CN113149856A - Amide-containing bio-based benzoxazine resin and preparation method thereof - Google Patents
Amide-containing bio-based benzoxazine resin and preparation method thereof Download PDFInfo
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- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
- C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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Abstract
The invention belongs to the technical field of thermosetting resin, discloses amide-containing bio-based benzoxazine resin and a preparation method thereof, and solves the problem of poor thermal stability of a high molecular substance derived from diphenolic acid. The benzoxazine monomer structure contains amide groups, so that the thermal property of the benzoxazine resin can be obviously improved, and the glass transition temperature of the benzoxazine resin can be improved.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin, and particularly relates to amide structure-containing all-bio-based benzoxazine resin and a preparation method thereof.
Background
As a novel thermosetting resin, the polybenzoxazine has the advantages of no release of small molecules in the thermal ring opening polymerization process, high thermal stability, good mechanical property, volume change close to zero after curing, low thermal expansion coefficient, good flame retardance and the like, and has low dielectric constant, low surface free energy and low water absorption rate. Compared with other polymers, the most attractive feature of benzoxazine is that the molecular structure can be flexibly designed, so that high performance and functionalization of the material are further realized.
At present, the bio-based benzoxazine has received extensive attention of researchers due to the advantages of renewable raw materials, small environmental pollution and the like. To obtain high-performance bio-based benzoxazines, it is critical to find suitable phenol and amine resources in nature.
The bisphenol A with wide application range and large dosage in the petrochemical industry is synthesized by phenol and acetone. Bisphenol A is proved to have harmfulness to the reproductive system of a human body, is difficult to decompose in nature, and threatens the environment to become a problem which can be continuously developed and is urgently needed to be solved in society. Levulinic acid is a cheap biomass platform compound, is condensed with phenol to obtain diphenolic acid, is similar to bisphenol A in structure, but is safe and non-toxic to human bodies, and in recent years, diphenolic acid is considered to be a good substitute product of bisphenol A, and is widely used for synthesis of high polymer materials such as polybenzoxazine, polycarbonate and polyester. However, carboxyl functional groups in diphenolic acid are easy to undergo decarboxylation at about 200 ℃ to release carbon dioxide gas, which causes poor thermal performance of high polymer materials or material defects such as bubbles in products, and limits the application of the diphenolic acid in various fields. In order to prevent decarboxylation at high temperatures, a common method is to esterify or decarboxylate a carboxyl group, but neither of them can completely solve the problem of poor thermal properties.
Disclosure of Invention
The invention provides a solution for synthesizing high-performance bio-based polybenzoxazine resin by amidating diphenolic acid carboxyl. The technical scheme adopted by the invention is as follows:
firstly, carboxylic acid functional groups of diphenolic acid are converted into amide through reaction with amine substances, and the specific synthetic method comprises the steps of mixing diphenolic acid and a diamine solution, heating to 180 ℃, reacting for 3-6 hours under a reduced pressure condition, completing amidation reaction, and recrystallizing to obtain biological phenol with four phenol group structures. Wherein the diamine raw material can be one of ethylenediamine, hexamethylenediamine and spermine, and the solvent can be one of ethylene glycol phenyl ether, polyethylene glycol 200 and polyethylene glycol 400.
The amidated diphenolic acid compound has the following structural formula:
wherein R may be of the structure:
the bio-based phenol is taken as a raw material, and primary amine compounds and aldehyde substances are subjected to condensation cyclization reaction to synthesize a benzoxazine monomer, wherein the phenolic group of the benzoxazine monomer is converted into a benzoxazine ring structure, the molecular structure contains four oxazine ring structures in total, and the molecular structural formula is shown in the following figure,
wherein R is1The following structure is possible:
the benzoxazine monomer can be synthesized by the following method, wherein the amidated diphenolic acid phenolic compound, primary amine and paraformaldehyde are mixed in a solvent, the mixture is heated to 80-110 ℃, the reaction is carried out for 3-6 hours, and the bio-based benzoxazine monomer is obtained after alkali washing, water washing and drying. The primary amine can be one of furfuryl amine, lauryl amine and stearyl amine, and the solvent can be dioxane, etc.
