CN115725063B - Polycarbonate and preparation method thereof - Google Patents
Polycarbonate and preparation method thereof Download PDFInfo
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- CN115725063B CN115725063B CN202211444694.9A CN202211444694A CN115725063B CN 115725063 B CN115725063 B CN 115725063B CN 202211444694 A CN202211444694 A CN 202211444694A CN 115725063 B CN115725063 B CN 115725063B
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- carbon atoms
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- polycarbonate
- alkyl group
- hydroxide
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 43
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 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 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000004104 aryloxy group Chemical group 0.000 claims description 16
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 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 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 5
- 150000005690 diesters Chemical class 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 150000005347 biaryls Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- -1 tetrabutylammonium tetraphenylborate Chemical compound 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
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 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
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-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
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000004301 calcium benzoate Substances 0.000 claims description 2
- 235000010237 calcium benzoate Nutrition 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 claims description 2
- BLUMOBPWAAOPOY-UHFFFAOYSA-M cesium;benzoate Chemical compound [Cs+].[O-]C(=O)C1=CC=CC=C1 BLUMOBPWAAOPOY-UHFFFAOYSA-M 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- TYJOJLOWRIQYQM-UHFFFAOYSA-L disodium;phenyl phosphate Chemical compound [Na+].[Na+].[O-]P([O-])(=O)OC1=CC=CC=C1 TYJOJLOWRIQYQM-UHFFFAOYSA-L 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 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
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- JGIZKLDQCIOYLH-UHFFFAOYSA-L magnesium;phenyl phosphate Chemical compound [Mg+2].[O-]P([O-])(=O)OC1=CC=CC=C1 JGIZKLDQCIOYLH-UHFFFAOYSA-L 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000004300 potassium benzoate Substances 0.000 claims description 2
- 235000010235 potassium benzoate Nutrition 0.000 claims description 2
- 229940103091 potassium benzoate Drugs 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 229910000018 strontium 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
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 1
- CZMILNXHOAKSBR-UHFFFAOYSA-N tetraphenylazanium Chemical compound C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CZMILNXHOAKSBR-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229920005668 polycarbonate resin Polymers 0.000 description 6
- 239000004431 polycarbonate resin Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- MDOBPGJMVOGJQP-UHFFFAOYSA-N 2-[4-(9h-fluoren-1-yl)phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 MDOBPGJMVOGJQP-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- PKPMMGIFZKHHPY-UHFFFAOYSA-N carbonic acid;1,2-xylene Chemical compound OC(O)=O.CC1=CC=CC=C1C PKPMMGIFZKHHPY-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses polycarbonate, which is characterized in that: the polycarbonate comprises structural units shown in the formula I and the formula II. The invention also discloses a preparation method of the polycarbonate. Compared with the prior art, the polycarbonate has high refractive index, low birefringence and simple synthesis.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to polycarbonate and a preparation method thereof.
Background
The polycarbonate has the characteristics of good dimensional stability, good heat resistance, high light transmittance, high refractive index, easy molding and the like, and is widely applied to the fields of mobile phone lenses, vehicle-mounted lenses, VR/AR glasses, optical discs, packaging materials and the like. Compared with other optical plastics such as polymethacrylate, cycloolefin copolymer and the like, the polycarbonate has higher refractive index, so that when the polycarbonate is manufactured into a lens element, the thickness of the lens can be reduced, the lens is smaller and lighter, and the application prospect is wider.
The traditional bisphenol A polycarbonate has larger birefringence phenomenon and cannot be applied to the field of high-end optical materials. This is because the polycarbonate is easily aligned in the direction of applied stress during melt processing, and the residual stress in the polymer after processing is large, and these factors eventually lead to the occurrence of birefringence. In order to eliminate the birefringence of polycarbonate, the most commonly used method is to introduce structural units with negative birefringence and structural units with positive birefringence into the polycarbonate main chain, and to combine them in a proper proportion to prepare a polycarbonate material with low birefringence.
The invention patent of optical lens with the patent application number of CN201310062561.X (publication number of CN 103257376A) adopts 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, bisphenol A and diphenyl carbonate to react to prepare the polycarbonate with low birefringence, but the highest refractive index of the obtained polycarbonate is only 1.639, and a larger improvement space is still provided.
