CN116478386A - Polyester catalyst based on 2, 5-furandicarboxylic acid activation and preparation method and application thereof - Google Patents
Polyester catalyst based on 2, 5-furandicarboxylic acid activation and preparation method and application thereof Download PDFInfo
- Publication number
- CN116478386A CN116478386A CN202211525567.1A CN202211525567A CN116478386A CN 116478386 A CN116478386 A CN 116478386A CN 202211525567 A CN202211525567 A CN 202211525567A CN 116478386 A CN116478386 A CN 116478386A
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- CN
- China
- Prior art keywords
- ion
- polyester
- furandicarboxylic acid
- silica gel
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229920000728 polyester Polymers 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000004913 activation Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000741 silica gel Substances 0.000 claims abstract description 44
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 5
- -1 oxygen ion Chemical class 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 28
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 claims description 6
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940063013 borate ion Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 claims description 6
- 229940085991 phosphate ion Drugs 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 claims description 3
- 229940005993 chlorite ion Drugs 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 229940079826 hydrogen sulfite Drugs 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940005654 nitrite ion Drugs 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 229940006280 thiosulfate ion Drugs 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 229920001634 Copolyester Polymers 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 230000003213 activating effect Effects 0.000 abstract description 3
- 125000002541 furyl group Chemical group 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000002194 synthesizing effect Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 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 description 7
- 238000009489 vacuum treatment Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QBWYVJBARUOINS-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) diphenyl phosphate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 QBWYVJBARUOINS-UHFFFAOYSA-N 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- YKLISTPTSZVJEI-UHFFFAOYSA-N 2-di(propan-2-yloxy)phosphorylaniline Chemical compound CC(C)OP(=O)(OC(C)C)c1ccccc1N YKLISTPTSZVJEI-UHFFFAOYSA-N 0.000 description 2
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 description 2
- RVJLDRWCSNDJTK-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(O)OC2=CC=C(C=C2)O Chemical compound C1=CC=C(C=C1)P(=O)(O)OC2=CC=C(C=C2)O RVJLDRWCSNDJTK-UHFFFAOYSA-N 0.000 description 2
- DRBXETAUXNKALW-UHFFFAOYSA-N Cc1cc(C)c(C(=O)c2ccccc2P(O)(O)=O)c(C)c1 Chemical compound Cc1cc(C)c(C(=O)c2ccccc2P(O)(O)=O)c(C)c1 DRBXETAUXNKALW-UHFFFAOYSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- QHGRPTNUHWYCEN-UHFFFAOYSA-N dioctyl phenyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)OC1=CC=CC=C1 QHGRPTNUHWYCEN-UHFFFAOYSA-N 0.000 description 2
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- ITJNARMNRKSWTA-UHFFFAOYSA-N nisoxetine Chemical compound C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1OC ITJNARMNRKSWTA-UHFFFAOYSA-N 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- SDLFRXZYUSIEBE-UHFFFAOYSA-N [Si][Ti][Co] Chemical compound [Si][Ti][Co] SDLFRXZYUSIEBE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000013142 basic testing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XNLLYEBENAYXGZ-UHFFFAOYSA-N ethane-1,2-diol;[4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCCO.OCC1CCC(CO)CC1 XNLLYEBENAYXGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 108010007425 oligomycin sensitivity conferring protein Proteins 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
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- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the field of polyesters, and discloses a polyester catalyst based on activation of 2, 5-furandicarboxylic acid, and a preparation method and application thereof. The polyester catalyst of the invention is silica gel supported metal complex M x L y @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: m is central metal, L is ligand ion, M and L are loaded in silica gel carrier. The polyester catalyst of the invention can not catalyze the copolymerization of non-furyl dibasic acid and dihydric alcohol when being singly existed, and can catalyze and synthesize PEF or 2, 5-furandicarboxylic acid copolyester when 2, 5-furandicarboxylic acid exists in a polymerization system, and the 2,5 is presumedFurandicarboxylic acid acts as an activating catalyst during the reaction. The polyester catalyst has the advantages of strong stability, high selectivity, high activity and environment friendliness, and the prepared 2, 5-furandicarboxylic acid polyester has high intrinsic viscosity and good hue.
Description
Technical Field
The invention relates to the field of polyesters, in particular to a polyester catalyst based on activation of 2, 5-furandicarboxylic acid, and a preparation method and application thereof.
Background
The bio-based polyester takes renewable resources as main raw materials, reduces the consumption of petroleum resources and the pollution to the environment in the production process of petroleum-based raw materials, and has the dual effects of saving petroleum resources and protecting the environment. Therefore, the development of the high-performance bio-based polyester is in accordance with the green environment-friendly energy-saving concept. The poly (ethylene 2, 5-furandicarboxylate) (PEF) synthesized from the biological source of 2, 5-furandicarboxylic acid and ethylene glycol is superior to polyethylene terephthalate (PET) in gas barrier property, heat resistance, antistatic property and the like, and is a bio-based polyester with excellent comprehensive performance and great application potential. However, 2, 5-furandicarboxylic acid is easy to undergo side reactions such as decarboxylation under high temperature conditions, so that the 2, 5-furandicarboxylic acid polyester has the problems of low viscosity number, yellow color, and the like. Therefore, the optimization of the polymerization process or the design of a novel catalytic system to obtain the 2, 5-furandicarboxylic acid-based polyester with high intrinsic viscosity and excellent hue is the direction and aim of the vast technological workers.