The benzoxazine monomer is heated and cured in a range of 160-260 ℃ in stages, and the ring-opening polymerization of a benzoxazine ring structure is carried out, so that the polybenzoxazine resin is obtained.
Benefits that can be achieved by the present invention compared to the prior art include, but are not limited to, (1) conversion of carboxylic acid functionality to amide, addressingThe problem of poor thermal stability caused by heating deacidification reaction is specifically represented by 5 percent of thermal decomposition weight loss (T) in a Thermal Gravimetric Analysis (TGA) curved5) Temperature and 10% weight loss by pyrolysis (T)d10) The temperature is increased. (2) Meanwhile, the amido bond can enhance the strength and the number of hydrogen bond structures in the thermosetting resin, thereby improving the glass transition temperature (T) of the polybenzoxazine resing) And mechanical properties, in particular as measured by dynamic thermomechanical analysis (DMA) methodgIncrease in the value and enhancement of the storage modulus (T)gThe temperature is increased from 280 ℃ to 326 ℃, and the storage modulus is increased from 2700MPa to 3500 MPa).
Drawings
FIGS. 1a and 1b are respectively an infrared spectrum and a nuclear magnetic spectrum of the amidated diphenolic acid obtained in example 1;
fig. 2a and 2b are an infrared spectrum and a nuclear magnetic spectrum of the bio-based benzoxazine monomer obtained in example 1, respectively.
FIG. 3: example 1 is a thermogram of the obtained bio-based benzoxazine monomer and carboxyl group-containing diphenolic acid benzoxazine monomer.
FIG. 4: example 1 dynamic thermo-mechanical analysis curves of the resulting bio-based benzoxazine monomer and carboxyl group-containing diphenolic acid benzoxazine monomer.
Detailed Description
The invention is further illustrated with reference to specific examples, without however being limited thereto. Those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the present invention should fall within the scope of the claimed invention.
Example 1
Preparation of benzoxazine resin poly (DHA-fa): DPA (11.44g, 40.00mmol) and 1, 6-hexanediamine (2.32g, 20.00mmol) were mixed in PEG-200(60mL), heated at 180 ℃ under reduced pressure for 3 hours, cooled to room temperature, and recrystallized from a mixed solvent of ethanol/water (7:3 ratio) to give white DHA powder.
Furfuryl amine (4.85g, 50.00mmol) and paraformaldehyde (3.30g, 110.00mmol) were mixed at room temperature for 30min, DHA (8.15g, 12.50mmol) and PEG-200(20mL) were added, heated at 120 ℃ for 90min, and cooled to room temperature. After further mixing with 2-butanone (20mL), the mixture was washed with 1N aqueous NaOH and deionized water, and dried under vacuum to give yellow DHA-fa powder.
And putting the DHA-fa into a forced air drying box for segmented curing to obtain the bio-based benzoxazine resin poly (DHA-fa).
The method comprises the following specific steps of segmented curing: heating at 160 deg.C for 1h, heating at 180 deg.C for 1h, heating at 200 deg.C for 1h, heating at 220 deg.C for 1h, heating at 240 deg.C for 2h, and heating at 260 deg.C for 2 h.
The molecular structures of DHA and DHA-fa obtained in this example are as follows,
FIG. 1 shows the infrared spectrum and nuclear magnetic hydrogen spectrum of the amidated diphenolic acid prepared in this example. In the infrared spectrogram, 1237cm-1Represents the C-N stretching vibration peak, 1513cm-1Representing the C-N tensile vibration peak, N-H flexural vibration peak, 1616cm-1Represents a C ═ O stretching vibration peak. In the nuclear magnetic hydrogen spectrum, the formation of amide bond was confirmed by a chemical shift of 2.9 ppm. In conclusion, this example shows that DHA has been successfully synthesized.
