CN116376000A - High-refraction polymer, preparation method and application - Google Patents
High-refraction polymer, preparation method and application Download PDFInfo
- Publication number
- CN116376000A CN116376000A CN202310000497.6A CN202310000497A CN116376000A CN 116376000 A CN116376000 A CN 116376000A CN 202310000497 A CN202310000497 A CN 202310000497A CN 116376000 A CN116376000 A CN 116376000A
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- CN
- China
- Prior art keywords
- general formula
- group
- high refractive
- polymer
- compound represented
- Prior art date
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- Pending
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- 229920000642 polymer Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 230000003287 optical effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 26
- 239000006227 byproduct Substances 0.000 claims description 24
- -1 n-octyl group Chemical group 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 238000002834 transmittance Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 10
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 9
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 claims description 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 claims description 6
- WHLKCPQPGTUZBU-UHFFFAOYSA-N 1-[4-[9-(4-pyren-1-ylphenyl)fluoren-9-yl]phenyl]pyrene Chemical compound C1=C2C(C3=CC=C(C=C3)C3(C=4C=CC(=CC=4)C=4C5=CC=C6C=CC=C7C=CC(C5=C76)=CC=4)C4=CC=CC=C4C=4C3=CC=CC=4)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WHLKCPQPGTUZBU-UHFFFAOYSA-N 0.000 claims description 5
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- BWNYAKOZXVLZQO-UHFFFAOYSA-N 1,1-dibromocyclohexane Chemical compound BrC1(Br)CCCCC1 BWNYAKOZXVLZQO-UHFFFAOYSA-N 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- SAWCWRKKWROPRB-UHFFFAOYSA-N 1,1-dibromohexane Chemical compound CCCCCC(Br)Br SAWCWRKKWROPRB-UHFFFAOYSA-N 0.000 claims description 3
- STBMZSJLFYGOJU-UHFFFAOYSA-N 1,1-dibromooctane Chemical compound CCCCCCCC(Br)Br STBMZSJLFYGOJU-UHFFFAOYSA-N 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 2
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- LUOAEJWSKPQLJD-UHFFFAOYSA-N syringyl alcohol Natural products COC1=CC(CO)=CC(OC)=C1O LUOAEJWSKPQLJD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 claims description 2
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 24
- 238000012545 processing Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001212 derivatisation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000007965 phenolic acids Chemical class 0.000 description 3
- 235000009048 phenolic acids Nutrition 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PKPMMGIFZKHHPY-UHFFFAOYSA-N carbonic acid;1,2-xylene Chemical compound OC(O)=O.CC1=CC=CC=C1C PKPMMGIFZKHHPY-UHFFFAOYSA-N 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- ZLUGESOGDIWBKF-UHFFFAOYSA-N hexyl 4-hydroxy-3,5-dimethoxybenzoate Chemical compound CCCCCCOC(=O)C1=CC(OC)=C(O)C(OC)=C1 ZLUGESOGDIWBKF-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- INHKGYQHYVEHRR-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]-1,2-dinaphthalen-1-ylfluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=C(C4=C(C=C3)C5=CC=CC=C5C4(C6=CC=C(C=C6)OCCO)C7=CC=C(C=C7)OCCO)C8=CC=CC9=CC=CC=C98 INHKGYQHYVEHRR-UHFFFAOYSA-N 0.000 description 1
- 206010060800 Hot flush Diseases 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VKDPSTNROWSESS-UHFFFAOYSA-N OCCOC1(C(=C2C=CC=CC2=CC1)C1=CC=CC2=CC=CC=C12)OCCO Chemical group OCCOC1(C(=C2C=CC=CC2=CC1)C1=CC=CC2=CC=CC=C12)OCCO VKDPSTNROWSESS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- TUOSEEPBHUCCAO-UHFFFAOYSA-N butyl 4-hydroxy-3-methoxybenzoate Chemical compound CCCCOC(=O)C1=CC=C(O)C(OC)=C1 TUOSEEPBHUCCAO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JGJWEXOAAXEJMW-UHFFFAOYSA-N dimethyl naphthalene-1,2-dicarboxylate Chemical compound C1=CC=CC2=C(C(=O)OC)C(C(=O)OC)=CC=C21 JGJWEXOAAXEJMW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a high-refraction polymer, a preparation method and application thereof, wherein the high-refraction polymer comprises a structural unit derived from a bio-based monomer shown in a general formula (Y)
Further comprising structural units derived from the compounds of the general formula (A)
And a structural unit derived from a compound represented by the general formula (B)
Description
Technical Field
The invention relates to the field of bio-based polymers, in particular to a high-refraction polymer, a preparation method thereof and application thereof in the field of optical lenses.
