CN117551051A - Full biomass-based benzoxazine monomer and preparation method and application thereof - Google Patents

Full biomass-based benzoxazine monomer and preparation method and application thereof Download PDF

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Publication number
CN117551051A
CN117551051A CN202311492971.8A CN202311492971A CN117551051A CN 117551051 A CN117551051 A CN 117551051A CN 202311492971 A CN202311492971 A CN 202311492971A CN 117551051 A CN117551051 A CN 117551051A
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biomass
based benzoxazine
benzoxazine monomer
full
full biomass
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付飞
朱雪莲
李金玲
刘慧涛
朱理想
王东平
贾振华
罗德平
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Henan University of Technology
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Henan University of Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D265/00Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/041,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/121,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/141,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/161,3-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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The invention discloses a full biomass-based benzoxazine monomer, a preparation method and application thereof. The full biomass-based benzoxazine monomer is prepared by taking biomass resources as raw materials through a one-pot reaction, and the preparation method is simple and has mild reaction conditions; meanwhile, the polymer prepared from the full biomass-based benzoxazine monomer has good thermal stability, flame retardance and hydrophobicity.

Description

Full biomass-based benzoxazine monomer and preparation method and application thereof
Technical Field
The invention relates to a full biomass-based benzoxazine monomer, and a preparation method and application thereof, and belongs to the technical field of natural resource utilization.
Background
Benzoxazines are novel monomers which contain a N, O atom six-membered oxazine heterocyclic structure and are linked together with a benzene ring. The benzoxazine is prepared from phenolic compounds, primary amine compounds and aldehyde compounds through condensation reaction dehydration, so that the benzoxazine has molecular design flexibility. In the presence of high temperature or a catalyst, the benzoxazine monomer can undergo ring-opening polymerization to form a nitrogen-containing network structure resembling phenolic resin, known as a benzoxazine resin. Benzoxazine resin is used as a novel phenolic resin, and firstly, the advantages of the traditional phenolic resin, such as excellent heat resistance, flame retardance, electrical insulation, low raw material price and the like, are maintained. Because of its structural characteristics, it has many unique properties, such as bridge structure in crosslinked network makes benzoxazine resin possess better toughness than phenolic aldehyde, benzene ring imparts rigidity, heat resistance and chemical resistance, and phenolic hydroxyl group makes it possess certain chemical reactivity and lower hygroscopicity. In addition, the monomer can not generate small molecule byproducts in the ring opening process, so the resin has the characteristic of zero volume shrinkage, and the defect of the phenolic resin is overcome.
Benzoxazine resin has relatively wide application in various fields due to its excellent properties, and the demand of people for benzoxazine resin has been increasing year by year. However, the starting materials for the current preparation of benzoxazines are mainly derived from petroleum-based compounds such as bisphenol a, phenol, aniline, etc. With the increasing scarcity of petrochemical resources and the consequent environmental and sustainability issues, researchers have sought to use green renewable biomass-based monomers to make biomass-based benzoxazines instead of non-renewable petroleum-based monomers.
The benzoxazine monomer is synthesized mainly by three parts of phenol source, formaldehyde and amine source. Biomass methanol can be prepared through biochemical reactions such as crop straw fermentation and the like, and the high-purity biomass methanol reaches the scale of industrial production nowadays, so that biomass formaldehyde can be obtained through oxidation of the biomass methanol. At present, biomass-based monomers commonly used for preparing benzoxazine mainly comprise vanillin, cardanol, naringin, magnolol, diphenol, coumarin, catechol, eugenol, guaiacol, sesamol, resveratrol, furfuryl amine, stearylamine, dehydroabietylamine, chitosan and the like. Notably, amine-derived monomers used in the synthesis of biomass-based benzoxazines are much lower than phenolic-derived monomers, especially biomass-based diamines. Therefore, the source of the biomass amine compound is widened, and the development of biomass-based benzoxazine is facilitated.
Disclosure of Invention
In order to solve the defects of few biomass-based amine sources and the like in the prior art for synthesizing biomass-based benzoxazine, the invention provides a full biomass-based benzoxazine monomer, a preparation method and application thereof, wherein the full biomass-based benzoxazine monomer is prepared by a one-pot method, and a polymer is prepared by taking the full biomass-based benzoxazine monomer as a raw material, and has good hydrophobicity, thermal stability and the like.
