CN110669216B - Bio-based semi-aromatic polyamide and preparation method thereof - Google Patents
Bio-based semi-aromatic polyamide and preparation method thereof Download PDFInfo
- Publication number
- CN110669216B CN110669216B CN201910998898.9A CN201910998898A CN110669216B CN 110669216 B CN110669216 B CN 110669216B CN 201910998898 A CN201910998898 A CN 201910998898A CN 110669216 B CN110669216 B CN 110669216B
- Authority
- CN
- China
- Prior art keywords
- acid
- bio
- aromatic polyamide
- based semi
- parts
- 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.)
- Active
Links
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 39
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 furan dicarboxylic acid diester Chemical class 0.000 claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006068 polycondensation reaction Methods 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 150000001263 acyl chlorides Chemical class 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229940073490 sodium glutamate Drugs 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 235000013922 glutamic acid Nutrition 0.000 claims description 9
- 239000004220 glutamic acid Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 7
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 6
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 235000021314 Palmitic acid Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical group CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims description 4
- BXZBGYJQEFZICM-UHFFFAOYSA-N icosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCC(Cl)=O BXZBGYJQEFZICM-UHFFFAOYSA-N 0.000 claims description 4
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 235000021357 Behenic acid Nutrition 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 claims description 3
- 235000021353 Lignoceric acid Nutrition 0.000 claims description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 3
- 229940116226 behenic acid Drugs 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 claims description 3
- QTHQYNCAWSGBCE-UHFFFAOYSA-N docosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCC(Cl)=O QTHQYNCAWSGBCE-UHFFFAOYSA-N 0.000 claims description 3
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- ICDQUAGMQCUEMY-UHFFFAOYSA-N heptadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCC(Cl)=O ICDQUAGMQCUEMY-UHFFFAOYSA-N 0.000 claims description 3
- KXHFYBWOKFEEMI-UHFFFAOYSA-N hexacosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(Cl)=O KXHFYBWOKFEEMI-UHFFFAOYSA-N 0.000 claims description 3
- MAGMAMZGOLLUAU-UHFFFAOYSA-N octacosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(Cl)=O MAGMAMZGOLLUAU-UHFFFAOYSA-N 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 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 claims description 3
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 claims description 3
- SQQKMLPDURPFNG-UHFFFAOYSA-N tetracosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(Cl)=O SQQKMLPDURPFNG-UHFFFAOYSA-N 0.000 claims description 3
- LPWCRLGKYWVLHQ-UHFFFAOYSA-N tetradecanoyl chloride Chemical compound CCCCCCCCCCCCCC(Cl)=O LPWCRLGKYWVLHQ-UHFFFAOYSA-N 0.000 claims description 3
- GQEACALFLNZJGW-UHFFFAOYSA-N triacontanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(Cl)=O GQEACALFLNZJGW-UHFFFAOYSA-N 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001924 fatty-acyl group Chemical group 0.000 claims 5
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims 4
- IQGSGEFJTGIVAY-UHFFFAOYSA-N 3,4-bis(2-methylpropyl)furan-2,5-dicarboxylic acid Chemical compound CC(C)Cc1c(CC(C)C)c(oc1C(O)=O)C(O)=O IQGSGEFJTGIVAY-UHFFFAOYSA-N 0.000 claims 1
- SXULPFQMFZDBIC-UHFFFAOYSA-N 3,4-dibutylfuran-2,5-dicarboxylic acid Chemical compound CCCCC1=C(C(O)=O)OC(C(O)=O)=C1CCCC SXULPFQMFZDBIC-UHFFFAOYSA-N 0.000 claims 1
- JODJLOUEMNZRNF-UHFFFAOYSA-N 3,4-diethylfuran-2,5-dicarboxylic acid Chemical compound CCC1=C(C(O)=O)OC(C(O)=O)=C1CC JODJLOUEMNZRNF-UHFFFAOYSA-N 0.000 claims 1
- NVWMHICCPUEWLL-UHFFFAOYSA-N 3,4-dimethylfuran-2,5-dicarboxylic acid Chemical compound CC=1C(C)=C(C(O)=O)OC=1C(O)=O NVWMHICCPUEWLL-UHFFFAOYSA-N 0.000 claims 1
- NDCKJSSRIIGRNF-UHFFFAOYSA-N 3,4-dipropylfuran-2,5-dicarboxylic acid Chemical compound CCCC1=C(C(O)=O)OC(C(O)=O)=C1CCC NDCKJSSRIIGRNF-UHFFFAOYSA-N 0.000 claims 1
- MAIWQMPWMWZUOL-UHFFFAOYSA-N CC(C)C1=C(OC(=C1C(C)C)C(=O)O)C(=O)O Chemical compound CC(C)C1=C(OC(=C1C(C)C)C(=O)O)C(=O)O MAIWQMPWMWZUOL-UHFFFAOYSA-N 0.000 claims 1
- XYVIPOVOUMZRJP-UHFFFAOYSA-N CCC(C)C1=C(OC(=C1C(C)CC)C(=O)O)C(=O)O Chemical compound CCC(C)C1=C(OC(=C1C(C)CC)C(=O)O)C(=O)O XYVIPOVOUMZRJP-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 12
- 239000002861 polymer material Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229920013724 bio-based polymer Polymers 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical group NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000000539 dimer Substances 0.000 description 5
- 150000002190 fatty acyls Chemical group 0.000 description 5
- 238000004321 preservation Methods 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
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- NLHUMZUNLXZWNW-UHFFFAOYSA-N dibutyl furan-2,5-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)O1 NLHUMZUNLXZWNW-UHFFFAOYSA-N 0.000 description 3
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 3
- NTHBPOCRARSMRT-UHFFFAOYSA-N dipropan-2-yl furan-2,5-dicarboxylate Chemical compound O1C(=CC=C1C(=O)OC(C)C)C(=O)OC(C)C NTHBPOCRARSMRT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- XINTUFOSGUJJSO-UHFFFAOYSA-N bis(2-methylpropyl) furan-2,5-dicarboxylate Chemical compound O1C(=CC=C1C(=O)OCC(C)C)C(=O)OCC(C)C XINTUFOSGUJJSO-UHFFFAOYSA-N 0.000 description 2
- CIAIXOZNEZJCAN-UHFFFAOYSA-N dibutan-2-yl furan-2,5-dicarboxylate Chemical compound O1C(=CC=C1C(=O)OC(C)CC)C(=O)OC(C)CC CIAIXOZNEZJCAN-UHFFFAOYSA-N 0.000 description 2
- INULFORHAGYOGB-UHFFFAOYSA-N dipropyl furan-2,5-dicarboxylate Chemical compound CCCOC(=O)C1=CC=C(C(=O)OCCC)O1 INULFORHAGYOGB-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- RZYPIWDAAHKAAK-UHFFFAOYSA-N 4,5-dimethylfuran-2,3-dicarboxylic acid Chemical compound CC=1OC(C(O)=O)=C(C(O)=O)C=1C RZYPIWDAAHKAAK-UHFFFAOYSA-N 0.000 description 1
- LKWSTQPRPRGLDP-UHFFFAOYSA-N 4-(azacycloundecane-1-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCCCCCC1 LKWSTQPRPRGLDP-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention relates to a bio-based semi-aromatic polyamide and a preparation method thereof, belonging to the technical field of polymer synthesis. The invention provides a bio-based semi-aromatic polyamide, which has a structural formula shown in the specification, wherein n is 10-200, x + y is more than 0 and less than or equal to 1, x is not equal to 0, and y is not equal to 0. The method takes monomers, furan dicarboxylic acid diester, sebacic acid and diamine as raw materials, and under the action of a catalyst, the raw materials are polymerized to generate a bio-based semi-aromatic polyamide prepolymer, and the prepolymer is dried and then further polycondensed at high temperature to obtain the bio-based semi-aromatic polyamide resin with high molecular weight; the method has the advantages of easily obtained raw materials, simple operation and high yield, and the carbon element of the obtained resin is a complete bio-based source and has the advantages of low water absorption, easy processing and high mechanical strength.
