CN102585180B - Copolyester based on 2, 3-butanediol and preparation method thereof - Google Patents
Copolyester based on 2, 3-butanediol and preparation method thereof Download PDFInfo
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- CN102585180B CN102585180B CN201110008430.4A CN201110008430A CN102585180B CN 102585180 B CN102585180 B CN 102585180B CN 201110008430 A CN201110008430 A CN 201110008430A CN 102585180 B CN102585180 B CN 102585180B
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- ester
- phthalic acid
- monomer
- butanediol
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- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 27
- -1 diol phthalate Chemical class 0.000 claims abstract description 23
- 229920000728 polyester Polymers 0.000 claims abstract description 16
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 46
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 29
- 239000011541 reaction mixture Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 230000032050 esterification Effects 0.000 claims description 23
- 238000005886 esterification reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 claims description 10
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 claims description 10
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 claims description 10
- 101150019148 Slc7a3 gene Proteins 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 4
- 150000001463 antimony compounds Chemical class 0.000 claims description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 150000003606 tin compounds Chemical class 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- PKNFHOAVUNAOHX-UHFFFAOYSA-N bis(2,2-dimethylpropyl) benzene-1,4-dicarboxylate Chemical compound CC(C)(C)COC(=O)C1=CC=C(C(=O)OCC(C)(C)C)C=C1 PKNFHOAVUNAOHX-UHFFFAOYSA-N 0.000 claims description 2
- LQKWPGAPADIOSS-UHFFFAOYSA-N bis(2-methylpropyl) benzene-1,4-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(C(=O)OCC(C)C)C=C1 LQKWPGAPADIOSS-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 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
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 claims description 2
- MLIPQTRXLNTCRS-UHFFFAOYSA-N dihexyl benzene-1,4-dicarboxylate Chemical compound CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC)C=C1 MLIPQTRXLNTCRS-UHFFFAOYSA-N 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 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
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- HCEPYODGJFPWOI-UHFFFAOYSA-N tridecane-1,13-diol Chemical class OCCCCCCCCCCCCCO HCEPYODGJFPWOI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- PCGGKRXVRHWQGH-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.CC(C(C)O)O Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.CC(C(C)O)O PCGGKRXVRHWQGH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000463 material Substances 0.000 description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 150000002009 diols Chemical class 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
- 239000011654 magnesium acetate Substances 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000013022 venting Methods 0.000 description 4
- IVKSEWDYQMVWGI-UHFFFAOYSA-N C(C1=CC=C(C(=O)O)C=C1)(=O)O.CC(C(C)O)O Chemical compound C(C1=CC=C(C(=O)O)C=C1)(=O)O.CC(C(C)O)O IVKSEWDYQMVWGI-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 150000007520 diprotic acids Chemical group 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GAHSOBODSWGWHR-UHFFFAOYSA-N bis(2,2-dimethylpropyl) benzene-1,2-dicarboxylate Chemical compound CC(C)(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)(C)C GAHSOBODSWGWHR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a copolyester based on 2, 3-butanediol and a preparation method thereof, wherein the copolyester has the following repeated structural units:
Description
Technical field
The invention belongs to materials synthesis preparation field, relate to a kind of high molecular 2,3-butanediol copolyesters and preparation method thereof.
Background technology
Start since nineteen forty-one utilizes terephthalic acid and ethylene glycol successfully to obtain polyethylene terephthalate (PET), polyester just progresses into the routine work of people with in life as a kind of engineering plastics, and plays the effect become more and more important.Polybutylene terephthalate (PBT), as the homologous series polyester of PET, by terephthalic acid or become ester derivative and BDO polycondensation to prepare, has the Good All-around Property similar to PET.Due to its fusing point and second-order transition temperature lower than PET, and crystallization velocity is more faster than PET, and forming process is easy more than PET.(He Siqian, Huang Jia etc., saturated polyester and polycondensation, Science Press, 1986), all obtain a wide range of applications in electronic apparatus, automotive industry and various mechanical manufacturing field for this reason.(Deng Dechun, Wang Yanping, Jiang Qikang, the solid phase polycondensation of polybutylene terephthalate, New Chemical Materials, 2000,28,22)
2,3-butanediol, as the isomers of BDO, is the dibasic alcohol with two branched chain methyl.Constantly expand in energy demand, fossil energy worsening shortages, oil supply anxiety, reproducible biomass resource can be utilized to be produced by conversion technology for raw material, effectively avoiding a large amount of uses of this Nonrenewable resources of oil, is the important directions of biochemical industry development.
