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 PDFInfo
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- 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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- based benzoxazine
- benzoxazine monomer
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- 239000002028 Biomass Substances 0.000 title claims abstract description 108
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000000178 monomer Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000005580 one pot reaction Methods 0.000 claims abstract description 4
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 30
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 claims description 15
- 229960001867 guaiacol Drugs 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006683 Mannich reaction Methods 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- -1 primary amine compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 150000005130 benzoxazines Chemical class 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- 239000001606 7-[(2S,3R,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-3-[(2S,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-5-hydroxy-2-(4-hydroxyphenyl)chroman-4-one Substances 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- UIOFUWFRIANQPC-JKIFEVAISA-N Floxacillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C1=C(C)ON=C1C1=C(F)C=CC=C1Cl UIOFUWFRIANQPC-JKIFEVAISA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 description 1
- LUSZGTFNYDARNI-UHFFFAOYSA-N Sesamol Natural products OC1=CC=C2OCOC2=C1 LUSZGTFNYDARNI-UHFFFAOYSA-N 0.000 description 1
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 description 1
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 description 1
- 229940052490 naringin Drugs 0.000 description 1
- 229930019673 naringin Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229940016667 resveratrol Drugs 0.000 description 1
- 235000021283 resveratrol Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (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
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 ℃.
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| 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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