CN114075100A - Resin monomer based on resveratrol and high-heat-resistance resin based on resin monomer - Google Patents
Resin monomer based on resveratrol and high-heat-resistance resin based on resin monomer Download PDFInfo
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- CN114075100A CN114075100A CN202010797097.9A CN202010797097A CN114075100A CN 114075100 A CN114075100 A CN 114075100A CN 202010797097 A CN202010797097 A CN 202010797097A CN 114075100 A CN114075100 A CN 114075100A
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- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 239000000178 monomer Substances 0.000 title claims abstract description 58
- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940016667 resveratrol Drugs 0.000 title claims abstract description 38
- 235000021283 resveratrol Nutrition 0.000 title claims abstract description 38
- 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 title claims abstract description 29
- 238000002679 ablation Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004382 potting Methods 0.000 claims 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009477 glass transition Effects 0.000 abstract description 6
- 229920001568 phenolic resin Polymers 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000005011 phenolic resin Substances 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000001723 curing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HRDCVMSNCBAMAM-UHFFFAOYSA-N 3-prop-2-ynoxyprop-1-yne Chemical compound C#CCOCC#C HRDCVMSNCBAMAM-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- -1 titanium modified phenolic resin Chemical class 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3327—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkene-based
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
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- C08G2261/592—Stability against heat
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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- Chemical & Material Sciences (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a resveratrol-based resin monomer and a high-heat-resistance resin based on the resveratrol-based resin monomer. Specifically, monomers having the structure of formula I are provided; the resin formed by curing the monomer can resist high heat, has high glass transition temperature and storage modulus, resists ablation, has carbon residue rate of 70 percent at 1000 ℃, and is far higher than that of the common epoxy resinAnd a phenolic resin.
Description
Technical Field
The invention relates to a resveratrol-based resin monomer and a high-heat-resistance resin based on the resveratrol-based resin monomer.
Background
With the rapid development of industrial technologies, the requirements for materials are higher and higher, and especially the heat resistance and ablation resistance of materials used in high-speed and high-heat environments such as aerospace and detection are particularly important.
The heat-resistant and ablation-resistant materials widely used at present mainly include phenolic resin, silicone resin, epoxy resin and the like, but the materials have difficulty in meeting the current development requirements. Therefore, the skilled person in the art would like to improve the heat resistance and ablation resistance of the material by modifying the conventional polymer material.
Because of their low cost and excellent thermal and ablation resistance, phenolic resins have been extensively studied for modification, including: 1. boron-modified phenolic resin; 2. molybdenum-modified phenolic resin; 3. titanium modified phenolic resin; 4. and the modification research of the phenolic composite material and the like. Although these methods improve the heat resistance and the ablation resistance of the phenolic resin to a certain extent, the carbon residue of the modified phenolic at 1000 ℃ for representing the ablation resistance of the material is difficult to reach 70 percent due to the limitation of the phenolic resin.
Therefore, there is a need in the art to provide more high heat, ablation resistant resins.
Disclosure of Invention
The invention aims to provide a resveratrol-based resin monomer and a high-heat-resistant and ablation-resistant resin based on the monomer.
In a first aspect of the invention, a resveratrol propargyl resin monomer is provided, which is characterized in that the monomer has a structure of formula I:
in a second aspect of the present invention, there is provided a process for preparing a monomer according to the first aspect of the present invention, the process comprising the steps of:
reacting resveratrol with 3-halopropyne in an organic solvent in the presence of an inorganic base to obtain the monomer.
In another preferred embodiment, the halogen is selected from the group consisting of: chlorine, bromine and iodine.
In another preferred embodiment, the inorganic base is selected from the group consisting of: potassium hydroxide, sodium carbonate, potassium carbonate, or a combination thereof.
In another preferred embodiment, the organic solvent is selected from the group consisting of: acetone, cyclohexanone, dichloromethane, chloroform, ethanol, DMF, DMAC, DMSO, NMP, or combinations thereof.
In another preferred embodiment, the reaction temperature is 40 ℃ to 100 ℃, preferably 50 ℃ to 80 ℃.
In another preferred embodiment, the reaction time is 1 to 100 hours, preferably 12 to 90 hours, more preferably 24 to 80 hours.
In another preferred embodiment, the molar ratio of the resveratrol to the inorganic base is 1: 1-6, preferably, 1:2-5, more preferably, 1: 3-4.
In another preferred embodiment, the molar ratio of the resveratrol to the 3-halopropyne is 1: 1-6, preferably, 1:2-5, more preferably, 1: 3-4.
In another preferred embodiment, the molar ratio of the resveratrol, the inorganic base and the 3-halopropyne is 1:1-5:1-5, preferably 1:2-4: 2-4.