Then, a method for modifying 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is adopted to prepare a novel fluorene-containing skeleton structure derivative, and the novel fluorene-containing skeleton structure derivative is used for polycarbonate synthesis, for example, the polycarbonate resin with stable high refractive index, a preparation method and application of the polycarbonate resin disclosed in the invention patent with the publication number of CN202110380139.3 (publication number of CN 112961336A) report that the refractive index of the polycarbonate resin can reach up to about 1.7, but the polycarbonate contains a complex aromatic structure, and has the defects of difficult synthesis, high cost and the like, and industrial large-scale production is difficult to realize effectively.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a polycarbonate with high refractive index, low birefringence and simple synthesis, which aims at the current state of the art.
The second technical problem to be solved by the invention is to provide a preparation method of the polycarbonate.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a polycarbonate, characterized in that: the polycarbonate comprises structural units shown in a formula I and a formula II;
in the formula I, X represents alkylene with 1-6 carbon atoms;
n is any integer between 0 and 5;
r1 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
r2 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
r3 represents one of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms;
r4 represents one of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms;
in the formula II, Y represents alkylene with 1-6 carbon atoms;
m is any integer between 0 and 5;
r5 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
r6 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
l represents one of a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl alkyl group having 6 to 20 carbon atoms, or a biaryl alkyl group.
Preferably, the method comprises the steps of,
x represents an alkylene group having 1 to 2 carbon atoms;
n is any integer between 0 and 1;
r1 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
r2 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
r3 represents one of a hydrogen atom and a methyl group;
r4 represents one of a hydrogen atom and a methyl group.
Further, the structural unit shown in the formula I comprises at least one of structural units shown in A1 and A2;
preferably, the method comprises the steps of,
y represents an alkylene group having 1 to 2 carbon atoms;
m is any integer between 0 and 1;
r5 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
r6 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
l represents a branched or branched alkyl group having 1 to 5 carbon atoms, an aryl alkyl group having 6 to 15 carbon atoms, or a biaryl alkyl group.
Further, the structural unit shown in the formula II comprises at least one of structural units shown in A3, A4 and A5;
preferably, the structural units of formula I comprise from 5% to 80%, more preferably from 40% to 80%, of the total moles of all structural units in the polycarbonate.
The polycarbonate resin may contain various additives within a range not to impair the polycarbonate performance in order to improve the polycarbonate performance. The additives may be additives such as antioxidants, dyes, bluing agents, flame retardants, mold release agents, ultraviolet absorbers, lubricants, crystal nucleating agents, reinforcing agents, antistatic agents, and antibacterial agents.
The invention solves the second technical problem by adopting the technical proposal that: the preparation method of the polycarbonate is characterized by comprising the following steps: taking dihydroxyl compounds shown in the formulas III and IV and carbonic diester as raw materials, and preparing the required polycarbonate by melt polycondensation in the presence of an alkaline catalyst;
the novel large-steric-hindrance dihydroxy monomer is adopted, and the polycarbonate resin is obtained by melt polymerization of other common dihydroxy monomers and carbonic acid diester in a proper proportion, so that the refractive index of the polymer can be effectively improved, and the birefringence phenomenon of the polymer can be reduced.
Preferably, the dihydroxy compound shown in formula III is at least one of B1 and B2;
the dihydroxyl compound shown in the formula IV is at least one of bisphenol A, 9-bis (4-hydroxyphenyl) fluorene and 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene;
the carbonic diester is at least one of diphenyl carbonate, dimethylbenzene carbonate, dimethyl carbonate and diethyl carbonate, and more preferably diphenyl carbonate;
the alkaline catalyst is at least one of lithium hydroxide, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium hydrogencarbonate, magnesium hydrogencarbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium hydrogencarbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, lithium acetate, sodium acetate, magnesium acetate, potassium acetate, calcium acetate, strontium acetate, barium acetate, sodium stearate, magnesium stearate, potassium stearate, calcium stearate, lithium benzoate, sodium benzoate, potassium benzoate, calcium benzoate, cesium benzoate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, disodium phenylphosphate, magnesium phenylphosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetrabenzylborate, and the like, more preferably at least one of sodium hydroxide, sodium bicarbonate, sodium carbonate;