Pure 2,3-butanediol is the liquid chemical of colorless and odorless, has very high boiling point and low zero pour, is widely used as the monomer of Macroscopic single crystal.The commercial use of this dibasic alcohol is not limited only to prepare divinyl and be used as frostproofer.As everyone knows, 2,3-butanediol is a kind of of great value chemical feedstocks, because it can be used as solvent, chemical fuel and the intermediate as a lot of synthetic polymer and resin.The thermal capacitance of 2,3-butanediol is 27200J/g, suitable with ethanol (29100J/g), methyl alcohol (22100J/g), thus can be used as liquid fuel and fuel dope.2,3-butanediol dehydration obtains industrial solvent butanone, and dehydration generates 1,3-butadiene (elastomeric starting raw material is also the important monomer of polymer industry) further.Butanone hydrogenation obtains high-octane high quality flight fuel, and the diacetate that catalytic dehydrogenation esterification obtains is a kind of foodstuff additive of high price.
When it and diprotic acid forms polyester time, although 2,3-butanediol has the molecular structure similar with BDO, its two hydroxyls are all secondary hydroxyls, and reactive behavior is lower, be difficult to be polymerized the polyester obtaining high molecular with diprotic acid.The molecular weight of polyesters utilizing one or more diprotic acid and 2,3-butanediol to prepare known is at present all very little, can not meet the requirement of engineering plastics.US Patent 2502686 discloses a kind of lower molecular weight (1000 ~ 3000) polyester utilizing phthalic acid and 2,3-butanediol to prepare, and the molecular weight that this kind polyester is lower makes them not to be used as molded article, as film, sheet material etc.
Utilize 2,3-butyleneglycol colinearity glycol (such as ethylene glycol, 1,4-butyleneglycol) copolymerization is when preparing poly terephthalic acid 2,3-butanediol copolyesters, and two hydroxyls due to linear diols are all primary hydroxyl, reactive behavior is high, when linear diols content is less, be easy to first be polymerized the inside being positioned at copolyesters molecular chain, then 2,3-butyleneglycol is connected on the two ends increasing molecular chain and forms end-blocking effect, can not get the copolyesters product of high molecular equally.US Patent 4600768 discloses 2 of a kind of utilization at least 50%, 3-butyleneglycol and other linear diols mix the method that diol monomer and aromatic acid prepare polyester, the molecular weight of final gained polyester only has about 6000, does not reach the service requirements of engineering plastics far away.When linear diols content is more, the 2,3-butanediol accounting for less content is drawn out of in polycondensation phase greatly, and the content therefore in final copolyesters product, far below the ratio in raw material, can not get the copolyesters of 2,3-butanediol truly.U.S.Pat.No.3714126 using the properties-correcting agent of 2,3-butanediol as PET, but is only added to 8% at most.
Summary of the invention
The object of the invention is to the defect for prior art and a kind of copolyesters based on 2,3-butanediol and preparation method thereof is provided.This copolyesters has higher molecular weight, higher second-order transition temperature T
g, the transparency and excellent mechanical property etc. preferably.
To achieve these goals, the technical solution used in the present invention is as follows:
Based on a copolyesters for 2,3-butanediol, this copolyesters has following repeated structural unit:
Described
Described
Described
Described n=1 ~ 10, m=1 ~ 100, o=2 ~ 13;
Described R
1with R
2can identical also can be different.