Description
Technical Field
The invention relates to a bio-based semi-aromatic polyamide and a preparation method thereof, belonging to the technical field of polymer synthesis.
Background
With the development of the human industrialization process, the consumption of fossil resources such as coal and oil is increasing, and along with the emission of a large amount of carbon dioxide, the greenhouse effect is increasing, and extreme weather is frequent all over the world. Human production and life can not be separated from organic matters, so that human activities are the process of carbon consumption and carbon emission, and therefore people advocate low carbon to reduce the emission of carbon dioxide so as to achieve the aim of protecting the environment. The photosynthesis of the plant can absorb carbon dioxide in the air and generate oxygen, and can reduce the content of the carbon dioxide and reduce the greenhouse effect. Chemical feedstocks extracted from plants or animals are referred to as bio-based feedstocks because they consume no or little fossil resources. The polymer material synthesized by adopting the bio-based raw material is the bio-based polymer material.
With the attention of people on environmental protection, bio-based polymer materials are rapidly developed. The bio-based polymer materials are classified according to the proportion of the bio-based carbon elements in the total carbon elements, and can be divided into complete bio-based polymer materials (the proportion of the bio-based carbon elements is 100%) and partial bio-based polymer materials (the proportion of the bio-based carbon elements is less than 100%). The completely bio-based polymer materials, such as polyamino acid, have the disadvantages of poor heat resistance, low mechanical strength and the like, and are limited in application. Compared with the completely bio-based polymer material, the partially bio-based polymer material has obviously improved performance, reaches the level which can be comparable to the polymer material from fossil raw materials, and has wider application range.
The semi-aromatic polyamide has the advantages of high temperature resistance, corrosion resistance, low water absorption and the like, and is widely applied to the fields of electronic appliances, LED illumination, automobile industry and the like. Currently, the main sources of bio-based raw materials that have been used to synthesize semi-aromatic polyamides are as follows: 1. the glucide is fermented into lysine, and the pentanediamine is prepared through secondary fermentation. 2. Preparing sebacic acid from castor oil, or further ammoniating and hydrogenating sebacic acid to obtain decanediamine. 3. The furfural is produced from corncobs and the like under the action of sulfuric acid, or hydroxymethyl furfural is generated by oxidizing fructose, and then furan dicarboxylic acid or dimethyl furan dicarboxylic acid is further prepared. 4. The oleic acid is extracted from animal and vegetable oil, and the hydrogenated dimer acid is prepared by further dimerization and hydrogenation.
The poly (decamethylene terephthalamide) (PA10T) prepared from terephthalic acid and decamethylene diamine belongs to partial bio-based semi-aromatic polyamide, has the melting point of 317 ℃, has excellent heat resistance and is sold in the market. However, decamethylenediamine is expensive, the cost of raw materials is high, and the market competitiveness is poor.
Chinese patent CN110041520A takes dimer acid, terephthalic acid, isophthalic acid and aliphatic diamine as raw materials, and obtains the semi-aromatic polyamide containing the dimer acid structure through the steps of salifying, prepolymerization, solid-phase polycondensation and the like. However, the dimer acid is a mixture of various chain, single-ring and double-ring structures, cis-form and trans-form differences exist in hydrogenation, and the structure of mixed acid in the hydrogenated dimer acid can reach more than ten. The obtained resin is a copolymer of a plurality of monomers, so that the crystallinity of the polymer is obviously reduced, and the mechanical property is poor. Meanwhile, due to the introduction of long-chain branched chains and aliphatic rings, the mobility of molecular chains is weak, so that the flowability of the resin is poor.
Saturated fatty acid can be used as a molecular weight regulator or a terminating agent for synthesizing semi-aromatic polyamide. For example, chinese patents CN102786794A and CN102796368A both report that lauric acid, palmitic acid, stearic acid, and the like are used as molecular weight regulators for the synthesis of semi-aromatic polyamide. But the addition amount is lower and the proportion of the bio-based carbon element is low compared with the addition amount directly used for polymerizing the monomer.
In Chinese patent CN106191145A, dimethyl furandicarboxylate and aliphatic diamine are used as raw materials, candida sp.99-125 lipase is used as a catalyst, and the raw materials react in an organic solvent at 60-100 ℃ for 48-96 hours to obtain semi-aromatic polyamide based on furandicarboxylic acid through polymerization. The aliphatic diamine adopts pentanediamine and decamethylenediamine to obtain the polyfurandicarboxypentyldiamine and polyfurandicarboxypentyldiamine with complete biological groups. However, a large amount of organic solvent is required, and the polymerization reaction time is too long, resulting in low production efficiency.
Therefore, it is necessary to develop a bio-based semi-aromatic polyamide.
Disclosure of Invention
The invention aims to provide a biology-based semi-aromatic polyamide and a preparation method thereof aiming at the defects of the prior art, and the biology-based semi-aromatic polyamide is characterized in that a monomer, furan dicarboxylic acid diester, sebacic acid and diamine are taken as raw materials, a biology-based semi-aromatic polyamide prepolymer is generated by polymerization under the action of a catalyst, and the high molecular weight biology-based semi-aromatic polyamide resin is obtained by further polycondensation at high temperature after the prepolymer is dried; the method has the advantages of easily obtained raw materials, simple operation and high yield, and the carbon element of the obtained resin is a complete bio-based source and has the advantages of low water absorption, easy processing and high mechanical strength.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a bio-based semi-aromatic polyamide, which has a structural formula as follows:
wherein n is 10-200, x + y is more than 0 and less than or equal to 1, x is not equal to 0, and y is not equal to 0;
R1＝-(CH2)8CH3、-(CH2)10CH3、-(CH2)12CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)18CH3、-(CH2)20CH3、-(CH2)22CH3、-(CH2)24CH3、-(CH2)26CH3or- (CH)2)28CH3At least one of;
R2＝-(CH2)5-and/or- (CH)2)10-。
Further, the bio-based semi-aromatic polyamide is prepared by adopting the following method: preparing amidated glutamic acid monomer with sodium glutamate and long-chain fatty acyl chloride as material; mixing the amidated glutamic acid monomer with furan dicarboxylic acid diester, sebacic acid and diamine, and preparing a bio-based semi-aromatic polyamide prepolymer by adopting a high-temperature solution polymerization method; and further performing polycondensation on the prepolymer to obtain the bio-based semi-aromatic polyamide.
