CN112876509A - Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin - Google Patents
Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin Download PDFInfo
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- CN112876509A CN112876509A CN202110395796.5A CN202110395796A CN112876509A CN 112876509 A CN112876509 A CN 112876509A CN 202110395796 A CN202110395796 A CN 202110395796A CN 112876509 A CN112876509 A CN 112876509A
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- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000000178 monomer Substances 0.000 title claims abstract description 80
- 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 title claims abstract description 58
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 56
- 239000004593 Epoxy Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012312 sodium hydride Substances 0.000 claims abstract description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 8
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical group CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 7
- 238000007707 calorimetry Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 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 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 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 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000008436 biogenesis Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
- C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
-
- 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
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- 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
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a bio-based flame-retardant magnolol epoxy monomer, a preparation method and application in flame-retardant epoxy resin. The preparation method of the bio-based flame-retardant magnolol epoxy monomer comprises the following steps: (1) stirring a mixed solution of magnolol, sodium hydride and tetrahydrofuran under the protection of inert gas; then reacting with diphenylphosphinic chloride to obtain an intermediate shown as a formula II; (2) and (3) reacting the solution of the intermediate shown in the formula II with m-chloroperoxybenzoic acid to obtain the bio-based flame-retardant magnolol epoxy monomer shown in the formula I. The bio-based flame-retardant magnolol epoxy monomer shown in formula I is prepared for the first time, is a novel bio-based phosphorus-containing epoxy structure, is a good flame-retardant auxiliary agent, is low in usage amount, has excellent compatibility in epoxy resin, is free of phosphorus removal after being cured, is high in safety, and has great market application value.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to a bio-based flame-retardant magnolol epoxy monomer, a preparation method and application thereof in flame-retardant epoxy resin.
Background
The bio-based polymer material mainly takes natural renewable resources such as starch, protein, cellulose, chitin, vegetable oil and the like as initial raw materials, and pays attention to the biogenesis and the renewability of the raw materials. It includes both degradable or compostable plastics and non-degradable plastics; either a thermoplastic material or a thermosetting resin. The polymer material takes renewable resources as main raw materials, reduces the dependence on petrochemical products and reduces CO2The emission of (2) is an important development direction of the current high polymer materials. At present, the research on bio-based polymer materials is mainly limited to some natural polymers or thermoplastic materials such as starch plastics, cellulose-based materials, bio-based materials, etc., and the research on bio-based thermosetting resins is relatively rare.
Epoxy resin is one of the most widely used thermosetting resins, and the worldwide production is about 500 million tons at present, wherein bisphenol A epoxy resin accounts for more than 85%. Although biocyclopropanols (derived from biobased glycerol) have been industrialized and are being produced in greater and greater quantities. Meanwhile, the research reports that bisphenol A has potential threat to the health of a living body. In view of the fact that the overall capacity of the bisphenol A epoxy resin market is still huge at present, a related new substitute product is developed on the basis, and the excellent performance of the novel epoxy resin can be further explored while a substitute effect is generated.
Based on the development of bio-based functional materials, the research on bio-based flame retardant materials is also initially promoted. 2019, patent CN201910539977.3 discloses a bio-based furan flame-retardant epoxy resin, a furan epoxy resin monomer is prepared based on hydroxymethylfurfural derivatization, and on the basis, the furan epoxy resin monomer is cured with different types of curing agents to develop a bio-based flame-retardant furan epoxy resin with a flame-retardant structure and a flame-retardant effect. The epoxy resin has the advantages of wide biological source, environmental protection, simple reaction process and good flame retardant property.
In recent years, the preparation of bio-based epoxy resins has progressed relatively rapidly, but the research on the flame retardant properties thereof as a whole has been relatively small. Therefore, it is important to develop a new epoxy monomer to optimize and replace bisphenol a epoxy resin.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a bio-based flame-retardant magnolol epoxy monomer shown in a formula I aiming at the defects of the prior art.
The invention also aims to solve the technical problem of providing a preparation method of the bio-based flame-retardant magnolol epoxy monomer.
The invention further aims to solve the technical problem of providing the application of the bio-based flame-retardant magnolol epoxy monomer.
