CN115197174B - Binaphthol-based epoxy resin monomer, preparation method thereof and application thereof in preparation of all-bio-based epoxy resin - Google Patents
Binaphthol-based epoxy resin monomer, preparation method thereof and application thereof in preparation of all-bio-based epoxy resin Download PDFInfo
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- CN115197174B CN115197174B CN202210942640.9A CN202210942640A CN115197174B CN 115197174 B CN115197174 B CN 115197174B CN 202210942640 A CN202210942640 A CN 202210942640A CN 115197174 B CN115197174 B CN 115197174B
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- 239000000178 monomer Substances 0.000 title claims abstract description 91
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 72
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 25
- QQYNRBAAQFZCLF-UHFFFAOYSA-N furan-maleic anhydride adduct Chemical compound O1C2C3C(=O)OC(=O)C3C1C=C2 QQYNRBAAQFZCLF-UHFFFAOYSA-N 0.000 claims description 11
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000001419 dependent effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 241001274216 Naso Species 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- KCKZIWSINLBROE-UHFFFAOYSA-N 3,4-dihydro-1h-naphthalen-2-one Chemical compound C1=CC=C2CC(=O)CCC2=C1 KCKZIWSINLBROE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- -1 binaphthol compound Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 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 1
- 230000036541 health Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000013501 sustainable material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
-
- 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
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a binaphthol-based epoxy resin monomer, a preparation method thereof and application thereof in preparing full-biology-based epoxy resin, wherein the binaphthol-based epoxy resin monomer is a compound (S) -BOYB or a compound (+/-) -BOYB; the compound (+ -) -BOYB is a racemic mixture of the compound (S) -BOYB and the compound (R) -BOYB. The invention utilizes the glycidation of phenolic hydroxyl groups at two ends of binaphthol to obtain binaphthol-based epoxy resin monomer, and the invention also provides a bio-based epoxy resin material obtained by curing the bio-based epoxy resin monomer and a bio-based curing agent. The bio-based epoxy resin material prepared by the invention has the advantages of simple production process, simple operation process and green reaction raw materials, and solves the technical problems that the epoxy resin material in the prior art is excessively dependent on petrochemical resources and has toxicity; and the bio-based epoxy resin obtained in the polymerization process has good heat resistance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a bio-based epoxy resin monomer based on chiral binaphthol, a preparation method thereof and application thereof in preparation of epoxy resin.
Background
In recent years, bio-based polymers have attracted great attention, mainly due to excessive use of fossil fuels and reservoirs and increased emission of greenhouse gases, causing serious environmental problems. Bio-based polymers can be synthesized from renewable, non-edible, sustainable materials such as sucrose, lignin, and vegetable oils that do not interfere with human and animal foods. DGEBA is one of the most widely used thermosetting polymer types due to its excellent chemical and mechanical properties as an epoxy resin. Thermosetting polymers are widely used in various applications such as coatings, adhesives, composites, and the like. However, petroleum-based epoxy resins account for a significant proportion of the current epoxy market, and are heavily dependent on fossil sources. Moreover, the raw materials used for the production of bisphenol a (BPA) have serious effects on human health and the environment, and have been proven to be toxic to organisms as endocrine disruptors. In some countries, such as Canada and France, the use of BPA in the food packaging industry and food related materials has been banned. Accordingly, a great deal of research and development is devoted to replacing DGEBA with more environmentally friendly alternatives, and we have made a great deal of effort in terms of bisphenol a-substituted bio-based and environmentally friendly materials.
The epoxy resin can be synthesized from various types of bio-based materials, bio-based binaphthol can be prepared by bio-based cinnamic acid conversion, and is a good candidate for synthesizing the bio-based epoxy resin because the bio-based epoxy resin consists of aromatic rings and has higher mechanical and thermal properties. Furthermore, simultaneous curing based on bio-based curing agents to give novel polymers has not been reported. Therefore, the patent aims to construct a corresponding novel polymeric structure and initially take the novel polymeric structure as a raw material to construct a chiral heat-resistant bio-based epoxy resin material model.