In the prior art for synthesizing furan dicarboxylic acid polyester, as disclosed in patent document CN 102453242B, a method for preparing 2, 5-furan dicarboxylic acid polyester by direct esterification polymerization is disclosed, 2, 5-furan dicarboxylic acid reacts with low-carbon dihydric alcohol under the action of a catalyst, and high-quality polyfuran dicarboxylic acid ester is formed by direct esterification, polymerization reaction and purification and separation.
Patent document CN 102516513B discloses a preparation method of low yellowing 2, 5-furandicarboxylic acid polyester, white powdery 2, 5-furandicarboxylic acid polyester is obtained under mild reaction conditions by adopting a solution polymerization mode, and ageing degradation yellowing of polyester caused by melt polycondensation can be avoided by adopting the method, but the solution polymerization production cost is high, the solvent recovery difficulty is high, and the molecular weight of the obtained polymer is low.
Patent document CN 106243331B discloses a preparation method of polyethylene furandicarboxylate, which adopts a nitrogen-containing catalyst with good stability to prepare a colorless or light-colored polymer, but the preparation process of the catalyst involves a loading process and is relatively complex.
Patent document CN 107098875B discloses a preparation method of a polyfurandicarboxylic acid glycol ester, which comprises the steps of firstly synthesizing furandicarboxylic acid glycol monomethyl ester, and then synthesizing furandicarboxylic acid polyester without yellowing by taking furandicarboxylic acid glycol monomethyl ester as a monomer raw material, wherein the steps are complicated, and the production cost is increased.
Patent document CN 108727575B discloses a preparation method of bio-based 2, 5-furandicarboxylic acid copolyester, which comprises uniformly mixing an esterified product generated by the reaction of dibasic acid, aliphatic dihydric alcohol and 2, 5-furandicarboxylic acid with a titanium-silicon-cobalt composite catalyst, and sequentially reacting to obtain the bio-based 2, 5-furandicarboxylic acid copolyester, wherein cobalt element has certain toxicity to living bodies as a 2B type carcinogen.
Patent document CN 109810248B discloses a furandicarboxylic acid copolyester and a preparation method thereof, wherein one of an antimony catalyst, a germanium catalyst and a tin catalyst is used as a catalytic system to copolymerize dihydric alcohols such as furandicarboxylic acid/furandicarboxylic acid ester, cyclohexanedimethanol and the like and polyhydric alcohols with hydroxyl number more than or equal to 3, so that the furandicarboxylic acid copolyester with excellent hue can be prepared, the antimony catalyst in the catalytic system can generate serious environmental pollution, and the chain extension effect formed by the polyhydric alcohols improves the technical difficulty in the production process.
Patent document CN 111269405A discloses a preparation method of a bio-based polyester for inhibiting discoloration, namely, by reducing the esterification temperature, the decarboxylation side reaction of 2, 5-furandicarboxylic acid is avoided, the purpose of improving the hue of the furandicarboxylic acid-based polyester is achieved, the process for reducing the esterification temperature will sacrifice the esterification rate, and finally the production efficiency is reduced.
The paper literature reports that polyethylene 2, 5-furandicarboxylate with excellent hue is synthesized by using a transesterification method by using elemental zinc as a catalyst by the institute of chemical and physical large company, china academy of sciences Zhou Guangyuan et al, and the intrinsic viscosity of the obtained polyester is 0.68dL/g. Compared with the direct esterification method, the transesterification method has the disadvantages of complex polymerization process, high toxicity of the byproduct methanol and the like (J.IND.ENG.CHEM., 2021, 99, 422-430).
In summary, no patent and literature report that a catalytic system which is environment-friendly, easy to store, high in activity and high in selectivity can be used for synthesizing colorless 2, 5-furandicarboxylic acid based polyester with high intrinsic viscosity by a direct esterification method is available at present.
Disclosure of Invention
Aiming at the technical problems of few types of existing catalytic systems for synthesizing 2, 5-furandicarboxylic acid polyester, complicated preparation steps, poor catalytic effect and the like, the invention provides a polyester catalyst based on activation of 2, 5-furandicarboxylic acid, and a preparation method and application thereof. The polyester catalyst disclosed by the invention can not catalyze the copolymerization of non-furyl dicarboxylic acid and dihydric alcohol when being singly existed, and can catalyze the copolymerization of the dibasic acid and dihydric alcohol when 2, 5-furandicarboxylic acid exists in a polymerization system, and the 2, 5-furandicarboxylic acid participates in polymerization to form the 2, 5-furandicarboxylic acid polyester. The polyester catalyst synthesized and loaded by double decomposition reaction has strong stability, high selectivity, high activity and environment friendliness, and the prepared 2, 5-furandicarboxylic acid polyester has high intrinsic viscosity and good hue.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a polyester catalyst based on activation of 2, 5-furandicarboxylic acid, which is a silica gel supported metal complex M x L y @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: m is central metal, L is ligand ion, M and L are loaded in silica gel carrier.
The team of the invention finds that the polyester catalyst can not catalyze the copolymerization of non-furyl dibasic acid and dihydric alcohol when the polyester catalyst exists alone, and can catalyze and synthesize PEF or 2, 5-furandicarboxylic acid copolyester when 2, 5-furandicarboxylic acid exists in a polymerization system, and the 2, 5-furandicarboxylic acid is presumed to play a role in activating the catalyst in the reaction process. The polyester catalyst has the advantages of strong stability, high selectivity, high activity and environment friendliness, and the prepared 2, 5-furandicarboxylic acid polyester has high intrinsic viscosity and good hue.
