CN113683900B - Modified lignin-polyamide-based thermosetting composite material and preparation method thereof - Google Patents
Modified lignin-polyamide-based thermosetting composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified lignin-polyamide-based thermosetting composite material and a preparation method thereof; the modified lignin-polyamide-based thermosetting composite material is prepared from raw materials containing modified lignin, polyamide and bismaleimide; the modified lignin is obtained by modifying lignin by an anhydride compound. The composite material of the invention forms a semi-interpenetrating network structure, has a lignin cross-linked network phase and a polyamide crystal phase, maintains excellent mechanical properties, gives a high-temperature shape memory effect, and can realize rapid high-temperature shape recovery at 180 ℃.
Description
Technical Field
The invention relates to the technical field of bio-based functional materials, in particular to a modified lignin-polyamide-based thermosetting composite material and a preparation method thereof.
Background
Thermosetting resins represented by epoxy resins, phenolic resins, and the like are important components of high-performance composite materials and play an important role in daily life and industrial production, however, most of thermosetting materials are derived from fossil fuels, and the growing environmental problems and the inherent requirement of "carbon neutralization" provide power for the development of bio-based thermosetting materials.
Lignin is a natural biomass polymer with the second reserve amount to cellulose, is used as a byproduct in the papermaking and biorefinery industries, has huge yield, still does not fully exert the use value, and urgently needs to be utilized with high value. The main structural units of the lignin are p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol, and the three units are connected together through carbon-carbon bonds and ether bonds to form an amorphous hyperbranched structure. Lignin has a variety of functional groups, with phenolic and aliphatic hydroxyl groups being the reaction sites for lignin, which allows lignin to act as a natural cross-linker. The lignin is used as a copolymerization component to prepare thermosetting materials such as phenolic resin, polyurethane resin and the like, the thermosetting materials are mostly non-crystalline or low-melting-point materials, and the use of the lignin for preparing high-melting-point thermosetting composite materials is not reported. Therefore, the invention provides a modified lignin-polyamide-based thermosetting composite material and a preparation method thereof.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a modified lignin-polyamide-based thermosetting composite material.
The technical problem to be solved by the invention is to provide a preparation method of the modified lignin-polyamide-based thermosetting composite material.
The invention idea is as follows: the invention provides a new idea of a lignin-based semi-interpenetrating network composite material, aims to utilize the structural characteristics of lignin, introduces a thermal crosslinking group through modified lignin, compounds the lignin with polyamide with a higher melting point and crosslinks the lignin in situ, obtains the composite material with a special structure in which a lignin crosslinking network and a polyamide crystal phase coexist, not only maintains excellent mechanical properties, but also embodies a high-temperature shape memory effect, and provides a technical reference for the development of a bio-based intelligent material.
In order to solve the first technical problem, the invention discloses a modified lignin-polyamide based thermosetting composite material, wherein a semi-interpenetrating network structure is formed between the modified lignin and the polyamide, and the modified lignin and the polyamide have semi-crystallinity and shape memory performance.
Wherein the thermosetting composite material is prepared from raw materials containing modified lignin, polyamide and bismaleimide.
The modified lignin is obtained by modifying lignin by an anhydride compound and an imidazole compound.
Wherein the lignin includes, but is not limited to, kraft lignin, organic lignin, alkali lignin, enzymatic lignin, and lignin sulfate.
Wherein, the acid anhydride compound includes but is not limited to maleic anhydride.
Wherein the imidazole compounds include but are not limited to 1-methyl-imidazole.
The weight part ratio of the lignin to the anhydride compound to the imidazole compound is 10: (1.5-2.5): (0.25-0.75).
Wherein the modified solvent includes, but is not limited to, tetrahydrofuran; wherein the dosage of the solvent depends on the dosage of the lignin and only needs to be dissolved; preferably, the mass concentration of lignin in the reaction solution is 12% to 15%.
Wherein the temperature of the modification is 20 to 100 ℃, preferably 40 to 80 ℃, more preferably 50 to 70 ℃, and still more preferably 60 ℃.
Wherein the modification time is 0.5-5.5h, preferably 1-5h, more preferably 2-4h, and even more preferably 3 h.
After the modification and reaction are finished, removing the solvent, washing, filtering and drying to obtain modified lignin; preferably, after the reaction is finished, the solvent is removed by rotary evaporation, and the modified lignin is obtained by washing, filtering and drying.
Wherein the weight fraction ratio of the modified lignin, the polyamide and the bismaleimide is (40-60): (40-60): (20-30).