Further, in the method for preparing the bio-based semi-aromatic polyamide, the long-chain fatty acid chloride is any one of decanoyl chloride, dodecanoyl chloride, tetradecanoyl chloride, hexadecanoyl chloride, heptadecanoyl chloride, octadecanoyl chloride, eicosanoyl chloride, docosanoyl chloride, tetracosanoyl chloride, hexacosanoyl chloride, octacosanoyl chloride or triacontanoyl chloride.
Further, in the above method for producing a bio-based semi-aromatic polyamide, the furandicarboxylic acid diester is at least one of dimethyl 2, 5-furandicarboxylate, diethyl 2, 5-furandicarboxylate, di-n-propyl 2, 5-furandicarboxylate, diisopropyl 2, 5-furandicarboxylate, di-n-butyl 2, 5-furandicarboxylate, diisobutyl 2, 5-furandicarboxylate, and di-sec-butyl 2, 5-furandicarboxylate.
Further, in the method for preparing the bio-based semi-aromatic polyamide, the diamine is pentamethylene diamine and/or decamethylene diamine.
Further, the bio-based semi-aromatic polyamide prepolymer is prepared by the following preparation steps:
(1) adding 301-581 parts of monomer, 184-2260 parts of furan dicarboxylic acid diester, 0-1010 parts of sebacic acid, 210-2800 parts of diamine, 1-30 parts of catalyst, 5-80 parts of molecular weight regulator and 100-2000 parts of alcohol into a reaction kettle, introducing nitrogen, stirring, heating to 60-90 ℃ within 0.5-1 hour
(2) Stopping introducing nitrogen, sealing the reaction kettle, heating to 180-240 ℃ within 1-3 hours, and maintaining the temperature for reaction for 2-5 hours;
(3) opening an exhaust valve, discharging mixed steam of alcohol and water within 0.5-2 hours to reduce the pressure in the kettle to 0.5-1.5 MPa, and maintaining the temperature to be not more than 240-260 ℃;
(4) closing an exhaust valve, and continuously stirring and reacting at 240-260 ℃ for 0.5-2 hours to homogenize the materials; then cooling to room temperature, discharging, drying the product until the water content is less than or equal to 0.3 percent, and obtaining the bio-based semi-aromatic polyamide prepolymer;
in the step (1), the structural formula of the monomer is as follows:
wherein:
R1＝-(CH2)8CH3、-(CH2)10CH3、-(CH2)12CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)18CH3、-(CH2)20CH3、-(CH2)22CH3、-(CH2)24CH3、-(CH2)26CH3or- (CH)2)28CH3Any one of the above.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, the monomer is prepared by the following method, and the method comprises the following steps:
1) adding 190.5-470.5 parts of long-chain fatty acyl chloride and 100-1000 parts of solvent into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution;
2) adding 169 parts of sodium glutamate, 80-138 parts of alkaline compound and 200-2000 parts of deionized water into a reactor with a stirrer, a thermometer, a condenser and a freezing water cooling device; introducing chilled water, and stirring and reacting for 1-3 hours at 0-30 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution obtained in the step 1) into the reactor within 0.5-2 hours; after the dropwise addition is finished, continuously maintaining the temperature for reaction for 0.5-1 hour;
3) heating to 36-81 ℃, and evaporating the solvent; continuously heating to age the reaction solution at 50-90 ℃ for 1-2 hours;
4) filtering while the mixture is hot, and then cooling to 20-40 ℃; adding acid with the concentration of 1.0-12.0 mol/L into the filtrate until the pH value is 0-3, standing at room temperature for 6-24 hours, and fully precipitating a product; the monomer is obtained by filtering, washing and drying.
Further, in the above method for preparing the monomer, the solvent in step 1) is any one of dichloromethane, n-pentane, n-hexane or cyclohexane.
Further, in the above method for preparing a monomer, the basic compound in step 2) is any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
Further, in the above method for producing a monomer, the acid in step 4) is any one of hydrochloric acid, sulfuric acid, or phosphoric acid.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, in the step (1), the catalyst is at least one of phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, sodium phosphate, sodium phosphite, sodium hypophosphite or sodium tripolyphosphate.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, in the step (1), the molecular weight regulator is any one of acetic acid, caproic acid, caprylic acid, capric acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid and triacontanoic acid.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, in the step (1), the alcohol is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or sec-butanol; methanol is preferred.
Further, in the preparation method of the bio-based semi-aromatic polyamide, the bio-based semi-aromatic polyamide prepolymer is subjected to polycondensation reaction at 220-330 ℃ to obtain the bio-based semi-aromatic polyamide.
Further, in the preparation method of the bio-based semi-aromatic polyamide, the method for further polycondensing the bio-based semi-aromatic polyamide prepolymer at high temperature is at least one of vacuum solid-phase polycondensation, solid-phase polycondensation under the protection of water vapor and/or inert gas, solid-phase polycondensation under the protection of inert liquid, solid-phase reaction extrusion, melt polycondensation under the protection of water vapor and/or inert gas, melt polycondensation under the protection of inert liquid, vacuum melt polycondensation or melt reaction extrusion; wherein the inert gas is at least one of nitrogen, argon or helium; the inert liquid is at least one of diphenyl ether, diphenyl sulfone, dimethyl silicone oil or diphenyl silicone oil.
The second technical problem to be solved by the present invention is to provide a method for preparing the above bio-based semi-aromatic polyamide, the method comprising: preparing amidated glutamic acid monomer with sodium glutamate and long-chain fatty acyl chloride as material; mixing the amidated glutamic acid monomer with furan dicarboxylic acid diester, sebacic acid and diamine, and preparing a bio-based semi-aromatic polyamide prepolymer by adopting a high-temperature solution polymerization method; and further performing polycondensation on the prepolymer to obtain the bio-based semi-aromatic polyamide.
Further, in the above method for producing a bio-based semi-aromatic polyamide, the long-chain fatty acid chloride may be any one of decanoyl chloride, dodecanoyl chloride, tetradecanoyl chloride, hexadecanoyl chloride, heptadecanoyl chloride, octadecanoyl chloride, eicosanoyl chloride, docosanoyl chloride, tetracosanoyl chloride, hexacosanoyl chloride, octacosanoyl chloride, or triacontanoyl chloride.
