CN111205420A - Full-bio-based benzoxazine resin and preparation method thereof - Google Patents
Full-bio-based benzoxazine resin and preparation method thereof Download PDFInfo
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- CN111205420A CN111205420A CN202010182659.9A CN202010182659A CN111205420A CN 111205420 A CN111205420 A CN 111205420A CN 202010182659 A CN202010182659 A CN 202010182659A CN 111205420 A CN111205420 A CN 111205420A
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- benzoxazine
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- benzoxazine resin
- monomer
- bisphenol
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229920005989 resin Polymers 0.000 title claims abstract description 70
- 239000011347 resin Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 52
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical group C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 claims abstract description 43
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 37
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 12
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 12
- 235000012141 vanillin Nutrition 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
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 7
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 7
- 235000005513 chalcones Nutrition 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical group 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007142 ring opening reaction Methods 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
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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-bio-based benzoxazine resin and a preparation method thereof. The method comprises the following steps: mixing the chalcone structure bisphenol, furfuryl amine and aldehyde compounds in an organic solvent, reacting for 8-48 h at 75-115 ℃, and purifying to obtain a total-biology-based benzoxazine monomer; curing and reacting the benzoxazine monomer at 80-260 ℃ for 1-24 h to obtain the benzoxazine monomer; or irradiating the benzoxazine monomer by ultraviolet light for 0.5-4 h, and then carrying out curing reaction at 80-140 ℃ for 4-24 h to obtain the benzoxazine monomer. The invention further reduces the curing temperature of the benzoxazine monomer containing the chalcone structure, improves the thermal property and the crosslinking degree of the obtained benzoxazine resin, and the obtained resin has high glass transition temperature (304-376 ℃), high carbon residue rate (50-70%), high limiting oxygen index (30.3-42.2) and low dielectric constant (2.0-2.9).
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a full-bio-based benzoxazine monomer, a full-bio-based benzoxazine resin and a preparation method of the full-bio-based benzoxazine resin.
Background
The benzoxazine resin is a novel phenolic resin, and is prepared by taking a phenolic compound, an amine compound and an aldehyde compound as raw materials, carrying out Mannich reaction to synthesize a six-membered heterocyclic compound, and carrying out high-temperature curing. The phenolic resin keeps excellent thermal property, flame retardance and electrical insulation of the traditional phenolic resin, and also has the advantages that the traditional phenolic resin does not have small molecules to be released in the processing and curing process, the prepared product has low porosity and near zero shrinkage of volume, and the prepared product has better high-temperature thermal stability, flame retardance, mechanical property, chemical stability and low water absorption. In addition, strong acid or strong base catalysis is not needed in the preparation process, so that the damage to equipment is reduced. Therefore, the method has wide application prospect in the fields of friction materials, electronic packaging, aerospace and the like. However, benzoxazine resins also have some inherent disadvantages, such as the high curing temperature of most benzoxazine monomers, typically above 220 ℃; the resin has low crosslinking density and is brittle; the thermal properties thereof are yet to be further improved.
Currently, petroleum resources are gradually exhausted, the price of crude oil rises, and environmental problems are very prominent. With the deep implementation of the strategy of sustainable development, people pay more and more attention to bio-based raw materials. In particular, benzoxazine resin has the characteristic of flexible molecular design, thereby providing possibility for utilizing bio-based raw materials. Lin reports a benzoxazine resin containing a chalcone structure for the first time (RSC adv.,2017,7, 37844-37851), and the benzoxazine resin is prepared by synthesizing bisphenol containing the chalcone structure by using p-hydroxybenzaldehyde and p-hydroxyacetophenone and then reacting the bisphenol with aniline and paraformaldehyde. The glass transition temperature of the thermosetting resin is 254-294 ℃ at the temperature of 180-240 ℃, and the glass transition temperature of the resin obtained by continuous procedures of ultraviolet light irradiation (0.5h) and thermosetting (180-240 ℃) is 273-328 ℃. Lin employs aniline from petroleum resources as an amine source and is not environmentally friendly and sustainable in development. Further, for practical application of thermosetting resins, the degree of crosslinking and the glass transition temperature of the cured resin are required to be further improved.
Disclosure of Invention
In order to further reduce the curing temperature of the benzoxazine monomer containing the chalcone structure and improve the thermal property and the crosslinking degree of the obtained benzoxazine resin, the invention provides a full-bio-based benzoxazine monomer containing the chalcone structure, a full-bio-based benzoxazine resin containing the chalcone structure and a preparation method thereof.