Disclosure of Invention
The invention aims to: attempts in the process of the invention were made to provide by biobased monomer design and design of cure strategies:
1) Aiming at the defects of the existing monomer structure, the invention provides the bio-based epoxy resin monomer with different binaphthol chiral structures.
2) The invention also solves the technical problem of providing a preparation method of the binaphthol bio-based epoxy resin monomer.
3) The invention also solves the technical problem of providing all-bio-based epoxy resin high-molecular polymers with different compositions.
4) The invention also solves the technical problem of providing a preparation method of all-bio-based epoxy resin high-molecular polymer with different compositions.
In order to solve the first technical problem, the invention discloses a binaphthol bio-based epoxy resin monomer, wherein the binaphthol bio-based epoxy resin monomer is a compound (S) -BOYB or a compound (+/-) -BOYB;
wherein the compound (+ -) -BOYB is a racemic mixture of the compound (S) -BOYB and the compound (R) -BOYB;
in order to solve the second technical problem, the invention discloses a preparation method of the binaphthol bio-based epoxy resin monomer (S) -BOYB and (+/-) -BOYB, wherein the reaction path is shown in figure 1, and the preparation method comprises the following steps:
s1: carrying out a first reaction on raw material binaphthol and Epichlorohydrin (ECH) and a part of phase transfer catalyst;
s2: adding the rest of phase transfer catalyst and alkaline solution into the reaction material obtained in the step S1 to carry out a second reaction to obtain binaphthol epoxy resin monomer;
in step S1, the binaphthol compound includes (S) -1,1 '-binaphthol and (. + -.) -1,1' -binaphthol; when (S) -1,1' -binaphthol is adopted, the obtained epoxy resin monomer is (S) -BOYB; when (+ -) -BOYB is used, the epoxy resin monomer obtained is (+ -) -BOYB.
In step S1, the phase transfer catalyst includes, but is not limited to, benzyltriethylammonium chloride (tecac), tetraethylammonium bromide, tetrabutylammonium bromide, and the like.
In the step S1, the mol ratio of the binaphthol to the epichlorohydrin to the phase transfer catalyst is 1 (15-25): 0.1-0.2.
In step S1, the temperature of the first reaction is 70 to 90 ℃, preferably 80 ℃.
In the step S1, the time of the first reaction is 3-6 h.
In the step S2, the alkaline solution is any one or a combination of several of potassium carbonate solution, sodium hydroxide solution and potassium hydroxide solution; the mass concentration of the alkaline solution is 40% -60%, preferably 50%.
In the step S2, the molar ratio of the alkali in the alkaline solution to the epichlorohydrin is 1 (0.5-5), preferably 1 (4-5).
In the step S2, the mass ratio of the residual phase transfer catalyst to the partial phase transfer catalyst in the step S1 is 1 (0.5-1.5), preferably 1:1.
In step S2, the temperature of the second reaction is room temperature.
In the step S2, the time of the second reaction is 1-4 h.
In step S2, after the second reaction is finished, adding water for dilution, extracting reaction liquid, drying, filtering, decompressing filtrate, spin-removing solvent, and purifying to obtain binaphthol bio-based epoxy resin monomer (S) -BOYB or (+/-) -BOYB.
Wherein, the reaction is carried out in the stirring state with the rotating speed of 500-800 rpm, and the drying agent used in the post-treatment of the reaction synthesis step is anhydrous sodium sulfate.
In order to solve the third technical problem, the invention discloses a binaphthol bio-based epoxy resin which is a binary polymer formed by a monomer A1 or a monomer A and a monomer B; the monomer A is formed by mixing a monomer A1 and a monomer A2; namely, the binaphthol bio-based epoxy resin is a binary polymer composed of a monomer A1 and a monomer B, or a binary polymer composed of a mixture of a monomer A1 and a monomer A2 and a monomer B.