Specifically:
m is selected from K + 、Ca 2+ 、Sc 3+ 、Ti 4+ 、V 3+ 、V 4+ 、V 5+ 、Cr 3+ 、Mn 2+ 、Mn 4+ 、Fe 2+ 、Fe 3+ 、Ni 2+ 、Cu + 、Cu 2+ 、Zn 2+ 、Ga 3+ 、Ge 2+ 、Ge 4+ One or more of the following.
The invention discovers that the fourth-period metal element has moderate Lewis acidity compared with other periodic metal elements, can keep good polymerization activity and can avoid excessive side reactions.
L is selected from one or more of oxygen ion, hydroxyl ion, borate ion, formate ion, acetate ion, oxalate ion, hydrogen oxalate ion, carbonate ion, bicarbonate ion, nitrite ion, aluminosilicate ion, silicate ion, metasilicate ion, phosphate ion, phosphite ion, monohydrogen phosphate ion, dihydrogen phosphate ion, sulfate ion, hydrogen sulfate ion, sulfite ion, hydrogen sulfite ion, thiosulfate ion, hypobromite ion, chlorite ion, hypochlorous acid ion, arsenate ion, C1-C20 alkoxy, C1-C20 aryloxy.
The invention discovers that the oxygen element shows stronger polarity, and the good coordination ability of the oxygen-containing ligand can effectively assist the metal ions to carry out selective catalytic polymerization reaction.
Preferably, M is selected from V 3+ 、Mn 2+ 、Fe 2+ 、Cu + 、Ge 2+ One or more of the following.
The invention further discovers that the metal ions with stronger reducibility have excellent antioxidation effect and can assist the antioxidants to avoid high-temperature oxidation reaction caused by trace air in the reaction process.
Preferably, L is selected from one or more of oxygen ion, borate ion, acetate ion, hydrogen oxalate ion, hydrogen carbonate ion.
The present invention further found that none of the above ligand ions exhibit oxidizing properties in polyester reaction systems.
In a second aspect, the invention provides a method for preparing a polyester catalyst, comprising the steps of:
a) Dissolving the compound A containing M in a good solvent A, adding silica gel, and performing ultrasonic treatment to obtain a compound A solution in which the silica gel is dispersed.
b) And weighing a corresponding amount of the compound B containing L according to a valence balance theory.
c) The compound B containing L was dissolved in a good solvent B to obtain a compound B solution.
d) Gradually dropwise adding the compound A solution in which silica gel is dispersed into the compound B solution in an inert gas atmosphere until the reaction system is neutral, concentrating the solvent, and then placing the mixture in a low-temperature environment for precipitation.
e) Filtering, cleaning and vacuum drying to obtain the silica gel supported metal complex M x L y @SiO 2 。
Preferably, in the step a), the good solvent a is one or more selected from ethanol, water and petroleum ether.
Preferably, in the step a), the amount of M is 8 to 12mmol, and the amount of the good solvent A is 80 to 200mL.
Preferably, in the step a), the silica gel has a particle size of 300 to 400 mesh.
Preferably, in step a), the amount of silica gel is 5 to 20 equivalents relative to M.
Preferably, in step a), the sonication time is from 1 to 3 hours.
Preferably, in step c), the good solvent B is one or more selected from ethanol, water, and petroleum ether.
Preferably, in the step c), the amount of the good solvent B is 80 to 200mL.
Preferably, in step d), the dropping speed is 1 to 3mL/min.
Preferably, in step d), the solvent is concentrated to 50 to 100mL and then precipitated in an environment of-40 to 5 ℃.
In a third aspect, the present invention provides the use of the above polyester catalyst in the preparation of a 2, 5-furandicarboxylic acid based polyester comprising the steps of: placing 2, 5-furandicarboxylic acid, other dibasic acid, dihydric alcohol and catalyst with the weight of 10-1000 ppm (based on the total mass of the reaction raw materials) in a polyester reaction kettle, esterifying under the protection of inert gas, carrying out polycondensation under vacuum condition after the esterification is completed, and discharging after the polycondensation is completed to obtain the 2, 5-furandicarboxylic acid polyester.
When the polyester catalyst is applied to the synthesis of 2, 5-furandicarboxylic acid, the catalyst and the 2, 5-furandicarboxylic acid form an active center for high-selectivity catalytic polycondensation reaction in the esterification stage, so that the high activity is maintained, and side reactions in the polymerization process can be effectively avoided. The 2, 5-furandicarboxylic acid participates in the polymerization reaction after activating the catalyst to form the 2, 5-furandicarboxylic acid based polyester. The 2, 5-furandicarboxylic acid based polymer obtained by the above method has a number average molecular weight of 0.1X10 4 ～30×10 4 Da, the intrinsic viscosity is 0.5-1.5 dL/g, L value>50. b value<20. The glass transition temperature is 0-200 ℃.
Preferably, the molar ratio of the dihydric alcohol to the alkyd of all the dibasic acids is 1.0-3.0:1.