A preparation method for the above-mentioned copolyesters based on 2,3-butanediol, comprises the following steps:
(1) monomer a is joined according to a certain percentage together with monomer b and catalyzer Cat1 in the flask or reactor that whipping appts and condensing works are housed, vacuumize, oxygen in inflated with nitrogen removing reaction unit, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, in stirring, react under condensing condition, until the by product of transesterify and esterification reaches more than 92% (theoretical amount is the twice of the molar weight of monomer a) of theoretical amount, obtain phthalic acid linear diols ester,
(2) by monomer c and 2, 3-butyleneglycol and catalyzer Cat2 join in the flask or reactor that whipping appts and condensing works are housed together according to a certain percentage, vacuumize, oxygen in inflated with nitrogen removing reaction unit, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, in stirring, react under condensing condition, until the by product of transesterify and esterification reaches more than 92% (theoretical amount is the twice of the molar weight of monomer c) of theoretical amount,
(3) add catalyzer Cat3, at 240 ~ 280 DEG C, vacuumize (< 500Pa) stir 0.5 ~ 6h; Add the phthalic acid linear diols ester obtained above, at 240 ~ 280 DEG C, continue to vacuumize (< 500Pa) stir 0.5 ~ 6h, stopped reaction.
(4) reaction mixture is taken out from bottle/still, cooling forming in water, obtain the copolyesters based on 2,3-butanediol.
Described monomer a and c is selected from phthalic acid, the ester derivative of phthalic acid, phthalic acid or their mixture;
Described monomer b is selected from linear aliphatic race dibasic alcohol;
Described monomer a and the mol ratio of monomer b are 1: 1.2 ~ 1: 3;
Described monomer a and the mol ratio of monomer c are 1: 1 ~ 1: 9;
Described monomer c and the mol ratio of 2,3-butanediol are 1: 1.2 ~ 1: 3;
The weight fraction that described catalyzer Cat1, Cat2, Cat3 account for reactive component a, b, c and 2,3-butanediol is respectively 0.001% ~ 0.5%, preferably 0.005% ~ 0.3%.
Described phthalic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid or their mixture; Preferred terephthalic acid or m-phthalic acid.
The ester derivative of described phthalic acid is selected from dimethyl terephthalate (DMT), terephthalic acid diethyl ester, terephthalic acid diη-propyl ester, terephthalic acid diisobutyl ester, terephthalic acid two n-pentyl ester, terephthalic acid di neo-pentyl ester, terephthalic acid di-n-hexyl ester, dimethyl isophthalate, m-phthalic acid diethyl ester, m-phthalic acid diη-propyl ester, m-phthalic acid diisobutyl ester, m-phthalic acid two n-pentyl ester, m-phthalic acid di neo-pentyl ester, m-phthalic acid di-n-hexyl ester, dimethyl phthalate, diethyl phthalate, phthalic acid diη-propyl ester, o-benzene butyl phthalate ester, phthalic acid two n-pentyl ester, phthalic acid di neo-pentyl ester, phthalic acid di-n-hexyl ester, or their mixture, be selected from dimethyl terephthalate (DMT) or dimethyl isophthalate.
Described phthalic acid is selected from terephthalic anhydride, Tetra hydro Phthalic anhydride or isophthalic anhydride; Preferred Tetra hydro Phthalic anhydride.
Described linear aliphatic race dibasic alcohol is selected from C
2~ C
13linear straight chain alkane glycol: ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane, 1,12-dodecanediol, 1,13-tridecane diols; Preferred BDO, ethylene glycol or 1,3-PD.
Described catalyzer Cat1, Cat2, Cat3 are conventional catalyst transesterify and/or esterification to katalysis, as based on following element: the metallic compound of Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li and Ga.
Described catalyst component Cat1, Cat2 are selected from one or both the mixture in titanium compound, acetate.
Described catalyst component Cat3 is selected from a kind of in titanium compound, tin compound, antimony compounds or their any mixture.