In order to solve the first technical problem, the invention discloses a bio-based flame-retardant magnolol epoxy monomer shown as a formula I,
in order to solve the second technical problem, the invention discloses that the bio-based flame-retardant magnolol epoxy monomer is constructed by magnolol shown in a formula VII;
specifically, the preparation method of the bio-based flame-retardant magnolol epoxy monomer comprises the following steps:
(1) stirring a mixed solution of magnolol, sodium hydride and tetrahydrofuran shown in a formula VII under the protection of inert gas; then reacting with diphenylphosphinic chloride to obtain an intermediate shown as a formula II;
(2) reacting the solution of the intermediate shown in the formula II with m-chloroperoxybenzoic acid to obtain a bio-based flame-retardant magnolol epoxy monomer shown in the formula I;
in the step (1), the mixed solution is prepared by adding excessive tetrahydrofuran into magnolol and sodium hydride under ice bath.
In the step (1), the dosage ratio of magnolol, sodium hydride and tetrahydrofuran is 1 mmol: 1.7-2.7 mmol: 4.8-5.8 mL; preferably, the ratio of the magnolol to the sodium hydride to the tetrahydrofuran is 1 mmol: 2.2 mmol: 5.3-5.4 mL.
In step (1), the inert gas is preferably nitrogen.
In the step (1), the stirring is performed in an ice bath.
In the step (1), the stirring time is 5-25 min; preferably, the stirring time is 15 min.
In the step (1), the mole ratio of magnolol to diphenylphosphine chloride is 1: 1.7-2.7; preferably, the mole ratio of magnolol to diphenylphosphine chloride is 1: 2.2.
in the step (1), the reaction is carried out under a stirring state.
In the step (1), the reaction temperature is 20-30 ℃; preferably, the temperature of the reaction is room temperature.
In the step (1), the reaction time is 1-5 h; preferably, the reaction time is 3 h.
In the step (1), after the reaction is finished, adding a mixture of ethyl acetate and water into the cooled reaction solution, standing, adding saturated saline solution, extracting, collecting an organic phase, drying, filtering, concentrating under reduced pressure, and carrying out column chromatography to obtain the intermediate shown in the formula II.
Wherein, in the mixture, the volume ratio of the ethyl acetate to the water is 1: 0.2-1.8; preferably, the volume ratio of ethyl acetate to water in the mixture is 1: 1.
wherein the standing time is 10-50 min; preferably, the standing time is 30 min.
Wherein the column chromatography is silica gel column chromatography.
In the step (2), the solution is prepared by adding excessive solvent into the intermediate shown in the formula II under ice bath.
In the step (2), the solvent of the solution is dichloromethane.
In the step (2), the concentration of the intermediate in the solution is 0.19-0.29 mmol/mL; preferably, the concentration of the intermediate in the solution is 0.24 mmol/mL.
In the step (2), under the condition that the m-chloroperoxybenzoic acid is in an ice bath, the m-chloroperoxybenzoic acid is added into the solution in batches within 20-40 min.
In the step (2), the molar ratio of the intermediate to m-chloroperoxybenzoic acid is 0.2-0.3: 1; preferably, the molar ratio of the intermediate to m-chloroperoxybenzoic acid is 0.25: 1.
in the step (2), the reaction is carried out under a stirring state.
In the step (2), the reaction temperature is 20-30 ℃; preferably, the temperature of the reaction is room temperature.
In the step (2), the reaction time is 1-7 h; preferably, the reaction time is 4 h.
In the step (2), after the reaction is finished, neutralizing residual m-chloroperoxybenzoic acid with a saturated sodium bicarbonate aqueous solution, washing the reaction solution for multiple times with a saturated saline solution, combining organic phases, drying, filtering, concentrating, and carrying out column chromatography to obtain the bio-based flame-retardant magnolol epoxy monomer shown in the formula I.
Wherein the column chromatography is silica gel column chromatography.
In order to solve the third technical problem, the invention discloses an application of the bio-based flame-retardant magnolol epoxy monomer in preparation of epoxy resin.
Wherein the application comprises the following steps:
(i) introducing inert gas into an epoxy resin monomer containing the bio-based flame-retardant magnolol epoxy monomer shown in the formula I to obtain deoxidized epoxy resin;
(ii) under inert gas, melting the deoxidized epoxy resin monomer obtained in the step (i) and a curing agent at high temperature, uniformly stirring, and pouring into a mold;
(iii) and (iii) curing the mold obtained in the step (ii) at high temperature in an inert gas atmosphere, and demolding to obtain the epoxy resin.
