CN109641823B - Monomers, polymers, preparation method and use thereof - Google Patents
Monomers, polymers, preparation method and use thereof Download PDFInfo
- Publication number
- CN109641823B CN109641823B CN201780052243.1A CN201780052243A CN109641823B CN 109641823 B CN109641823 B CN 109641823B CN 201780052243 A CN201780052243 A CN 201780052243A CN 109641823 B CN109641823 B CN 109641823B
- Authority
- CN
- China
- Prior art keywords
- polymer
- methyl
- preparation
- formula
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 197
- 239000000178 monomer Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 99
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 135
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 129
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 112
- 150000001875 compounds Chemical class 0.000 claims description 100
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 81
- -1 methoxy, ethoxy, n-propoxy, isopropoxy Chemical group 0.000 claims description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 57
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 56
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 36
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- 235000011181 potassium carbonates Nutrition 0.000 claims description 18
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000003586 protic polar solvent Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 3
- BWTMTZBMAGYMOD-UHFFFAOYSA-N (2,2,3,3,4,4,5,5-octafluoro-6-prop-2-enoyloxyhexyl) prop-2-enoate Chemical compound C=CC(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)COC(=O)C=C BWTMTZBMAGYMOD-UHFFFAOYSA-N 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- MBNMGGKBGCIEGF-UHFFFAOYSA-N 1,1-diethoxypropane Chemical compound CCOC(CC)OCC MBNMGGKBGCIEGF-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- HTWRFCRQSLVESJ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C(C)=C HTWRFCRQSLVESJ-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 208000010412 Glaucoma Diseases 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- XXRPVRKDBVYBAT-UHFFFAOYSA-N [2,2,3,3,4,4-hexafluoro-5-(2-methylprop-2-enoyloxy)hexyl] 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCC(C(C(C(C)OC(C(=C)C)=O)(F)F)(F)F)(F)F XXRPVRKDBVYBAT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 125000004344 phenylpropyl group Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 57
- 239000013078 crystal Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 82
- 238000002390 rotary evaporation Methods 0.000 description 67
- 238000012360 testing method Methods 0.000 description 64
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 54
- 230000003595 spectral effect Effects 0.000 description 45
- 238000005160 1H NMR spectroscopy Methods 0.000 description 41
- 150000002500 ions Chemical class 0.000 description 41
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 41
- 239000002904 solvent Substances 0.000 description 41
- 238000003756 stirring Methods 0.000 description 41
- 239000011734 sodium Substances 0.000 description 40
- 125000000217 alkyl group Chemical group 0.000 description 38
- 239000007788 liquid Substances 0.000 description 36
- 238000001228 spectrum Methods 0.000 description 33
- 150000003254 radicals Chemical class 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 235000019439 ethyl acetate Nutrition 0.000 description 28
- 238000004440 column chromatography Methods 0.000 description 27
- 238000004090 dissolution Methods 0.000 description 27
- 238000000926 separation method Methods 0.000 description 27
- YKONWVIRECCMQE-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methyl-6-prop-2-enylphenol Chemical compound CC1=CC(CC=C)=C(O)C(N2N=C3C=CC=CC3=N2)=C1 YKONWVIRECCMQE-UHFFFAOYSA-N 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 125000003545 alkoxy group Chemical group 0.000 description 19
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 125000003282 alkyl amino group Chemical group 0.000 description 14
- 239000012043 crude product Substances 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 14
- 125000003342 alkenyl group Chemical group 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 12
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 12
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 12
- 125000000304 alkynyl group Chemical group 0.000 description 10
- FOLYKNXDLNPWGC-UHFFFAOYSA-N 1-chloro-3-methoxypropan-2-ol Chemical compound COCC(O)CCl FOLYKNXDLNPWGC-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 125000004414 alkyl thio group Chemical group 0.000 description 9
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 9
- 125000004104 aryloxy group Chemical group 0.000 description 8
- 125000001188 haloalkyl group Chemical group 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 6
- XHIINWKFCZSGNY-UHFFFAOYSA-N 1-chloro-3-ethoxypropan-2-ol Chemical compound CCOCC(O)CCl XHIINWKFCZSGNY-UHFFFAOYSA-N 0.000 description 5
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CQLYXIUHVFRXLT-UHFFFAOYSA-N 2-methoxyethylbenzene Chemical compound COCCC1=CC=CC=C1 CQLYXIUHVFRXLT-UHFFFAOYSA-N 0.000 description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 4
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 4
- 208000002847 Surgical Wound Diseases 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- VCDHBSWDETVGCI-UHFFFAOYSA-N 1-ethoxy-3-(4-phenoxyphenoxy)propan-2-ol Chemical compound C(C)OCC(COC1=CC=C(C=C1)OC1=CC=CC=C1)O VCDHBSWDETVGCI-UHFFFAOYSA-N 0.000 description 3
- TYRUSIJKQXMLLQ-UHFFFAOYSA-N 1-ethoxy-3-phenoxypropan-2-ol Chemical compound CCOCC(O)COC1=CC=CC=C1 TYRUSIJKQXMLLQ-UHFFFAOYSA-N 0.000 description 3
- OXUZKCMICJWVFP-UHFFFAOYSA-N 1-methoxy-3-phenoxypropan-2-ol Chemical compound COCC(O)COC1=CC=CC=C1 OXUZKCMICJWVFP-UHFFFAOYSA-N 0.000 description 3
- ILZXXGLGJZQLTR-UHFFFAOYSA-N 2-phenylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=CC=C1 ILZXXGLGJZQLTR-UHFFFAOYSA-N 0.000 description 3
- OAOTXJJNMHSOOX-UHFFFAOYSA-N COCC(O)COc1ccc(Oc2ccccc2)cc1 Chemical compound COCC(O)COc1ccc(Oc2ccccc2)cc1 OAOTXJJNMHSOOX-UHFFFAOYSA-N 0.000 description 3
- 229910003827 NRaRb Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000004438 haloalkoxy group Chemical group 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 125000006413 ring segment Chemical group 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000001356 surgical procedure Methods 0.000 description 3
- MXGPEWGYQSGFDR-UHFFFAOYSA-N (1-ethoxy-3-phenoxypropan-2-yl) prop-2-enoate Chemical compound CCOCC(OC(=O)C=C)COC1=CC=CC=C1 MXGPEWGYQSGFDR-UHFFFAOYSA-N 0.000 description 2
- VBAHPKAZOVMUTL-UHFFFAOYSA-N (1-methoxy-3-phenoxypropan-2-yl) prop-2-enoate Chemical compound C(C=C)(=O)OC(COC)COC1=CC=CC=C1 VBAHPKAZOVMUTL-UHFFFAOYSA-N 0.000 description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 2
- QAEPWVOTNLNFNR-UHFFFAOYSA-N 1-ethoxy-3-(4-phenylphenoxy)propan-2-ol Chemical compound C(C)OCC(COC1=CC=C(C=C1)C1=CC=CC=C1)O QAEPWVOTNLNFNR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 2
- GJPDDECAMBDARC-UHFFFAOYSA-N COCC(O)COc1ccc(cc1)-c1ccccc1 Chemical compound COCC(O)COc1ccc(cc1)-c1ccccc1 GJPDDECAMBDARC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 208000002177 Cataract Diseases 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000262 haloalkenyl group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- IMNBHNRXUAJVQE-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound OC1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 IMNBHNRXUAJVQE-UHFFFAOYSA-N 0.000 description 1
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- HPSGLFKWHYAKSF-UHFFFAOYSA-N 2-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1=CC=CC=C1 HPSGLFKWHYAKSF-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- UGEJOEBBMPOJMT-UHFFFAOYSA-N 3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1 UGEJOEBBMPOJMT-UHFFFAOYSA-N 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- FAYGEALAEQKPDI-UHFFFAOYSA-N 4-(2-methoxyethyl)phenol Chemical compound COCCC1=CC=C(O)C=C1 FAYGEALAEQKPDI-UHFFFAOYSA-N 0.000 description 1
- WDRJNKMAZMEYOF-UHFFFAOYSA-N 4-(trifluoromethoxy)phenol Chemical compound OC1=CC=C(OC(F)(F)F)C=C1 WDRJNKMAZMEYOF-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004452 carbocyclyl group Chemical group 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 210000001525 retina Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/164—Unsaturated ethers containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/26—Monomers containing oxygen atoms in addition to the ether oxygen
Abstract
The invention provides a monomer, a polymer, a preparation method and application thereof. The monomer has a structure shown as a formula (I), wherein R1、R2、R3And n have the meanings as described in the specification. The polymer containing the monomer has higher refractive index and excellent mechanical property, and the polymer prepared by using the monomer has high refractive index, good transmittance and excellent mechanical property, is particularly suitable for preparing eye medical devices, and can meet the requirements of preparing thin and foldable artificial crystals.
Description
Technical Field
The invention relates to the field of ophthalmic medical devices, in particular to a monomer and a polymer applied to a foldable artificial lens, a preparation method and application thereof.
Background
Ophthalmic medical devices, such as intraocular lenses, contact lenses, artificial corneas, intracorneal rings or intracorneal lenses, are artificial materials or lenses that can be implanted into the eye, mainly for replacing natural lenses in the eye that become cloudy due to diseases such as cataracts, or for correcting the vision of the eye by means of wear, refractive surgery, and the like. Such ocular medical devices are typically comprised of a circular optic and peripheral supports. Wherein, the optical part is made of transparent polymer material. Intraocular lenses made of soft polymers, also often referred to as foldable intraocular lenses, can be implanted into the eye through a small surgical incision after being folded or rolled, and can be automatically unfolded after entering the eye. Most of the current intraocular lenses are foldable intraocular lenses, and most of the soft materials used for preparing foldable intraocular lenses are poly (meth) acrylate polymers.
However, the polymers, monomers and methods for their preparation currently used for the preparation of ophthalmic medical devices are still in need of improvement.
Disclosure of Invention
The present application is made based on the discovery and recognition by the inventors of the following facts and problems:
the foldable artificial lens at present generally has the problem that the foldable artificial lens is difficult to implant through a small-size incision which can be realized by the current surgical technology. In particular, with the development of cataract surgery techniques, surgery through smaller incisions has been possible regardless of the size of the ocular medical device (e.g., intraocular lens) being implanted. However, it is difficult to realize the current medical device for eyes folded to the size that can be realized by the surgical incision under the condition of ensuring that the performance of the device is not affected. Thus, ophthalmic medical devices such as foldable intraocular lenses have somewhat hindered the performance of small incision procedures. The inventors have conducted extensive studies and extensive experiments to find that this is mainly due to the fact that the refractive index and mechanical properties of the polymers currently used for preparing ocular medical devices are difficult to meet the requirements. For foldable intraocular lenses, if optical properties of the foldable intraocular lens need to be guaranteed on the premise that the foldable intraocular lens can be folded to a smaller size, the material for preparing the intraocular lens is required to have better refractive index and mechanical properties at the same time: when the refractive index of the polymer for preparing the ocular medical device is not high enough, the requirement of the device on the optical performance needs to be met by increasing the thickness of the ocular medical device, and conversely, if the ocular medical device is required to have a sufficiently thin thickness, the polymer for preparing the device needs to have a sufficiently high refractive index; in addition, because the foldable intraocular lens needs to be automatically unfolded after entering the eye, the polymer for preparing the intraocular lens needs to have enough impact resistance, so that the intraocular lens cannot be broken off in the using process, and meanwhile, the polymer needs to have proper elasticity, so that the peripheral support can support the optical part to be stabilized in the eye without moving, and the damage to the eye caused by the excessively violent unfolding process is avoided.