Catalyzer Cat1, Cat2, Cat3 can be same substance in the reaction, also can be different substances.
Described acetate is selected from a kind of in zinc acetate, magnesium acetate, manganese acetate, Cobaltous diacetate, acetic acid zirconium or their any mixture.
Described titanium compound is selected from tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyl, titanium isopropylate, the different monooctyl ester of metatitanic acid four, tetrabutyl titanate or their any mixture;
Described tin compound is selected from a kind of in dibutyltin oxide, stannous octoate, dibutyl tin dilaurate, tin protochloride or their any mixture;
Described antimony compounds is selected from one or both the mixture in antimony acetate, antimonous oxide.
The polyester that the inventive method prepares vacuumizes and obtains molecular weight at 240 ~ 280 DEG C, and in order to prevent unnecessary degraded and/or side reaction, described method, before often step vacuumizes, adds thermo-stabilizer further.
The weight fraction that described thermo-stabilizer accounts for all reactive components is 0.001% ~ 2%, preferably 0.002% ~ 1%.。
Described thermo-stabilizer is selected from a kind of in triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, trimethyl phosphite 99, triphenylphosphate, triethyl phosphate or their any mixture.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, the inventive method is by introducing other highly active linear aliphatic race dibasic alcohol, and effectively overcome the shortcoming that 2,3-butanediol two secondary hydroxyl polycondensations are difficult to obtain high molecular weight polyesters, gained copolyesters molecular weight is higher, reaches actual operation requirements.
2, the copolyesters prepared of the present invention is owing to having 2, the existence of two pendant methyl in 3-butyleneglycol, destroys the regularity of molecular chain, and 2,3-butyleneglycol accounts for the content of diol reaction monomer at least more than 50%, and thus gained copolyesters has higher glass transition temperature T
g, highly transparent polyester articles, be applicable to multiple fields, as film, clear sheet etc.
3, the present invention prepares the copolyesters of high molecular by introducing highly active linear aliphatic race dibasic alcohol, has good mechanical property, can be used as the structure unit of various product.
4, copolyesters of the present invention is by 2, the copolyesters that 3-butyleneglycol and various linear diols obtain with phthalic acid copolymerization, thus resulting polymers can have continually varying second-order transition temperature T within the specific limits because of the difference of the kind of linear diols, content
g, the diversity requirements of different field to material can be met.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.In the following embodiment provided, adopt following detection method:
Adopt differential scanning calorimeter Perkin Elmer DSC7, under following type of heating, measure second-order transition temperature T
g:
First time scanning, with 50 DEG C/min, is warming up to 280 DEG C from 10 DEG C;
Second time scanning, with 10 DEG C/min, is cooled to 10 DEG C from 280 DEG C;
Third time scanning, with 20 DEG C/min, is warming up to 280 DEG C from 10 DEG C.
Weight-average molecular weight M
wwaters 600E series GPC system measures, and wherein chloroform is used for working curve as elutriant and polystyrene standard sample.
Embodiment 1
(1) by 49g (0.25mol) dimethyl terephthalate (DMT) (DMT), (monomer a), the BDO (monomer b) of 55g (0.61mol), 0.03g tetra-n-butyl titanate join and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 2h at 220 DEG C, in the process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (methyl alcohol theoretical amount is the twice of DMT molar weight) of theoretical amount, obtain transesterify terephthalic acid two BDO ester completely.
(2) 49g (0.25mol) dimethyl terephthalate (DMT) (DMT) (monomer c), the 2,3-butanediol of 55g (0.61mol), 0.05g zinc acetate are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 5h at 190 DEG C, and in the process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (methyl alcohol theoretical amount is the twice of DMT molar weight) of theoretical amount.0.03g stannous octoate, 0.05g triethyl phosphate join in reaction mixture respectively as the catalyzer of polycondensation, thermo-stabilizer.Polyreaction vacuumizes and stirs 2h at the temperature of 270 DEG C.
