CN114195803A - Coumarin-based bio-based bifunctional benzoxazine resin and preparation method thereof - Google Patents
Coumarin-based bio-based bifunctional benzoxazine resin and preparation method thereof Download PDFInfo
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- CN114195803A CN114195803A CN202110973728.2A CN202110973728A CN114195803A CN 114195803 A CN114195803 A CN 114195803A CN 202110973728 A CN202110973728 A CN 202110973728A CN 114195803 A CN114195803 A CN 114195803A
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- 229920005989 resin Polymers 0.000 title claims abstract description 58
- 239000011347 resin Substances 0.000 title claims abstract description 58
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229960000956 coumarin Drugs 0.000 title claims abstract description 23
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 23
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- ZFCWURBGTORKKO-UHFFFAOYSA-N 3,4-dihydroxychromen-2-one Chemical compound C1=CC=CC2=C1OC(=O)C(O)=C2O ZFCWURBGTORKKO-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 amine compound Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical group CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 5
- 229960001669 kinetin Drugs 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 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
- 238000006683 Mannich reaction Methods 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/14—Ortho-condensed systems
-
- 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
Abstract
The invention belongs to the technical field of thermosetting resin, and relates to a coumarin-based bio-based bifunctional benzoxazine resin and a preparation method thereof, in particular to a coumarin structure-containing bifunctional benzoxazine, wherein the preparation method comprises the following steps: mixing dihydroxycoumarin, amine compound and paraformaldehyde, adding into an organic solvent, reacting at 60-120 ℃ for 6-14h, and performing rotary evaporation and drying after reaction to obtain the product. The invention has the advantages that the bio-based dihydroxy coumarin is used as the phenol source, the raw materials are environment-friendly, and the resin preparation meets the requirements of green sustainable development; the coumarin structure can effectively reduce the curing temperature and further improve the crosslinking density when the bifunctional resin structure is cured; the dihydroxycoumarin has phenolic hydroxyl with two functionalities, so that the synthesized bifunctionality benzoxazine has more excellent thermodynamic property; the synthesis steps are simple, and the yield is high; and the cured polybenzoxazine resin has excellent comprehensive performance. The invention has simple synthesis process and low requirement on equipment, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin, and particularly relates to coumarin-based bio-based bifunctional benzoxazine resin and a preparation method thereof.
Background
Benzoxazine is a high-performance thermosetting resin, is generally prepared by a phenolic compound, primary amine and formaldehyde or paraformaldehyde through a Mannich reaction under certain conditions, and can be subjected to ring-opening polymerization to form a cross-linked network structure similar to phenolic aldehyde under the action of heating and/or introducing a catalyst, namely polybenzoxazine. The benzoxazine resin has wide material source, flexible molecular design and good processing performance, can be co-blended and copolymerized with various resins without using strong acid and strong alkali as catalysts during curing, and has the advantages of high strength, high modulus, good heat resistance, thermal stability, flame retardance and the like, so that the benzoxazine resin is more and more widely concerned.
With the expansion of the application field, people pursue high-performance polybenzoxazine materials, and meanwhile, environmental influence and utilization of renewable resources become key considerations for resin preparation. The development of materials with both high performance and environmental friendliness has become the direction of researchers and researchers in the industry. The product of the full-bio-based benzoxazine resin prepared by the patent number (CN107759615A) is monofunctional, and a high-crosslinking resin network structure is difficult to form, so that the thermal property needs to be improved. The patent No. (CN106674214A) adopts a three-step method to synthesize the furyldiamide type benzoxazine resin, the reaction steps are complicated, the process is complex, the preparation time is long, and low-cost large-scale production is difficult to carry out.
Disclosure of Invention
In view of the defects of the prior thermosetting resin material, the invention takes the bio-based dihydroxy coumarin as the phenol source, and takes the bio-based raw material to replace the petroleum-based raw material, so that the heat and mechanical properties of the resin material after crosslinking and curing are greatly improved by synthesizing the benzoxazine through the bio-based coumarin bisphenol substance while conforming to the green sustainable development; at present, the reports related to coumarin are all monofunctional, and the curing of monofunctional benzoxazine is difficult to highly crosslink, so that the thermodynamic performance is defective; the invention forms a highly cross-linked structure through double functions, so that the cured resin material has high temperature resistance; in addition, the resin has simple synthesis process, high yield and low requirement on equipment, and is suitable for large-scale production.
