CN115636737B - Alkyl functionalized column hexaarene stationary phase, capillary gas chromatographic column, and preparation methods and applications thereof - Google Patents
Alkyl functionalized column hexaarene stationary phase, capillary gas chromatographic column, and preparation methods and applications thereof Download PDFInfo
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- CN115636737B CN115636737B CN202211214480.2A CN202211214480A CN115636737B CN 115636737 B CN115636737 B CN 115636737B CN 202211214480 A CN202211214480 A CN 202211214480A CN 115636737 B CN115636737 B CN 115636737B
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- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 59
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000003738 xylenes Chemical class 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 37
- 238000003965 capillary gas chromatography Methods 0.000 claims description 32
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 25
- 239000012159 carrier gas Substances 0.000 claims description 24
- 238000013375 chromatographic separation Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical class BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical class CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 claims description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 12
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 12
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 12
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 12
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 12
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 claims description 12
- XPQPWPZFBULGKT-UHFFFAOYSA-N methyl undecanoate Chemical compound CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 claims description 12
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 11
- 150000001448 anilines Chemical class 0.000 claims description 11
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical class ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical class BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001555 benzenes Chemical class 0.000 claims description 10
- MMGPQYJNRFGRQK-UHFFFAOYSA-N 1,4-didecoxybenzene Chemical compound CCCCCCCCCCOC1=CC=C(OCCCCCCCCCC)C=C1 MMGPQYJNRFGRQK-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 150000003935 benzaldehydes Chemical class 0.000 claims description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229940094933 n-dodecane Drugs 0.000 claims description 9
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 claims description 8
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 7
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims description 7
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- GLZPCOQZEFWAFX-YFHOEESVSA-N (Z)-Geraniol Chemical compound CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 6
- 239000005968 1-Decanol Substances 0.000 claims description 6
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 6
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 claims description 6
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 claims description 6
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 claims description 6
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical class BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 claims description 6
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical class ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 claims description 6
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical class INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 claims description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 6
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 6
- FQTLCLSUCSAZDY-SDNWHVSQSA-N (6E)-nerolidol Chemical compound CC(C)=CCC\C(C)=C\CCC(C)(O)C=C FQTLCLSUCSAZDY-SDNWHVSQSA-N 0.000 claims description 5
- FQTLCLSUCSAZDY-SZGZABIGSA-N (E)-Nerolidol Natural products CC(C)=CCC\C(C)=C/CC[C@@](C)(O)C=C FQTLCLSUCSAZDY-SZGZABIGSA-N 0.000 claims description 5
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims description 5
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 5
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 5
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- ZLWGOLLBNDIBMM-UHFFFAOYSA-N trans-nerolidol Natural products CC(C)C(=C)C(O)CCC=C(/C)CCC=C(C)C ZLWGOLLBNDIBMM-UHFFFAOYSA-N 0.000 claims description 5
- GLZPCOQZEFWAFX-JXMROGBWSA-N (E)-Geraniol Chemical compound CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 claims description 4
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 4
- QVFHFKPGBODJJB-UHFFFAOYSA-N 1,3-oxathiane Chemical compound C1COCSC1 QVFHFKPGBODJJB-UHFFFAOYSA-N 0.000 claims description 4
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 4
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical group NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 claims description 4
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 claims description 4
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 claims description 4
- FFCSRWGYGMRBGD-UHFFFAOYSA-N 3-iodoaniline Chemical compound NC1=CC=CC(I)=C1 FFCSRWGYGMRBGD-UHFFFAOYSA-N 0.000 claims description 4
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 4
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 4
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 claims description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 claims description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
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- GFISDBXSWQMOND-PHDIDXHHSA-N (2r,5r)-2,5-dimethoxyoxolane Chemical compound CO[C@H]1CC[C@H](OC)O1 GFISDBXSWQMOND-PHDIDXHHSA-N 0.000 claims description 3
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- GFISDBXSWQMOND-OLQVQODUSA-N (2r,5s)-2,5-dimethoxyoxolane Chemical compound CO[C@@H]1CC[C@H](OC)O1 GFISDBXSWQMOND-OLQVQODUSA-N 0.000 claims description 3
- OXMIDRBAFOEOQT-OLQVQODUSA-N (2r,5s)-2,5-dimethyloxolane Chemical compound C[C@H]1CC[C@@H](C)O1 OXMIDRBAFOEOQT-OLQVQODUSA-N 0.000 claims description 3
- FQTLCLSUCSAZDY-KAMYIIQDSA-N (6Z)-nerolidol Chemical compound CC(C)=CCC\C(C)=C/CCC(C)(O)C=C FQTLCLSUCSAZDY-KAMYIIQDSA-N 0.000 claims description 3
- FQTLCLSUCSAZDY-ATGUSINASA-N (Z)-Nerolidol Natural products CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 3
- FAHUKNBUIVOJJR-UHFFFAOYSA-N 1-(4-fluorophenyl)-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine Chemical compound C1=CC(F)=CC=C1C1C2=CC=CN2CCN1 FAHUKNBUIVOJJR-UHFFFAOYSA-N 0.000 claims description 3
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 claims description 3
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- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 3
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- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 3
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- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 3
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- SFPQFQUXAJOWNF-UHFFFAOYSA-N 1,3-diiodobenzene Chemical compound IC1=CC=CC(I)=C1 SFPQFQUXAJOWNF-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- JRLPEMVDPFPYPJ-UHFFFAOYSA-N 1-ethyl-4-methylbenzene Chemical compound CCC1=CC=C(C)C=C1 JRLPEMVDPFPYPJ-UHFFFAOYSA-N 0.000 description 1
- ZLCSFXXPPANWQY-UHFFFAOYSA-N 3-ethyltoluene Chemical compound CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- NNBZCPXTIHJBJL-AOOOYVTPSA-N cis-decalin Chemical compound C1CCC[C@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-AOOOYVTPSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KVWWIYGFBYDJQC-MNOVXSKESA-N methyl 2-[(1r,2s)-3-oxo-2-pentylcyclopentyl]acetate Chemical compound CCCCC[C@H]1[C@@H](CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-MNOVXSKESA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- JNYIQRMXGCWKOU-UHFFFAOYSA-M sodium methanol chloride Chemical class [Na+].[Cl-].OC JNYIQRMXGCWKOU-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- NNBZCPXTIHJBJL-MGCOHNPYSA-N trans-decalin Chemical compound C1CCC[C@@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-MGCOHNPYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an alkyl functionalized column hexaarene stationary phase, a capillary gas chromatographic column, a preparation method and application thereof, and belongs to the technical field of chromatographic analysis, wherein the chemical formula of the alkyl functionalized column hexaarene stationary phase is P6A-C10. The capillary gas chromatographic column prepared by the alkyl functionalized column hexaarene stationary phase can solve the problem of poor separation performance of column arene aiming at xylene isomers and halogenated aniline in the prior art.