In a third aspect, the present invention provides the use of a monomer according to the first aspect of the invention for the preparation of a heat and/or ablation resistant resin.
In another preferred embodiment, the 5% thermal weight loss temperature of the resin is more than or equal to 400 ℃.
In another preferred embodiment, the resin has a char yield of not less than 65%, preferably not less than 70%, at 1000 ℃.
In a fourth aspect of the present invention, there is provided a resin prepared from a composition comprising or obtained by curing by heating a monomer according to the first aspect of the present invention.
In another preferred embodiment, the curing comprises a shaping step.
In another preferred embodiment, the heat curing method is selected from the group consisting of: a cast method, a solution spin coating method, or a solution drop coating method.
In a fifth aspect of the present invention, there is provided a method of preparing a resin according to the fourth aspect of the present invention, the method comprising the steps of heating and curing.
In another preferred embodiment, the preparation method (injection molding method) comprises the following steps: heating the resveratrol propargyl resin monomer of claim 1 to 80 ℃ -100 ℃ (preferably 85 ℃ -90 ℃) to convert it to a uniform transparent liquid state;
removing bubbles in the melt under vacuum (e.g., 150-165 ℃);
precuring at 170-200 ℃ in a nitrogen atmosphere to obtain a prepolymer; and
finally keeping the temperature at 220-240 ℃ for 3-6h to obtain the cured resin.
In another preferred example, the preparation method (solution method) includes the steps of: dissolving the resveratrol propargyl resin monomer of claim 1 in an organic solvent to obtain a uniform transparent solution;
raising the temperature to 160-180 ℃ under nitrogen and keeping the temperature for 2-4 hours to obtain a prepolymer;
coating the prepolymer solution on the surface of the glass fiber or the carbon fiber, and volatilizing the solvent under vacuum (such as 150 ℃ C. and 165 ℃ C.); and
and keeping the temperature at 220-240 ℃ for 3-6h to obtain the cured resin (fiber reinforced cured resin).
In another preferred embodiment, the solvent is selected from the group consisting of: cyclohexanone, trimethylbenzene, DMF, DMAC, and NMP, or a combination thereof.
In a sixth aspect of the invention, there is provided an article comprising or consisting of a resin according to the fourth aspect of the invention.
In another preferred embodiment, the article is a block, a plate or a coating.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a Thermogravimetric (TGA) curve of a cured product of resveratrol propargyl resin monomer;
FIG. 2 is a Coefficient of Thermal Expansion (CTE) curve for a cured product of resveratrol propargyl resin monomer;
fig. 3 is a dynamic thermo-mechanical analysis (DMA) curve of a resveratrol propargyl resin monomer cured product.
Detailed Description
The inventor provides a resveratrol-based monomer of formula I through extensive and intensive research, and through a large number of screening and tests, the resin generated after the monomer is cured has high glass transition temperature, high carbon residue rate, high storage modulus and low thermal expansion coefficient, is high temperature resistant, ablation resistant and good in processability, and is particularly suitable for being applied in high-temperature environment. Based on the above findings, the inventors completed the present invention.
Term(s) for
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "comprising" or "includes" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
Resin monomer
The present invention provides a resin monomer of formula I:
method for preparing monomer
A preparation method of propargyl ether monomer based on biomass resveratrol is provided. The resveratrol is characterized in that resveratrol is used as a raw material and reacts with propargyl bromide in an organic solvent at a certain temperature in the presence of inorganic base to prepare the resveratrol.
Resin composition
The invention also provides a resin based on the monomer of the formula I, wherein the resin is prepared from a composition containing the monomer of claim 1 or is prepared by heating and curing the monomer of claim 1.
The above monomers may be used alone to form the resin or together with other monomers or reagents, such as auxiliaries commonly used in the art, to form the resin.
The resins may be used to form high heat, ablation resistant blocks, plates, coatings or other composites.
The resin is cured by heating and curing the propargyl resin monomer of the resveratrol.
Preparation of the resin
The curing and molding method can be carried out by the following molding process: and (4) pouring a mold, performing solution spin coating, or performing solution drop coating.
In a preferred embodiment, the mold filling method comprises the following steps: heating the resveratrol propargyl resin monomer of claim 1 to 85-90 ℃ to convert it to a uniform transparent liquid state. Removing air bubbles in the melt under vacuum at 150-160 ℃, pre-curing at 170-180 ℃ in a nitrogen atmosphere, finally keeping at 230 ℃ for 5 hours to obtain cured resin,
solution-process prepolymerization procedure the resveratrol propargyl resin monomer of claim 1 is dissolved in an organic solvent to obtain a homogeneous transparent solution, heated to 170 ℃ under nitrogen and held at that temperature for 2 hours to obtain a prepolymer. And coating the prepolymer solution on the surface of the glass fiber or the carbon fiber, volatilizing the solvent at 150 ℃ under vacuum, and performing post-curing treatment according to the mold filling mode to obtain the fiber-reinforced cured resin. The solvent is selected from the following group: cyclohexanone, trimethylbenzene, DMF, DMAC, and NMP, or a combination thereof.