In order to achieve the purpose, the technical scheme is as follows:
a full-bio-based benzoxazine resin is obtained by curing a benzoxazine monomer shown in a formula 1, wherein the molecular structure of the benzoxazine resin is shown in a formula 2 or a formula 3;
according to the scheme, the benzoxazine monomer shown in the formula 1 is prepared in the following way:
mixing chalcone structure bisphenol, furfuryl amine and aldehyde compounds in an organic solvent, reacting for 8-48 h at 75-115 ℃, and purifying to obtain a total-biology-based benzoxazine monomer; the chalcone structural bisphenol is shown as a formula 4:
according to the scheme, the benzoxazine resin shown in the formula 2 is cured in the following way:
and curing and reacting the benzoxazine monomer shown in the formula 1 at 80-260 ℃ for 1-24 h to obtain the benzoxazine resin.
According to the scheme, the benzoxazine resin shown in the formula 3 is cured in the following way:
and (2) irradiating the benzoxazine monomer shown in the formula 1 by ultraviolet light for 0.5-4 h, and then carrying out curing reaction at 80-140 ℃ for 4-24 h to obtain the benzoxazine resin.
The preparation method of the all-bio-based benzoxazine resin comprises the following steps:
1) preparation of benzoxazine monomers
Mixing the chalcone structure bisphenol, furfuryl amine and aldehyde compounds in an organic solvent, reacting for 8-48 h at 75-115 ℃, and purifying to obtain a total-biology-based benzoxazine monomer; the reaction equation is as follows:
2) preparation of benzoxazine resins
Curing and reacting the benzoxazine monomer at 80-260 ℃ for 1-24 h to obtain the benzoxazine monomer;
or irradiating the benzoxazine monomer by ultraviolet light for 0.5-4 h, and then carrying out curing reaction at 80-140 ℃ for 4-24 h to obtain the benzoxazine monomer.
According to the scheme, the chalcone structure bisphenol in the step 1 is prepared in the following mode:
mixing vanillin and p-hydroxyacetophenone in an organic solvent according to the molar ratio of aldehyde group to ketone group functional group of 1:1, and reacting for 4 hours at 55 ℃ by using boron trifluoride diethyl etherate as a catalyst; pouring the reaction liquid into a mixed solution of methanol and water in a volume ratio of 1:1 for recrystallization to obtain golden yellow crystals, and drying to obtain chalcone structure bisphenol powder. The reaction equation is as follows:
according to the scheme, the molar ratio of phenolic hydroxyl groups, amino groups and aldehyde functional groups of the chalcone bisphenol, furfuryl amine and aldehyde compounds in the step 1 is (1-6): (1-4): (6-12).
According to the scheme, the optimized preparation method in the step 1 comprises the following steps:
mixing an aldehyde compound and furfuryl amine in an organic solvent, and reacting at 75-115 ℃ for 6-12 h;
adding bisphenol with a chalcone structure, and continuously reacting for 2-36 hours at the temperature of 75-115 ℃;
and pouring the reaction liquid into a methanol solution for precipitation to obtain yellow suspension, standing, removing supernatant to obtain yellow precipitate, drying the yellow precipitate, and grinding to obtain the total-bio-based benzoxazine monomer.
According to the scheme, the aldehyde compound in the step 1 is formaldehyde or paraformaldehyde.
According to the scheme, the organic solvent is any one or mixture of toluene, xylene, ethanol, chloroform, dimethylformamide and 1, 4-dioxane.
Compared with the prior art, the invention has the beneficial effects that:
the preparation process is simple and convenient, the raw materials are natural and easy to obtain, the vanillin/p-hydroxyacetophenone chalcone structure bisphenol is taken as a phenol source, the furfuryl amine is taken as an amine source, the all-biobased benzoxazine monomer is synthesized by a solvent method, and the monomer is finally cured by introducing the furfuryl amine to obtain the all-biobased benzoxazine resin with a highly crosslinked structure.
