CN115286655A - Bio-based epoxy resin suitable for wet-process winding carbon fiber hydrogen storage bottle and preparation method thereof - Google Patents
Bio-based epoxy resin suitable for wet-process winding carbon fiber hydrogen storage bottle and preparation method thereof Download PDFInfo
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- CN115286655A CN115286655A CN202210915119.6A CN202210915119A CN115286655A CN 115286655 A CN115286655 A CN 115286655A CN 202210915119 A CN202210915119 A CN 202210915119A CN 115286655 A CN115286655 A CN 115286655A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 62
- 238000004804 winding Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 20
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000003860 storage Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005770 Eugenol Substances 0.000 claims abstract description 16
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960002217 eugenol Drugs 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 20
- 239000013067 intermediate product Substances 0.000 claims description 19
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004046 wet winding Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000004593 Epoxy Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 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 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 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 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005490 dry winding Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/02—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
- F17C1/04—Protecting sheathings
- F17C1/06—Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0658—Synthetics
- F17C2203/0663—Synthetics in form of fibers or filaments
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a bio-based epoxy resin suitable for a wet-process winding carbon fiber hydrogen storage bottle and a preparation method thereof, belonging to the technical field of epoxy resin preparation. The structural formula of the bio-based epoxy resin is shown as a formula (1), the invention also provides a preparation method of the bio-based epoxy resin, the method utilizes eugenol and dichlorodiphenylsilane as raw materials for preparing epoxy monomers, the thermal stability of the materials can be improved due to more aromatic structures of the bio-based epoxy resin, the reaction raw materials belong to renewable resources, the cost is low, the quality is excellent and non-toxic, the reaction process does not need too harsh reaction conditions, and the prepared resin has good mechanical property, thermal stability and excellent fluidity, has good application value in industry and can be suitable for winding carbon fiber hydrogen storage bottles by a wet method.
Description
Technical Field
The invention belongs to the technical field of epoxy resin preparation, and particularly relates to bio-based epoxy resin suitable for a wet-process winding carbon fiber hydrogen storage bottle and a preparation method thereof.
Background
The epoxy resin is a high molecular oligomer which contains two or more epoxy groups, takes aliphatic or aromatic groups as a framework, and can generate a thermosetting product through the reaction of the epoxy groups and other active groups. The epoxy resin has a large amount of active and polar groups, and as a thermosetting resin, the epoxy resin is widely applied to the fields of coatings, composite materials, adhesives, electronic packaging materials, engineering plastics, civil engineering and building materials and the like due to excellent comprehensive performance, good cohesiveness, excellent mechanical property, small curing shrinkage, good manufacturability, excellent electric insulation property and corrosion resistance.
However, the development of high performance epoxy resins faces two obstacles (1) the unsustainability of their petroleum-based raw materials in the life cycle, from production, use to disposal; (2) The special properties such as dielectric property and flame retardant property are further improved. At present, most of epoxy resin is derived from petroleum resources, particularly bisphenol A epoxy resin, and petroleum resources are non-renewable resources, and the cost of high polymer materials derived from petroleum resources is increased along with the gradual reduction of reserves of the petroleum resources. In addition, bisphenol a is suspected of having physiological toxicity and has been restricted in use in many countries such as europe, and thus under the current situation of increasingly depleted petroleum resources, there is an urgent need to use raw materials from other sources to produce epoxy resins, and to reduce the dependence on petroleum resources. The search for sustainable, high-quality, inexpensive, non-toxic alternatives to petroleum is a key to the existence and development of the polymer industry, and it is particularly important to develop alternatives with renewable resources and possessing comparable properties. In the past, halogenated organic additives such as polybrominated biphenyls and polybrominated diphenyl ethers have been widely used in the production of flame retardant epoxy materials. Unfortunately, these halogenated additives have proven to be harmful to the human endocrine system. Under such circumstances, the development of low flammability bio-based epoxy resins, while avoiding the introduction of halogen elements, is very important for reducing potential fire and health hazards. Some researchers have introduced organophosphate groups into epoxy molecules to improve their flame retardancy, but have resulted in high hygroscopicity and low thermal stability, resulting in poor processability of coatings, adhesives and fiber-reinforced composites. In addition, in view of the use of epoxy resins, a particularly low dielectric constant is also necessary because they are widely used as insulating materials for electronic devices (e.g., central processing units) and exhibit good dielectric properties. However, the research on bio-based epoxy resins has rarely solved this problem.