Background
The camera is a key component in the fields of mobile intelligent terminals, automobile intellectualization, security monitoring and the like, and materials used for the camera mainly comprise optical glass and optical resin. The optical glass has the advantages of high cost, difficult molding, high technical difficulty, difficulty in meeting the use requirements of daily life, easy molding, high production efficiency, low cost and the like, and becomes the main stream of the market gradually.
Currently, the main optical resins on the market include high refractive PC, high refractive polyester, cyclic olefin polymer COC and COP, wherein the high refractive PC is an indispensable material for optical lenses because of its higher refractive index. The monomers related to the high refraction PC reported in the market and the patent at present are bisphenol or diether compounds derived from fluorene ring and naphthalene ring. The high refraction PC patent manufacturer mainly protects the proportion of the monomer to the monomer, in Mitsubishi patent, the core monomer is mainly binaphthol and bisphenol fluorene compound, in Di patent, the core monomer is diether fluorene, methyl bisphenol fluorene, binaphthol and bisphenol anthrone compound;
patent document CN201310062561.X proposes a polycarbonate containing 9, 9-bis- (4- (2-hydroxyethoxy) phenyl) fluorene and its derivatives, and patent document CN104769007a discloses a polycarbonate containing 2, 2-bis- (2-hydroxyethoxy) -1, 1-binaphthyl and its derivatives; patent document CN110741030a discloses a polycarbonate containing 9, 9-bis (4- (2-hydroxyethoxy) phenyl) dinaphthyl fluorene structural units.
The above mentioned monomers are all derived from coal tar, and the coal tar has the characteristics of complex composition, high boiling point and the like, and the purification needs higher energy consumption, on the other hand, the monomers are non-bio-based and non-degradable, while bio-based polymer materials have more and more attention in recent years due to the advantages of sustainable development, small environmental pollution, good biocompatibility, easy degradation and the like, and research hot flushes are initiated in various fields such as petroleum-based polymer material substitutes and the like, and bio-based high refraction PC is also an object of attention.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-refraction polymer and a preparation method thereof, and the system contains a bio-based monomer through the construction of a structure and has the advantages of good biocompatibility of a bio-based material and the like; in addition, the byproducts generated in the reaction process contain alcohol, which is favorable for separating and collecting phenol, reduces the energy consumption of industrial production and reduces the risk of pipeline blockage. The high refractive polymer is suitable for preparing optical lenses or optical films, and the impact strength and the sheet rate of the high refractive polymer are obviously improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the present invention provides a high refractive polymer comprising:
structural units derived from biobased monomers of the general formula (Y),
in the general formula (Y), R 1 Each independently represents a hydrogen atom, a methyl group; r is R 2 Each independently represents a C2-C15 alkyl group, a C5-C15 cycloalkyl group, preferably a C4-C8 alkyl group, a C6-C10 cycloalkyl group, more preferably a n-butyl group, a n-hexyl group, a n-octyl group, a cyclohexyl group; r is R 3 Represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, preferably a C6-C12 cycloalkyl group, a C6-C20 alkyl group, more preferably a hexyl group, an octyl group or a cyclohexyl group;
structural units derived from a compound represented by the general formula (A),
in the general formula (A), R 4 、R 5 Each independently represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group;
structural units derived from a compound represented by the general formula (B),
in the general formula (B), R 6 、R 7 Each independently represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a CC20 cycloalkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group;
wherein the structural unit derived from the compound represented by the general formula (a) and the structural unit derived from the compound represented by the general formula (B) are optionally one or both of them;
the high refractive polymer has a terminal hydroxyl content of less than 1000ppm, preferably 300 to 500ppm.
In the present invention, the compound represented by the general formula (A) is at least one compound selected from the following structural compounds BPEF, BPPF, BAAPEF
The compound shown in the general formula (B) is at least one of the following structural compounds BHEBN and BHEBBN
In the present invention, the high refractive polymer is terminated with benzene rings, and the terminal hydroxyl group content is less than 1000ppm, preferably 300 to 500ppm, mainly derived from the monomer of the general formula (A) and/or the general formula (B).
In the invention, the content of small molecule byproducts in the high refractive polymer is lower than 500ppm, preferably 100-300ppm; the small molecule byproducts include phenol, C4-C8 alcohols, such as butanol, hexanol, octanol, and the like. The small molecule by-products in the composition of the invention are mainly derived from carbonic acid diester and/or monomer of general formula (Y), mainly phenol.
The polymer has low terminal hydroxyl content and small molecular byproducts, the reduction of the terminal hydroxyl and small molecular byproducts in the system reduces hydrolysis groups in the system, improves the stability of the polymer, is beneficial to avoiding degradation in the processing process of the product, reduces the hydrogen bond influence of the high-refraction polyester product, reduces the rigidity of the product, reduces Tg (glass transition temperature), and improves the processability of the product, especially the impact strength and the sheet rate. The invention greatly improves phenomena of yellowing, degradation and the like in the reprocessing process of products by limiting terminal hydroxyl groups and small molecular byproducts in the system.