Preferably, the diol has the structure of formula I:
wherein R is selected from C2-C20 alkyl, C6-C20 aryl, C2-C20 alkoxy, C6-C20 aryloxy, C2-C20 alkylthio, C6-C20 arylthio, C2-C20 alkylamino, C6-C20 arylamino, C2-C20 alkylphosphino, C6-C20 arylphosphino;
preferably, the diol monomer (I) has a structure represented by A to X:
preferably, the diacid also has the structure of formula II:
wherein R' is selected from the group consisting of C2-C20 alkyl, C6-C20 aryl, C2-C20 alkoxy, C6-C20 aryloxy, C2-C20 alkylthio, C6-C20 arylthio, C2-C20 alkylamino, C6-C20 arylamino, C2-C20 alkylphosphino, and C6-C20 arylphosphino.
Preferably, the diacid monomer (II) has the structure shown in A 'to X':
preferably, the esterification reaction temperature is 150-250 ℃ and the time is 0.25-5 h.
Preferably, the polycondensation reaction temperature is 200 to 300 ℃ and the time is 0.5 to 10 hours.
Preferably, a stabilizer and/or an antioxidant is added in the polyester reaction kettle. The amount of the stabilizer is 10 to 1000ppm (based on the total mass of the reaction raw materials); the antioxidant is used in an amount of 10 to 500ppm based on the total mass of the reaction raw materials.
Further, the stabilizer is a phosphorus compound; one or more selected from phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, triethyl phosphite, n-butyl phosphate, isopropyl phosphate, triphenyl phosphate, phenylphosphoric acid, ethyldiphenyl phosphate, polyphenylphosphonic acid disulfonate, 4-hydroxyphenyl phenylphosphonate, 2,4, 6-trimethylbenzoyl phenylphosphonic acid, diisopropyl 2-aminophenylphosphonate, dibutyl 2-hydroxyphenyl phosphonate, dioctylphenyl phosphate, pentafluorophenyl diphenyl phosphate. Preferably one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, and triethyl phosphate.
Further, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 1425, antioxidant 168, antioxidant 1790 and antioxidant 1098.
Compared with the prior art, the invention has the beneficial effects that:
(1) The polyester catalyst disclosed by the invention can not catalyze the copolymerization of non-furyl dicarboxylic acid and dihydric alcohol when being singly existed, and can catalyze the copolymerization of the dibasic acid and dihydric alcohol when 2, 5-furandicarboxylic acid exists in a polymerization system, and the 2, 5-furandicarboxylic acid participates in polymerization to form the 2, 5-furandicarboxylic acid polyester. The polyester catalyst has the advantages of strong stability, high selectivity, high activity and environment friendliness.
(2) The 2, 5-furandicarboxylic acid based polyesters prepared by catalysis of the polyester catalyst of the invention have high intrinsic viscosity and good hue and have a number average molecular weight of 0.1X10 4 ～30×10 4 Da, the intrinsic viscosity is 0.5-1.5 dL/g, L value>50. b value<20. The glass transition temperature is 0-200 ℃.
Drawings
FIG. 1 is a photograph of a sample of polyethylene 2, 5-furandicarboxylate (PEF) prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of polyethylene 2, 5-furandicarboxylate (PEF) prepared in example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of poly (1, 4-cyclohexanedimethanol ethylene glycol) ester of 2, 5-furandicarboxylic acid (PECF) prepared in example 2;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of poly (ethylene 2, 5-furandicarboxylate terephthalate) (PEFT) prepared in example 2;
FIG. 5 is a photograph of a sample of polyethylene 2, 5-furandicarboxylate (PEF) produced in comparative example 1.
Detailed Description
The invention is further described below with reference to examples.
General examples
Based on 2, 5-furandimethanolAcid activated polyester catalyst, silica gel supported metal complex M x L y @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: m is central metal, L is ligand ion, M and L are loaded in silica gel carrier. Specifically:
m is selected from K + 、Ca 2+ 、Sc 3+ 、Ti 4+ 、V 3+ 、V 4+ 、V 5+ 、Cr 3+ 、Mn 2+ 、Mn 4+ 、Fe 2+ 、Fe 3+ 、Ni 2+ 、Cu + 、Cu 2+ 、Zn 2+ 、Ga 3+ 、Ge 2+ 、Ge 4+ One or more of the following. Preferably, M is selected from V 3+ 、Mn 2+ 、Fe 2+ 、Cu + 、Ge 2+ One or more of the following.
L is selected from one or more of oxygen ion, hydroxyl ion, borate ion, formate ion, acetate ion, oxalate ion, hydrogen oxalate ion, carbonate ion, bicarbonate ion, nitrite ion, aluminosilicate ion, silicate ion, metasilicate ion, phosphate ion, phosphite ion, monohydrogen phosphate ion, dihydrogen phosphate ion, sulfate ion, hydrogen sulfate ion, sulfite ion, hydrogen sulfite ion, thiosulfate ion, hypobromite ion, chlorite ion, hypochlorous acid ion, arsenate ion, C1-C20 alkoxy, C1-C20 aryloxy. Preferably, L is selected from one or more of oxygen ion, borate ion, acetate ion, hydrogen oxalate ion, and hydrogen carbonate ion.
