CN115636737A - Alkyl functionalized column hexaaromatic hydrocarbon stationary phase, capillary gas chromatographic column, and preparation method and application thereof - Google Patents
Alkyl functionalized column hexaaromatic hydrocarbon stationary phase, capillary gas chromatographic column, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115636737A CN115636737A CN202211214480.2A CN202211214480A CN115636737A CN 115636737 A CN115636737 A CN 115636737A CN 202211214480 A CN202211214480 A CN 202211214480A CN 115636737 A CN115636737 A CN 115636737A
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- Prior art keywords
- column
- isomers
- methyl
- stationary phase
- trans
- Prior art date
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Links
- 230000005526 G1 to G0 transition Effects 0.000 title claims abstract description 61
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 39
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000003738 xylenes Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 13
- MMGPQYJNRFGRQK-UHFFFAOYSA-N 1,4-didecoxybenzene Chemical compound CCCCCCCCCCOC1=CC=C(OCCCCCCCCCC)C=C1 MMGPQYJNRFGRQK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000006266 etherification reaction Methods 0.000 claims abstract description 4
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 4
- 238000003965 capillary gas chromatography Methods 0.000 claims description 47
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 24
- 239000012159 carrier gas Substances 0.000 claims description 24
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 23
- 238000013375 chromatographic separation Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 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
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 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
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical class CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 claims description 12
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 12
- 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
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical class BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- -1 polyhexamethylene Polymers 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 150000003935 benzaldehydes Chemical class 0.000 claims description 9
- 150000001555 benzenes Chemical class 0.000 claims description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 9
- 229940094933 n-dodecane Drugs 0.000 claims description 9
- 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
- 238000000746 purification Methods 0.000 claims description 7
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-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
- 150000001298 alcohols Chemical class 0.000 claims description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 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
- 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
- 239000005640 Methyl decanoate Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 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
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical compound 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
- 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
- 230000035484 reaction time Effects 0.000 claims description 4
- CZCBTSFUTPZVKJ-ZJUUUORDSA-N (2R,4R)-rose oxide Chemical compound C[C@@H]1CCO[C@@H](C=C(C)C)C1 CZCBTSFUTPZVKJ-ZJUUUORDSA-N 0.000 claims description 3
- 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
- OXMIDRBAFOEOQT-PHDIDXHHSA-N (2r,5r)-2,5-dimethyloxolane Chemical compound C[C@@H]1CC[C@@H](C)O1 OXMIDRBAFOEOQT-PHDIDXHHSA-N 0.000 claims description 3
- 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-SDNWHVSQSA-N (6E)-nerolidol Chemical compound CC(C)=CCC\C(C)=C\CCC(C)(O)C=C FQTLCLSUCSAZDY-SDNWHVSQSA-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-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 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
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 3
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 3
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 claims description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 3
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000005641 Methyl octanoate Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 16
- 238000004587 chromatography analysis Methods 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 230000003993 interaction Effects 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012491 analyte Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 4
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001612 separation test Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000005171 halobenzenes Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GLZPCOQZEFWAFX-YFHOEESVSA-N (Z)-Geraniol Chemical compound CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- CCOQPGVQAWPUPE-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-ol Chemical compound CC(C)(C)C1CCC(O)CC1 CCOQPGVQAWPUPE-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- GKGOLPMYJJXRGD-HTQZYQBOSA-N (2r,4r)-2-methyl-4-propyl-1,3-oxathiane Chemical compound CCC[C@@H]1CCO[C@@H](C)S1 GKGOLPMYJJXRGD-HTQZYQBOSA-N 0.000 description 1
- GKGOLPMYJJXRGD-JGVFFNPUSA-N (2s,4r)-2-methyl-4-propyl-1,3-oxathiane Chemical compound CCC[C@@H]1CCO[C@H](C)S1 GKGOLPMYJJXRGD-JGVFFNPUSA-N 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N (E)-Geraniol Chemical compound CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- RJUIDDKTATZJFE-NSCUHMNNSA-N (e)-but-2-enoyl chloride Chemical compound C\C=C\C(Cl)=O RJUIDDKTATZJFE-NSCUHMNNSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- SFPQFQUXAJOWNF-UHFFFAOYSA-N 1,3-diiodobenzene Chemical compound IC1=CC=CC(I)=C1 SFPQFQUXAJOWNF-UHFFFAOYSA-N 0.000 description 1
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- 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
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 1
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- NNBZCPXTIHJBJL-AOOOYVTPSA-N cis-decalin Chemical compound C1CCC[C@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-AOOOYVTPSA-N 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 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
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- 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
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An alkyl functionalized column hexaaromatic hydrocarbon stationary phase, a capillary gas chromatographic column and a preparation method and application thereof, and belongs to the technical field of chromatographic analysis, wherein the chemical formula of the alkyl functionalized column hexaaromatic hydrocarbon stationary phase is P6A-C10, the invention uses 1,4-hydroquinone as a raw material, firstly 1,4-bis (decyloxy) benzene is obtained through etherification reaction, and secondly 1,4-bis (decyloxy) benzene is subjected to cyclization reaction to obtain the alkyl functionalized column hexaaromatic hydrocarbon derivative P6A-C10, the reaction conditions in the whole experimental operation process are mild, the price of the used raw material is low, the structure of the stationary phase is novel, the separation effect is obvious, and the obtained final product is stable and has good performance. The capillary gas chromatographic column prepared by the alkyl functionalized column hexaaromatic stationary phase can solve the problem of poor separation performance of the column aromatic against 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 hexaaromatic hydrocarbon stationary phase, a capillary gas chromatographic column, and preparation and application thereof.