(3) by transesterify obtained above completely terephthalic acid two BDO ester join in reaction mixing, at 270 DEG C after atmospheric agitation 0.5h, continue to vacuumize and stir 2.5h, stopped reaction.
(4) reaction mixture is taken out from bottle, cooling forming in water, obtain poly terephthalic acid BDO-(50%mol) 2,3-butanediol copolyesters.
After testing, its weight-average molecular weight is 32200, T to gained copolyesters
g=68 DEG C, ultimate strength is 39MPa.
Embodiment 2
(1) by 24g (0.13mol) dimethyl isophthalate, (monomer a), the ethylene glycol (monomer b) of 18g (0.29mol), 0.04g manganese acetate join and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 3h at 200 DEG C, in the process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (methyl alcohol theoretical amount is the twice of dimethyl isophthalate molar weight) of theoretical amount, obtain transesterify m-phthalic acid binaryglycol ester completely.
(2) 73g (0.38mol) dimethyl terephthalate (DMT) (DMT) (monomer c), the 2,3-butanediol of (0.89mol) 80g, 0.04g tetraethyl titanate are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 5.5h at 190 DEG C, and in the process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (methyl alcohol theoretical amount is the twice of DMT molar weight) of theoretical amount.0.04g tin protochloride, 0.06g triphenyl phosphite join in reaction mixture respectively as the catalyzer of polycondensation, thermo-stabilizer.Polyreaction vacuumizes and stirs 2.5h at the temperature of 260 DEG C.
(3) by transesterify obtained above completely m-phthalic acid binaryglycol ester join in reaction mixing, at 265 DEG C after atmospheric agitation 0.5h, continue to vacuumize and stir 2h, stopped reaction.
(4) reaction mixture is taken out from bottle, cooling forming in water, obtain poly-m-phthalic acid ethylene glycol-(75%mol) terephthalic acid 2,3-butanediol copolyesters.
After testing, its weight-average molecular weight is 21700, T to gained copolyesters
g=87 DEG C, ultimate strength is 27MPa.
Embodiment 3
(1) by 9g (0.063mol) Tetra hydro Phthalic anhydride, (monomer a), the BDO (monomer b) of 7g (0.078mol), the ethylene glycol (monomer b) of 4.5g (0.073mol), 0.01g magnesium acetate join and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 2.5h at 200 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculated amount is Tetra hydro Phthalic anhydride equimolar amount) of theoretical amount, obtain esterification O-phthalic acid diethylene glycol-co-1,4-butanediol ester completely.
(2) 2,3-butanediol of 85g (0.44mol) dimethyl terephthalate (DMT) (DMT) (monomer c), 95g (1.06mol), 0.06g metatitanic acid four n-propyl are joined and be equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 7h at 185 DEG C, and in the process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (methyl alcohol theoretical amount is the twice of DMT molar weight) of theoretical amount.0.04g tetra-n-butyl titanate, 0.07g triphenylphosphate join in reaction mixture respectively as the catalyzer of polycondensation, thermo-stabilizer.Polyreaction vacuumizes and stirs 4h at the temperature of 255 DEG C.
(3) by transesterify obtained above completely O-phthalic acid diethylene glycol-co-1,4-butanediol ester join in reaction mixing, at 255 DEG C after atmospheric agitation 0.5h, continue to vacuumize and stir 1.5h, stopped reaction.
(4) reaction mixture is taken out from bottle, cooling forming in water, obtain poly-phthalic acid ethylene glycol-(6.25%mol) BDO-terephthalic acid (87.5%mol) 2,3-butanediol copolyesters.
After testing, its weight-average molecular weight is 14800, T to gained copolyesters
g=92 DEG C, ultimate strength is 16MPa.
Embodiment 4
(1) by 1660g (10mol) terephthalic acid (PTA), (monomer a), the BDO (monomer b) of 2000g (22.22mol), 0.7g tetra-n-butyl titanate join in the reactor of 15L.After all material add, inflated with nitrogen, venting, the oxygen in removing reactor, to ensure that esterification is carried out under a nitrogen atmosphere.Esterification stirs 3h at 220 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculated amount is the twice of PTA molar weight) of theoretical amount, obtain esterification terephthalic acid two BDO ester completely.