Wherein, the structural units of the monomer A1, the monomer A2 and the monomer B are respectively as follows:
wherein, the binary polymer formed by the monomer A1 and the monomer B has a repeated structural unit shown in a formula I; the binary polymer formed by the monomer A and the monomer B has a repeated structural unit shown in a formula II;
wherein,,
in the formula I, the a zone is formed by a monomer A1; zone B is formed from monomer B; m is more than or equal to 2, n is more than or equal to 2;
in the formula II, the a ' area is formed by mixing a monomer A1, a monomer A2 or a monomer A1 and a monomer A2, wherein the a ' area is not the monomer A1 at the same time, and the a ' area is not the monomer A2 at the same time; zone B is formed from monomer B; m is m 1 +m 2 ≥2，n≥2。
In order to solve the fourth technical problem, the invention discloses a preparation method of binaphthol-based bio-based epoxy resin, which comprises the steps of mixing binaphthol-based bio-based epoxy resin monomer with bio-based curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione, heating to completely melt, uniformly injection molding, and continuously heating and curing to obtain binaphthol-based all-bio-based epoxy resin.
In some embodiments, the preparation method of the binaphthol bio-based epoxy resin comprises the steps of mixing binaphthol bio-based epoxy resin monomer with bio-based curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione and catalyst 2-ethyl-4-methylimidazole, heating to completely melt, uniformly injecting the mixture, and continuously heating and curing the mixture to obtain the binaphthol full bio-based epoxy resin.
Wherein, the 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione biological curing agent can be prepared according to the prior art: the bio-based maleic anhydride and DCM are placed in a round bottom flask with a stirring magnet, the rotating speed is adjusted to 450rmp, and after the mixture is stirred uniformly, the bio-based furan is gradually added dropwise. After adding a condensing device, heating to 100 ℃, reacting for 1h, stopping the reaction, cooling and crystallizing at normal temperature, after crystallization is completed, placing in a sand core funnel for suction filtration, and repeatedly leaching with trace petroleum ether. The residual liquid was removed by rotary evaporation to give 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione as shown below as white crystals.
Wherein the molar ratio of the epoxy group in the binaphthol bio-based epoxy resin monomer to the anhydride in the bio-based curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione curing agent is (0.6-2.5): 1, preferably (0.6-1.4): 1, and more preferably (0.9-1.1): 1.
Wherein the temperature is raised to make the temperature of complete melting be 90-170 ℃.
Wherein the temperature of the heating and curing is 200-230 ℃.
Wherein the curing time is 2-5 h.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) The chiral binaphthol bio-based novel epoxy resin monomer structure and the preparation method thereof provided by the invention have the advantages that the prepared epoxy monomer is novel in structure, high in green degree, simple in reaction step, mild in condition and easy in raw material acquisition.
(2) The novel chiral polymer material with a novel structure is constructed based on the newly synthesized monomer structure, and development of the bio-based epoxy resin product can promote development of the bio-based material, and has important significance for promoting sustainable development of the whole high polymer material and other fields.
(3) The binaphthol can be prepared from the raw material binaphthol by a biological preparation method, namely cinnamic acid, beta-tetralone and beta-naphthol, and finally the bio-based raw material binaphthol is prepared, so that the monomer has high biological added value and good biological safety.
(4) The invention uses the full biological base structural unit component epoxy resin for the first time, the prepared biological base epoxy resin material has the advantages of simple production process, simple and convenient operation process and green reaction raw materials, and the technical problems that the epoxy resin material in the prior art is excessively dependent on petrochemical resources and has toxicity are solved; and the bio-based epoxy resin obtained in the polymerization process has good heat resistance.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 shows the reaction path of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of epoxy monomer (S) -BOYB.
FIG. 3 is a nuclear magnetic resonance carbon spectrum of epoxy monomer (S) -BOYB.
Fig. 4 shows the nmr hydrogen spectrum of the epoxy resin monomer (±) -bobb.
Fig. 5 shows the nmr carbon spectrum of the epoxy monomer (±) -bobb.
FIG. 6 is a Fourier infrared spectrum of the (S) -BOYB epoxy polymer of example 3.
