CN111925513A - Bio-based polycarbonate compound and preparation method thereof - Google Patents
Bio-based polycarbonate compound and preparation method thereof Download PDFInfo
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- CN111925513A CN111925513A CN201910400267.2A CN201910400267A CN111925513A CN 111925513 A CN111925513 A CN 111925513A CN 201910400267 A CN201910400267 A CN 201910400267A CN 111925513 A CN111925513 A CN 111925513A
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- bio
- carbonate
- based polycarbonate
- hydroxide
- furandimethanol
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 82
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 82
- 150000001875 compounds Chemical class 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title abstract description 16
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 120
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 11
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940031993 lithium benzoate Drugs 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 239000004300 potassium benzoate Substances 0.000 claims description 3
- 235000010235 potassium benzoate Nutrition 0.000 claims description 3
- 229940103091 potassium benzoate Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 229960003885 sodium benzoate Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- AIWZOHBYSFSQGV-LNKPDPKZSA-M sodium;(z)-4-oxopent-2-en-2-olate Chemical compound [Na+].C\C([O-])=C\C(C)=O AIWZOHBYSFSQGV-LNKPDPKZSA-M 0.000 claims description 3
- XVHQFGPOVXTXPD-UHFFFAOYSA-M tetraphenylphosphanium;hydroxide Chemical compound [OH-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XVHQFGPOVXTXPD-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 27
- 239000000178 monomer Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000010902 straw Substances 0.000 abstract description 5
- 241000196324 Embryophyta Species 0.000 abstract description 4
- 150000005690 diesters Chemical class 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 240000008042 Zea mays Species 0.000 abstract description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 2
- 235000005822 corn Nutrition 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910001220 stainless steel Inorganic materials 0.000 description 27
- 239000010935 stainless steel Substances 0.000 description 27
- 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 25
- 239000006227 byproduct Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000002028 Biomass Substances 0.000 description 15
- 229960002479 isosorbide Drugs 0.000 description 14
- 229940106691 bisphenol a Drugs 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 11
- 150000002148 esters Chemical group 0.000 description 11
- 238000007689 inspection Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- -1 Tetralin phosphonium hydroxide Chemical compound 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000085 chronic toxic effect Toxicity 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
Images
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
- C08G64/305—General preparatory processes using carbonates and alcohols
-
- 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
- C08G64/02—Aliphatic polycarbonates
- C08G64/0291—Aliphatic polycarbonates unsaturated
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses 2, 5-furandimethanol-based polycarbonate and a preparation method thereof, belonging to the technical field of bio-based polycarbonate. The structural formula of the 2, 5-furandimethanol-based polycarbonate is shown as (I), and the 2, 5-furandimethanol-based polycarbonate is prepared by taking 2, 5-furandimethanol and carbonic diester as raw materials, adding a catalyst and carrying out an esterification-polycondensation process. The 2, 5-furandimethanol monomer adopted by the invention is derived from plant straws of corn and the like, has wide raw material sources and abundant reserves, can be regenerated, can be used as supplement and partial replacement of non-renewable fossil raw material monomers, so as to synthesize high-performance environment-friendly polycarbonate, can be used as engineering plastics in the fields of electronic appliances, automobiles, packaging and optics, and has important scientific significance and application value.
Description
Technical Field
The invention relates to a bio-based polycarbonate compound and a preparation method thereof, and 2, 5-furandimethanol-based polycarbonate and a preparation method thereof, wherein a 2, 5-furandimethanol monomer is derived from biomass resources, and belongs to the technical field of bio-based polycarbonate.
Background
Polycarbonate (PC) is a polymer containing carbonate groups in the main chain of a polymer, and is classified into various types, mainly aliphatic, aromatic, aliphatic-aromatic, and the like. Aliphatic and aliphatic-aromatic PCs have limited their large-scale application due to their low glass transition temperature, poor thermal stability and poor mechanical properties. Aromatic PC, mainly refers to bisphenol A type PC, the flexible carbonate bond in the main chain of the macromolecule is combined with the rigid aralkylene alternately, thereby endowing the bisphenol A type PC with super impact strength, high and low temperature resistance, electric insulation, dimensional stability and transparency. At present, as the only plastic with high transparency in five general engineering plastics, the consumption of bisphenol A type PC is second to that of polyamide, and the bisphenol A type PC is also the engineering plastic with the fastest increase of the demand in the year, and is widely applied to the industries of buildings, automobiles, electronic and electric appliances, optical disks, packages, office equipment, industrial mechanical parts, medical appliances, agricultural films and the like.