Further, in the above method for producing a bio-based semi-aromatic polyamide, the furandicarboxylic acid diester is at least one of dimethyl 2, 5-furandicarboxylate, diethyl 2, 5-furandicarboxylate, di-n-propyl 2, 5-furandicarboxylate, diisopropyl 2, 5-furandicarboxylate, di-n-butyl 2, 5-furandicarboxylate, diisobutyl 2, 5-furandicarboxylate, and di-sec-butyl 2, 5-furandicarboxylate.
Further, in the above method for preparing bio-based semi-aromatic polyamide, the diamine is pentamethylenediamine and/or decamethylenediamine.
Further, the bio-based semi-aromatic polyamide prepolymer is prepared by the following preparation steps:
(1) adding 301-581 parts of monomer, 184-2260 parts of furan dicarboxylic acid diester, 0-1010 parts of sebacic acid, 210-2800 parts of diamine, 1-30 parts of catalyst, 5-80 parts of molecular weight regulator and 100-2000 parts of alcohol into a reaction kettle, introducing nitrogen, stirring, heating to 60-90 ℃ within 0.5-1 hour
(2) Stopping introducing nitrogen, sealing the reaction kettle, heating to 180-240 ℃ within 1-3 hours, and maintaining the temperature for reaction for 2-5 hours;
(3) opening an exhaust valve, discharging mixed steam of alcohol and water within 0.5-2 hours to reduce the pressure in the kettle to 0.5-1.5 MPa, and maintaining the temperature to be not more than 240-260 ℃;
(4) closing an exhaust valve, and continuously stirring and reacting at 240-260 ℃ for 0.5-2 hours to homogenize the materials; then cooling to room temperature, discharging, drying the product until the water content is less than or equal to 0.3 percent, and obtaining the bio-based semi-aromatic polyamide prepolymer;
in the step (1), the structural formula of the monomer is as follows:
wherein:
R1＝-(CH2)8CH3、-(CH2)10CH3、-(CH2)12CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)18CH3、-(CH2)20CH3、-(CH2)22CH3、-(CH2)24CH3、-(CH2)26CH3or- (CH)2)28CH3Any one of the above.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, the monomer is prepared by the following method, and the method comprises the following steps:
1) adding 190.5-470.5 parts of long-chain fatty acyl chloride and 100-1000 parts of solvent into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution;
2) adding 169 parts of sodium glutamate, 80-138 parts of alkaline compound and 200-2000 parts of deionized water into a reactor with a stirrer, a thermometer, a condenser and a freezing water cooling device; introducing chilled water, and stirring and reacting for 1-3 hours at 0-30 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution obtained in the step 1) into the reactor within 0.5-2 hours; after the dropwise addition is finished, continuously maintaining the temperature for reaction for 0.5-1 hour;
3) heating to 36-81 ℃, and evaporating the solvent; continuously heating to age the reaction solution at 50-90 ℃ for 1-2 hours;
4) filtering while the mixture is hot, and then cooling to 20-40 ℃; adding acid with the concentration of 1.0-12.0 mol/L into the filtrate until the pH value is 0-3, standing at room temperature for 6-24 hours, and fully precipitating a product; the monomer is obtained by filtering, washing and drying.
Further, in the above method for preparing the monomer, the solvent in step 1) is any one of dichloromethane, n-pentane, n-hexane or cyclohexane.
Further, in the above method for preparing a monomer, the basic compound in step 2) is any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
Further, in the above method for producing a monomer, the acid in step 4) is any one of hydrochloric acid, sulfuric acid, or phosphoric acid.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, in the step (1), the catalyst is at least one of phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, sodium phosphate, sodium phosphite, sodium hypophosphite or sodium tripolyphosphate.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, in the step (1), the molecular weight regulator is any one of acetic acid, caproic acid, caprylic acid, capric acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid and triacontanoic acid.
Further, in the preparation method of the bio-based semi-aromatic polyamide prepolymer, in the step (1), the alcohol is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or sec-butanol; methanol is preferred.
Further, in the preparation method of the bio-based semi-aromatic polyamide, the bio-based semi-aromatic polyamide prepolymer is subjected to polycondensation reaction at 220-330 ℃ to obtain the bio-based semi-aromatic polyamide.
Further, in the preparation method of the bio-based semi-aromatic polyamide, the method for further polycondensing the bio-based semi-aromatic polyamide prepolymer at high temperature is at least one of vacuum solid-phase polycondensation, solid-phase polycondensation under the protection of water vapor and/or inert gas, solid-phase polycondensation under the protection of inert liquid, solid-phase reaction extrusion, melt polycondensation under the protection of water vapor and/or inert gas, melt polycondensation under the protection of inert liquid, vacuum melt polycondensation or melt reaction extrusion; wherein the inert gas is at least one of nitrogen, argon or helium; the inert liquid is at least one of diphenyl ether, diphenyl sulfone, dimethyl silicone oil or diphenyl silicone oil.
In the invention, the raw materials are in parts by weight except for special specifications.
The invention has the beneficial effects that:
1. the invention takes sodium glutamate and long-chain fatty acyl chloride as raw materials, firstly amidated glutamic acid monomer is prepared; and mixing the monomer with furan dicarboxylic acid diester, sebacic acid and diamine, preparing a bio-based semi-aromatic polyamide prepolymer by adopting high-temperature solution polymerization, and further performing polycondensation to prepare the bio-based semi-aromatic polyamide. The method uses less raw materials from petroleum sources, and has the advantages of energy conservation and environmental protection.
2. The main raw material sodium glutamate of the invention is the main component of monosodium glutamate, is a product which is produced and used in large scale at present, and has the advantages of low price, wide raw material source and low cost.
3. The bio-based semi-aromatic polyamide obtained by the invention is a complete bio-based high polymer material, has low water absorption rate and has the advantage of good dimensional stability.
4. The invention adopts various polymerization methods to prepare the bio-based semi-aromatic polyamide, has simple operation and mature process, and the obtained product has stable quality.
Drawings
FIG. 1 is a thermogravimetric analysis of the bio-based semi-aromatic polyamide obtained in example 1.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustrating the present invention and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations to the invention described above based on the disclosure of the present invention.
Example 1
1905g of decanoyl chloride and 2000g of dichloromethane were added to the dissolution kettle and stirred uniformly to obtain an acid chloride solution. 1690g of sodium glutamate, 800g of sodium hydroxide and 4000g of deionized water are added into a reactor with a stirrer, a thermometer, a condenser and a frozen water cooling device; introducing chilled water, and stirring and reacting for 2 hours at 20 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution into the reactor within 1 hour; after the dropwise addition is finished, the temperature is continuously maintained for reaction for 0.5 hour; heating to 40 ℃, and distilling off dichloromethane; continuing to heat up, and aging the reaction solution at 60 ℃ for 1 hour; filtering while the solution is hot, and cooling to 35 ℃; adding hydrochloric acid with the concentration of 5.0mol/L into the filtrate until the PH value is 1, standing for 15 hours at room temperature, and fully separating out a product; the monomer is obtained by filtering, washing and drying.