Fig. 2 shows an infrared spectrum and a nuclear magnetic hydrogen spectrum of the bio-based benzoxazine monomer prepared in the present example. In an infrared spectrogram, 934cm-1Representing the plane vibration peaks of oxazine rings, 1230 and 1012cm-1Represents the symmetric stretching vibration peak and the asymmetric stretching vibration peak of oxazine ring C-O-C, 1322cm-1The peak at (A) is due to the-CH of the benzooxazine ring2Swing at 1500cm-1The absorption peak at (A) is ascribed to the trisubstituted benzene ring. Furthermore, by using a probe at 734 and 1081cm-1The characteristic absorption peak of (A) confirms that the furan ring is successfully introduced into the benzoxazine structure. In the nuclear magnetic hydrogen spectrum, peaks at 4.77 and 3.85ppm were assigned to O-CH of the oxazine ring, respectively2-N and Ar-CH2-N structure, whereas peaks at 7.34, 6.26 and 6.17ppm are assigned to furan rings. In conclusion, the benzoxazine monomer DHA-fa is successfully synthesized in the example.
FIG. 3 shows the thermogravimetric analysis curves of the bio-based benzoxazine resin poly (DHA-fa) prepared in this example and the carboxyl group-containing benzoxazine resin poly (DPA-fa) directly synthesized with diphenolic acid and furfuryl amine. Poly (DHA-fa) has excellent thermal stability before 300 ℃ compared with poly (DPA-fa) degradation reaction starting from 200 ℃, and Td5And Td10384 and 405 ℃ respectively. The amidation strategy is demonstrated to solve the problem of poor thermal stability of carboxyl-containing benzoxazines.
FIG. 4 shows the dynamic thermo-mechanical analysis curves of bio-based benzoxazine resin poly (DHA-fa) prepared in this example and carboxyl group-containing benzoxazine resin poly (DPA-fa) directly synthesized with diphenolic acid and furfuryl amine. The glass transition temperature derived from tan delta, the value of poly (DHA-fa) (326 ℃) is far higher than that of poly (DPA-fa), and the glass transition temperature has higher storage modulus (3500MPa), and shows excellent thermo-mechanical properties.
Example 2
Preparation of benzoxazine resin poly (DEA-fa):
DPA (11.44g, 40.00mmol) and ethylenediamine (1.20g, 20.00mmol) were mixed in PEG-200(60mL), heated at 160 ℃ under reduced pressure for 3 hours, cooled to room temperature, and recrystallized from a mixed solvent of ethanol/water (7:3 ratio) to give white DEA powder.
Furfuryl amine (4.85g, 50.00mmol) and paraformaldehyde (3.30g, 110.00mmol) were mixed at room temperature for 30min, DEA (7.45g, 12.50mmol) and PEG-200(20mL) were added, heated at 120 ℃ for 90min, and cooled to room temperature. After further mixing with 2-butanone (20mL), the mixture was washed with 1N aqueous NaOH and deionized water, and dried under vacuum to give yellow DHA-fa powder.
And (3) putting DEA-fa into a forced air drying box for sectional curing to obtain the bio-based benzoxazine resin poly (DEA-fa).
The method comprises the following specific steps of segmented curing: heating at 160 deg.C for 1h, heating at 180 deg.C for 1h, heating at 200 deg.C for 1h, heating at 220 deg.C for 1h, heating at 240 deg.C for 2h, and heating at 260 deg.C for 2 h.
The molecular structures of DEA and DEA-fa obtained in this example are as follows,
1230cm in the infrared spectrogram of DEA-1Represents the peak of C-N stretching vibration, 1515cm-1Representing the C-N stretching vibration peak N-H bending vibration peak, 1660cm-1Represents a C ═ O stretching vibration peak. In the nuclear magnetic hydrogen spectrum, the formation of an amide bond was confirmed by a chemical shift of 3.4 ppm. In conclusion, this example shows that DEA has been successfully synthesized.
