CN109293907B - High molecular weight polyester based on biomass as monomer, preparation method and application - Google Patents
High molecular weight polyester based on biomass as monomer, preparation method and application Download PDFInfo
- Publication number
- CN109293907B CN109293907B CN201810649973.6A CN201810649973A CN109293907B CN 109293907 B CN109293907 B CN 109293907B CN 201810649973 A CN201810649973 A CN 201810649973A CN 109293907 B CN109293907 B CN 109293907B
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- Prior art keywords
- polyester
- molecular weight
- monomer
- high molecular
- biomass
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- 229920000728 polyester Polymers 0.000 title claims abstract description 113
- 239000002028 Biomass Substances 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 37
- 150000002148 esters Chemical group 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- YIHLHMMKAVROOJ-UHFFFAOYSA-N dimethyl 2,5-dimethoxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(OC)=C(C(=O)OC)C=C1OC YIHLHMMKAVROOJ-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- -1 aliphatic diols Chemical class 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 4
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 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
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 claims description 3
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 claims description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 3
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- WCKIDCVWRJUPFY-UHFFFAOYSA-L zinc;oxalate;dihydrate Chemical compound O.O.[Zn+2].[O-]C(=O)C([O-])=O WCKIDCVWRJUPFY-UHFFFAOYSA-L 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims description 2
- BJEJEBOUUCXCRZ-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(COC=1C(=CC=CC=1)O)O BJEJEBOUUCXCRZ-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 claims description 2
- IWYVYUZADLIDEY-UHFFFAOYSA-N 4-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(S(O)(=O)=O)C=C1 IWYVYUZADLIDEY-UHFFFAOYSA-N 0.000 claims description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- CYIKHROZRQTQKS-UHFFFAOYSA-M C(C)(=O)[O-].C(C)[Pb+] Chemical compound C(C)(=O)[O-].C(C)[Pb+] CYIKHROZRQTQKS-UHFFFAOYSA-M 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- RAKMKCZMVZBODU-PIQLPZBWSA-L barium(2+);(z)-12-hydroxyoctadec-9-enoate Chemical compound [Ba+2].CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O.CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O RAKMKCZMVZBODU-PIQLPZBWSA-L 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- ZAWFOIKMHASSJG-UHFFFAOYSA-N bis(4-methylpentyl) decanedioate Chemical compound CC(C)CCCOC(=O)CCCCCCCCC(=O)OCCCC(C)C ZAWFOIKMHASSJG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000071 blow moulding Methods 0.000 claims description 2
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 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
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 claims description 2
- QIGBZGQZFNVXIS-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium(2+) hydrochloride Chemical compound Cl.[Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QIGBZGQZFNVXIS-UHFFFAOYSA-N 0.000 claims description 2
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 claims description 2
- CSEGCHWAMVIXSA-UHFFFAOYSA-L cyclopenta-1,3-diene;hafnium(4+);dichloride Chemical compound [Cl-].[Cl-].[Hf+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 CSEGCHWAMVIXSA-UHFFFAOYSA-L 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 2
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- TXSUIVPRHHQNTM-UHFFFAOYSA-N n'-(3-methylanilino)-n-phenyliminobenzenecarboximidamide Chemical compound CC1=CC=CC(NN=C(N=NC=2C=CC=CC=2)C=2C=CC=CC=2)=C1 TXSUIVPRHHQNTM-UHFFFAOYSA-N 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 229950000244 sulfanilic acid Drugs 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- WYKQDEPZMVTTSJ-UHFFFAOYSA-J titanium(4+);tetrabenzoate Chemical compound [Ti+4].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 WYKQDEPZMVTTSJ-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005591 trimellitate group Chemical group 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical compound OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims 1
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- 230000015572 biosynthetic process Effects 0.000 abstract description 4
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- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
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- 229920002961 polybutylene succinate Polymers 0.000 description 31
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- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 17