The olefinic bond of the chalcone structure has photoreaction activity, and can generate a branched benzoxazine prepolymer structure containing a cyclobutane structure through ultraviolet light illumination, so that benzoxazine can easily form a network structure, and the curing temperature of the benzoxazine is reduced. In addition, the electron-withdrawing group of the chalcone structure bisphenol containing the electron-withdrawing carbonyl group is favorable for reducing the energy domain of the ring opening of an oxazine ring, so that the curing temperature of the synthesized full-bio-based benzoxazine is further reduced, the temperature can be reduced from 220 ℃ to 80-140 ℃ to complete thermosetting, and the processing performance of the bisphenol is effectively improved.
The invention selects vanillin with a structure similar to that of p-hydroxybenzaldehyde, which is from renewable natural resources, and synthesizes bisphenol containing chalcone structure with p-hydroxyacetophenone which is also from natural resources.
In particular, by selecting furfuryl amine from renewable resources, the raw material source is wide, the environment is protected, and petroleum resources can be saved. The invention can synthesize the full-biology-based benzoxazine monomer containing furan rings, and is remarkable in that the furan rings can be further crosslinked during the ring-opening reaction of benzoxazine curing, and form a new crosslinking bond with nitrogen atoms on a Mannich bridge formed after the ring-opening of the oxazine rings, so that the crosslinking density of the cured resin is effectively improved, the glass transition temperature and the thermal stability of the cured resin are improved, and the flame retardant property is also obviously improved.
By selecting chalcone structure bisphenol containing an electron-withdrawing bridging group, a new hydrogen bond effect is formed between the bridging carbonyl and hydroxyl generated by ring opening of benzoxazine. Furthermore, methoxy groups from vanillin can also participate in hydrogen bonding. In addition, the furfuryl amine also contains oxygen atoms and can form new hydrogen bond interaction with hydroxyl generated by ring opening of the benzoxazine. Thus, the hydrogen bonding action of the benzoxazine resin is effectively enhanced, resulting in further improvement of heat resistance and flame retardancy of the cured resin.
After double bonds in the chalcone structure bisphenol are irradiated by ultraviolet light, a cyclobutane structure can be generated, so that a large-volume nonpolar functional group is introduced into benzoxazine resin, and a four-branched benzoxazine resin network structure is generated, so that the free volume of the full-bio-based benzoxazine resin is increased, and the dielectric property of the cured resin is improved. And the generated cyclobutane structure leads to the increase of the crosslinking density of the resin, and correspondingly, the thermal property and the flame retardant property of the resin are also improved.
The total bio-based benzoxazine resin obtained by the method has high glass transition temperature (the glass transition temperature of the resin prepared by thermosetting is 304-326 ℃, and the glass transition temperature of the resin obtained by continuous procedures of ultraviolet light irradiation and thermosetting is 329-376 ℃), high carbon residue rate (50-70%), high limiting oxygen index (30.3-42.2) and low dielectric constant (2.0-2.9). Compared with the reported benzoxazine resin based on chalcone structure bisphenol, the benzoxazine resin has the advantages of obviously different chemical structures, higher crosslinking density, the highest glass transition temperature increased by nearly 50 ℃, obviously reduced curing temperature and explored application in the fields of high-frequency communication and photoresist. The result shows that the full-bio-based benzoxazine resin designed and prepared by the invention has excellent processability, heat resistance, flame retardant property and dielectric property, and has great practical application potential.
Drawings
FIG. 1: an infrared spectrum of vanillin/p-hydroxyacetophenone type chalcone structure bisphenol obtained in example 1;
FIG. 2: the infrared spectrogram of the full-bio-based benzoxazine monomer containing the chalcone structure obtained in the example 3.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparation of vanillin/p-hydroxyacetophenone type chalcone structure bisphenol:
adding 13.6g of vanillin (0.1mol) and 15.3g of p-hydroxyacetophenone (0.1mol) into a reaction vessel, adding 50mL of toluene for dissolving, taking 2mL of boron trifluoride diethyl etherate as a catalyst, reacting for 4h at 55 ℃, and pouring a reaction solution into a reactor with methanol/water ratio of 1: 1(v/v) mixed solution to obtain golden yellow crystals, and drying to obtain the bisphenol powder with the chalcone structure.
FIG. 1 shows the IR spectrum of bisphenol with vanillin/p-hydroxyacetophenone type chalcone structure prepared in this example at 3410cm-1Represents a characteristic absorption peak of phenol-OH, 1640cm-1Represents a characteristic absorption peak of C ═ O, 1593cm-1Represents C ═ C, 1234cm-1represents-OCH3The characteristic absorption peak of the compound shows that the synthesized product is vanillin/p-hydroxyacetophenone type chalcone structure bisphenol, and the molecular structural formula of the compound is shown in 4.
