperature of the second polymerization reaction is preferably 140-200 ℃, more preferably 150-180 ℃, and the time of the second polymerization reaction is preferably 10-200 min, more preferably 30-180 min. The invention can dynamically carry out the polymerization reaction by carrying out the first polymerization reaction and the second polymerization reaction in sequence and carrying out the polymerization reaction in two sections, because the energy required by the reaction is higher and higher along with the increase of the crosslinking degree and the molecular weight, the dynamic temperature rise is beneficial to the gradual reaction, and the uniform rise of the molecular weight is ensured.
In the present invention, the first polymerization reaction and the second polymerization reaction are preferably carried out under reduced pressure distillation. The invention can discharge byproducts through reduced pressure distillation.
In the invention, the temperature of the curing reaction is preferably 150-200 ℃, more preferably 155-180 ℃, and the time of the curing reaction is preferably 1-20 h, more preferably 5-10 h. In the present invention, the aging reaction is preferably performed under a negative pressure, and the pressure of the negative pressure is preferably 10 to 300pa, more preferably 10 to 100pa. The device for the aging reaction is not particularly limited, and a conventional heating device may be used. In the invention, the product obtained after the second polymerization reaction is a pre-cured product, has higher viscosity and is not beneficial to discharging and later industrial production. The pre-cured product obtained by the second polymerization reaction is taken out for curing, so that the invention is more beneficial to subsequent discharging and industrial production.
The linear diamine is derived from biomass raw materials, can reduce the application of petrochemical resources, can lead imine bonds to be introduced into polymers, and enables the crosslinked polyamide to have reworkability, self-repairing property and degradability, and the method is simple to operate, does not need to add an organic solvent or a toxic catalyst, and is low in process cost and more environment-friendly.
The invention also provides the bio-based crosslinked polyamide which is prepared by the preparation method and can be repeatedly processed.
The invention introduces imine bond into polymer, so that the cross-linked polyamide has reworkability, self-repairing property and degradability, and the application amount of petrochemical resources is reduced by adopting biological-based raw materials.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of bio-based cross-linked polyamide capable of being repeatedly processed comprises the following steps:
(1) Adding decanediamine and terephthalaldehyde into a reaction kettle according to the mass ratio of 3:2, introducing nitrogen to raise the temperature to 130 ℃, reacting for 30min at the temperature, keeping the nitrogen atmosphere unchanged, decompressing to 600Pa, continuing to react for 100min, and finishing the prepolymerization reaction to obtain an amino-terminated prepolymer;
(2) Adding trimethyl citrate into the reaction kettle of the amino-terminated prepolymer obtained in the step (1) according to the mass ratio of-COOCH 3/-NH2 of 1:1, mixing the two, carrying out polymerization reaction, carrying out reduced pressure distillation, continuously heating to 140 ℃ and reacting for 100min for carrying out first polymerization reaction, heating to 150 ℃ and reacting for 100min for carrying out second polymerization reaction, taking out the obtained pre-cured product, and heating in a 155 ℃ vacuum oven for 5h for curing to obtain the bio-based cross-linked polyamide capable of being repeatedly processed.
The structural formula of the bio-based cross-linked polyamide that can be repeatedly processed is prepared in this example is as follows:
Example 2
A preparation method of bio-based cross-linked polyamide capable of being repeatedly processed comprises the following steps:
(1) Adding decanediamine and terephthalaldehyde into a reaction kettle according to the mass ratio of 4:3, introducing nitrogen to raise the temperature to 140 ℃, reacting for 30min at the temperature, keeping the nitrogen atmosphere unchanged, decompressing to 500Pa, and continuing to react for 110min to complete the prepolymerization reaction to obtain an amino-terminated prepolymer;
(2) Adding trimethyl citrate into the reaction kettle of the amino-terminated prepolymer obtained in the step (1) according to the mass ratio of-COOCH 3/-NH2 of 1:1, mixing the two, carrying out polymerization reaction, carrying out reduced pressure distillation, continuously heating to 150 ℃ and reacting for 110min for carrying out first polymerization reaction, heating to 160 ℃ and reacting for 110min for carrying out second polymerization reaction, taking out the obtained pre-cured product, and heating in a vacuum oven at 165 ℃ for 5h for curing to obtain the bio-based cross-linked polyamide capable of being repeatedly processed.