In order to solve the second technical problem, the invention discloses a preparation method of the thermosetting composite material, which comprises the steps of pouring a mixed solution containing lignin, polyamide and bismaleimide into a flat mold, casting the mixed solution into a film in the mold, volatilizing at room temperature to remove a solvent, and curing.
The mixed solution containing lignin, polyamide and bismaleimide can be prepared by mixing and dissolving the three solutions according to a common method, or by respectively dissolving the modified lignin, polyamide and bismaleimide in a solvent and then mixing, preferably by respectively dissolving the modified lignin, polyamide and bismaleimide in a solvent, and then mixing the three solutions after ultrasonic centrifugation.
Wherein the solvent of the mixed solution is hexafluoroisopropanol and/or tetrahydrofuran.
Wherein, in the mixed solution, the ratio of the total weight of the lignin, the polyamide and the bismaleimide to the weight of the solvent is (12-13): (85-110).
Wherein the curing temperature is 150-250 ℃, preferably 170-220 ℃, more preferably 190-210 ℃, and even more preferably 200 ℃.
Wherein the curing time is 5-45min, preferably 15-35min, and more preferably 20-30 min.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the lignin content of the modified lignin-polyamide-based thermosetting composite material prepared by the invention is up to 40 wt%, the utilization efficiency of biomass resources is higher, and the use of other materials is reduced.
(2) The composite material is prepared by adopting a solution coating method, the preparation method is simple, and the matching degree with the existing production process is high.
(3) The invention fully utilizes the structural characteristics of rich lignin functional groups, obtains the modified lignin capable of being thermally crosslinked by derivatization modification, and the crosslinking temperature is matched with the material processing temperature window.
(4) The composite material of the invention forms a semi-interpenetrating network structure, has a lignin cross-linked network phase and a polyamide crystal phase, maintains excellent mechanical properties, gives a high-temperature shape memory effect, and can realize rapid high-temperature shape recovery at 180 ℃.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a rheological analysis of a thermoset composite; (a) example 1, (b) comparative example 1, (c) example 2, (d) comparative example 2, (e) example 3, (f) comparative example 3.
FIG. 2 is a DSC analysis of a thermoset composite.
FIG. 3 is a graph showing the shape memory behavior of the thermosetting material in example 3; (a) original shape, (b) temporary shape, (c-f) shape recovery process, and (g) final recovered shape.
FIG. 4) shape memory behavior of the thermosetting material in comparative example 3.
FIG. 5 is a phosphorus spectrum analysis of modified lignin.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) 10g of kraft lignin and 2g of maleic anhydride and 0.5ml of 1-methyl-imidazole are dissolved in 80ml of tetrahydrofuran and stirred under reflux at 60 ℃ for 3 hours. After completion, the solvent was removed by rotary evaporation. Washing with ultrapure water, filtering, and vacuum drying at 75 ℃ for 24h to obtain the modified lignin.
(2) Respectively dissolving 5g of modified lignin, 5g of polyamide 12 and 2g of bismaleimide in 40ml, 40ml and 16ml of hexafluoroisopropanol; the three obtained solutions are mixed after ultrasonic centrifugation to ensure that the three solutions are uniformly mixed; pouring the mixed solution into a mould, and casting the solution into a film.
(3) And (3) after the formed film is kept at the high temperature of 200 ℃ for 20min, curing is finished, and the thermosetting composite material with the shape memory potential is obtained.
Comparative example 1
(1) 5g of kraft lignin, 5g of polyamide 12 and 2g of bismaleimide are respectively dissolved in 40ml, 40ml and 16ml of hexafluoroisopropanol; the three obtained solutions are mixed after ultrasonic centrifugation to ensure that the three solutions are uniformly mixed; pouring the mixed solution into a mould, and casting the solution into a film.
(2) And (3) keeping the formed film at the high temperature of 200 ℃ for 20min, and finishing curing to obtain the thermosetting composite material.
Example 2
(1) 10g of kraft lignin and 2g of maleic anhydride and 0.5ml of 1-methyl-imidazole are dissolved in 80ml of tetrahydrofuran and stirred under reflux at 60 ℃ for 3 hours. After completion, the solvent was removed by rotary evaporation. Washing with ultrapure water, filtering, and vacuum drying at 75 deg.C for 24 hr to obtain modified lignin.
(2) Respectively dissolving 5g of modified lignin, 5g of polyamide 12 and 2.5g of bismaleimide in 40ml, 40ml and 20ml of hexafluoroisopropanol; the three obtained solutions are mixed after ultrasonic centrifugation to ensure that the three solutions are uniformly mixed; pouring the mixed solution into a mould, and casting the solution into a film.
(3) And (3) after the formed film is kept at the high temperature of 200 ℃ for 20min, curing is finished, and the thermosetting composite material with the shape memory potential is obtained.
Comparative example 2
(1) Dissolving 5g of kraft lignin, 5g of polyamide 12 and 2.5g of bismaleimide in 40ml, 40ml and 20ml of hexafluoroisopropanol respectively; the three obtained solutions are mixed after ultrasonic centrifugation to ensure that the three solutions are uniformly mixed; pouring the mixed solution into a mould, and casting the solution into a film.
(2) And (3) keeping the formed film at the high temperature of 200 ℃ for 20min, and finishing curing to obtain the thermosetting composite material.
Example 3
(1) 10g of kraft lignin and 2g of maleic anhydride and 0.5ml of 1-methyl-imidazole are dissolved in 80ml of tetrahydrofuran and stirred under reflux at 60 ℃ for 3 hours. After completion, the solvent was removed by rotary evaporation. Washing with ultrapure water, filtering, and vacuum drying at 75 deg.C for 24 hr to obtain modified lignin.
(2) Respectively dissolving 5g of modified lignin, 5g of polyamide 12 and 3g of bismaleimide in 40ml, 40ml and 25ml of hexafluoroisopropanol; mixing the above solutions uniformly; pouring the mixed solution into a mould, and casting the solution into a film.
(3) And (3) after the formed film is kept at the high temperature of 200 ℃ for 20min, curing is finished, and the thermosetting composite material with the shape memory potential is obtained.
Comparative example 3
(1) Dissolving 5g of kraft lignin, 5g of polyamide 12 and 3g of bismaleimide in 40ml, 40ml and 25ml of hexafluoroisopropanol respectively; mixing the above solutions uniformly; pouring the mixed solution into a mould, and casting the solution into a film.
(2) And (3) keeping the formed film at the high temperature of 200 ℃ for 20min, and finishing curing to obtain the thermosetting composite material.
Example 4: detection of
(1) Rotary rheometer
The rheological properties of the composite films obtained in step (2) of examples 1, 2 and 3 and of the composite films obtained in step (3) of comparative examples 1, 2 and 3 were characterized by a rotary rheometer, model MARS II, germany, in an air atmosphere. The storage modulus (G ') and loss modulus (G') of the samples are shown in FIG. 1 as a function of temperature profile and time. The intersection point of the composite films G 'and G' obtained in the step (2) in the examples 1, 2 and 3 is about 15-17min, and the values of G 'and G' tend to be stable at 25 min. In contrast, in comparative examples 1, 2 and 3, the intersection point of the composite films G 'and G' obtained in step (1) was about 25min and reached 45min, and the values of G 'and G' were not stable. Therefore, it was demonstrated that the composite membranes obtained in step (2) of examples 1, 2 and 3 were capable of rapidly forming a crosslinked network at 200 ℃.
(2)DSC
Differential Scanning Calorimetry (DSC) was performed using TA DSC25 to characterize the change in thermal properties of the polymer at a heating rate of 10 deg.C/min. As can be seen from FIG. 2 and Table 1, the cured thermoset samples were semi-crystalline, and in examples 1-3, Tm was 175-176 ℃ and Δ Hm was 15-16J/g, which is lower than Tm (180.6 ℃) and Δ Hm (35.4J/g) of polyamide 12, indicating that the thermoset polymer chains still had crystallinity, but the crystallinity was somewhat reduced, laterally confirming the formation of a network structure. Whereas in comparative examples 1-3 the Tm is much lower than that of polyamide 12. This is a good indication of the low perfection of the crystalline regions of the samples obtained in comparative examples 1-3.
TABLE 1 thermal Properties of cured thermoset samples
| Sample (I) | T m (℃) | ΔH m (J/g) |
| Nylon | 180.6 | 35.4 |
| Example 1 | 176.1 | 17.6 |
| Example 2 | 176.0 | 17.6 |
| Example 3 | 175.5 | 16.2 |
| Comparative example 1 | 170.6 | 14.4 |
| Comparative example 2 | 172.3 | 15.2 |
| Comparative example 3 | 174.2 | 17.0 |
(3) Shape memory performance
Qualitatively representing the shape memory behavior, placing the rectangular bar sample in an oven at 190 deg.C, standing for 5min, applying external force to deform, taking out, cooling completely at room temperature, crystallizing, and shaping, at this time, removing force. And (3) putting the deformed sample into an oven at the temperature of 190 ℃ for 5min under the condition of no external force to recover the shape.