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- BHCMUFPNGREEFT-UHFFFAOYSA-N O(O)O.C(CCC)[Sn]CCCC Chemical compound O(O)O.C(CCC)[Sn]CCCC BHCMUFPNGREEFT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- KCBWDPZQPRKSRE-RWUXNGIBSA-L barium(2+);(e)-3-phenylprop-2-enoate Chemical compound [Ba+2].[O-]C(=O)\C=C\C1=CC=CC=C1.[O-]C(=O)\C=C\C1=CC=CC=C1 KCBWDPZQPRKSRE-RWUXNGIBSA-L 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- BGOLHCLBIYUVRD-UHFFFAOYSA-N chloro hypochlorite;dibutyltin Chemical compound ClOCl.CCCC[Sn]CCCC BGOLHCLBIYUVRD-UHFFFAOYSA-N 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Landscapes
- 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 a high molecular weight polyester based on biomass as a monomer, a preparation method and application thereof, belonging to the field of polyester synthesis. Heating the monomer 2, 5-dimethoxy dimethyl terephthalate, dihydric alcohol and a catalyst to 120-180 ℃ under the protection of nitrogen to perform normal pressure ester exchange reaction for 2-4 h to obtain an ester exchange product; heating the ester exchange product to 220-250 ℃ under high vacuum with the pressure less than 20Pa to perform polycondensation reaction for 2-4 h to obtain a polyester crude product; finally, the target product of the invention is obtained by solvent extraction, precipitant precipitation, filtration and drying: a high molecular weight polyester. The polyesters obtained by the process of the invention have a weight-average molecular weight MwA value of 110000-150000 Da and a molecular weight distribution Mw/MnThe value is 1.7-2.2, and the polyester synthesized by the method has the characteristics of high molecular weight, high thermal property, good mechanical property and the like. The high molecular weight polyester prepared by the invention based on biomass as a monomer can be used as a main component for processing bottle-grade polyester materials and can also be used as a component raw material for preparing other polyester processing materials.
Description
Technical Field
The invention relates to a high molecular weight polyester based on biomass as a monomer and a preparation method thereof, in particular to a high molecular weight polyester based on biomass as a monomer, which is prepared by taking 2, 5-dimethoxy dimethyl terephthalate and dihydric alcohol as raw materials through two steps of reaction of catalytic ester exchange reaction and catalytic polycondensation, belongs to the field of polyester synthesis, and particularly relates to the high molecular weight polyester based on biomass as a monomer, the preparation method and the application thereof.
Background
The polyester material has the characteristics of light weight, low price, good performance, easy processing and the like, and is widely applied to the aspects of food, chemical industry, construction, automobiles, medicine, agriculture, packaging industry, electronics and the like. The consumption of synthetic polyester materials in daily life is huge, a part of polyester materials do not have good degradability, the problem of white pollution is gradually serious when people discard the synthetic polyester materials at will, the waste pollutes the soil environment and water quality, and when the synthetic polyester materials are eaten by some living things accidentally, the synthetic polyester materials can also die for a long time.
In recent years, much attention has been paid to the research of polyesters that are degradable under natural environmental conditions (microorganisms such as water, soil, air, bacteria, etc.). The main chain of the polyester polymer capable of being naturally degraded is mostly formed by connecting aliphatic structural units through ester bonds which are easy to hydrolyze, and the main chain is soft and smooth, so the polyester polymer is easy to degrade in compost or in natural soil environment. However, with the progress of research, the drawbacks of the aliphatic polyester itself have been gradually revealed as follows: low melting point, poor mechanical property and poor processability, and is difficult to meet the requirements of practical application on various aspects of material properties.
The raw material 2, 5-dimethoxy terephthalic acid dimethyl ester adopted by the invention has a ring-shaped rigid aromatic ring structure, and the processing performance and the mechanical performance of the polyester can be enhanced by introducing the ring-shaped rigid aromatic ring structure into the polyester; and 2, 5-dimethoxy terephthalic acid dimethyl ester is a biomass raw material which can be prepared by succinic acid through series conversion, the natural source of the succinic acid is amber formed by resin of Pinus, and the succinic acid also widely exists in tissues of various plants and animals, has wide sources, is cheap and easy to obtain, can greatly reduce the dependence on fossil raw materials to a certain extent, and has wide prospects.
