CN115197174A - 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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- CN115197174A CN115197174A CN202210942640.9A CN202210942640A CN115197174A CN 115197174 A CN115197174 A CN 115197174A CN 202210942640 A CN202210942640 A CN 202210942640A CN 115197174 A CN115197174 A CN 115197174A
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- 239000000178 monomer Substances 0.000 title claims abstract description 92
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 78
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 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 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000001723 curing Methods 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 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
- QQYNRBAAQFZCLF-UHFFFAOYSA-N furan-maleic anhydride adduct Chemical compound O1C2C3C(=O)OC(=O)C3C1C=C2 QQYNRBAAQFZCLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 1
- 239000003637 basic solution Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000001419 dependent effect Effects 0.000 abstract description 2
- 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
- 238000003756 stirring Methods 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000243 solution Substances 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
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 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
- 238000001228 spectrum Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000004018 acid anhydride group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 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
- 125000001624 naphthyl group Chemical group 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
- 238000005303 weighing Methods 0.000 description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229930016911 cinnamic acid Natural products 0.000 description 3
- 235000013985 cinnamic acid Nutrition 0.000 description 3
- 238000001816 cooling Methods 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
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 238000009987 spinning Methods 0.000 description 3
- 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
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- 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 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-O 2-ethyl-5-methyl-1h-imidazol-3-ium Chemical compound CCC=1NC(C)=C[NH+]=1 ULKLGIFJWFIQFF-UHFFFAOYSA-O 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
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 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
- 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
- 238000005984 hydrogenation reaction 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
- 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
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 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
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 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
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-
- 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 all-bio-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 a binaphthol-based epoxy resin monomer, and 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 and operationThe process is simple and convenient, the reaction raw materials are green, 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.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a chiral binaphthol-based bio-based epoxy resin monomer, a preparation method thereof, and application thereof in preparation of epoxy resin.
Background
In recent years, bio-based polymers have attracted considerable attention, mainly due to the overuse of fossil fuels and reservoirs and the increase in greenhouse gas emissions, creating 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 food. DGEBA is one of the most widely used thermosetting polymer types as an epoxy resin due to its excellent chemical and mechanical properties. Thermosetting polymers are widely used in various applications such as coatings, adhesives, composites, and the like. However, petroleum-based epoxy resins account for a large proportion of the current epoxy market and are heavily dependent on fossil sources. But also the raw materials for the production of bisphenol a (BPA) have serious impact on human health and 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 has been devoted to replacing DGEBA with a more environmentally friendly alternative, and we have made a great deal of effort in terms of bisphenol a alternative biobased and environmentally friendly materials.
The epoxy resin can be synthesized by various types of bio-based materials, and the bio-based binaphthol can be prepared by converting bio-based cinnamic acid, so that the epoxy resin is a good candidate for synthesizing the bio-based epoxy resin, and has higher mechanical and thermal properties because the epoxy resin consists of aromatic rings. Furthermore, the simultaneous curing based on bio-based curing agents to give novel polymers has not been reported. Therefore, the method aims to construct a corresponding novel polymeric structure, and initially takes the polymeric structure as a raw material to construct a chiral heat-resistant biological epoxy resin material model.
Disclosure of Invention
The purpose of the invention is as follows: in the course of the present invention, attempts were made to provide, through bio-based monomer design and curing strategy design:
1) The invention aims to solve the technical problem of providing bio-based epoxy resin monomers with different binaphthol chiral structures aiming at the defects of the existing monomer structure.
2) The invention also aims to solve the technical problem of providing a preparation method of the binaphthol bio-based epoxy resin monomer.
3) The invention also aims to solve the technical problem of providing the all-biological epoxy resin high molecular polymer with different compositions.
4) The invention also aims to solve the technical problem of providing a preparation method of the all-biological epoxy resin high molecular polymer with different compositions.
In order to solve the first technical problem, the invention discloses a binaphthol biological epoxy resin monomer, wherein the binaphthol biological 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-based bio-based epoxy resin monomers (S) -BOYB and (+/-) -BOYB, wherein the reaction path is shown in fig. 1 and comprises the following steps:
s1: performing a first reaction on raw materials binaphthol, epichlorohydrin (ECH) and a partial phase transfer catalyst;
s2: adding the residual phase transfer catalyst and alkaline solution into the reaction material obtained in the step S1 to carry out a second reaction to obtain a binaphthol-based epoxy resin monomer;
in step S1, the binaphthol compound comprises (S) -1,1 '-binaphthol and (+/-) -1,1' -binaphthol; when (S) -1,1' -binaphthol is adopted, the obtained epoxy resin monomer is (S) -BOYB; when the (+/-) -BOYB is adopted, the obtained epoxy resin monomer is (+/-) -BOYB.