In the present invention, the weight average molecular weight of the high refractive polymer is 10000 to 150000, preferably 20000 to 130000, more preferably 30000 to 120000.
In the invention, the refractive index of the high refractive polymer is 1.625-1.685 at 23 ℃ and the wavelength of 589 nm;
in the invention, the Abbe number of the high-refraction polymer is not higher than 24, the light transmittance of the high-refraction polymer is more than 88%, the haze is less than 0.7%, and the b value is less than 2.
In addition, the high-refraction polymer disclosed by the invention has the advantages of stability, high light transmittance, excellent dimensional stability, good product flexibility, strong plasticity, lower rigidity and Tg, and improved product processability.
In the present invention, the high refractive polymer comprises a structural unit derived from a biobased monomer represented by the general formula (Y) and either one or both of a structural unit derived from a compound represented by the general formula (a) and a structural unit derived from a compound represented by the general formula (B), wherein the molar ratio of the structural unit derived from the biobased monomer represented by the general formula (Y) to the structural unit derived from the compound represented by the general formula (a) and the structural unit derived from the compound represented by the general formula (B) is 1:0 to 20:0 to 20, preferably 1:0.1 to 15:0.1 to 15, and the structural unit derived from the compound represented by the general formula (A) and the structural unit derived from the compound represented by the general formula (B) are not 0 at the same time.
In the invention, the bio-based monomer shown in the general formula (Y) has no special requirement on the source, can be directly purchased or self-made, can be prepared by a technician by adopting any realizable method according to the needs based on the prior art, and is not particularly limited in the specific preparation process; in some examples, the method for preparing a bio-based monomer of formula (Y) comprises the steps of:
(1) The intermediate C is prepared by esterification reaction of vanillic acid or syringic acid and alcohol;
(2) And (3) performing polymerization reaction on dibromoalkane and the intermediate C prepared in the step (1) to prepare the bio-based monomer shown in the general formula (Y).
The step (1) of the preparation method of the invention is carried out in the presence of a catalyst, the scheme adopted is a technology disclosed in the prior art, the invention does not require any specific requirements, for example, reference can be made to the literature of partial bio-based poly (amide imide) s by polycondensation of aromatic diacylhydrazides based on lignin-derived phenolic acids and aromatic dianhydrides: synthesis, development, and computational publications.journal of Polymer Science Part A: polymer chemistry.2017;55:3636-3645.
In some examples, in step (1), the alcohol is selected from at least one of butanol, hexanol, octanol, cyclohexanol;
the molar ratio of the vanillic acid or the syringic acid to the alcohol is 1:1 to 4, preferably 1:1.5 to 2.5;
the esterification reaction is carried out at a temperature of 100-150, preferably 120-140; the time is 1 to 12, preferably 2 to 6;
the esterification reaction is carried out under the action of a catalyst, and the catalyst is preferably sulfuric acid;
preferably, the catalyst is used in an amount of 0.5 to 3wt% based on the mass of the alcohol.
The intermediate prepared in the step (1) of the preparation method has a structure shown in a general formula (C):
in the formula (C), R 1 、R 2 And R in the general formula (Y) 1 、R 2 The same applies.
The preparation method of the invention comprises the step (2) of carrying out polymerization reaction in the presence of a catalyst, wherein the scheme adopted is a disclosed process in the prior art, and the invention does not require specific requirements, for example, reference can be made to the literature of partial bio-based poly (amide imide) s by polycondensation of aromatic diacylhydrazides based on lignin-derived phenolic acids and aromatic dianhydrides: synthesis, development, and computational publications.journal of Polymer Science Part A: polymer chemistry.2017;55:3636-3645.
In some examples, in step (2), the dibromoalkane is selected from at least one of dibromohexane, dibromooctane, 1.4 dibromocyclohexane;
the molar ratio of dibromoalkane to intermediate C prepared in step (1) is 1:0.4 to 0.8, preferably 1:0.5 to 0.6;
the reaction temperature is 80-140 ℃, preferably 100-120 ℃; the time is 8-20, preferably 12-16;
the polymerization reaction is carried out under the action of a catalyst, preferably potassium carbonate;
preferably, the molar ratio of the catalyst to dibromoalkane is 1:0.5 to 1.
