CN109111479B - High-refractive-index optical resin based on natural product eugenol and preparation method thereof - Google Patents
High-refractive-index optical resin based on natural product eugenol and preparation method thereof Download PDFInfo
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 title claims abstract description 149
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000005770 Eugenol Substances 0.000 title claims abstract description 82
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229960002217 eugenol Drugs 0.000 title claims abstract description 82
- 230000003287 optical effect Effects 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 229930014626 natural product Natural products 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000003553 thiiranes Chemical group 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 58
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 54
- 239000004593 Epoxy Substances 0.000 claims description 53
- -1 hexaeugenol oxygen Chemical compound 0.000 claims description 44
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 20
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 17
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 17
- 238000002390 rotary evaporation Methods 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000012044 organic layer Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 8
- 239000010413 mother solution Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a high-refractive index optical resin based on a natural product eugenol and a preparation method thereof, belonging to the technical field of organic polymers. The monomer is a resin prepared based on eugenol and is used for optical lenses. The star-shaped molecule obtained by taking the phosphazene ring as the core has certain flame retardance, and the stability and the mechanical property of the polymer are improved due to the benzene ring structure in the eugenol, so that the application prospect is wider; the refractive index of the polymer obtained after ring-opening polymerization of the episulfide group is improved, and the dispersion degree is increased due to no introduction of a biphenyl structure.
Description
Technical Field
The invention belongs to the field of optical resin synthesis, and particularly relates to eugenol derivative episulfide resin and a preparation method thereof.
Background
Conventional optical resin materials such as: the refractive index of PMMA (1.492), PCR-39(n is 1.50), and the like is limited, and increasing the refractive index of the optical material can reduce the curvature, thickness, and mass of the material, which is advantageous for the development of light weight and miniaturization of the optical material, and also for the expansion of the application range in the fields of optical research, optical devices, and the like.
The optical properties of the polymer are related to the molecular structure. One way to increase the refractive index of optical resins is to introduce sulfur. The sulfur atoms not only have high molar refraction degree, but also have lower dispersion and density, and are beneficial to balancing physicochemical properties and other optical properties. The sulfur-containing optical resin includes optical resins containing polythioether, sulfolane, sulfur-containing polyimide, polyurethane, and the like. The high refractive index episulfide resin is one of the more popular research directions at present. The epoxy resin has a structure with an episulfide group, has higher reactivity, can be cured at low temperature, has high curing speed and higher refractive index compared with epoxy resin, and has higher refractive index along with the increase of sulfur content.
One way is to synthesize 1, 3, 5-thiocyclopropyl mercaptomethylbenzene with the refractive index of 1.662 and the Abbe number of 46 by using mesitylene as a raw material, and obtain a transparent film with the refractive index of 1.671 and the Abbe number of 31 after polymerization.
One way is to obtain allyl bisphenol A epoxy resin by diallyl bisphenol A and epichlorohydrin and then react with potassium thiocyanate to obtain partially ring-vulcanized epoxy/episulfide resin.
One way is to obtain bisphenol A episulfide resin by the reaction of bisphenol A epoxy compound and thiourea, wherein the weight ratio of episulfide epoxy is 1: the refractive index at 3 is 1.65.
However, the research raw materials of the method are all derived from petrochemical resources, and the resources are not renewable resources.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a method for synthesizing high refractive index episulfide resin monomer (HECP-ES) using eugenol (Eu), a natural product. .
The technical scheme of the invention is as follows:
a high refractive index optical resin (HECP-ES) based on natural product eugenol, characterized by the structural formula:
A preparation method of high-refractive-index optical resin based on natural product eugenol is characterized by comprising the following steps:
s1, dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in a proper solvent, and after adding eugenol dropwise, adding N2Adding a catalyst under protection, heating and stirring for reaction; cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on mother liquor, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product; recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol oxygen-based cyclotriphosphazene (HECP); the reaction equation is as follows:
s2, epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene; dissolving the product (HECP) in the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice-water bath, filtering after the reaction is finished, and washing the mother liquor by using potassium carbonate solution saturated saline water; after the liquid separation, the organic layer was dried over anhydrous sodium sulfate overnight; filtering, and performing rotary evaporation on the filtrate to obtain eugenol cyclotriphosphazene epoxide (HECP-EO); the reaction equation is as follows:
wherein n is 1, 2, 3, 4, 5, 6.