Description
Technical Field
The invention belongs to the technical field of chromatographic analysis, and particularly relates to an alkyl functionalized column hexaarene stationary phase, a capillary gas chromatographic column, and preparation and application thereof.
Background
The pillar aromatics consist of 1, 4-dialkoxybenzene units connected by methylene bridges in the 2-and 5-positions, which have been of great interest in supermolecular chemistry and material chemistry due to the unique pillar-like framework and precise cavities. In addition, the synthesis of the column aromatics is easy and easy to functionalize with different substituents, and so far, the synthesis, functionalization, host-guest properties and potential applications of the column aromatics have been widely studied.
Gas chromatography is one of the best means for qualitative and quantitative analysis of complex substances, and capillary gas chromatography is a milestone for development of gas chromatography, and has been widely used for sample analysis in various fields due to its advantages of high sensitivity, high selectivity, short analysis time, low cost, etc.
For chromatographic separation in capillary gas phase columns, baseline separation of components in the sample is beneficial to the accuracy of analytical sample determination, and development of a high-performance stationary phase is key to obtaining high resolution for complex samples. The stationary phase is generally required to have basic properties such as high chemical and thermal stability, proper viscosity, low vapor pressure, and good film forming properties. However, with the continuous development of technology, the structure of the sample to be separated is more and more complex, and the difficulty of separating the sample is also more and more difficult.
Reference 1: chinese patent document with patent publication No. CN114276257 a.
Reference 1 discloses a preparation method and application of an amino-functionalized column pentaarene stationary phase, wherein the amino-functionalized column pentaarene is used as a stationary phase of a capillary gas chromatographic column, and the amino-functionalized column pentaarene stationary phase has good separation performance in the aspect of separating compounds such as methylnaphthalene isomers, xylenol isomers, benzaldehyde isomers and halogenated benzene isomers. But its separation performance against xylene isomers and halogenated anilines is very poor.
Reference 2: chinese patent document with patent publication No. CN113075346 a.
Reference 2 discloses a gas chromatographic separation analysis method and application based on arene macrocycles, molecular cages and column quinones, and specifically describes column [5] arene, methyl column [5] arene, ethyl column [5] arene, column [6] arene, methyl column [6] arene, ethyl column [6] arene and the like, and the stationary phase can be used for analysis and detection of o/m/p-xylene, mono/meta/mesitylene, o/m/p-difluorobenzene, o/m/p-dichlorobenzene, o/m/p-dibromobenzene, o/m/p-diiodobenzene/o-bromoiodobenzene, o/m/p-ethyltoluene after being prepared into a chromatographic column. But it has been tested by the applicant that it shows a low resolution for the above isomers and does not allow efficient separation of the xylene isomers.
Disclosure of Invention
The invention aims to solve the problem of poor separation performance of column arene aiming at xylene isomers and halogenated aniline in the prior art, and provides an alkyl functionalized column hexaarene stationary phase, a capillary gas chromatographic column, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following specific scheme: an alkyl functionalized column hexaarene stationary phase, wherein the chemical formula of the alkyl functionalized column hexaarene stationary phase is P6A-C10, and the chemical structural formula is:
a method for preparing an alkyl functionalized column hexaarene stationary phase, comprising the following steps:
1) Carrying out etherification reaction on 1, 4-hydroquinone, 1-bromodecane, potassium hydroxide and ethanol to obtain 1, 4-bis (decyloxy) benzene;
2) And (3) taking 1, 4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride diethyl etherate and chlorocyclohexane for cyclization reaction, and carrying out aftertreatment and purification on the reacted product to obtain the alkyl functionalized column hexaarene.
As a further optimization of the above technical solution, in step 1): the reaction temperature is 80-85 ℃; the reaction time is 7.5-8.5h; the addition ratio of 1, 4-hydroquinone to 1-bromodecane, potassium hydroxide and ethanol was 1.1g:6.63 to 6.85g:1.68 to 1.74g:25mL.
As a further optimization of the above technical solution, in step 2): the reaction temperature is 35 ℃; the reaction time is 3-4 h; the addition ratio of 1, 4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride etherate and chlorocyclohexane was 2.00g: 0.153-0.169 g: 0.726-0.799 g:30mL.
As a further optimization of the above technical solution, in step 2): column chromatography was used for purification, and petroleum ether in eluent: the volume ratio of dichloromethane is 10:3.
The capillary gas chromatographic column is prepared from the alkyl functionalized column hexaarene stationary phase.
As a further optimization of the technical scheme, the preparation mode of the capillary gas chromatographic column is static coating.
The application of the capillary gas chromatographic column can separate xylene isomer, substituted benzaldehyde isomer, 12 groups of cis-trans isomers, 21 groups of complex mixtures, halogenated benzene isomer, halogenated aniline isomer, mixed alkane, mixed ester and mixed alcohol.