The present invention is directed to solving, at least to some extent, one of the above technical problems in the related art. To this end, the invention proposes a monomer. The structure of the monomer is shown as the formula (I):
wherein the content of the first and second substances,
R1is hydrogen or methyl;
R2is an alkyl group;
R3each independently is-L-M, wherein L is a bond, alkylene, -O-, -NR-, -C (O) -NR-, -S (O)2-or-S (═ O)2-NR-, M is hydrogen, alkyl, halogen, cyano, hydroxyl, nitro, aldehyde, haloalkyl, alkoxy, alkylthio, alkylamino, alkenyl, alkynyl, aryl, arylalkyl or aryloxy; each R is independently hydrogen, hydroxy, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C6-10Aryl or C6-10Aryl radical C1-6An alkyl group; and
n is 0, 1,2,3,4 or 5.
The polymer containing the monomer has higher refractive index and excellent mechanical property, and the polymer prepared by using the monomer has high refractive index, good transmittance and excellent mechanical property, is particularly suitable for preparing eye medical devices, and can meet the requirements of preparing thin and foldable artificial crystals.
The refractive index of the monomer and the polymer provided by the invention is not less than 1.53, and the spectral transmittance is not less than 80% in the visible light range of 400nm-800 nm.
The polymer provided by the invention has higher tensile strength, proper elastic modulus and larger elongation at break, and the foldable intraocular lens prepared by the polymer provided by the invention can not damage human eyes due to too violent opening and can not influence the use effect due to poor mechanical properties.
The invention also provides a method for preparing the monomer, which comprises the step of carrying out condensation reaction on the compound shown in the formula (II) and the compound shown in the formula (III):
the compound shown in the formula (II) is obtained by carrying out substitution reaction on a compound shown in a formula (IV) and a compound shown in a formula (V),
wherein n and R1、R2And R3Having the definitions as described herein; r4is-Cl, -Br, -OTs or-OMs. The method has simple operation and high yield, and is particularly suitable for industrial scale-up production.
The invention also provides a polymer. The monomers constituting the polymer include the aforementioned monomers. The polymer containing the monomer has high refractive index, good transmittance and excellent mechanical property, and is particularly suitable for preparing eye medical devices.
The invention also proposes the use of the aforementioned polymers for the preparation of ophthalmic medical devices. When the polymer is used for preparing the medical device for the eyes, the ideal device performance can be realized under the condition of smaller thickness, and the implantation of the medical device for the eyes can be realized by using smaller surgical incisions.
Finally, the invention also provides a process for preparing the aforementioned polymers. The method comprises the following steps: subjecting a raw material mixture to gradient heating treatment so as to obtain the polymer, wherein the raw material mixture contains the monomer of the invention and at least one selected from the group consisting of the compound represented by the formula (VI), a crosslinking agent, an initiator and an ultraviolet absorber.
Drawings
FIG. 1 shows a graph of the spectral transmittance test of a polymer A-1 according to the invention;
FIG. 2 shows a graph of the spectral transmittance test of the polymer A-2 according to the invention;
FIG. 3 shows a graph showing a spectral transmittance test of the polymer A-3 according to the present invention;
FIG. 4 shows a graph of the spectral transmittance test of the polymer A-4 according to the invention;
FIG. 5 shows a graph of the spectral transmittance test of the polymer A-5 according to the invention;
FIG. 6 shows a graph of the spectral transmittance test of the polymer A-6 according to the invention;
FIG. 7 shows a graph of the spectral transmittance test of the polymer A-7 according to the present invention;
FIG. 8 shows a graph of the spectral transmittance test of the polymer A-8 according to the invention;
FIG. 9 shows a graph of the spectral transmittance test of Polymer A-9 according to the present invention;
FIG. 10 shows a graph of the spectral transmittance test of Polymer A-10 according to the present invention;
FIG. 11 shows a graph of the spectral transmittance test of the polymer A-11 according to the present invention;
FIG. 12 shows a graph of the spectral transmittance test of polymer A-12 according to the present invention;
FIG. 13 shows a graph of spectral transmittance measurements for polymer A-13 according to the present invention;
FIG. 14 shows a graph of the spectral transmittance test of polymers A-14 according to the invention;
FIG. 15 shows a graph of the spectral transmittance test of polymers A-15 according to the invention;
FIG. 16 shows a graph of the spectral transmittance test of Polymer A-16 according to the present invention;
FIG. 17 shows a graph of spectral transmittance measurements for polymer A-17 according to the present invention;
FIG. 18 shows a graph of the spectral transmittance test of Polymer A-18 according to the present invention;
FIG. 19 shows a graph of the spectral transmittance test of polymers A-19 according to the present invention;
FIG. 20 shows a graph of the spectral transmittance test of Polymer A-20 according to the present invention;
FIG. 21 shows a graph of spectral transmittance measurements for polymer A-21 according to the present invention;
FIG. 22 shows a graph of the spectral transmittance test of Polymer A-22 according to the present invention;
FIG. 23 shows a graph of the spectral transmittance test of Polymer A-23 according to the present invention;
FIG. 24 shows a graph of the spectral transmittance test of Polymer A-24 according to the present invention;
FIG. 25 shows a graph of spectral transmittance measurements for polymer A-25 according to the present invention;
FIG. 26 shows a graph of the spectral transmittance test of polymers A-26 according to the present invention;
FIG. 27 shows a graph of the spectral transmittance test of Polymer A-27 according to the present invention;
FIG. 28 shows a graph of the spectral transmittance test of Polymer A-28 in accordance with the present invention;
FIG. 29 shows a graph of the spectral transmittance test of Polymer A-29 according to the present invention;
FIG. 30 shows a graph of spectral transmittance measurements for polymer A-30 according to the present invention;
FIG. 31 shows a spectral transmittance test chart of Polymer A-31 according to the present invention;
FIG. 32 shows a graph of the spectral transmittance measurements for polymers A-32 according to the present invention;
FIG. 33 shows a graph of spectral transmittance measurements for polymers A-33 according to the present invention; and
FIG. 34 shows a graph of the spectral transmittance test of polymers A-34 according to the invention.
Detailed description of the invention
Definition of terms
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
In the present disclosure, all numbers disclosed herein are approximate values, whether or not the word "about" or "approximately" is used. There may be differences below 10% in the value of each number or reasonably considered by those skilled in the art, such as differences of 1%, 2%, 3%, 4% or 5%.
The term "refractive index" refers to the ratio of the propagation velocity of light in vacuum to the propagation velocity of light in the medium. The higher the refractive index of the material, the greater the ability to refract incident light. For lenses of equivalent power, the thinner the lens, the higher the refractive index of the material used.
In the present invention, the term "optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, "optionally substituted phenyl" means that the phenyl group may be unsubstituted or substituted with alkyl, halogen, nitro, cyano, aldehyde, amino, alkoxy, haloalkyl, haloalkoxy, and the like.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" denotes a saturated straight or branched chain hydrocarbon group. In one embodiment, the alkyl group contains 1 to 20 carbon atoms; in another embodiment, the alkyl group contains 1 to 12 carbon atoms; in another embodiment, the alkyl group contains 1 to 8 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
The term "alkylene" denotes a saturated divalent hydrocarbon radical resulting from the removal of two hydrogen atoms from a saturated straight or branched chain hydrocarbon. In one embodiment, the alkylene group contains 1 to 12 carbon atoms. In another embodiment, the alkylene group contains 1 to 6 carbon atoms; in another embodiment, the alkylene group contains 1 to 4 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 3 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 2 carbon atoms. Non-limiting examples include methylene (-CH)2-, ethylene (-CH)2CH2-, isopropylidene (-CH (CH)3)CH2-) and the like.
The term "alkenyl" denotes at least one carbon-carbon sp2A linear or branched hydrocarbon group of a double bond, which includes the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 20 carbon atoms; in another embodiment, alkenyl groups contain 2 to 12 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 8 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) And so on.
The term "alkynyl" denotes a straight or branched chain hydrocarbon group having at least one carbon-carbon sp triple bond. In one embodiment, alkynyl groups contain 2-20 carbon atoms; in another embodiment, alkynyl groups contain 2-12 carbon atoms; in yet another embodiment, alkynyl groups contain 2-8 carbon atoms; in yet another embodiment, alkynyl groups contain 2-6 carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl (-C.ident.CH), propargyl (-CH)2C.ident.CH), 1-propynyl (-C.ident.C-CH)3) And so on.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 1 to 12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 3 carbon atoms. The alkoxy group is optionally substituted with one or more substituents described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) And so on.
The term "alkylthio" refers to C1-6The linear or branched alkyl group is attached to the rest of the molecule through a sulfur atom. In one embodiment, alkylthio is lower C1-4Alkylthio groups, and such examples include, but are not limited to, methylthio (CH)3S-). The alkylthio group is optionally substituted with one or more substituents described herein.
The term "alkylamino" or "alkylamino" includes "N-alkylamino" and "N, N-dialkylamino" wherein the amino groups are each independently substituted with one or two alkyl groups, wherein the alkyl groups have the meaning as described herein. In one embodiment, alkylamino is one or two C1-6Lower alkylamino groups in which the alkyl group is attached to the nitrogen atom. In another embodiment, alkylamino is C1-4Lower alkylamino groups of (a). Suitable alkylamino groups can be monoalkylamino or dialkylamino, and such examples include, but are not limited to, N-methylamino, N-ethylamino, N-dimethylamino, N-diethylamino, and the like. The alkylamino group is optionally substituted with one or more substituents described herein.
The terms "halogen" and "halo" refer to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
The terms "haloalkyl", "haloalkenyl" or "haloalkoxy" mean alkyl, alkenyl or alkoxy groups, respectively, substituted with one or more halogen atoms, wherein alkyl, alkenyl and alkoxy groups have the meaning described herein, and examples include, but are not limited to, difluoromethyl, trifluoromethyl, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2,2,3, 3-tetrafluoropropoxy, and the like. The haloalkyl, haloalkenyl, or haloalkoxy group is optionally substituted with one or more substituents described herein.
The term "alkoxyalkyl" means an alkyl group substituted with one or more alkoxy groups, wherein the alkyl group and alkoxy group have the meaning as described herein, examples of which include, but are not limited to, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, and the like.
The term "alkylaminoalkyl" denotes an alkyl group substituted with one or more alkylamino groups, wherein alkyl and alkylamino groups have the meaning as described herein.
The term "alkylthioalkyl" means that the alkyl group is substituted with one or more alkylthio groups, wherein the alkyl group and the alkylthio group have the meaning as described herein.
The term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. Examples of the aryl group may include phenyl, naphthyl and anthracenyl. When the aryl group may be optionally substituted, the substituted group may be fluorine, chlorine, bromine, iodine, cyano, azido, nitro, amino, hydroxyl, mercapto, alkylamino, alkoxy, alkylthio, alkyl, haloalkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, aryl, or heteroaryl.
The term "arylalkyl" means an alkyl group substituted with one or more aryl groups; wherein the alkyl group and the aryl group have the meanings as described herein, and examples of the arylalkyl group include, but are not limited to, benzyl, phenethyl and the like.
The term "aryloxy" or "aryloxy" refers to an optionally substituted aryl group, as defined herein, attached to and linked from an oxygen atom to the rest of the molecule, wherein the aryl group has the meaning as described herein. Examples of aryloxy groups include, but are not limited to, phenoxy, halophenoxy, cyano-substituted phenoxy, hydroxy-substituted phenoxy, and the like.
The term "aryloxyalkyl" refers to an alkyl group substituted with one or more aryloxy groups; wherein the aryloxy and alkyl groups have the meaning as indicated in the present invention. Examples of aryloxyalkyl groups include, but are not limited to, phenoxymethyl, fluorophenoxymethyl (such as (2-fluorophenoxy) methyl, (3-fluorophenoxy) methyl, or (4-fluorophenoxy) methyl), chlorophenoxymethyl, and the like.
The term "arylalkoxy" means that the alkoxy group is substituted with one or more aryl groups; wherein the alkoxy groups and aryl groups have the meaning as described in the present invention. Examples of the arylalkoxy group include, but are not limited to, benzyloxy, fluorobenzyloxy, chlorobenzyloxy, cyano-substituted benzyloxy, methanesulfonyl-substituted benzyloxy, phenylethoxy, and the like.