(2) 2,3-butanediol of 1660g (10mol) terephthalic acid (PTA) (monomer c), 2100g (23.33mol), 0.6g zinc acetate, the different monooctyl ester of 0.3g metatitanic acid four are joined in the reactor of 15L.After all material add, inflated with nitrogen, venting, the oxygen in removing reactor, to ensure that esterification is carried out under a nitrogen atmosphere.Esterification stirs 4h at 190 DEG C, and in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculated amount is the twice of PTA molar weight) of theoretical amount.1.0g tin protochloride, 1.1g triphenyl phosphite join in reaction mixture respectively as the catalyzer of polycondensation, thermo-stabilizer.Polyreaction vacuumizes and stirs 1.5h at the temperature of 260 DEG C.
(3) by transesterify obtained above completely terephthalic acid two BDO ester join in reaction mixing, at 240 DEG C after atmospheric agitation 0.5h, continue to vacuumize and stir 5h, stopped reaction.
(4) reaction mixture is taken out from bottle, cooling forming in water, obtain poly terephthalic acid BDO (50%mol) 2,3-butanediol copolyesters.
After testing, its weight-average molecular weight is 41300, T to gained copolyesters
g=69 DEG C, ultimate strength is 41MPa.
Embodiment 5
(1) by 830g (5mol) m-phthalic acid (monomer a), 500g (5.60mol) 1, the 1,3-PD (monomer b) of 4-butyleneglycol (monomer b), 450g (5.92mol), 0.2g magnesium acetate, 0.3g metatitanic acid four n-propyl join in the reactor of 15L.After all material add, inflated with nitrogen, venting, the oxygen in removing reactor, to ensure that esterification is carried out under a nitrogen atmosphere.Esterification stirs 3.5h at 215 DEG C, in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculated amount is the twice of PTA molar weight) of theoretical amount, obtain esterification m-phthalic acid 21 completely, ammediol-co-1,4-butanediol ester.
(2) 2910g (15mol) dimethyl terephthalate (DMT) (DMT) (monomer c), the 2,3-butanediol of 4050g (45mol), 0.4g magnesium acetate, 0.4g manganese acetate are joined in the reactor of 15L.After all material add, inflated with nitrogen, venting, the oxygen in removing reactor, to ensure that esterification is carried out under a nitrogen atmosphere.Esterification stirs 4h at 190 DEG C, and in the process, water is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% (water theory calculated amount is the twice of PTA molar weight) of theoretical amount.1.2g antimonous oxide, 0.7g triethyl-phosphite, 0.4g triphenyl phosphite join in reaction mixture respectively as the catalyzer of polycondensation, thermo-stabilizer.Polyreaction vacuumizes and stirs 2h at the temperature of 265 DEG C.
(3) by transesterify obtained above m-phthalic acid two 1,3-PD-co-1 completely, 4-butanediol ester joins in reaction mixing, at 250 DEG C after atmospheric agitation 0.5h, continues to vacuumize and stirs 4h, stopped reaction.
(4) reaction mixture is taken out from bottle, cooling forming in water, obtain poly-m-phthalic acid 1,3-PD-(12.5%mol) BDO-(75%mol) terephthalic acid 2,3-butanediol copolyesters.
After testing, its weight-average molecular weight is 29400, T to gained copolyesters
g=88 DEG C, ultimate strength is 28MPa.