Example 2
Preparation of vanillin/p-hydroxyacetophenone type chalcone structure bisphenol:
adding 13.6g of vanillin (0.1mol) and 15.3g of p-hydroxyacetophenone (0.1mol) into a reaction vessel, adding 50mL of toluene/ethanol (2: 1v/v) mixed solution for dissolving, taking 2mL of boron trifluoride diethyl ether as a catalyst, reacting for 4h at 55 ℃, and pouring a reaction solution into a reactor with methanol/water ratio of 1: 1(v/v) mixed solution to obtain golden yellow crystals, and drying to obtain the bisphenol powder with the chalcone structure.
Example 3
Preparing a full-bio-based benzoxazine monomer:
8.10g (0.03mol) of chalcone structure bisphenol prepared in example 1, 3.88g (0.04mol) of furfuryl amine, and 3.60g (0.12mol) of paraformaldehyde were charged into a 250mL three-necked flask equipped with a condenser, a magneton stirrer, and a thermometer, and the molar ratio of phenolic hydroxyl group, amine group, and aldehyde group functional groups was 6: 4: 12, adding 75mL of toluene solvent, uniformly mixing, heating to 115 ℃ for reaction for 8h, pouring the reaction solution into 100mL of methanol solution for precipitation after the reaction is finished to obtain brown yellow suspension, standing for 12h, removing supernatant to obtain brown yellow precipitate, vacuum-drying the brown yellow precipitate at 60 ℃ for 8h, and finally grinding the dried product to obtain brown yellow powder, namely the full-bio-based benzoxazine monomer.
FIG. 2 is an infrared spectrum 922cm of the total bio-based benzoxazine monomer prepared in this example-1Is located at the stretching vibration peak of C-H on the oxazine ring, 1234cm-1Is C-O-C and-OCH on the oxazine ring3Characteristic absorption peak of (1), 1150cm-1Is a characteristic absorption peak of C-N-C on the oxazine ring, 1650cm-1The peak of stretching vibration of C ═ O, 1580, 980 and 1606cm-1The peak is the characteristic absorption peak of furan ring and chalcone. In summary, the synthesized product of this example is a total bio-based benzoxazine monomer, and the molecular structural formula thereof is shown in formula 1.
Example 4
Preparing a full-bio-based benzoxazine monomer:
8.10g (0.03mol) of chalcone structure bisphenol prepared in example 1, 5.82g (0.06mol) of furfuryl amine, 21.6g (0.72mol) of paraformaldehyde were charged into a 250mL three-necked flask equipped with a condenser, a magneton stirrer, and a thermometer, and the molar ratio of phenolic hydroxyl group, amine group, and aldehyde group functional groups was 1: 1: 12, adding 75mL of dimethylformamide solvent, uniformly mixing, heating to 100 ℃ for reaction for 48h, pouring the reaction solution into 100mL of methanol solution for precipitation after the reaction is finished to obtain brown yellow suspension, standing for 12h, removing supernatant to obtain brown yellow precipitate, vacuum-drying the brown yellow precipitate at 120 ℃ for 8h, and finally grinding the dried product to obtain brown yellow powder, namely the full-bio-based benzoxazine monomer.
Example 5
Preparing a full-bio-based benzoxazine monomer:
8.10g (0.03mol) of chalcone structure bisphenol prepared in example 2, 5.82g (0.06mol) of furfuryl amine, 10.80g (0.36mol) of paraformaldehyde were accurately weighed, and the molar ratio of the phenolic hydroxyl group, the amine group and the aldehyde group functional group was 1: 1: 6. adding furfuryl amine and paraformaldehyde into a 250mL three-neck flask with a condenser pipe, a magneton stirrer and a thermometer, adding 75mL of a xylene/ethanol mixed solvent (the volume ratio of xylene to ethanol is 1:1), uniformly mixing, heating to 80 ℃ for reaction for 12 hours, adding chalcone structure bisphenol, continuing to react for 36 hours, pouring a reaction solution into 100mL of a methanol solution for precipitation after the reaction is finished to obtain a brownish yellow suspension, standing for 12 hours, removing a supernatant to obtain a brownish yellow precipitate, performing vacuum drying on the brownish yellow precipitate at 100 ℃ for 8 hours, and finally grinding a dried product to obtain brownish yellow powder, namely the all-bio-based benzoxazine monomer.