A method for preparing a polyester catalyst, comprising the steps of:
a) Dissolving 8-12mmol of compound A in 80-200 mL of good solvent A, adding 300-400 mesh silica gel in an equivalent amount of 5-20 to M, and carrying out ultrasonic treatment for 1-3 h to obtain compound A solution in which the silica gel is dispersed. The good solvent A is one or more selected from ethanol, water and petroleum ether.
b) And weighing a corresponding amount of the compound B containing L according to a valence balance theory.
c) The compound B containing L is dissolved in 80-200 mL of good solvent B to obtain compound B solution. The good solvent B is one or more selected from ethanol, water and petroleum ether.
d) Gradually dropwise adding the compound A solution in which the silica gel is dispersed into the compound B solution at a dropwise speed of 1-3 mL/min in an inert gas atmosphere until the reaction system is neutral, concentrating the solvent to 50-100 mL, and then placing the mixture in an environment of-40-5 ℃ for precipitation.
e) Filtering, cleaning and vacuum drying to obtain the silica gel supported metal complex M x L y @SiO 2 。
A method for preparing 2, 5-furandicarboxylic acid based polyester, comprising the following steps: placing 2, 5-furandicarboxylic acid, other dibasic acid, dihydric alcohol, 10-1000 ppm (based on the total mass of the reaction raw materials) of catalyst, 10-1000 ppm (based on the total mass of the reaction raw materials) of stabilizer and 10-500 ppm (based on the total mass of the reaction raw materials) of antioxidant in a polyester reaction kettle, esterifying for 0.25-5 h at 150-250 ℃ under the protection of inert gas, polycondensing for 0.5-10 h at 200-300 ℃ under vacuum condition after the esterification is completed, and discharging after the polycondensation is completed to obtain the 2, 5-furandicarboxylic acid polyester. The molar ratio of the dihydric alcohol to the alkyd of all the dibasic acids is 1.0-3.0:1.
The dihydric alcohol has a structure shown in the following general formula I:
wherein R is selected from C2-C20 alkyl, C6-C20 aryl, C2-C20 alkoxy, C6-C20 aryloxy, C2-C20 alkylthio, C6-C20 arylthio, C2-C20 alkylamino, C6-C20 arylamino, C2-C20 alkylphosphino, C6-C20 arylphosphino; preferably, the diol monomer (I) has a structure represented by A to X:
the dibasic acid has a structure of the following di formula II:
wherein R' is selected from the group consisting of C2-C20 alkyl, C6-C20 aryl, C2-C20 alkoxy, C6-C20 aryloxy, C2-C20 alkylthio, C6-C20 arylthio, C2-C20 alkylamino, C6-C20 arylamino, C2-C20 alkylphosphino, and C6-C20 arylphosphino.
Preferably, the diacid monomer (II) has the structure shown in A 'to X':
the stabilizer is a phosphorus compound; one or more selected from phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, triethyl phosphite, n-butyl phosphate, isopropyl phosphate, triphenyl phosphate, phenylphosphoric acid, ethyldiphenyl phosphate, polyphenylphosphonic acid disulfonate, 4-hydroxyphenyl phenylphosphonate, 2,4, 6-trimethylbenzoyl phenylphosphonic acid, diisopropyl 2-aminophenylphosphonate, dibutyl 2-hydroxyphenyl phosphonate, dioctylphenyl phosphate, pentafluorophenyl diphenyl phosphate. Preferably one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, trimethyl phosphate, and triethyl phosphate.
The antioxidant is one or more selected from antioxidant 1010, antioxidant 1076, antioxidant 1425, antioxidant 168, antioxidant 1790 and antioxidant 1098.
Example 1
Preparation of polyester catalyst:
5mmol FeCl 2 And 5mmol GeCl 2 Dissolving in 80mL pure water, adding 6g 300 mesh silica gel, and ultrasonic treating for 2 hr to obtain FeCl dispersed with silica gel 2 ·GeCl 2 An aqueous solution.
Weighing 20mmol NaHCO according to valence balance theory 3 And 20mmol NaHCO 3 Dissolved in 80mL of purified water.
In a nitrogen atmosphere, naHCO is added to 3 Dropping speed of 2mL/min in solutionGradually dropwise adding FeCl dispersed with silica gel 2 The aqueous solution is neutral to the reaction system, the solvent is concentrated to 50mL and then is placed in an environment of 5 ℃ for standing and precipitation.
Filtering, cleaning and vacuum drying to obtain silica gel supported metal complex Fe (HCO) 3 ) 2 ·Ge(HCO 3 ) 2 @SiO 2 。
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, 312g of 2, 5-furandicarboxylic acid, 198g of glycol and 500ppm of Fe (HCO) 3 ) 2 ·Ge(HCO 3 ) 2 @SiO 2 Adding 50ppm phosphoric acid and 50ppm antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 210 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 230 ℃ for 3 hours, and discharging to obtain the poly (2, 5-furandicarboxylic acid) glycol ester.
As can be seen from FIG. 1, this example gives colorless polyethylene 2, 5-furandicarboxylate.
Example 2
Preparation of polyester catalyst:
10mmol Cu 2 8O 4 Dissolving in 80mL pure water, adding 6g 300 mesh silica gel, and performing ultrasonic treatment for 2h to obtain Cu with silica gel dispersed therein 2 SO 4 An aqueous solution.
Weighing 20mmol of NaHC according to valence balance theory 2 O 4 And 20mmol of NaHC was added 2 O 4 Dissolved in 100mL of purified water.
In a nitrogen atmosphere, naHC was introduced into 2 O 4 Gradually dropwise adding Cu dispersed with silica gel into the solution at a dropwise rate of 2mL/min 2 SO 4 The aqueous solution is neutral to the reaction system, the solvent is concentrated to 50mL and then is placed in an environment of 5 ℃ for standing and precipitation.