In step S1, the phase transfer catalyst includes, but is not limited to, benzyltriethylammonium chloride (TEBAC), tetraethylammonium bromide, tetrabutylammonium bromide, and the like.
In the step S1, the molar ratio of the binaphthol to the epichlorohydrin to the phase transfer catalyst is 1 (15-25) to 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 more of potassium carbonate solution, sodium hydroxide solution and potassium hydroxide solution; the mass concentration of the alkaline solution is 40-60%, preferably 50%.
In 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 step S2, the mass ratio of the residual phase transfer catalyst to the partial phase transfer catalyst in 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 to dilute, extracting reaction liquid, drying, filtering, decompressing and removing the solvent by spinning, and purifying to obtain the binaphthol bio-based epoxy resin monomer (S) -BOYB or (+/-) -BOYB.
Wherein, the reaction is carried out in the process under the stirring state with the rotating speed of 500-800 rpm, and drying agents used for post-treatment in the reaction synthesis step are 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 the monomer A1 and the monomer B, or a binary polymer composed of the monomer B and a mixture of the monomer A1 and the 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 repeating structural unit shown in a formula I; the binary polymer formed by the monomer A and the monomer B has a repeating structural unit shown as a formula II;
wherein the content of the first and second substances,
in formula I, the a region is composed of a monomer A1; the B region is composed of a 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 a monomer A1, a monomer A2 or a mixture of the monomer A1 and the monomer A2, and 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; the B area is composed of a monomer B; m is 1 +m 2 ≥2，n≥2。
In order to solve the fourth technical problem, the invention discloses a preparation method of the binaphthol-based bio-based epoxy resin, which comprises the steps of mixing a binaphthol-based bio-based epoxy resin monomer with a bio-based curing agent 4,10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3,5-diketone, heating to completely melt, uniformly injecting a mold, and then continuously heating and curing to obtain the binaphthol-based all-bio-based epoxy resin.
In some embodiments, the preparation method of the binaphthol-based bio-based epoxy resin comprises the steps of mixing a binaphthol-based bio-based epoxy resin monomer, a bio-based curing agent 4,10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3,5-dione and a catalyst 2-ethyl-4-methylimidazole, heating to completely melt, uniformly injecting, and then continuously heating and curing to obtain the binaphthol-based all-bio-based epoxy resin.
Wherein, the 4,10-dioxane [5.2.1.02,6] deca-8-ene-3,5-diketone biological curing agent can be prepared according to the prior art: placing the bio-based maleic anhydride and DCM into a round-bottom flask with a stirring magneton, adjusting the rotating speed to 450rmp, and gradually dropwise adding the bio-based furan after uniformly stirring. And (3) adding a condensing device, heating to 100 ℃, reacting for 1h, terminating the reaction, cooling and crystallizing at normal temperature, placing in a sand core funnel for suction filtration after complete crystallization, and repeatedly leaching with trace petroleum ether. The residual liquid was removed by rotary evaporator to obtain 4,10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3,5-dione 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-diketone 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 rise enables the temperature of complete melting to be 90-170 ℃.
Wherein the temperature for raising the temperature and curing is 200-230 ℃.
Wherein the curing time is 2-5 h.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) According to the structure of the novel chiral binaphthol bio-based epoxy resin monomer and the preparation method thereof, the prepared epoxy monomer is novel in structure, high in greenization degree, simple in reaction steps, mild in conditions and easy to obtain raw materials.
(2) The invention constructs a chiral polymer material with a novel structure based on a newly synthesized monomer structure, and the development of the biological epoxy resin product can promote the development of a biological base material and has important significance for promoting the sustainable development of the fields of the whole high polymer material and the like.
(3) The binaphthol can be prepared by a biological preparation method, and the raw material binaphthol can be prepared from cinnamic acid through hydrogenation of cinnamic acid, beta-tetralone and beta-naphthol, so that the biological additional value of the monomer is high, and the biological safety is good.
(4) The invention uses the epoxy resin of the full-bio-based structural unit component for the first time, and the prepared bio-based epoxy resin material has the advantages of simple production process, simple and convenient operation process and green reaction raw materials, and solves the technical problems that the epoxy resin material in the prior art excessively depends on petrochemical resources and has toxicity; 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 further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a reaction scheme of the present invention.