Disclosure of Invention
The existing aliphatic polyester has the problems of low melting point, poor mechanical property, poor processability and the like, and is difficult to meet the requirements of practical application on various material properties. In view of the above problems in the prior art, the main object of the present invention is to provide a high molecular weight polyester based on biomass as monomer, a preparation method and a use thereof, specifically: the polyester with high molecular weight based on biomass as a monomer is prepared by taking dimethyl 2, 5-dimethoxyterephthalate and dihydric alcohol as raw materials and carrying out two-step reaction of catalytic ester exchange reaction and catalytic polycondensation. Compared with the aliphatic polyester reported in the existing literature, the polyester with high molecular weight based on biomass as a monomer has the advantages of high melting point, good thermal stability, strong mechanical property and good service performance.
The invention adopts the following technical scheme:
in order to better realize the technical scheme of the invention, the invention discloses a high molecular weight polyester based on biomass as a monomer and a preparation method thereof, wherein the preparation method of the high molecular weight polyester comprises the following steps:
1) taking monomer 2, 5-dimethoxy dimethyl terephthalate and dihydric alcohol as reaction raw materials, and carrying out ester exchange reaction for 2-4 h under the action of a catalyst, nitrogen atmosphere, normal pressure and 120-180 ℃ magnetic stirring condition to obtain an ester exchange product; then, the ester exchange product is subjected to polycondensation reaction for 2 to 4 hours under the conditions that the pressure is less than 20Pa and the high vacuum is between 220 and 250 ℃, so as to obtain a crude polyester product.
2) Adding a proper amount of chloroform into the crude polyester product, soaking for 2-3 h, and filtering; and (3) dropwise adding the clear liquid into sufficient methanol to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with methanol, and filtering again to obtain a solid, and performing vacuum drying at 60-70 ℃ to obtain the purified target polyester.
More preferably, in the step 1), the diol is one of the following aliphatic diols: 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, neopentyl glycol, 2-methyl-1, 3-propanediol; or one of the following aliphatic cyclic diols: 1, 3-cyclopentanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, tricyclo [5.2.1O (2, 6) ] decanedimethanol (i.e. tricyclodecanedimethanol), 2,4,8, 10-tetraoxaspiro [5, 5] undecane-3, 9-diethanol (i.e. Spiropentanediol (SPG)); or one of the following aromatic diols: hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, catechol dihydroxyethyl ether, bis (2-hydroxyethyl) terephthalate.
More preferably, in the step 1), the molar ratio of dimethyl 2, 5-dimethoxyterephthalate to glycol is: 1: 1.2-1.5.
More preferably, in the step 1), the catalyst is one of sulfonic acid catalysts (methanesulfonic acid, benzenesulfonic acid, sulfamic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, sulfanilic acid, p-methoxybenzenesulfonic acid, p-nitrobenzenesulfonic acid), group IVB metal catalysts (titanium dioxide, potassium hexafluorotitanate, potassium oxalate, tetrabutyl titanate, isopropyl titanate, titanium tetrabenzoate, titanocene dichloride, zirconocene hydrochloride, hafnocene dichloride), and other metal catalysts (antimony trioxide, antimony acetate, ethylene glycol antimony, zinc oxalate dihydrate, molybdenum dichlorometallocene, tungsten dichlorometallocene, vanadium dichlorometallocene, butylstannoic acid, stannous octoate, dibutyltin oxide, dibutyltin oxyhydroxide, dibutyltin chlorooxide). The amount of the catalyst material is 0.1-1% of the amount of the material of the dimethyl 2, 5-dimethoxyterephthalate.