Example 3
A preparation method of bio-based cross-linked polyamide capable of being repeatedly processed comprises the following steps:
(1) Adding decanediamine and terephthalaldehyde into a reaction kettle according to the mass ratio of 5:4, introducing nitrogen to raise the temperature to 150 ℃, reacting for 30min at the temperature, keeping the nitrogen atmosphere unchanged, decompressing to 400Pa, continuing to react for 120min, and finishing the prepolymerization reaction to obtain an amino-terminated prepolymer;
(2) Adding trimethyl citrate into the reaction kettle of the amino-terminated prepolymer obtained in the step (1) according to the mass ratio of-COOCH 3/-NH2 of 1:1, mixing the two, carrying out polymerization reaction, carrying out reduced pressure distillation, continuously heating to 160 ℃ and reacting for 120min to carry out first polymerization reaction, heating to 170 ℃ and reacting for 120min to carry out second polymerization reaction, taking out the obtained pre-cured product, and heating in a 175 ℃ vacuum oven for 5h to carry out curing, thus obtaining the bio-based cross-linked polyamide capable of being repeatedly processed.
Example 4
A preparation method of bio-based cross-linked polyamide capable of being repeatedly processed comprises the following steps:
(1) Adding decanediamine and terephthalaldehyde into a reaction kettle according to the mass ratio of 6:5, introducing nitrogen to raise the temperature to 150 ℃, reacting for 30min at the temperature, keeping the nitrogen atmosphere unchanged, decompressing to 300Pa, continuing to react for 130min, and finishing the prepolymerization reaction to obtain an amino-terminated prepolymer;
(2) Adding trimethyl citrate into the reaction kettle of the amino-terminated prepolymer obtained in the step (1) according to the mass ratio of-COOCH 3/-NH2 of 1:1, mixing the two, carrying out polymerization reaction, carrying out reduced pressure distillation, continuously heating to 160 ℃ and reacting for 130min for carrying out first polymerization reaction, heating to 170 ℃ and reacting for 130min for carrying out second polymerization reaction, taking out the obtained pre-cured product, and heating in a 185 ℃ vacuum oven for 5h for curing to obtain the bio-based cross-linked polyamide capable of being repeatedly processed.
Comparative example 1
A preparation method of polyamide:
(1) Adding decanediamine and terephthalaldehyde into a reaction kettle according to the mass ratio of 6:5, introducing nitrogen to raise the temperature to 150 ℃, reacting for 30min at the temperature, keeping the nitrogen atmosphere unchanged, decompressing to 300Pa, continuing to react for 130min, and finishing the prepolymerization reaction to obtain an amino-terminated prepolymer;
(2) Adding trimethyl citrate into the reaction kettle of the amino end-capped prepolymer obtained in the step (1) according to the mass ratio of-COOCH 3/-NH2 of 1:1, mixing the two, carrying out polymerization reaction, carrying out reduced pressure distillation, continuously heating to 160 ℃ and reacting for 130min for carrying out first polymerization reaction, heating to 170 ℃ and reacting for 130min for carrying out second polymerization reaction, and obtaining the pre-cured product. Direct compression molding was performed without further aging, and the resulting product was as shown in FIG. 10. As can be seen from fig. 10, the polymer obtained by the method of the comparative example cannot be pressed into a smooth sample because the method of the comparative example cannot sufficiently react and crosslink the polymer, so that the obtained polyamide material has poor properties and cannot be repeatedly processed.
Comparative example 2
A preparation method of polyamide comprises the following steps:
(1) Adding decanediamine and sebacic acid into a reaction kettle according to the mass ratio of 6:5, introducing nitrogen to raise the temperature to 170 ℃, reacting for 30min at the temperature, keeping the nitrogen atmosphere unchanged, reducing the pressure to 300Pa, continuing to react for 130min, and finishing the prepolymerization reaction to obtain an amino-terminated prepolymer;
(2) Adding trimethyl citrate into the reaction kettle of the amino-terminated prepolymer obtained in the step (1) according to the mass ratio of-COOCH 3/-NH2 of 1:1, mixing the two, carrying out polymerization reaction, carrying out reduced pressure distillation, continuously heating to 180 ℃ and reacting for 130min for carrying out first polymerization reaction, heating to 185 ℃ and reacting for 130min for carrying out second polymerization reaction, taking out the obtained pre-cured product, and heating in a 185 ℃ vacuum oven for 5h for curing to obtain the bio-based cross-linked polyamide.
As can be seen from fig. 11, the product prepared in this comparative example has cracks and cannot be integrated, and is not repeatedly processed because it does not contain an imine bond.