934cm in DEA-fa infrared spectrogram-1Representing the plane vibration peaks of oxazine rings, 1230 and 1012cm-1Represents the symmetric stretching vibration peak and the asymmetric stretching vibration peak of oxazine ring C-O-C, 1322cm-1The peak at (A) is due to the-CH of the benzoxazine ring2Swing at 1500cm-1The absorption peak at (A) is ascribed to the trisubstituted benzene ring. Furthermore, by using a probe at 734 and 1081cm-1The characteristic absorption peak of (A) confirms that the furan ring is successfully introduced into the benzoxazine structure. In the nuclear magnetic hydrogen spectrum, peaks at 4.77 and 3.85ppm were assigned to the O-CH groups of the oxazine ring, respectively2-N and Ar-CH2-N structure, whereas peaks at 7.34, 6.26 and 6.17ppm are assigned to furan rings. In conclusion, the benzoxazine monomer DHA-fa is successfully synthesized in the example.
T of poly (DHE-fa) in thermogravimetric analysis curved5And Td10390 and 420 c, respectively. In the dynamic thermo-mechanical analysis curve, the glass transition temperature derived from tan delta, the value of poly (DEA-fa) was 340 ℃ and the storage modulus was 3700 MPa.
Example 3
Preparation of benzoxazine resin poly (DHA-sa):
DPA (11.44g, 40.00mmol) and 1, 6-hexanediamine (2.32g, 20.00mmol) were mixed in PEG-200(60mL), heated at 180 ℃ under reduced pressure for 3 hours, cooled to room temperature, and recrystallized from a mixed solvent of ethanol/water (7:3 ratio) to give white DHA powder.
Stearylamine (5.40g, 50.00mmol) and paraformaldehyde (3.30g, 110.00mmol) were mixed at room temperature for 30min, DHA (8.15g, 12.50mmol) and PEG-200(20mL) were added, heated at 120 ℃ for 5h, and cooled to room temperature. After further mixing with 2-butanone (20mL), the mixture was washed with 1N aqueous NaOH and deionized water and dried under vacuum to give yellow DHA-sa powder.
And putting the DHA-sa into a forced air drying oven for segmented curing to obtain the bio-based benzoxazine resin poly (DHA-sa).
The method comprises the following specific steps of segmented curing: heating at 160 deg.C for 1h, heating at 180 deg.C for 1h, heating at 200 deg.C for 1h, heating at 220 deg.C for 1h, heating at 240 deg.C for 2h, and heating at 260 deg.C for 2 h.
The molecular structures of DHA and DHA-sa obtained in this example are as follows,
in the infrared spectrogram of DHA-sa, 934cm-1Represents the vibration peak of oxazine ring plane, 1200 and 1012cm-1Represents the symmetric stretching vibration peak and the asymmetric stretching vibration peak of oxazine ring C-O-C, 1322cm-1The peak at (A) is due to the-CH of the benzoxazine ring2Swing at 1500cm-1The absorption peak at (A) is ascribed to the trisubstituted benzene ring. In the nuclear magnetic hydrogen spectrum, peaks at 5.01 and 3.70ppm were assigned to O-CH of the oxazine ring, respectively2-N and Ar-CH2-an N structure. In conclusion, the example shows that the benzoxazine monomer DHA-sa is successfully synthesized.
T of poly (DHA-sa) in thermogravimetric analysis curved5And Td10356 and 388 ℃ respectively. In the dynamic thermo-mechanical analysis curve, the glass transition temperature derived from tan delta, the value of poly (DHA-sa) was 150 ℃ and the storage modulus was 2000 MPa. The thermal property is lower than that of benzoxazine containing furfuryl amine.
Example 4
Preparation of benzoxazine resin poly (DPA-fa):
PEG-200, furfuryl amine (4.85g, 50.00mmol) and paraformaldehyde (3.00g, 100.00mmol) were mixed at room temperature for 30 min. DPA (7.15g, 25.00mmol) and PEG-200(20mL) were added to the mixture, heated at 100 ℃ for 3h, and cooled to room temperature. After further mixing with 2-butanone (20ml), the mixture was washed with deionized water (30ml, three times) and dried under vacuum to give yellow DPA-fa powder.