A biomass-based monomeric high molecular weight polyester according to claim 1, which is used mainly as a main component for processing bottle-grade polyester materials, and can be used for manufacturing storage tanks, protective sleeves and other hollow containers or sleeves which use polyester as a main component. The method is characterized in that: fully mixing the components according to the mass ratio of 100: 40-60: 1-3 of high molecular weight polyester, plasticizer and stabilizer based on biomass as a monomer; after the mixing is finished, the mixture can be subjected to subsequent forming processing such as extrusion, mold closing, blow molding and the like to form a hollow container, or can be subjected to mixing and injection molding to form a storage tank, a protective sleeve and the like. The plasticizer is one of triethyl citrate, acetyl tri-n-butyl citrate, tri-n-hexyl acetyl citrate, epoxidized soybean oil, triglycerin trimellitate, trioctyl trimellitate, dioctyl terephthalate, diisohexyl sebacate, diethylene glycol dibenzoate, triphenyl phosphate, trimethyl phosphate, triethyl phosphonoacetate and the like; the stabilizer is one of barium stearate, barium cinnamate, barium ricinoleate, calcium stearate, calcium ricinoleate, magnesium stearate, zinc stearate, 2-ethyl lead acetate, dibutyltin bis (monobutyl maleate), di-n-octyl tin bis (isobutyl thioglycolate), di-n-octyl tin dilaurate and di-n-octyl tin maleate.
Has the advantages that:
1. careful selection of raw materials: 2, 5-dimethoxy terephthalic acid dimethyl ester can be prepared from succinic acid through serial conversion to obtain a biomass raw material, the natural source of succinic acid is amber formed by resin of Pinus, and the succinic acid also can be widely existed in tissues of various plants and animals, and has the characteristics of wide source, low price and easy obtainment, so that the raw material cost is low, the raw material can be regenerated, and the problem of petroleum-dependent resource shortage in polyester synthesis can be effectively relieved.
2. The synthesized polyester has excellent mechanical property and thermal property: the introduction of 2, 5-dimethoxy terephthalic acid dimethyl ester with a cyclic rigid aromatic ring structure greatly improves the mechanical properties (including tensile strength, tensile modulus, bending strength, bending modulus and impact strength) of polyester, improves the thermal properties of the polyester, and greatly improves the thermal decomposition temperature if the melting point is far higher than that of poly butylene succinate PBS.
3. Compared with the prior aliphatic poly butylene succinate PBS, the polyester P synthesized by the invention1～P6Weight average molecular weight M ofwWeight average molecular weight M of PBSwHigher by 2.6X 104~4.69×104Da; polyester P1～P6Temperature T required for thermal decomposition of 10%10%The temperature T is 10 percent higher than that required by thermal decomposition of poly (butylene succinate) PBS10%The height is 7-23 ℃; polyester P1～P6The melting point or softening point of the poly (butylene succinate) is 72.9-97.9 ℃ higher than that of the poly (butylene succinate) PBS; polyester P1～P6The tensile strength of the poly (butylene succinate) is 106.5-141.6 MPa higher than that of poly (butylene succinate) PBS(ii) a Polyester P1～P6The elongation at break of the poly (butylene succinate) is 38.2-71.3% higher than that of the poly (butylene succinate) PBS; polyester P1～P6The bending strength of the material is 26.4-29.4 MPa higher than that of poly butylene succinate PBS; polyester P1～P6The impact strength of the material is 14.9-17.3 MPa higher than that of poly (butylene succinate) PBS. Based on the data, the molecular weight, the thermal property, the mechanical property and the like of the polyester prepared by the invention are obviously improved.
4. The polyester prepared by the invention adopts high-efficiency sulfonic acid catalysts or high-efficiency catalysts such as IVB group metal catalysts and the like, and the polyester with good service performance is prepared by two-step reaction of catalytic ester exchange and catalytic polycondensation. The same catalyst is used in the two-step reaction, the catalyst does not need to be separated in the reaction process, the catalyst consumption is small, the catalysis cost is low, the high molecular weight polyester with the weight average molecular weight of 110000-150000 Da is obtained, and the polyester product has pure color and extremely low metal content or does not contain metal, so that the requirements of the fields of packaging materials and medical materials of high-grade beverage and food industries on the color quality of raw materials are met.