Comparative examples
By the 2,3-butanediol of 98g dimethyl terephthalate (DMT) (DMT), 120g, 0.1g tetra-n-butyl titanate joins and is equipped with in the 250mL there-necked flask of mechanical stirring device.After all material add, assemble a set of condensing works to flask, vacuumize, inflated with nitrogen three times, the oxygen in removing reaction vessel is to ensure that transesterification reaction is carried out under a nitrogen atmosphere.Transesterification reaction stirs 5h at 190 DEG C, and in the process, methyl alcohol is distilled out of from reaction mixture as byproduct, until the amount of cut liquid reaches 92% of theoretical amount.(methyl alcohol theoretical amount is the twice of DMT molar weight).0.05g titanium isopropylate, 0.05g triphenyl phosphite join in reaction mixture respectively as the catalyzer of polycondensation, thermo-stabilizer.Polyreaction vacuumizes and stirs 5h, stopped reaction at the temperature of 270 DEG C.
Taken out from bottle by reaction mixture, cooling forming in water, obtains 2,3-polybutylece terephthalate.
After testing, its weight-average molecular weight is 2300, T to gained copolyesters
g=98 DEG C, ultimate strength is 5MPa.
By implementation process and the detected result of each embodiment, knownly can effectively avoid 2,3-butanediol polycondensation to be difficult to obtain the shortcoming of high molecular weight polyesters by preparation method of the present invention, final copolyesters is for having higher molecular weight, higher glass transition temperature T
gtransparent non-crystalline copolyesters, be applicable to multiple Application Areas, as film, transparent products etc.By regulate various linear diols kind and with 2, the mol ratio of 3-butyleneglycol, conveniently can regulate the thermomechanical property of copolyesters, for the polymkeric substance obtaining having required specified property provides a method very easily, expand the use range of product further.
The above-mentioned description to embodiment can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (7)
1. based on a copolyesters for 2,3-butanediol, it is characterized in that: described copolyesters has following repeated structural unit:
Described
described
or
described
Described n=1 ~ 10, m=1 ~ 100, o=2 ~ 13;
The weight-average molecular weight of described copolyesters is 14800,21700,29400,32200 and 41300.
2. prepare a method for the copolyesters based on 2,3-butanediol according to claim 1, it is characterized in that: comprise the following steps:
(1) monomer a is joined according to a certain percentage together with monomer b and catalyzer Cat1 in the flask or reactor that whipping appts and condensing works are housed, vacuumize, oxygen in inflated with nitrogen removing reaction unit, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, in stirring, react under condensing condition, until the by product of transesterify and esterification reaches more than 92% of theoretical amount, theoretical amount is the twice of the molar weight of monomer a, obtain phthalic acid linear diols ester,
(2) by monomer c and 2, 3-butyleneglycol and catalyzer Cat2 join in the flask or reactor that whipping appts and condensing works are housed together according to a certain percentage, vacuumize, oxygen in inflated with nitrogen removing reaction unit, ensure that transesterify and/or esterification are carried out under a nitrogen atmosphere, be heated to after reaction mixture melts/be dissolved into homogeneous system completely, controlling temperature of reaction is 170 ~ 230 DEG C, in stirring, react under condensing condition, until the by product of transesterify and esterification reaches more than 92% of theoretical amount, theoretical amount is the twice of the molar weight of monomer c,
(3) add catalyzer Cat3, at 240 ~ 280 DEG C, vacuumize stirring 0.5 ~ 6h; Add the phthalic acid linear diols ester obtained above, continue to vacuumize stirring 0.5 ~ 6h, stopped reaction at 240 ~ 280 DEG C;
(4) reaction mixture is taken out from bottle/still, cooling forming in water, obtain the copolyesters based on 2,3-butanediol;
Described monomer a is selected from terephthalic acid, m-phthalic acid, dimethyl terephthalate (DMT), terephthalic acid diethyl ester, terephthalic acid diη-propyl ester, terephthalic acid diisobutyl ester, terephthalic acid two n-pentyl ester, terephthalic acid di neo-pentyl ester, terephthalic acid di-n-hexyl ester, dimethyl isophthalate, m-phthalic acid diethyl ester, m-phthalic acid diη-propyl ester, m-phthalic acid diisobutyl ester, m-phthalic acid two n-pentyl ester, m-phthalic acid di neo-pentyl ester, m-phthalic acid di-n-hexyl ester, terephthalic anhydride, isophthalic anhydride,
Described monomer c is selected from m-phthalic acid, dimethyl isophthalate, m-phthalic acid diethyl ester, m-phthalic acid diη-propyl ester, m-phthalic acid diisobutyl ester, m-phthalic acid two n-pentyl ester, m-phthalic acid di neo-pentyl ester, m-phthalic acid di-n-hexyl ester, isophthalic anhydride;
Described monomer b is selected from linear aliphatic race dibasic alcohol; Described linear aliphatic race dibasic alcohol is selected from C
2~ C
13linear straight chain alkane glycol: ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane, 1,12-dodecanediol, 1,13-tridecane diols;
Described catalyzer Cat1, Cat2, Cat3 are conventional catalyst transesterify and/or esterification to katalysis; The described conventional catalyst having a katalysis to transesterify and/or esterification is selected from the metallic compound based on following Ti, Ge, Zn, Fe, Mn, Co, Zr, Mg, Sb, Sn, V, Ir, La, Ce, Li and Ga.