Example 6
Preparing a full-bio-based benzoxazine monomer:
8.10g (0.03mol) of chalcone bisphenol prepared in example 2, 3.88g (0.04mol) of furfuryl amine, 1.80g (0.06mol) of paraformaldehyde were accurately weighed, and the molar ratio of the phenolic hydroxyl group, the amine group and the aldehyde group functional group was 6: 4: 6. adding furfuryl amine and paraformaldehyde into a 250mL three-neck flask with a condenser pipe, a magneton stirrer and a thermometer, adding 75mL of an ethanol solvent, uniformly mixing, heating to 75 ℃ for reacting for 6 hours, adding chalcone structure bisphenol, continuing to react for 2 hours, pouring reaction liquid into 100mL of a methanol solution for precipitation after the reaction is finished to obtain brown yellow suspension, standing for 12 hours, removing supernatant to obtain brown yellow precipitate, performing vacuum drying on the brown yellow precipitate at 80 ℃ for 8 hours, and finally grinding the dried product to obtain brown yellow powder, namely the full-biology-based benzoxazine monomer.
Example 7
Preparing the full-bio-based polybenzoxazine resin:
the total bio-based benzoxazine monomer prepared in example 3 was poured into a curing mold, and cured in a hot press at 260 ℃ for 1 hour to obtain a total bio-based benzoxazine resin having a glass transition temperature (dynamic thermomechanical analyzer DMA) of 326 ℃, a char yield (thermogravimetric analyzer TA) of 57%, a limiting oxygen index (GB 2406-80) of 31.5, a high frequency dielectric constant (vector network analyzer) of 2.80(5GHz), and a 2.68(10 GHz).
Example 8
Preparing the full-bio-based polybenzoxazine resin:
the total bio-based benzoxazine monomer prepared in the example 4 is poured into a curing mould, and is placed in a hot press to be cured for 24 hours at the temperature of 80 ℃ to obtain the total bio-based benzoxazine resin, wherein the glass transition temperature of the resin is 304 ℃, the carbon residue rate of the resin can reach 50 percent at the temperature of 800 ℃, the limiting oxygen index can reach 30.3, and the dielectric constant is 2.90(5GHz) and 2.70(10 GHz).
Example 9
Preparing the full-bio-based polybenzoxazine resin:
the total bio-based benzoxazine monomer prepared in the example 5 is poured into a curing mould, firstly irradiated for 0.5h under ultraviolet light, and then placed in a hot press to be cured for 24h at 80 ℃ to obtain the total bio-based benzoxazine resin, wherein the glass transition temperature is 329 ℃, the carbon residue rate at 800 ℃ can reach 65%, the limiting oxygen index can reach 42.2, and the dielectric constant is 2.58(5GHz) and 2.42(10 GHz).
Example 10
Preparing the full-bio-based polybenzoxazine resin:
the total bio-based benzoxazine monomer prepared in the embodiment 6 is poured into a curing mould, firstly irradiated for 4 hours under ultraviolet light, and then placed in a hot press to be cured for 4 hours at 140 ℃ to obtain the total bio-based benzoxazine resin, wherein the glass transition temperature is 376 ℃, the carbon residue rate at 800 ℃ can reach 70%, the limiting oxygen index can reach 38.0, and the dielectric constant is 2.00(5GHz) and 2.37(10 GHz).
Claims (10)
1. The full-bio-based benzoxazine resin is characterized by being obtained by curing a benzoxazine monomer shown in a formula 1, wherein the molecular structure of the benzoxazine resin is shown in a formula 2 or a formula 3;
2. the biobased benzoxazine resin according to claim 1, wherein the benzoxazine monomer of formula 1 is prepared in the following manner:
mixing chalcone structure bisphenol, furfuryl amine and aldehyde compounds in an organic solvent, reacting for 8-48 h at 75-115 ℃, and purifying to obtain a total-biology-based benzoxazine monomer; the chalcone structural bisphenol is shown as a formula 4:
3. the biobased benzoxazine resin according to claim 1, wherein the benzoxazine resin of formula 2 is cured in the following manner:
and curing and reacting the benzoxazine monomer shown in the formula 1 at 80-260 ℃ for 1-24 h to obtain the benzoxazine resin.