The invention aims to provide novel benzoxazine taking bio-based dihydroxy coumarin as a phenol source and a preparation method thereof by preparing bio-based dihydroxy coumarin difunctional benzoxazine resin and keeping excellent thermal property and mechanical property of the resin on the basis of using environment-friendly bio-based raw materials.
The purpose of the invention is realized by the following technical scheme:
one of the purposes of the invention is to provide a coumarin-based bio-based bifunctional benzoxazine resin, the molecular chemical structural formula of which is shown as follows:
wherein the content of the first and second substances,
is one of the following structures:
the second purpose of the invention is to provide a preparation method of benzoxazine resin with bio-based dihydroxy coumarin as a phenol source.
The benzoxazine is prepared by taking dihydroxy coumarin, amine compounds and paraformaldehyde as raw materials, and the chemical reaction equation is shown in figure 5 of the attached drawing of the specification.
The structural formula of the amine compound is R-NH2Is one of the following structures:
the method specifically comprises the following steps:
adding dihydroxycoumarin, amine compounds and paraformaldehyde into a flask, adding an organic solvent, reacting at 60-120 ℃ for 6-14h, stopping the reaction, carrying out rotary evaporation on the reaction liquid, and drying to obtain a solid product, namely the coumarin bio-based bifunctional benzoxazine resin.
The molar ratio of the dihydroxycoumarin to the amine compound to the paraformaldehyde is 1: 2: 4-1: 2: 5.
further, the optimal molar ratio of the dihydroxycoumarin to the amine compound to the paraformaldehyde is 1: 2: 4.21.
the organic solvent is one or a mixture of several of toluene, ethyl acetate, xylene and dioxane.
Compared with the prior art, the invention has the advantages that:
the invention takes the bio-based dihydroxy coumarin as the phenol source to synthesize the bifunctional benzoxazine resin containing the coumarin, the coumarin structure can also effectively reduce the ring-opening curing temperature of the benzoxazine and improve the curing crosslinking degree of the benzoxazine, tests show that the polybenzoxazine cured by the benzoxazine has excellent thermal property and mechanical property, the curing peak temperature is 160-240 ℃, the residue rate is 50-85% at 800 ℃ in an inert gas atmosphere, and the glass transition temperature is 250-450 ℃.
Drawings
FIG. 1 nuclear magnetic resonance hydrogen spectrum of benzoxazine resin obtained in example 1;
FIG. 2 is an infrared spectrum of the benzoxazine resin obtained in example 1;
FIG. 3 DSC spectrum of benzoxazine resin obtained in example 1;
FIG. 4 TGA spectrum of cured benzoxazine resin obtained in example 1;
FIG. 5 is a chemical reaction equation for preparing benzoxazine resin by using bio-based dihydroxy coumarin as a phenol source.
FIG. 6 shows the chemical reaction equation involved in example 1.
Detailed Description
The following provides a specific embodiment of the coumarin bio-based difunctional benzoxazine-based resin of the present invention. It is to be noted that: the following examples are intended only to illustrate the present invention in more detail, and do not narrow the scope of the present invention. Modifications and adaptations of the present invention may occur to those skilled in the art after reading the present invention and may be made without departing from the spirit and scope of the present invention as defined by the appended claims.
Example 1
2-furanmethanamine is used as an amine source. 1g (0.0056mol) of dihydroxycoumarin, 1.088g (0.0112mol) of 2-furanmethanamine, 1.482g (0.0247mol) of paraformaldehyde were charged in a flask, 20ml of a toluene solution was added, a condenser tube was attached, and stirring and reaction were carried out at 120 ℃ for 10 hours. After the reaction was stopped, the reaction was rotary evaporated and dried in a vacuum oven at 50 ℃ for one day to obtain 2.03g of benzoxazine monomer with a yield of 86%. Chemical reaction equation figure 6 shows:
in this example, the structure of the obtained oxazine product is:
the nuclear magnetic resonance hydrogen spectrogram, Fourier infrared transform spectrogram, DSC curve chart and thermogravimetry curve chart of the product are shown in figure 1, figure 2, figure 3 and figure 4.
FIG. 1 shows a NMR chart. Chemical shifts of about 5.00 ppm and 5.06ppm, and 4.17 ppm and 4.22ppm are characteristic peaks of methylene on the oxazine ring. FIG. 2 is an infrared spectrum of 923cm-1And 1218cm-1The position is a characteristic absorption peak of the benzoxazine ring. FIG. 3 is a DSC graph showing that the curing exothermic peak temperature of the benzoxazine monomer is 188 ℃. FIG. 4 is a TGA graph of the cured resin material, and it can be seen that the temperature of the benzoxazine resin is 358 ℃ when the thermal weight loss is 5%, and the carbon residue rate is 55% at 800 ℃. The glass transition temperature of the resin material after curing was 305 ℃.