Test case
(1) The infrared spectra of the amino-terminated prepolymers prepared in step (1) of examples 1 to 4 are shown in FIG. 1. In FIG. 1, Y3 to 2, Y4 to 3, Y5 to 4 and Y6 to 5 are the infrared spectra of the amino-terminated prepolymer prepared in step (1) of examples 1 to 4 in this order.
The infrared spectra of the reworkable bio-based crosslinked polyamide prepared in examples 1-4 are shown in FIG. 2. In FIG. 2, J3 to 2, J4 to 3, J5 to 4 and J6 to 5 are the infrared spectrograms of the repeatedly processable bio-based crosslinked polyamide prepared in examples 1 to 4 in this order,
In FIG. 1, 3300cm -1 is a blocked amino characteristic peak, and 1640cm -1 is an imine bond characteristic peak. In fig. 2, 3400cm -1 is the N-H stretching vibration peak in the amide bond, 1738cm -1 is the carbonyl (c=o) stretching vibration peak of trimethyl citrate, which is not present, demonstrating that trimethyl citrate participates in the reaction and formation of the crosslinked product. As can be seen from FIGS. 1 and 2, the present invention introduces imine bonds into biobased crosslinked polyamides.
(2) The hydrogen spectrum of the amino-terminated prepolymer prepared in the step (1) of examples 1-4 is shown in FIG. 3, and the carbon spectrum is shown in FIG. 4. The structure of the amino-terminated prepolymer can be derived from fig. 3 and 4, and an imine bond is included in the structure.
(3) DSC test curves of the reworkable bio-based crosslinked polyamide prepared in examples 1 to 4 are shown in FIG. 5. As can be seen from fig. 5, it is seen that the glass transition temperature and the melting temperature of the bio-based crosslinked polyamide gradually increase with the increase in the molecular weight of the prepolymer.
(4) The sample pictures obtained after the chips and re-pressing of the reworkable bio-based crosslinked polyamide prepared in examples 1 to 4 are shown in fig. 6. In fig. 6, the same column corresponds to a picture of chips of bio-based crosslinked polyamide prepared in the same example and a sample pressed by the chips, the pressing temperature for the chips was 150 ℃,10MPa, and the pressing time was 15min. As can be seen from FIG. 6, the bio-based crosslinked polyamide prepared by the present invention is crushed and then subjected to thermal energy to reform, thereby having the property of being reproducible.
(5) The reworkable biobased crosslinked polyamides prepared in examples 1-4 were tested for tensile strength and elongation at break.
The calculation formula of the tensile strength retention is shown in the following formula (1):
tensile strength retention = a 1/B1 x 100% (1)
In the formula (1), B 1 is a tensile strength test result of the bio-based crosslinked polyamide, A 1 is a result obtained by crushing the bio-based crosslinked polyamide, pressing fragments, and performing the tensile strength test, wherein the pressing temperature is 150 ℃ and the pressing time is 15min. The tensile strength test was performed with international standard GB-T1040.1-2006.
The calculation formula of the elongation at break retention is shown in the following formula (2):
elongation at break retention = a 2/B2 x 100% formula (2)
In the formula (2), B 2 is the breaking elongation test result of the bio-based crosslinked polyamide, A 2 is the breaking elongation test result of the bio-based crosslinked polyamide obtained by crushing and pressing fragments, wherein the pressing temperature is 150 ℃ and the pressing time is 15min. The international standard for elongation at break test execution is GB-T1040.1-2006.
The tensile strength and elongation at break of the reworkable biobased crosslinked polyamides prepared in examples 1-4 (before reworking) are shown in Table 1:
TABLE 1 tensile Strength and elongation at break of reworkable biobased crosslinked polyamides
| Tensile Strength/MPa | Elongation at break/% | |
| Example 1 | 18.1 | 10.3 |
| Example 2 | 23.5 | 12.5 |
| Example 3 | 24.2 | 15.7 |
| Example 4 | 25.4 | 22.0 |
As can be seen from Table 1, the tensile strength of the products prepared in examples 1-4 is greater than 18MPa, and the elongation at break is greater than 10%.
The thermogravimetric curves of the reworkable biobased crosslinked polyamides prepared in examples 1-4 are shown in figure 7. As can be seen from fig. 7. The 5% thermal decomposition temperature of the reworkable bio-based crosslinked polyamide prepared by the embodiment of the invention is more than 260 ℃.