Detailed description of the invention
In one aspect of the invention, a monomer is provided. According to an embodiment of the present invention, the monomer has a structure represented by formula (I):
wherein R is1Is hydrogen or methyl; r2Is an alkyl group; n is 0, 1,2,3,4 or 5, and R3 are each independently-L-M, wherein L is a bond, alkylene, -O-, -NR-, -C (═ O) NR-, -S (═ O)2-or-S (═ O)2N-, M is hydrogen, alkyl, halogen, hydroxyl, cyano, nitro, aldehyde, haloalkyl, alkoxy, alkylthio, alkylamino, alkenyl, alkynyl, aryl, arylalkyl or aryloxy; each R is independently hydrogen, hydroxy, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C6-10Aryl or C6-10Aryl radical C1-6An alkyl group; that is, when n is greater than 1, a plurality of R in the monomer3May or may not be the same.
In one embodiment of the present invention, R is2Can be C1-C6An alkyl group; in another embodiment of the present invention, R is as defined above2And may be methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In one embodiment of the present invention, L may be a bond, alkylene, -O-, -NR-, -C (═ O) NR-, -S (═ O)2-or-S (═ O)2N-; in another embodiment of the present invention, L may be a bond, C1-8Alkylene or-O-; in another embodiment of the present invention, L may be a bond, C1-4-alkylene or-O-; in still another embodiment of the present invention, the above L may be a bond, methylene, ethylene, propylene or-O-.
In one embodiment of the present invention, M may be hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, aldehyde, C1-6Alkyl radical, C1-6Haloalkyl, C1-6Alkoxy radical, C1-6Alkylthio radical, C1-6Alkylamino radical, C2-6An alkenyl group,C2-6Alkynyl, C6-10Aryl radical, C6-10Aryl radical C1-6Alkyl or C6-12An aryloxy group; in one embodiment of the present invention, M may be hydrogen, fluorine, chlorine, bromine, iodine, C1-6Alkyl radical, C1-6Haloalkyl, C1-6Alkoxy or C6-C10An aryl group; in another embodiment of the present invention, M may be hydrogen or C1-4Alkyl radical, C1-4Haloalkyl, C1-4Alkoxy or C6-10An aryl group; in still another embodiment of the present invention, the above M may be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, propoxy, butoxy, phenyl.
In one embodiment of the invention, R3Each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, aldehyde, -NRaRb、-C(＝O)Rc、-S(＝O)2Rc、-C(＝O)NRaRb、-S(＝O)2NRaRb、C1-6Alkyl radical, C1-6Alkoxy radical, C1-6Alkylthio, halo C1-6Alkyl, halo C1-6Alkoxy radical, C1-6Alkoxy radical C1-6Alkyl radical, C1-6Alkylamino radical C1-6Alkyl radical, C1-6Alkylthio group C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C6-12Aryl radical, C6-12Aryl radical C1-6Alkyl radical, C6-12Aryloxy radical, C6-12Aryloxy radical C1-6Alkyl or C6-12Aryl radical C1-6An alkoxy group; and each Ra、RbAnd RcIndependently hydrogen, hydroxy, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C6-10Aryl or C6-10Aryl radical C1-6An alkyl group.
Preferably, R3Each independently is hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, nitro, aldehyde group, -NH2、-N(CH3)2、-C(＝O)CH3、-C(＝O)OH、-C(＝O)OCH3、-CONH2、-CON(CH3)2Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, trifluoromethyl, trifluoromethoxy, trifluoroethyl, trifluoroethoxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, phenyl, benzyl, phenethyl, phenylpropyl, phenoxy, phenoxymethyl, phenoxyethyl, benzyloxy, phenylethoxy.
In another embodiment of the invention, R1May be hydrogen or methyl, with R2May be methyl or ethyl; r3Each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy, trifluoromethyl, trifluoroethyl, trifluoromethoxy, trifluoroethoxy, methoxymethyl, methoxyethyl, methoxypropyl, phenyl, phenoxy or benzyl.
Specifically, the monomer of the present invention may be:
When the monomer is used for preparing the polymer, the obtained polymer has good mechanical property and high refractive index, and can meet the requirements of preparing slim foldable intraocular lenses and other eye medical devices. The monomer according to the invention has a refractive index of not less than 1.53 and a spectral transmittance of not less than 80% in the visible light range of 400nm to 800 nm.
In another aspect of the invention, the invention provides a process for preparing the monomer of formula (I) of the invention. The method has simple operation and high yield, and is particularly suitable for industrial scale-up production. The method is to obtain the polymer by condensation reaction of two compounds shown in the following formula:
wherein n and R1、R2And R3Having the above definitions of the invention, further description is omitted here.
In one embodiment of the present invention, the condensation reaction is carried out in an aprotic solvent. The aprotic solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 1-trichloroethane, chlorobenzene, dichlorobenzene, pentane, n-hexane, methylcyclohexane, 1, 1-diethoxypropane, 1, 1-dimethoxymethane, 2-dimethoxypropane, 1,2,3, 4-tetrahydronaphthalene, decahydronaphthalene, benzene, toluene, xylene, cumene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1, 4-dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethyl acetate, and butyl acetate.
In another embodiment of the present invention, the above condensation reaction is carried out in the presence of an aprotic solvent and a base. The base may include at least one of triethylamine, diisopropylethylamine, diethylamine, pyridine, N-dimethyl-pyridine, triethylenediamine, tetramethylethylenediamine, N-methylmorpholine, 1, 8-diazabicycloundecen-7-ene, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide.
Further, the compound represented in formula (II) can be obtained by the following reaction: and (b) carrying out substitution reaction on the compound shown in the formula (IV) and the compound shown in the formula (V).
Wherein n and R2And R3Having the above definitions of the present invention, further description is omitted herein; r4May be-Cl, -Br, -OTs (p-toluenesulfonyl) or-OMs (methylsulfonyl).
In one embodiment of the present invention, the substitution reaction is carried out in a protic solvent. For example, the protic solvent may include at least one of ethanol, isopropanol, N-butanol, N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, and dioxane.
In another embodiment of the present invention, the substitution reaction is carried out in the presence of a protic solvent and an inorganic base. The inorganic base may include at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide.
In another aspect of the invention, the invention features a polymer. The monomers constituting the polymer include at least one of the monomers described above in the present invention. Therefore, the polymer has at least one of the advantages of high refractive index, excellent mechanical property, suitability for preparing ocular medical devices and the like.
In an embodiment of the present invention, the monomers constituting the polymer include one of the monomers of the present invention. In another embodiment of the present invention, two or more of the aforementioned monomers may be included in the monomers constituting the above-mentioned polymer.
In another embodiment of the present invention, the monomer constituting the above-mentioned polymer is not limited to the monomers set forth previously in the present invention. For example, the monomers constituting the above polymer may further include a compound represented by the formula (VI):
wherein R is5Is H or methyl; l is1Is a bond, - (CH)2)6-O-or C1-6An alkylene group; ar is phenyl optionally substituted with 1,2,3,4, or 5 substituents selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, azido, nitro, amino, hydroxy, mercapto, alkylamino, alkoxy, alkylthio, alkyl, haloalkyl, alkenyl, alkynyl, and aryl.
In one embodiment of the present invention, the compound having the structural formula satisfying formula (VI) above may be:
in order to further improve the performance of the polymer, the raw materials for forming the polymer can further comprise at least one of a cross-linking agent, an initiator and an ultraviolet absorber.
In one embodiment of the present invention, the crosslinking agent may include at least one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 3-propanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol diacrylate, trimethylolpropane trimethacrylate, 1, 5-bis (methacryloyloxy) -2,2,3,3,4, 4-hexafluorohexane, 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, and pentaerythritol tetraacrylate. The cross-linking agent can play a better role in cross-linking each monomer, thereby further improving the performance of the polymer. In one embodiment, the crosslinking agent may be used in an amount of 2 to 7% by weight, based on the total weight of monomers used to synthesize the polymer. When the amount of the crosslinking agent is within the above range, a good crosslinking reaction effect can be obtained, and the obtained polymer has high mechanical strength and is less likely to undergo plastic deformation.
In one embodiment of the present invention, the initiator may include at least one of benzoyl peroxide, t-butyl hydroperoxide, cumyl hydroperoxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile, and azobis (2, 4-dimethylvaleronitrile). In one embodiment, the initiator may be used in an amount of 0.1 to 5% by weight, based on the total weight of monomers used to synthesize the polymer.
In one embodiment of the present invention, the ultraviolet absorber may include at least one of a copolymerizable benzotriazole-based compound and a copolymerizable benzophenone-based compound. In the present invention, the "copolymerizable benzotriazole-based compound" and the "copolymerizable benzophenone-based compound" are compounds containing a corresponding group (benzotriazole or benzophenone) copolymerizable with at least one of the above-mentioned monomers of the present invention (including the monomers proposed in the present invention and the compounds satisfying the formula (VI)), the initiator and the crosslinking agent. Those skilled in the art can select suitable compounds as the uv absorber within the above range depending on the actual situation, for example, the specific requirements of the ophthalmic medical device for the polymer. In one embodiment, the UV absorber can include 2- (2' -hydroxy-3 ' -methallyl-5 ' -methylphenyl) benzotriazole, 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] ethyl 2-methacrylate, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol, 2- (5-chloro-2H-benzo [ d ] [1,2,3] triazole) -4-methyl-6- (2-allyl) phenol, 4-allyl-2- (5-chloro-2H-benzo [ d ] [1, at least one of 2,3] triazole) -6-methoxyphenol, 2- (5-chloro-2H-1, 2, 3-benzo [ d ] [1,2,3] triazole) -4-methyl-6-allylphenol, 2-hydroxy-4- (methacryloyloxy) benzophenone, and 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate. The ultraviolet absorbent added into the raw material of the polymer can absorb most of ultraviolet rays and prevent the retina of the eye from being damaged by exposure to the ultraviolet rays. The polymer added with the ultraviolet absorbent has the ultraviolet transmittance of 10 percent, the cut-off wavelength of not less than 360nm, the ultraviolet transmittance of the material in the range of less than the cut-off wavelength is lower, the maximum value of the visible light transmittance is not less than 80 percent, and the polymer has excellent ultraviolet light absorption capacity and visible light transmittance. The amount of the ultraviolet absorber used may be 1 to 2% by weight based on the total weight of monomers used to synthesize the polymer. When the content of the ultraviolet absorber is within the above range, most of ultraviolet rays can be effectively absorbed without adversely affecting the refractive index and flexibility of the polymer.
In summary, the polymer including the monomer provided by the invention has at least one of the advantages of high refractive index, good transmittance, excellent mechanical properties and the like, so that when the polymer is used for preparing an ocular medical device, more ideal device performance can be realized under a smaller thickness, and implantation of the ocular medical device can be realized by using a smaller surgical incision.
The refractive index of the polymer is not less than 1.53, and is greatly improved compared with the refractive index of the existing polymer for the ocular medical device, so that the thickness and the performance of the ocular medical device prepared by using the polymer can be obviously reduced. The polymers have high spectral transmittance in the visible light range. The polymer has higher tensile strength, proper elastic modulus and larger elongation at break, and the foldable intraocular lens prepared by the polymer provided by the invention can not damage human eyes due to too violent opening, and can not influence the use effect due to poor mechanical properties.
In a further aspect of the invention, the invention proposes the use of a polymer as described above for the preparation of an ophthalmic medical device. The polymer has high refractive index, good transmittance and excellent mechanical property, so that when the polymer is used for preparing the eye medical device, more ideal device performance can be realized under a smaller thickness, and the implantation of the eye medical device can be realized by using a smaller operation incision.
In the present invention, the above-mentioned ocular medical device may be an artificial lens, an intraocular lens, a contact lens, a corneal modifier, an intracorneal lens, a corneal inlay, a corneal ring, a glaucoma filter device, or the like. Thus, the use effect of the ocular medical device can be further improved.