Filtering, cleaning and vacuum drying to obtain the silica gel supported metal complex CuHC 2 O 4 @SiO 2 。
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 264 g of 2, 5-furandicarboxylic acid, 496g of ethylene glycol and 50ppm of CuHC 2 O 4 @SiO 2 Adding 50ppm phosphoric acid and 50ppm antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 210 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 235 ℃ for 2 hours, and discharging to obtain the poly (2, 5-furandicarboxylic acid) glycol ester.
As can be seen from FIG. 2, the polyethylene 2, 5-furandicarboxylate obtained in this example can be clearly characterized by nuclear magnetic resonance hydrogen spectrum.
Example 3
Preparation of polyester catalyst:
5mmol FeCl 2 And 5mmol GeCl 2 Dissolving in 80mL pure water, adding 3g of 300 mesh silica gel, and performing ultrasonic treatment for 3h to obtain FeCl dispersed with silica gel 2 ·GeCl 2 An aqueous solution.
Weighing 20mmol of CH according to valence balance theory 3 COONa and 20mmol CH 3 COONa was dissolved in 80mL of pure water.
To CH in nitrogen atmosphere 3 FeCl in which silica gel was dispersed was gradually added dropwise to COONa solution at a dropping rate of 3mL/min 2 ·GeCl 2 The aqueous solution is neutral to the reaction system, the solvent is concentrated to 50mL and then is placed in an environment of 5 ℃ for standing and precipitation.
Filtering, cleaning and vacuum drying to obtain silica gel supported metal complex Fe (CH) 3 COO) 2 ·Ge(CH 3 COO) 2 @SiO 2 。
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 264 g of 2, 5-furandicarboxylic acid, 396g of glycol and 10ppm of Fe (CH) 3 COO) 2 ·Ge(CH 3 COO) 2 @SiO 2 Triphenyl phosphate in an amount of 50ppmAdding 50ppm antioxidant 1010 into the reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 220 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, and discharging after polycondensation for 3 hours at 230 ℃ to obtain the poly (ethylene 2, 5-furandicarboxylate).
Example 4
Preparation of polyester catalyst:
10mmol VCl 3 Dissolving in 80mL pure water, adding 3g 300 mesh silica gel, and ultrasonic treating for 2 hr to obtain VCl dispersed with silica gel 3 An aqueous solution.
Weighing 30mmol of CH according to valence balance theory 3 COONa and 30mmol CH 3 COONa was dissolved in 80mL of pure water.
To CH in nitrogen atmosphere 3 VCl dispersed with silica gel is gradually dripped into COONa solution at a dripping speed of 3mL/min 3 The aqueous solution is neutral to the reaction system, the solvent is concentrated to 50mL and then is placed in an environment of 5 ℃ for standing and precipitation.
Filtering, cleaning and vacuum drying to obtain silica gel supported metal complex V (CH) 3 COO) 3 @SiO 2 。
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 264 g of 2, 5-furandicarboxylic acid, 396g of glycol and 50ppm of V (CH) 3 COO) 3 @SiO 2 Adding 50ppm of triphenyl phosphate and 100ppm of antioxidant 1076 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 220 ℃ for esterification reaction, starting water from a reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, performing polycondensation for 3 hours at 240 ℃, and discharging to obtain the polyethylene 2, 5-furandicarboxylate.
Example 5
Preparation of polyester catalyst:
5mmol of Ca (CH 3 CH 2 O) 2 And 5mmol Fe(CH 3 CH 2 O) 2 Dissolving in 100mL ethanol, adding 6g 300 mesh silica gel, and ultrasonic treating for 2 hr to obtain Ca (CH) dispersed with silica gel 3 CH 2 O) 2 ·Fe(CH 3 CH 2 O) 2 Ethanol solution.
Weighing 20mmol C according to valence balance theory 6 H 5 ONa, and 20mmol C 6 H 5 ONa was dissolved in 50mL ethanol.
In a nitrogen atmosphere, to C 6 H 5 Gradually dropwise adding Ca (CH) dispersed with silica gel into ONa solution at a dropwise rate of 2mL/min 3 CH 2 O) 2 The ethanol solution is neutral to the reaction system, the solvent is concentrated to 30mL and then is placed in an environment of minus 20 ℃ for standing precipitation.
Filtering, cleaning and vacuum drying to obtain silica gel supported metal complex Ca (C) 6 H 5 O) 2 ·Fe(C 6 H 5 O) 2 @SiO 2 。
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 264 g of 2, 5-furandicarboxylic acid, 396g of glycol and 100ppm of Ca (C) 6 H5O) 2 ·Fe(C 6 H 5 O) 2 @SiO 2 Adding 50ppm of triphenyl phosphate and 100ppm of antioxidant 1076 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 210 ℃ for esterification reaction, starting water from a reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, performing polycondensation for 2 hours at 230 ℃, and discharging to obtain the polyethylene 2, 5-furandicarboxylate.
Example 6
Preparation of polyester catalyst: same as in example 3.
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 264 g of 2, 5-furandicarboxylic acid, 396g of glycol and 50ppm of Fe (CH) 3 COO) 2 ·Ge(CH 3 COO) 2 @SiO 2 Adding 50ppm of triphenyl phosphate and 50ppm of antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 220 ℃ for esterification reaction, starting water from a reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 240 ℃ for 1h, and discharging to obtain the polyethylene 2, 5-furandicarboxylate.
Example 7
Preparation of polyester catalyst: same as in example 3.