FIG. 2 shows the NMR spectrum of epoxy monomer (S) -BOYB.
FIG. 3 is a carbon nuclear magnetic resonance spectrum of epoxy monomer (S) -BOYB.
FIG. 4 is a NMR spectrum of an epoxy monomer (+ -) -BOYB.
FIG. 5 is a NMR carbon spectrum of an epoxy monomer (+ -) -BOYB.
FIG. 6 is a Fourier infrared spectrum of (S) -BOYB epoxy resin polymer of example 3.
FIG. 7 is a TGA trace of the (S) -BOYB epoxy polymer of example 3.
FIG. 8 is a Fourier infrared spectrum of the (+ -) -BOYB epoxy resin polymer of example 4.
FIG. 9 is a TGA plot of the (+ -) -BOYB epoxy resin polymer of example 4.
FIG. 10 is a Fourier infrared spectrum of (S) -BOYB epoxy resin polymer of example 5.
FIG. 11 is a Fourier infrared spectrum of the (+ -) -BOYB epoxy resin 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 are commercially available, unless otherwise specified.
EXAMPLE 1 preparation of Bionaphthol Biobased epoxy resin monomer (S) -BOYB
(1) Under the stirring condition, the raw materials of (S) -binaphthol (15 g), ECH (96.96 g) and TEACC (1.18 g) are respectively added into a reaction bottle in a stirring way, after the addition is finished, the stirring and the heating are carried out, when the temperature of the system is raised to 80 ℃, the timing is started, the TLC monitoring is carried out, and the reaction is finished for 3 h.
(2) The heating was stopped, the magneton stirring was maintained and the system was allowed to cool to room temperature (25 ℃). TEABAC (1.18 g) and NaOH (8.4 g) were weighed out and NaOH (8.4 g) was made up with purified water (8.4 g) as an aqueous solution. And sequentially adding the TEBAC and the NaOH aqueous solution into the reaction bottle, continuously stirring the reaction at room temperature, monitoring by TLC, and finishing the reaction for 1.5 h.
(3) The reaction flask was removed and the bottom of the flask was observed to contain a precipitate formed by the reaction. Purified water was added to the reaction flask and shaken until the precipitate was completely dissolved. EA is used for extraction, and water washing is carried out to remove salt impurities. Adding a proper amount of anhydrous NaSO 4 The resulting solution is subjected to a water removal operation until anhydrous NaSO is added 4 No more caking. Performing suction filtration operation with suction filtration funnel to remove anhydrous NaSO 4 After the solid, the reaction solution was concentrated.
(4) Separating the obtained product by silica gel chromatography column, selecting PE/EA =2:1 system as eluent, removing solvent by spinning, drying to obtain white powdery solid 12.6g, namely the separated product (S) -BOYB, wherein the hydrogen spectrum is shown in figure 2, the carbon spectrum is 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 Bioepoxy resin monomers (+ -) -BOYB of binaphthol
(1) Under the stirring condition, respectively adding the raw materials (+/-) -binaphthol (14 g), ECH (90.56 g) and TEBAC (1.12 g) into a reaction bottle, starting magneton stirring and heating, starting timing when the temperature of the system is raised to 80 ℃, monitoring by TLC, and finishing the reaction for 3 h.
(2) The heating was stopped, the magneton stirring was maintained and the system was allowed to cool to room temperature (25 ℃). TEABAC (1.12 g) and NaOH (7.84 g) were weighed out and prepared as an aqueous solution with NaOH (7.84 g) and purified water (7.84 g). And sequentially adding the TEBAC and the NaOH aqueous solution into the reaction bottle, continuously stirring the reaction at room temperature, monitoring by TLC, and finishing the reaction for 1.5 h.
(3) The reaction flask was removed and the bottom of the flask was observed to contain a precipitate formed by the reaction. Purified water was added to the reaction flask and shaken until the precipitate was completely dissolved. EA is used for extraction, and water washing is carried out to remove salt impurities. Adding a proper amount of anhydrous NaSO 4 The resulting solution was subjected to a water removal operation until no NaSO was added 4 No more caking. Performing suction filtration operation with suction filtration funnel to remove anhydrous NaSO 4 And (3) a solid.