S3, epoxy episulfide conversion of eugenol cyclotriphosphazene epoxide (HECP-EO) to obtain a target episulfide monomer; mixing eugenol cyclotriphosphazene epoxy derivative (HECP-EO), a thioreagent and a solvent, and stirring for reaction at a constant temperature; after the reaction is finished, separating to obtain eugenol cyclotriphosphazene episulfide derivative (HECP-ES), and obtaining the high-refractive index optical resin monomer of eugenol; the reaction equation is as follows:
in the general structural formula, n is 1, 2, 3, 4, 5 and 6.
Further, in the step S1, the catalyst is one or more of sodium, anhydrous potassium carbonate, and the like, and the molar ratio of the used amount of the catalyst to hexachlorocyclotriphosphazene is 6-20: 1.
further, in step S1, the solvent is one or more of tetrahydrofuran, acetonitrile, acetone, and the like.
Further, in the step S1, the temperature of the heating reaction is 85 to 95 ℃.
Further, in the step S1, the molar ratio of the eugenol to the hexachlorocyclotriphosphazene is 6-12: 1.
further, in the step S2, the solvent is one or more of dichloromethane, tetrahydrofuran, acetone, cyclohexanone, toluene, xylene, cyclohexane, dichloroethane, tetrachloroethane, etc.
Further, in the step S2, the molar ratio of m-chloroperoxybenzoic acid to hexaeugenol epoxy cyclotriphosphazene is 1-12: 1.
further, in the step S3, the thioreagent is one or more of potassium thiocyanate, thiourea, ammonium thiocyanate and the like; the molar ratio of the thionating agent to the eugenol cyclotriphosphazene epoxy derivative is 1-12: 1.
further, in the step S3, the reaction temperature is 10-70 ℃, and the solvent is one or more of tetrahydrofuran, acetone, dichloromethane, dioxane, water, and the like.
By the scheme, the invention at least has the following advantages:
(1) the eugenol is a renewable resource, so that the dependence on fossil resources is effectively reduced, and the concept of green development is reflected;
(2) the star-shaped molecule obtained by taking the phosphazene ring as the core has certain flame retardance, and the stability and the mechanical property of the polymer are improved due to the benzene ring structure in the eugenol, so that the application prospect is wider;
(3) the refractive index of the polymer obtained after ring-opening polymerization of the episulfide group is improved, and the dispersion degree is increased due to no introduction of a biphenyl structure.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a graph showing the performance test of example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of hexaeugenol oxygen-based cyclotriphosphazene (HECP).
FIG. 3 is a nuclear magnetic hydrogen spectrum of eugenol cyclotriphosphazene epoxide (HECP-EO).
FIG. 4 is a nuclear magnetic hydrogen spectrum of the obtained eugenol cyclotriphosphazene episulfide (HECP-ES).
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, and after dropwise adding eugenol, adding N2The air was replaced and protected and then heated to 85 ℃ to stir the reaction for 48 h. And cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on the mother solution, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 9: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in a mixed solvent of dichloromethane, ethanol and water (the ratio is 1: 2: 1), and stirring for reaction at room temperature. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 8: 1.
example 2
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, and after dropwise adding eugenol, adding N2The air was replaced and protected and then heated to 85 ℃ to stir the reaction for 48 h. Cooling and filtering after the reaction is finishedAnd mother liquor is evaporated and concentrated in a rotary mode and then is precipitated in a potassium carbonate water solution, and a crude product is obtained. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 9: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in a mixed solvent of dichloromethane, ethanol and water (the ratio is 1: 2: 1), heating to 50 ℃, and stirring for reaction. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 8: 1.
example 3
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, and after dropwise adding eugenol, adding N2The air was replaced and protected and then heated to 85 ℃ to stir the reaction for 48 h. And cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on the mother solution, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 9: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in an acetone-water mixed solvent (4: 1), and stirring for reaction at room temperature. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 8: 1;
example 4
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, and after dropwise adding eugenol, adding N2The air was replaced and protected and then heated to 85 ℃ to stir the reaction for 48 h. And cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on the mother solution, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 9: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in a dioxane water mixed solvent (4: 1), and stirring for reaction at room temperature. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 8: 1.
example 5
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, dropwise adding eugenol,N2the air was replaced and protected and then heated to 90 ℃ to stir the reaction for 48 h. And cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on the mother solution, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 9: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in a dioxane water mixed solvent (4: 1), and stirring for reaction at 50 ℃. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 8: 1.