In the step (I), the epoxy resin monomer is a bio-based flame-retardant magnolol epoxy monomer shown in formula I, or a mixture of the bio-based flame-retardant magnolol epoxy monomer shown in formula I and a monomer shown in formula III; preferably, the epoxy resin monomer is a mixture of a bio-based flame-retardant magnolol epoxy monomer shown in formula I and a monomer shown in formula III;
in the step (I), the addition amount of the bio-based flame-retardant magnolol epoxy monomer shown in the formula I is controlled, so that the content of the P element in the bio-based flame-retardant magnolol epoxy monomer shown in the formula I accounts for 0.5-8 wt% of the total amount of the epoxy resin monomer and the curing agent; preferably, the addition amount of the bio-based flame-retardant magnolol epoxy monomer shown in the formula I is controlled so that the content of the P element in the bio-based flame-retardant magnolol epoxy monomer shown in the formula I accounts for 2-6 wt% of the total amount of the epoxy resin monomer and the curing agent.
In step (i), the inert gas is preferably nitrogen.
In step (ii), the inert gas is preferably nitrogen.
In the step (ii), the curing agent is a diamine curing agent; preferably, the curing agent is menthane diamine shown in formula IV;
in the step (ii), the addition amount of the curing agent is controlled so that the molar ratio of the ethylene oxide in the epoxy monomer to the-NH functional group in the curing agent is 1: 0.15-0.85; preferably, the curing agent is added in an amount such that the molar ratio of ethylene oxide in the epoxy monomer to-NH functional groups in the curing agent is 1: 0.20-0.45.
In the step (ii), the high-temperature melting temperature is 55-180 ℃; preferably, the temperature of the high-temperature melting is 100-.
In step (iii), the inert gas is preferably nitrogen.
In step (iii), the temperature of the high-temperature curing is 180-245 ℃; preferably, the temperature of the high-temperature curing is 195-225 ℃.
In the step (iii), the high-temperature curing time is 2-10 h; preferably, the high-temperature curing time is 2-4 h.
Wherein the epoxy resin is a repeating unit structure network structure shown in formula VI or a network structure composed of structural units shown in formula V and formula VI;
wherein m and n are independently selected from 2 to 1000.
Wherein the maximum heat release rate of the epoxy resin is 134.75-431.95W/g; wherein the maximum heat release rate is according to the micro combustion calorimetry test (Umesh Choudhury, Aambid A. Mir, and Todd Emrick, Soluble, alkali-Functionalized deoxybenzene Polymers, Macromolecules2017, 50, 3772-) -3778).
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the raw material of the biological-based raw material magnolol is wide in source and high in biological safety, can fully realize high-efficiency utilization of biological resources, and meets the development requirement of green chemistry. The curing agent used in the invention is a bio-based derivative, belongs to a bio-based curing agent, and has low toxicity and relatively high biological safety.
(2) The epoxy resin material disclosed by the invention is simple and efficient in curing process, very suitable for large-scale production, and high in greening level compared with halogen-containing flame-retardant materials.
(3) The bio-based flame-retardant magnolol epoxy monomer shown in formula I is prepared for the first time, is a novel bio-based phosphorus-containing epoxy structure, is a good flame-retardant additive, is low in usage amount, has excellent compatibility in epoxy resin, is free of phosphorus removal after being cured, is high in safety, and has great market application value.
(4) The melting process of the bio-based flame-retardant magnolol epoxy monomer shown in the formula I and the monomer shown in the formula III is transparent and uniform, which shows that the blend of the bio-based flame-retardant magnolol epoxy monomer and the monomer shown in the formula III can form a homogeneous system and the two have high compatibility.
(5) The bio-based flame-retardant magnolol epoxy monomer prepared by the invention does not contain an olefin structure, has good structural stability, is not sensitive to low temperature and high temperature, is not easy to deteriorate and is easy to store.
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 shows the BOBDB of epoxy resin monomer1H-NMR。
Figure 2 is an IR spectrum of the magnolol polymer prepared (examples 2-5 and comparative example 1).
FIG. 3 is a TG spectrum of the prepared magnolol polymer (examples 2-5 and comparative example 1).
Figure 4 is an MCC spectrum of the magnolol polymer prepared (examples 2-5 and comparative example 1).
Figure 5 is a flame retardant experiment of the prepared magnolol polymer (example 4 and comparative example 1).
Detailed Description
The invention will be better understood from the following examples. However, it is easily understood by those skilled in the art that the descriptions of the embodiments are only for illustrating the present invention and should not be construed as limiting the detailed descriptions in the claims.
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.
In the following examples, the intermediate represented by formula II is intermediate DBDBD.
In the following examples, the bio-based flame retardant magnolol epoxy monomer shown in formula I is an epoxy resin monomer BOBDB; the monomer shown in the formula III is a DGEBA monomer.