At present, almost all epoxy resins are completely dependent on petroleum resources. With the increasing consumption of petroleum resources and energy, the replacement of traditional petroleum-based epoxy resins with renewable epoxy resins, particularly bio-based epoxy resins, is imminent. Many different plant sources are obtained through fermentation and chemical transformation, such as epoxidized vegetable oils, isosorbide, cardanol, vanillin, itaconic acid, and lignin derivatives, to synthesize bio-based epoxy thermosets. So as to meet the requirement of serving as a starting material for preparing the bio-based epoxy monomer. In recent years, the shift from petroleum-based to bio-based materials in combination with inorganic nano-molecules to the synthesis of new resins is currently a major goal.
The carbon fiber winding forming process can be divided into wet winding and dry winding, wherein the wet winding is widely applied due to low cost and good manufacturability, and the wet winding equipment mainly comprises a fiber frame, tension control equipment, a glue dipping tank, a silk spinning nozzle and a rotary core mold structure. The international advanced six-dimensional winding technology can well control the trend of the fiber and realize the combination of annular winding, spiral winding and plane winding. The mode that combines together is wound to the spiral direction and hoop winding to the adoption in the actual production more, and hoop winding can eliminate the gas cylinder and receive the hoop stress that internal pressure and produced, and the spiral direction winding can provide longitudinal stress, promotes gas cylinder wholeness ability. The carbon fiber hydrogen storage cylinder resin matrix not only needs to meet the requirements of the cylinder on mechanical strength and toughness, but also needs a high-strength, high-toughness and fatigue-resistant resin system to ensure the service life of the cylinder because the matrix is easy to generate fatigue damage in the use environment of long-term inflation and deflation. Resin matrices for wet winding molding are required to have a low initial viscosity at a working temperature and a long pot life at that temperature, in addition to satisfying the respective properties.
Disclosure of Invention
The invention aims to solve the problems that the existing resin system is difficult to impregnate carbon fibers and raw materials are non-renewable, and provides a bio-based epoxy resin suitable for a wet-process winding carbon fiber hydrogen storage bottle and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the invention firstly provides a bio-based epoxy resin suitable for a wet-process winding carbon fiber hydrogen storage bottle, which has a structural formula shown in a formula (1):
the invention also provides a preparation method of the bio-based epoxy resin suitable for the wet-process winding carbon fiber hydrogen storage bottle shown in the formula (1), which comprises the following steps:
step one, adding eugenol, triethylamine and a solvent into a reaction vessel, and then adding dichlorodiphenylsilane to obtain an intermediate product DSi;
and step two, dripping the intermediate product DSi obtained in the step one into a suspension of meta-hydroperoxybenzoic acid, keeping the temperature of a reaction mixture below-5 ℃ in the dripping process, slowly heating to room temperature, stirring, and performing post-treatment to obtain the bio-based epoxy resin which is shown in the formula (1) and is suitable for the wet-process winding carbon fiber hydrogen storage bottle.
Preferably, the mol ratio of the eugenol, the triethylamine and the dichlorodiphenylsilane in the step one is (3-5): (1-3).
Preferably, the solvent of the first step is dichloromethane.
Preferably, the reaction temperature of the first step is 30-90 ℃, and the reaction time is 2-8h.
Preferably, the molar ratio of the intermediate product DSi to the m-chloroperoxybenzoic acid in the second step is 1 (3-5).
Preferably, the stirring time of the second step is 24-150h.
Preferably, the post-treatment in the second step is to filter the obtained mixture, and the filtrate is washed by saturated sodium thiosulfate solution and saturated sodium bicarbonate solution in sequence. The mixture was then dried over anhydrous sodium sulfate and the reaction product was filtered and rotary evaporated to remove CH 2 C1 2 Thereafter, further drying at 30-90 ℃ under vacuum.
The invention has the advantages of
The invention provides a bio-based epoxy resin suitable for a wet-process winding carbon fiber hydrogen storage bottle and a preparation method thereof, the structural formula of the bio-based epoxy resin is shown as a formula (1), and a siloxane-containing chain segment in the structure has the characteristics of low polarity, high dissociation energy, spiral molecular structure, large molecular volume and the like, so that the bio-based epoxy resin has excellent fluidity; the invention also provides a preparation method of the bio-based epoxy resin, which uses eugenol and dichlorodiphenylsilane as raw materials for preparing epoxy monomers, and because the aromatic structures are more, the thermal stability of the materials can be improved, the reaction raw materials belong to renewable resources, the price is low, the quality is excellent and non-toxic, the reaction process does not need too harsh reaction conditions, and the prepared resin has good mechanical properties, thermal stability and excellent fluidity, has good application value in industry, and can be suitable for winding carbon fiber hydrogen storage bottles by a wet method.