(4) Separating the obtained product by using a silica gel chromatographic column, selecting a PE/EA =2:1 system as an eluent, removing the solvent by spinning, and drying to obtain 7.9g of yellow high-viscosity liquid, namely the separated product (+/-) -BOYB, wherein a hydrogen spectrum is shown in figure 4, a carbon spectrum is shown in figure 5, and the yield is 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 Bio-based epoxy resin
Weighing binaphthol bio-based epoxy resin monomer (S) -BOYB (0.199 g) in a reaction bottle, adding curing agent 4,10-dioxane [5.2.1.02,6] dec-8-ene-3,5-diketone (0.083 g) in a metering manner at 25 ℃ in nitrogen atmosphere, raising the temperature to 130 ℃ while rapidly stirring, ensuring that the materials are fully melted, uniformly mixing, and gradually raising the temperature to form a completely uniform solution until the solution is cured, wherein the curing temperature is recorded as 200 ℃. The temperature was maintained for curing for 2h, and after cooling, a brown clear epoxy polymer was obtained.
Through thermogravimetric data analysis under nitrogen, as shown in figure 7, the initial decomposition temperature is 315 ℃, the maximum decomposition temperature is 417 ℃, and the obtained material has good heat resistance. By judging the infrared data, as shown in FIG. 6, the infrared peaks (840 and 901 cm) of ethylene oxide in the original epoxy substrate -1 Equi-intensity stretching vibration) and infrared peaks (1858 and 1789 cm) belonging to acid anhydride group -1 ) The epoxy groups of the epoxy resin and the acid anhydride groups were completely polymerized (having the structure shown in formula I, m was 0.0005mol, n was 0.0005 mol).
Polymer infrared data attribution: 1083cm -1 C-O-C carbon-oxygen bond vibration of ether bond C-O-C; 1619cm -1 Being a olefinic bondVibration of the medium C = C key; 1590,1506,1456cm -1 C = C stretching vibration of the benzene ring; 746cm -1 The left and right peaks are bending vibrations of = C-H bond on benzene ring connected to tetrahydro on naphthalene ring; 3400cm -1 The broad absorption peak at (a) is a peak formed by the occurrence of OH groups due to the ring opening of ethylene oxide.
EXAMPLE 4 preparation of (+ -) -binaphthol bio-based epoxy resin
Weighing binaphthol bio-based epoxy resin monomer (+/-) -BOYB (0.199 g) in a reaction bottle, adding curing agent 4,10-dioxane [5.2.1.02,6] dec-8-ene-3,5-diketone (0.083 g) in a metering manner at 25 ℃ in nitrogen atmosphere, heating to 130 ℃ while rapidly stirring, ensuring that the materials are fully melted, uniformly mixing, and gradient heating to form a completely uniform solution until curing is realized, wherein the recording curing temperature is 200 ℃. The temperature was maintained for curing for 2h, and after cooling, a brown clear epoxy polymer was obtained.
Through thermogravimetric data analysis under nitrogen, as shown in figure 9, the initial decomposition temperature is 344 ℃, the maximum decomposition temperature is 432 ℃, and the obtained material has good heat resistance. By judging the infrared data, as shown in FIG. 8, the infrared peaks (840 and 900 cm) of ethylene oxide in the original epoxy substrate -1 Equi-intensity stretching vibration) and infrared peaks (1858 and 1789 cm) belonging to acid anhydride group -1 ) Elapsed, indicating that the epoxy group and the acid anhydride group of the epoxy resin have been completely polymerized (having the structure shown in formula II, m) 1 +m 2 0.0005mol, n 0.0005 mol).
Polymer infrared data attribution: 1083cm -1 C-O-C vibration of the carbon-oxygen bond in the ether bond; 1620cm -1 Stretching vibration of C = C bond in olefinic bond; 1590,1506,1455cm -1 Stretching and vibrating a benzene ring; 745cm -1 The left and right peaks are bending vibrations of = C-H bond on benzene ring connected to tetrahydro on naphthalene ring; 3421cm -1 The broad absorption peak at (A) is a peak formed by the presence of OH groups resulting from the ring-opening of ethylene oxide.
Example 5 preparation of 2-Ethyl-4-methylimidazole catalyzed (S) -binaphthol Bio-based epoxy resin
Weighing binaphthol bio-based epoxy resin monomer (S) -BOYB (0.199 g) in a reaction bottle, adding curing agent 4,10-dioxane [5.2.1.02,6] dec-8-ene-3,5-diketone (0.083 g) and catalyst 2-ethyl-4-methylimidazole (0.00415 g) in a metering manner at 25 ℃ in nitrogen atmosphere, heating to 90 ℃ and rapidly stirring to ensure that the materials are fully melted and uniformly mixed. After mixing well, continue to heat until cured, record the curing temperature as 110 ℃. The temperature was maintained for 2h of cure and cooled under N2 to give a brown clear epoxy polymer. Infrared is shown in fig. 10.