Example 1: preparation of a bio-based flame-retardant magnolol epoxy monomer:
firstly, magnolol (9.98g, 37.5mmol) and sodium hydride (1.98g, 82.5mmol) are sequentially added into a clean three-necked bottle, excessive tetrahydrofuran (200mL) is added under ice bath to be fully dissolved, a reaction system is filled with nitrogen and stirred for 15min under the ice bath condition, diphenylphosphinic chloride (19.52g, 82.5mmol) is slowly added into a 50mL syringe and stirred for 3h at room temperature, and when the reaction is finished, the volume ratio of ethyl acetate to deionized water is 1: adding the solution 1 (60 mL each) into the reaction solution cooled in an ice bath, standing for 30min, adding a small amount of saturated saline solution, extracting the reaction solution with ethyl acetate, combining organic phases, drying the organic phases with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to obtain an intermediate DBDBDBD crude product; the crude product (PE: EA, 2/1 to 1/2) was eluted with a gradient of silica gel column chromatography to yield the white intermediate DBDBDBD (24g) in 93% yield.
The second step is that: adding a certain amount of intermediate DBDBDBD (24g, 36mmol) into an eggplant-shaped bottle, adding excessive dichloromethane (150mL) under ice bath to fully dissolve the intermediate DBDBDBD, uniformly stirring, adding m-chloroperoxybenzoic acid (24.850g, 0.144mol) in batches within 30min under ice bath condition, stirring for 4h at room temperature, neutralizing the residual m-chloroperoxybenzoic acid in the reaction solution by using saturated sodium bicarbonate aqueous solution when the reaction is completely carried out, washing the reaction solution for multiple times by using saturated salt water, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, filtering, and carrying out reduced pressure distillation to obtain a crude product of the bio-based flame-retardant magnolol epoxy monomer shown in the formula I; the crude product was eluted with a gradient of silica gel column chromatography (PE: EA, 1/1 to 1/2) to give the white epoxy resin monomer BOBDB (44.1g) in 89% yield with a hydrogen spectrum as shown in FIG. 1.
Example 2
Weighing DGEBA monomer (0.1g, 0.29mmol) and epoxy resin monomer BOBDB (0.037g, 0.053mmol) in a sample bottle, wherein the content of P element in the epoxy resin monomer BOBDB accounts for 2 wt% of the total mass of a reaction system, introducing nitrogen, removing oxygen components, adding menthane diamine (0.025g, 0.145mmol) in the nitrogen atmosphere, further removing air, heating to 55 ℃, melting the two (transparent and uniform in the melting process), uniformly mixing, and curing at 200 ℃ for 3 hours to obtain a light yellow transparent epoxy resin polymer. Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 431.95W/g.
Example 3
Weighing DGEBA monomer (0.1g, 0.29mmol) and epoxy resin monomer BOBDB (0.11g, 0.016mmol) in a sample bottle, namely the content of P element in the epoxy resin monomer BOBDB accounts for 4 wt% of the total mass of a reaction system, introducing nitrogen, removing oxygen components, adding menthane diamine (0.025g, 0.145mmol) under the nitrogen atmosphere, further removing air, heating to 65 ℃ to melt the two (the melting process is transparent and uniform), uniformly mixing, curing at 200 ℃ for 3h to obtain a light yellow transparent epoxy resin polymer. Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 303.24W/g.
Example 4
Weighing DGEBA monomer (0.1g, 0.29mmol) and epoxy resin monomer BOBDB (0.27g, 0.39mmol) in a sample bottle, namely the content of P element in the epoxy resin monomer BOBDB accounts for 6 wt% of the total mass of a reaction system, introducing nitrogen, removing oxygen components, adding menthane diamine (0.025g, 0.145mmol) under the nitrogen atmosphere, further removing air, heating to 80 ℃ to melt the two (the melting process is transparent and uniform), uniformly mixing, curing at 220 ℃ for 3h, and obtaining a light yellow transparent epoxy resin polymer. Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 134.75W/g.
Example 5
Weighing BOBDB monomer (0.1g, 0.14mmol) in a sample bottle, introducing nitrogen, removing oxygen components, adding menthane diamine (0.012g, 0.07mmol) in the atmosphere of nitrogen, further removing air, heating to 75 ℃ to melt and uniformly mix the BOBDB monomer and the menthane diamine, curing at 225 ℃ for 3h to obtain a light yellow transparent epoxy resin polymer. Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 154.25W/g.
