CN114573842B - High-temperature-resistant reworkable benzoxazine thermosetting resin and synthetic method and application thereof - Google Patents
High-temperature-resistant reworkable benzoxazine thermosetting resin and synthetic method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature resistant reworkable benzoxazine thermosetting resin, and a synthetic method and application thereof. Firstly, allyl amine, phenolic compounds and formaldehyde are used as raw materials, and a benzoxazine monomer with double bonds is synthesized through Mannich reaction; then preparing the benzoxazine oligomer containing double bonds through a heating ring-opening reaction. Finally, the thiol containing borate bond and double bond are utilized to carry out 'thiol-ene' click chemistry reaction to prepare the borate bond crosslinked reworkable benzoxazine resin. The benzoxazine resin synthesized by the invention has excellent reworkability, mechanical property and heat resistance, and the recovery rate of tensile strength after three times of reworking can still reach 84%, T g Can reach 227 ℃, and the tensile strength reaches 31MPa.
Description
Technical Field
The invention relates to a benzoxazine oligomer containing double bonds through boric acid ester bonds, which is used for preparing high-temperature-resistant and reworkable benzoxazine thermosetting resin, and belongs to the field of high-temperature-resistant thermosetting resins.
Background
Thermosetting polymers have been widely used for structural materials and insulating materials because of their high temperature resistance, solvent resistance, dimensional stability, excellent insulating properties, and the like. However, the traditional thermosetting polymer contains an irreversible covalent bond crosslinking structure, so that the thermosetting polymer is insoluble and infusible after solidification and cannot be processed and recycled again, thereby causing resource waste and environmental pollution. In recent years, the introduction of dynamic covalent bonds in polymer networks has been a breakthrough progress in solving the above-mentioned problems. Dynamic covalent bonds refer to covalent bonds that can reversibly break and form under certain conditions, and by introducing dynamic covalent bonds at backbone or cross-linking positions of the polymer network, a response to a stimulus (e.g., a thermally induced response, etc.) can be achieved, thereby achieving reproducible processability.
In general, dynamic covalent bonds can be classified into two types, dissociation type and association type, depending on the mechanism of exchange. In the former, the bond is cleaved first and then reorganized, such as a Diels-Alder addition reaction; in the latter case, cleavage and recombination are performed simultaneously, such as a borate bond, disulfide bond, acylhydrazone bond, and the like. The boric acid ester bond is used as an association type dynamic covalent bond with high bond energy (515 kJ/mol), the crosslinking density is kept almost constant in the bond exchange process, and the boric acid ester bond is favorable for becoming an ideal crosslinking bond for preparing high-temperature resistant and reworkable thermosetting resin.
Polybenzoxazines have been attracting attention as a novel thermosetting resin because of their excellent heat resistance, excellent flame retardancy, high hydrophobicity, and other properties. As with conventional thermosetting resins, the inherent cross-linked structure makes it unusable for recycling.
In addition, CN113292691a discloses a cardanol-based benzoxazine resin, and a preparation method and application thereof, wherein the adopted preparation method is to form a dual network of dynamic borate bond crosslinking and benzoxazine self-crosslinking by performing high-temperature curing on benzoxazine monomers containing borate bonds. However, the cardanol-based benzoxazine resin has no dynamic covalent bond due to the self-crosslinked benzoxazine network, so that the mechanical strength recovery rate after reprocessing is greatly reduced.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the defect of low mechanical strength recovery rate of the current reworkable benzoxazine resin after reworking, the invention provides a high-temperature-resistant reworkable benzoxazine thermosetting resin which is crosslinked by boric acid ester bonds and has high reversible purity, so as to realize high heat resistance and high mechanical strength recovery rate of the reworked resin.
Specifically, firstly, allylamine, formaldehyde and phenolic compounds are used as raw materials to synthesize benzoxazine monomers, and then the benzoxazine monomers are heated for ring-opening polymerization to prepare the benzoxazine oligomer containing double bonds. The boric acid ester cross-linking agent containing mercaptan and double bond are utilized to carry out 'mercaptan-alkene' click chemical reaction, so that a cross-linked network which is only crosslinked by dynamic boric acid ester bonds and has high reversibility is prepared. The benzoxazine resin has excellent thermal performance and high mechanical strength recovery rate.