Example 2
The amine source compound 2-furanmethanamine in example 1 was replaced with aniline. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the aniline is as follows:
the amounts of reactants were changed to: 1g (0.0056mol) of dihydroxycoumarin, 1.043g (0.0112mol) of aniline, and 1.478g (0.0247mol) of paraformaldehyde were weighed out, and the yield was 85%.
The latent curing type benzoxazine resin monomer obtained in the embodiment has a curing exothermic peak temperature of 192 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a temperature of 361 ℃ when the thermal weight loss is 5%, a carbon residue rate of 56% when the polybenzoxazine resin is in an inert gas atmosphere of 800 ℃, and a glass transition temperature of 298 ℃ after curing.
Example 3
The amine source compound 2-furanmethanamine in example 1 was replaced with 4-methylaniline. The other steps were the same as in example 1.
Wherein the specific chemical structural formula of the 4-methylaniline is as follows:
the amounts of reactants were changed to: 1g (0.0056mol) of dihydroxycoumarin, 1.200g (0.0112mol) of 4-methylaniline and 1.478g (0.0247mol) of paraformaldehyde were weighed. The yield thereof was found to be 92%.
The latent curing type benzoxazine resin monomer obtained in the embodiment has a curing exothermic peak temperature of 195 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a temperature of 363 ℃ when the thermal weight loss is 5%, a carbon residue rate of 57% when the polybenzoxazine resin is in an inert gas atmosphere of 800 ℃, and a glass transition temperature of 287 ℃ after curing.
Example 4
The amine source compound 2-furanmethanamine in example 1 was replaced with m-ethynylaniline. The other steps were the same as in example 1.
The specific chemical structural formula of the octadecyl amine is as follows:
the amounts of reactants were changed to: 1g (0.0056mol) of dihydroxycoumarin, 1.312g (0.0112mol) of m-ethynylaniline, and 1.478g (0.0247mol) of paraformaldehyde were weighed. The yield thereof was found to be 89%.
The latent curing type benzoxazine resin monomer obtained in the embodiment has a curing exothermic peak temperature of 174 ℃, and after further curing and crosslinking, the polybenzoxazine resin has a temperature of 406 ℃ when the thermal weight loss is 5%, a carbon residue rate of 78% when the polybenzoxazine resin is in an inert gas atmosphere of 800 ℃, and a glass transition temperature of a cured resin material of 405 ℃.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A coumarin bio-based bifunctional benzoxazine resin is characterized in that: the molecular formula is as follows:
wherein the content of the first and second substances,
is one of the following structures:
2. the coumarin-based bio-based bifunctional benzoxazine resin according to claim 1, wherein the curing peak temperature of the benzoxazine resin is 160-240 ℃, the benzoxazine resin is further cured and crosslinked to obtain the polybenzoxazine resin, and the benzoxazine resin has a char yield of 50-85% and a glass transition temperature of 250-450 ℃ in an inert atmosphere of 800 ℃.
3. The preparation method of the coumarin bio-based difunctional benzoxazine resin according to any one of claims 1-2, which comprises the following steps:
adding dihydroxycoumarin, amine compounds and paraformaldehyde into a flask, adding an organic solvent, reacting at 60-120 ℃ for 6-14h, stopping the reaction, carrying out rotary evaporation on the reaction liquid, and drying to obtain a solid product, namely the coumarin bio-based bifunctional benzoxazine resin.
4. The preparation method of coumarin bio-based difunctional benzoxazine resin according to claim 3, wherein the amine compound has the structural formula of R-NH2Is one of the following structures:
5. the method for preparing the coumarin bio-based bifunctional benzoxazine resin according to claim 3, wherein the molar ratio of the dihydroxycoumarin to the amine compound to the paraformaldehyde is 1: 2: 4-1: 2: 5.
6. the method for preparing coumarin bio-based bifunctional benzoxazine resin according to claim 5, wherein the optimal molar ratio of dihydroxycoumarin, amine compound and paraformaldehyde is 1: 2: 4.21.
7. the method for preparing the coumarin bio-based difunctional benzoxazine resin according to claim 3, wherein the organic solvent is one or a mixture of toluene, ethyl acetate, xylene and dioxane.
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2021
- 2021-08-24 CN CN202110973728.2A patent/CN114195803B/en active Active
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