In yet another aspect of the invention, the invention provides a method of making the aforementioned polymer. The method obtains the polymer by carrying out gradient heating treatment, namely gradient heating treatment on the raw material mixture. Wherein the feed mixture contains the monomers of the invention as set forth above. The specific types of the above monomers have been described in detail above and will not be described in detail here. In order to further improve the performance of the polymer prepared by the method, at least one of a cross-linking agent, an initiator and an ultraviolet absorber can be further included in the raw material mixture. The method has simple and convenient operation steps and short production period, and the obtained polymer has ideal refractive index.
In one embodiment, the gradient heat treatment may include:
a first reaction stage:
in the first reaction stage, the raw material mixture is heated to 40-70 ℃ for reaction, and the reaction time can be 1-24 hours. Thereby avoiding violent reaction and making the material more uniform.
And a second reaction stage:
in the second reaction stage, the raw material mixture after the first reaction stage is heated to 80-120 ℃ for reaction, and the reaction time can be 1-24 hours. Therefore, the conversion rate of the reaction raw materials can be further improved, and the material properties are more stable.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the examples described below, all temperatures are given in degrees Celsius unless otherwise indicated. The reagents used are either commercially available or can be prepared by the methods described herein.
Synthesis of monomers
EXAMPLE 1 preparation of 1-ethoxy-3-phenoxy-2-propyl acrylate (formula)
(1) Preparation of 1-ethoxy-3-phenoxy-2-propanol
Phenol (14.0g, 14.9mmol), potassium carbonate (28.0g, 20mmol) and absolute ethanol (200mL) were added sequentially to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-ethoxy-2-propanol (13.9g, 10mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (10% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (13g, 66%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：219[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.33-7.28(m,2H)，7.00-6.94(m,3H)，4.09-4.02(m,1H)，3.67-3.56(m,4H)，2.62(s,1H)，1.30-1.22(t,3H)。
(2) preparation of 1-ethoxy-3-phenoxy-2-propyl acrylate
1-ethoxy-3-phenoxy-2-propanol (5g, 25.5mmol), diisopropylethylamine (12.0g, 93.0mmol), 4-dimethylaminopyridine (1.2g, 10.0mmol) and tetrahydrofuran (70mL) were added sequentially to a single-neck flask, and after sufficient dissolution, acryloyl chloride (10.0g, 111.1mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (2.5g, 40%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：273[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.32-7.28(t,2H)，7.00-6.94(t,3H)，6.49-6.46(d,1H)，6.22-6.171(t,1H)，5.89-5.87(d,1H)，5.42-5.39(m,1H)，4.26-4.18(m,2H)，3.76-3.75(d,2H)，3.61-3.54(m,2H)，1.24-1.20(t,3H)。
example 2 preparation of 1-ethoxy-3-phenoxy 2-propyl methacrylate (formula shown below)
1-ethoxy-3-phenoxy-2-propanol (4.0g, 20mmol), diisopropylethylamine (5.6g, 43.0mmol), 4-dimethylaminopyridine (0.3g, 2.3mmol) and tetrahydrofuran (70mL) were added in this order to a single-neck flask, and after sufficient dissolution, methacryloyl chloride (8.8g, 84.6mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation, dissolved in dichloromethane (200mL), and stirred overnight with aqueous sodium hydroxide (5% wt, 80 mL). After separation the solvent was removed by rotary evaporation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (2.5g, 63%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：287[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.32-7.28(t,2H)，7.00-6.94(t,3H)，6.17(s,1H)，5.61(s,1H)，5.40-5.35(m,1H)，4.26-4.18(m,2H)，3.76-3.75(d,2H)，3.61-3.54(m,2H)，1.98(s,3H)，1.24-1.20(t,3H)。
EXAMPLE 3 preparation of 1-ethoxy-3- (4-phenylphenyl) oxy-2-propyl acrylate (formula)
(1) Preparation of 1-ethoxy-3- (4-phenylphenyl) oxy-2-propanol
4-phenylphenol (25.8g, 152.0mmol), potassium carbonate (21.0g, 152.0mmol) and anhydrous ethanol (200mL) were added in this order to a three-necked flask, and after the mixture was stirred at reflux for 1 hour, 1-chloro-3-ethoxy-2-propanol (14.0g, 100.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate for 2 hours, filtered and the solvent removed by rotary evaporation to give the title compound as a white solid (26.1g, 95%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：295[M+H]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.58-7.54(t,4H)，7.46-7.42(t,2H)，7.35-7.28(m,1H)，7.03-7.01(d,2H)，4.23-4.18(m,1H)，4.13-4.07(m,2H)，3.69-3.58(m,4H)，2.61-2.60(d,1H)，1.27-1.24(t,3H)。
(2) preparation of 1-ethoxy-3- (4-phenylbenzene) oxy-2-propyl acrylate to a single-neck flask were added 1- (4-phenylbenzene) oxy-3-ethoxy-2-propanol (13.0g, 47.8mmol), triethylamine (9.7g, 95.6mmol), 4-dimethylaminopyridine (1.2g, 9.6mmol), and tetrahydrofuran (70mL) in that order, and after sufficient dissolution, acryloyl chloride (6.5g, 71.7mmol) was slowly added dropwise thereto, and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 100/1) to give a colorless viscous liquid (9.0g, 57.8% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：349[M+Na]+；
1H NMR(400MHz，CDCl3)δ：7.60-7.55(t,4H)，7.47-7.43(t,2H)，7.36-7.32(t,1H)，7.05-7.03(d,2H)，6.53-6.48(d,1H)，6.26-6.19(t,1H)，5.91-5.89(d,1H)，5.47-5.42(m,1H)，4.31-4.24(m,2H)，3.79-3.78(d,2H)，3.66-3.55(m,2H)，1.26-1.23(t,3H)。
example 4 preparation of 1-ethoxy-3- (4-phenylphenyl) oxy-2-propyl methacrylate (formula below):
to a one-necked flask, 1- (4-phenylphenyl) oxy-3-ethoxy-2-propanol (13.0g, 47.8mmol), triethylamine (9.7g, 95.6mmol), 4-dimethylaminopyridine (1.2g, 9.6mmol) and tetrahydrofuran (70mL) were added in this order, and after sufficient dissolution, acryloyl chloride (6.5g, 71.7mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 100/1) to give a colorless viscous liquid (9.0g, 57.8% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：363[M+Na]+；
1H NMR(400MHz，CDCl3)δ：7.58-7.53(t,4H)，7.46-7.42(t,2H)，7.35-7.31(t,1H)，7.04-7.02(d,2H)，6.18(s,1H)，5.62(s,1H)，5.42-5.37(m,1H)，4.30-4.23(m,2H)，3.78-3.77(d,2H)，3.65-3.54(m,2H)，1.99(s,3H)，1.25-1.21(t,3H)。
example 5 preparation of 1-ethoxy-3- (4-benzylbenzene) oxy-2-propyl acrylate (formula below):
(1) preparation of 1-ethoxy-3- (4-benzylbenzene) oxy-2-propanol
4-Benzylphenol (15.0g, 81.5mmol), potassium carbonate (14.2g, 102.2mmol) and absolute ethanol (100mL) were added in this order to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-ethoxy-2-propanol (8.1g, 58.3mmol) was slowly added dropwise thereto and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 6). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a white solid (12g, yield 72%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：309[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.62-7.28(t,2H)，7.23-7.18(t,3H)，7.13-7.11(d,2H)，6.88-6.86(d,2H)，4.19-4.14(m,1H)，4.05-3.99(m,2H)，3.95(s,2H)，3.66-3.54(m,4H)，1.26-1.22(t,3H)。
(2) preparation of 1-ethoxy-3- (4-benzylbenzene) oxy-2-propyl acrylate
To a single-neck flask were added 1-ethoxy-3- (4-benzylbenzene) oxy-2-propanol (12.0g, 16.5mmol), triethylamine (7.5g, 74.3mmol), 4-dimethylaminopyridine (1.1g, 8.2mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, acryloyl chloride (10.2g, 113.3mmol) was slowly added dropwise thereto, and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. After separation, the solvent was removed by rotary evaporation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give a colorless viscous liquid (6.4g, 45% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：363[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.32-7.28(t,2H)，7.23-7.18(t,3H)，7.13-7.11(d,2H)，6.88-6.86(d,2H)，6.49-6.44(t,1H)，6.22-6.15(t,1H)，5.88-5.86(t,1H)，5.41-5.36(m,1H)，4.22-4.15(m,2H)，3.95(s,2H)，3.75-3.74(m,2H)，3.60-3.53(m,2H)，1.23-1.19(t,3H)。
example 6 preparation of 1-ethoxy-3- (4-benzylbenzene) oxy-2-propyl methacrylate (formula below):
to a single-necked flask were added 1-ethoxy-3- (4-benzylbenzene) oxy-2-propanol (12.3g, 43.0mmol), triethylamine (9.2g, 91.1mmol), 4-dimethylaminopyridine (0.5g, 4.2mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (6.5g, 62.5mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. After separation, the solvent was removed by rotary evaporation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 20/1) to give a colorless viscous liquid (8.3g, 54% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：377[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.31-7.28(t,3H)，7.22-7.18(m,2H)，7.12-7.10(d,2H)，6.88-6.86(d,2H)，6.14(s,1H)，5.59(s,1H)，5.37-5.32(m,1H)，4.22-4.14(m,2H)，3.94(s,2H)，3.74-3.73(d,2H)，3.60-3.52(m,2H)，1.96(s,3H)，1.22-1.19(t,3H)。
example 7 preparation of 1-ethoxy-3- (3-methoxybenzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-ethoxy-3- (3-methoxybenzene) oxy-2-propanol
3-methoxyphenol (18.9g, 152.0mmol), potassium carbonate (14.0g, 101.0mmol) and absolute ethanol (100mL) were added sequentially to a three-necked flask, and after the mixture was stirred at reflux for 1 hour, 1-chloro-3-ethoxy-2-propanol (14.0g, 100.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a white solid (18g, yield 79%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：249[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.22-7.18(t,1H)，6.56-6.51(m,3H)，4.19-4.16(t,1H)，4.04-4.01(m,2H)，3.81(s,3H)，3.66-3.56(m,4H)，2.61-2.60(d,1H)，1.26-1.21(m,3H)。
(2) preparation of 1-ethoxy-3- (3-methoxybenzene) oxy-2-propyl acrylate
To a single-neck flask were added step 1-ethoxy-3- (3-methoxybenzene) oxy-2-propanol (8.8g, 38.9mmol), triethylamine (7.9g, 77.8mmol), 4-dimethylaminopyridine (1.0g, 8.1mmol) and tetrahydrofuran (70mL) in that order, and after sufficient dissolution, acryloyl chloride (5.3g, 58.4mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was filtered, tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give a colorless viscous liquid (7g, 62% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：303[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.21-7.17(t,1H)，6.55-6.45(m,4H)，6.23-6.16(m,1H)，5.89-5.86(m,1H)，5.40-5.38(t,1H)，4.23-4.15(m,2H)，3.81(s,3H)，3.75-3.73(d,2H)，3.61-3.52(m,2H)，1.23-1.20(t,3H)。