Summary of the invention:
firstly, adopting allylamine, phenolic compounds and formaldehyde to synthesize benzoxazine monomers through Mannich reaction; preparing a benzoxazine oligomer containing double bonds through a heating ring-opening reaction; the re-added benzoxazine resin with the cross-linked structure of dynamic boric acid ester bonds, excellent heat resistance and high mechanical strength recovery rate is prepared by taking boric acid ester containing mercaptan as a cross-linking agent and carrying out 'mercaptan-alkene' click chemistry reaction.
Detailed description of the invention:
the technical scheme of the invention is as follows:
the novel high temperature resistant reworkable benzoxazine resin crosslinked by boric acid ester bonds has the following structure:
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 ＝-CH 3 ，-C(CH 3 ) 3 ，-CH 2 -CH＝CH 2 ；
n＝2-100。
according to the invention, the preparation method of the boric acid ester bond crosslinked high-temperature resistant reworkable benzoxazine resin comprises the following steps:
firstly, adopting allylamine, formaldehyde and phenolic compounds as raw materials to synthesize a benzoxazine monomer, and then heating for ring-opening polymerization to prepare a benzoxazine oligomer containing double bonds; finally, boric acid ester containing mercaptan is used as a cross-linking agent, and the high-temperature resistant reworkable benzoxazine resin crosslinked by boric acid ester bonds is prepared through 'mercaptan-alkene' click chemical reaction. The benzoxazine resin has a dynamic borate bond structure, excellent heat resistance and high mechanical strength recovery rate.
According to the present invention, preferably, the preparation method of the borate ester bond crosslinked high temperature resistant reworkable benzoxazine resin comprises the following steps:
(1) Mixing allylamine, phenolic compound, formaldehyde and solvent, stirring uniformly, reacting at 80-100 ℃, removing the solvent after the reaction, and vacuum drying to obtain benzoxazine monomer containing double bonds;
(2) Adding p-tert-butylphenol into a benzoxazine monomer, uniformly mixing, and heating for ring-opening polymerization to obtain a benzoxazine oligomer containing double bonds;
(3) Uniformly mixing terephthalyl acid and 3-mercaptan-1, 2-propanediol in ethanol, reacting for 14-28h at room temperature, removing solvent after the reaction, and vacuum drying to obtain diboron ester dithiol;
(4) Uniformly mixing the products in the step (2) and the step (3) in a solvent, and carrying out 'thiol-ene' click chemical reaction on the boric acid ester containing thiol and double bonds to prepare the boric acid ester bond crosslinked and reworkable benzoxazine resin.
According to the present invention, it is preferable that the phenolic compound in the step (1) is any one of phenol, p-cresol, p-tert-butylphenol, cardanol, and p-allylphenol.
According to the present invention, preferably, the formaldehyde in the step (1) is paraformaldehyde or an aqueous formaldehyde solution.
According to the invention, it is preferred that the molar ratio of allylamine, phenolic compound, formaldehyde in step (1) is 1:1 (2-2.5).
According to the present invention, it is preferable that the temperature of the heated ring-opening polymerization reaction in the step (2) is 140 to 150 ℃.
According to the invention, it is preferred that the molar ratio of diboron ester dithiol added in step (4) to double bonds in the benzoxazine oligomer is 1 (2-3).
According to the present invention, it is preferable that the thermal initiation polymerization temperature of the "thiol-ene" click chemistry reaction in the step (4) is 75℃and the reaction time is 6 hours, and then the reaction is gradually raised to 100, 120, 140℃for 2 hours.
According to the invention, the use of the novel, high temperature resistant, reworkable benzoxazine resin crosslinked with a borate linkage as described above in reworking resins;
preferably, the reprocessing steps are as follows: grinding damaged reworkable benzoxazine resin into powder, and hot pressing at 140-160 deg.c and 16-20MPa for 2-5 hr.