preferably, the molar ratio of the carbonic acid diester to the dihydroxy compound is 1 to 1.1, more preferably 1 to 1.05;
the molar ratio of the basic catalyst to the dihydroxy compound is 10 -8 ～10 -3 More preferably 10 -6 ～10 -4 。
Preferably, the melt polycondensation specifically comprises the steps of:
(1) Adding a dihydroxy compound, carbonic diester and an alkaline catalyst into a reactor, and replacing the reactor with nitrogen for 3-5 times, so as to keep the normal pressure state in the reactor;
(2) Heating to 150-190 ℃, preferably 165-175 ℃, reacting for 5-10 min, then reducing the pressure in the kettle to 15-35 kPa, preferably 20-30 kPa, reacting for 20-40 min, preferably 25-35min;
(3) Heating to 190-220 ℃, preferably 210-220 ℃, reducing the pressure in the kettle to 5-25 kPa, preferably 10-20 kPa, and reacting for 10-30 min, preferably 10-20min;
(4) Heating to 220-250 ℃, preferably 230-240 ℃, reducing the pressure in the kettle to 1-5 kPa, preferably 5kPa, and reacting for 10-30 min, preferably 15-25 min;
(5) Heating to 250-290 ℃, preferably 260-280 ℃, continuously reducing the pressure in the kettle to 0.1-1 kPa, preferably 0.1-0.5 kPa, and continuously reacting for 30-90 min, preferably 40-60 min;
(6) Stopping heating after the reaction is finished, introducing nitrogen, cooling to room temperature, adding a proper amount of tetrahydrofuran dissolution product, and settling and separating in absolute ethyl alcohol;
(7) The precipitated polymer is filtered by suction and washed by ethanol for a plurality of times, and the required polycarbonate is obtained by vacuum drying.
Compared with the prior art, the invention has the advantages that:
(1) The structural units shown in the formula I and the formula II are matched to form polycarbonate, on one hand, compared with the traditional bisphenol A, the structural unit shown in the formula I has higher weight in unit volume and higher refractive index, and the refractive index (more than 1.64) of the polymer can be improved; on the other hand, the structural unit shown in the formula I and the structural unit shown in the formula II respectively have negative birefringence and positive birefringence, so that the birefringence phenomenon can be eliminated;
(2) The functional monomer does not need to introduce a large amount of complex aromatic ring structures, is simple to synthesize and low in cost, does not contain hetero atoms such as sulfur, nitrogen and the like, is not easy to generate adverse phenomena such as yellowing and the like in the processing and application processes, and can be applied to the fields of optical parts, electronic products, medical products and the like.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Synthetic route for compound B1:
12.1g of p-benzoquinone and 10g of anthracene are mixed and then dissolved in 100ml of anhydrous toluene, and reflux reaction is carried out for 4 hours; subsequently, the reaction solution was cooled to room temperature, and the precipitated solid was collected by filtration and washed with 10ml of toluene, and then placed in a vacuum oven to dry overnight; the crude product obtained is dissolved in 350ml of acetic acid solution, 48% hydrobromic acid solution is added dropwise, and white solid is immediately separated out; the white solid was washed with 15ml of acetic acid and 30ml of n-hexane and dried to obtain the B1 compound in 80% yield.
Synthetic route for compound B2:
compound B1 and ethylene carbonate, according to 1: 2mol percent of the mixture is dissolved in DMF after being mixed, 5 mol percent of potassium carbonate catalyst is added, and the mixture is heated and refluxed for reaction for 10 hours; cooling to room temperature after the reaction is finished, adding water, standing to precipitate a large amount of solids, and recrystallizing and purifying by using 95% ethanol to obtain a product B2 with a yield of 78%.
Example 1:
(1) 50.61g of diphenyl carbonate (0.21 mol), 13.70 bisphenol A (0.060 mol), 40.04g of B1 (0.140 mol), 1.6X10 mol) are reacted at room temperature -4 g sodium hydroxide (4.00X 10) -6 mol), adding the mixture into a reactor, and replacing air in the reactor for 5 times by using nitrogen, and keeping the normal pressure state in the reactor;
(2) Raising the temperature in the kettle to 170 ℃ within 20min, reacting for 10min, then reducing the pressure in the kettle to 25kPa within 5min, and continuing the reaction for 30min;
(3) Raising the temperature in the kettle to 210 ℃ within 10min, reducing the pressure in the kettle to 15kPa, and reacting for 20min;
(4) Raising the temperature in the kettle to 240 ℃ within 10min, reducing the pressure in the kettle to 5kPa, and reacting for 20min;
(5) Raising the temperature in the kettle to 260 ℃ within 10min, reducing the pressure in the kettle to 0.1kPa, and continuing the reaction for 60min;
(6) Stopping heating after the reaction is finished, introducing nitrogen, cooling to room temperature, adding a proper amount of tetrahydrofuran dissolution product, and settling and separating in 1L of absolute ethyl alcohol;
(7) The precipitated polymer is filtered by suction and washed by ethanol for multiple times, and the polymer is dried in vacuum at 80 ℃ for 8 hours to obtain the required product.