Adding 1505g of the monomer, 920g of 2, 5-furandicarboxylic acid dimethyl ester, 1050g of pentamethylene diamine, 10g of polyphosphoric acid, 60g of octadecanoic acid and 800g of methanol into a reaction kettle, introducing nitrogen, stirring, and heating to 60 ℃ within 0.5 hour; stopping introducing nitrogen, sealing the reaction kettle, heating to 220 ℃ within 2 hours, and maintaining the temperature for reaction for 3 hours; opening an exhaust valve, discharging mixed steam of alcohol and water within 1 hour to reduce the pressure in the kettle to 1.2MPa, and maintaining the temperature not to exceed 240 ℃; closing an exhaust valve, heating to 240 ℃, and maintaining the temperature for reaction for 2 hours to homogenize the materials; then cooling to room temperature, discharging, and drying the product until the water content is less than or equal to 0.3 percent to obtain the bio-based semi-aromatic polyamide prepolymer.
2200g of the prepolymer is added into a solid phase polycondensation kettle, and the mixture is vacuumized to-0.08 MPa; gradually heating to 240 ℃ under continuous stirring, and reacting for 8 hours under heat preservation; cooling and discharging to obtain high molecular weight bio-based semi-aromatic polyamide resin with intrinsic viscosity [ eta ]]＝0.81dL·g-1Melt index 84 g.10 min-1. The performance parameters of each example are shown in table 1.
And (3) performance testing: the thermogravimetric analysis adopts the company of NETZSCH TG 209, and the heating rate is 10 ℃ min-1Nitrogen atmosphere, test temperature range: the temperature is between room temperature and 600 ℃, and the 5 percent weight loss temperature is taken as the thermal decomposition temperature; FIG. 1 is a thermogravimetric analysis of the bio-based semi-aromatic polyamide obtained in example 1; as is clear from FIG. 1, the thermal decomposition temperature of the bio-based semi-aromatic polyamide obtained in example 1 was 394.2 ℃.
Example 2
Adding 3025g of octadecanoyl chloride and 4000g of n-hexane into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution. 1690g of sodium glutamate, 1380g of potassium carbonate and 12000g of deionized water were added to a reactor equipped with a stirrer, a thermometer, a condenser and a chilled water cooling device; introducing chilled water, and stirring and reacting for 3 hours at the temperature of 30 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution into the reactor within 1.5 hours; after the dropwise addition is finished, the temperature is continuously maintained for reaction for 1 hour; heating to 70 ℃, and evaporating n-hexane; continuing to heat up, and aging the reaction solution at 80 ℃ for 2 hours; filtering while the solution is hot, and cooling to 25 ℃; adding sulfuric acid with the concentration of 2.0mol/L into the filtrate until the pH value is 3, standing for 18 hours at room temperature, and fully separating out a product; the monomer is obtained by filtering, washing and drying.
2065g of the monomer, 2970g of diethyl 2, 5-furandicarboxylate, 1010g of sebacic acid, 4430g of decanediamine, 20g of sodium hypophosphite, 100g of hexadecanoic acid and 2200g of ethanol are added into a reaction kettle, nitrogen is introduced, stirring is carried out, and the temperature is raised to 65 ℃ within 1 hour; stopping introducing nitrogen, sealing the reaction kettle, heating to 230 ℃ within 3 hours, and maintaining the temperature for reaction for 4 hours; opening an exhaust valve, discharging mixed steam of alcohol and water within 2 hours to reduce the pressure in the kettle to 1.0MPa, and maintaining the temperature not to exceed 245 ℃; closing an exhaust valve, heating to 250 ℃, and maintaining the temperature for reaction for 1 hour to homogenize the materials; then cooling to room temperature, discharging, and drying the product until the water content is less than or equal to 0.3 percent to obtain the bio-based semi-aromatic polyamide prepolymer.
6500g of the prepolymer is added into a solid phase polycondensation kettle, the temperature is raised to 100 ℃, and nitrogen is introduced: taking mixed gas with the volume ratio of water vapor of 8:2 as protective gas; gradually heating to 250 ℃ under continuous stirring, and reacting for 6 hours under heat preservation; vacuumizing to-0.09 MPa, heating to 260 ℃, and reacting for 4 hours in a heat preservation way; cooling and discharging to obtain high molecular weight bio-based semi-aromatic polyamide resin with intrinsic viscosity [ eta ]]＝0.83dL·g-1Melt index 302 g.10 min-1。
Example 3
Adding 274.5g of hexadecanoyl chloride and 500g of n-pentane into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution. 169g of sodium glutamate, 106g of sodium carbonate and 900g of deionized water were added to a reactor equipped with a stirrer, a thermometer, a condenser and a chilled water cooling device; introducing chilled water, and stirring and reacting for 1 hour at 10 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution into the reactor within 0.5 hour; after the dropwise addition is finished, the temperature is continuously maintained for reaction for 1 hour; heating to 36 deg.c to evaporate n-pentane; continuing to heat up, and aging the reaction solution at 50 ℃ for 1.5 hours; filtering while the solution is hot, and cooling to 20 ℃; adding hydrochloric acid with the concentration of 12.0mol/L into the filtrate until the PH value is 0, standing for 24 hours at room temperature, and fully separating out a product; the monomer is obtained by filtering, washing and drying.
192.5g of the above monomer, 206.5g of the monomer prepared in example 2, 678g of di-n-butyl 2, 5-furandicarboxylate, 101g of sebacic acid, 430g of pentanediamine, 86g of decanediamine, 3g of phosphoric acid, 1g of sodium triphosphate, 5g of acetic acid and 600g of n-butanol were added to a reaction vessel, nitrogen was introduced, stirring was carried out, and the temperature was raised to 90 ℃ within 0.5 hour; stopping introducing nitrogen, sealing the reaction kettle, heating to 200 ℃ within 1 hour, and maintaining the temperature for reaction for 5 hours; opening an exhaust valve, discharging mixed steam of alcohol and water within 0.5 hour to reduce the pressure in the kettle to 0.5MPa, and maintaining the temperature to be not more than 250 ℃; closing an exhaust valve, heating to 255 ℃, and maintaining the temperature for reaction for 1.5 hours to homogenize the materials; then cooling to room temperature, discharging, and drying the product until the water content is less than or equal to 0.3 percent to obtain the bio-based semi-aromatic polyamide prepolymer.