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 264 g of 2, 5-furandicarboxylic acid, 396g of glycol and 50ppm of Fe (CH) 3 COO) 2 ·Ge(CH 3 COO) 2 @SiO 2 Adding 100ppm trimethyl phosphate and 50ppm antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 220 ℃ for esterification reaction, starting water from a reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 230 ℃ for 3 hours, and discharging to obtain the polyethylene 2, 5-furandicarboxylate.
Example 8
Preparation of polyester catalyst: same as in example 5.
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, carrying out vacuum treatment on 624g of 2, 5-furandicarboxylic acid, 496g of ethylene glycol and 50ppm of Ca (C 6 H 5 O) 2 ·Fe(C 6 H 5 O) 2 @SiO 2 Adding 50ppm phosphoric acid and 50ppm antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 210 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 240 ℃ for 2 hours, and discharging to obtain the poly (2, 5-furandicarboxylic acid) glycol ester.
Example 9
Preparation of polyester catalyst: as in example 1.
And (3) synthesizing polyester:
vacuum-pumping 2.5L reactor to 50Pa, charging nitrogen, and under inert gas protection, making 624g 2, 5-furandicarboxylic acid, 277g glycol, 276g1, 4-cyclohexanedimethanol, 100ppm Fe (HCO) 3 ) 2 ·Ge(HCO 3 ) 2 @SiO 2 Adding 50ppm of triphenyl phosphate and 100ppm of antioxidant 1076 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 220 ℃ to perform esterification reaction, starting water from a reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, performing polycondensation for 2 hours at 230 ℃, and discharging to obtain poly (2, 5-furandicarboxylic acid-1, 4-cyclohexanedimethanol-ethylene glycol) ester.
From fig. 3, it can be seen that the poly (2, 5-furandicarboxylic acid-1, 4-cyclohexanedimethanol-ethylene glycol) ester obtained in this example can be clearly characterized by nuclear magnetic resonance hydrogen spectroscopy.
Example 10
Preparation of polyester catalyst: as in example 1.
And (3) synthesizing polyester:
vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, 312g of 2, 5-furandicarboxylic acid, 332g of terephthalic acid, 396g of ethylene glycol and 100ppm of Fe (HCO) 3 ) 2 ·Ge(HCO 3 ) 2 @SiO 2 Adding 50ppm phosphoric acid and 100ppm antioxidant 1524 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 240 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 260 ℃ for 2 hours, and discharging to obtain poly (2, 5-furandicarboxylic acid-terephthalic acid-ethylene glycol) ester.
From fig. 4, it can be seen that the poly (2, 5-furandicarboxylic acid-terephthalic acid-ethylene glycol) ester obtained in this example can be clearly characterized by nuclear magnetic resonance hydrogen spectroscopy.
Comparative example 1
Vacuumizing a 2.5L reaction kettle to 50Pa, charging nitrogen, and under the protection of inert gas, 312g of 2, 5-furandicarboxylic acid, 198g of glycol and 50ppm of Ti (OnBu) 4 Adding 50ppm phosphoric acid and 50ppm antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 210 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 230 ℃ for 3 hours, and discharging to obtain the poly (2, 5-furandicarboxylic acid) glycol ester.
As can be seen from FIG. 5, the polyethylene 2, 5-furandicarboxylate obtained in this example was dark yellow.
Comparative example 2
The 2.5L reactor was evacuated to 50Pa, purged with nitrogen, and then 332g of terephthalic acid, 198g of ethylene glycol, and 50ppm of Fe (HCO) were purged under inert gas 3 ) 2 ·Ge(HCO 3 ) 2 @SiO 2 Adding 50ppm phosphoric acid and 50ppm antioxidant 1010 into a reaction kettle, closing a feed inlet, charging nitrogen to 2 atmospheres, exhausting to 1 atmosphere, repeating for three times, starting stirring, gradually heating to 250 ℃ for esterification reaction, starting water from the reaction system to 4 atmospheres, vacuumizing the reaction system to 50Pa after water is discharged, polycondensing at 270 ℃ for 3 hours, and discharging to obtain the low-viscosity esterified liquid.