In order to solve the technical problems, the invention provides a full biomass-based benzoxazine monomer, which has a molecular structural formula as follows:
preferably, the full biomass benzoxazine monomer is prepared by taking full biomass resources as raw materials through one-pot Mannich reaction, wherein the reaction process is as follows:
preferably, guaiacol, menthanediamine and paraformaldehyde are reacted at 60-150 ℃ to prepare the full biomass-based benzoxazine monomer.
Preferably, guaiacol, menthanediamine and paraformaldehyde are dissolved in a solvent and reacted at 60-150 ℃ to prepare the full biomass-based benzoxazine monomer.
Preferably, the molar ratio is (3-2): 1: the guaiacol, the menthane diamine and the paraformaldehyde of (4-6) are dissolved in a solvent and react for 5-48 hours at the temperature of 60-150 ℃ to generate the full biomass-based benzoxazine monomer.
Preferably, the solvent is at least one of dioxane, toluene, chloroform, dimethylformamide or dimethyl sulfoxide.
The invention also provides application of the full biomass-based benzoxazine monomer in preparing a polymer.
Preferably, the application method of the all-biomass-based benzoxazine monomer in preparing the polymer material is as follows:
heating and curing the all biomass-based benzoxazine monomer to obtain the all biomass-based benzoxazine polymer, wherein the heating and curing process comprises the following steps:
after curing for 1-3 h at 130-160 ℃, curing for 2-4 h at 180-220 ℃ and finally curing for 2-4 h at 230-270 ℃.
The technology not mentioned in the present invention refers to the prior art.
(1) According to the full biomass-based benzoxazine monomer, the natural products of the menthanediamine, the guaiacol and the paraformaldehyde are used as raw materials, and the full biomass-based benzoxazine monomer is prepared through Mannich reaction, so that the preparation method is simple, and the reaction condition is mild; meanwhile, the polymer is prepared by taking the full biomass-based benzoxazine monomer as a raw material, and the prepared polymer has good hydrophobicity, flame retardance, thermal stability and the like;
(2) The turpentine derivative-menthanediamine is a newly discovered biomass-based amine source for preparing the all-biomass-based benzoxazine monomer.
(3) According to the full biomass-based benzoxazine monomer, the preparation method and the application thereof, the water contact angle of the polymer obtained by ring-opening polymerization of the full biomass-based benzoxazine monomer reaches 99 degrees, and the thermal decomposition temperature (T) 5% ) Can reach 251 DEG CThe carbon residue rate is up to 41.3% at 800 ℃;
(4) The invention discloses a biomass-based amine source, which provides more possibilities for preparing the biomass-based benzoxazine monomer and reduces the use of petrochemical resources.
Drawings
FIG. 1 is an infrared spectrum of an all biomass-based benzoxazine monomer;
FIG. 2 is a nuclear magnetic hydrogen spectrum of an all biomass-based benzoxazine monomer;
FIG. 3 is a nuclear magnetic carbon spectrum of an all biomass-based benzoxazine monomer;
FIG. 4 is a mass spectrum of an all biomass-based benzoxazine monomer;
FIG. 5 is a graph of differential scanning calorimetry of an all biomass based benzoxazine monomer;
FIG. 6 is a water contact angle of an all biomass-based benzoxazine resin;
fig. 7 is the thermal stability of the all biomass-based benzoxazine resin.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
A full biomass-based benzoxazine monomer has a molecular structural formula as follows:
the preparation method of the full biomass-based benzoxazine monomer comprises the following steps:
14.4g of guaiacol, 9.88g of menthanediamine and 6.96g of paraformaldehyde are added into a round-bottomed flask, reacted for 6 hours at 120 ℃, cooled to room temperature and then recrystallized by adding 80mL of ethanol to obtain white solid: all biomass based benzoxazine monomers.
The infrared spectrogram of the obtained full biomass-based benzoxazine monomer is shown in fig. 1, and as can be seen from fig. 1, characteristic peaks of hydroxyl and amino appear in guaiacol and menthanediamine, all the characteristic peaks disappear in the full biomass-based benzoxazine monomer, and an obvious characteristic peak of an oxazine ring appears, which indicates the generation of the full biomass-based benzoxazine monomer.
The nuclear magnetic hydrogen spectrum of the obtained full biomass-based benzoxazine monomer is shown in figure 2, and the signal appearing at the position of 6.78-6.59ppm belongs to hydrogen proton on benzene ring, oxazine ring O-CH 2 -N and Ar-CH 2 Characteristic peaks of hydrogen protons on methylene and methylene in N appear at 5.05ppm and 4.05ppm, respectively, characteristic peaks of hydrogen protons on methoxy groups appear at 3.85ppm, signals appearing at 2.16-1.15ppm belong to hydrogen protons on methylene and methylene in six-membered rings, and characteristic peaks of hydrogen protons on methyl appear at 1.11-0.94ppm.
The nuclear magnetic carbon spectrum of the obtained full biomass-based benzoxazine monomer is shown in figure 3, the signal of the carbon atom on the benzene ring appears in 148.13-108.80ppm, and the oxazine ring is O-CH 2 -N and Ar-CH 2 Characteristic peaks of the carbon atoms on the methylene group in N appear at 79.82-79.36ppm and 44.52-43.84ppm, respectively, characteristic peaks of the carbon atoms on the methoxy group appear at 55.76ppm, signals found at 36.90ppm and 26.75ppm are caused by the carbon atoms on the methyl group, and characteristic peaks of the methylene and methine groups on the six-membered ring in the menthanediamine appear at 45.42,36.90 and 22.22ppm, respectively, and nuclear magnetic patterns of the monomers confirm successful preparation of the all biomass-based benzoxazine monomer.
The mass spectrum of the obtained all-biomass-based benzoxazine monomer is shown in fig. 4, and the all-biomass-based benzoxazine (C 28 H 38 N 2 O 4 ) Is 466.28, [ M+H ]] + 467.28.
The resulting differential scanning calorimetry plot of the full biomass based benzoxazine monomer is shown in fig. 5, the melting point of the full biomass based benzoxazine monomer is 127 ℃, and the monomer begins to cure at around 200 ℃ and peaks at 250 ℃.
Example 2
A full biomass-based benzoxazine monomer has a molecular structural formula as follows:
the preparation method of the full biomass-based benzoxazine monomer comprises the following steps:
16.8g of guaiacol, 9.88g of menthanediamine and 7.06g of paraformaldehyde are dissolved in 300mL of chloroform and added into a round bottom flask to react for 36h at 60 ℃, and 80mL of ethanol is added to recrystallize after cooling to room temperature to obtain white solid: all biomass based benzoxazine monomers.
Example 3
A full biomass-based benzoxazine monomer has a molecular structural formula as follows:
the preparation method of the full biomass-based benzoxazine monomer comprises the following steps:
17.8g of guaiacol, 10.0g of menthanediamine and 7.26g of paraformaldehyde are dissolved in 200mL of toluene and added to a round-bottomed flask to react for 18h at 100 ℃, and 80mL of ethanol is added to recrystallize after cooling to room temperature to obtain a white solid: all biomass based benzoxazine monomers.
Example 4
A full biomass-based benzoxazine monomer has a molecular structural formula as follows:
the preparation method of the full biomass-based benzoxazine monomer comprises the following steps:
16.8g of guaiacol, 9.88g of menthanediamine and 7.06g of paraformaldehyde are dissolved in 150mL of toluene and added to a round-bottomed flask, reacted at 100 ℃ for 18h, cooled to room temperature and then recrystallized by adding 80mL of ethanol to obtain a white solid: all biomass based benzoxazine monomers.
Example 5
A full biomass-based benzoxazine monomer has a molecular structural formula as follows:
the preparation method of the full biomass-based benzoxazine monomer comprises the following steps:
guaiacol 18.2g, menthanediamine 10.0g, paraformaldehyde 7.92g were dissolved in 120mL of N, N-dimethylformamide and added to a round bottom flask, reacted at 150 ℃ for 12h, cooled to room temperature, and then recrystallized from 80mL of ethanol to give a white solid: all biomass based benzoxazine monomers.
Application example 1
5.0g of the full biomass-based benzoxazine monomer obtained in the example 1 is heated and solidified in an electrothermal constant temperature drying oven, and the heating and solidifying procedures are as follows: curing for 1h at 150 ℃, curing for 3h at 200 ℃, and finally curing for 3h at 240 ℃ to obtain the full biomass-based benzoxazine resin.
The water contact angle of the obtained all-biomass-based benzoxazine resin is shown in fig. 6, and the water contact angle of the all-biomass-based benzoxazine resin is 99 degrees, so that the all-biomass-based benzoxazine resin has good hydrophobicity.
The thermal stability of the obtained full biomass-based benzoxazine resin is shown in fig. 7, the temperature of the full biomass-based benzoxazine resin at the thermal weight loss of 5% is 251 ℃, the carbon residue rate at 800 ℃ is 41.3%, and the full biomass-based benzoxazine resin has good thermal stability and flame retardance.
Application example 2
5.0g of the full biomass-based benzoxazine monomer obtained in the example 1 is heated and solidified in an electrothermal constant temperature drying oven, and the heating and solidifying procedures are as follows: curing for 1h at 160 ℃, curing for 3h at 210 ℃, and finally curing for 2h at 240 ℃ to obtain the full biomass-based benzoxazine resin.
Application example 3
5.0g of the full biomass-based benzoxazine monomer obtained in the example 1 is heated and solidified in an electrothermal constant temperature drying oven, and the heating and solidifying procedures are as follows: curing for 1h at 160 ℃, curing for 4h at 200 ℃, and finally curing for 4h at 230 ℃ to obtain the full biomass-based benzoxazine resin.
The turpentine derivative-menthanediamine is a newly discovered biomass-based amine source for preparing the full biomass-based benzoxazine monomer, and the full biomass-based benzoxazine monomer is prepared by taking natural products of the menthanediamine, guaiacol and paraformaldehyde as raw materials through Mannich reaction, and the preparation method is simple and has mild reaction conditions; meanwhile, the polymer is prepared by taking the full biomass-based benzoxazine monomer as a raw material, and the prepared polymer has good hydrophobicity, flame retardance, thermal stability and the like; the water contact angle of the polymer obtained by ring-opening polymerization of the all biomass-based benzoxazine monomer reaches 99 degrees, and the thermal decomposition temperature (T 5% ) The carbon residue rate can reach 251 ℃ and reach 41.3% at 800 ℃.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.