The monomers for producing PC are mainly derived from non-renewable fossil resources such as petroleum. With the increase in the number of the world population and the continuous progress of social economy, the demand for synthetic materials represented by PC has been increasing year by year, thereby accelerating the consumption of petroleum resources, resulting in the gradual decrease of petroleum resources, which is not favorable for the sustainable development of society. Also, the consumption of excessive fossil resources causes the emission of a large amount of greenhouse gases, resulting in the aggravation of the greenhouse effect. In addition, a series of intermediate products and wastes which pollute the environment and are harmful to human health are generated in the production process of the petroleum-based PC monomer, and the core concept of 'green chemical industry' is violated. Meanwhile, for example, bisphenol a type PC, its polymerized monomer bisphenol a (bpa) is derived from fossil resources, has estrogen effect and chronic toxic effect, is one of the recently identified "environmental endocrine disruptors", has certain harm to the health of human beings, especially newborn infants and the surrounding environment, and is also identified to be related to cancer and obesity caused by metabolic disorders. This greatly limits the use of bisphenol-A PC in the fields of food packaging, medical devices, biopolymer materials, etc., and European Union, Canada, USA, and China have successively announced the ban of the import and sale of polycarbonate baby bottles containing bisphenol-A components. Therefore, the development of the environment-friendly PC taking renewable resources as raw materials has important social significance and ecological value according to the multiple requirements of sustainable development, environmental protection and human health protection.
The biomass resource is a renewable resource and has the advantages of rich stock, wide source, biodegradability and the like. In addition, the biomass resource is considered to realize zero emission of carbon dioxide in the whole utilization period, and the greenhouse effect can be slowed down to a certain extent, so that the production of PC by adopting the biomass-based monomer based on the biomass resource has very important significance.
In the prior art, Chinese patent CN102395618A adopts isosorbide from biomass resources and the content of isosorbide is 4 multiplied by 10-3A copolymerized polycarbonate excellent in heat resistance, thermal stability and moldability is synthesized by melt polycondensation of an aliphatic diol having a boiling point of 180 ℃ or higher under reduced pressure of MPa and a carbonic acid diester. It comprises 50 to 99 mol% of a carbonate structural unit (1) represented by the following formula and 50 to 1 mol% of a carbonate structural unit represented by the formula 4X 10-3A copolymerized polycarbonate of a carbonate structural unit (2) derived from an aliphatic diol having a boiling point under reduced pressure of 180 ℃ or higher under MPa. Wherein X is a group as follows: byA combination of groups selected from arylene with 5-20 carbon atoms, alkylene with 1-20 carbon atoms, cycloalkylene with 5-20 carbon atoms and oxygen atoms, wherein the total number of carbon atoms is 13-30, and at least one of alkylene with 1-20 carbon atoms and cycloalkylene with 5-20 carbon atoms is contained.
Chinese patent CN105315445A describes the melt transesterification of bisphenol a and isosorbide with dimethyl oxalate, respectively, followed by polycondensation of the two products to obtain bisphenol a-isosorbide type copolymer polycarbonate. The bisphenol A and the isosorbide in the chain segment of the bisphenol A-isosorbide type copolymer polycarbonate are randomly ordered, and the isosorbide is a biomass product originally, and the secondary carbon carbonyl group of the isosorbide has lower activity than the phenol carbonyl group of the bisphenol A, so that the ester group formed by the isosorbide and the dimethyl oxalate in the product after the polymerization reaction is more easily broken under the action of microorganisms or degrading enzymes. At the same time, the obtained bisphenol A-isosorbide type copolymer polycarbonate can ensure the rigidity characteristic of the bisphenol A type polycarbonate because the isosorbide is of a chiral structure, is suitable for application in the fields of automobiles, electric appliances, buildings, packaging and the like, and does not pollute the natural environment. However, the secondary hydroxyl group on isosorbide derived from biomass resources has lower activity than the phenolic hydroxyl group on bisphenol a, i.e. has poor reactivity with carbonic acid diester, which is not favorable for producing high molecular weight PC, and also causes problems of hindered molecular weight increase, yellow color and poor transparency of the synthesized PC polymer chain due to the greater difficulty in purification of isosorbide and poor thermal stability of isosorbide.