The synthetic route of the novel benzoxazine resin which is crosslinked by the boric acid ester bond, resistant to high temperature and capable of being reprocessed is shown as follows:
the beneficial effects of the invention are as follows:
1. in the aspect of synthesis, the benzoxazine oligomer and the borate bond are designed to crosslink, so that the crosslinked structures in a crosslinked network are all dynamic borate bonds, other irreversible crosslinked structures are not contained, and the reversible purity of the network is high.
2. In terms of performance, the benzoxazine resin synthesized by the method has a reversible cross-linked network with high purity, so that the benzoxazine resin has excellent reworkability, and the recovery rate of the tensile strength after three times of reworking can still reach 84%.
3. In terms of performance, the benzoxazine resin synthesized by the invention adopts a dynamic borate bond with high bond energy, so the benzoxazine resin has excellent heat resistance and T g Can reach 227 ℃.
4. Because the benzoxazine resin synthesized by the invention has high crosslinking density, the product has high mechanical strength which can reach 31MPa.
Drawings
FIG. 1 is a graph of cardanol, allylamine and cardanol based benzoxazine monomers and oligomers from example 1 1 HNMR (nuclear magnetic resonance spectroscopy) diagram.
FIG. 2 is a FT-IR (Fourier transform infrared spectroscopy) plot of a thiol-containing borate ester linkage crosslinker, allylamine and cardanol-based benzoxazine monomer, and allylamine and cardanol-based reworkable benzoxazine resin crosslinked with borate ester linkages of example 1.
Fig. 3 is a SEC (gel permeation chromatography) diagram of allylamine and cardanol based benzoxazine monomers and oligomers in example 1.
FIG. 4 is a schematic representation of thiol-containing borate ester linkage cross-linker of example 1 1 HNMR (nuclear magnetic resonance spectroscopy) diagram.
FIG. 5 is a graph of allylamine and p-cresol based benzoxazine monomers and oligomers of example 2 1 HNMR (nuclear magnetic resonance spectroscopy) diagram.
FIG. 6 is the tensile strength and elongation at break of the initial and tertiary reprocessing of the borate ester bond crosslinked allylamine and cardanol based reworkable benzoxazine resins of the test examples.
FIG. 7 is a DMA (dynamic thermal mechanical analysis) graph of initial and tertiary reprocessing of borate ester bond crosslinked allylamine and cardanol based reworkable benzoxazine resins in the test examples.
FIG. 8 is a TGA (thermogravimetric analysis) plot of initial and tertiary reprocessing of borate ester bond crosslinked allylamine and cardanol based reworkable benzoxazine resins in the test examples.
Detailed Description
The invention is further illustrated by, but not limited to, the following specific examples.
The reagents used in the examples were all conventional commercial products.
Example 1: reworkable benzoxazine resins based on allylamine and cardanol
(1) Allylamine (8.55 g,150 mmol), paraformaldehyde (9.47 g,300 mmol), triethylamine (5 mL) and toluene (300 mL) were added to a 500mL three-necked flask and stirred at room temperature for 0.5h. Cardanol (46.61 g,150 mmol) was added dropwise to the above mixture. The reaction was stirred at reflux for 12h. Vacuum drying at 60 ℃ gives benzoxazine monomer (BZ) in 83% yield.
Testing of benzoxazine monomers obtained in this example 1 HNMR data as follows:
1 H NMR(400MHz,CDCl 3 ,ppm):6.90-6.60(3H,Ar-H),5.84-5.76(1H,-CH 2 -CH＝CH 2 ),4.85(2H,O-CH 2 -N),5.28-5.15(2H,CH 2 ＝CH-),3.96(2H,Ar-CH 2 -N),3.41-3.35(2H,N-CH 2 -CH-),2.57-2.48(2H,Ar-CH 2 -),1.64-1.51(2H,Ar-CH 2 -CH 2 -CH 2 -). The map is shown in figure 1.
The benzoxazine monomer obtained in this example was tested for FT-IR data as follows:
FT-IR(KBr,cm -1 ) 2926 and 2854 (oxazine ring and CH of side chain alkyl group of cardanol) 2 ) 1640 (c=c for allyl), 1505 (c=c for benzene ring), 1242 (C-O-C for oxazine ring), 968 (oxazine ring). The map is shown in fig. 2.