Comparative example 1
Weighing DGEBA monomer (0.1g, 0.29mmol) in a sample bottle, introducing nitrogen, removing oxygen components, adding menthane diamine (0.025g, 0.145mmol) in the nitrogen atmosphere, further removing air, heating to 60 ℃ to melt and uniformly mix the DGEBA monomer and the menthane diamine, curing at 200 ℃ for 3h to obtain a light yellow transparent epoxy resin polymer. Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 483.01W/g.
Example 6: detection of magnolol epoxy resins prepared in examples 2 to 5 and Petroleum-based bisphenol A epoxy resin prepared in comparative example 1
(1) The IR and TG of magnolol epoxy resin (examples 2-5) and petroleum-based bisphenol A epoxy resin (comparative example 1) are shown in FIG. 2 and FIG. 3, respectively.
(2) Comparing the results of the Micro Combustion Calorimetry (MCC) experiments on magnolol epoxy resins (examples 2-5) and petroleum-based bisphenol a epoxy resins (comparative example 1), it can be seen from fig. 4 that the maximum heat release rate of the bio-based epoxy resin polymer material prepared by adding different phosphorus-containing magnolol epoxy resin monomers is significantly lower than that of the most widely used bisphenol a epoxy resin material in the current market, indicating that the bio-based epoxy resin polymer material has excellent flame retardancy.
(3) The cured epoxy was subjected to a flame test (as shown in fig. 5). Comparative example 1, which initially released heat by vigorous combustion and was still burning after 40s, failed to self-extinguish; while example 4 did not ignite, thus it is fully demonstrated that the novel magnolol epoxy resin polymer has good flame retardant properties.
The invention provides a bio-based flame-retardant magnolol epoxy monomer, a preparation method thereof, and a thought and a method for application in flame-retardant 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. A bio-based flame-retardant magnolol epoxy monomer shown as a formula I,
2. the preparation method of the bio-based flame-retardant magnolol epoxy monomer according to claim 1, comprising the steps of:
(1) stirring a mixed solution of magnolol, sodium hydride and tetrahydrofuran under the protection of inert gas; then reacting with diphenylphosphinic chloride to obtain an intermediate shown as a formula II;
(2) reacting the solution of the intermediate shown in the formula II with m-chloroperoxybenzoic acid to obtain a bio-based flame-retardant magnolol epoxy monomer shown in the formula I;
3. the preparation method according to claim 2, wherein in the step (1), the ratio of the magnolol, the sodium hydride and the tetrahydrofuran is 1 mmol: 1.7-2.7 mmol: 4.8-5.8 mL; the stirring is carried out in an ice bath; the stirring time is 5-25 min.
4. The method according to claim 2, wherein in the step (1), the molar ratio of magnolol to diphenylphosphinic chloride is 1: 1.7-2.7; the temperature of the reaction is 20-30 ℃.
5. The method according to claim 2, wherein in the step (2), the solvent of the solution is dichloromethane; in the solution, the concentration of the intermediate is 0.19-0.29 mmol/mL; the molar ratio of the intermediate to the m-chloroperoxybenzoic acid is 0.2-0.3: 1; the temperature of the reaction is 20-30 ℃.
6. Use of the bio-based flame retardant magnolol epoxy monomer of claim 1 in the preparation of an epoxy resin.
7. The use according to claim 6, characterized in that it comprises the following steps:
(i) introducing inert gas into an epoxy resin monomer containing the bio-based flame-retardant magnolol epoxy monomer shown in the formula I to obtain deoxidized epoxy resin;
(ii) melting the deoxidized epoxy resin monomer obtained in the step (i) and a curing agent at a high temperature, uniformly stirring, and pouring into a mold;
(iii) and (iii) curing the mold obtained in the step (ii) at high temperature in an inert gas atmosphere, and demolding to obtain the epoxy resin.
8. The use according to claim 6, wherein in step (I), the epoxy resin monomer is a bio-based flame retardant magnolol epoxy monomer of formula I, or a mixture of a bio-based flame retardant magnolol epoxy monomer of formula I and a monomer of formula III;
preferably, in the step (I), the addition amount of the bio-based flame-retardant magnolol epoxy monomer shown in the formula I is controlled so that the content of the P element in the bio-based flame-retardant magnolol epoxy monomer shown in the formula I accounts for 0.5-8 wt% of the total amount of the epoxy resin monomer and the curing agent.
9. The use according to claim 6, wherein in step (ii), the curing agent is a diamine-based curing agent; preferably, the curing agent is menthane diamine.
10. The use according to claim 6, wherein the epoxy resin is a network structure of a repeating unit structure shown in formula VI or a network structure composed of structural units shown in formula V and formula VI;
wherein m and n are independently selected from 2 to 1000.
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