Background
The pillared arenes, consisting of 1,4-dialkoxybenzene units linked by methylene bridges at the 2-and 5-positions, are of great interest in supramolecular and material chemistry due to the unique columnar backbone and precise cavity. In addition, the column arenes are also easy to synthesize and to functionalize with different substituents, and the synthesis, functionalization, host-guest properties and potential applications of column arenes have been extensively studied to date.
The appearance of capillary gas chromatography is a milestone in the development of gas chromatography, and has been widely applied to sample analysis in various fields due to the advantages of high sensitivity, high selectivity, short analysis time, low cost and the like.
For chromatographic separation in a capillary gas phase column, baseline separation of components in a sample is favorable for analyzing the accuracy of sample determination, and the development of a high-performance stationary phase is the key to obtain high resolution of a complex sample. The stationary phase generally requires the fundamental characteristics of high chemical and thermal stability, proper viscosity, low vapor pressure, and good film-forming property. However, with the continuous development of science and technology, the structure of the sample to be separated is more and more complex, and the difficulty of separating the sample is more and more large.
Reference 1: chinese patent publication No. CN114276257 a.
Reference 2: chinese patent publication No. CN113075346 a.
Disclosure of Invention
The invention aims to solve the problem of poor separation performance of the aromatic hydrocarbon in the prior art for xylene isomers and halogenated aniline, and provides an alkyl functionalized hexaaromatic hydrocarbon column 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 specific scheme that: an alkyl functionalized column hexaaromatic stationary phase, the chemical formula of the alkyl functionalized column hexaaromatic stationary phase is P6A-C10, and the chemical structural formula is as follows:
a preparation method of an alkyl functionalized column hexaaromatic stationary phase comprises the following steps:
1) Taking 1,4-hydroquinone, carrying out etherification reaction with 1-bromodecane, potassium hydroxide and ethanol to obtain 1,4-bis (decyloxy) benzene;
2) And (3) performing cyclization reaction on 1,4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride diethyl etherate and chlorocyclohexane, and performing post-treatment and purification on a product after the reaction to obtain the alkyl functionalized pillared 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 to 8.5 hours; 1,4-hydroquinone with 1-bromodecane, potassium hydroxide and ethanol were added in a ratio of 1.1g: 6.63-6.85 g: 1.68-1.74 g: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;1,4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride diethyl etherate, chlorocyclohexane were added in a ratio of 2.00g: 0.153-0.169 g:0.726 to 0.799g:30mL.
As a further optimization of the above technical solution, in step 2): column chromatography was used for purification, and petroleum ether: the volume ratio of dichloromethane is 10.
A capillary gas chromatography column is prepared from the alkyl functionalized column hexaaromatic hydrocarbon stationary phase.
As the further optimization of the technical scheme, the preparation method of the capillary gas chromatographic column is coating by a static method.
One such use is for a capillary gas chromatography column capable of separating xylene isomers, substituted benzaldehyde isomers, group 12 cis-trans isomers, group 21 complex mixtures, halogenated benzene isomers, halogenated aniline isomers, mixed alkanes, mixed esters and mixed alcohols.
As a further optimization of the above-mentioned technical solution,
the xylene isomers include ortho-xylene, meta-xylene, and para-xylene;
the substituted benzaldehyde isomers comprise methyl benzaldehyde isomers and bromobenzaldehyde isomers, wherein the methyl benzaldehyde isomers comprise o-methyl benzaldehyde, m-methyl benzaldehyde and p-methyl benzaldehyde; bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde;
the 12 sets of cis-trans isomers include 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-oxathiolane and trans-2-methyl-4-propyl-1,3-oxathiolane, 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-octadiene-1-ol and trans-35zxft 3579-cyclohexanol and trans-methyl cinnamate-3579-methyl cinnamate and trans-crotonaldehyde and cis-4-tert-butylcrotonyl chloride;
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 chlorotoluene isomers and dibromobenzene isomers, wherein the chlorotoluene isomers comprise o-chlorotoluene, m-chlorotoluene and p-chlorotoluene; the dibromobenzene isomers comprise o-dibromobenzene, m-dibromobenzene and p-dibromobenzene;
the halogenated aniline isomers include chloroaniline isomers, bromoaniline isomers and iodoaniline isomers: wherein the chloroaniline isomers comprise o-chloroaniline, m-chloroaniline and p-chloroaniline; the bromoaniline isomers comprise o-bromoaniline, m-bromoaniline and p-bromoaniline; the iodoaniline isomers include o-iodoaniline, m-iodoaniline and p-iodoaniline;
the mixed alkane is: including n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane;
the mixed esters include methyl valerate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, and methyl dodecanoate;
the mixed alcohol includes 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 p-xylene isomer in the capillary gas chromatographic column is that the temperature is kept for 1min at 40 ℃, the temperature is raised to 60 ℃ at the temperature rise rate of 5 ℃/min, and the flow rate of carrier gas is 0.4mL/min.