4. The biobased benzoxazine resin according to claim 1, wherein the benzoxazine resin of formula 3 is cured in the following manner:
and (2) irradiating the benzoxazine monomer shown in the formula 1 by ultraviolet light for 0.5-4 h, and then carrying out curing reaction at 80-140 ℃ for 4-24 h to obtain the benzoxazine resin.
5. A method for preparing the total bio-based benzoxazine resin according to any one of claims 1-4, characterized by comprising the steps of:
1) preparation of benzoxazine monomers
Mixing the chalcone structure bisphenol, furfuryl amine and aldehyde compounds in an organic solvent, reacting for 8-48 h at 75-115 ℃, and purifying to obtain a total-biology-based benzoxazine monomer;
2) preparation of benzoxazine resins
Curing and reacting the benzoxazine monomer at 80-260 ℃ for 1-24 h to obtain the benzoxazine monomer;
or irradiating the benzoxazine monomer by ultraviolet light for 0.5-4 h, and then carrying out curing reaction at 80-140 ℃ for 4-24 h to obtain the benzoxazine monomer.
6. The method for preparing total bio-based benzoxazine resin according to claim 5 wherein said chalcone structural bisphenol of step 1 is prepared by:
mixing vanillin and p-hydroxyacetophenone in an organic solvent according to the molar ratio of aldehyde group to ketone group of 1:1, and reacting for 4 hours at 55 ℃ by using boron trifluoride diethyl etherate as a catalyst; pouring the reaction liquid into a mixed solution of methanol and water in a volume ratio of 1:1 for recrystallization to obtain golden yellow crystals, and drying to obtain chalcone structure bisphenol powder.
7. The method for preparing total bio-based benzoxazine resin according to claim 5, wherein the molar ratio of phenolic hydroxyl, amino and aldehyde functional groups of the chalcone bisphenol, furfuryl amine and aldehyde compounds in step 1 is (1-6): (1-4): (6-12).
8. The method for preparing the total bio-based benzoxazine resin according to claim 5, wherein the optimized preparation method in step 1 is as follows:
mixing an aldehyde compound and furfuryl amine in an organic solvent, and reacting at 75-115 ℃ for 6-12 h;
adding bisphenol with a chalcone structure, and continuously reacting for 2-36 hours at the temperature of 75-115 ℃;
and pouring the reaction liquid into a methanol solution for precipitation to obtain yellow suspension, standing, removing supernatant to obtain yellow precipitate, drying the yellow precipitate, and grinding to obtain the total-bio-based benzoxazine monomer.
9. The method for preparing total bio-based benzoxazine resin according to claim 5, wherein said aldehyde compound in step 1 is formaldehyde or paraformaldehyde.
10. The method for preparing the total bio-based benzoxazine resin according to claim 5, wherein said organic solvent is any one or a mixture of toluene, xylene, ethanol, chloroform, dimethylformamide and 1, 4-dioxane.
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| CN112707932A (en) * | 2020-12-30 | 2021-04-27 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
| CN115232338A (en) * | 2022-07-19 | 2022-10-25 | 陕西科技大学 | Cross-linked modified P (VMA-MMA) dielectric film and preparation method and application thereof |
| CN115286621A (en) * | 2022-08-05 | 2022-11-04 | 中北大学 | Full-bio-based benzoxazine resin and preparation method thereof |
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| CHING HSUAN LIN ET AL: "Photo-sensitive benzoxazine II: chalconecontaining benzoxazine and its photo and thermal-cured thermoset", 《ROYAL SOCIETY OF CHEMISTRY》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707932A (en) * | 2020-12-30 | 2021-04-27 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
| CN112707932B (en) * | 2020-12-30 | 2021-12-28 | 厦门大学 | Benzoxazine, preparation method thereof, coating and method for forming coating on surface of substrate |
| CN115232338A (en) * | 2022-07-19 | 2022-10-25 | 陕西科技大学 | Cross-linked modified P (VMA-MMA) dielectric film and preparation method and application thereof |
| CN115232338B (en) * | 2022-07-19 | 2023-08-25 | 陕西科技大学 | Cross-linked modified P (VMA-MMA) dielectric film and preparation method and application thereof |
| CN115286621A (en) * | 2022-08-05 | 2022-11-04 | 中北大学 | Full-bio-based benzoxazine resin and preparation method thereof |
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