The invention also provides a preparation method of the high-refraction polymer, which can be prepared by adopting a polymerization reaction of a compound shown in a general formula (A) and/or a general formula (B) and a bio-based monomer shown in a general formula (Y), and optionally carbonic diester, wherein the method is a disclosed process in the prior art, and in some examples, the preferred conditions adopted by the invention are as follows:
according to the preparation method, the molar ratio of the sum of the bio-based monomer shown in the general formula (Y) and the carbonic acid diester to the sum of the compounds shown in the general formula (A) and the general formula (B) is 1-0.9:1, preferably 1-0.93:1.
According to the preparation method, the carbonic diester is selected from at least one of diphenyl carbonate, dimethylbenzene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, and preferably at least one of diphenyl carbonate and dimethylbenzene carbonate.
The preparation method of the invention can be prepared by a melt transesterification polycondensation method in the presence of a catalyst or in the absence of a catalyst;
the catalyst is at least one of sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, triethylamine, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, stannic chloride, stannic acetate, cerium acetylacetonate, zirconium acetate and tetrabutoxyzirconium, preferably at least one of sodium hydroxide, sodium bicarbonate, cesium carbonate, cerium acetylacetonate, zirconium acetate and zinc acetate;
the molar ratio of the catalyst to the sum of the bio-based monomer of the general formula (Y) and the carbonic acid diester is 1X 10 -8 ～1×10 -3 Preferably 1X 10 -6 ～1×10 -4 。
The preparation method comprises a material melting section, an ester exchange section and a polycondensation section; wherein the melting section has a melting temperature of 100-250 ℃, preferably 140-200 ℃, and the residence time of the stage is 20-50 min, preferably 30-40 min; transesterification section: the pressure is 20-80 KPa, the reaction temperature is 140-280 ℃, preferably 170-250 ℃, and the reaction time is 30-180 min, preferably 60-90 min; polycondensation section: the pressure is 5 to 1000Pa (A), preferably 50 to 150Pa (A), the temperature is 200 to 350 ℃, preferably 250 to 300 ℃, and the time is 5 to 90min, preferably 15 to 60min. During the reaction, the small molecular compounds formed are immediately removed by distillation.
The high refractive polymer is suitable for preparing optical lenses or optical films.
The traditional high-refraction polyester has strong molecular chain rigidity due to the fact that the structure contains a large number of rigid rings (such as naphthalene rings), on one hand, the product is whitened and becomes poor in transparency, and on the other hand, the product is not tough enough and is fragile. The invention solves the problems by introducing the bio-based monomer shown in the general formula (Y) and the optional compounds shown in the general formula (A) and the general formula (B), wherein the compounds shown in the general formula A and the general formula B ensure the high refractive index of a polymerized product, the bio-based monomer Y has a flexible long-chain structure, the rigidity of the product is reduced, and the performance of the material is improved through the synergistic effect of the two types of monomers. In addition, all or part of the high refraction polyester product is capped by benzene rings, the content of terminal hydroxyl groups is lower than 1000ppm, and the content of small molecule byproducts such as phenol and the like in the system is lower than 500ppm. The reduction of the hydroxyl content in the system reduces the hydrolysis groups in the system, improves the stability of the polymer, is beneficial to avoiding degradation in the processing process of the product, reduces the hydrogen bond influence of the high-refraction polymer product, reduces the rigidity of the product, reduces the Tg, improves the processability of the product, and particularly obviously improves the impact strength and the sheet rate. The limit of terminal hydroxyl and small molecular byproducts in the system greatly improves the phenomena of yellowing, degradation and the like in the reprocessing process of the product.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the bio-based monomer prepared from the vanillic acid/syringic acid and the alcohol is used for preparing the high-refraction polymer, has excellent dimensional stability, good product flexibility and strong plasticity, and is particularly suitable for being applied to aspheric small-size products such as optical lenses. Meanwhile, the glass has stable high light transmittance, greatly improves phenomena of yellowing, degradation and the like in the reprocessing process of the product, and meets the use requirements of the multi-lens.
The polymer system of the invention contains bio-based monomers, has sustainable development and small environmental pollution, and accords with the current policy and regulation.
Detailed Description
The invention will now be described with reference to specific embodiments. It should be understood that the embodiments are merely for further illustrating the present invention and should not be construed as limiting the scope of the invention, but are merely illustrative of the invention that insubstantial modifications and adaptations thereof may be made in accordance with the principles of the present invention.
The main performance test method adopted by the polymer of the invention is as follows:
1) Weight average molecular weight (Mw) and molecular weight distribution (PDI): a standard curve was prepared using Gel Permeation Chromatography (GPC) using methylene chloride as a developing solvent and standard polystyrene of known molecular weight (molecular weight distribution=1). Based on the standard curve, mw and PDI were calculated from the retention time of GPC.
2) The glass transition temperature (Tg) was measured by DSC-60A at a heating rate of 20 ℃/min.