Drawings
FIG. 1 shows a high molecular weight polyester P based on biomass monomers according to example 1 of the invention1Is/are as follows1H NMR chart.
FIG. 2 shows the high molecular weight polyesters P based on biomass monomers according to example 1 of the invention1GPC chart (A) of (B).
FIG. 3 shows the high molecular weight polyesters P based on biomass monomers according to example 1 of the invention1TG pattern of (a).
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples. The raw materials in the invention are all conventional and commercially available.
The polyesters prepared in the examples were all carried out using a nuclear magnetic resonance apparatus of the Bruker Avance DMX600 type1H NMR characterization with TMS as internal standard, CDCl3Is a solvent; GPC data are measured by a Waters-Breeze gel chromatograph, and the mobile phase is THF; thermogravimetry using Netzsch STA 449F 3 JupiterAnalyzer at N2 The flow rate was 40mL/min, and the temperature was increased from 25 ℃ to 500 ℃ at a temperature increase rate of 10 ℃/min to obtain a TG curve.
Mechanical testing in the examples: the tensile property test is carried out according to the GB/T1040.2-2006 standard; the bending performance is implemented according to the GB/T9341-2008 standard; impact performance is performed according to GB/T1843-2008 standard;
results were averaged over 5 test specimens each.
Yield =100% x actual amount of target product/theoretical amount of target product produced.
Example 1: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 1.862g (30 mmol) of 1, 2-ethanediol and 0.017 g (0.1 mmol) of p-toluenesulfonic acid are sequentially added into a 50mL single-neck flask, and ester exchange reaction is carried out for 3 hours under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 5.022g of polyester P1The yield thereof was found to be 89.59%.
To determine the polyester P prepared in this example1The polyester P prepared in example 1 was subjected to a Bruker Avance DMX600 nuclear magnetic resonance spectrometer, a Waters-Breeze gel chromatograph and a Netzsch STA 449F 3 Jupiter thermogravimetric analyzer1Relevant characterization and testing was performed.
FIG. 1 shows the preparation of polyester P1 in example 1 of the invention1H NMR chart of polyester P thereof1The hydrogen spectrum assignments are shown in formula I below:
FIG. 2 shows the polyester P prepared in example 1 of the present invention1GPC chart of (1), MwReaches 13.12 multiplied by 104Da。
FIG. 3 shows a polyester P prepared in example 1 of the present invention1From the TG diagram, it can be found that the temperature at which 10% mass loss occurs is 386 ℃ and that, therefore, the polyester P prepared in example 1 of the present invention can be obtained1Has good thermal stability.
Please refer to table 1 and table 2 for other test data, which are the same below and are not repeated.
Example 2: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 4.387g (30 mmol) of 1, 8-octanediol and 0.034 g (0.1 mmol) of tetrabutyl titanate are sequentially added into a 50mL single-neck flask, and ester exchange reaction is carried out for 3 hours under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 6.634g of polyester P2The yield thereof was found to be 91.01%.
Example 3: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 2.859g (28 mmol) of 1, 3-cyclopentanediol and 0.03 g (0.1 mmol) of antimony trioxide are sequentially added into a 50mL single-neck flask, and ester exchange reaction is carried out for 3h under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 5.699g of polyester P3The yield thereof was found to be 88.96%.
Example 4: in a 50mL single-neck flask were charged 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate and 4.038 (28 mmol) in that orderCarrying out transesterification reaction on 1, 4-cyclohexanedimethanol and 0.042 g (0.1 mmol) of ethylene glycol antimony under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ for 3 hours to obtain a transesterification product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 6.541g of polyester P4The yield thereof was found to be 90.24%.
Example 5: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 3.020g (26 mmol) of 1, 4-cyclohexanediol and 0.015 g (0.1 mmol) of zinc oxalate dihydrate are sequentially added into a 50mL single-neck flask, and ester exchange reaction is carried out for 3h under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 5.986g of polyester P5The yield thereof was found to be 89.52%.