As a further optimization of the above-mentioned solution,
the xylene isomers include ortho-xylene, meta-xylene, and para-xylene;
the substituted benzaldehyde isomers comprise methylbenzaldehyde isomers and bromobenzaldehyde isomers, wherein the methylbenzaldehyde isomers comprise o-methylbenzaldehyde, m-methylbenzaldehyde and p-methylbenzaldehyde; bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde;
the 12 groups of cis-trans isomers comprise cis-2, 5-dimethyltetrahydrofuran and trans-2, 5-dimethyltetrahydrofuran, cis-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dimethoxytetrahydrofuran, cis-25-dihydro-25-dimethoxyfuran and trans-25-dihydro-25-dimethoxyfuran, cis-2-methyl-4-propyl-1, 3-oxathiacyclohexane and trans-2-methyl-4-propyl-1, 3-oxathiacyclohexane, cis-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran and trans-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran, cis-nerolidol and trans-nerolidol, cis-3, 7-dimethyl-2, 6-octadien-1-ol and trans-3, 7-dimethyl-2, 6-octadien-1-ol, cis-decahydrojasmonate and trans-4-methyl-propyl-1, cis-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran and trans-nerolidol, cis-3, 7-dimethyl-2, 6-octadien-1-ol and trans-decan-3-methyl-3-octadien-ol;
the 21-component complex mixture consists of the following components: 2-heptanone, 1-heptanol, 1-bromohexane, n-butylbenzene, 1-octanol, o-chloroaniline, n-dodecane, 1,2, 3-trichlorobenzene, o-bromoaniline, 1-decanol, methyl decanoate, m-chloronitrobenzene, 1-methylnaphthalene, n-tetradecane, methyl undecanoate, m-bromonitrobenzene, 1-dodecanol, 2, 3-dimethylnaphthalene, p-chloronitrobenzene, n-hexadecane and 1-bromododecane;
the halogenated benzene isomers comprise a chlorotoluene isomer and a dibromobenzene isomer, wherein the chlorotoluene isomer comprises o-chlorotoluene, m-chlorotoluene and p-chlorotoluene; dibromobenzene isomers include ortho-dibromobenzene, meta-dibromobenzene, and para-dibromobenzene;
the halogenated aniline isomers include chloroaniline isomers, bromoaniline isomers and iodoaniline isomers: wherein, the chloroaniline isomer comprises o-chloroaniline, m-chloroaniline and p-chloroaniline; bromoaniline isomers include o-bromoaniline, m-bromoaniline and p-bromoaniline; the iodoaniline isomers include o-iodoaniline, m-iodoaniline and p-iodoaniline;
the mixed alkane: including n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane;
the mixed ester comprises methyl valerate, methyl caproate, methyl heptanoate, methyl caprylate, methyl pelargonate, methyl caprate, methyl undecanoate and methyl laurate;
the mixed alcohols include 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.
As a further optimization of the technical scheme, the chromatographic separation condition of the para-xylene isomer of the capillary gas chromatographic column is kept at 40 ℃ for 1min, the temperature is increased to 60 ℃ at the heating rate of 5 ℃/min, and the carrier gas flow rate is 0.4mL/min.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the capillary chromatographic column through the alkyl functionalized column hexaarene stationary phase, has better separation effect on the paraxylene isomer and the halogenated aniline isomer, and can realize the complete separation of each component in the paraxylene isomer mixture and the halogenated aniline isomer mixture (the separation degree is more than 1.5). For host guest chemistry, weak interactions play an important role, and pillar arenes and their derivatives can selectively recognize organic guest molecules through non-covalent interactions (such as van der Waals, pi-pi, and hydrogen bond interactions). The reasons why pillar aromatics and their derivatives can selectively recognize organic guest molecules include the following two aspects: on the one hand, almost all organic guest molecules contain C-H groups, and the C-H … pi interactions between them are ubiquitous; on the other hand, the C-H … pi interactions are weaker than classical hydrogen bonding interactions, and therefore, pillar arenes and their derivatives are more suitable for recognizing a few organic guest molecules with slightly different structures and properties. In addition, the column aromatics have a highly symmetrical and rigid column structure, the number of repeating aromatic units defining the cavity size of the column aromatics, and they can selectively capture specific objects suitable for their size in the nanoscale space. The characteristic that the column hexaarene is taken as the column hexaarene with a certain number of repeated aromatic units can capture a larger aromatic object has a great influence on the separation of xylene isomers based on shape selectivity, the alkyl functionalized column hexaarene is the derivative of the column hexaarene, and the derivatized decaneoxy group effectively improves the film forming property of the column hexaarene, reduces the melting point, so that the alkyl functionalized column hexaarene can meet the requirement of a gas chromatographic stationary phase, and meanwhile, the acting force between a fixed phase and an analyte is enriched in chromatographic separation. Thus, the present invention utilizes an alkyl functionalized column hexaarene stationary phase to solve the separation difficulties including xylene isomers.
Drawings
FIG. 1 is a reaction scheme of alkyl functionalized column hexaaromatics P6A-C10 prepared from 1, 4-hydroquinone in accordance with the present invention;
FIG. 2 is a thermogravimetric analysis of an alkyl functionalized column hexaarene stationary phase;
FIG. 3 is a graph showing the column effect (Golay curve) of a capillary gas chromatography column prepared according to the invention measured at 120℃using n-dodecane as the probe compound;
FIG. 4 shows the separation of different types of xylene isomers with different polarities by a capillary gas chromatography column prepared according to the present invention: o-xylene, M-xylene, p-xylene, and commercial columns DB-17, HP-5, HP-35, and PEG-20M;
FIG. 5 shows the separation of different types of methylbenzaldehyde isomers with different polarities by using a capillary gas chromatographic column prepared by the invention: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde and bromobenzaldehyde isomers: o-bromobenzaldehyde, M-bromobenzaldehyde, p-bromobenzaldehyde, and commercial columns DB-17, HP-5, HP-35, and PEG-20M were separated and compared;
FIG. 6 is a capillary gas chromatography column made in accordance with the present invention for separating halobenzene isomers, including chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene; dibromobenzene isomers: o-dibromobenzene, M-dibromobenzene, p-dibromobenzene, and commercial columns DB-17, HP-5, HP-35, and PEG-20M;
FIG. 7 shows the separation of 12 sets of cis-trans isomers with different polarities by using the capillary gas chromatographic column prepared by the invention;
FIG. 8 shows a sample of a complex mixture of 21 components separated by a capillary gas chromatographic column of the invention of different polarity and different types, in comparison with commercial columns DB-17, HP-5, HP-35 and PEG-20M;
FIG. 9 is a capillary gas chromatography column separation of the haloaniline isomers from commercial columns DB-17, HP-5, HP-35 and PEG-20M separation controls made in accordance with the present invention;
FIG. 10 is a Scanning Electron Microscope (SEM) of a capillary gas chromatography column prepared according to the invention, exhibiting good film forming properties for the P6A-C10 stationary phase.
FIG. 11 shows the separation of different polarity and different types of xylene isomers by the capillary gas chromatography column prepared according to the present invention: o-xylene, m-xylene and p-xylene, and a capillary gas chromatographic column prepared by adopting an amino-functionalized column pentaarene stationary phase;
FIG. 12 is a capillary gas chromatography column separation of haloaniline isomers made in accordance with the present invention, in comparison to a capillary gas chromatography column separation made using an amino functionalized column pentaarene stationary phase;
FIG. 13 is a capillary gas chromatography column prepared from column hexaaromatics of different alkoxy chain lengths for separation of xylene isomers, chlorotoluene isomers and bromobenzaldehyde isomers;
FIG. 14 is a capillary gas chromatography column prepared from column hexaaromatics of different alkoxy chain lengths for separation of mixed alkanes, mixed esters, and mixed alcohols;
FIG. 15 is a graph of column efficiency (Golay curve) of capillary gas chromatography columns made from column hexaaromatics of different alkoxy chain lengths;
FIG. 16 shows the separation of xylene isomers under different chromatographic separation conditions.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides an alkyl functionalized column hexaarene stationary phase and a preparation method thereof, wherein the structural formula of the alkyl functionalized column hexaarene stationary phase is as follows:
example 1
(1) 2.2g of 1, 4-hydroquinone, 13.26g of 1-bromodecane, 3.36g of potassium hydroxide and 50ml of ethanol are taken to react for 8 hours at 83 ℃ to obtain a compound (I), wherein the compound (I) is 1, 4-bis (decyloxy) benzene, and the structural formula of the compound (I) is as follows:
(2) 2.00g (5.12 mmol) of the obtained compound (I), 0.153g (5.12 mmol) of paraformaldehyde, 0.726g (5.12 mmol) of boron trifluoride diethyl ether and 30mL of chlorocyclohexane are added into a 50mL single-neck flask, reacted at 35 ℃ for 4 hours, 30mL of deionized water is added, the organic phase is washed with 30mL of saturated saline, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 2.001g of green crude product, and the crude product is purified by column chromatography, wherein the eluent is petroleum ether: dichloromethane = 10:3 (V: V) to afford alkyl functionalized column hexaarene as a white solid: 0.420g of alkyl functionalized column hexaaromatics of the formula:
the characterization data are as follows: m.p.85.0-87.1 ℃. 1 H NMR(400MHz,CDCl 3 )δ:6.71(s,12H),3.98-3.58(m,36H),1.70(d,J＝6.7Hz,24H),1.43(s,24H),1.27(s,144H),0.89(t,J＝6.7Hz,36H).IR(KBr,cm -1 ):1054.76(C-O-C),1208.91(C-O-C),1408.09(C＝C),1473.23(C＝C),1502.22(C＝C),2851.39(CH 2 ),2920.23(CH 2 ),2955.29(CH 3 ).ESI-MS:m/z calcd for C 162 H 276 O 12 :2418.1；found:2418.3[M] + 。
As shown in FIG. 2, P6A-C10 is used as the stationary phase of capillary gas chromatographic column, and has high thermal stability up to 278 ℃.
According to the invention, 1, 4-hydroquinone is used as a raw material, a compound (I) is obtained through etherification reaction, and then an alkyl functionalized column hexaarene derivative P6A-C10 (shown in figure 1) is obtained through cyclization reaction of the compound (I), so that the whole experimental operation process has mild reaction conditions, low price of the raw material, novel structure of a stationary phase and obvious separation effect, and the obtained final product is stable and has good performance.
Example 2
(1) 2.2g of 1, 4-hydroquinone, 13.4g of 1-bromodecane, 3.4g of potassium hydroxide and 50ml of ethanol are taken to react for 7.5 hours at the temperature of 85 ℃ to obtain a compound (I), wherein the compound (I) is 1, 4-bis (decyloxy) benzene;
(2) 1.00g (2.56 mmol) of the obtained compound (I), 0.084g (2.82 mmol) of paraformaldehyde, 0.39g (2.75 mmol) of boron trifluoride diethyl ether and 15mL of chlorocyclohexane were charged into a 50mL single-necked flask, reacted at 35℃for 3.5 hours, 20mL of deionized water was added, the organic phase was washed with 20mL of saturated saline, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 1.01g of a green crude product, which was purified by column chromatography with petroleum ether as an eluent: dichloromethane = 10:3 (V: V), yielding alkyl functionalized column hexaaromatics: 0.191g.
Example 3
(1) 2.75g of 1, 4-hydroquinone, 17.12g of 1-bromodecane, 4.35g of potassium hydroxide and 62.5ml of ethanol are taken to react for 8.5 hours at 80 ℃ to obtain a compound (I), wherein the compound (I) is 1, 4-bis (decyloxy) benzene;
(2) 1.00g (2.56 mmol) of the obtained compound (I), 0.08g (2.69 mmol) of paraformaldehyde, 0.380g (2.68 mmol) of boron trifluoride diethyl ether and 15mL of chlorocyclohexane are added into a 50mL single-neck flask, reacted for 4 hours at 35 ℃,20 mL of deionized water is added, the organic phase is washed with 20mL of saturated saline, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 0.98g of green crude product, and the crude product is purified by column chromatography, wherein the eluent is petroleum ether: dichloromethane = 10:3 (V: V), yielding alkyl functionalized column hexaaromatics: 0.192g.
Example 4
The invention also provides a capillary chromatographic column which is prepared by adopting the alkyl functionalized column hexaarene stationary phase provided by the invention, and concretely, the capillary chromatographic column can be prepared by adopting a static method coating:
(1) A quartz capillary tube with the length of 5m and the inner diameter of 250 mu m is cut, firstly, the quartz capillary tube is washed for 10min by methylene dichloride, and then aged for 2-3h at 200 ℃ under the protection of nitrogen, so that impurities in the capillary column flow out along with the nitrogen at high temperature.
(2) 1.31g of the ground NaCl powder was weighed and placed in 10mL of an anhydrous methanol solution, and the mixture was stirred vigorously for 45 minutes to obtain a saturated sodium chloride methanol solution. Adding 6mL of saturated solution into 8mL of chloroform solution with strong stirring, adding 0.6mL of absolute methanol solution, stirring for 5min, adding 8mL of chloroform solution, and stirring for 2min to obtain saturated colloid solution.
(3) The saturated colloidal solution was pressed into the capillary under nitrogen pressure of 0.01-0.02 MPa. And then blowing out the solution in the column by using nitrogen, and recrystallizing for 3 hours at 200 ℃ under the protection of nitrogen to finish roughening the inner surface of the capillary column.
(4) The experiment adopts a static method to prepare a column, P6A-C10 is dissolved in methylene dichloride solution to prepare a fixed liquid with the concentration of 0.2% (w/v), and ultrasonic treatment is carried out for 5min to remove bubbles in the fixed liquid.
(5) Pushing the fixing liquid into the capillary chromatographic column by using a syringe until the fixing liquid fills the whole chromatographic column, sealing one end of the capillary tube, connecting the other end of the capillary tube with a vacuum system, slowly evaporating the solvent in a constant-temperature water bath at 40 ℃, and uniformly dispersing the fixing liquid on the inner wall of the capillary column.
(6) Aging the coated capillary chromatographic column under the protection of nitrogen by adopting a temperature programming method: maintaining at 40deg.C for 30min, and then heating to 180deg.C at a rate of 1deg.C/min for 7 hr to obtain capillary gas chromatographic column.
According to the invention, P6A-C10 is used as the stationary phase of the capillary gas chromatographic column for the first time, and the P6A-C10 perfectly combines the advantages of the structural characteristics of column hexaarene and alkyl functionalization, so that the novel material is used as the stationary phase of the capillary gas chromatographic column, and a richer separation material is provided for the research of chromatographic separation.
As shown in FIG. 2, which is a thermogravimetric analysis diagram of an alkyl functionalized column hexaarene stationary phase, the invention uses P6A-C10 as the stationary phase of a capillary gas chromatographic column for the first time, and the heat stability is good and is up to 278 ℃.
The alkyl functionalized column hexaarene P6A-C10 stationary phase prepared by the invention has good effect in practical application due to the functional groups such as a column ring and an alkoxy chain of the stationary phase, and has various weak interaction forces with different analytes, wherein the method comprises the following steps: van der Waals force, hydrogen bond, pi-pi interaction, dipole-dipole interaction, CH-pi interaction and the like, thus the P6A-C10 column has good separation effect, and can be used for separating substituted benzaldehyde isomers, 12 groups of cis-trans isomers, 21 groups of complex mixtures, halogenated benzene isomers, mixed alkanes, mixed esters and mixed alcohols.
< separation Effect >
In order to analyze the separation effect of the capillary chromatographic column, the capillary chromatographic column provided by the invention is subjected to the following experiment:
(1) As shown in fig. 3, the Golay curve of n-dodecane was measured using the capillary gas chromatography column prepared in example 4, and the specific chromatographic conditions were: column box temperature 120 ℃, carrier gas: nitrogen, carrier gas flow rate: 0.3mL/min, the lowest theoretical plate height is: 0.31mm.
The invention selects P6A-C10 as a chromatographic separation stationary phase, and the capillary gas chromatographic column prepared by a static coating method has higher column efficiency.
(2) Separation of xylene isomers:
xylene isomers were selected as the analytes of separation (fig. 4), including o-xylene, m-xylene, p-xylene, chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 60℃at a heating rate of 5℃per min, and the carrier gas flow rate was 0.4mL/min. The capillary gas chromatography column prepared in example 4 was able to separate the substituted xylene isomers and was superior in effect to the polysiloxane commercial columns DB-17, HP-5 and HP-35 and the polyethylene glycol commercial column PEG-20M.
(3) Separating the substituted benzaldehyde isomer:
different benzaldehyde isomers were selected as separate analytes (fig. 5), including the methylbenzaldehyde isomer: o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde and bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min. The capillary gas chromatography column prepared in example 4 was able to separate the substituted benzaldehyde isomer and had better effect than the polysiloxane commercial columns DB-17, HP-5 and HP-35 and the polyethylene glycol commercial column PEG-20M.
(4) Separation of the halogenated benzene isomers:
3 different types of halogenated benzene isomers of different polarities were selected as separate analytes, including chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene, p-chlorotoluene; dibromobenzene isomers: o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
FIG. 6 is a chromatogram of the separation of the halogenated benzene isomers by the capillary gas chromatography column prepared in example 4, showing that the halogenated benzene isomers can be effectively separated, and the effect is superior to that of the polysiloxane commercial columns DB-17, HP-5 and HP-35 and the polyethylene glycol commercial column PEG-20M.