And (3) putting the DPA-fa into a forced air drying oven for sectional curing to obtain the bio-based benzoxazine resin poly (DPA-fa).
The method comprises the following specific steps of segmented curing: heating at 160 deg.C for 1h, heating at 180 deg.C for 1h, heating at 200 deg.C for 1h, heating at 220 deg.C for 1h, heating at 240 deg.C for 2h, and heating at 260 deg.C for 2 h.
The molecular structure of DPA-fa obtained in this example is as follows,
934cm in the infrared spectrogram of DPA-fa-1Representing oxazine ring plane vibration peaks, 1232 and 1013cm-1Represents the symmetric stretching vibration peak and the asymmetric stretching vibration peak of oxazine ring C-O-C, 1322cm-1The peak at (A) is due to the-CH of the benzoxazine ring2Oscillating at 1499cm-1The absorption peak at (A) is ascribed to the trisubstituted benzene ring. 1709cm-1The carboxylic acid carbonyl peak at (a) indicates the presence of a carboxyl group in the monomer structure. In the nuclear magnetic hydrogen spectrum, peaks at 5.01 and 3.70ppm were assigned to O-CH of the oxazine ring, respectively2-N and Ar-CH2-an N structure. In conclusion, the benzoxazine monomer DPA-fa was successfully synthesized in the example.
T of poly (DPA-fa) in thermogravimetric analysis curved5And Td10344 and 375 deg.c, respectively. In the dynamic thermo-mechanical analysis curve, the value of poly (DPA-fa) is 280 ℃ and the storage modulus is 2700MPa, from tan delta.
Example 5
Preparation of benzoxazine resin poly (BA-a):
and (3) putting the commercially available bisphenol A aniline benzoxazine BA-a into a forced air drying oven for segmented curing to obtain the bio-based benzoxazine resin poly (BA-a).
The method comprises the following specific steps of segmented curing: heating at 160 deg.C for 1h, heating at 180 deg.C for 1h, heating at 200 deg.C for 1h, heating at 220 deg.C for 1h, heating at 240 deg.C for 2h, and heating at 260 deg.C for 2 h.
The molecular structure of BA-a is as follows,
t of poly (BA-a) in thermogravimetric analysis curved5And Td10320 and 366 deg.c, respectively. In the dynamic thermomechanical analysis curve, the glass transition temperature, poly (BA-a) value, derived from tan delta, was 172 ℃ and the storage modulus was 2000 MPa.
Claims (3)
1. The molecular structure of bio-based phenol synthesized by the amidation reaction of diphenolic acid is characterized in that carboxylic acid functional groups in two diphenolic acid molecules are converted into amide, and are connected into one molecule through a linear short chain structure R, the molecule contains four phenol functional groups in total, and the molecular structural formula is as follows:
wherein R is one of the following structures:
2. a bio-based benzoxazine monomer, which is characterized in that the bio-based phenol of claim 1 is used as a raw material, and is synthesized by condensation cyclization reaction with primary amine compounds and aldehyde substances, wherein the phenol group is converted into a benzoxazine ring structure, the molecular structure contains four oxazine ring structures in total, and the molecular structural formula is as follows:
wherein R is1Is one of the following structures:
3. a method for preparing a bio-based benzoxazine monomer according to claim 2, characterized by comprising the steps of:
(1) synthesis of amidated diphenolic acid: mixing diphenolic acid and diamine, reacting for 3-6 hours at 180 ℃, recrystallizing, and drying to obtain bio-based bisphenol;
(2) synthesis of amide-containing bio-based benzoxazine monomer: mixing the amidated diphenolic acid obtained in the step (1) with a primary amine compound and paraformaldehyde, reacting in a solvent at 80-110 ℃ for 3-6 hours, and performing alkali washing, water washing and drying to obtain the bio-based benzoxazine monomer.
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