example 6
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, and after dropwise adding eugenol, adding N2The air was replaced and protected and then heated to 90 ℃ to stir the reaction for 48 h. And cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on the mother solution, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 6: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in a dioxane water mixed solvent (4: 1), and stirring for reaction at 50 ℃. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 8: 1.
example 7
Dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in anhydrous acetonitrile, and after dropwise adding eugenol, adding N2The air was replaced and protected and then heated to 90 ℃ to stir the reaction for 48 h. And cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on the mother solution, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product. Recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol epoxy cyclotriphosphazene. Wherein the molar ratio of hexachlorocyclotriphosphazene to eugenol to potassium carbonate is 1: 8: 15.
epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene. Dissolving the product of the first step in dichloromethane, adding m-chloroperoxybenzoic acid in batches in an ice water bath, and reacting for 48 hours. Then, the mixture was filtered, and the mother liquor was washed with a potassium carbonate solution saturated brine. After separation, the organic layer was dried over anhydrous sodium sulfate overnight. Filtering, and carrying out rotary evaporation on the filtrate to obtain the eugenol cyclotriphosphazene epoxy derivative. The molar ratio of the dosage of the m-chloroperoxybenzoic acid to the hexaeugenol oxygen-based cyclotriphosphazene is 3: 1.
and (3) carrying out epoxy episulfide conversion on the eugenol cyclotriphosphazene epoxy derivative to obtain the target episulfide monomer. Dissolving eugenol cyclotriphosphazene epoxy derivative and potassium thiocyanate in a dioxane water mixed solvent (4: 1), and stirring for reaction at 50 ℃. And separating after the reaction is finished to obtain the eugenol cyclotriphosphazene episulfide derivative. Wherein the molar ratio of the consumption of the potassium thiocyanate to the eugenol cyclotriphosphazene epoxy derivative is 4: 1.
the following performance tests were carried out using example 1 as an example:
as shown in FIG. 1, 5g of episulfide resin monomer (HECP-ES) obtained in example 1 was melted at 65 ℃, then 1% of N, N-dimethylaniline as a catalyst was added, the mixture was uniformly mixed and coated on a saline sheet for infrared test, infrared spectrum was measured once at room temperature as a control, then the infrared test was carried out after 1 hour of heat preservation at 65 ℃, then the infrared test was carried out after 1 hour of heat preservation at 75 ℃, and the like to observe whether the product was completely cured. Compared with the curing of epoxy resin monomer (HECP-EO), the curing agent has lower curing temperature and faster curing speed.
As shown in fig. 2, in the nuclear magnetic resonance hydrogen spectrum of HECP, peaks with chemical shifts δ of 6.92, 6.60, and 6.48ppm are assigned to three hydrogens No. 2, 1, and 3 on the benzene ring, peaks with chemical shifts δ of 5.90, and 5.04ppm are assigned to three hydrogens No. 6 and 7 on the allyl group, peaks with chemical shifts δ of 3.64ppm are assigned to the hydrogen of the methoxy group attached to the benzene ring, and peaks with chemical shifts δ of 3.28ppm are assigned to the hydrogen of the methylene group on the allyl group.
As shown in fig. 3, the nuclear magnetic resonance hydrogen spectrum of heceo has peaks with chemical shifts δ of 6.96, 6.69 and 6.59ppm assigned to three hydrogens No. 2, 1 and 3 on the benzene ring, a peak with chemical shift δ of 3.67ppm assigned to the hydrogen of the methoxy group attached to the benzene ring, a peak with chemical shift δ of 3.07ppm assigned to the hydrogen of methine No. 6 on the allyl group, a peak with chemical shift δ of 2.75ppm assigned to one hydrogen No. 7 on the epoxy group and the hydrogen of the methylene group attached to the benzene ring, and a peak with chemical shift δ of 2.51ppm assigned to the other hydrogen No. 7 on the epoxy group.
As shown in fig. 4, in the nuclear magnetic resonance hydrogen spectrum of HECPES, peaks with chemical shifts δ of 6.99 to 6.60ppm are assigned to hydrogen nos. 2, 1 and 3 on the benzene ring, peaks with chemical shifts δ of 3.70ppm are assigned to hydrogen of methoxy group connected to the benzene ring, peaks with chemical shifts δ of 3.13 and 2.99ppm are assigned to hydrogen of methylene group connected to the benzene ring, peaks with chemical shifts δ of 2.75ppm are assigned to hydrogen No. 6 on the methine group on the allyl group, and peaks with chemical shifts δ of 2.51 and 2.24ppm are assigned to hydrogen No. 7 on the methylene group in the epoxy group.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A high refractive index optical resin based on natural product eugenol is characterized in that the structural formula is as follows:
wherein N is 1, 2, 3, 4, 5, 6, N3P3Is cyclotriphosphazene.