However, among many bio-based monomers, 2, 5-furandimethanol can be converted from biomass resources containing hexose, pentose and the like by a "biorefinery" technology, has good reactivity and thermal stability, and can be used as a potential substitute for petroleum-based monomer BPA for the synthesis of aromatic polycarbonate.
Disclosure of Invention
The invention aims to synthesize novel environment-friendly bio-based polycarbonate by taking 2, 5-furandimethanol derived from biomass resources as a polymerization monomer and performing melt polycondensation with carbonic diester in the presence of a catalyst, and the monomer has high reaction activity, good stability, rich raw material reserves and wide sources.
First, the present invention provides a bio-based polycarbonate compound having a structural formula as shown in (i):
secondly, the present invention provides a method for preparing the bio-based polycarbonate compound, which comprises the following steps:
s1: under the protection of inert gas, adding 2, 5-furan dimethanol, carbonic acid diester and a catalyst into a reaction kettle to obtain a mixture, heating to 80-250 ℃, setting the absolute reaction pressure to be 3-100 kPa, and reacting for 20-240 min to obtain a prepolymer;
s2: heating the prepolymer obtained in S1 to 180-300 ℃, setting the absolute reaction pressure to be 0.01-5 kPa, and reacting for 20-300 min to obtain the bio-based polycarbonate compound.
Preferably, in the preparation method of the bio-based polycarbonate compound provided by the invention, the carbonic acid diester is selected from one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, methyl ethyl carbonate and diphenyl carbonate.
Preferably, in the preparation method of the bio-based polycarbonate compound provided by the invention, based on the molar mass of the 2, 5-furandimethanol, the molar ratio of the carbonic acid diester to the 2, 5-furandimethanol is 1-10: 1.
preferably, in the method for preparing a bio-based polycarbonate compound provided by the present invention, the catalyst is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, lithium acetate, sodium acetate, potassium acetate, sodium tetraborate, lithium benzoate, sodium benzoate, potassium benzoate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, magnesium acetate, calcium acetate, zinc oxide, monobutyltin oxide, dibutyltin oxide, titanium dioxide, tetrabutyl titanate, lanthanum acetylacetonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraphenylphosphonium hydroxide and tetranaphthylphosphonium hydroxide.
Preferably, in the preparation method of the bio-based polycarbonate compound provided by the invention, based on the molar mass of 2, 5-furandimethanol, the molar mass ratio of the catalyst to the molar mass of 2, 5-furandimethanol is: 0.00001-0.001:1.
Preferably, in the preparation method of the bio-based polycarbonate compound provided by the invention, in the S1, the reaction stirring speed is 50rpm to 200 rpm; in the S2, the reaction stirring speed is 20rpm-100 rpm.
Preferably, in the preparation method of the bio-based polycarbonate compound, the 2, 5-furandimethanol is prepared by fermenting, converting and purifying plant straws, and all the materials contain renewable organic carbon meeting the ASTM D6866 standard.
Finally, the present invention provides the use of the shanghai su bio-based polycarbonate compound, which can be used as an engineering plastic in the fields of electronics, automotive, packaging and optics.
The invention can also be stated in detail as follows:
the invention provides a 2, 5-furan dimethanol-based polycarbonate, which has a structural formula shown as (I):
secondly, the invention provides a preparation method of the 2, 5-furandimethanol-based polycarbonate, which is characterized in that 2, 5-furandimethanol and carbonic acid diester are used as polymerization monomers, and the 2, 5-furandimethanol-based polycarbonate is prepared by adopting an ester exchange-polycondensation synthesis process under the action of a catalyst, and the preparation method specifically comprises the following steps:
the first step is as follows: under the protection of inert gas, adding 2, 5-furan dimethanol, carbonic diester and a catalyst into a reaction kettle to obtain a mixture;
the second step is that: heating the mixture obtained in the first step to 80-250 ℃, vacuumizing to remove small molecular byproducts, setting the absolute reaction pressure to be 3-100 kPa, and reacting for 20-240 min to perform ester exchange reaction to obtain a prepolymer;
the third step: heating the prepolymer obtained in the second step to 180-300 ℃, further reducing the reaction pressure to promote the reaction to proceed towards the polycondensation direction, setting the absolute pressure of the reaction to be 0.01-5 kPa, reacting for 20-300 min, and performing the polycondensation reaction to obtain the bio-based polycarbonate.