FIG. 7 is a TGA graph of the (S) -BOYB epoxy resin polymer of example 3.
Fig. 8 is a fourier infrared spectrum of the (+ -) -bobb epoxy polymer of example 4.
Fig. 9 is a TGA profile of the (+ -) -bobb epoxy resin polymer of example 4.
Fig. 10 is a fourier infrared spectrum of the (S) -bobb epoxy polymer of example 5.
Fig. 11 is a fourier infrared spectrum of the (+ -) -bobb epoxy polymer of example 6.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1 preparation of binaphthol biobased epoxy monomer (S) -BOYB
(1) Under stirring, raw materials (S) -binaphthol (15 g), ECH (96.96 g) and TEBAC (1.18 g) were added to the reaction flask, and after the addition was completed, stirring and heating were performed, and when the temperature of the system was raised to 80 ℃, the time was started, TLC monitoring was performed, and the reaction was completed for 3 hours.
(2) Heating was stopped and the magnet was kept under stirring to cool the system to room temperature (25 ℃). TEBAC (1.18 g) and NaOH (8.4 g) were weighed out, and NaOH (8.4 g) and purified water (8.4 g) were formulated into an aqueous solution. The TEBAC and NaOH aqueous solution are added into the reaction bottle in sequence, the reaction is continuously stirred at room temperature, TLC monitoring is carried out, and the reaction is finished for 1.5 h.
(3) The reaction flask was removed, and a precipitate formed by the reaction was observed at the bottom of the flask. Purified water was added to the reaction flask and shaken until the precipitate was completely dissolved. And (3) extracting by using EA, and washing to remove salt impurities. Adding proper amount of anhydrous NaSO 4 The obtained solution is subjected to water removal operation until anhydrous NaSO is added 4 No longer agglomerates. Carrying out suction filtration operation by using a suction filtration funnel to remove anhydrous NaSO 4 The reaction mixture was concentrated after the solid.
(4) Separating the obtained product by silica gel chromatographic column, selecting PE/EA=2:1 system as eluent, spin-removing solvent, and drying to obtain white powdery solid 12.6g, wherein the separated product (S) -BOYB has hydrogen spectrum shown in figure 2 and carbon spectrum shown in figure 3, and the yield is 60.9%.
1 H NMR(400MHz,Chloroform-d)δ7.95(d,J＝9.0Hz,2H),7.91–7.80(m,2H),7.43(ddd,J＝9.0,3.8,2.8Hz,2H),7.34(ddd,J＝8.1,6.6,1.3Hz,2H),7.23(ddt,J＝9.7,6.7,1.4Hz,2H),7.14(ddt,J＝8.6,5.2,1.1Hz,2H),4.15(dddd,J＝24.5,11.4,5.9,3.2Hz,2H),4.06–3.93(m,2H),2.96(ddt,J＝7.2,4.3,2.1Hz,2H),2.60–2.50(m,2H),2.31(dddd,J＝12.1,9.4,4.6,2.7Hz,2H).
13C NMR(101MHz,CDCl3)δ154.08,153.99,153.94,133.99,129.66,129.61,129.54,127.97,126.44,126.41,125.49,125.46,123.97,123.94,120.72,120.63,116.23,116.21,116.07,116.01,70.57,69.99,69.88,50.36,50.34,44.49,44.38,44.33.
Example 2 preparation of binaphthol biobased epoxy monomer (. + -.) -BOYB
(1) Under stirring, raw materials (. + -.) -binaphthol (14 g), ECH (90.56 g) and TEBAC (1.12 g) were added to the reaction flask respectively, stirring was started with the magnet and heated, and when the temperature of the system was raised to 80 ℃, the time was started, TLC monitoring was performed, and the reaction was completed for 3 hours.
(2) Heating was stopped and the magnet was kept under stirring to cool the system to room temperature (25 ℃). TEBAC (1.12 g) and NaOH (7.84 g) were weighed out, and NaOH (7.84 g) and purified water (7.84 g) were formulated into an aqueous solution. The TEBAC and NaOH aqueous solution are added into the reaction bottle in sequence, the reaction is continuously stirred at room temperature, TLC monitoring is carried out, and the reaction is finished for 1.5 h.