3) Testing the content of polymer terminal hydroxyl and small molecule byproduct (phenol): after the sample is dissolved by methylene dichloride, trifluoroacetic anhydride is derived, and nuclear magnetic resonance 19F spectrum is tested after the derivative, and fluorobenzene is used as an internal standard quantity. The peak was found to be-74.7 ppm after phenol derivatization, at-74.8 ppm after primary hydroxyl derivatization, and at-75.3 ppm after secondary hydroxyl derivatization.
Instrument: bruker company AVANCE NEO 600M spectrometer; test probe: 5mm BBO probe; test solvent: CDCl 3 The method comprises the steps of carrying out a first treatment on the surface of the Test temperature: 25 ℃.
4) Refractive index (nD): the refractive index (nD) of the high refractive polymer of the present invention at 23℃and a wavelength of 589nm, and the refractive index (nD) at a wavelength of 589nm in the range of-10 to 50℃were measured by the method of GB/T7962.4-2010 using an Abbe refractometer.
5) Abbe number: abbe refractive indices of 486nm, 589nm and 656nm at 23℃were measured using an Abbe refractometer, abbe numbers v were further calculated using the following formula,
ν＝(nD－1)/(nF－nC)。
6) Transmittance and haze: the measurement was carried out by the method of JIS-K-7361-1 using a nephelometer.
7) b value: injection molding was performed using an injection molding machine at a cylinder temperature of 270℃and a mold temperature of Tg-10℃to obtain a disk-shaped test plate sheet having a diameter of 50mm and a thickness of 3 mm. The b value was measured in accordance with JIS K7105 using the sheet.
8) Impact test: izod notched impact strength was measured according to ASTM D256 at 25℃under a relative humidity of 50% and the tester model was Instron CEAST 9050.
9) Processing a spherical lens: after vacuum drying at 120℃for 8 hours, the molding temperature was set at Tg+110℃and the mold temperature was set at Tg-10℃and lenses having a thickness of 0.2mm, a convex radius of curvature of 5mm, a concave radius of curvature of 4mm and a phi of 5mm were molded by injection molding using an SE30DU injection molding machine manufactured by Sumitomo heavy machinery Co., ltd.
In each example and comparative example of the present invention, the main raw materials were obtained by purchasing the following raw materials and reagents, all obtained by the common commercial route unless otherwise specified:
diphenyl carbonate: shanghai taitant;
BPEF: jiangsu Yongxing;
BPPF Jiangsu Yongxing (Jiangsu Yongxing)
BHEBN: jiangsu Yongxing;
2, 2-bis (2-hydroxyethoxy) -5, 5-diphenyl-1, 1-binaphthyl (BHEBBN): prepared by the method disclosed in patent CN114957954 a;
preparation of biobased monomer (Y-1 Compound) represented by general formula (Y)
(1) The method comprises the steps of taking vanillic acid and butanol as raw materials, and according to the literature of partial bio-based poly (amide) s by polycondensation of aromatic diacylhydrazides based on lignin-derived phenolic acids and aromatic dianhydrides:Synthesis, chemistry, and computational publications, journal of Polymer Science Part A:Polymer chemistry 2017;55:3636-3645. Butyl vanillic acid is prepared.
(2) Butyl vanillate and dibromohexane are used as raw materials, and a Y-1 compound is prepared according to the document Vanillin-based polyschiff vitrimers: reprocessability and chemical recyclability (J) ACS Sustand. Chem. Eng, 2018,6:15463-15470, wherein R is shown in the structural formula 1 Is hydrogen, R 2 Is butyl, R 3 Is hexyl.
Preparation of biobased monomer (Y-2 compound) of general formula (Y): the preparation method is referred to as Y-1 compound method, except that: step (1) preparing butyl syringate by taking syringic acid and butanol as raw materials, and step (2) preparing a Y-2 compound by taking butyl syringate and dibromooctane as raw materials, wherein R in the structural formula 1 Is methoxy, R 2 Is butyl, R 3 Is octyl.
Preparation of biobased monomer (Y-3 compound) of general formula (Y): the preparation method is referred to as Y-1 compound method, except that: step (1) preparing octyl syringate by using syringic acid and octanol as raw materials, and step (2) preparing a Y-3 compound by using octyl syringate and 1.4 dibromocyclohexane as raw materialsR in the structure 1 Is methoxy, R 2 Is octyl, R 3 Is cyclohexyl.
Preparation of biobased monomer (Y-4 compound) of formula (Y): the preparation method is referred to as Y-1 compound method, except that: step (1) preparing hexyl syringate by taking syringic acid and hexanol as raw materials, and step (2) preparing a Y-4 compound by taking hexyl syringate and 1.4 dibromocyclohexane as raw materials, wherein R in the structural formula 1 Is methoxy, R 2 Is hexyl, R 3 Is cyclohexyl.