SEC spectra, as shown in figure 3.
(2) P-tert-butylphenol (1.5 g) was added to benzoxazine monomer (15 g), stirred at 100 ℃ for 5min until completely and uniformly mixed, and the resulting mixture was polymerized at 150 ℃ for 10h and cooled to room temperature to obtain a reddish-white solid. The crude product obtained was dissolved in n-hexane, poured into 500mL of methanol, suction filtered and the solid collected and dried in vacuo at 50 ℃ to give the benzoxazine Oligomer (OBZ) in 70% yield. 1 HNMR profile, as shown in fig. 1; FT-IR spectrum as shown in FIG. 2;
SEC profile as shown in figure 3.
(3) 1, 4-Benzenedicarboxylic acid (3.03 g,18.1 mmol) and 3-thiol-1, 2-propanediol (4.12 g,36.2 mmol) were dissolved in ethanol (65 mL), stirred at room temperature for 24 hours, and after the completion of the reaction, ethanol was removed by rotary evaporation under reduced pressure to give the title compound as a white solid, designated BDB (6.58 g, 92%).
Testing of benzoxazine monomers obtained in this example 1 H NMR data as follows:
1 H NMR(400MHz,CDCl 3 ,ppm):1.48(2H,-SH),2.81(4H,HS-CH 2 (-), 4.18 and 4.49 (4H, O-CH) 2 -),4.74(2H,O-CH-(CH 2 -) 2 ) 7.83 (4H, ar-H). The map is shown in fig. 4.
FT-IR spectrum as shown in FIG. 2.
(4) Under the protection of argon, the benzoxazine oligomer (3.02 g) in the step (2) and the thiol-containing borate cross-linking agent (1.51 g) in the step (3) are respectively dissolved in anisole at 75 ℃, and the benzoxazine oligomer and the thiol-containing borate cross-linking agent are mixed and cooled to room temperature. AIBN (0.13 g) dissolved in anisole was added to the above system, and after stirring well, poured into an aluminum foil tank and put into an oven: reacting at 75 ℃ for 12 hours, gradually heating up to 100, 120 and 140 ℃ for 2 hours, and vacuum drying at 100 ℃ to obtain the wine red transparent film.
FT-IR spectrum as shown in FIG. 2.
Example 2: reworkable benzoxazine resins based on allylamine and p-cresol.
(1) Allylamine (8.55 g,0.15 mol), paraformaldehyde (9.90 g,0.33 mol), p-cresol (16.20 g,0.15 mol), triethylamine (4 mL) and 200mL toluene were added to a 500mL three-necked flask, stirred under reflux for 4h, cooled to room temperature after the reaction, and dried under vacuum at 60℃to give a benzoxazine monomer with a yield of 70%.
Testing of benzoxazine monomers obtained in this example 1 HNMR data as follows:
1 H NMR(400MHz,CDCl 3 ,ppm)：6.87-6.61(3H,Ar-H)；5.89-5.79(1H,-CH 2 -CH＝CH 2 ),5.18-5.12(2H,-CH 2 -CH＝CH 2 ),4.77(2H,O-CH 2 -N),3.89(2H,Ar-CH 2 -N),3.31(2H,-CH 2 -CH＝CH 2 ),2.18(3H,Ar-CH 3 ). The map is shown in fig. 5.
(2) P-tert-butylphenol (1.5 g) was added to benzoxazine monomer (15 g), stirred at 100 ℃ for 5min until completely and uniformly mixed, and the resulting mixture was polymerized at 150 ℃ for 10h, cooled to room temperature to obtain pale yellow solid. The crude product obtained is dissolved in toluene, poured into 500mL of normal hexane, filtered and the solid is collected, and dried in vacuum at 50 ℃ to obtain the pale yellow benzoxazine oligomer.