Adding 200g of the prepolymer and 240g of dimethyl silicone oil into a reaction kettle, and replacing air in the kettle with nitrogen for 3 times; gradually heating to 250 ℃ under continuous stirring, and reacting for 7 hours under heat preservation; cooling, discharging, filtering, washing the solid with dichloromethane and water in sequence, drying to obtain high molecular weight biological radical semi-aromatic polyamide resin with intrinsic viscosity [ eta ]]＝0.73dL·g-1Melt index 96 g.10 min-1。
Example 4
Adding 33.05g of eicosanoyl chloride and 60g of cyclohexane into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution. 16.9g of sodium glutamate, 11.2g of potassium hydroxide and 130g of deionized water are added to a reactor with a stirrer, a thermometer, a condenser and a chilled water cooling device; introducing chilled water, and stirring and reacting for 2 hours at 25 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution into the reactor within 1 hour; after the dropwise addition is finished, the temperature is continuously maintained for reaction for 1 hour; heating to 81 ℃, and evaporating cyclohexane; continuing to heat up, and aging the reaction solution for 1 hour at 90 ℃; filtering while the solution is hot, and cooling to 30 ℃; adding phosphoric acid with the concentration of 1.0mol/L into the filtrate until the PH value is 1, standing for 12 hours at room temperature, and fully separating out a product; the monomer is obtained by filtering, washing and drying.
Adding 22.05g of the monomer, 84.8g of diisopropyl 2, 5-furandicarboxylate, 83.4g of decamethylenediamine, 1.5g of sodium phosphate, 2.5g of decanoic acid and 75g of isopropanol into a reaction kettle, introducing nitrogen, stirring, and heating to 60 ℃ within 0.5 hour; stopping introducing nitrogen, sealing the reaction kettle, heating to 210 ℃ within 2 hours, and maintaining the temperature for reaction for 4 hours; opening an exhaust valve, discharging mixed steam of alcohol and water within 2 hours to reduce the pressure in the kettle to 0.8MPa, and maintaining the temperature not to exceed 245 ℃; closing an exhaust valve, heating to 260 ℃, and maintaining the temperature for reaction for 1 hour to homogenize the materials; then cooling to room temperature, discharging, and drying the product until the water content is less than or equal to 0.3 percent to obtain the bio-based semi-aromatic polyamide prepolymer.
Adding 20g of the prepolymer into a quartz reaction tube, gradually heating to 260 ℃ under the protection of argon, and carrying out heat preservation reaction for 8 hours; cooling and discharging to obtain high molecular weight bio-based semi-aromatic polyamide resin with intrinsic viscosity [ eta ]]＝0.98dL·g-1。
Example 5
Adding 19.05kg of decanoyl chloride and 12.00kg of dichloromethane into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution. 16.90kg of sodium glutamate, 8.00kg of sodium hydroxide and 35.00kg of deionized water were added to a reactor equipped with a stirrer, a thermometer, a condenser and a chilled water cooling device; introducing chilled water, and stirring and reacting for 2 hours at the temperature of 30 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution into the reactor within 2 hours; after the dropwise addition is finished, the temperature is continuously maintained for reaction for 1 hour; heating to 40 ℃, and distilling off dichloromethane; continuing to heat up, and aging the reaction solution at 60 ℃ for 1 hour; filtering while the solution is hot, and cooling to 25 ℃; adding hydrochloric acid with the concentration of 6.0mol/L into the filtrate until the PH value is 1, standing for 24 hours at room temperature, and fully separating out a product; the monomer is obtained by filtering, washing and drying.
Adding 24.08kg of the monomer, 14.72kg of dimethyl 2, 5-furandicarboxylate, 16.80kg of pentanediamine, 0.12kg of sodium tripolyphosphate, 0.60kg of octadecanoic acid and 7.50kg of methanol into a reaction kettle, introducing nitrogen, stirring, and heating to 60 ℃ within 0.5 hour; stopping introducing nitrogen, sealing the reaction kettle, heating to 225 ℃ within 3 hours, and maintaining the temperature for reaction for 3 hours; opening an exhaust valve, discharging mixed steam of alcohol and water within 2 hours to reduce the pressure in the kettle to 0.9MPa, and maintaining the temperature to be not more than 240 ℃; closing an exhaust valve, heating to 250 ℃, and maintaining the temperature for reaction for 2 hours to homogenize the materials; then cooling to room temperature, discharging, and drying the product until the water content is less than or equal to 0.3 percent to obtain the bio-based semi-aromatic polyamide prepolymer.
Adding 35.00kg of the bio-based semi-aromatic polyamide into a reaction extruder, and performing melt extrusion at 320 ℃ and under vacuum of-0.08 MPa; the yield is 10kg/h, and the material retention time is 9 min; cooling, drawing, granulating and drying the extrudate to obtain the high molecular weight bio-based semi-aromatic polyamide resin with intrinsic viscosity [ eta ])]＝0.84dL·g-1Melt index 103 g.10 min-1。
TABLE 1 Performance parameters of the bio-based semi-aromatic polyamides obtained in examples 1 to 5
| Intrinsic viscosity (dL g)-1) | Melting Point (. degree.C.) | Melt index (g 10 min)-1) | |
| Example 1 | 0.81 | 306 | 84 |
| Example 2 | 0.83 | 287 | 302 |
| Example 3 | 0.73 | 312 | 96 |
| Example 4 | 0.98 | 311 | - |
| Example 5 | 0.84 | 304 | 103 |
a. Intrinsic viscosity test: and (3) dissolving the sample in concentrated sulfuric acid at the temperature of 30 +/-0.1 ℃, testing in an Ubbelohde viscometer, and calculating by adopting a one-point method.
b. Melting point test: in the nitrogen atmosphere, the heating rate and the cooling rate are both 10 ℃/min, and a melting peak of a DSC second heating curve is taken.
c. Melt index test conditions: capillary diameter 2.095mm, 5kg load. Examples 1, 2,5 were tested at 325 ℃, example 3 at 335 ℃ and example 4 was not enough tested.
Claims (13)
1. A bio-based semi-aromatic polyamide, characterized in that the bio-based semi-aromatic polyamide has the structural formula:
wherein n is 10-200, x + y is more than 0 and less than or equal to 1, x is not equal to 0, and y is not equal to 0;
R1＝-(CH2)8CH3、-(CH2)10CH3、-(CH2)12CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)18CH3、-(CH2)20CH3、-(CH2)22CH3、-(CH2)24CH3、-(CH2)26CH3or- (CH)2)28CH3At least one of;
R2＝-(CH2)5-and/or- (CH)2)10-。
2. The bio-based semi-aromatic polyamide according to claim 1, characterized in that it is obtained by the following process: preparing amidated glutamic acid monomer with sodium glutamate and long-chain fatty acyl chloride as material; mixing the amidated glutamic acid monomer with furan dicarboxylic acid diester, sebacic acid and diamine, and preparing a bio-based semi-aromatic polyamide prepolymer by adopting a high-temperature solution polymerization method; finally, the prepolymer is further condensed to prepare the bio-based semi-aromatic polyamide.