Compared with the prior art, the invention has the main advantages that:
(1) the invention provides a biomass resveratrol-based resin monomer, which reduces the dependence on fossil resources and is a green and economic material. Since biomass chenoponol is commonly used as a food additive and a fine chemical, the present invention also widens the application field of chenoponol.
(2) The resin monomer of the invention has simple synthesis steps (one-step synthesis), mild process conditions and high yield, and can be used for industrial large-scale production.
(4) Surprisingly, the monomer is cured by heating without adding a catalyst or a curing agent, and the use of the monomer as a resin raw material can reduce the cost and simplify the operation.
(3) The resin obtained by heating and curing the monomer provided by the invention has the advantages of high glass transition temperature, high carbon residue rate (up to 70%), high storage modulus, low thermal expansion coefficient, high temperature resistance, ablation resistance and good processability, and is especially suitable for being applied in high-temperature environments (such as the fields of aerospace and the like).
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
General procedure
Thermogravimetric analysis (TGA), instrument model: TG 209F1
The test range is as follows: 40 to 1000 ℃, and the heating rate is 10 ℃ for min-1。
Coefficient of thermal expansion analysis (CTE) Instrument model DIL 402 expedisi
The test conditions were: heating from room temperature to 400 deg.C in nitrogen atmosphere at a heating rate of 5 deg.C for min-1。
Dynamic thermomechanical analysis (DMA) Instrument model DMA Q800
The test conditions were: in nitrogen atmosphere, the temperature is raised from room temperature to 400 ℃ at the rate of 5 ℃ for min-1The test frequency was 1.0 Hz.
Resveratrol:
example 1
Synthesis of resveratrol propargyl ether monomer
In a 250mL three-necked flask, resveratrol (10.00g,43.81mmol), acetone (100mL), and anhydrous K were added under a nitrogen atmosphere2CO3(20.00g,144.57mmol) and 3-bromopropyne (17.20g,144.57 mmol). The mixture was stirred at 60 ℃ for 72 hours and then cooled to room temperature. The solid was removed by filtration, the filter cake was washed with acetone, the filtrates were combined, and the solvent was concentrated by distillation under reduced pressure. The crude product was recrystallized from methanol to give a pale yellow solid in 63% yield.1H NMR(400MHz,CDCl3)δ7.45(d,2H),7.08～6.85(m,4H),6.74(d,J＝2.1Hz,2H),6.52(t,J＝2.1Hz,1H),4.71(t,J＝5.6Hz,6H),2.54(dt,J＝5.6Hz,3H).13C NMR(101MHz,CDCl3)δ158.98,157.53,139.83,130.74,129.05,127.79,126.66,115.18,106.11,101.46,78.52,75.83,55.93.
Example 2 Synthesis of resveratrol propargyl ether monomer
The same as example 1, but the solvent was ethanol, the reaction time was 20 hours, and the yield was 74%.
Example 3 Synthesis of resveratrol propargyl ether monomer
The same as example 2, but the inorganic base is potassium hydroxide, the reaction time is 5 hours, and the yield is 90%.
Example 4 Synthesis of resveratrol propargyl ether monomer
The same as example 1, but with DMSO as the solvent, the reaction time was 5 hours and the yield was 90%.
Example 5 Synthesis of resveratrol propargyl ether monomer
The same as example 1, but the solvent was DMAC, the reaction time was 10 hours, and the yield was 80%.
EXAMPLE 6 curing of resveratrol propargyl ether monomers
2.0g of the monomer obtained in example 1 were introduced into a flat-bottomed glass tube having a diameter of 2.0cm, heated to 90 ℃ and kept under reduced pressure for 3 hours, to remove air and any volatile substances. After the bubbles disappeared, the tube was heated to 160 ℃ and maintained at this temperature for 3 hours, and then maintained at 180 ℃, 200 ℃, 220 ℃ and 240 ℃ for 2 hours in nitrogen. Finally, the tube was slowly cooled to room temperature to give a fully cured resin.
Example 7 thermal stability Studies of cured resins
The cured resin obtained in example 6 was subjected to TGA test in a nitrogen atmosphere.