Example 2:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 11.28g of bisphenol A (0.049 mol), 58.52g of B2 (0.156 mol), 1.6X10 mol) -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Example 3:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 10.92g of bisphenol A (0.048 m)ol), 18.23g of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (0.042 mol), 44.32g of B2 (0.119 mol), 1.6X10 mol) -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Example 4:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 5.58g of 4,4' -dihydroxybiphenyl (0.03 mol), 3.50g of 9, 9-bis (4-hydroxyphenyl) fluorene (0.010 mol), 59.84g of B2 (0.160 mol), 1.6X10 -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Example 5:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 9.13g of bisphenol A (0.040 mol), 42.10g of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (0.096 mol), 23.94g of B2 (0.064 mol), 1.6X10 -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Example 6:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 7.76g of bisphenol A (0.034 mol), 57.88g of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (0.132 mol), 23.94g of B2 (0.034 mol), 1.6X10 mol) -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Example 7:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 11.41g of bisphenol A (0.050 mol), 30.70g of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (0.070 mol), 22.88g of B1 (0.080 mol), 1.6X10 mol) -4 g sodium hydroxide (4.00X 10) -6 mol), addAnd (3) putting the mixture into a reactor, and replacing air in the reactor for 5 times by using nitrogen, so as to keep the normal pressure state in the reactor.
The remaining steps are described in example 1.
Example 8:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 5.48g of bisphenol A (0.024 mol), 72.79g of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (0.166 mol), 3.74g of B2 (0.010 mol), 1.6X10 -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Comparative example 1:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol), 45.66g of bisphenol A (0.20 mol), 1.6X10 -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Comparative example 2:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol); 22.83g bisphenol A (0.10 mol), 43.85g9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (0.10 mol), 1.6X10 -4 g sodium hydroxide (4.00X 10) - 6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
Comparative example 3:
the raw material ratio was adjusted to 50.61g of diphenyl carbonate (0.21 mol); 74.8g B2 (0.20 mol), 1.6X10 -4 g sodium hydroxide (4.00X 10) -6 mol), and the mixture was added to the reactor, and the air in the reactor was replaced with nitrogen 5 times, thereby maintaining the normal pressure state in the reactor.
The remaining steps are described in example 1.
The experimental test results of all examples and comparative examples are shown in table 1.
The specific test steps are as follows:
(1) Glass transition temperature: tg is measured by dynamic differential thermal analysis (DSC) according to ASTM E1356;
(2) Refractive index (1.0 mm film): the refractive index nD (wavelength: 589 nm) at 25℃was measured on the sample piece using an Abbe refractometer;
(3) Birefringence: molding the polymer into a film with a specific thickness, and measuring the birefringence delta n by using an ellipsometer;
(4) Light transmittance test: a film of 0.1mm formed from the polycarbonate resin produced in the examples was measured by the method of ASTM D1003 using a haze meter.
Table 1: experimental test results of all examples and comparative examples
As can be seen from table 1:
(1) By incorporating structural units of formula I into the polycarbonate, the refractive index of the polymer is effectively increased because the structural units of formula I have a higher weight per unit volume and a higher refractive index than conventional bisphenol A;
(2) By copolymerizing the carbonic acid diester with different dihydroxy compounds, the birefringence phenomenon can be effectively reduced while the high refractive index is maintained, because the structural unit shown in the formula I and the structural unit shown in the formula II respectively have negative birefringence and positive birefringence, thereby eliminating the birefringence phenomenon;
in conclusion, the polycarbonate prepared by the invention has the advantages of high refractive index, low birefringence, high light transmittance, good heat resistance and the like, and the functional monomer is simple to synthesize, low in cost and free of hetero atoms such as sulfur, nitrogen and the like, so that adverse phenomena such as yellowing and the like are not easy to generate in the processing and application processes, and the polycarbonate can be applied to the fields of optical parts, electronic products, medical products and the like.