2. A preparation method of high-refractive-index optical resin based on natural product eugenol is characterized by comprising the following steps:
the preparation method comprises the following steps:
s1, dissolving hexachlorocyclotriphosphazene and anhydrous potassium carbonate in a proper solvent, and heating and stirring for reaction under the protection of N2 after adding eugenol dropwise; cooling and filtering after the reaction is finished, carrying out rotary evaporation and concentration on mother liquor, and then precipitating in a potassium carbonate aqueous solution to obtain a crude product; recrystallizing with ethanol and dichloromethane mixed solvent to obtain hexaeugenol oxygen-based cyclotriphosphazene; the molar ratio of the anhydrous potassium carbonate to hexachlorocyclotriphosphazene is 6-20: 1;
the reaction equation is as follows:
in the step S1, the solvent is one or more of tetrahydrofuran, acetonitrile, and acetone;
in the step S1, the molar ratio of the eugenol to the hexachlorocyclotriphosphazene is 6-12: 1;
s2, epoxidizing the obtained hexaeugenol oxygen-based cyclotriphosphazene; dissolving the product of the first step in a solvent, adding m-chloroperoxybenzoic acid in batches in an ice water bath, filtering after the reaction is finished, and washing the mother liquor by saturated saline solution of potassium carbonate; after the liquid separation, the organic layer was dried over anhydrous sodium sulfate overnight; filtering, and performing rotary evaporation on the filtrate to obtain eugenol cyclotriphosphazene epoxide;
in the step S2, the molar ratio of m-chloroperoxybenzoic acid to hexaeugenol epoxy cyclotriphosphazene is 1-12: 1;
the reaction equation is as follows:
wherein n is 1, 2, 3, 4, 5, 6;
s3, performing epoxy episulfide conversion on eugenol cyclotriphosphazene epoxide to obtain a target episulfide monomer; mixing eugenol cyclotriphosphazene epoxy derivative, a thioreagent and a solvent, and stirring for reaction at a constant temperature; after the reaction is finished, separating to obtain the eugenol cyclotriphosphazene episulfide derivative, and obtaining the eugenol high-refractive index optical resin monomer; in the step S3, the thionating agent is one or more of potassium thiocyanate, thiourea, and ammonium thiocyanate; the molar ratio of the thionating agent to the eugenol cyclotriphosphazene epoxy derivative is 1-12: 1.
the reaction equation is as follows:
in the general structural formula, n is 1, 2, 3, 4, 5 and 6.
3. The method for preparing high refractive index optical resin based on natural product eugenol as claimed in claim 2, wherein: in the step S1, the temperature of the heating and stirring reaction is 85 to 95 ℃.
4. The process for the preparation of high refractive index optical resin based on natural product eugenol as claimed in claim 2, wherein: in the step S2, the solvent is one or more of dichloromethane, tetrahydrofuran, acetone, cyclohexanone, toluene, xylene, cyclohexane, dichloroethane, and tetrachloroethane.
5. The method for preparing high refractive index optical resin based on natural product eugenol as claimed in claim 2, wherein: in the step S3, the reaction temperature is 10-70 ℃, and the solvent is one or more of tetrahydrofuran, acetone, dichloromethane, dioxane and water.
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| EP2144092A1 (en) * | 2007-04-27 | 2010-01-13 | Hoya Corporation | Method for production of plastic lens |
| CN102219905A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院化学研究所 | Organic silicon episulfide resin and preparation method thereof |
| CN102329298A (en) * | 2011-07-22 | 2012-01-25 | 镇江俊视光学有限公司 | Optical resin monomer with high refractive index and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2144092A1 (en) * | 2007-04-27 | 2010-01-13 | Hoya Corporation | Method for production of plastic lens |
| CN102219905A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院化学研究所 | Organic silicon episulfide resin and preparation method thereof |
| CN102329298A (en) * | 2011-07-22 | 2012-01-25 | 镇江俊视光学有限公司 | Optical resin monomer with high refractive index and preparation method thereof |
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