The retention of the reworkable bio-based crosslinked polyamide prepared in examples 1 to 4 was as shown in table 2:
TABLE 2 maintenance of the Reprocessable Property of the Reprocessed biobased crosslinked polyamides
| Examples | Example 1 | Example 2 | Example 3 | Example 4 |
| Tensile strength retention/% | 93 | 99 | 98 | 99 |
| Elongation at break retention/% | 89 | 94 | 97 | 94 |
From the results of Table 2, it can be seen that the bio-based crosslinked polyamide prepared according to the present invention can be re-compressed into a tablet after crushing, has a reproducible processing property, and the re-compressed sample has an excellent mechanical retention rate.
(6) The reworkable bio-based crosslinked polyamide prepared in examples 1 to 4 was placed in a hydrochloric acid solution having a concentration of 0.5mol/L, respectively, and allowed to stand at room temperature for 24 hours. Fig. 8 is a photograph of the mixture at rest for 0h, and fig. 9 is a photograph of the mixture at rest for 24h. From fig. 8 and 9, it can be seen that the bio-based crosslinked polyamide prepared by the invention not only can be repeatedly processed, but also has better degradation performance.
As can be seen from the results of the examples, the present invention introduces an imine bond in the preparation of the polyamide, so that the bio-based crosslinked polyamide prepared by the present invention has reproducible processing properties, and has excellent mechanical retention and degradability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for preparing a bio-based cross-linked polyamide that can be repeatedly processed, comprising the steps of:
(1) Mixing linear diamine and phthalaldehyde, and performing a prepolymerization reaction in an inert atmosphere to obtain an amino-terminated prepolymer;
(2) Mixing the amino-terminated prepolymer obtained in the step (1) with trimethyl citrate, and carrying out polymerization reaction to obtain the bio-based cross-linked polyamide capable of being repeatedly processed;
the linear diamine in step (1) comprises one or more of butanediamine, pentanediamine, and decanediamine;
The ratio of the amount of the materials of-COOCH 3 of trimethyl citrate and-NH 2 of the amino-terminated prepolymer in the step (2) is (0.9-1.1): 1;
the polymerization reaction in the step (2) comprises a first polymerization reaction, a second polymerization reaction and a curing reaction which are sequentially carried out, wherein the temperature of the second polymerization reaction is higher than that of the first polymerization reaction.
2. The method according to claim 1, wherein the ratio of the amounts of the linear diamine and the phthalaldehyde in the step (1) is (3-6): 2-5.
3. The preparation method according to claim 1, wherein the temperature of the prepolymerization reaction in the step (1) is 100-150 ℃, and the time of the prepolymerization reaction is 10-200 min.
4. The preparation method according to claim 1, wherein the temperature of the first polymerization reaction is 130-180 ℃, and the time of the first polymerization reaction is 10-200 min.
5. The preparation method according to claim 1, wherein the temperature of the second polymerization reaction is 140-200 ℃, and the time of the second polymerization reaction is 10-200 min.
6. The preparation method according to claim 1, wherein the curing reaction is carried out at a temperature of 150-200 ℃ for 1-20 hours.
7. The method according to claim 1 or 6, wherein the aging reaction is performed under a negative pressure of 10 to 300pa.
8. The reworkable bio-based crosslinked polyamide produced by the process of any one of claims 1 to 7.
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| CN202410608072.8A CN118325075B (en) | 2024-05-16 | 2024-05-16 | Bio-based crosslinked polyamide capable of being repeatedly processed and preparation method thereof |
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| CN118325075B true CN118325075B (en) | 2025-03-07 |
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| CN115772276A (en) * | 2022-12-07 | 2023-03-10 | 陕西科技大学 | A kind of bio-based polyamidoimide Vitrimer material and preparation method using absolute ethanol as base solvent |
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| RU2012149242A (en) * | 2010-04-20 | 2014-05-27 | Мицубиси Гэс Кемикал Компани, Инк. | POLYAMIDE COMPOUND |
| TWI841234B (en) * | 2017-04-28 | 2024-05-01 | 美商盧伯利索先進材料有限公司 | Matted polyamide-pud |
| JP2024501671A (en) * | 2020-12-23 | 2024-01-15 | ベーアーエスエフ・エスエー | Binder composition for composite articles comprising one or more polyamines and 1,3-dihydroxyacetone, glycolaldehyde, and/or glyceraldehyde |
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| CN115772276A (en) * | 2022-12-07 | 2023-03-10 | 陕西科技大学 | A kind of bio-based polyamidoimide Vitrimer material and preparation method using absolute ethanol as base solvent |
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