In the preparation method of the 2, 5-furandimethanol-based polycarbonate provided by the present invention, in the second transesterification, the stirring speed is not particularly limited, preferably 50rpm to 200rpm, so as to improve the transesterification rate and the monomer conversion rate.
In the preparation method of the 2, 5-furandimethanol-based polycarbonate provided by the invention, in the third step of polycondensation reaction, the stirring speed is not particularly limited, preferably 20rpm-100rpm, so that small molecular byproducts can be more effectively removed from a polymer system, and finally the bio-based polycarbonate is obtained.
In the preparation method of the 2, 5-furandimethanol-based polycarbonate provided by the invention, the source of the 2, 5-furandimethanol is not particularly limited, and the 2, 5-furandimethanol-based polycarbonate is preferably prepared by fermenting, converting and purifying plant straws and contains renewable organic carbon meeting the ASTM D6866 standard.
In the method for preparing the 2, 5-furandimethanol-based polycarbonate provided by the present invention, the type of the carbonic acid diester is not particularly limited, and the carbonic acid diester includes, but is not limited to, one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, ethyl methyl carbonate, diphenyl carbonate, etc. The amount of the carbonic acid diester is not particularly limited, and the molar ratio of the carbonic acid diester to the 2, 5-furandimethanol is 1 to 10:1 based on the molar amount of the 2, 5-furandimethanol. If the molar ratio of carbonic acid diester to 2, 5-furandimethanol is less than 1:1, the amount of the carbonic acid diester is too small, so that the unbalance of the end groups of the prepolymer and the final molecular weight are caused; if the molar ratio of carbonic acid diester to 2, 5-furandimethanol is greater than 10:1, the amount of carbonic acid diester used is too large, which also results in an imbalance in the end groups of the prepolymer and a lower final molecular weight.
In the above-mentioned process for producing a 2, 5-furandimethanol-based polycarbonate, the type of the catalyst is not particularly limited, but is preferably lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium sulfite, lithium acetate, sodium acetate, potassium acetate, sodium tetraborate, lithium benzoate, sodium benzoate, potassium benzoate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, magnesium acetate, calcium acetate, zinc oxide, monobutyltin oxide, dibutyltin oxide, titanium dioxide, tetrabutyl titanate, lanthanum acetylacetonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraphenylphosphonium hydroxide, Tetralin phosphonium hydroxide, etc. The amount of the catalyst used is not particularly limited either, and is 0.001 to 0.1% by molar mass of 2, 5-furandimethanol. If the molar mass of the catalyst is less than 0.001% of the molar mass of 2, 5-furandimethanol, too little amount will result in slower reaction rate and lower final molecular weight; if the molar mass of the catalyst is more than 0.1% of the molar mass of 2, 5-furandimethanol, an excessive amount of the catalyst is used, resulting in difficulty in controlling the polymerization reaction and deterioration of the hue of the polymer.
The 2, 5-furandimethanol-based polycarbonate provided by the invention can be used as engineering plastics in the fields of electronics, electric appliances, automobiles, packaging and optics.
The invention has the advantages and beneficial effects that:
1. the adopted polymerized monomer 2, 5-furandimethanol is derived from renewable biomass resources such as corn straws and the like, namely, the synthesized polycarbonate is a bio-based polymer, so that the biomass resources which are originally in a waste state can be effectively utilized, the application range of the biomass resources is widened, waste is turned into wealth, the biomass raw materials are rich in reserves and wide in sources, and the biomass raw materials are inexhaustible, so that the sustainable development of the resources is facilitated.
2. The synthesized 2, 5-furandimethanol-based polycarbonate can be used as a partial substitute of bisphenol A polycarbonate, thereby reducing the consumption of fossil resources and the emission of toxic wastes, following the concept of 'green chemical industry', reducing the emission intensity of greenhouse gases and being beneficial to alleviating the greenhouse effect. More importantly, the synthesized polycarbonate does not contain harmful bisphenol A, so that the 2, 5-furandimethanol-based polycarbonate can be used in the related fields of baby feeding bottles, food packaging and the like.