Taking the sample of example 3 (fig. 3a) as an example, when heated to above Tm (190 ℃), the crystalline phase melts resulting in enhanced mobility of the molecular chains, while the crosslinked network still constrains the movement of the molecular chains, so that the material does not change to a viscous state. At this time, an external force is applied to the sample to deform it. The material is cooled while the external force is maintained, the material reforms into a crystalline phase, and a stable new shape, i.e. a temporary shape, is obtained after the external force is removed (fig. 3 b). The shape of the device is maintained by reversible phase, the molecular chain is directionally frozen along the direction of external force, and the fixed phase is in a high stress deformation state. When the temporary shape is heated to a shape recovery temperature of 190 ℃, the crystalline phase melts to recover the mobility of the molecular chain, disorients under the recovery stress of the stationary phase, and gradually reaches a thermodynamic equilibrium state (fig. 3 cdef). To this end, the material recovered macroscopically its original shape (fig. 3g), and only 9s were needed for recovery.
Taking the sample of comparative example 3 (fig. 4a) as an example, when heated to a temperature above Tm (190 ℃), the sample is deformed by applying an external force, but the material portion turns into a viscous state, and its original shape is destroyed by the external force (fig. 4 b).
(4) Phosphorus spectrum
Phosphorus spectra were measured on a Varian Mercury 400MHz NMR spectrometer. Collecting parameters: 25 c, 11 990 hz spectral windows, 256 scans, 20 seconds delay between pulses. The calculation of the hydroxyl groups is based on the integration of the following spectral regions: as shown in FIG. 5, alcoholic hydroxyl group (149.6-145.6 ppm), 5-substituted unit (144.2-141.2 ppm), guaiacyl-hydroxyl group (141.0-138.7 ppm), p-hydroxyphenylhydroxyl group (138.7-137.2 ppm) and carboxylic acid (135.9-133. ppm). Cholesterol was used as an internal standard. Calculation shows that the hydroxyl in the modified lignin is obviously reduced, which indicates that the hydroxyl of the lignin is reacted with maleic anhydride, and simultaneously verifies that the alcoholic hydroxyl of the lignin is easier to react with the maleic anhydride than the phenolic hydroxyl.
TABLE 2 Lignin 31 Quantitative analysis result of P-NMR
| Unmodified lignin (mmol/g) | Modified lignin (mmol/g) | |
| Alcoholic hydroxyl group | 0.63 | 0.22 |
| Condensed phenolic hydroxyl group | 0.23 | 0.21 |
| Syringol hydroxy | 0.20 | 0.19 |
| Guaiacol hydroxy | 0.43 | 0.39 |
| P-hydroxyphenyl type phenolic hydroxyl group | 0.29 | 0.28 |
| Hydroxy in carboxyl group | 0.58 | 0.63 |
The present invention provides a modified lignin-polyamide based thermosetting composite material and a method for preparing the same, and a method and a way for implementing the technical scheme are numerous, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and the improvements and modifications should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (5)
1. A modified lignin-polyamide-based thermosetting composite material is characterized by being prepared from raw materials containing modified lignin, polyamide and bismaleimide;
the modified lignin is obtained by modifying lignin by maleic anhydride and 1-methyl-imidazole; the weight part ratio of the lignin, the maleic anhydride and the 1-methyl-imidazole is 10: (1.5-2.5): (0.25-0.75); the modification temperature is 50-70 ℃, and the modification time is 2-4 h;
the preparation method of the modified lignin-polyamide-based thermosetting composite material comprises the steps of placing a mixed solution containing modified lignin, polyamide and bismaleimide in a mold, carrying out tape casting to form a film, removing a solvent, and curing; the curing temperature is 150-250 ℃; the weight fraction ratio of the modified lignin, the polyamide and the bismaleimide is (40-60): (40-60): (20-30).
2. The thermoset composite material of claim 1, wherein the thermoset composite material has shape memory properties.
3. The thermosetting composite material according to claim 1, wherein the solvent of the mixed solution is hexafluoroisopropanol and/or tetrahydrofuran.
4. The thermosetting composite material according to claim 1, wherein the ratio of the total weight of the modified lignin, the polyamide and the bismaleimide to the weight of the solvent in the mixed solution is (12-13): (85-110).
5. The thermoset composite material of claim 1, wherein the curing time is from 5 to 45 min.
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