Polymer infrared data attribution: 1083cm -1 C-O-C carbon-oxygen bond vibration of ether bond C-O-C; 1620cm -1 Vibration of C = C bond in olefinic bond; 1590,1506,1455cm -1 C = C stretching vibration of benzene ring; 746cm -1 The left and right peaks are bending vibrations of = C-H bond on benzene ring connected to tetrahydro on naphthalene ring; 3421cm -1 The broad absorption peak at (a) is a peak formed by the occurrence of OH groups due to the ring opening of ethylene oxide.
Comparing the curing temperatures of example 3 and example 5, it can be seen that the use of imidazole catalyst can significantly reduce the melting temperature and curing temperature and improve the polymerization efficiency.
EXAMPLE 6 preparation of 2-Ethyl-4-methylimidazolium catalyzed (. + -.) -binaphthol Bio-based epoxy resin
Weighing binaphthol bio-based epoxy resin monomer (+/-) -BOYB (0.199 g) in a reaction bottle, and adding curing agent 4,10-dioxane [5.2.1.02,6] in a metering manner at 25 ℃ in nitrogen atmosphere]Deca-8-ene-3,5-dione (0.083 g) and catalyst 2-ethyl-4-methylimidazole (0.00415 g) are heated to 90 ℃ and rapidly stirred at the same time, so that the materials are fully melted and uniformly mixed. After mixing well, continue to heat until cured, record the curing temperature as 110 ℃. Curing at this temperature for 2h and N 2 And then cooled to obtain a brown clear epoxy resin polymer. Infrared is shown in fig. 11.
Polymer infrared data attribution: 1083cm -1 C-O-C vibration of the carbon-oxygen bond in the ether bond; 1619cm -1 Vibration of C = C bond in olefinic bond; 1591,1507,1457cm -1 Benzene ring C = C stretching vibration; 748cm -1 The left and right peaks are bending vibrations of = C-H bond on benzene ring connected to tetrahydro on naphthalene ring; 3415cm -1 Is a ringThe ring opening of ethylene oxide results in the appearance of OH groups.
The invention provides a dinaphthol-based epoxy resin monomer, a preparation method thereof, and a thought and a method for application in preparation of a full-bio-based epoxy resin, and a plurality of methods and ways for realizing the technical scheme are provided. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. The binaphthol-based epoxy resin monomer is characterized in that the binaphthol-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;
2. the method for preparing the binaphthol-based epoxy resin monomer according to claim 1, comprising the steps of:
s1: performing a first reaction on binaphthol, epoxy chloropropane and a part of phase transfer catalyst;
s2: and (3) adding the residual phase transfer catalyst and alkaline solution into the reaction material obtained in the step (S1) to perform a second reaction to obtain the binaphthol-based epoxy resin monomer.
3. The preparation method as claimed in claim 2, wherein in step S1, the molar ratio of the binaphthol to the epichlorohydrin to the phase transfer catalyst is 1 (15-25) to (0.1-0.2).
4. The process according to claim 2, wherein in step S2, the molar ratio of the base in the basic solution to epichlorohydrin is 1 (0.5-5).
5. The 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 repeating structural unit shown in a formula I; the binary polymer formed by the monomer A and the monomer B has a repeating structural unit shown as a formula II;
wherein the content of the first and second substances,
in formula I, the a region is composed of a monomer A1; the B region is composed of a 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 a monomer A1 and a monomer A2 or a mixture of the monomer A1 and the monomer A2, and the a ' area is not simultaneously the monomer A1, and the a ' area is not simultaneously the monomer A2; the B region is composed of a monomer B; m is 1 +m 2 ≥2，n≥2。
6. The preparation method of the binaphthol bio-based epoxy resin as claimed in claim 5, wherein the binaphthol bio-based epoxy resin is prepared by mixing, melting and curing a binaphthol epoxy resin monomer and a bio-based curing agent 4,10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3,5-diketone.
7. The preparation method of claim 6, wherein the binaphthol-based epoxy resin monomer is mixed with a bio-based curing agent 4,10-dioxatricyclo [5.2.1.02,6] dec-8-ene-3,5-diketone and a catalyst 2-ethyl-4-methylimidazole, and then the mixture is melted and cured to obtain the binaphthol-based epoxy resin.
8. The preparation method according to claim 6, 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 (0.6-2.5): 1.
9. The method of claim 6, wherein the melting temperature is 90 to 170 ℃.
10. The method according to claim 6, wherein the curing temperature is 200 to 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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