The 2, 5-furan dimethanol monomer has good reactivity and thermal stability, can be condensed and polymerized with carbonic diester into high molecular weight polycarbonate in the presence of a catalyst, and meanwhile, oxygen atoms on furan rings in a main chain endow the novel bio-based polycarbonate with different material properties.
Drawings
FIG. 1 is a flow diagram of the preparation of a 2, 5-furandimethanol based bio-based polycarbonate.
Detailed Description
The present invention will be described in detail with reference to specific examples for better understanding, but the present invention is not limited to these examples.
The 2, 5-furandimethanol described in the specific examples was produced by fermentation, conversion, purification of plant straw and comprised a renewable source of organic carbon meeting ASTM D6866 standard.
Example 1
Performing air tightness inspection on the stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-base is addedMonomers 2, 5-furandimethanol, 1.05mol of diphenyl carbonate and 5X 10-4Adding mol of lithium hydroxide catalyst into the reaction kettle to obtain a mixture.
And heating the mixture to 180 ℃, removing a small molecular byproduct phenol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 3kPa, setting the stirring speed to be 150rpm, and keeping the reaction for 60min to perform an ester exchange reaction to obtain a prepolymer.
The obtained prepolymer was gradually heated to 280 ℃ and the absolute pressure of the reaction was gradually reduced to 0.1kPa, and by further reducing the reaction pressure, phenol and diphenyl carbonate, which were by-products of the reaction, were removed to promote the reaction toward polycondensation, with the stirring speed set at 80rpm, and the polycondensation reaction continued for 150min, to obtain 123g of bio-based polycarbonate having a viscosity average molecular weight of 2.27 ten thousand.
Example 2
Performing air tightness inspection on a stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-based monomer 2, 5-furandimethanol, 10mol of dimethyl carbonate and 1 multiplied by 10-3Adding mol of lithium acetylacetonate catalyst into the reaction kettle to obtain a mixture.
And heating the mixture to 120 ℃, removing a small molecular byproduct methanol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 6kPa, setting the stirring speed to be 180rpm, and continuing the reaction for 240min to perform an ester exchange reaction to obtain a prepolymer.
The obtained prepolymer was gradually heated to 225 ℃, the absolute pressure of the reaction was gradually reduced to 0.05kPa, and by further reducing the reaction pressure, the reaction byproducts methanol and dimethyl carbonate were removed, thereby promoting the reaction to proceed toward the polycondensation, the stirring speed was set to 90rpm, and the polycondensation reaction was continued for 300min, to finally obtain 131g of bio-based polycarbonate having a viscosity average molecular weight of 3.35 ten thousand.
Example 3
Performing air tightness inspection on the stainless steel reaction kettle, and vacuumizing and introducing nitrogen to ensure that the stainless steel reaction kettle is hollow after the stainless steel reaction kettle is inspected to be intactReplacing gas for three times, and adding 1mol of bio-based monomers 2, 5-furandimethanol, 1.05mol of diphenyl carbonate and 7.5X 10-4Adding mol of tetraethylammonium hydroxide catalyst into the reaction kettle to obtain a mixture.
And heating the mixture to 180 ℃, removing a small molecular byproduct phenol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 3kPa, setting the stirring speed to be 150rpm, and keeping the reaction for 80min to perform an ester exchange reaction to obtain a prepolymer.
The obtained prepolymer was gradually heated to 280 ℃ and the absolute pressure of the reaction was gradually reduced to 0.1kPa, and by further reducing the reaction pressure, phenol and diphenyl carbonate, which were by-products of the reaction, were removed to promote the reaction toward polycondensation, with the stirring speed set at 80rpm, and the polycondensation reaction continued for 170min, to finally obtain 126g of bio-based polycarbonate having a viscosity average molecular weight of 2.64 ten thousand.
Example 4
Performing air tightness inspection on a stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-based monomer 2, 5-furandimethanol, 8mol of dibutyl carbonate and 1 multiplied by 10-3Adding mol of monobutyl tin oxide catalyst into a reaction kettle to obtain a mixture.
And heating the mixture to 140 ℃, removing a small molecular byproduct butanol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 4kPa, setting the stirring speed to be 170rpm, and continuing the reaction for 220min to perform an ester exchange reaction to obtain a prepolymer.