example 8 preparation of 1-ethoxy-3- (3-methoxybenzene) oxy-2-propyl methacrylate (formula:
to a single-neck flask were added 1-ethoxy-3- (3-methoxybenzene) oxy-2-propanol (8.1g, 35.4mmol), triethylamine (7.2g, 70.8mmol), 4-dimethylaminopyridine (0.9g, 7.2mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (5.5g, 53.1mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 20/1) to give a colorless viscous liquid (7.4g, 71% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：317[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.21-7.17(t,1H)，6.55-6.51(m,3H)，6.16(s,1H)，5.61-5.60(d,1H)，5.37-5.35(t,1H)，4.23-4.16(m,2H)，3.81(s,3H)，3.75-3.73(d,2H)，3.60-3.53(m,2H)，1.97(s,3H),1.23-1.19(t,3H)。
example 9 preparation of 1-ethoxy-3- (4-phenoxyphenyl) oxy-2-propyl acrylate (formula:
(1) preparation of 1-ethoxy-3- (4-phenoxyphenyl) oxy-2-propanol
4-Phenoxyphenol (38.6g, 210.9mmol), potassium carbonate (30.0g, 217.3mmol) and absolute ethanol (100mL) were added in this order to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-ethoxy-2-propanol (13.2g, 95.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 6). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (23.5g, yield 81%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：311[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.34-7.30(t,2H)，7.08-7.05(t,1H)，7.01-6.91(m,6H)，4.22-4.15(m,1H)，4.07-4.00(m,2H)，3.66-3.57(m,4H)，2.60-2.58(d,1H)，1.27-1.23(t,3H)。
(2) preparation of 1-ethoxy-3- (4-phenoxyphenyl) oxy-2-propyl acrylate
To a single-neck flask were added successively 1-ethoxy-3- (4-phenoxyphenyl) oxy-2-propanol (39.0g, 135.4mmol) obtained in step (1), triethylamine (30.0g, 297.0mmol), 4-dimethylaminopyridine (3.3g, 27.0mmol) and tetrahydrofuran (70mL), and after sufficient dissolution, acryloyl chloride (10.2g, 113.3mmol) was slowly added dropwise thereto, and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give a colorless viscous liquid (33g, 71% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：365[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.34-7.30(t,2H)，7.08-7.05(t,1H)，7.01-6.91(m,6H)，6.50-6.45(t,1H)，6.24-6.21(t,1H)，5.90-5.88(t,1H)，5.42-5.37(m,1H)，4.24-4.16(m,2H)，3.76-3.75(m,2H)，3.62-3.54(m,2H)，1.27-1.23(t,3H)。
example 10 preparation of 1-ethoxy-3- (4-phenoxyphenyl) oxy-2-propyl methacrylate (formula:
to a single-neck flask were added 1-ethoxy-3- (4-phenoxyphenyl) oxy-2-propanol (12.0g, 41.7mmol), triethylamine (10.7g, 105.9mmol), 4-dimethylaminopyridine (1.3g, 10.9mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (8.5g, 81.7mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 20/1) to give a colorless viscous liquid (10.8g, 68% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：379[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.34-7.30(t,2H)，7.08-7.05(t,1H)，7.01-6.91(m,6H)，6.17(s,1H)，5.62(s,1H)，5.39-5.34(m,1H)，4.24-4.17(m,2H)，3.76-3.74(m,2H)，3.64-3.52(m,2H)，1.98(s,3H)，1.2,4-1.20(t,3H)。
EXAMPLE 11 preparation of 1-methoxy-3-phenoxy-2-propyl acrylate (formula)
(1) Preparation of 1-methoxy-3-phenoxy-2-propanol
Phenol (19.2g, 204.3mmol), potassium carbonate (28g, 20mmol) and absolute ethanol (200mL) were added sequentially to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (13.9g, 10mmol) was slowly added dropwise thereto and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (12g, 33%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：205[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.33-7.29(t,2H)，7.00-6.99(m,3H)，4.22-4.16(m,1H)，4.08-4.01(m,2H)，3.63-3.55(m,2H)，3.44(s,3H)，2.63-2.62(d,1H)。
(2) preparation of 1-methoxy-3-phenoxy-2-propyl acrylate
1-methoxy-3-phenoxy-2-propanol (5.0g, 25.5mmol), triethylamine (12.0g, 93.0mmol), 4-dimethylaminopyridine (1.2g, 10mmol) and tetrahydrofuran (70mL) were added in this order to a single-neck flask, and after sufficient dissolution, acryloyl chloride (10.0g, 111.1mmol) was slowly added dropwise thereto and stirring was continued for 24 h. Filtering the reaction solution, and removing tetrahydrofuran by rotary evaporationAnd dissolved in methylene chloride (200mL), and stirred for 0.5h by adding an aqueous solution of sodium hydroxide (5% wt, 80 mL). The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (2.5g, 40%). The mass and nuclear magnetic H spectrum test data are as follows: LC-MS (ESI, pos. ion) m/z: 259[ M + Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.32-7.28(t,2H)，7.00-6.94(t,3H)，6.49-6.46(d,1H)，6.22-6.17(t,1H)，5.89-5.87(d,1H)，5.42-5.39(m,1H)，4.26-4.18(m,2H)，3.76-3.75(d,2H)，3.61-3.54(m,2H)，1.24-1.20(t,3H)。
Example 12 preparation of 1-methoxy-3-phenoxy 2-propyl methacrylate (formula:
1-methoxy-3-phenoxy-2-propanol (6.0g, 32.2mmol), triethylamine (7.2g, 71.3mmol), 4-dimethylaminopyridine (0.8g, 6.9mmol) and tetrahydrofuran (70mL) were added in this order to a single-neck flask, and after sufficient dissolution, methacryloyl chloride (6.2g, 59.6mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation, dissolved in dichloromethane (200mL), and stirred overnight with aqueous sodium hydroxide (5% wt, 80 mL). The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (5.8g, 70%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：273[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.33-7.29(t,2H)，7.00-6.95(m,3H)，6.18(s,1H)，5.62(s,1H)，5.43-5.37(m,1H)，4.22-4.21(d,2H)，3.74-3.73(d,2H)，3.42(s,3H)，1.98(s,3H)。
example 13 preparation of 1-methoxy-3- (3-methylbenzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (3-methylbenzene) oxy-2-propanol
3-methylphenol (33.2g, 307.4mmol), potassium carbonate (44g, 316.5mmol) and absolute ethanol (200mL) were added sequentially to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (25.0g, 200.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (33g, 84%).
LC-MS(ESI,pos.ion)m/z：219[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.21-7.17(t,1H)，6.81-6.74(m,3H)，4.21-4.15(m,1H)，4.06-4.00(m,2H)，3.63-3.54(m,2H)，3.44(s,3H)，2.61-2.60(d,1H)，2.35(s,3H)。
(2) Preparation of 1-methoxy-3- (3-methylbenzene) oxy-2-propyl acrylate
1-methoxy-3- (3-methylbenzene) oxy-2-propanol (12.0g, 61.2mmol), triethylamine (12.4g, 122.8mmol), 4-dimethylaminopyridine (0.5g, 4.1mmol) and tetrahydrofuran (70mL) were added in this order to a single-neck flask, and after sufficient dissolution, acryloyl chloride (11.0g, 122.2mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (7g, 46%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：273[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.20-7.16(t,1H)，6.81-6.76(m,3H)，6.46-6.45(d,1H)，6.23-6.20(t,1H)，5.89-5.87(d,1H)，5.43-5.38(m,1H)，4.22-4.15(m,2H)，3.73-3.72(t,2H)，3.42(s,3H)，2.35(s,3H)。
example 14 preparation of 1-methoxy-3 (3-methylbenzene) oxy 2-propyl methacrylate (formula:
to a single-neck flask were added 1-methoxy-3- (3-methylbenzene) oxy-2-propanol (11.2g, 57.1mmol), triethylamine (10.3g, 102.0mmol), 4-dimethylaminopyridine (0.5g, 4.1mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (9.6g, 92.3mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation, dissolved in dichloromethane (200mL), and stirred overnight with aqueous sodium hydroxide (5% wt, 80 mL). The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (12g, 79%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：287[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.19-7.16(t,1H)，6.80-6.74(m,3H)，6.18(s,1H)，5.61(s,1H)，5.39-5.34(m,1H)，4.22-4.15(m,2H)，3.75-3.69(t,2H)，3.42(s,3H)，2.34(s,3H)，1.97(s,3H)。
example 15 preparation of 1-methoxy-3- (4-phenylphenyl) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (4-phenylphenyl) oxy-2-propanol
4-phenylphenol (50.2g, 295.3mmol), potassium carbonate (42.6g, 306.5mmol) and anhydrous ethanol (200mL) were added in this order to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (25.0g, 200.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (30g, 58%).
LC-MS(ESI,pos.ion)m/z：281[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.58-7.53(t,4H)，7.46-7.42(t,2H)，7.34-7.31(t,1H)，7.03-7.01(d,2H)，4.25-4.19(m,1H)，4.12-4.06(m,2H)，3.65-3.57(m,2H)，3.45(s,3H)，2.62-2.61(d,1H)。
(2) Preparation of 1-methoxy-3- (4-phenylbenzene) oxy-2-propyl acrylate to a single-neck flask were added 1- (4-phenylbenzene) oxy-3-methoxy-2-propanol (15.0g, 58.1mmol), triethylamine (11.7g, 116.0mmol), 4-dimethylaminopyridine (1.4g, 11.7mmol) and tetrahydrofuran (70mL) in that order, and after sufficient dissolution, acryloyl chloride (7.9g, 87.2mmol) was slowly added dropwise thereto, and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 100/1) to give a colorless viscous liquid (3.5g, 19.3% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：335[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.58-7.54(t,4H)，7.46-7.42(t,2H)，7.35-7.31(t,1H)，7.03-7.01(d,2H)，6.52-6.47(d,1H)，6.25-6.18(t,1H)，5.91-5.89(d,1H)，5.46-5.42(m,1H)，4.29-4.22(m,2H)，3.75-3.74(d,2H)，3.44(s,3H)。
example 16 preparation of 1-methoxy-3- (4-phenylphenyl) oxy-2-propyl methacrylate (formula:
to a one-necked flask, 1- (4-phenylphenyl) oxy-3-methoxy-2-propanol (15.0g, 58.1mmol), triethylamine (11.8g, 117.0mmol), 4-dimethylaminopyridine (1.5g, 11.9mmol) and tetrahydrofuran (70mL) were added in this order, and after sufficient dissolution, methacryloyl chloride (9.1g, 87.5mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 100/1) to give a colorless viscous liquid (6.0g, 31.7% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：349[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.58-7.53(t,4H)，7.46-7.42(t,2H)，7.35-7.31(t,1H)，7.04-7.01(d,2H)，6.19(s,1H)，5.62(s,1H)，5.43-5.38(m,1H)，4.26-4.25(d,2H)，3.75-3.74(d,2H)，3.44(s,3H)，1.99(s,3H)。
example 17 preparation of 1-methoxy-3- (4-benzylbenzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (4-benzylbenzene) oxy-2-propanol
4-Benzylphenol (24.8g, 81.5mmol), potassium carbonate (19.0g, 138.0mmol) and absolute ethanol (100mL) were added to a three-necked flask in that order, and after the mixture was stirred under reflux for 1h, 1-chloro-3-methoxy-2-propanol (11.2g, 90.0mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 6). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a white solid (16.4g, yield 67%).