Example 1
The preparation method of the high refractive polymer comprises the following steps:
0.036mol of BPEF, 0.06mol BHEBN,0.041molY-1, 0.059mol of diphenyl carbonate, 5.0X10 mol of -7 The mol sodium hydroxide is added into a reaction kettle with a stirrer and a distillation device. Nitrogen is replaced for 3 times, the mixture is heated to 140 ℃ under normal pressure and stays for 30min, the pressure is regulated to 40Kpa (A) after the raw materials are completely melted, the temperature is raised to 240 ℃, the byproducts are distilled off, the reaction is maintained for 90min, then the temperature is raised to 250 ℃, the pressure is reduced by a program, the pressure is gradually reduced to 100Pa (A) within 1 h, the reaction is completed for 30min, and the reaction is ended.
And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, and the hydroxyl content of the tail end of the polymer is 723ppm, and the content of free micromolecular byproducts is 210ppm.
Molecular weight 119340, PDI 1.9, refractive index 1.647, abbe number 22.2, light transmittance 88.9%, haze 0.32%, b value 1.34, tg 135 ℃, izod notched impact strength 48J/m 2 。
Processing into spherical lens with sheeting rate of 99.8%, and processing into sheet with molecular weight 118300 and PDI of 2.0.
Comparative example 1
The polymer was prepared according to the method of example 1, except that: the Y-1 compound is replaced by diphenyl carbonate with equal molar quantity, and other operation and conditions are unchanged, so that the polymer is prepared.
Taking out the generated high refractive polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high refractive polymer are shown as follows, wherein the hydroxyl content of the tail end of the polymer is 703ppm, and the content of free micromolecular byproducts is 235ppm;
molecular weight 117820, PDI 1.8, refractive index 1.642, abbe number 22.1, light transmittance 88.2%, haze 0.39%, b value 1.39, tg 142 ℃, izod notched impact strength 33J/m 2 。
Processing into spherical lens with sheeting rate of 87.2%, and processing into sheet with molecular weight of 117230 and PDI of 2.4.
Example 2
Adding 0.029mol of BPEF, 0.07mol of BHEBBN, 0.1mol of Y-2 compound and 4.0X10-7 mol of tetrabutylammonium hydroxide into a reaction kettle with a stirrer and a distillation device, replacing nitrogen for 3 times, heating to 180 ℃ under normal pressure, staying for 30min, heating to 230 ℃ after the raw materials are completely melted, starting stirring, regulating the pressure to 60Kpa (A), distilling off byproducts (phenol and butanol), maintaining the reaction for 60min, then heating to 250 ℃, reducing the pressure by a program, gradually reducing the pressure to 100Pa (A) within 1 hour, reacting for 45min, and ending the reaction.
And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, and the hydroxyl group content of the tail end of the polymer is 621ppm, and the content of free small molecular byproducts is 182ppm.
Molecular weight 62830, PDI 1.81, refractive index 1.663, abbe number 23.2, light transmittance 89.6%, haze 0.33%, b value 1.52, tg 132 ℃, izod notched impact strength 38J/m 2 。
Processing into spherical lens with sheeting rate of 99.6%, and processing into sheet with molecular weight of 61235 and PDI of 1.92.
Comparative example 2
The reaction was carried out under the same conditions as above, and the amount of 0.029mol of BPEF was increased to 0.035mol of BPEF, with other operations and conditions unchanged, to obtain a polymer.
And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, wherein the hydroxyl content of the tail end of the product is 3690ppm, and the content of free micromolecular byproducts is 1139ppm.
Molecular weight 63455, PDI 1.82, refractive index 1.661, abbe number 23.1, light transmittance 88.7%, haze 0.41%, b value 1.57, tg 133℃and Izod notched impact strength 29J/m 2 。
Processing into spherical lens with sheeting rate of 76.2%, and processing into sheet with molecular weight 39801 and PDI of 3.51.
Example 3
Adding 0.094mol of BPPF and 0.004mol BHEBN,0.04molY-3 compound, 0.06mol of diphenyl carbonate and 5.0X10-6 mol of tin acetate into a reaction kettle with a stirrer and a distillation device, replacing 3 times with nitrogen, heating to 160 ℃ under normal pressure, staying for 30min, completely melting raw materials, starting stirring, adjusting the pressure to 30Kpa (A), heating to 250 ℃, distilling off byproducts (phenol and octanol), maintaining the reaction for 80min, then heating to 300 ℃, reducing the pressure by a program, gradually reducing the pressure to 100Pa (A) within 1 hour, reacting for 15min, and ending the reaction.
And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, and the hydroxyl content of the tail end of the polymer is 321ppm, and the content of free micromolecular byproducts is 154ppm.
Molecular weight 92350, PDI 1.87, refractive index 1.672, abbe number 21.2, light transmittance 90.3%, haze 0.29%, b value 1.41, tg 141 ℃, izod notched impact strength 38J/m 2 。
Processed into spherical lenses with a sheeting rate of 98.9%, and processed into sheets with a molecular weight of 91000 and a PDI of 2.11.
Comparative example 3
The polymer was prepared by the method of reference example 3, except that: the polymer was prepared by reacting under the same conditions as described above, changing only the Y-3 compound to an equimolar amount of dimethyl terephthalate, with other operations and conditions unchanged.
And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, and the hydroxyl content of the tail end of the product is 355ppm and the content of free micromolecular byproducts is 182ppm.
Molecular weight 95430, PDI 1.92, refractive index 1.669, abbe number 22.5, light transmittance 89.3%,haze 0.33%, b value 1.45, tg 139 ℃, izod notched impact strength 21J/m 2 。
Processing into spherical lens with sheeting rate of 60.1%, processing into sheet with molecular weight 91230, PDI 2.03.
Example 4
0.075mol BPPF, 0.02mol BHEBBN, 0.012mol Y-4 compound, 0.088mol diphenyl carbonate, 1.0X10-6 mol tin acetate are added into a reaction kettle with a stirrer and a distillation device, nitrogen is replaced for 3 times, the mixture is heated to 2000 ℃ under normal pressure, the mixture stays for 20min, the stirring is started, the pressure is regulated to 80Kpa (A), the temperature is raised to 250 ℃, byproducts (phenol and octanol) are distilled off, the reaction is maintained for 90min, then the temperature is raised to 270 ℃, the pressure is reduced by a program, the pressure is gradually reduced to 100Pa (A) within 1 h, the reaction is carried out for 30min, and the reaction is ended. And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, and the hydroxyl content of the tail end of the product is 391ppm, and the content of free micromolecular byproducts is 114ppm.
51350, PDI 1.72, refractive index 1.681, abbe number 21.8, light transmittance 89.8%, haze 0.33%, b value 1.41, tg 133 ℃, izod notched impact strength 35J/m 2 。
Processing into spherical lens with sheeting rate of 98.2%, processing into sheet with molecular weight of 49000, and PDI of 1.98.
Comparative example 4
The polymer was prepared by the method of reference example 4, except that: the Y-4 compound is changed into equimolar amount of dimethyl naphthalene dicarboxylate, and other operations and conditions are unchanged, so that the polymer is prepared.
And taking out the generated high-refraction polymer, and performing performance evaluation, wherein physical parameters measured by the obtained high-refraction polymer are shown as follows, wherein the hydroxyl content of the tail end of the product is 402ppm, and the content of free micromolecular byproducts is 134ppm.
Molecular weight 53420, PDI 1.82, refractive index 1.678, abbe number 20.7, light transmittance 88.3%, haze 0.34%, b value 1.52, tg 129 ℃, izod notched impact strength 24J/m 2 。
Processed into spherical lenses with a sheeting rate of 73.2%, and processed into sheets with a molecular weight 51905 and a PDI of 1.97.
Claims (10)
1. A high refractive polymer, said polymer comprising:
structural units derived from biobased monomers of the general formula (Y),
in the general formula (Y), R 1 Each independently represents a hydrogen atom, a methyl group; r is R 2 Each independently represents a C2-C15 alkyl group, a C5-C15 cycloalkyl group, preferably a C4-C8 alkyl group, a C6-C10 cycloalkyl group, more preferably a n-butyl group, a n-hexyl group, a n-octyl group, a cyclohexyl group; r is R 3 Represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, preferably a C6-C12 cycloalkyl group, a C6-C20 alkyl group, more preferably a hexyl group, an octyl group or a cyclohexyl group;
structural units derived from a compound represented by the general formula (A),
in the general formula (A), R 4 、R 5 Each independently represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C5-C20 cycloalkyl group, a C5-C20 cycloalkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, preferably a hydrogen atom, a C1-C3 alkyl group, or a C6-C12 aryl group;
structural units derived from a compound represented by the general formula (B),
in the general formula (B), R 6 、R 7 Independently represent a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkyl groupOxy, C5-C20 cycloalkyl, CC20 cycloalkoxy, C6-C20 aryl, C6-C20 aryloxy, preferably hydrogen atom, C1-C3 alkyl, C6-C12 aryl;
wherein the structural unit derived from the compound represented by the general formula (A) and the structural unit derived from the compound represented by the general formula (B) are optionally one or two of them;
the high refractive polymer has a terminal hydroxyl content of less than 1000ppm, preferably 300 to 500ppm.
2. The high refractive polymer according to claim 1, wherein the compound represented by the general formula (A) is at least one selected from the following structural compounds BPEF and BPPF
The compound shown in the general formula (B) is at least one of the following structural compounds BHEBN and BHEBBN
3. The high refractive polymer according to claim 1 or 2, wherein the content of small molecule by-products in the high refractive polymer is less than 500ppm, preferably 100-300ppm; the small molecule byproducts include phenol, C4-C8 alcohols, such as butanol, hexanol, octanol;
the high refractive polymer has a weight average molecular weight of 10000 to 150000, preferably 20000 to 130000, more preferably 30000 to 120000;
the refractive index of the high refractive polymer is 1.625-1.685 at 23 ℃ and the wavelength of 589 nm;
the high refractive polymer has an abbe number of not more than 24;
the high refractive polymer has a light transmittance of more than 88%, a haze of less than 0.7% and a b value of less than 2.
4. A high refractive polymer according to any one of claims 1 to 3, wherein the high refractive polymer comprises a structural unit derived from a bio-based monomer represented by the general formula (Y) and either or both of a structural unit derived from a compound represented by the general formula (a) and a structural unit derived from a compound represented by the general formula (B), wherein the molar ratio of the structural unit derived from the bio-based monomer represented by the general formula (Y) to the structural unit derived from the compound represented by the general formula (a) and the structural unit derived from the compound represented by the general formula (B) is 1:0 to 20:0 to 20, preferably 1:0.1 to 15:0.1 to 15, and the structural unit derived from the compound represented by the general formula (A) and the structural unit derived from the compound represented by the general formula (B) are not 0 at the same time.
5. The high refractive polymer according to any one of claims 1 to 4, wherein the method for preparing the bio-based monomer represented by the general formula (Y) comprises the steps of:
(1) The intermediate C is prepared by esterification reaction of vanillic acid or syringic acid and alcohol;
(2) And (3) performing polymerization reaction on dibromoalkane and the intermediate C prepared in the step (1) to prepare the bio-based monomer shown in the general formula (Y).
6. The high refractive polymer according to any one of claims 1 to 5, wherein in step (1), the alcohol is at least one selected from butanol, hexanol, octanol, cyclohexanol;
the molar ratio of the vanillic acid or the syringic acid to the alcohol is 1:1 to 4, preferably 1:1.5 to 2.5;
the esterification reaction is carried out at a temperature of 100-150, preferably 120-140; the time is 1 to 12, preferably 2 to 6;
the esterification reaction is carried out under the action of a catalyst, wherein the catalyst is sulfuric acid;
preferably, the catalyst is used in an amount of 0.5 to 3wt% based on the mass of the alcohol;
in the step (2), the dibromoalkane is at least one selected from dibromohexane, dibromooctane and 1.4 dibromocyclohexane;
the molar ratio of dibromoalkane to intermediate C prepared in step (1) is 1:0.4 to 0.8, preferably 1:0.5 to 0.6;
the reaction temperature is 80-140 ℃, preferably 100-120 ℃; the time is 8-20, preferably 12-16;
the polymerization reaction is carried out under the action of a catalyst, wherein the catalyst is potassium carbonate;
preferably, the molar ratio of the catalyst to dibromoalkane is 1:0.5 to 1.
7. A process for preparing a high refractive polymer according to any one of claims 1 to 6, wherein the polymer is prepared by polymerizing a compound represented by the general formula (A) and/or the general formula (B), a biobased monomer represented by the general formula (Y), and optionally a carbonic acid diester.
8. The process according to claim 7, wherein the molar ratio of the sum of the bio-based monomer of formula (Y) and the carbonic acid diester to the sum of the compounds of formula (a) and formula (B) is 1 to 0.9:1, preferably 1 to 0.93:1;
the carbonic diester is selected from at least one of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, preferably at least one of diphenyl carbonate and dimethyl carbonate.
9. The preparation method according to claim 7 or 8, characterized in that the preparation is carried out by a melt transesterification polycondensation method in the presence of a catalyst or in the absence of a catalyst;
the catalyst is at least one of sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, triethylamine, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, stannic chloride, stannic acetate, cerium acetylacetonate, zirconium acetate and tetrabutoxyzirconium, preferably at least one of sodium hydroxide, sodium bicarbonate, cesium carbonate, cerium acetylacetonate, zirconium acetate and zinc acetate;
the molar ratio of the catalyst to the sum of the bio-based monomer of the general formula (Y) and the carbonic acid diester is 1X 10 -8 ～1×10 -3 Preferably 1X 10 -6 ～1×10 -4 。
10. A high refractive polymer according to any one of claims 1 to 6 or a high refractive polymer prepared by the preparation method according to any one of claims 7 to 9 in an optical lens.
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| CN202310000497.6A CN116376000A (en) | 2023-01-03 | 2023-01-03 | High-refraction polymer, preparation method and application |
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