(3) The reaction flask was removed, and a precipitate formed by the reaction was observed at the bottom of the flask. Purified water was added to the reaction flask and shaken until the precipitate was completely dissolved. And (3) extracting by using EA, and washing to remove salt impurities. Adding proper amount of anhydrous NaSO 4 The solution obtained is subjected to a water removal operation until no NaSO is added 4 No longer agglomerates. Carrying out suction filtration operation by using a suction filtration funnel to remove anhydrous NaSO 4 A solid.
(4) Separating the obtained product by silica gel chromatographic column, selecting PE/EA=2:1 system as eluent, spin-removing solvent, and drying to obtain yellow high-viscosity liquid 7.9g, wherein the separated product (. + -.) -BOYB has hydrogen spectrum shown in figure 4, and carbon spectrum shown in figure 5, and has yield of 40.5%.
1H NMR(400MHz,Chloroform-d)δ7.96(dd,J＝9.0,1.2Hz,2H),7.87(dd,J＝8.3,1.2Hz,2H),7.44(ddd,J＝9.0,3.8,2.8Hz,2H),7.34(ddd,J＝8.1,6.7,1.3Hz,2H),7.23(ddt,J＝8.2,6.7,1.5Hz,2H),7.20–7.11(m,2H),4.16(dddd,J＝24.6,11.4,5.9,3.2Hz,2H),4.06–3.95(m,2H),2.97(dtd,J＝7.2,4.2,2.8Hz,2H),2.60–2.51(m,2H),2.31(dddd,J＝12.1,9.5,5.0,2.7Hz,2H).
13C NMR(101MHz,CDCl3)δ154.09,154.08,153.98,153.93,133.98,129.66,129.54,127.96,126.44,126.41,125.49,125.46,123.97,123.94,120.72,120.63,116.22,116.20,116.07,116.01,70.57,69.99,69.88,50.36,50.34,44.49,44.38,44.33.
Example 3 preparation of (S) -binaphthol biobased epoxy resin
The binaphthol bio-based epoxy resin monomer (S) -BOYB (0.199 g) is weighed in a reaction bottle, a curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione (0.083 g) is metered in under the nitrogen atmosphere at 25 ℃, the temperature is raised to 130 ℃ while the materials are rapidly stirred, the materials are fully melted, uniformly mixed, the temperature is raised in a gradient way until a completely uniform solution is formed until the materials are cured, and the curing temperature is recorded to be 200 ℃. Curing for 2h at this temperature and cooling gave a brown clear epoxy polymer.
According to thermogravimetric data analysis under nitrogen, as shown in fig. 7, the initial decomposition temperature is 315 ℃, the maximum decomposition temperature is 417 ℃, and the obtained material has good heat resistance. As shown in FIG. 6, the infrared peaks (840 and 901cm of ethylene oxide in the original epoxy substrate are shown by judging the infrared data -1 Equi-intensity stretching vibration) and infrared peaks (1858 and 1789 cm) belonging to the anhydride group -1 ) The passage indicates that the epoxy groups of the epoxy resin have been completely polymerized with the anhydride groups (having the structure shown in formula I, m is 0.0005 mole, n is 0.0005 mole).
Polymer infrared data attribution: 1083cm -1 Vibrating carbon-oxygen bond in ether bond C-O-C; 1619cm -1 Is the vibration of the c=c bond in the olefinic bond; 1590,1506,1456cm -1 C=c stretching vibration of the benzene ring; 746cm -1 The left and right peaks are flexural vibrations of the four-hydrogen connected benzene ring on the naphthalene ring=c—h bond; 3400cm -1 The broad absorption peak at this point is the peak formed by the ring opening of the ethylene oxide leading to the appearance of OH groups.