Drawings
FIG. 1 is an infrared spectrum of the bio-based epoxy resin prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the bio-based epoxy resin of example 1;
FIG. 3 is a NMR spectrum of a bio-based epoxy resin of example 2;
FIG. 4 is a differential thermogravimetric analysis plot of the bio-based epoxy resin of example 1;
FIG. 5 is a graph of viscosity analysis of the bio-based epoxy resin of example 1.
Detailed Description
The invention firstly provides a bio-based epoxy resin suitable for a wet-process winding carbon fiber hydrogen storage bottle, which has a structural formula shown in a formula (1),
the invention also provides a preparation method of the bio-based epoxy resin suitable for the wet-process winding carbon fiber hydrogen storage bottle shown in the formula (1), which comprises the following steps:
adding eugenol, triethylamine and a solvent into a reaction vessel, wherein the solvent is preferably dichloromethane, then dissolving dichlorodiphenylsilane into dichloromethane to obtain a dichlorodiphenylsilane solution, slowly dripping the dichlorodiphenylsilane solution into the reaction vessel, wherein the reaction temperature is preferably 30-90 ℃, the reaction time is preferably 2-8h, the obtained product is preferably filtered, washing the filtrate with deionized water, and drying with sodium sulfate. After filtration, dichloromethane was removed from the organic layer by rotary evaporation. Finally, drying in a vacuum oven to obtain an intermediate product DSi; the mol ratio of the eugenol, the triethylamine and the dichlorodiphenylsilane is preferably (3-5) to (1-3). The reaction process is as follows:
step two, dripping the intermediate product DSi obtained in the step one into the suspension of m-chloroperoxybenzoic acid, and keeping the temperature of the reaction mixture in the dripping processSlowly heating to room temperature below 5 ℃, stirring for 24-150h, and performing post-treatment to obtain the bio-based epoxy resin shown in the formula (1) and suitable for the wet-process winding carbon fiber hydrogen storage bottle; the mol ratio of the intermediate product DSi to the m-chloroperoxybenzoic acid is preferably 1 (3-5), the post-treatment is preferably that the obtained mixture is filtered, the filtrate is washed by saturated sodium thiosulfate solution and saturated sodium bicarbonate solution in sequence, then the mixture is dried on anhydrous sodium sulfate, and the reaction product is filtered and rotary evaporated to remove CH 2 C1 2 Thereafter, further drying is carried out at 30-90 ℃ under vacuum. The reaction process is as follows:
the present invention is further illustrated by reference to the following specific examples, in which the starting materials are all commercially available.
Example 1
The infrared spectrum of the flame-retardant bio-based epoxy resin prepared in example 1 is shown in figure 1, and 3535cm of eugenol curve -1 Disappearance of the-OH peak at (C) and 773cm in the DSi curve of the novel intermediate -1 The disappearance of the Si-Cl bond signal peak represents the successful reaction of eugenol and dichlorodiphenylsilane, and 1122cm are shown in the ESR curve of the novel epoxy resin -1 This was also demonstrated by the formation of Si-O-C bonds, 1645cm in the eugenol feedstock curve -1 Peak value of (2) is represented by CH = CH 2 Caused by stretching vibration of the groups, disappears in the ESR curve of the novel epoxy resin, and simultaneously the ESR of the product is 909cm -1 And 829cm -1 The signal peak at the epoxy group confirms the formation of the epoxy group in EUEP.
The nuclear magnetic resonance hydrogen spectrum of the flame-retardant bio-based epoxy resin prepared in example 1 is shown in fig. 2, and the chemical shifts and the integral areas of all peaks are well matched with protons in the chemical structure of the novel epoxy resin ESR, which indicates that the target compound is successfully synthesized.
Example 1 differential thermogravimetric analysis graph of bio-based epoxy resin as shown in fig. 4, TGA curves of DDM cured bisphenol a type epoxy resin and novel epoxy resin ESR under nitrogen atmosphere, bisphenol a type epoxy resin has slightly higher initial decomposition temperature than novel epoxy resin ESR, but carbon residue rate of novel epoxy resin ESR is much higher than that of bisphenol a type epoxy resin, and excellent thermal stability is shown.