Claims (10)
1. A polycarbonate, characterized in that: the polycarbonate comprises structural units shown in a formula I and a formula II;
；
in the formula I, X represents alkylene with 1-6 carbon atoms;
n is any integer between 1 and 5;
r1 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
r2 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
r3 represents one of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms;
r4 represents one of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms;
；
in the formula II, Y represents alkylene with 1-6 carbon atoms;
m is any integer between 0 and 5;
r5 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
r6 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 20 carbon atoms;
l represents one of a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl alkyl group having 6 to 20 carbon atoms, or a biaryl alkyl group.
2. The polycarbonate of claim 1, wherein:
x represents an alkylene group having 1 to 2 carbon atoms;
n is 1;
r1 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
r2 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
r3 represents one of a hydrogen atom and a methyl group;
r4 represents one of a hydrogen atom and a methyl group.
3. The polycarbonate of claim 2, wherein: the structural unit shown in the formula I comprises a structural unit shown in A2;
。
4. the polycarbonate of claim 1, wherein:
y represents an alkylene group having 1 to 2 carbon atoms;
m is any integer between 0 and 1;
r5 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
r6 represents one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 5 to 10 carbon atoms, an aryl group or an aryloxy group having 6 to 12 carbon atoms;
l represents a branched or branched alkyl group having 1 to 5 carbon atoms, an aryl alkyl group having 6 to 15 carbon atoms or a biaryl alkyl group.
5. The polycarbonate of claim 4, wherein: the structural unit shown in the formula II comprises at least one of structural units shown in A3, A4 and A5;
；
；
。
6. the polycarbonate of any of claims 1-5, wherein: the structural unit shown in the formula I accounts for 5% -80% of the total mole number of all structural units in the polycarbonate.
7. A process for the preparation of a polycarbonate as defined in any one of claims 1 to 6, comprising the steps of: taking dihydroxyl compounds shown in the formulas III and IV and carbonic diester as raw materials, and preparing the required polycarbonate by melt polycondensation in the presence of an alkaline catalyst;
；
。
8. the method of manufacturing according to claim 7, wherein: the dihydroxy compound shown in the formula III is B2;
；
the dihydroxyl compound shown in the formula IV is at least one of bisphenol A, 9-bis (4-hydroxyphenyl) fluorene and 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene;
the carbonic diester is at least one of diphenyl carbonate, dimethyl carbonate and diethyl carbonate;
the alkaline catalyst is at least one of lithium hydroxide, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium bicarbonate, magnesium bicarbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium bicarbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, lithium acetate, sodium acetate, magnesium acetate, potassium acetate, calcium acetate, strontium acetate, barium acetate, sodium stearate, magnesium stearate, potassium stearate, calcium stearate, lithium benzoate, sodium benzoate, potassium benzoate, calcium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium phenylphosphate, magnesium phenylphosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, diethylamine, triethylamine, dimethylbenzylamine, triphenylamine, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenyltetraborate, and the like.
9. The method of manufacturing according to claim 7, wherein: the molar ratio of the carbonic acid diester to the dihydroxyl compound is 1-1.1;
the molar ratio of the basic catalyst to the dihydroxy compound is 10 -8 ~10 -3 。
10. The method of manufacturing according to claim 7, wherein: the melt polycondensation specifically comprises the following steps:
(1) Adding a dihydroxy compound, carbonic acid diester and an alkaline catalyst into a reactor, and replacing the reactor with nitrogen for 3-5 times, so as to keep the normal pressure state in the reactor;
(2) Heating to 150-190 ℃, reacting for 5-10 min, then reducing the pressure in the kettle to 15-35 kPa, and reacting for 20-40 min;
(3) Heating to 190-220 ℃, reducing the pressure in the kettle to 5-25 kPa, and reacting for 10-30 min;
(4) Heating to 220-250 ℃, reducing the pressure in the kettle to 1-5 kPa, and reacting for 10-30 min;
(5) Heating to 250-290 ℃, continuously reducing the pressure in the kettle to 0.1-1 kPa, and continuously reacting for 30-90 min;
(6) Stopping heating after the reaction is finished, introducing nitrogen, cooling to room temperature, adding a proper amount of tetrahydrofuran dissolution product, and settling and separating in absolute ethyl alcohol;
(7) The precipitated polymer is filtered by suction and washed by ethanol for a plurality of times, and the required polycarbonate is obtained by vacuum drying.
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