The obtained prepolymer is gradually heated to 240 ℃, the absolute pressure of the reaction is gradually reduced to 0.1kPa, butanol and dibutyl carbonate which are reaction byproducts are removed by further reducing the reaction pressure, so that the reaction is promoted to be carried out towards the polycondensation direction, the stirring speed is set to 80rpm, the polycondensation reaction lasts for 280min, and 133g of bio-based polycarbonate with the viscosity-average molecular weight of 3.04 ten thousand is finally obtained.
Example 5
The stainless steel reaction kettle is subjected to air tightness inspection, after the stainless steel reaction kettle is inspected to be perfect,the air in a stainless steel reaction kettle is replaced three times by adopting the modes of vacuumizing and introducing nitrogen, and 1mol of bio-based monomer 2, 5-furandimethanol, 1.05mol of diphenyl carbonate and 5 multiplied by 10 are added under the protection of nitrogen-4Adding a tetrabutylammonium hydroxide transesterification catalyst into a reaction kettle in mol to obtain a mixture.
And heating the mixture to 180 ℃, removing a small molecular byproduct phenol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 3kPa, setting the stirring speed to be 150rpm, and keeping the reaction for 90min to perform an ester exchange reaction to obtain a prepolymer.
The pressure in the reaction kettle is recovered to normal pressure under the protection of nitrogen, and 1 multiplied by 10 is added-4And (2) gradually heating the obtained prepolymer to 280 ℃ by mol of lithium acetylacetonate polycondensation catalyst, gradually reducing the absolute pressure of the reaction to 0.1kPa, further reducing the reaction pressure to remove reaction by-products phenol and diphenyl carbonate, thereby promoting the reaction to be carried out in the polycondensation direction, setting the stirring speed to 80rpm, and continuing the polycondensation reaction for 190min to finally obtain 138g of bio-based polycarbonate with the viscosity-average molecular weight of 3.23 ten thousand.
Example 6
Performing air tightness inspection on the stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-based monomer 2, 5-furandimethanol, 5mol of methyl ethyl carbonate and 4 multiplied by 10-5Adding mol of sodium sulfite transesterification catalyst into the reaction kettle to obtain a mixture.
Heating the mixture to 200 ℃, removing small molecular by-products of methanol and ethanol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 15kPa, setting the stirring speed to 100rpm, and keeping the reaction for 150min to perform ester exchange reaction to obtain the prepolymer.
The obtained prepolymer is gradually heated to 295 ℃, the absolute pressure of the reaction is gradually reduced to 0.01kPa, reaction byproducts of methanol, ethanol and methyl ethyl carbonate are removed by further reducing the reaction pressure, so that the reaction is promoted to be carried out towards the polycondensation direction, the stirring speed is set to 40rpm, the polycondensation reaction lasts for 240min, and finally 120g of bio-based polycarbonate is obtained, wherein the viscosity-average molecular weight is 3.46 ten thousand.
Example 7
Performing air tightness inspection on a stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-based monomer 2, 5-furandimethanol, 2mol of dibutyl carbonate and 1 multiplied by 10-4Adding mol of calcium carbonate catalyst into the reaction kettle to obtain a mixture.
And heating the mixture to 160 ℃, removing a small molecular byproduct butanol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 30kPa, setting the stirring speed to be 170rpm, and continuing the reaction for 220min to perform an ester exchange reaction to obtain a prepolymer.
The obtained prepolymer is gradually heated to 260 ℃, the absolute pressure of the reaction is gradually reduced to 1kPa, butanol and dibutyl carbonate which are reaction byproducts are removed by further reducing the reaction pressure, so that the reaction is promoted to be carried out towards the polycondensation direction, the stirring rotation speed is set to be 60rpm, the polycondensation reaction lasts for 280min, and finally 115g of bio-based polycarbonate is obtained, wherein the viscosity-average molecular weight is 2.18 ten thousand.
Example 8
Performing air tightness inspection on the stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-based monomer 2, 5-furandimethanol, 0.6mol of diphenyl carbonate, 0.6mol of diethyl carbonate and 8 multiplied by 10-4Adding mol of tetrabutyl titanate catalyst into the reaction kettle to obtain a mixture.
And heating the mixture to 230 ℃, removing small molecular by-products of phenol and ethanol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 3kPa, setting the stirring speed to 160rpm, and keeping the reaction for 120min to perform ester exchange reaction to obtain the prepolymer.