Example 1 the viscosity analysis profile of the bio-based epoxy resin is shown in FIG. 5, wherein a is a shear rate of 50rpm s -1 When the viscosity is changed with the temperature at 30-100 ℃, the viscosity of the bisphenol A type epoxy resin is firstly sharply reduced along with the temperature rise within 25-65 ℃; then keeping the temperature from 65 to 100 ℃ stable; in contrast, the viscosity of the ESR of the novel epoxy resin of the present invention is not significantly reduced from 25 to 100 ℃ and the viscosity of the ESR of the novel epoxy resin at 100 ℃ is still lower than that of the commercial bisphenol A type epoxy resin.
b is the viscosity at 25 ℃ with shear rate from 1 to 10 rpm.s -1 According to the change rule, the viscosity of the novel epoxy resin ESR and the viscosity of the bisphenol A epoxy resin are basically kept unchanged under different shear rates, and the constant viscosity is respectively 3.2130 Pa · s and 8.2144Pa · s. The viscosity of commercial bisphenol A is 2.6 times of ESR of the novel epoxy resin synthesized by the invention, which shows that the resin of the invention is beneficial to improving the processing performance.
Example 2
The nuclear magnetic resonance hydrogen spectrum of the bio-based epoxy resin prepared in example 2 is shown in fig. 3, and the chemical shifts and the integral areas of all peaks are well matched with the protons in the chemical structure of the ESR of the novel epoxy resin, which indicates that the target compound is successfully synthesized.
Example 3
Example 4
Example 5
Claims (8)
1. The bio-based epoxy resin suitable for the wet-process winding carbon fiber hydrogen storage bottle is characterized in that the structural formula is shown as the formula (1):
2. the method for preparing bio-based epoxy resin suitable for wet-winding carbon fiber hydrogen storage bottle as shown in formula (1) of claim 1, comprising:
step one, adding eugenol, triethylamine and a solvent into a reaction container, and then adding dichlorodiphenylsilane to obtain an intermediate product DSi;
and step two, dripping the intermediate product DSi obtained in the step one into a suspension of meta-hydroperoxybenzoic acid, keeping the temperature of a reaction mixture below-5 ℃ in the dripping process, slowly heating to room temperature, stirring, and performing post-treatment to obtain the bio-based epoxy resin which is shown in the formula (1) and is suitable for the wet-process winding carbon fiber hydrogen storage bottle.
3. The method as set forth in claim 2, wherein the molar ratio of eugenol, triethylamine and dichlorodiphenylsilane in the first step is (3-5): (3-5): 1-3.
4. The method according to claim 2, wherein the solvent used in the first step is dichloromethane.
5. The preparation method of claim 2, wherein the reaction temperature of the first step is 30-90 ℃ and the reaction time is 2-8h.
6. The preparation method of claim 2, wherein the molar ratio of the intermediate product DSi to the m-chloroperoxybenzoic acid in the second step is 1 (3-5).
7. The preparation method according to claim 2, wherein the stirring time of the second step is 24-150h.
8. The preparation method according to claim 2, wherein the post-treatment in the second step is to filter the obtained mixture, and the filtrate is washed with saturated sodium thiosulfate solution and saturated sodium bicarbonate solution in sequence. The mixture was then dried over anhydrous sodium sulfate and the reaction product was filtered and rotary evaporated to remove CH 2 C1 2 Thereafter, further drying is carried out at 30-90 ℃ under vacuum.
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| CN106589317A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Biomass-based epoxy resin and preparation method thereof |
| CN110835402A (en) * | 2019-11-20 | 2020-02-25 | 长春工业大学 | Low-viscosity bio-based epoxy resin based on vanillin and preparation method thereof |
| US20200062888A1 (en) * | 2016-12-03 | 2020-02-27 | Soochow University | Biomass-based epoxy resin and preparation method thereof |
| CN113583216A (en) * | 2021-09-15 | 2021-11-02 | 福建蓝海黑石新材料科技有限公司 | Bio-based epoxy resin containing silicon-oxygen bond and preparation and application methods thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589317A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Biomass-based epoxy resin and preparation method thereof |
| US20200062888A1 (en) * | 2016-12-03 | 2020-02-27 | Soochow University | Biomass-based epoxy resin and preparation method thereof |
| CN110835402A (en) * | 2019-11-20 | 2020-02-25 | 长春工业大学 | Low-viscosity bio-based epoxy resin based on vanillin and preparation method thereof |
| CN113583216A (en) * | 2021-09-15 | 2021-11-02 | 福建蓝海黑石新材料科技有限公司 | Bio-based epoxy resin containing silicon-oxygen bond and preparation and application methods thereof |
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