Compared with the prior art, the invention has the following beneficial effects:
the capillary chromatographic column is prepared by the alkyl functionalized column hexaaromatic stationary phase, the p-xylene isomer and the halogenated aniline isomer have better separation effect, and the complete separation of each component in the p-xylene isomer mixture and the halogenated aniline isomer mixture (the separation degree is more than 1.5) can be realized. For host-guest chemistry, weak interactions play an important role, and the pillared arenes and their derivatives can selectively recognize organic guest molecules through non-covalent interactions (such as van der waals forces, pi-pi and hydrogen bonding interactions). The reason why the pillar arene and the derivatives thereof can selectively recognize the organic guest molecule includes the following two aspects: on the one hand, almost all organic guest molecules contain C-H groups, and the C-H … pi interaction between them is ubiquitous; on the other hand, the C-H … pi interaction is weaker than the classical hydrogen bonding interaction, and therefore, the pillared arenes and their derivatives are more suitable for recognizing some organic guest molecules with slightly different structures and properties. In addition, the pillared aromatics have a highly symmetric and rigid pillar structure, the number of repeating aromatic units defines the cavity size of the pillared aromatics, and they can selectively capture specific guests appropriate for their size in nanoscale space. The alkyl functionalized column hexaarene is a derivative of the column hexaarene, and the derivatized decyl alkoxy group effectively improves the film-forming property of the column arene and reduces the melting point, so that the alkyl functionalized column hexaarene can meet the requirements of a gas chromatography stationary phase, and simultaneously, the acting force between a stationary phase and an analyte is enriched in the chromatographic separation. Therefore, the alkyl functionalized column hexaaromatic stationary phase is utilized in the invention to solve the separation difficulty including xylene isomers.
Drawings
FIG. 1 is a reaction scheme of an alkyl functionalized pillared hexaarenes P6A-C10 prepared from 1,4-hydroquinone as a starting material in accordance with the present invention;
FIG. 2 is a thermogravimetric analysis of an alkyl functionalized column hexaaromatic stationary phase;
FIG. 3 is a graph of the column efficiency (Golay curve) of a capillary gas chromatography column made according to the present invention measured with n-dodecane as a probe compound at 120 ℃;
FIG. 4 is a capillary gas chromatography column made in accordance with the present invention for separating xylene isomers of different polarities: o-xylene, M-xylene, p-xylene, against commercial columns DB-17, HP-5, HP-35, and PEG-20M;
FIG. 5 is a capillary gas chromatography column prepared according to the present invention for separating tolualdehyde isomers of different polarities: o-methyl benzaldehyde, m-methyl benzaldehyde, p-methyl benzaldehyde and bromobenzaldehyde isomers: o-bromobenzaldehyde, M-bromobenzaldehyde and p-bromobenzaldehyde, which are separated from commercial columns DB-17, HP-5, HP-35 and PEG-20M in comparison;
FIG. 6 shows the capillary gas chromatography column separation of halogenated benzene isomers according to the present invention, which includes chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene and p-chlorotoluene; dibromobenzene isomer: o-dibromobenzene, M-dibromobenzene, p-dibromobenzene, against 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 a capillary gas chromatography column according to the present invention;
FIG. 8 is a sample of a complex mixture of 21 components of different polarity and type separated by a capillary gas chromatography column according to the present invention, in comparison to commercial columns DB-17, HP-5, HP-35 and PEG-20M;
FIG. 9 is a control of the capillary gas chromatography column separation of halogenated aniline isomers from commercial columns DB-17, HP-5, HP-35 and PEG-20M made in accordance with the present invention;
FIG. 10 is a Scanning Electron Micrograph (SEM) of a capillary gas chromatography column made according to the present invention, demonstrating the good film-forming properties of the P6A-C10 stationary phase.
FIG. 11 is a capillary gas chromatography column made in accordance with the present invention for separating xylene isomers of different polarities: o-xylene, m-xylene, p-xylene, and capillary gas chromatographic column separation control prepared from amino functionalized pentaaromatic hydrocarbon stationary phase;
FIG. 12 is a capillary gas chromatography column separation of haloaniline isomers made in accordance with the present invention, as compared to capillary gas chromatography column separations made using an amino-functionalized pentaarene stationary phase;
FIG. 13 is a diagram of a capillary gas chromatography column made of column hexaarenes of different alkoxy chain lengths for the separation of xylene isomers, chlorotoluene isomers, and bromobenzaldehyde isomers;
FIG. 14 is a capillary gas chromatography column made of column hexaarenes of different alkoxy chain lengths for separation of mixed alkanes, mixed esters, and mixed alcohols;
FIG. 15 is a plot of column efficiency (Golay curves) for capillary gas chromatography columns made from column hexaarenes of varying alkoxy chain lengths;
FIG. 16 is a graph of xylene isomers separated under different chromatographic separation conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an alkyl functionalized column hexaaromatic hydrocarbon stationary phase and a preparation method thereof, wherein the structural formula of the alkyl functionalized column hexaaromatic hydrocarbon stationary phase is as follows:
example 1
(1) Taking 2.2g of 1,4-hydroquinone, 13.26g of 1-bromodecane, 3.36g of potassium hydroxide and 50ml of ethanol to react for 8h 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) Adding the obtained 2.00g (5.12 mmol) of compound (I), 0.153g (5.12 mmol) of paraformaldehyde, 0.726g (5.12 mmol) of boron trifluoride diethyl etherate and 30mL of chlorocyclohexane into a 50mL single-neck flask, reacting at 35 ℃ for 4 hours, adding 30mL of deionized water, washing an organic phase with 30mL of saturated saline solution, drying over anhydrous magnesium sulfate, filtering, evaporating to dryness to obtain 2.001g of a green crude product, and performing column chromatography purification, wherein an eluent is petroleum ether: dichloromethane =10 (V: V), yielding an alkyl functionalized pillared hexaarene white solid: 0.420g, the structural formula of the alkyl functionalized pillared hexaarene is:
the characterization data are as follows: m.p.85.0-87.1 deg.C. 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 has good thermal stability as high as 278 ℃ as the stationary phase of the capillary gas chromatographic column.
The method takes 1,4-hydroquinone as a raw material, firstly obtains a compound (I) through etherification reaction, and then obtains an alkyl functionalized column hexaarene derivative P6A-C10 (shown as a figure 1) through cyclization reaction of the compound (I).
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 7.5h at 85 ℃ to obtain a compound (I), wherein the compound (I) is 1,4-bis (decyloxy) benzene;
(2) Adding 1.00g (2.56 mmol) of the compound (I), 0.084g (2.82 mmol) of paraformaldehyde, 0.39g (2.75 mmol) of boron trifluoride diethyl etherate and 15mL of chlorocyclohexane into a 50mL single-neck flask, reacting at 35 ℃ for 3.5h, adding 20mL of deionized water, washing an organic phase with 20mL of saturated saline solution, drying over anhydrous magnesium sulfate, filtering, evaporating to dryness to obtain 1.01g of a green crude product, and performing column chromatography purification, wherein an eluent is petroleum ether: dichloromethane =10 (V: V), yielding alkyl functionalized column hexaarene: 0.191g.
Example 3
(1) Taking 2.75g of 1,4-hydroquinone, 17.12g of 1-bromodecane, 4.35g of potassium hydroxide and 62.5ml of ethanol to react for 8.5h at 80 ℃ to obtain a compound (I), wherein the compound (I) is 1,4-bis (decyloxy) benzene;
(2) Adding 1.00g (2.56 mmol) of the compound (I), 0.08g (2.69 mmol) of paraformaldehyde, 0.380g (2.68 mmol) of boron trifluoride diethyl etherate and 15mL of chlorocyclohexane into a 50mL single-neck flask, reacting at 35 ℃ for 4 hours, adding 20mL of deionized water, washing an organic phase with 20mL of saturated saline solution, drying over anhydrous magnesium sulfate, filtering, evaporating to dryness to obtain 0.98g of a green crude product, and performing column chromatography purification, wherein an eluent is petroleum ether: dichloromethane =10 (V: V), yielding alkyl functionalized column hexaarene: 0.192g.
Example 4
The invention also provides a capillary chromatographic column which is prepared by adopting the alkyl functionalized column hexaaromatic hydrocarbon stationary phase provided by the invention, and specifically can be prepared by adopting a static coating method:
(1) Cutting a quartz capillary tube with the length of 5m and the inner diameter of 250 mu m, firstly washing the quartz capillary tube with dichloromethane for 10min, and then aging the quartz capillary tube at 200 ℃ for 2-3h under the protection of nitrogen, so that impurities in the capillary tube 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 vigorously stirred for 45min to obtain a saturated sodium chloride methanol solution. Adding 6mL of saturated solution into 8mL of chloroform solution which is stirred strongly, adding 0.6mL of anhydrous methanol solution, stirring for 5min, adding 8mL of chloroform solution, and continuing stirring for 2min to obtain saturated colloidal solution.
(3) The saturated colloidal solution was pressed into the capillary under a nitrogen pressure of 0.01 to 0.02 MPa. Then blowing out the solution in the column by using nitrogen, and recrystallizing for 3h at 200 ℃ under the protection of nitrogen to finish roughening the inner surface of the capillary column.
(4) In the experiment, a static column method is adopted, P6A-C10 is dissolved in dichloromethane solution to prepare fixing solution with the concentration of 0.2% (w/v), and ultrasonic treatment is carried out for 5min to remove bubbles in the fixing solution.
(5) Pushing the fixing solution into the capillary chromatographic column by using an injector until the fixing solution is filled in the whole chromatographic column, sealing one end of the capillary, connecting the other end of the capillary with a vacuum system, and slowly evaporating the solvent in a constant-temperature water bath at 40 ℃ so that the fixing solution can be uniformly dispersed on the inner wall of the capillary column.
(6) Aging the coated capillary chromatographic column by adopting a temperature programming method under the protection of nitrogen: keeping the temperature at 40 ℃ for 30min, then increasing the temperature to 180 ℃ at the speed of 1 ℃/min, and keeping the temperature for 7h, thus finishing the aging of the chromatographic column and obtaining the capillary gas chromatographic column.
The invention takes P6A-C10 as the stationary phase of the capillary gas chromatographic column for the first time, and the P6A-C10 perfectly combines the structural characteristics of the hexaarene column and the advantages of alkyl functionalization, so that the novel material can be 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 hexaaromatic stationary phase, the invention uses P6A-C10 as the stationary phase of a capillary gas chromatographic column for the first time, and the thermal stability is good and is up to 278 ℃.
In the alkyl functionalized column hexaaromatic hydrocarbon P6A-C10 stationary phase prepared by the invention, the functional groups such as the column ring, the alkoxy chain and the like of the stationary phase cause the stationary phase to have good effect in practical application, and have a plurality of different weak interaction forces with different analytes, wherein the weak interaction forces comprise: van der waals force, hydrogen bond, pi-pi interaction, dipole-dipole interaction, CH-pi interaction and the like, so that the P6A-C10 column has a good separation effect, and can also be used for separating substituted benzaldehyde isomers, 12 sets of cis-trans isomers, 21 sets 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 following experiments were performed on the capillary chromatographic column provided by the present invention:
(1) As shown in fig. 3, golay's curve of n-dodecane was determined using the capillary gas chromatography column prepared in example 4 under the following specific chromatographic conditions: column box temperature 120 ℃, carrier gas: nitrogen, carrier gas flow rate: 0.3mL/min, the minimum 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 analytes for separation (fig. 4), including ortho-xylene, meta-xylene, para-xylene, chromatographic separation conditions: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 60 ℃ at the heating rate of 5 ℃/min, and the flow rate of the carrier gas is 0.4mL/min. The capillary gas chromatography column prepared in example 4 was able to separate substituted xylene isomers with superior results to polysiloxane Shang Pinzhu DB-17, HP-5 and HP-35, and polyethylene glycol commercial column PEG-20M.
(3) Isolation of substituted benzaldehyde isomers:
different benzaldehyde isomers were selected as the analytes to be separated (fig. 5), including the tolualdehyde isomers: o-methyl benzaldehyde, m-methyl benzaldehyde, p-methyl benzaldehyde and bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde. Chromatographic separation conditions: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min. The capillary gas chromatographic column prepared in example 4 can separate substituted benzaldehyde isomers, and the effect is better than that of polysiloxane Shang Pinzhu DB-17, HP-5 and HP-35 and polyethylene glycol commercial column PEG-20M.
(4) Isolation of the halobenzene isomers:
3 different types of halobenzene isomers with different polarities are selected as separated analytes, wherein the halobenzene isomers comprise chlorotoluene isomers: o-chlorotoluene, m-chlorotoluene and p-chlorotoluene; dibromobenzene isomer: o-dibromobenzene, m-dibromobenzene and p-dibromobenzene, and the chromatographic separation conditions are as follows: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min.
FIG. 6 is a chromatogram of the capillary gas chromatography column prepared in example 4 for separating halogenated benzene isomers, showing that the chromatographic column can effectively separate halogenated benzene isomers, and the effect is better than that of polysiloxane Shang Pinzhu DB-17, HP-5 and HP-35 and polyethylene glycol commercial column PEG-20M.
(5) Separation of 12 sets of cis-trans isomers:
selecting 12 groups of cis-trans isomers with different polarities as analytes, and separating the isomers by using the capillary gas chromatographic column prepared in the embodiment under the chromatographic separation conditions: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min.
FIG. 7 is a chromatogram of a capillary gas chromatography column prepared in example 4 for separating 12 sets of cis-trans isomers with different polarities, 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 with trans-25-dihydro-25-dimethoxyfuran, d: cis-2-methyl-4-propyl-1,3-oxathiane and trans-2-methyl-4-propyl-1,3-oxathiane, 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 with 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 chromatography column prepared in example 4 can completely separate each set of cis-trans isomers, shows the advantages of separating cis-trans isomers by P6A-C10 stationary phase, and is fast and efficient in separation.
(6) Separation of 21-component complex mixture:
a complex mixture of 21 fractions 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 is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min.
Fig. 8 is a chromatogram of a capillary gas chromatography column separating a complex mixture of 21 components, 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: decanoic acid methyl ester, 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 21-component complex mixtures, more kinds of analytes and wider polarity range, shows good characteristics that the P6A-C10 stationary phase is suitable for separating complex mixtures, and has better effect than polysiloxane Shang Pinzhu DB-17, HP-5 and HP-35 and polyethylene glycol commercial column PEG-20M.
(7) Separation of haloaniline isomers
3 haloaniline isomers were selected as analytes, including chloroaniline isomers: o-chloroaniline, m-chloroaniline, p-chloroaniline; bromophenylamine isomer: o-bromoaniline, m-bromoaniline, p-bromoaniline; iodoaniline isomers: o-iodoaniline, m-iodoaniline, p-iodoaniline. The sample was separated using the capillary gas chromatography column prepared in example 4. Chromatographic separation conditions: the temperature is kept for 1min at 40 ℃, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, the flow rate of carrier gas is 0.6mL/min, as shown in figure 9, the P6A-C10 chromatographic column prepared by the method can separate the halogenated aniline isomer, and the effect is better than that of polysiloxane Shang Pinzhu DB-17, HP-5 and HP-35 and polyethylene glycol commercial column PEG-20M.
(8) Good film forming property
FIG. 10 is a Scanning Electron Micrograph (SEM) of a capillary gas chromatography column made according to the present invention, demonstrating the good film-forming properties of the P6A-C10 stationary phase.
The alkyl functionalized pillared hexaarene derivatives P6A-C10 prepared by the invention combine the unique molecular recognition capability and the alkyl functionalized advantages of the pillared arene and mutually make up the respective disadvantages, wherein the pillared arene has good internal rigidity, can be freely adjusted and has a pi electron-rich column ring flexibility and certain induction matching capability, so that object molecules can be recognized, but the defects of high melting point, poor film forming property and the like exist; the method has the advantages that the columnar aromatic hydrocarbon is easy to functionalize, so that the property of the columnar aromatic hydrocarbon as a gas chromatography stationary phase can be improved by introducing the long alkoxy chain at the lower edge of the columnar aromatic hydrocarbon, the melting point of the columnar aromatic hydrocarbon can be reduced by introducing the long alkoxy chain, the film forming property of the columnar aromatic hydrocarbon is improved, and the separation performance of the columnar aromatic hydrocarbon as a chromatographic stationary phase relative to a target compound is improved.
< comparative example 1>
Xylene isomers were separated using the capillary gas chromatography column prepared in example 4 and the capillary gas chromatography column prepared using an amino-functionalized pentaarene stationary phase, respectively.
Xylene isomers were selected as analytes for separation (fig. 11), including ortho-xylene, meta-xylene, and para-xylene, and chromatographic separation conditions: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 60 ℃ at the heating rate of 5 ℃/min, and the flow rate of the carrier gas is 0.4mL/min. As can be seen from fig. 11, the capillary gas chromatography column prepared in example 4 was able to separate xylene isomers, but the capillary gas chromatography column prepared with the amino-functionalized column pentaarene stationary phase was not able to separate xylene isomers. This is related to the feature that the pillared hexaarenes possess more repeating aromatic units and larger pi-conjugated cavities than the pillared pentaarenes, which can capture larger aromatic guests.
< comparative example 2>
The haloaniline isomers were separated using the capillary gas chromatography column prepared in example 4 and the capillary gas chromatography column prepared using an amino-functionalized pentaarene column stationary phase, respectively.
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 above samples were separated using the capillary gas chromatography column prepared in the examples. Chromatographic separation conditions: the temperature is kept at 40 ℃ for 1min, the temperature is raised to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of carrier gas is 0.6mL/min, as shown in figure 12, the P6A-C10 chromatographic column prepared by the method can separate halogenated aniline isomers, and the effect is better than that of a capillary gas chromatographic column prepared by an amino functionalized column pentaarene stationary phase, which is related to that a column hexaarene has more repeated aromatic units and larger pi-conjugated cavities than a column pentaarene.
< comparative example 3>
Separation tests of xylene isomers, chlorotoluene isomers and bromobenzaldehyde isomers were carried out using capillary gas chromatography columns made of column hexaarenes of different alkoxy chain lengths.
The capillary gas chromatographic columns adopted in the separation test are respectively 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 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 coated according to the static method of the present invention to prepare P6A-C4 and P6A-C2 chromatography columns.