Example 6: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 5.154g (26 mmol) of hydroquinone dihydroxyethyl ether and 0.030 g (0.1 mmol) of molybdenum dichlorodicyclopentadienyl are sequentially added into a 50mL single-neck flask, and ester exchange reaction is carried out for 3h under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 7.639g of polyester P6Yield ofIt was 91.73%.
Example 7: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 4.757g (24 mmol) of resorcinol dihydroxyethyl ether and 0.021 g (0.1 mmol) of butyl stannoic acid are sequentially added into a 50mL single-neck flask, and the ester exchange reaction is carried out for 3 hours under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 7.325g of polyester P7The yield thereof was found to be 87.96%.
Example 8: 5.084g (20 mmol) of dimethyl 2, 5-dimethoxyterephthalate, 6.102g (24 mmol) of bis (2-hydroxyethyl) terephthalate and 0.025g (0.1 mmol) of dibutyltin oxide are sequentially added into a 50mL single-neck flask, and ester exchange reaction is carried out for 3h under the conditions of nitrogen atmosphere, normal pressure and magnetic stirring at 150 ℃ to obtain an ester exchange product; then, carrying out polycondensation reaction on the ester exchange product for 3 hours under the conditions of pressure less than 20Pa, high vacuum and magnetic stirring at 250 ℃ to obtain a polyester crude product; adding 50mL of chloroform into the crude polyester product, soaking for 3h, and filtering; adding the clear liquid into methanol dropwise to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with 10mL of methanol, filtering, and vacuum drying at 60 deg.C to obtain 8.566g of polyester P8The yield thereof was found to be 90.66%.
TABLE 1 comparison of molecular weight and thermal Properties of samples of polyesters P1-P8 from examples 1-8 with PBS literature data for polybutylene succinate
| Sample (I) | MW/(104Da) | PDI | T10%/℃ | Melting or softening point/. degree.C |
| P1 | 13.12 | 2.05 | 386 | 188.9 |
| P2 | 13.68 | 2.12 | 389 | 204.8 |
| P3 | 12.85 | 2.01 | 386 | 198.7 |
| P4 | 11.80 | 1.86 | 392 | 199.6 |
| P5 | 13.42 | 2.07 | 395 | 213.9 |
| P6 | 12.78 | 1.84 | 383 | 209.1 |
| P7 | 12.37 | 1.98 | 394 | 189.6 |
| P8 | 13.89 | 2.13 | 379 | 193.8 |
| TBOT-TiO2 a[1] | 9.20 | 2.0 | 372 | 116 |
M in Table 1wIs the weight average molecular weight of the sample, PDI is the molecular weight distribution of the sample, T10%The temperature required for the thermal decomposition of the sample to 10%
[1] Xundong, He Wen, Huangwei, and the like, the research on the synthesis of polybutylene succinate by using a two-component titanium catalyst [ J ] ion exchange and adsorption, 2018,34(1):1-8.
Table 2 comparison of mechanical properties of polyester P1-P6 samples in examples 1-6 with that of poly (butylene succinate) PBS
| Sample (I) | Tensile strength/MPa | Elongation at break/% | Flexural Strength/MPa | Impact Strength/(kJ. m)-2 ) |
| P1 | 156.3 | 346.3 | 50.9 | 26.9 |
| P2 | 137.5 | 361.1 | 48.1 | 25.1 |
| P3 | 169.9 | 329.3 | 49.4 | 24.5 |
| P4 | 158.3 | 343.2 | 48.9 | 25.4 |
| P5 | 139.5 | 357.9 | 51.1 | 25.3 |
| P6 | 151.2 | 333.2 | 50.5 | 25.7 |
| P7 | 134.8 | 362.4 | 49.8 | 24.9 |
| P8 | 146.4 | 349.8 | 48.7 | 26.5 |
| PBS[2] | 28.3 | 291.1 | 21.7 | 9.6 |
[2] Yangming, Zhang Zheya, Tianqingliang, etc. the influence of the coupling agent on the mechanical property and the degradation property of the PBS/wheat straw powder composite material [ J ] plastics science and technology, 2017, 45(11):67-71.