The TGA test results are shown in FIG. 1, wherein the 5% thermal weight loss temperature of the cured resin is 420 ℃ and the carbon residue rate at 1000 ℃ is 70% (carbon residue rate ═ m)After heating/mBefore heating). The resin performance parameters of the invention are far better than bisphenol A propargyl resin, the 5 percent thermal weight loss temperature of the bisphenol A propargyl resin is only 340 ℃, and the carbon residue rate is 43 percent at 700 ℃. The fact shows that the resveratrol-based propargyl resin has very excellent heat resistance and has great potential to be applied to the fields with harsh conditions such as aerospace and the like in the future.
The cured resin obtained in example 6 was subjected to a CTE test.
The CTE test results are shown in FIG. 2, and it can be seen from FIG. 2 that the coefficient of thermal expansion of the cured resin was 42.3ppm deg.C-1The glass transition temperature was 365 ℃. The linear thermal expansion coefficient of the resin of the invention is far lower than that of epoxy resin, phenolic resin and the like which are widely used at present. Meanwhile, the glass transition temperature of the triazine propargyl resin is only 323 ℃ at most, which shows that the resin has excellent thermal property.
EXAMPLE 8 thermomechanical Properties of the cured resin
The cured resin obtained in example 2 was subjected to a DMA test.
The DMA test results are shown in figure 3. As can be seen from FIG. 3, the storage modulus of the cured product was 2.8GPa, and no significant glass transition temperature was observed up to 300 ℃.
The high storage modulus indicates that the material has high hardness and is not easy to deform, and the material of the invention has high storage modulus before the decomposition temperature, which indicates that the resin of the invention can keep excellent mechanical properties at high temperature.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A resveratrol propargyl resin monomer, wherein the monomer has the structure of formula I:
2. a method for preparing the monomer of claim 1, comprising the steps of:
reacting resveratrol with 3-halopropyne in an organic solvent in the presence of an inorganic base to obtain the monomer.
3. The method of claim 2, wherein the inorganic base is selected from the group consisting of: potassium hydroxide, sodium carbonate, potassium carbonate, or a combination thereof.
4. The method of claim 2, wherein the molar ratio of resveratrol to 3-halopropyne is 1: 1-6, preferably, 1:2-5, more preferably, 1: 3-4.
5. Use of the monomer according to claim 1 for the preparation of a heat and/or ablation resistant resin.
6. A resin prepared from a composition comprising the monomer of claim 1 or prepared by curing the monomer of claim 1 by heating.
7. A method of preparing the resin of claim 6, comprising the steps of heating and curing.
8. A method for preparing the resin according to claim 7, wherein the preparation method (potting method) comprises the steps of: heating the resin monomer of claim 1 to 80-100 ℃ to convert it to a homogeneous transparent liquid state;
removing bubbles in the melt under vacuum (e.g., 150-165 ℃);
precuring at 170-200 ℃ in a nitrogen atmosphere to obtain a prepolymer; and
finally keeping the temperature at 220-240 ℃ for 3-6h to obtain the cured resin.
9. A method for producing the resin according to claim 7, characterized in that the production method (solution method) comprises the steps of: dissolving the resin monomer of claim 1 in an organic solvent to obtain a homogeneous transparent solution;
raising the temperature to 160-180 ℃ under nitrogen and keeping the temperature for 2-4 hours to obtain a prepolymer;
coating the prepolymer solution on the surface of the glass fiber or the carbon fiber, and volatilizing the solvent under vacuum (such as 150 ℃ C. and 165 ℃ C.); and
and keeping the temperature at 220-240 ℃ for 3-6h to obtain the cured resin (fiber reinforced cured resin).
10. An article comprising or consisting of the resin of claim 4.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262586A (en) * | 2014-10-22 | 2015-01-07 | 中国科学院上海有机化学研究所 | Epoxy resin with high modulus and high glass transition temperature as well as preparation and application thereof |
| CN111040131A (en) * | 2019-12-20 | 2020-04-21 | 中国科学院上海有机化学研究所 | Synthesis and application of epoxy resin based on catechin |
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2020
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262586A (en) * | 2014-10-22 | 2015-01-07 | 中国科学院上海有机化学研究所 | Epoxy resin with high modulus and high glass transition temperature as well as preparation and application thereof |
| CN111040131A (en) * | 2019-12-20 | 2020-04-21 | 中国科学院上海有机化学研究所 | Synthesis and application of epoxy resin based on catechin |
Non-Patent Citations (1)
| Title |
|---|
| HOU, JIAREN等: "A facile conversion of a bio-based resveratrol to the high-performance polymer with high Tg and high char yield", POLYMER, vol. 200, 12 May 2020 (2020-05-12), pages 1 - 6, XP086176954, DOI: 10.1016/j.polymer.2020.122570 * |
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