3. A bio-based semi-aromatic polyamide according to claim 2,
the long-chain fatty acyl chloride is any one of decanoyl chloride, dodecanoyl chloride, tetradecanoyl chloride, hexadecanoyl chloride, heptadecanoyl chloride, octadecanoyl chloride, eicosanoyl chloride, docosanoyl chloride, tetracosanoyl chloride, hexacosanoyl chloride, octacosanoyl chloride or triacontanoyl chloride; or:
the furan dicarboxylic acid diester is at least one of dimethyl 2, 5-furan dicarboxylic acid, diethyl 2, 5-furan dicarboxylic acid, di-n-propyl 2, 5-furan dicarboxylic acid, diisopropyl 2, 5-furan dicarboxylic acid, di-n-butyl 2, 5-furan dicarboxylic acid, diisobutyl 2, 5-furan dicarboxylic acid or di-sec-butyl 2, 5-furan dicarboxylic acid; or:
the diamine is pentanediamine and/or decamethylenediamine.
4. The bio-based semi-aromatic polyamide according to claim 2 or 3, wherein the bio-based semi-aromatic polyamide prepolymer is prepared by the following preparation steps:
(1) adding 301-581 parts of monomer, 184-2260 parts of furan dicarboxylic acid diester, 0-1010 parts of sebacic acid, 210-2800 parts of diamine, 1-30 parts of catalyst, 5-80 parts of molecular weight regulator and 100-2000 parts of alcohol into a reaction kettle, introducing nitrogen, stirring, and heating to 60-90 ℃ within 0.5-1 hour;
(2) stopping introducing nitrogen, sealing the reaction kettle, heating to 180-240 ℃ within 1-3 hours, and maintaining the temperature for reaction for 2-5 hours;
(3) opening an exhaust valve, discharging mixed steam of alcohol and water within 0.5-2 hours to reduce the pressure in the kettle to 0.5-1.5 MPa, and maintaining the temperature not to exceed a certain temperature value of 240-260 ℃;
(4) closing an exhaust valve, and continuously stirring and reacting at 240-260 ℃ for 0.5-2 hours to homogenize the materials; then cooling to room temperature, discharging, drying the product until the water content is less than or equal to 0.3 percent, and obtaining the bio-based semi-aromatic polyamide prepolymer;
in the step (1), the structural formula of the monomer is as follows:
wherein:
R1＝-(CH2)8CH3、-(CH2)10CH3、-(CH2)12CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)18CH3、-(CH2)20CH3、-(CH2)22CH3、-(CH2)24CH3、-(CH2)26CH3or- (CH)2)28CH3Any one of the above.
5. A bio-based semi-aromatic polyamide according to claim 4, characterized in that said monomers are prepared by a process comprising the steps of:
1) adding 190.5-470.5 parts of long-chain fatty acyl chloride and 100-1000 parts of solvent into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution;
2) adding 169 parts of sodium glutamate, 80-138 parts of alkaline compound and 200-2000 parts of deionized water into a reactor with a stirrer, a thermometer, a condenser and a freezing water cooling device; introducing chilled water, and stirring and reacting for 1-3 hours at 0-30 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution obtained in the step 1) into the reactor within 0.5-2 hours; after the dropwise addition is finished, continuously maintaining the temperature for reaction for 0.5-1 hour;
3) heating to 36-81 ℃, and evaporating the solvent; continuously heating to age the reaction solution at 50-90 ℃ for 1-2 hours;
4) filtering while the mixture is hot, and then cooling to 20-40 ℃; adding acid with the concentration of 1.0-12.0 mol/L into the filtrate until the pH value is 0-3, standing at room temperature for 6-24 hours, and fully precipitating a product; the monomer is obtained by filtering, washing and drying.
6. A bio-based semi-aromatic polyamide according to claim 5,
the solvent in the step 1) is any one of dichloromethane, n-pentane, n-hexane or cyclohexane; or:
the alkaline compound in the step 2) is any one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate; or:
the acid in the step 4) is any one of hydrochloric acid, sulfuric acid or phosphoric acid.
7. The method of claim 5 or 6, wherein in the step (1),
the catalyst is at least one of phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, sodium phosphate, sodium phosphite, sodium hypophosphite or sodium tripolyphosphate; or:
the molecular weight regulator is any one of acetic acid, caproic acid, caprylic acid, capric acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid or triacontanoic acid; or:
the alcohol is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or sec-butanol.
8. The method of claim 7, wherein in the step (1), the alcohol is methanol.
9. The method for preparing the bio-based semi-aromatic polyamide as claimed in claim 2, wherein the bio-based semi-aromatic polyamide prepolymer is subjected to polycondensation reaction at 220-330 ℃ to obtain the bio-based semi-aromatic polyamide.
10. The bio-based semi-aromatic polyamide according to claim 2, wherein the bio-based semi-aromatic polyamide prepolymer is further polycondensed by at least one of vacuum solid phase polycondensation, solid phase polycondensation under the protection of water vapor and/or inert gas, solid phase polycondensation under the protection of inert liquid, solid phase reaction extrusion, melt polycondensation under the protection of water vapor and/or inert gas, melt polycondensation under the protection of inert liquid, vacuum melt polycondensation or melt reaction extrusion; wherein the inert gas is at least one of nitrogen, argon or helium; the inert liquid is at least one of diphenyl ether, diphenyl sulfone, dimethyl silicone oil or diphenyl silicone oil.
11. The process for producing a bio-based semi-aromatic polyamide according to any one of claims 1 to 10, wherein the process comprises: preparing amidated glutamic acid monomer with sodium glutamate and long-chain fatty acyl chloride as material; mixing the amidated glutamic acid monomer with furan dicarboxylic acid diester, sebacic acid and diamine, and preparing a bio-based semi-aromatic polyamide prepolymer by adopting a high-temperature solution polymerization method; finally, the prepolymer is further condensed to prepare the bio-based semi-aromatic polyamide.
12. The method for preparing the bio-based semi-aromatic polyamide according to claim 11, wherein the bio-based semi-aromatic polyamide prepolymer is prepared by the following steps:
(1) adding 301-581 parts of monomer, 184-2260 parts of furan dicarboxylic acid diester, 0-1010 parts of sebacic acid, 210-2800 parts of diamine, 1-30 parts of catalyst, 5-80 parts of molecular weight regulator and 100-2000 parts of alcohol into a reaction kettle, introducing nitrogen, stirring, and heating to 60-90 ℃ within 0.5-1 hour;
(2) stopping introducing nitrogen, sealing the reaction kettle, heating to 180-240 ℃ within 1-3 hours, and maintaining the temperature for reaction for 2-5 hours;
(3) opening an exhaust valve, discharging mixed steam of alcohol and water within 0.5-2 hours to reduce the pressure in the kettle to 0.5-1.5 MPa, and maintaining the temperature not to exceed a certain temperature value of 240-260 ℃;
(4) closing an exhaust valve, and continuously stirring and reacting at 240-260 ℃ for 0.5-2 hours to homogenize the materials; then cooling to room temperature, discharging, drying the product until the water content is less than or equal to 0.3 percent, and obtaining the bio-based semi-aromatic polyamide prepolymer;
in the step (1), the structural formula of the monomer is as follows:
wherein:
R1＝-(CH2)8CH3、-(CH2)10CH3、-(CH2)12CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)18CH3、-(CH2)20CH3、-(CH2)22CH3、-(CH2)24CH3、-(CH2)26CH3or- (CH)2)28CH3Any one of the above.