EXAMPLE 4 preparation of (+ -) -binaphthol biobased epoxy resin
The binaphthol bio-based epoxy resin monomer (+/-) -BOYB (0.199 g) is weighed in a reaction bottle, the curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione (0.083 g) is metered in under the nitrogen atmosphere at 25 ℃, the temperature is raised to 130 ℃ while the materials are rapidly stirred, the materials are fully melted, uniformly mixed, the temperature is raised in a gradient way until a completely uniform solution is formed until the materials are cured, and the curing temperature is recorded to be 200 ℃. Curing for 2h at this temperature and cooling gave a brown clear epoxy polymer.
As shown in FIG. 9, the initial decomposition temperature was 344℃and the most suitable was obtained by thermogravimetric data analysis under nitrogenThe large decomposition temperature is 432 ℃, and the obtained material has good heat resistance. As shown in FIG. 8, the infrared peaks (840 and 900 cm) of ethylene oxide in the original epoxy substrate are shown by judging the infrared data -1 Equi-intensity stretching vibration) and infrared peaks (1858 and 1789 cm) belonging to the anhydride group -1 ) The passage indicates that the epoxy groups of the epoxy resin have been completely polymerized with the anhydride groups (having the structure shown in formula II, m 1 +m 2 0.0005mol and n 0.0005 mol).
Polymer infrared data attribution: 1083cm -1 Vibrating carbon-oxygen bond in ether bond C-O-C; 1620cm -1 Is the stretching vibration of C=C bond in the ethylenic bond; 1590,1506,1455cm -1 Telescoping vibration of benzene ring; 745cm -1 The left and right peaks are flexural vibrations of the four-hydrogen connected benzene ring on the naphthalene ring=c—h bond; 3421cm -1 The broad absorption peak at this point is the peak formed by the ring opening of the ethylene oxide leading to the appearance of OH groups.
Example 5 2 preparation of (S) -binaphthol biobased epoxy resin catalyzed by ethyl-4-methylimidazole
The binaphthol bio-based epoxy resin monomer (S) -BOYB (0.199 g) is weighed in a reaction bottle, and under the nitrogen atmosphere, the curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione (0.083 g) and the catalyst 2-ethyl-4-methylimidazole (0.00415 g) are metered in at 25 ℃, and the materials are heated to 90 ℃ and are stirred rapidly, so that the materials are melted fully and mixed uniformly. After mixing uniformly, heating is continued until solidification, and the solidification temperature is recorded to be 110 ℃. The temperature was maintained for 2h and cooled under N2 to give a brown clear epoxy polymer. The infrared is shown in fig. 10.
Polymer infrared data attribution: 1083cm -1 Vibrating carbon-oxygen bond in ether bond C-O-C; 1620cm -1 Is the vibration of the c=c bond in the olefinic bond; 1590,1506,1455cm -1 C=c stretching vibration of the benzene ring; 746cm -1 The left and right peaks are flexural vibrations of the four-hydrogen connected benzene ring on the naphthalene ring=c—h bond; 3421cm -1 The broad absorption peak at this point is the peak formed by the ring opening of the ethylene oxide leading to the appearance of OH groups.
Comparing the curing temperatures of example 3 and example 5 shows that the use of imidazole catalyst can significantly reduce the melting temperature and curing temperature, and increase the polymerization efficiency.
Example 62 preparation of (. + -.) -binaphthol biobased epoxy resin catalyzed by Ethyl-4-methylimidazole
The binaphthol bio-based epoxy resin monomer (+ -) -BOYB (0.199 g) is weighed in a reaction bottle, and the curing agent 4, 10-dioxatricyclo [5.2.1.02,6] is metered in under the nitrogen atmosphere at 25 DEG C]Decan-8-ene-3, 5-dione (0.083 g), catalyst 2-ethyl-4-methylimidazole (0.00415 g), was heated to 90 ℃ while stirring rapidly, to ensure adequate melting and uniform mixing of the materials. After mixing uniformly, heating is continued until solidification, and the solidification temperature is recorded to be 110 ℃. Curing for 2h at this temperature and under N 2 Cooling down gave a brown clear epoxy polymer. The infrared is shown in fig. 11.