As shown in fig. 13, (a) is a xylene isomer selected as the analyte for separation, wherein the xylene isomer comprises ortho-xylene, meta-xylene and para-xylene, and the chromatographic separation conditions are as follows: the temperature was maintained at 40 ℃ for 1min, and the temperature was raised to 60 ℃ at a rate of 5 ℃/min, with a carrier gas flow rate of 0.4mL/min. As can be seen from part (a) of fig. 13, the P6A-C10 chromatographic column can accurately separate xylene isomers, but neither the P6A-C4 chromatographic column nor the P6A-C2 chromatographic column can effectively separate xylene isomers, which is related to that the longer decanoxy chain better improves the physicochemical properties of column aromatics including film-forming property and melting point to meet the requirements of the gas chromatography stationary phase, and also has richer forces between analyte molecules in the chromatographic separation.
As shown in fig. 13, (b) is selecting chlorotoluene isomers as separated analytes, wherein o-chlorotoluene, m-chlorotoluene and p-chlorotoluene are included, and chromatographic analysis conditions are as follows: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min. As can be seen from part (b) of fig. 13, the P6A-C10 column can separate the chlorotoluene isomer, but neither the P6A-C4 column nor the P6A-C2 column can separate the chlorotoluene isomer.
As shown in fig. 13, (c) is the selection of bromobenzaldehyde isomers as the isolated analyte, which include the bromobenzaldehyde isomers: o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde, and the chromatographic analysis conditions are as follows: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min. As shown in fig. 13 (C), the P6A-C10 column can separate the bromobenzaldehyde isomer, but neither the P6A-C4 column nor the P6A-C2 column can separate the bromobenzaldehyde isomer.
< comparative example 4>
Separation tests of mixed alkanes, mixed esters and mixed alcohols were performed using capillary gas chromatography columns made from column hexaarenes of different alkoxy chain lengths.
The capillary gas chromatography columns used in the separation test were a P6A-C10, a P6A-C4, and a P6A-C2 chromatography column, respectively, where the P6A-C10 chromatography column was the capillary gas chromatography column prepared in example 4.
As shown in fig. 14, (a) is a mixed alkane selected as the separated analyte, wherein the mixed alkane includes n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane, and the chromatographic separation conditions are as follows: keeping the temperature at 60 ℃ for 1min, increasing the temperature to 160 ℃ at the heating rate of 10 ℃/min, and enabling the flow rate of the carrier gas to be 0.6mL/min. As can be seen from FIG. 14 (a), the P6A-C10 column can separate mixed alkanes, and the effect is superior to the P6A-C4 column and the P6A-C2 column.
As shown in fig. 14, (b) is a mixed ester selected as the separated analytes, wherein the mixed ester comprises methyl valerate, methyl caproate, methyl heptanoate, methyl caprylate, methyl nonanoate, methyl decanoate, methyl undecanoate, and methyl dodecanoate, and the chromatographic separation conditions are as follows: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min. As shown in FIG. 14 (b), the P6A-C10 column was able to separate mixed esters and was superior to the P6A-C4 column and the P6A-C2 column.
As shown in fig. 14, (c) is a mixed alcohol selected as the separated analytes, wherein the mixed alcohol comprises 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol, and the chromatographic separation conditions are as follows: the temperature is kept at 40 ℃ for 1min, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min, and the flow rate of the carrier gas is 0.6mL/min. As can be seen from part (C) of fig. 14, the P6A-C10 column can separate mixed alcohols and is superior to the P6A-C4 column and the P6A-C2 column.
< comparative example 5>
The column effect of the capillary gas chromatographic column is obtained by adopting column hexaaromatic hydrocarbons with different alkoxy chain lengths.
FIG. 15 is a graph showing the column efficiency (Golay curve) of P6A-C10, P6A-C4 and P6A-C2 capillary gas chromatography columns prepared according to the present invention, measured at 120 ℃ using n-dodecane as a probe compound. It is known that the P6A-C10 capillary gas chromatographic column has higher column efficiency.
< comparative example 6>
Chromatographic separation condition of xylene isomer
As shown in FIG. 16, (a) is the separation of different types of xylene isomers with different polarities when the capillary gas chromatography column (i.e., P6A-C10 chromatography column) prepared in the present example is maintained at 40 ℃ for 1min under the condition of different stationary phase concentrations, and is increased to 60 ℃ at the temperature increasing rate of 5 ℃/min, and the carrier gas flow rate is 0.4mL/min. From the results of the separation experiments, it was found that the effect of separating p-xylene isomers was good and the separation was rapid when the stationary phase concentration was 0.2% w/v, and the combined effect was superior to that when the stationary phase concentration was 0.1% w/v and 0.3% w/v.
(b) In a P6A-C10 column, the stationary phase concentration was maintained at 0.2% w/v, the column was maintained at 40 ℃ for 1min, the temperature was raised to 60 ℃ at a temperature rise rate of 5 ℃/min, and the separation of the P-xylene isomers was carried out at different carrier gas flow rates. Among them, when the flow rate of the carrier gas is 0.4mL/min, the separation effect of the p-xylene isomers is the best, and is better than that when the flow rate of the carrier gas is 0.3mL/min, 0.5mL/min, 0.6mL/min, 0.7 mL/min.