LC-MS(ESI,pos.ion)m/z：295[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.33-7.28(m,2H)，7.24-7.19(m,3H)，7.14-7.12(d,2H)，6.89-6.86(d,2H)，4.20-4.16(m,1H)，4.06-4.01(m,2H)，3.99-3.95(d,2H)，3.62-3.54(m,2H)，3.44-3.42(d,3H)，2.63-2.62(d,1H)。
(2) Preparation of 1-methoxy-3- (4-benzylbenzene) oxy-2-propyl acrylate
To a single-neck flask were added 1-methoxy-3- (4-benzylbenzene) oxy-2-propanol (8.1g, 26.9mmol), triethylamine (6.0g, 59.3mmol), 4-dimethylaminopyridine (0.8g, 6.3mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, acryloyl chloride (4.0g, 44.1mmol) was slowly added dropwise thereto, and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give a colorless viscous liquid (6.6g, 68.8% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：349[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.23-7.28(t,2H)，7.23-7.28(m,3H)，7.13-7.11(d,2H)，6.88-6.86(d,2H)，6.49-6.45(m,1H)，6.22-6.15(m,1H)，5.89-5.86(m,1H)，5.41-5.38(t,1H)，4.18-4.16(m,2H)，3.95(s,2H)，3.72-3.71(d,2H)，3.42(s,3H)。
example 18 preparation of 1-methoxy-3- (4-benzylbenzene) oxy-2-propyl methacrylate (formula:
to a single-neck flask were added 1-methoxy-3- (4-benzylbenzene) oxy-2-propanol (8.0g, 29.4mmol), triethylamine (6.0g, 58.9mmol), 4-dimethylaminopyridine (0.8g, 7.3mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (4.6g, 44.1mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 20/1) to give a colorless viscous liquid (7.9g, 79% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：363[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.32-7.19(m,5H)，7.13-7.11(d,2H)，6.89-6.86(d,2H)，6.16(s,1H)，5.60(s,1H)，5.39-5.34(m,1H)，4.20-4.17(m,2H)，3.95(s,2H)，3.73-3.71(d,2H)，3.43-3.42(s,3H)，1.97(s,3H)。
example 19 preparation of 1-methoxy-3- (3-methoxybenzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (3-methoxybenzene) oxy-2-propanol
3-methoxyphenol (37.5g, 302.4mmol), potassium carbonate (51.2g, 368.3mmol) and absolute ethanol (200mL) were added sequentially to a three-necked flask, and after the mixture was stirred at reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (25.0g, 200.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (33g, 77%).
LC-MS(ESI,pos.ion)m/z：235[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.22-7.18(t,1H)，6.56-6.51(m,3H)，4.22-4.15(m,1H)，4.06-4.02(m,2H)，3.99(s,3H)，3.62-3.54(m,2H)，3.44(s,3H)，2.62-2.61(d,1H)。
(2) Preparation of 1-methoxy-3- (3-methoxybenzene) oxy-2-propyl acrylate
To a single-neck flask were added 1-methoxy-3- (3-methoxybenzene) oxy-2-propanol (9.2g, 43.3mmol), triethylamine (8.3g, 82.2mmol), 4-dimethylaminopyridine (1.1g, 8.2mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, acryloyl chloride (14.8g, 164.4mmol) was slowly added dropwise and stirring was continued for 24 h. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (4.5g, 30%).
LC-MS(ESI,pos.ion)m/z：289[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.19-7.17(t,1H)，6.54-6.53(t,2H)，6.51-6.51(d,1H)，6.48-6.45(d,1H)，6.21-6.17(t,1H)，5.88-5.86(d,1H)，5.42-5.38(m,1H)，4.20-4.15(m,2H)，3.79-3.78(s,3H)，3.73-3.68(m,2H)，3.41-3.40(d,3H)。
EXAMPLE 20 preparation of 1-methoxy-3 (3-methoxybenzene) oxy 2-propyl methacrylate (formula
To a single-neck flask were added 1-methoxy-3- (3-methoxybenzene) oxy-2-propanol (9.5g, 44.8mmol), triethylamine (8.3g, 82.2mmol), 4-dimethylaminopyridine (1.2g, 9.8mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (7.1g, 68.3mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation, dissolved in dichloromethane (200mL), and stirred overnight with aqueous sodium hydroxide (5% wt, 80 mL). The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (8.3g, 66%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：303[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.21-7.17(t,1H)，6.55-6.51(m,3H)，6.17(s,1H)，5.61(s,1H)，5.40-5.35(m,1H)，4.19-4.18(d,2H)，3.81(s,3H)，3.72-3.7(d,2H)，3.42(s,3H)，1.97(s,3H)。
example 21 preparation of 1-methoxy-3- (4-phenoxyphenyl) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (4-phenoxyphenyl) oxy-2-propanol
4-phenoxy phenol (28.1g, 150.0mmol), potassium carbonate (14.2g, 100.0mmol) and absolute ethanol (100mL) were added sequentially to a three-necked flask, and after the mixture was stirred at reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (12.8g, 100.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 6). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a white solid (16.7g, yield 61%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：297[M+Na]+；
H-NMR(400MHz，CDCl3)δ(ppm)：7.34-7.28(m,2H)，7.09-7.05(t,1H)，7.01-6.91(m,6H)，4.21-4.17(m,1H)，4.04-4.01(m,2H)，3.64-3.55(m,2H)，3.45(s,3H)，2.66-2.65(d,1H)。
(2) preparation of 1-methoxy-3- (4-phenoxyphenyl) oxy-2-propyl acrylate
To a single-necked flask, 1-methoxy-3- (4-phenoxyphenyl) oxy-2-propanol (8.7g, 135.4mmol) obtained in step (1), triethylamine (6.4g, 297.0mmol), 4-dimethylaminopyridine (0.8g, 6.5mmol) and tetrahydrofuran (70mL) were added in this order, and after sufficient dissolution, acryloyl chloride (4.3g, 48.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give a colorless viscous liquid (6.6g, 64% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：351[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.34-7.28(m,2H)，7.09-7.07(t,1H)，7.0-6.91(m,6H)，6.51-6.46(d,1H)，6.24-6.17(m,1H)，5.91-5.88(m,1H)，5.42-5.40(t,1H)，4.20-4.18(m,2H)，3.73-3.72(m,2H)，3.43(s,3H)。
example 22 preparation of 1-methoxy-3- (4-phenoxyphenyl) oxy-2-propyl methacrylate (formula:
to a single-neck flask were added 1-methoxy-3- (4-phenoxyphenyl) oxy-2-propanol (8.1g, 29.6mmol), triethylamine (6.5g, 64.0mmol), 4-dimethylaminopyridine (1.0g, 8.2mmol), and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (4.6g, 44.6mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 20/1) to give a colorless viscous liquid (8.7g, 87.9% yield). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：365[M+Na]+；
1H-NMR(400MHz，CDCl3)δ(ppm)：7.34-7.28(m,2H)，7.08-7.05(t,1H)，7.00-6.91(m,6H)，6.18(s,1H)，5.62(s,1H)，5.40-5.35(m,1H)，4.23-4.16(m,2H)，3.73-3.72(d,2H)，3.45-3.43(s,3H)，1.98-1.95(d,3H)。
example 54 preparation of 1-methoxy-3- (3-trifluoromethylbenzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (3-trifluoromethylbenzene) oxy-2-propanol
3-trifluoromethylphenol (22.5g, 138.9mmol), potassium carbonate (12.8g, 92.6mmol) and absolute ethanol (200mL) were added sequentially to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (11.5g, 92.6mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (15.5g, 67%).
LC-MS(ESI,pos.ion)m/z：273[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.43-7.39(t,1H)，7.25-7.23(d,1H)，7.16(s,1H)，7.13-7.10(d,1H)，4.24-4.17(m,1H)，4.11-4.04(m,2H)，3.63-3.56(m,2H)，3.44(s,3H)，2.63-2.62(d,1H)。
(2) Preparation of 1-methoxy-3- (3-trifluoromethylbenzene) oxy-2-propyl acrylate
To a single-neck flask were added 1-methoxy-3- (3-trifluoromethylbenzene) oxy-2-propanol (7.5g, 28.2mmol), triethylamine (6.1g, 60.0mmol), 4-dimethylaminopyridine (0.7g, 6.0mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, acryloyl chloride (4.1g, 45.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (5.7g, 62.9%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：327[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.43-7.39(t,1H)，7.25-7.25(d,1H)，7.18(s,1H)，7.12-7.10(d,1H)，6.50-6.46(d,1H)，6.22-6.15(m,1H)，5.91-5.88(d,1H)，5.44-5.39(m,1H)，4.28-4.21(m,2H)，3.72-3.71(d,2H)，3.48(s,3H)。
example 55 preparation of 1-methoxy-3 (3-trifluoromethylbenzene) oxy 2-propyl methacrylate (formula:
to a single-neck flask were added 1-methoxy-3- (3-trifluoromethylbenzene) oxy-2-propanol (7.5g, 30.0mmol), triethylamine (6.1g, 60.0mmol), 4-dimethylaminopyridine (0.7g, 60mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (4.7g, 45.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation, dissolved in dichloromethane (200mL), and stirred overnight with aqueous sodium hydroxide (5% wt, 80 mL). The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (5.1g, 53.7%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：341[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.43-7.39(t,1H)，7.25-7.23(d,1H)，7.18(s,1H)，7.13-7.11(d,1H)，6.16(s,1H)，5.62(s,1H)，5.41-5.36(m,1H)，4.28-4.21(m,2H)，3.72-3.71(d,2H)，3.43(s,3H)，1.97(s,3H)。
example 56 preparation of 1-methoxy-3- (4-trifluoromethoxybenzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (4-trifluoromethoxybenzene) oxy-2-propanol
4-trifluoromethoxyphenol (32.4g, 200.0mmol), potassium carbonate (18.4g, 136.3mmol) and absolute ethanol (200mL) were added in this order to a three-necked flask, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (16.5g, 133.4mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (24.4g, 73.3%).
LC-MS(ESI,pos.ion)m/z：289[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.17-7.15(d,2H)，6.94-6.92(d,2H)，4.22-4.15(m,1H)，4.04-4.00(m,2H)，3.62-3.54(m,2H)，3.44(s,3H)，2.59-2.57(d,1H)。
(2) Preparation of 1-methoxy-3- (4-trifluoromethoxybenzene) oxy-2-propyl acrylate
To a one-necked flask were added 1-methoxy-3- (4-trifluoromethoxybenzene) oxy-2-propanol (12.1g, 48.4mmol), triethylamine (9.9g, 96.8mmol), 4-dimethylaminopyridine (1.2g, 9.7mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, acryloyl chloride (6.5g, 72.6mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was filtered, the tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (8.0g, 54.6%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：343[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.17-7.15(d,2H)，6.94-6.92(d,2H)，6.50-6.45(d,1H)，6.22-6.15(m,1H)，5.90-5.88(d,1H)，5.42-5.37(m,1H)，4.23-4.16(m,2H)，3.71-3.70(d,2H)，3.42(s,3H)。
example 57 preparation of 1-methoxy-3 (4-trifluoromethoxybenzene) oxy 2-propyl methacrylate (formula:
to a single-neck flask were added 1-methoxy-3- (4-trifluoromethoxybenzene) oxy-2-propanol (12.1g, 48.4mmol), triethylamine (9.8g, 96.8mmol), 4-dimethylaminopyridine (1.2g, 9.7mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, methacryloyl chloride (7.6g, 72.6mmol) was slowly added dropwise thereto and stirring was continued for 24 h. The reaction was filtered, tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), and aqueous sodium hydroxide (5% wt, 80mL) was added and stirred overnight. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (8.7g, 56.7%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：357[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.17-7.14(d,2H)，6.94-6.92(d,2H)，6.15(s,1H)，5.61(s,1H)，5.39-5.34(m,1H)，4.23-4.16(m,2H)，3.71-3.70(d,2H)，3.42(s,3H)，1.97(s,3H)。
example 58 preparation of 1-methoxy-3- (4- (2-methoxyethyl) benzene) oxy-2-propyl acrylate (formula:
(1) preparation of 1-methoxy-3- (4- (2-methoxyethyl) benzene) oxy-2-propanol
4- (2-methoxyethyl) phenol (15.2g, 100.0mmol), potassium carbonate (13.8g, 100.0mmol) and absolute ethanol (200mL) were added to a three-necked flask in this order, and after the mixture was stirred under reflux for 1 hour, 1-chloro-3-methoxy-2-propanol (6.5g, 50.0mmol) was slowly added dropwise thereto, and stirring was continued for 24 hours. The reaction was cooled to room temperature, filtered, the filtrate was rotary evaporated to remove ethanol, the crude product was diluted with dichloromethane (200mL) and washed with aqueous sodium hydroxide (5% wt, 80mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporation to give the title compound as a pale yellow liquid (11.9g, 99.4%).