As is clear from the comparison of data in Table 1, the polyester P synthesized in the present invention using dimethyl 2, 5-dimethoxyterephthalate and diol as raw materials1～P6Weight average molecular weight M ofwWeight average molecular weight M of PBSwHigher by 2.6X 104~4.69×104Da, polyester P1～P6Temperature T required for thermal decomposition of 10%10%The temperature T is 10 percent higher than that required by thermal decomposition of poly (butylene succinate) PBS10%Polyester P with the temperature of 7-23 ℃ higher1～P6The melting point or softening point of the poly (butylene succinate) is 72.9-97.9 ℃ higher than that of the poly (butylene succinate) PBS.
As can be seen from the comparison of the data in Table 2, the tensile strength of PBS is 28.3MPa, and the polyester P synthesized by using dimethyl 2, 5-dimethoxyterephthalate and dihydric alcohol as raw materials in the invention1～P6The tensile strength of the composite material is 106.5-141.6 MPa higher than that of PBS (poly butylene succinate); the elongation at break of polybutylene succinate PBS is 2911% by weight, and the invention takes dimethyl 2, 5-dimethoxyterephthalate and dihydric alcohol as raw materials to synthesize the polyester P1～P6The elongation at break of the poly (butylene succinate) is 38.2-71.3% higher than that of the poly (butylene succinate) PBS; the bending strength of the poly butylene succinate PBS is 21.7Mpa, and the invention takes 2, 5-dimethoxy terephthalic acid dimethyl ester and dihydric alcohol as raw materials to synthesize the polyester P1～P6The bending strength of the material is 26.4-29.4 MPa higher than that of poly butylene succinate PBS; the impact strength of PBS is 9.6Mpa, and the invention uses 2, 5-dimethoxy terephthalic acid dimethyl ester and dihydric alcohol as raw materials to synthesize polyester P1～P6The impact strength of the material is 14.9-17.3 MPa higher than that of poly (butylene succinate) PBS.
From the above data, it can be seen that the polyester P synthesized by the present invention using dimethyl 2, 5-dimethoxyterephthalate and diol as raw materials1～P6Compared with poly (butylene succinate) PBS, the molecular weight, thermal property, mechanical property and the like of the poly (butylene succinate) PBS are remarkably improved.
In conclusion, the aliphatic polyesters reported in the prior documents have the defects of low melting point, poor mechanical properties and processability and the like, and are difficult to meet the requirements of practical application on various material properties. In order to solve the problems in the prior art, the invention mainly aims to provide a high molecular weight polyester based on biomass as a monomer, a preparation method and application thereof, and specifically relates to a high molecular weight polyester based on biomass as a monomer, which is prepared by taking dimethyl 2, 5-dimethoxyterephthalate and dihydric alcohol as raw materials and performing two-step reactions of catalytic ester exchange reaction and catalytic polycondensation. Compared with the existing aliphatic polyester, the high molecular weight polyester based on biomass as a monomer has the advantages of high melting point, good thermal stability, strong mechanical property and good service performance. Therefore, the invention discloses 'a high molecular weight polyester based on biomass as a monomer, a preparation method and application', and the high molecular weight polyester based on biomass as a monomer has high melting point, good mechanical property and good market prospect.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. A preparation method of high molecular weight polyester based on biomass as a monomer is characterized by comprising the following steps:
1) taking monomer 2, 5-dimethoxy dimethyl terephthalate and dihydric alcohol as reaction raw materials, and carrying out ester exchange reaction for 2-4 h under the action of a catalyst, nitrogen atmosphere, normal pressure and magnetic stirring condition at 120-180 ℃ to obtain an ester exchange product; then carrying out polycondensation reaction on the ester exchange product for 2-4 h under the conditions that the pressure is less than 20Pa and the high vacuum is between 220 and 250 ℃ to obtain a polyester crude product;
2) adding a proper amount of chloroform into the crude polyester product, soaking for 2-3 h, and filtering; dropwise adding the clear liquid into sufficient methanol to obtain a turbid system, centrifuging to obtain a precipitate, filtering, washing with methanol, and performing vacuum drying on the solid obtained after secondary filtration at 60-70 ℃ to obtain purified target polyester;
in the step 1), the dihydric alcohol is one of the following aliphatic diols: 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, neopentyl glycol, 2-methyl-1, 3-propanediol; or one of the following aliphatic cyclic diols: 1, 3-cyclopentanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol; or one of the following aromatic diols: hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, catechol dihydroxyethyl ether, bis (2-hydroxyethyl) terephthalate.
2. The method of claim 1, wherein the molar ratio of dimethyl 2, 5-dimethoxyterephthalate to glycol in step 1) is: 1: 1.2-1.5.
3. The method of claim 1, wherein in step 1), the catalyst is one of sulfonic acid catalyst selected from sulfamic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, sulfanilic acid, p-methoxybenzenesulfonic acid and p-nitrobenzenesulfonic acid, or one of group IVB metal catalysts selected from titanium dioxide, potassium hexafluorotitanate, tetrabutyl titanate, isopropyl titanate, titanium tetrabenzoate, titanocene dichloride, zirconocene hydrochloride and hafnocene dichloride, or one of other metal catalysts selected from antimony trioxide, antimony acetate, antimony glycol, zinc oxalate dihydrate, molybdenum dichloride, tungsten dichloride, vanadium dichloride, butylstannoic acid, stannous octoate and dibutyltin oxide; the amount of the catalyst material is 0.1-1% of the amount of the material of the dimethyl 2, 5-dimethoxyterephthalate.
4. Use of the polyester obtained by the method for preparing a high molecular weight polyester based on biomass as a monomer according to claim 1 as a main component in the processing of bottle-grade polyester materials, wherein: fully mixing the components according to the mass ratio of 100: 40-60: 1-3 of high molecular weight polyester, plasticizer and stabilizer based on biomass as a monomer; after the mixing is finished, subsequent extruding, die closing and blow molding can be carried out to process the mixture into a polyester bottle; the plasticizer is one of triethyl citrate, acetyl tri-n-butyl citrate, tri-n-hexyl acetyl citrate, epoxidized soybean oil, triglycerin trimellitate, trioctyl trimellitate, dioctyl terephthalate, diisohexyl sebacate, diethylene glycol dibenzoate, triphenyl phosphate, trimethyl phosphate and triethyl phosphonoacetate; the stabilizer is one of barium stearate, barium cinnamoate, barium ricinoleate, calcium stearate, calcium ricinoleate, magnesium stearate, zinc stearate, 2-ethyl lead acetate, di-n-octyl tin dilaurate and di-n-octyl tin maleate.
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| US4611049A (en) * | 1984-06-07 | 1986-09-09 | Teijin Limited | Process for producing aromatic polyester |
| US5856423A (en) * | 1996-12-23 | 1999-01-05 | E. I. Du Pont De Nemours And Company | Apparatus and process for a polycondensation reaction |
| CN1759333A (en) * | 2003-03-11 | 2006-04-12 | 新日本石油株式会社 | Optical film and liquid crystal display device |
| CN101250259A (en) * | 2008-03-28 | 2008-08-27 | 中国石油天然气股份有限公司 | Preparation method of poly (1, 3-propylene glycol terephthalate) |
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|---|---|---|---|---|
| FR1378333A (en) * | 1962-11-20 | 1964-11-13 | Glanzstoff Ag | Process for the preparation of optically lightened polyesters |
| US4611049A (en) * | 1984-06-07 | 1986-09-09 | Teijin Limited | Process for producing aromatic polyester |
| US5856423A (en) * | 1996-12-23 | 1999-01-05 | E. I. Du Pont De Nemours And Company | Apparatus and process for a polycondensation reaction |
| CN1759333A (en) * | 2003-03-11 | 2006-04-12 | 新日本石油株式会社 | Optical film and liquid crystal display device |
| CN101250259A (en) * | 2008-03-28 | 2008-08-27 | 中国石油天然气股份有限公司 | Preparation method of poly (1, 3-propylene glycol terephthalate) |
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