Testing of benzoxazine monomers obtained in this example 1 HNMR data as follows:
1 H NMR(400MHz,CDCl 3 ,ppm)：6.93–6.69(2H,Ar-H),5.96(1H,-CH 2 -CH＝CH 2 ),5.20(2H,-CH 2 -CH＝CH 2 ),3.67(4H,Ar-CH 2 -N),3.12(2H,-CH 2 -CH＝CH 2 ),2.21(3H,Ar-CH 3 ). The map is shown in fig. 5.
(3) 1, 4-Benzenedicarboxylic acid (3.03 g,18.1 mmol) and 3-thiol-1, 2-propanediol (4.12 g,36.2 mmol) were dissolved in ethanol (65 mL), stirred at room temperature for 24 hours, and after the completion of the reaction, ethanol was removed by rotary evaporation under reduced pressure to give the title compound as a white solid (6.58 g, 92%).
(4) Under the protection of argon, the benzoxazine oligomer (4.02 g) in the step (2) and the boric acid ester cross-linking agent (2.71 g) containing mercaptan in the step (3) are respectively dissolved in anisole at 75 ℃, and the benzoxazine oligomer and the boric acid ester cross-linking agent are mixed and cooled to room temperature. AIBN (0.18 g) dissolved in anisole was added to the above system, and after stirring well, poured into an aluminum foil tank and put into an oven: reacting at 75 ℃ for 12 hours, gradually heating up to 100, 120 and 140 ℃ for 2 hours, and vacuum drying at 100 ℃ to obtain the yellowish transparent film.
Example 3: reworkable benzoxazine resins based on allylamine and p-tert-butylphenol.
(1) Allylamine (8.55 g,0.15 mol), paraformaldehyde (9.90 g,0.33 mol), p-tert-butylphenol (22.5 g,0.15 mol), triethylamine (4 mL) and 250mL chloroform were added to a 500mL three-necked flask, the mixture was stirred under reflux for 4 hours, and after the reaction was completed, the mixture was cooled to room temperature and dried under vacuum at 40℃to obtain a benzoxazine monomer.
(2) P-tert-butylphenol (1.5 g) was added to benzoxazine monomer (15 g), stirred at 100 ℃ for 5min until completely and uniformly mixed, and the resulting mixture was polymerized at 150 ℃ for 10h, cooled to room temperature to obtain pale yellow solid. The crude product obtained is dissolved in toluene, poured into 500mL of normal hexane, filtered and the solid is collected, and dried in vacuum at 50 ℃ to obtain the benzoxazine oligomer.
(3) 1, 4-Benzenedicarboxylic acid (3.03 g,18.1 mmol) and 3-thiol-1, 2-propanediol (4.12 g,36.2 mmol) were dissolved in ethanol (65 mL), stirred at room temperature for 24 hours, and after the reaction, ethanol was removed by rotary evaporation under reduced pressure to give the title compound as a white solid.
(4) Under the protection of argon, the benzoxazine oligomer (3.86 g) in the step (2) and the thiol-containing borate cross-linking agent (2.21 g) in the step (3) are respectively dissolved in anisole at 75 ℃, and the benzoxazine oligomer and the thiol-containing borate cross-linking agent are mixed and cooled to room temperature. AIBN (0.17 g) dissolved in anisole was added to the above system, and after stirring well, poured into an aluminum foil tank and put into an oven: reacting at 75 ℃ for 12 hours, gradually heating up to 100, 120 and 140 ℃ for 2 hours, and vacuum drying at 100 ℃ to obtain the final product.
Test example: reworkable experiments based on allylamine and cardanol.
The sample prepared in example 1 was ground into powder, fully filled into a stainless steel mold, hot pressed at 16mpa at 160 ℃ for 2 hours to obtain reworkable dumbbell-shaped bars and tested for mechanical properties.
The tensile strength and elongation at break properties of the initial and tertiary reprocessed of the borate ester bond crosslinked allylamine and cardanol based reprocessable benzoxazine resins are shown in fig. 6. It can be seen that the initial tensile strength is 31MPa, 84% of the tensile strength remains after three reworkable processes, and good reworkability is exhibited.
DMA graphs of initial and tertiary reprocessing of the borate ester bond crosslinked allylamine and cardanol based reprocessable benzoxazine resins are shown in fig. 7. It can be seen that the glass transition temperature after both the initial and the reprocessing process is higher than 200 ℃.