Polymer infrared data attribution: 1083cm -1 Vibrating carbon-oxygen bond in ether bond C-O-C; 1619cm -1 Is the vibration of the c=c bond in the olefinic bond; 1591,1507,1457cm -1 Benzene ring c=c stretching vibration; 748cm -1 The left and right peaks are flexural vibrations of the four-hydrogen connected benzene ring on the naphthalene ring=c—h bond; 3415cm -1 The broad absorption peak at this point is the peak formed by the ring opening of the ethylene oxide leading to the appearance of OH groups.
The invention provides a binaphthol-based epoxy resin monomer, a preparation method thereof and an application thought and a method for preparing an all-bio-based epoxy resin, and the method and the way for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by a person skilled in the art without departing from the principle of the invention, and the improvements and the modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (9)
1. The preparation method of the binaphthol-based epoxy resin monomer is characterized by comprising the following steps:
s1: carrying out a first reaction on binaphthol and epichlorohydrin and a part of phase transfer catalyst; the phase transfer catalyst is selected from benzyl triethyl ammonium chloride, tetraethyl ammonium bromide and tetrabutyl ammonium bromide; the temperature of the first reaction is 70-90 ℃;
s2: adding the rest of phase transfer catalyst and alkaline solution into the reaction material obtained in the step S1 to carry out a second reaction to obtain binaphthol epoxy resin monomer; the temperature of the second reaction is room temperature;
the binaphthol-based epoxy resin monomer is a compound(S)-bobb, or compound(±)-BOYB；
Wherein the compound is(±)-BOYB is a compound(S)BOYB and Compounds(R)-a racemic mixture of bobbs;
。
2. the preparation method according to claim 1, wherein in the step S1, the molar ratio of binaphthol to epichlorohydrin to the phase transfer catalyst is 1 (15-25): 0.1-0.2.
3. The preparation method according to claim 1, wherein in the step S2, the molar ratio of the alkali in the alkaline solution to the epichlorohydrin is 1 (0.5-5).
4. A binaphthol bio-based epoxy resin is characterized by being a binary polymer formed by a monomer A1 or a monomer A and a monomer B; the monomer A is formed by mixing a monomer A1 and a monomer A2;
wherein, the structural units of the monomer A1, the monomer A2 and the monomer B are respectively as follows:
；
wherein, the binary polymer formed by the monomer A1 and the monomer B has a repeated structural unit shown in a formula I; the binary polymer formed by the monomer A and the monomer B has a repeated structural unit shown in a formula II;
wherein,,
in the formula I, the a zone is formed by a monomer A1; zone B is formed from monomer B; m is more than or equal to 2, n is more than or equal to 2;
in the formula II, the a ' area is formed by mixing a monomer A1, a monomer A2 or a monomer A1 and a monomer A2, wherein the a ' area is not the monomer A1 at the same time, and the a ' area is not the monomer A2 at the same time; zone B is formed from monomer B; m is m 1 +m 2 ≥2，n≥2。
5. The process for preparing binaphthol bio-based epoxy resin according to claim 4, wherein binaphthol based epoxy resin monomer and bio-based curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione are mixed, melted and cured to obtain the binaphthol bio-based epoxy resin.
6. The preparation method of claim 5, wherein binaphthol-based epoxy resin monomer, bio-based curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione and catalyst 2-ethyl-4-methylimidazole are mixed, melted and cured to obtain the epoxy resin.
7. The method according to claim 5, wherein the molar ratio of the epoxy group in the binaphthol-based epoxy resin monomer to the anhydride in the bio-based curing agent 4, 10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3, 5-dione is (0.6 to 2.5): 1.
8. The method according to claim 5, wherein the melting temperature is 90-170 ℃.
9. The method according to claim 5, wherein the curing temperature is 200-230 ℃.
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| JPH06184131A (en) * | 1992-12-17 | 1994-07-05 | Dainippon Ink & Chem Inc | Epoxy resin, its production, epoxy resin composition and semiconductor sealing material |
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