3. method according to claim 2, is characterized in that: described monomer a and the mol ratio of monomer b are 1:1.2 ~ 1:3; Or the mol ratio of described monomer a and monomer c is 1:1 ~ 1:9; Or the mol ratio of described monomer c and 2,3-butanediol is 1:1.2 ~ 1:3; Or the weight fraction that described catalyzer Cat1, Cat2, Cat3 accounts for reactive component a, b, c and 2,3-butanediol is respectively 0.001% ~ 0.5%.
4. method according to claim 2, is characterized in that: described catalyst component Cat1, Cat2 are selected from titanium compound; Described catalyst component Cat3 is selected from a kind of in titanium compound, tin compound, antimony compounds or their any mixture; Catalyzer Cat1, Cat2, Cat3 is same substance or different substances in the reaction.
5. method according to claim 4, is characterized in that: described titanium compound is selected from tetra-n-butyl titanate, tetraethyl titanate, metatitanic acid four n-propyl, titanium isopropylate, the different monooctyl ester of metatitanic acid four, tetrabutyl titanate or their any mixture; Described tin compound is selected from a kind of in dibutyltin oxide, stannous octoate, dibutyl tin dilaurate, tin protochloride or their any mixture; Described antimony compounds is selected from one or both the mixture in antimony acetate, antimonous oxide.
6. method according to claim 2, is characterized in that: described polyester vacuumizes and obtains molecular weight at 240 ~ 280 DEG C; Described method, before often step vacuumizes, adds thermo-stabilizer further.
7. method according to claim 2, is characterized in that: the weight fraction that described thermo-stabilizer accounts for all reactive components is 0.001% ~ 2%; Described thermo-stabilizer is selected from a kind of in triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, trimethyl phosphite 99, triphenylphosphate, triethyl phosphate or their any mixture.
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| US3714126A (en) * | 1967-11-27 | 1973-01-30 | Ici Ltd | Antimony compound catayzed ethylene glycol polyesterification with added second diol |
| US4554344A (en) * | 1985-04-12 | 1985-11-19 | Eastman Kodak Company | Process for preparation of polyesters with improved molecular weight from glycols containing a vicinal secondary hydroxyl group |
| US4600768A (en) * | 1985-10-18 | 1986-07-15 | Eastman Kodak Company | Aromatic polyesters derived from 2,3-butanediol |
| CN101525414A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Polyester |
| CN102093543A (en) * | 2009-12-14 | 2011-06-15 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing 2,3-polybutylece terephthalate and copolyester thereof |
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| CN102585180A (en) | 2012-07-18 |
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Denomination of invention: Correlation module identifying method based on 2-type heterogeneous network Effective date of registration: 20191202 Granted publication date: 20150325 Pledgee: Chuzhou economic and Technological Development Corporation Pledgor: Shanghai Jieshijie New Materials (Group) Co., Ltd. Registration number: Y2019980000815 |