Claims (8)

1. The full biomass-based benzoxazine monomer is characterized by having a molecular structural formula:
2. the preparation method of the full biomass-based benzoxazine monomer according to claim 1, wherein the full biomass-based benzoxazine monomer is prepared by using full biomass resources as raw materials through a one-pot Mannich reaction, and the reaction process is as follows:
3. the method for preparing the full biomass-based benzoxazine monomer according to claim 2, wherein the full biomass-based benzoxazine monomer is prepared by reacting guaiacol, menthanediamine and paraformaldehyde at 60-150 ℃.
4. The method for preparing the full biomass based benzoxazine monomer according to claim 3, wherein guaiacol, menthanediamine and paraformaldehyde are dissolved in a solvent and reacted at 60-150 ℃ to prepare the full biomass based benzoxazine monomer.
5. The method for producing a full biomass based benzoxazine monomer according to claim 4, wherein the molar ratio is (3-2): 1: the guaiacol, the menthane diamine and the paraformaldehyde of (4-6) are dissolved in a solvent and react for 5-48 hours at the temperature of 60-150 ℃ to generate the full biomass-based benzoxazine monomer.
6. The method for preparing a full biomass based benzoxazine monomer according to claim 5, wherein the solvent is at least one of dioxane, toluene, chloroform, dimethylformamide or dimethyl sulfoxide.
7. Use of the all biomass-based benzoxazine monomer according to claim 1 or prepared by the method for preparing the all biomass-based benzoxazine monomer according to any one of claims 2 to 6 in the preparation of polymers.
8. The use of the all biomass based benzoxazine monomer according to claim 7 in the preparation of a polymer material, wherein the method for the use of the all biomass based benzoxazine monomer in the preparation of a polymer material is as follows:
heating and curing the all biomass-based benzoxazine monomer to obtain the all biomass-based benzoxazine polymer, wherein the heating and curing process comprises the following steps:
after curing for 1-3 h at 130-160 ℃, curing for 2-4 h at 180-220 ℃ and finally curing for 2-4 h at 230-270 ℃.
CN202311492971.8A 2023-11-10 2023-11-10 Full biomass-based benzoxazine monomer and preparation method and application thereof Pending CN117551051A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117887019A (en) * 2024-03-15 2024-04-16 常州宏巨电子科技有限公司 Main chain type benzoxazine resin based on menthane diamine and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117887019A (en) * 2024-03-15 2024-04-16 常州宏巨电子科技有限公司 Main chain type benzoxazine resin based on menthane diamine and preparation method thereof
CN117887019B (en) * 2024-03-15 2024-05-28 常州宏巨电子科技有限公司 Benzoxazine resin based on main chain of menthane diamine and preparation method thereof

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