The obtained prepolymer was gradually heated to 275 ℃, the absolute pressure of the reaction was gradually reduced to 0.03kPa, and by further reducing the reaction pressure, by-products of the reaction, phenol, ethanol, diphenyl carbonate, and diethyl carbonate, were removed, thereby promoting the reaction to proceed in the polycondensation direction, the stirring rotation speed was set to 100rpm, and the polycondensation reaction was continued for 200min, to finally obtain 135g of bio-based polycarbonate having a viscosity average molecular weight of 3.61 ten thousand.
Example 9
Performing air tightness inspection on a stainless steel reaction kettle, after the stainless steel reaction kettle is inspected to be intact, replacing air in the stainless steel reaction kettle for three times by adopting a vacuumizing and nitrogen introducing mode, and under the protection of nitrogen, 1mol of bio-based monomer 2, 5-furandimethanol, 1.1mol of dipropyl carbonate and 1 × 10mol of dipropyl carbonate-5mol of dibutyltin oxide and 1X 10-5Adding mol of sodium dihydrogen phosphate catalyst into the reaction kettle to obtain a mixture.
And heating the mixture to 210 ℃, removing the micromolecular byproduct 1-propanol by adopting a vacuumizing mode, gradually reducing the absolute pressure of the reaction from normal pressure to 10kPa, setting the stirring speed to be 150rpm, and continuing the reaction for 240min to perform ester exchange reaction to obtain the prepolymer.
The obtained prepolymer was gradually heated to 270 ℃ and the absolute pressure of the reaction was gradually reduced to 0.01kPa, and by further reducing the reaction pressure, the reaction byproducts 1-propanol and dipropyl carbonate were removed, thereby promoting the reaction to proceed in the polycondensation direction, setting the stirring rotation speed at 50rpm, and continuing the polycondensation reaction for 260min, to finally obtain 125g of bio-based polycarbonate having a viscosity average molecular weight of 2.38 ten thousand.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A bio-based polycarbonate compound, characterized in that it has the structural formula (I):
2. a method for producing a bio-based polycarbonate compound according to claim 1, comprising the steps of:
s1: under the protection of inert gas, adding 2, 5-furan dimethanol, carbonic acid diester and a catalyst into a reaction kettle to obtain a mixture, heating to 80-250 ℃, setting the absolute reaction pressure to be 3-100 kPa, and reacting for 20-240 min to obtain a prepolymer;
s2: heating the prepolymer obtained in S1 to 180-300 ℃, setting the absolute reaction pressure to be 0.01-5 kPa, and reacting for 20-300 min to obtain the bio-based polycarbonate compound.
3. The method for preparing bio-based polycarbonate compound according to claim 2, wherein the carbonic acid diester is one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, ethyl methyl carbonate and diphenyl carbonate.
4. The method for producing a bio-based polycarbonate compound according to claim 2 or 3, wherein the molar ratio of the carbonic acid diester to the 2, 5-furandimethanol is 1 to 10: 1.
5. the method for producing a bio-based polycarbonate compound according to claim 2, the catalyst is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, lithium acetate, sodium acetate, potassium acetate, sodium tetraborate, lithium benzoate, sodium benzoate, potassium benzoate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, magnesium acetate, calcium acetate, zinc oxide, monobutyltin oxide, dibutyltin oxide, titanium dioxide, tetrabutyl titanate, lanthanum acetylacetonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraphenylphosphonium hydroxide and tetranaphthylphosphonium hydroxide.
6. The method for producing a bio-based polycarbonate compound according to claim 2 or 5, wherein the molar mass of the catalyst to the molar mass of 2, 5-furandimethanol is: 0.00001-0.001:1.
7. The method for preparing a bio-based polycarbonate compound according to claim 2, wherein in the step S1, the reaction stirring rotation speed is 50rpm to 200 rpm;
in the S2, the reaction stirring speed is 20rpm-100 rpm.
8. The method of claim 2, wherein the 2, 5-furandimethanol is produced by fermenting, converting and purifying plant stalks, and contains organic carbon of renewable origin according to ASTM D6866 standard.
9. The use of the bio-based polycarbonate compound according to claim 1, wherein the bio-based polycarbonate compound is used as an engineering plastic in the fields of electronics, automobiles, packaging, and optics.
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| CN102702500A (en) * | 2012-06-18 | 2012-10-03 | 陕西延长石油（集团）有限责任公司 | Preparation method of aromatic polycarbonate |
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