Performance testing
Basic test data for the polyester samples obtained for each example and comparative example are shown in the following table:
TABLE 1 Performance parameters of the polyester samples obtained in examples and comparative examples
| Intrinsic viscosity (dL/g) | Diethylene glycol (mol%) | Terminal carboxyl group (mol%) | b value | |
| Example 1 | 0.65 | 1.8 | 14.5 | 5.1 |
| Example 2 | 0.62 | 1.6 | 20.0 | 11.2 |
| Example 3 | 0.71 | 2.5 | 16.7 | 9.8 |
| Example 4 | 0.58 | 2.1 | 22.9 | 12.0 |
| Example 5 | 0.62 | 2.1 | 10.9 | 11.8 |
| Example 6 | 0.69 | 2.8 | 9.8 | 15.9 |
| Example 7 | 0.55 | 1.9 | 19.8 | 7.8 |
| Example 8 | 0.60 | 3.0 | 15.7 | 12.5 |
| Example 9 | 0.68 | 1.8 | 12.5 | 6.2 |
| Example 10 | 0.71 | 2.5 | 9.2 | 4.2 |
| Comparative example 1 | 0.68 | 2.3 | 16.8 | 25.8 |
| Comparative example 2 | 0.21 | 3.5 | 44.8 | - |
As can be seen from the comparison of the above table data, the polyester samples prepared in examples 1 to 10 have both high intrinsic viscosity and good hue (b value), whereas comparative example 1 uses Ti (OnBu) 4 The polyester sample obtained had a high intrinsic viscosity, but the product appeared dark yellow in color and had a poor hue. In contrast, in comparative example 2, since the diacid monomer does not contain 2, 5-furandicarboxylic acid, the polyester catalyst cannot be activated, and thus only a low-viscosity esterified liquid is prepared.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A polyester catalyst based on activation of 2, 5-furandicarboxylic acid, characterized in that: is silica gel supported metal complex M x L y @SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the M is central metal, L is ligand ion, M and L are loaded in a silica gel carrier;
m is selected from K + 、Ca 2+ 、Sc 3+ 、Ti 4+ 、V 3+ 、V 4+ 、V 5+ 、Cr 3+ 、Mn 2+ 、Mn 4+ 、Fe 2+ 、Fe 3+ 、Ni 2+ 、Cu + 、Cu 2+ 、Zn 2+ 、Ga 3+ 、Ge 2+ 、Ge 4+ One or more of the following;
l is selected from one or more of oxygen ion, hydroxyl ion, borate ion, formate ion, acetate ion, oxalate ion, hydrogen oxalate ion, carbonate ion, bicarbonate ion, nitrite ion, aluminosilicate ion, silicate ion, metasilicate ion, phosphate ion, phosphite ion, monohydrogen phosphate ion, dihydrogen phosphate ion, sulfate ion, hydrogen sulfate ion, sulfite ion, hydrogen sulfite ion, thiosulfate ion, hypobromite ion, chlorite ion, hypochlorous acid ion, arsenate ion, C1-C20 alkoxy, C1-C20 aryloxy.
2. The polyester catalyst of claim 1, wherein:
m is selected from V 3+ 、Mn 2+ 、Fe 2+ 、Cu + 、Ge 2+ One or more of the following;
l is one or more selected from oxygen ion, borate ion, acetate ion, hydrogen oxalate ion and hydrogen carbonate ion.
3. A process for the preparation of a polyester catalyst as claimed in claim 1 or 2, characterized by comprising the steps of:
a) Dissolving a compound A containing M in a good solvent A, adding silica gel, and performing ultrasonic treatment to obtain a compound A solution in which the silica gel is dispersed;
b) Weighing a corresponding amount of a compound B containing L according to a valence balance theory;
c) Dissolving a compound B containing L in a good solvent B to obtain a compound B solution;
d) Gradually dropwise adding the compound A solution in which silica gel is dispersed into the compound B solution in an inert gas atmosphere until a reaction system is neutral, concentrating a solvent, and then placing the mixture in an environment of-40-5 ℃ for precipitation;
e) Filtering, cleaning and vacuum drying to obtain the silica gel supported metal complex M x L y @SiO 2 。
4. A method of preparation as claimed in claim 3, wherein: in the step a) of the process, the process comprises,
the good solvent A is one or more selected from ethanol, water and petroleum ether;
the dosage of M is 8-12mmol, and the dosage of good solvent A is 80-200 mL;
the particle size of the silica gel is 300-400 meshes;
the dosage of the silica gel is 5-20 equivalent relative to M;
the ultrasonic treatment time is 1-3 h.
5. A method of preparation as claimed in claim 3, wherein: in the step c) of the process, the process is carried out,
the good solvent B is one or more selected from ethanol, water and petroleum ether;
the dosage of the good solvent B is 80-200 mL.
6. A method of preparation as claimed in claim 3, wherein: in the step d) of the process, the process is carried out,
the dropping speed is 1-3 mL/min;
concentrating the solvent to 50-100 mL, and then placing the solvent in an environment of-40-5 ℃ for precipitation.
7. Use of a polyester catalyst according to claim 1 or 2 or obtainable by a process according to any one of claims 3 to 6 for the preparation of a 2, 5-furandicarboxylic acid based polyester.
8. A process for preparing 2, 5-furandicarboxylic acid based polyesters using a polyester catalyst as claimed in claim 1 or 2 or a polyester catalyst obtainable by a process as claimed in any one of claims 3 to 6, characterized by comprising the steps of: placing 2, 5-furandicarboxylic acid, other dibasic acid, dihydric alcohol and catalyst with the weight of 10-1000 ppm into a polyester reaction kettle, esterifying under the protection of inert gas, carrying out polycondensation under vacuum condition after the esterification is completed, and discharging after the polycondensation is completed to obtain the 2, 5-furandicarboxylic acid polyester.
9. The method of preparing as claimed in claim 8, wherein: the molar ratio of the dihydric alcohol to the alkyd of all the dibasic acids is 1.0-3.0:1.
10. The method of preparing as claimed in claim 8, wherein:
the dihydric alcohol has a structure shown in the following general formula I:
wherein R is selected from C2-C20 alkyl, C6-C20 aryl, C2-C20 alkoxy, C6-C20 aryloxy, C2-C20 alkylthio, C6-C20 arylthio, C2-C20 alkylamino, C6-C20 arylamino, C2-C20 alkylphosphino, C6-C20 arylphosphino;
the dibasic acid has a structure shown in the following general formula II:
wherein R' is selected from the group consisting of C2-C20 alkyl, C6-C20 aryl, C2-C20 alkoxy, C6-C20 aryloxy, C2-C20 alkylthio, C6-C20 arylthio, C2-C20 alkylamino, C6-C20 arylamino, C2-C20 alkylphosphino, and C6-C20 arylphosphino.
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