(5) Separation of 12 sets of cis and trans isomers:
12 groups of cis-trans isomers with different polarities are selected as analytes, and the isomers are separated by adopting a capillary gas chromatographic column prepared by the embodiment, wherein chromatographic separation conditions are as follows: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
FIG. 7 is a chromatogram of a capillary gas chromatography column prepared in example 4 separating 12 sets of cis-trans isomers of different polarity, wherein a: cis-2, 5-dimethyltetrahydrofuran and trans-2, 5-dimethyltetrahydrofuran, b: cis-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dimethoxytetrahydrofuran, c: cis-25-dihydro-25-dimethoxyfuran and trans-25-dihydro-25-dimethoxyfuran, d: cis-2-methyl-4-propyl-1, 3-oxathiolane and trans-2-methyl-4-propyl-1, 3-oxathiolane, e: cis-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran and trans-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran, f: cis-nerolidol and trans-nerolidol, g: cis-3, 7-dimethyl-2, 6-octadien-1-ol and trans-3, 7-dimethyl-2, 6-octadien-1-ol, h: cis-decalin and trans-decalin, i: cis-methyl dihydrojasmonate and trans-methyl dihydrojasmonate, j: cis-crotonyl chloride and trans-crotonyl chloride, k: cis- α -amyl cinnamic aldehyde and trans- α -amyl cinnamic aldehyde, l: cis-4-tert-butylcyclohexanol and trans-4-tert-butylcyclohexanol. As shown in FIG. 7, the capillary gas chromatographic column prepared in example 4 can completely separate each group of cis-trans isomers, and has the advantage of separating the cis-trans isomers by the P6A-C10 stationary phase, and is rapid and efficient in separation.
(6) Separation 21 of a complex mixture of components:
a complex mixture of 21 components was selected as the analyte and the sample was separated using the capillary gas chromatography column prepared in example 4. Chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min.
Fig. 8 is a chromatogram of a capillary gas chromatography column separating a 21-component complex mixture, wherein 1: 2-heptanone, 2: 1-heptanol, 3: 1-bromohexane, 4: n-butylbenzene, 5: 1-octanol, 6: o-chloroaniline, 7: n-dodecane, 8:1,2, 3-trichlorobenzene, 9: o-bromoaniline, 10: 1-decanol, 11: methyl decanoate, 12: m-chloronitrobenzene, 13: 1-methylnaphthalene, 14: n-tetradecane, 15: methyl undecanoate, 16: m-bromonitrobenzene, 17: 1-dodecanol, 18:2, 3-dimethylnaphthalene, 19: p-chloronitrobenzene, 20: n-hexadecane, 21: 1-bromododecane. The capillary gas chromatographic column prepared in example 4 has good separation effect on the complex mixture of 21 components, more types of analytes and wider polarity range, shows good characteristics of the P6A-C10 stationary phase suitable for separating the complex mixture, and has better effect than polysiloxane commodity columns DB-17, HP-5 and HP-35 and polyethylene glycol commodity column PEG-20M.
(7) Separation of halogenated aniline isomers
3 haloaniline isomers were selected as analytes, including chloroaniline isomers: o-chloroaniline, m-chloroaniline, p-chloroaniline; bromoaniline isomers: o-bromoaniline, m-bromoaniline, p-bromoaniline; iodoaniline isomers: o-iodoaniline, m-iodoaniline, p-iodoaniline. The samples were separated using the capillary gas chromatography column prepared in example 4. Chromatographic separation conditions: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, the carrier gas flow rate is 0.6mL/min, and as shown in figure 9, the P6A-C10 chromatographic column prepared by the invention can separate halogenated aniline isomers, and the effect is superior to that of polysiloxane commodity columns DB-17, HP-5 and HP-35 and polyethylene glycol commodity column PEG-20M.
(8) Good film forming property
FIG. 10 is a Scanning Electron Microscope (SEM) of a capillary gas chromatography column prepared according to the invention, exhibiting good film forming properties for the P6A-C10 stationary phase.
The alkyl functionalized column hexaarene derivative P6A-C10 prepared by the invention combines the unique molecular recognition capability and alkyl functionalization advantages of the column arene, and mutually compensates the respective defects, wherein the column hexaarene has good rigidity, free adjustment and pi-electron rich column ring flexibility and certain induced fit capability, so that guest molecules can be recognized, but the defects of high melting point, poor film forming property and the like; the advantage of easy functionalization of the column arene makes it possible to improve the properties of the column arene as a stationary phase for gas chromatography by introducing long alkoxy chains along the lower edge of the column arene, which can reduce the melting point of the column arene, increase the film forming properties of the column arene and the separation properties of the column arene as a chromatographic fixation relative to the target compound.
Comparative example 1 ]
Xylene isomers were separated separately using the capillary gas chromatography column prepared in example 4 and the capillary gas chromatography column prepared using the amino-functionalized column pentaarene stationary phase.
Xylene isomers were selected as the analytes of separation (fig. 11), including ortho-xylene, meta-xylene, para-xylene, chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 60℃at a heating rate of 5℃per min, and the carrier gas flow rate was 0.4mL/min. As can be seen from fig. 11, the capillary gas chromatography column prepared in example 4 was capable of separating xylene isomers, but the capillary gas chromatography column prepared from the amino-functionalized pentaarene stationary phase was not capable of separating xylene isomers. This is related to the feature that the column hexaaromatics possess more repeat aromatic units and a larger pi-conjugated cavity than the column pentaaromatics, which can capture a larger aromatic guest.
Comparative example 2 ]
The haloaniline isomers were separated separately using the capillary gas chromatography column prepared in example 4 and the capillary gas chromatography column prepared using the amino-functionalized column pentaarene stationary phase.
As shown in fig. 12, 3 haloaniline isomers were selected as analytes, including chloroaniline isomers: o-chloroaniline, m-chloroaniline, p-chloroaniline; bromoaniline isomers: o-bromoaniline, m-bromoaniline, p-bromoaniline; iodoaniline isomers: o-iodoaniline, m-iodoaniline, p-iodoaniline. The samples were separated using the capillary gas chromatography column prepared in the examples. Chromatographic separation conditions: the temperature is maintained at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, the carrier gas flow rate is 0.6mL/min, as shown in figure 12, the P6A-C10 chromatographic column prepared by the invention can separate halogenated aniline isomers, and the effect is superior to that of a capillary gas chromatographic column prepared by an amino functionalized column pentaarene stationary phase, which is related to that the column hexaarene has more repeated aromatic units and a larger pi-conjugated cavity compared with the column pentaarene.
Comparative example 3 ]
And (3) performing separation tests on xylene isomers, chlorotoluene isomers and bromobenzaldehyde isomers by using capillary gas chromatographic columns prepared from column hexaaromatics with different alkoxy chain lengths.
The capillary gas chromatographic columns adopted in the separation test are a P6A-C10 chromatographic column, a P6A-C4 chromatographic column and a P6A-C2 chromatographic column, wherein the P6A-C10 chromatographic column is the capillary gas chromatographic column prepared in the embodiment 4 of the invention. P6A-C4 and P6A-C2 were synthesized according to the literature (J.Cao, Y. -H.Shang, B.Qi, X. -Z.Sun, L.Zhang, H. -W.Liu, H. -B.Zhang and X.H.Zhou, rsc adv.,2015,5,9993) and were coated according to the static method in the present invention to prepare P6A-C4 and P6A-C2 columns.
As shown in fig. 13, (a) is to select xylene isomers as the separated analytes, wherein the separation conditions include o-xylene, m-xylene, p-xylene, and chromatography: the temperature was maintained at 40℃for 1min, the temperature was raised to 60℃at a heating rate of 5℃per min, and the carrier gas flow rate was 0.4mL/min. As can be seen from part (a) of FIG. 13, the P6A-C10 column can accurately separate xylene isomers, but neither the P6A-C4 column nor the P6A-C2 column can effectively separate xylene isomers, which is related to the fact that longer decyloxy chains better improve physicochemical properties of column aromatics including film forming property and melting point to meet the requirements of a gas chromatography stationary phase, and meanwhile, have more abundant acting force among analyte molecules in chromatographic separation.
As shown in fig. 13, (b) is to select chlorotoluene isomers as the separated analytes, wherein the analytes include o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, chromatographic analysis conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min. As is clear from FIG. 13, the P6A-C10 column is capable of separating the chlorotoluene isomer, but neither the P6A-C4 column nor the P6A-C2 column is capable of separating the chlorotoluene isomer.
As shown in fig. 13, (c) to select bromobenzaldehyde isomers as the isolated analytes, wherein bromobenzaldehyde isomers are included: o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde, and chromatographic analysis conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min. As is clear from FIG. 13, the P6A-C10 column is capable of separating bromobenzaldehyde isomers, but neither the P6A-C4 column nor the P6A-C2 column is capable of separating bromobenzaldehyde isomers.
Comparative example 4 ]
And (3) performing separation tests on the mixed alkane, the mixed ester and the mixed alcohol by using capillary gas chromatographic columns prepared from column hexaaromatics with different alkoxy chain lengths.
The capillary gas chromatographic columns used in the separation test are P6A-C10 chromatographic columns, P6A-C4 chromatographic columns and P6A-C2 chromatographic columns, respectively, wherein the P6A-C10 chromatographic columns are the capillary gas chromatographic columns prepared in example 4.
As shown in fig. 14, (a) is to select mixed alkanes as the separated analytes, which include n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, chromatographic separation conditions: the temperature was kept at 60℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min. As is clear from FIG. 14, the P6A-C10 column is capable of separating mixed alkanes and has better effect than the P6A-C4 column and the P6A-C2 column.
As shown in fig. 14, (b) is to select a mixed ester as the isolated analyte, which includes methyl valerate, methyl caproate, methyl heptanoate, methyl caprylate, methyl pelargonate, methyl caprate, methyl undecanoate, methyl laurate, chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min. As can be seen from FIG. 14, the P6A-C10 column is capable of separating mixed esters and is superior to the P6A-C4 column and the P6A-C2 column.
As shown in fig. 14, (c) for selecting a mixed alcohol as the analyte of separation, including 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, chromatographic separation conditions: the temperature was maintained at 40℃for 1min, the temperature was raised to 160℃at a heating rate of 10℃per min, and the carrier gas flow rate was 0.6mL/min. As is clear from FIG. 14, the P6A-C10 column is capable of separating mixed alcohols and has better effect than the P6A-C4 column and the P6A-C2 column.
Comparative example 5]
The column effect of the capillary gas chromatographic column is prepared by adopting column hexaaromatics with different alkoxy chain lengths.
FIG. 15 shows the column effect (Golay curve) of the capillary gas chromatography columns of the invention, P6A-C10, P6A-C4 and P6A-C2, using n-dodecane as the probe compound, at 120 ℃. The P6A-C10 capillary gas chromatographic column has higher column efficiency.
Comparative example 6]
Chromatographic separation conditions for xylene isomers
As shown in FIG. 16, (a) shows the separation of different types of xylene isomers with different polarities when the capillary gas chromatographic column (i.e., P6A-C10 chromatographic column) prepared in the embodiment of the invention is kept at 40℃for 1min under the condition of different stationary phase concentrations, and the temperature rise rate of 5℃per min is raised to 60℃and the carrier gas flow rate of 0.4mL/min. According to the results of the separation test, the separation effect of the paraxylene isomer is good and the separation is faster when the stationary phase concentration is 0.2% w/v, and the combined effect is better than when the stationary phase concentration is 0.1% w/v and 0.3% w/v.
(b) In the P6A-C10 chromatographic column, the concentration of the stationary phase is kept at 0.2% w/v, the stationary phase is kept at 40 ℃ for 1min, the temperature is increased to 60 ℃ at the heating rate of 5 ℃/min, and the separation of paraxylene isomers is carried out under different carrier gas flow rates. Wherein, when the carrier gas flow rate is 0.4mL/min, the separation effect of the paraxylene isomer is best and better than that when the carrier gas flow rate is 0.3mL/min, 0.5mL/min, 0.6mL/min and 0.7 mL/min.
(c) In the P6A-C10 chromatographic column, the concentration of a stationary phase is kept at 0.2% w/v, the stationary phase is kept at 40 ℃ for 1min, the temperature is raised to 60 ℃ at different heating rates, the flow rate of carrier gas is 0.4mL/min, according to experimental results, the separation effect of the paraxylene isomer is good and the separation is quicker when the heating rate is 5 ℃/min, and the comprehensive effect is better than the separation effect of the paraxylene isomer when the heating rate is 1 ℃/min, 2 ℃/min, 3 ℃/min, 10 ℃/min and 15 ℃/min.
As is apparent from the above, the conditions for chromatographic separation of xylene isomers of different polarities were maintained at 40℃for 1min, and the temperature was raised to 60℃at a heating rate of 5℃per min, with a carrier gas flow rate of 0.4mL/min.
It should be noted that the above embodiments are only for illustrating the present invention, but the present invention is not limited to the above embodiments, and any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention falls within the protection scope of the present invention.
Claims (8)
1. An alkyl functionalized column hexaarene stationary phase, characterized in that: the chemical formula of the alkyl functionalized column hexaarene stationary phase is P6A-C10, and the chemical structural formula is:
2. a method of preparing the alkyl functionalized column hexaarene stationary phase according to claim 1, comprising the steps of:
1) Carrying out etherification reaction on 1, 4-hydroquinone, 1-bromodecane, potassium hydroxide and ethanol to obtain 1, 4-bis (decyloxy) benzene;
2) And (3) taking 1, 4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride diethyl etherate and chlorocyclohexane for cyclization reaction, and carrying out aftertreatment and purification on the reacted product to obtain the alkyl functionalized column hexaarene.
3. The method for preparing an alkyl functionalized column hexaarene stationary phase according to claim 2, wherein in step 1): the reaction temperature is 80-85 ℃; the reaction time is 7.5-8.5h; the addition ratio of 1, 4-hydroquinone to 1-bromodecane, potassium hydroxide and ethanol was 1.1g:6.63 to 6.85g:1.68 to 1.74g:25mL.
4. The method for preparing an alkyl functionalized column hexaarene stationary phase according to claim 2, wherein in step 2): the reaction temperature is 35 ℃; the reaction time is 3-4 h; the addition ratio of 1, 4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride etherate and chlorocyclohexane was 2.00g: 0.153-0.169 g: 0.726-0.799 g:30mL.
5. The method for preparing an alkyl functionalized column hexaarene stationary phase according to claim 2, wherein in step 2): column chromatography was used for purification, and petroleum ether in eluent: the volume ratio of dichloromethane is 10:3.
6. A capillary gas chromatography column prepared from the alkyl functionalized column hexaarene stationary phase of claim 1;
the capillary gas chromatographic column is prepared by static coating.
7. Use of the capillary gas chromatography column according to claim 6, wherein: the capillary gas chromatographic column is used for separating xylene isomer, substituted benzaldehyde isomer, 12 groups of cis-trans isomers, 21 groups of complex mixtures, halogenated benzene isomer, halogenated aniline isomer, mixed alkane, mixed ester and mixed alcohol; the xylene isomers are ortho-xylene, meta-xylene and para-xylene;
the substituted benzaldehyde isomers are methylbenzaldehyde isomers and bromobenzaldehyde isomers, wherein the methylbenzaldehyde isomers are o-methylbenzaldehyde, m-methylbenzaldehyde and p-methylbenzaldehyde; the bromobenzaldehyde isomers are o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde;
the 12 cis-trans isomers are cis-2, 5-dimethyltetrahydrofuran and trans-2, 5-dimethyltetrahydrofuran, cis-2, 5-dimethoxytetrahydrofuran and trans-2, 5-dimethoxytetrahydrofuran, cis-25-dihydro-25-dimethoxyfuran and trans-25-dihydro-25-dimethoxyfuran, cis-2-methyl-4-propyl-1, 3-oxathiacyclohexane and trans-2-methyl-4-propyl-1, 3-oxathiacyclohexane, cis-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran and trans-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran, cis-nerolidol and trans-nerolidol, cis-3, 7-dimethyl-2, 6-octadien-1-ol and trans-3, 7-dimethyl-2, 6-octadien-1-ol, cis-decahydrojasmonate and trans-4-propyl-1, cis-decahydrojasmonate and trans-dihydrojasmonate, cis-4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran and trans-nerolidol and trans-4-t-butyl-alpha-butyl aldehyde;
the 21-component complex mixture consists of the following components: 2-heptanone, 1-heptanol, 1-bromohexane, n-butylbenzene, 1-octanol, o-chloroaniline, n-dodecane, 1,2, 3-trichlorobenzene, o-bromoaniline, 1-decanol, methyl decanoate, m-chloronitrobenzene, 1-methylnaphthalene, n-tetradecane, methyl undecanoate, m-bromonitrobenzene, 1-dodecanol, 2, 3-dimethylnaphthalene, p-chloronitrobenzene, n-hexadecane and 1-bromododecane;
the halogenated benzene isomers are chlorotoluene isomers and dibromobenzene isomers, wherein the chlorotoluene isomers are o-chlorotoluene, m-chlorotoluene and p-chlorotoluene; the dibromobenzene isomer is o-dibromobenzene, m-dibromobenzene and p-dibromobenzene; the halogenated aniline isomers are chloroaniline isomers, bromoaniline isomers and iodoaniline isomers: wherein the chloroaniline isomer is o-chloroaniline, m-chloroaniline and p-chloroaniline; the bromoaniline isomer is o-bromoaniline, m-bromoaniline and p-bromoaniline; the iodoaniline isomer is o-iodoaniline, m-iodoaniline and p-iodoaniline;
the mixed alkane is n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane;
the mixed ester is methyl valerate, methyl caproate, methyl heptanoate, methyl caprylate, methyl pelargonate, methyl caprate, methyl undecanoate and methyl laurate;
the mixed alcohols are 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol and 1-dodecanol.
8. The use of a capillary gas chromatography column according to claim 7, wherein: the chromatographic separation condition of the para-xylene isomer of the capillary gas chromatographic column is kept at 40 ℃ for 1min, the temperature is raised to 60 ℃ at the heating rate of 5 ℃/min, and the carrier gas flow rate is 0.4mL/min.
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