13. The process for the preparation of bio-based semi-aromatic polyamides according to claim 12, characterized in that the monomers are prepared by a process comprising the following steps:
1) adding 190.5-470.5 parts of long-chain fatty acyl chloride and 100-1000 parts of solvent into a dissolving kettle, and uniformly stirring to obtain an acyl chloride solution;
2) adding 169 parts of sodium glutamate, 80-138 parts of alkaline compound and 200-2000 parts of deionized water into a reactor with a stirrer, a thermometer, a condenser and a freezing water cooling device; introducing chilled water, and stirring and reacting for 1-3 hours at 0-30 ℃; maintaining stirring and temperature, and dropwise adding the acyl chloride solution obtained in the step 1) into the reactor within 0.5-2 hours; after the dropwise addition is finished, continuously maintaining the temperature for reaction for 0.5-1 hour;
3) heating to 36-81 ℃, and evaporating the solvent; continuously heating to age the reaction solution at 50-90 ℃ for 1-2 hours;
4) filtering while the mixture is hot, and then cooling to 20-40 ℃; adding acid with the concentration of 1.0-12.0 mol/L into the filtrate until the pH value is 0-3, standing at room temperature for 6-24 hours, and fully precipitating a product; the monomer is obtained by filtering, washing and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910998898.9A CN110669216B (en) | 2019-10-21 | 2019-10-21 | Bio-based semi-aromatic polyamide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910998898.9A CN110669216B (en) | 2019-10-21 | 2019-10-21 | Bio-based semi-aromatic polyamide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110669216A CN110669216A (en) | 2020-01-10 |
| CN110669216B true CN110669216B (en) | 2022-02-08 |
Family
ID=69083308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910998898.9A Active CN110669216B (en) | 2019-10-21 | 2019-10-21 | Bio-based semi-aromatic polyamide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110669216B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062949B (en) * | 2020-09-11 | 2023-04-25 | 中鼎凯瑞科技成都有限公司 | Semi-aromatic polyamino acid, semi-aromatic polyamino acid-based bone repair material and preparation thereof |
| CN114181390B (en) * | 2021-12-23 | 2023-02-10 | 北京化工大学 | Bio-based high-temperature-resistant polyamide and preparation method thereof |
| CN115505120A (en) * | 2022-10-31 | 2022-12-23 | 中国五环工程有限公司 | High-performance bio-based copolymerized nylon and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013006963A (en) * | 2011-06-24 | 2013-01-10 | Unitika Ltd | Polyamide and molded article thereof |
| CN105885401A (en) * | 2016-04-20 | 2016-08-24 | 南京工业大学 | Graphene, CNT (carbon nano tube) and bio-based nylon ternary composite material and preparation method thereof |
| CN106191145A (en) * | 2016-07-22 | 2016-12-07 | 南京工业大学 | A kind of semi-aromatic polyamide based on furandicarboxylic acid and preparation method thereof |
-
2019
- 2019-10-21 CN CN201910998898.9A patent/CN110669216B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013006963A (en) * | 2011-06-24 | 2013-01-10 | Unitika Ltd | Polyamide and molded article thereof |
| CN105885401A (en) * | 2016-04-20 | 2016-08-24 | 南京工业大学 | Graphene, CNT (carbon nano tube) and bio-based nylon ternary composite material and preparation method thereof |
| CN106191145A (en) * | 2016-07-22 | 2016-12-07 | 南京工业大学 | A kind of semi-aromatic polyamide based on furandicarboxylic acid and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of 2,5-furandicarboxylic acid-based heat-resistant polyamides under existing industrialization process;Min Cao et al;《Macromolecular Research》;20170731;第25卷(第7期);第722-729页 * |
| 含呋喃环生物基聚酰胺的合成;黄卫军 等;《化学进展》;20180926;第30卷(第12期);第1836-1843页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110669216A (en) | 2020-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110669216B (en) | Bio-based semi-aromatic polyamide and preparation method thereof | |
| CN110684190B (en) | Preparation method of bio-based high-temperature nylon | |
| CN109517165B (en) | Semi-aromatic bio-based polyamide and preparation method thereof | |
| CN104250377A (en) | Low-water absorption biological nylon material PA610T and preparation method thereof | |
| CN110028665B (en) | Semi-aromatic polyamide with high heat resistance and low water absorption and preparation method thereof | |
| CN114181390B (en) | Bio-based high-temperature-resistant polyamide and preparation method thereof | |
| CN114249890B (en) | Bio-based polyesteramide and preparation method thereof | |
| CN111234207A (en) | Transparent bio-based polyamide and preparation method thereof | |
| CN104774454B (en) | A kind of high temperature resistant nylon PA66T materials and preparation method thereof | |
| CN110483766B (en) | Method for preparing semi-aromatic polyamide by utilizing recycled polyester | |
| CN113896872A (en) | Preparation method for reducing melt index of carbon dioxide-based polyester-polycarbonate copolymer | |
| CN106893095A (en) | A kind of biological poly acid amides and its synthetic method | |
| CN112142963A (en) | Synthetic method and application of biodegradable high molecular weight polyester | |
| CN113999391A (en) | Bio-based polyamide and preparation method thereof | |
| CN106928450A (en) | A kind of high temperature resistant bio-based PA10T copolymer materials and preparation method thereof | |
| CN111116874A (en) | Biodegradable PBST copolyester and synthetic method thereof | |
| KR101557529B1 (en) | Method for producing polyamide | |
| CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
| CN115477750B (en) | High-performance bio-based polyamide PA6/5T and preparation method thereof | |
| CN103965466A (en) | Semi-aromatic biological nylon and preparation method thereof | |
| CN112979941B (en) | Continuous solid phase polycondensation method for producing high temperature resistant nylon | |
| CN110724258B (en) | Semi-aromatic polyamide based on glycine and preparation method thereof | |
| KR101653531B1 (en) | Syntheses of alternating copolymer from furane dicarboxyate, diamine, and adipic acid | |
| CN106916296A (en) | The preparation method and aliphatic transparent polyamide of a kind of aliphatic transparent polyamide | |
| CN112812549A (en) | Method for preparing carbon quantum dot enhanced anti-reflection nylon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240226 Address after: 261304 Longchi Town Industrial Park, Changyi City, Weifang City, Shandong Province Patentee after: WEIFANG SANLI BENNO CHEMICAL INDUSTRY CO.,LTD. Country or region after: China Address before: Room 1609, 16th floor, Hemei Haitang Center (Tianfu maker), 2039 Tianfu Avenue South, Tianfu New District, Chengdu, Sichuan 610065 Patentee before: SICHUAN SIPAIEN NEW MATERIAL CO.,LTD. Country or region before: China |