The TGA profile of the initial and tertiary reprocessing of the borate ester bond crosslinked allylamine and cardanol based reprocessable benzoxazine resins is shown in fig. 8. It can be seen that the initial temperature of the thermal decomposition temperature after the initial and reprocessing processes is higher than 260 ℃, which indicates that the material has good heat resistance and thermal stability.
Therefore, the benzoxazine resin synthesized by the invention has excellent reworkability and heat resistance, so that the benzoxazine resin has good prospect in recycling in the field of high temperature resistance.
While the foregoing description of the embodiments of the present invention has been presented with reference to the drawings, it is not intended to limit the scope of the invention, but rather, various modifications or variations can be made by those skilled in the art without the need of inventive effort on the basis of the technical solutions of the present invention.
Claims (10)
1. A method for preparing a high temperature resistant reworkable benzoxazine resin crosslinked with a borate ester linkage, the benzoxazine resin having the structure:
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 ＝-CH 3 ，-C(CH 3 ) 3 ，-CH 2 -CH＝CH 2 ；
n＝2-100；
the preparation method comprises the following steps:
(1) Mixing allylamine, phenolic compound, formaldehyde and solvent, stirring uniformly, reacting at 80-100 ℃, removing the solvent after the reaction, and vacuum drying to obtain benzoxazine monomer containing double bonds;
(2) Adding p-tert-butylphenol into a benzoxazine monomer, uniformly mixing, and heating for ring-opening polymerization to obtain a benzoxazine oligomer containing double bonds;
(3) Uniformly mixing terephthalyl acid and 3-mercaptan-1, 2-propanediol in ethanol, reacting for 14-28h at room temperature, removing solvent after the reaction, and vacuum drying to obtain diboron ester dithiol;
(4) Uniformly mixing the products in the step (2) and the step (3) in a solvent, and carrying out 'thiol-ene' click chemical reaction on the boric acid ester containing thiol and double bonds to prepare the boric acid ester bond crosslinked and reworkable benzoxazine resin.
2. The method for producing a high-temperature resistant reworkable benzoxazine resin crosslinked with a borate ester bond according to claim 1, wherein said phenolic compound in step (1) is any one of phenol, p-cresol, p-tert-butylphenol, cardanol, and p-allylphenol.
3. The method for producing a high-temperature resistant reworkable benzoxazine resin crosslinked by a borate ester bond according to claim 1, wherein said formaldehyde in step (1) is paraformaldehyde or an aqueous formaldehyde solution.
4. The method for producing a high-temperature resistant reworkable benzoxazine resin crosslinked by a borate ester bond according to claim 1, wherein the molar ratio of allylamine, phenolic compound, formaldehyde in step (1) is 1:1 (2-2.5).
5. The method for producing a high-temperature resistant reworkable benzoxazine resin crosslinked by a borate ester linkage according to claim 1, wherein the temperature of the heating ring-opening polymerization reaction in the step (2) is 140 to 150 ℃.
6. The method for producing a high-temperature resistant reworkable benzoxazine resin crosslinked by a borate ester linkage according to claim 1, wherein the molar ratio of diboron ester dithiol added in step (4) to double bonds in the benzoxazine oligomer is 1 (2-3).
7. The method for preparing a high temperature resistant reworkable benzoxazine resin crosslinked by a borate ester linkage according to claim 1, wherein the thermal initiation polymerization temperature of the "thiol-ene" click chemistry reaction in the step (4) is 75 ℃, the reaction time is 6 hours, and then the temperature is gradually raised to 100 ℃, 120 ℃ and 140 ℃ for 2 hours.
8. A benzoxazine resin prepared by the method for preparing a high temperature resistant reworkable benzoxazine resin crosslinked by a borate bond according to any one of claims 1-7.
9. Use of the benzoxazine resin according to claim 8 in reprocessing resins.
10. The use according to claim 9, characterized in that the reprocessing step is as follows: grinding damaged reworkable benzoxazine resin into powder, and hot pressing at 140-160 deg.c and 16-20MPa for 2-5 hr.
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