LC-MS(ESI,pos.ion)m/z：263[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.16-7.14(d,2H)，6.88-6.86(d,2H)，4.20-4.11(m,1H)，4.05-3.98(m,2H)，3.60-3.56(m,4H)，3.43(s,3H)，3.37(s,3H)，2.86-2.83(t,2H)。
(2) Preparation of 1-methoxy-3- (4- (2-methoxyethyl) benzene) oxy-2-propyl acrylate
To a single-neck flask were added 1-methoxy-3- (4- (2-methoxyethyl) benzene) oxy-2-propanol (10.1g, 42.0mmol), triethylamine (8.7g, 86.5mmol), 4-dimethylaminopyridine (1.0g, 8.5mmol) and tetrahydrofuran (70mL) in this order, and after sufficient dissolution, acryloyl chloride (8.1g, 88.6mmol) was slowly added dropwise thereto, and stirring was continued for 24 h. The reaction was filtered, tetrahydrofuran removed by rotary evaporation and dissolved in dichloromethane (200mL), aqueous sodium hydroxide (5% wt, 80mL) was added and stirred for 0.5 h. The solvent was removed by rotary evaporation after separation and the product was purified by column chromatography (n-Hexane/EtOAc (v/v) ═ 40/1) to give the title compound as a colorless viscous liquid (8.0g, 68.8%). The mass and nuclear magnetic H spectrum test data are as follows:
LC-MS(ESI,pos.ion)m/z：317[M+Na]+；
1H NMR(400MHz，CDCl3)δ(ppm)：7.16-7.14(d,2H)，6.88-6.86(d,2H)，6.49-6.44(t,1H)，6.22-6.20(m,1H)，5.89-5.86(t,1H)，5.42-5.37(m,1H)，4.21-4.14(m,2H)，3.72-3.71(d,2H)，3.59-3.56(t,2H)，3.41(s，3H)，3.36(s，3H)，2.86-2.82(t,2H)。
preparation of polymers
The components in the following examples are uniformly mixed according to the dosage proportion in the following examples to obtain a raw material mixture, then the raw material mixture is transferred to a mould consisting of two layers of glass and a polytetrafluoroethylene sheet, the mould is put into a 65 ℃ oven to react for 3 hours, the temperature of the oven is raised to 100 ℃ and kept for 3 hours to obtain a transparent elastic polymer, the obtained material is cleaned by absolute ethyl alcohol reflux to remove residual raw materials, and vacuum drying is carried out at 60 ℃ for 24 hours to obtain the following polymer.
Example 23: preparation of Polymer A-1
| Components | Component content (g) |
| The compound prepared in example 1 | 0.6000 |
| Compound prepared in example 2 | 0.4000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 24: preparation of Polymer A-2
| Components | Component content (g) |
| EXAMPLE 2 preparation ofThe compounds prepared | 0.7000 |
| Compound prepared in example 5 | 0.3000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 25: preparation of Polymer A-3
| Components | Component content (g) |
| The compound prepared in example 1 | 0.7000 |
| Compound prepared in example 10 | 0.3000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 26: preparation of Polymer A-4
| Components | Component content (g) |
| Compound prepared in example 5 | 0.7000 |
| 2-Phenylethyl methacrylate | 0.3000 |
| Ethylene glycol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Azodiisobutyronitrile | 0.0100 |
Example 27: preparation of Polymer A-5
| Components | Component content (g) |
| Compound prepared in example 5 | 0.5000 |
| Compound prepared in example 6 | 0.5000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 28: preparation of Polymer A-6
| Components | Component content (g) |
| Compound prepared in example 5 | 0.6000 |
| Compound prepared in example 14 | 0.4000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 29: preparation of Polymer A-7
| Components | Component content (g) |
| Compound prepared in example 5 | 0.6000 |
| Compound prepared in example 20 | 0.4000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) benzenePhenol and its salts | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonate | 0.0100 |
Example 30: preparation of Polymer A-8
| Components | Content of Components (g) |
| Compound prepared in example 6 | 0.4000 |
| 2-Phenylethyl acrylate | 0.6000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 31: preparation of Polymer A-9
| Components | Component content (g) |
| Compound prepared in example 6 | 0.3000 |
| Compound prepared in example 13 | 0.7000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 32: preparation of Polymer A-10
| Components | Component content (g) |
| Compound prepared in example 6 | 0.3000 |
| The compound prepared in example 19 | 0.7000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonate | 0.0100 |
Example 33: preparation of Polymer A-11
| Components | Component content (g) |
| Compound prepared in example 7 | 1.0000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 34: preparation of Polymer A-12
| Components | Component content (g) |
| Compound prepared in example 7 | 0.6000 |
| 2-Phenylethyl methacrylate | 0.4000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 35: preparation of Polymer A-13
| Components | Component content (g) |
| Compound prepared in example 7Article (A) | 0.3500 |
| Compound prepared in example 8 | 0.6500 |
| Ethylene glycol diacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Azodiisobutyronitrile | 0.0100 |
Example 36: preparation of Polymer A-14
| Components | Component content (g) |
| Compound prepared in example 8 | 0.5000 |
| Acrylic acid 2-phenyl ethyl ester | 0.5000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 37: preparation of Polymer A-15
| Components | Component content (g) |
| The compound prepared in example 9 | 0.9000 |
| Acrylic acid 2-phenyl ethyl ester | 0.1000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0200 |
Example 38: preparation of Polymer A-16
| Components | Component content (g) |
| Compound prepared in example 10 | 0.3000 |
| Acrylic acid 2-phenyl ethyl ester | 0.7000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonate | 0.0100 |
Example 39: preparation of Polymer A-17
| Components | Component content (g) |
| Compound prepared in example 11 | 1.0000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonate | 0.0100 |
Example 40: preparation of Polymer A-18
Example 41: preparation of Polymer A-19
| Components | Component content (g) |
| Compound prepared in example 12 | 0.2700 |
| Acrylic acid 2-phenyl ethyl ester | 0.7300 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0200 |
Example 42: preparation of Polymer A-20
| Components | Component content (g) |
| Compound prepared in example 13 | 1.000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 43: preparation of Polymer A-21
| Components | Component content (g) |
| Compound prepared in example 13 | 0.7000 |
| 2-Phenylethyl methacrylate | 0.3000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 44: preparation of Polymer A-22
| Components | Component content (g) |
| Compound prepared in example 13 | 0.7000 |
| Compound prepared in example 14 | 0.3000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 45: preparation of Polymer A-23
| Components | Component content (g) |
| The compound prepared in example 14 | 0.4000 |
| Acrylic acid 2-phenyl ethyl ester | 0.6000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 46: preparation of Polymer A-24
| Components | Component content (g) |
| Compound prepared in example 17 | 1.0000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 47: preparation of Polymer A-25
| Components | Component content (g) |
| Compound prepared in example 17 | 0.7500 |
| Acrylic acid 2-phenyl ethyl ester | 0.2500 |
| 1, 4-butanediol diacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0200 |
Example 48: preparation of Polymer A-26
| Components | Component content (g) |
| Compound prepared in example 18 | 0.2000 |
| Acrylic acid 2-phenyl ethyl ester | 0.8000 |
| 1, 4-butanediol diacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0200 |
Example 49: preparation of Polymer A-27
| Components | Component content (g) |
| The compound prepared in example 19 | 1.0000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 50: polymer A-28
Example 51: preparation of Polymer A-29
| Components | Component content (g) |
| The compound prepared in example 19 | 0.8000 |
| Compound prepared in example 20 | 0.2000 |
| Trimethylolpropane triacrylate | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 52: preparation of Polymer A-30
| Components | Component content (g) |
| Compound prepared in example 20 | 0.4000 |
| Acrylic acid 2-phenyl ethyl ester | 0.6000 |
| Trimethylolpropane triacrylateEsters | 0.0500 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonate | 0.0100 |
Example 53: preparation of Polymer A-31
| Components | Component content (g) |
| Compound prepared in example 21 | 0.3500 |
| Acrylic acid 2-phenyl ethyl ester | 0.6500 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonate | 0.0100 |
Example 59: preparation of Polymer A-32
| Components | Component content (g) |
| The compound prepared in example 54 | 0.8000 |
| Compound prepared in example 16 | 0.2000 |
| 1, 4-butanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Bis (4-tert-butylcyclohexyl) peroxydicarbonates | 0.0100 |
Example 60: preparation of Polymer A-33
Example 61: preparation of Polymer A-34
| Components | Component content (g) |
| The compound prepared in example 58 | 0.3500 |
| Compound prepared in example 22 | 0.6500 |
| 1, 6-hexanediol diacrylate | 0.0350 |
| 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-propenyl) phenol | 0.0150 |
| Azodiisobutyronitrile | 0.0100 |
Determination of refractive index of Polymer
The refractive indices of the polymers obtained in examples 23 to 53 and 59 to 61 were measured under the following conditions: the refractive index of the material at a wavelength of 589nm was determined at 20 ℃ using an antopa DR-M2 refractometer.
The test results are shown in table 1. It can be seen from the data presented in the table that the following polymers all have high refractive indices, substantially greater than 1.53, and are well suited for use in the preparation of ophthalmic medical devices.
Table 1: refractive indices of the polymers obtained in examples 23 to 53 and 59 to 61
Determination of spectral transmittance of Polymer
The polymers obtained in examples 23 to 53 and 59 to 61 above were tested for their spectral transmittance under the following conditions: the spectral transmittance of the material in the light wave range of 200nm-800nm is tested by an Agilent Cary60 ultraviolet-visible spectrophotometer at room temperature.
The test results show that the polymers of examples 23-53 and 59-61 have maximum values of spectral transmittance higher than 80% in the visible light range. Table 2 shows the UV transmission cutoff wavelengths (wavelength corresponding to 1% UV transmittance and wavelength corresponding to 10% UV transmittance) and the spectral transmittances (maximum values) of the polymers A-1 to A-34. As can be seen from Table 2, the following polymers all have higher spectral transmittances. And the wavelength corresponding to the transmittance of 10% in an ultraviolet region is not less than 360nm, which shows that the following polymers have better ultraviolet light interception effect.
Table 2: spectral transmittances of the polymers obtained in examples 25 to 53 and 59 to 61
Determination of mechanical Properties of polymers
And (3) tensile test: the material was cut into a predetermined rectangular specimen (effective size: width 0.83300mm, thickness 0.40000mm, length 14.00000mm) with a cutter, and tested at room temperature of 26 ℃ and air humidity of 77% with an INSTRON 3367 type material tester, and the displacement rate was 500.00000 mm/min. Tests show that the following polymers have relatively good mechanical properties and are suitable for preparing artificial crystals. The following polymers have better spectral transmittance and refractive index, so that the following polymers can be conveniently used for forming the foldable artificial lens with thinness and good optical performance.