(c) The method is characterized in that the method is carried out in a P6A-C10 chromatographic column, the concentration of a stationary phase is kept at 0.2 percent w/v, the stationary phase is kept at 40 ℃ for 1min, the temperature is increased to 60 ℃ at different heating rates, and the flow rate of carrier gas is 0.4mL/min.
From this, it can be seen that the chromatographic separation conditions for xylene isomers of different polarity and different types were 40 ℃ for 1min, the temperature was raised to 60 ℃ at a temperature rise rate of 5 ℃/min, and the flow rate of the carrier gas was 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 modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention fall within the protection scope of the present invention.
Claims (10)
1. An alkyl functionalized column hexaaromatic stationary phase, which is characterized in that: the chemical formula of the alkyl functionalized column hexaaromatic hydrocarbon stationary phase is P6A-C10, and the chemical structural formula is as follows:
2. a preparation method of an alkyl functionalized column hexaaromatic stationary phase is characterized by comprising the following steps:
1) Taking 1,4-hydroquinone, carrying out etherification reaction with 1-bromodecane, potassium hydroxide and ethanol to obtain 1,4-bis (decyloxy) benzene;
2) And (3) performing cyclization reaction on 1,4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride diethyl etherate and chlorocyclohexane, and performing post-treatment and purification on a product after the reaction to obtain the alkyl functionalized pillared hexaarene.
3. The method for preparing an alkyl functionalized column hexaaromatic stationary phase according to claim 2, wherein in step 1): the reaction temperature is 80-85 ℃; the reaction time is 7.5 to 8.5 hours; the adding amount ratio of 1,4-hydroquinone to 1-bromodecane, potassium hydroxide and ethanol is 1.1g: 6.63-6.85 g: 1.68-1.74 g:25mL.
4. The method for preparing an alkyl functionalized polyhexamethylene arene column stationary phase according to claim 2, wherein in step 2): the reaction temperature is 35 ℃; the reaction time is 3-4 h;1,4-bis (decyloxy) benzene, paraformaldehyde, boron trifluoride etherate, chlorocyclohexane in a ratio of 2.00g: 0.153-0.169 g:0.726 to 0.799g:30mL.
5. The process for preparing an alkyl functionalized polyhexamethylene arene column stationary phase according to claim 2, wherein in step 2): column chromatography was used for purification, and petroleum ether: the volume ratio of dichloromethane is 10.
6. A capillary gas chromatography column prepared from the alkyl-functionalized column hexaaromatic stationary phase of claim 1.
7. The capillary gas chromatography column of claim 6, wherein said capillary gas chromatography column is prepared by static coating.
8. Use of a capillary gas chromatography column according to claim 6, wherein: the capillary gas chromatography column is capable of separating xylene isomers, substituted benzaldehyde isomers, 12-group cis-trans isomers, 21-component complex mixtures, halogenated benzene isomers, halogenated aniline isomers, mixed alkanes, mixed esters and mixed alcohols.
9. Use of a capillary gas chromatography column according to claim 8, wherein:
the xylene isomers include ortho-xylene, meta-xylene, and para-xylene;
the substituted benzaldehyde isomers comprise methyl benzaldehyde isomers and bromobenzaldehyde isomers, wherein the methyl benzaldehyde isomers comprise o-methyl benzaldehyde, m-methyl benzaldehyde and p-methyl benzaldehyde; bromobenzaldehyde isomers include o-bromobenzaldehyde, m-bromobenzaldehyde and p-bromobenzaldehyde;
the 12 sets of cis-trans isomers include 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-oxathiolane and trans-2-methyl-4-propyl-1,3-oxathiolane, 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-octadiene-1-ol and trans-35zxft 3579-cyclohexanol and trans-methyl cinnamate-3579-methyl cinnamate and trans-crotonaldehyde and cis-4-tert-butylcrotonyl chloride;
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 chlorotoluene isomers and dibromobenzene isomers, wherein the chlorotoluene isomers comprise 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 isomers comprise o-chloroaniline, m-chloroaniline and p-chloroaniline; the bromoaniline isomers comprise o-bromoaniline, m-bromoaniline and p-bromoaniline; the iodoaniline isomers include o-iodoaniline, m-iodoaniline and p-iodoaniline;
the mixed alkane is: including n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane;
the mixed esters include methyl valerate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, and methyl dodecanoate;
the mixed alcohol includes 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.
10. Use of a capillary gas chromatography column according to claim 8, wherein: the chromatographic separation condition of the p-xylene isomer in the capillary gas chromatographic column is that the temperature is kept for 1min at 40 ℃, the temperature is increased to 60 ℃ at the temperature rising rate of 5 ℃/min, and the flow rate of carrier gas is 0.4mL/min.
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