Table 3: mechanical Property test of polymers obtained in examples 23 to 53 and 59 to 61
| Polymer numbering | Tensile Strength (MPa) | Elongation at Break (%) | Modulus of elasticity (MPa) |
| Polymer A-1 | 10.04 | 73.32 | 15.8046 |
| Polymer A-2 | 8.79 | 82.49 | 11.6138 |
| Polymer A-3 | 8.87 | 68.8 | 17.16716 |
| PolymerisationSubstance A-4 | 10.99 | 83.65 | 29.0687 |
| Polymer A-5 | 6.90 | 76.3 | 12.83947 |
| Polymer A-6 | 8.03 | 61.34 | 20.6429 |
| Polymer A-7 | 8.61 | 60.38 | 19.37559 |
| Polymer A-8 | 8.42 | 73.42 | 17.58814 |
| Polymer A-9 | 5.73 | 54.29 | 10.64846 |
| Polymer A-10 | 5.69 | 68.64 | 14.74738 |
| Polymer A-12 | 6.50 | 77.88 | 16.71942 |
| Polymer A-13 | 7.76 | 41.3 | 30.22717 |
| Polymer A-14 | 5.11 | 74.41 | 11.65524 |
| Polymer A-17 | 10.38 | 88.63 | 23.7015 |
| Polymer A-18 | 10.76 | 76.08 | 20.11333 |
| Polymer A-19 | 8.77 | 58.39 | 16.59514 |
| Polymer A-20 | 7.00 | 81.6 | 19.15054 |
| Polymer A-21 | 12.51 | 54.24 | 43.29495 |
| Polymer A-22 | 9.72 | 72.71 | 20.57469 |
| Polymer A-23 | 12.18 | 70.08 | 24.22184 |
| Polymer A-24 | 9.03 | 95.98 | 14.48699 |
| Polymer A-25 | 9.77 | 70.09 | 17.6174 |
| Polymer A-26 | 7.75 | 61.93 | 17.47411 |
| Polymer A-27 | 7.82 | 99.25 | 17.52005 |
| Polymer A-28 | 7.55 | 73.76 | 18.84236 |
| Polymer A-29 | 6.82 | 72.68 | 16.05403 |
| Polymer A-30 | 11.27 | 69.94 | 25.10842 |
| Polymer A-31 | 9.03 | 85.81 | 15.24632 |
| Polymer A-32 | 7.64 | 83.5 | 12.6215 |
| Polymer A-33 | 8.01 | 79.5 | 15.8156 |
| Polymer A-34 | 10.45 | 82.14 | 13.2617 |
In the description herein, references to the description of the terms "one embodiment," "another embodiment," "an example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the example or example is included in at least one example or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention and examples have been shown and described above, it is understood that the above embodiments, examples are illustrative and not to be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments, examples by those of ordinary skill in the art within the scope of the present invention.
Claims (24)
1. A monomer having the structure of formula (I):
wherein the content of the first and second substances,
R1is hydrogen or methyl;
R2is methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl;
n is 0, 1 or 2, R3Each independently hydrogen, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, trifluoroethyl, trifluoroethoxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, phenyl, benzyl, phenethyl, phenylpropyl, phenoxy.
2. The monomer of claim 1, wherein R is1Is hydrogen or methyl; the R is2Is methyl or ethyl; the R is3Each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoroethyl, trifluoromethoxy, trifluoroethoxy, methoxymethyl, methoxyethyl, methoxypropyl, phenyl, phenoxy or benzyl, and n is 0 or 1.
3. The monomer of claim 1, wherein the monomer is:
4. A method of preparing the monomer of any one of claims 1-2, comprising: subjecting a compound of formula (II) to a condensation reaction with a compound of formula (III) to obtain the monomer:
wherein n and R1、R2And R3Having the definition as set forth in any of claims 1-2.
5. The process according to claim 4, characterized in that the condensation reaction is carried out in an aprotic solvent.
6. The method according to claim 5, wherein the aprotic solvent is selected from at least one of dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 1-trichloroethane, chlorobenzene, dichlorobenzene, pentane, n-hexane, methylcyclohexane, 1, 1-diethoxypropane, 1, 1-dimethoxymethane, 2-dimethoxypropane, 1,2,3, 4-tetrahydronaphthalene, decahydronaphthalene, benzene, toluene, xylene, isopropylbenzene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1, 4-dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethyl acetate, and butyl acetate.
7. The process according to any one of claims 4 to 6, wherein the condensation reaction is carried out in the presence of a base.
8. The process according to claim 7, wherein the base is selected from at least one of triethylamine, diisopropylethylamine, diethylamine, pyridine, N-dimethyl-pyridine, triethylenediamine, tetramethylethylenediamine, N-methylmorpholine, 1, 8-diazabicycloundecen-7-ene, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide.
9. The method according to claim 6, wherein the compound of formula (II) is obtained by a substitution reaction between a compound of formula (IV) and a compound of formula (V),
wherein n and R2And R3Having the definition as set forth in any one of claims 1 to 3; r is4is-Cl, -Br, -OTs or-OMs.
10. The process according to claim 9, characterized in that the substitution reaction is carried out in a protic solvent.
11. The method according to claim 10, wherein the protic solvent is selected from at least one of ethanol, isopropanol, N-butanol, N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, and dioxane.
12. The process according to claim 9, characterized in that the substitution reaction is carried out in the presence of an inorganic base.
13. The method of claim 12, wherein the inorganic base is selected from at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide.
14. A polymer characterized in that the monomers constituting the polymer are selected from the monomers according to any one of claims 1 to 3.
15. The polymer according to claim 14, wherein the monomers constituting the polymer are further selected from compounds having a structural formula satisfying formula (VI):
wherein the content of the first and second substances,
R5is H or methyl;
L1is a bond or C1-6An alkylene group;
ar is optionally substituted phenyl.
16. The polymer of claim 14 or 15, wherein the monomers comprising the polymer are further selected from at least one of a crosslinker, an initiator, and an ultraviolet absorber.
17. The polymer of claim 16, wherein the cross-linking agent is selected from at least one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 3-propanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol diacrylate, trimethylolpropane trimethacrylate, 1, 5-bis (methacryloyloxy) -2,2,3,3,4, 4-hexafluorohexane, 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, and pentaerythritol tetraacrylate.
18. The polymer of claim 16, wherein the initiator is selected from at least one of benzoyl peroxide, t-butyl hydroperoxide, cumyl hydroperoxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile, and azobis (2, 4-dimethylvaleronitrile).
19. The polymer of claim 16, wherein the uv absorber is selected from at least one of a copolymerizable benzotriazole-based compound and a copolymerizable benzophenone-based compound.
20. The polymer of claim 16, wherein the cross-linking agent is present in an amount of 2 to 7 wt.%, based on the total weight of monomers used to synthesize the polymer;
based on the total weight of monomers used for synthesizing the polymer, the amount of the initiator is 0.1-5 wt%; and
the amount of the ultraviolet absorber is 1-2 wt% based on the total weight of monomers used to synthesize the polymer.
21. Use of a polymer according to any one of claims 14 to 20 in the manufacture of an ophthalmic medical device.
22. The use of claim 21 wherein the ocular medical device is an intraocular lens, contact lens, corneal modifier, intracorneal lens, corneal inlay, corneal ring, or glaucoma filtering device.
23. A process for preparing a polymer as claimed in any of claims 14 to 20,
subjecting the raw mixture to a gradient heating treatment so as to obtain said polymer,
wherein the raw material mixture contains at least one monomer according to any one of claims 1 to 3, and optionally at least one selected from the group consisting of a compound represented by formula (VI), a crosslinking agent, an initiator, and an ultraviolet absorber.
24. The method of claim 23, wherein the gradient heat treatment comprises:
a first reaction stage, wherein the temperature of the first reaction stage is 40-70 ℃, and the reaction time is 1-24 hours; and
and in the second reaction stage, the temperature of the second reaction stage is 80-120 ℃, and the reaction time is 1-24 hours.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016110617596 | 2016-11-24 | ||
| CN201611061759 | 2016-11-24 | ||
| PCT/CN2017/112635 WO2018095369A1 (en) | 2016-11-24 | 2017-11-23 | Monomer, polymer, method for preparation thereof and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109641823A CN109641823A (en) | 2019-04-16 |
| CN109641823B true CN109641823B (en) | 2022-05-06 |
Family
ID=62195763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780052243.1A Active CN109641823B (en) | 2016-11-24 | 2017-11-23 | Monomers, polymers, preparation method and use thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109641823B (en) |
| WO (1) | WO2018095369A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075122B (en) * | 2020-08-17 | 2024-01-02 | 康小林 | Hydrophilic azo compound and application thereof |
| JP7081032B1 (en) * | 2021-09-22 | 2022-06-06 | 東京応化工業株式会社 | Composition and photosensitive composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102812057A (en) * | 2010-04-01 | 2012-12-05 | 旭硝子株式会社 | Fluorine-containing compound and fluorine-containing polymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101267674B1 (en) * | 2010-11-12 | 2013-05-24 | 롬엔드하스전자재료코리아유한회사 | Photo-sensitivity resin composition, its Dielectric insulating film and Electronic device |
-
2017
- 2017-11-23 WO PCT/CN2017/112635 patent/WO2018095369A1/en active Application Filing
- 2017-11-23 CN CN201780052243.1A patent/CN109641823B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102812057A (en) * | 2010-04-01 | 2012-12-05 | 旭硝子株式会社 | Fluorine-containing compound and fluorine-containing polymer |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis and characterization of novel multifunctional poly(methyl methacrylate)s as potential fluorescent labels for electron-beam lithography";Liao, Shaowen 等;《Polymer International》;20050107;第54卷(第4期);第624页Scheme 2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109641823A (en) | 2019-04-16 |
| WO2018095369A1 (en) | 2018-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2599166B2 (en) | Benzotriazole compounds | |
| CN109641831B (en) | Monomers, polymers, preparation method and use thereof | |
| TWI449986B (en) | Light filters comprising a naturally occurring chromophore and derivatives thereof | |
| KR101592448B1 (en) | Uv/visible light absorbers for ophthalmic lens materials | |
| TWI473629B (en) | Visible light absorbers for ophthalmic lens materials | |
| US4868251A (en) | Ultraviolet light absorbing silicone compositions | |
| US7803359B1 (en) | UV-absorbers for ophthalmic lens materials | |
| CN102250282B (en) | Intraocular lenses essentially free from glistenings | |
| CA2683002C (en) | Uv-absorbers for ophthalmic lens materials | |
| CN110300744B (en) | Compounds for optically active devices | |
| CN110300747B (en) | Double-type compound for optical active device | |
| CA2631595A1 (en) | Polymer composition having a high refractive index | |
| TW201105639A (en) | UV/visible light absorbers for ophthalmic lens materials | |
| CN109641855B (en) | Azo compounds, polymers, and processes for their preparation and use | |
| JP2003084242A (en) | Dyestuff for intraocular lens and intraocular lens | |
| CN109641823B (en) | Monomers, polymers, preparation method and use thereof | |
| ES2676743T3 (en) | Acrylic ophthalmic materials with high refractive index and minimized glare | |
| EP3363787A1 (en) | Hydrophobic compounds for optically active devices | |
| CN110462448A (en) | The hydrophilic material of high refractive index | |
| CN110382628B (en) | Polymerizable dye compound, preparation method, polymer containing dye and application | |
| JP2020523120A (en) | Intraocular lens composition | |
| EP2427509A1 (en) | Polymer composition | |
| KR20150005650A (en) | Stable polymerizable uv-absorbing colorant for intraocular lens | |
| US7947849B2 (en) | UV-absorbers for ophthalmic lens materials | |
| Helmstetter et al. | High-refractive quinolinone-based polymers for ophthalmic devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190729 Address after: 523871 Room 301, 3rd floor, 368 Zhenan Middle Road, Sha Community, Chang'an Town, Dongguan City, Guangdong Province Applicant after: Dongguan Dongyang Sunshine Medical Intelligent Device R&D Co.,Ltd. Address before: 523808 Guangdong province Dongguan Songshan Lake Science and Technology Industrial Park Applicant before: SUNSHINE LAKE PHARMA Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Monomer, polymer, preparation method and application Effective date of registration: 20221114 Granted publication date: 20220506 Pledgee: China Development Bank Shenzhen Branch Pledgor: Dongguan Dongyang Sunshine Medical Intelligent Device R&D Co.,Ltd. Registration number: Y2022980021906 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20231117 Granted publication date: 20220506 Pledgee: China Development Bank Shenzhen Branch Pledgor: Dongguan Dongyang Sunshine Medical Intelligent Device R&D Co.,Ltd. Registration number: Y2022980021906 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Monomers, polymers, preparation methods and their applications Effective date of registration: 20231121 Granted publication date: 20220506 Pledgee: China Development Bank Shenzhen Branch Pledgor: Dongguan Dongyang Sunshine Medical Intelligent Device R&D Co.,Ltd. Registration number: Y2023980066753 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |