CN111072511A - Quaternary ammonium salt surfactant and preparation method and application thereof - Google Patents
Quaternary ammonium salt surfactant and preparation method and application thereof Download PDFInfo
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- CN111072511A CN111072511A CN201811212800.4A CN201811212800A CN111072511A CN 111072511 A CN111072511 A CN 111072511A CN 201811212800 A CN201811212800 A CN 201811212800A CN 111072511 A CN111072511 A CN 111072511A
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 101
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 69
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- -1 hydroxy, amino, mercapto Chemical class 0.000 claims description 29
- 150000002431 hydrogen Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N hexane carboxylic acid Natural products CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010779 crude oil Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 125000003342 alkenyl group Chemical group 0.000 description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- 238000004220 aggregation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 6
- 238000007112 amidation reaction Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000009435 amidation Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 4
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 4
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 4
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 4
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- HDDLVZWGOPWKFW-UHFFFAOYSA-N trimethyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound COC(=O)CC(O)(C(=O)OC)CC(=O)OC HDDLVZWGOPWKFW-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101001047650 Rhyparobia maderae Leucokinin-3 Proteins 0.000 description 2
- 150000001262 acyl bromides Chemical class 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 description 1
- GCDPERPXPREHJF-UHFFFAOYSA-N 1-iodododecane Chemical compound CCCCCCCCCCCCI GCDPERPXPREHJF-UHFFFAOYSA-N 0.000 description 1
- KMWHQYDMBYABKL-UHFFFAOYSA-N 1-iodohexadecane Chemical compound CCCCCCCCCCCCCCCCI KMWHQYDMBYABKL-UHFFFAOYSA-N 0.000 description 1
- FHQCFGPKNSSISL-UHFFFAOYSA-N 1-iodotetradecane Chemical compound CCCCCCCCCCCCCCI FHQCFGPKNSSISL-UHFFFAOYSA-N 0.000 description 1
- CAPCBAYULRXQAN-UHFFFAOYSA-N 1-n,1-n-diethylpentane-1,4-diamine Chemical compound CCN(CC)CCCC(C)N CAPCBAYULRXQAN-UHFFFAOYSA-N 0.000 description 1
- RRQHLOZQFPWDCA-UHFFFAOYSA-N 1-n,1-n-dimethylpropane-1,2-diamine Chemical compound CC(N)CN(C)C RRQHLOZQFPWDCA-UHFFFAOYSA-N 0.000 description 1
- FKJVYOFPTRGCSP-UHFFFAOYSA-N 2-[3-aminopropyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCCN(CCO)CCO FKJVYOFPTRGCSP-UHFFFAOYSA-N 0.000 description 1
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 description 1
- QBVIXYABUQQSRY-UHFFFAOYSA-N 3-[(3-carboxyphenyl)diazenyl]benzoic acid Chemical compound OC(=O)C1=CC=CC(N=NC=2C=C(C=CC=2)C(O)=O)=C1 QBVIXYABUQQSRY-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000005418 aryl aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CURJNMSGPBXOGK-UHFFFAOYSA-N n',n'-di(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)N(C(C)C)CCN CURJNMSGPBXOGK-UHFFFAOYSA-N 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000006488 t-butyl benzyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a quaternary ammonium salt surfactant, a preparation method and application thereof. The quaternary ammonium salt surfactant disclosed by the invention has a structure shown as a formula (I):
wherein the definition of each group is shown in the specification. The quaternary ammonium salt surfactant can be used as a high-efficiency low-consumption wetting agent for the field of tertiary oil recovery. In tertiary oil recoveryIn the process, the quaternary ammonium salt surfactant can effectively convert the surface of a carbonate reservoir wrapped by crude oil into water wettability or neutral wettability to realize wettability reversal, thereby being beneficial to the improvement of oil washing efficiency.
Description
Technical Field
The invention relates to a quaternary ammonium salt surfactant, in particular to a quaternary ammonium salt surfactant with high efficiency and low consumption.
Background
Oligomeric surfactants refer to a class of amphiphilic molecules containing two, three or more amphiphilic moieties in the molecule, wherein the amphiphilic moieties in the molecule are chemically linked together at or near the head group by a linking group. Compared with the traditional single-chain surfactant, the increase of the polymerization degree enables the synergistic effect among a plurality of amphiphilic elements in the oligomeric surfactant molecule to be stronger, thereby showing excellent performances with high efficiency and low consumption, and being expected to become a new-generation surfactant. On the other hand, CN105561865A suggests that branched surfactants have higher oil removing ability and ability to lower oil-water interfacial tension than linear oligomeric surfactants. Therefore, by adjusting the degree of oligomerization and the structure of the linking group, an oligomeric surfactant having excellent properties can be obtained.
At present, the synthesis of the oligomeric quaternary ammonium salt surfactant generally takes multi-level alcohol or multi-level amine as raw materials, and the linear or branched oligomeric quaternary ammonium salt surfactant is prepared through two-step reactions of amidation and quaternization. For example, the literature (Langmuir,2010,26,7922-7927) discloses a method for preparing a dendritic trimeric quaternary ammonium salt surfactant by using tri (2-aminoethyl) amine as a raw material through two steps of reactions of amidation and quaternization. The method has the main problems that chloroacetyl chloride which has high toxicity and is easy to inactivate when meeting water is used in the amidation reaction of polyamine, and the reaction conditions are harsh. In addition, the literature (ColloidsSurf. A,2014,457,374-381) discloses a method for preparing a star-shaped trimeric quaternary ammonium salt surfactant by taking tri (hydroxyethyl) amine as a raw material and through two steps of reactions of amidation and quaternization. The method needs bromoacetyl bromide during amidation reaction, and also has harsh reaction conditions, thus being not beneficial to industrial production.
In general, the method of synthesizing the oligomeric quaternary ammonium salt surfactant by two-step reaction of amidation and quaternization using polyol or polyamine as a starting material has the following disadvantages: (1) the polyamine serving as the starting raw material has strong corrosivity and strong irritation; the reaction activity of the polyhydric alcohol is low, and the solubility of the polyhydric alcohol in an organic solvent is poor; (2) in the reaction process, acyl chloride or acyl bromide with high toxicity is used, and the acyl chloride or acyl bromide is easy to inactivate when meeting water, so that the reaction conditions are harsh. Therefore, it is very critical to further select cheap and green starting materials and optimize the preparation method for expanding the theoretical research and industrial application of the oligomeric quaternary ammonium salt surfactant.
Disclosure of Invention
Aiming at the defects of the prior art, the inventor provides a quaternary ammonium salt surfactant and a preparation method and application thereof through diligent research.
The quaternary ammonium salt surfactant disclosed by the invention has a structure shown as a formula (I):
wherein a L groups, equal to or different from each other, are each independently selected from optionally substituted m-valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group, m is an integer of 1 to 20 (preferably an integer of 1 to 10), a is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1, 2 or 3); n is0Is composed of
Number of charges of group, n0Is an integer of 1 to 20 (preferably an integer of 1 to 10); n XZ-The radicals, equal to or different from each other, are each independently selected from F-、Cl-、Br-、I-And OH-N isAn integer of 1 to 20 (preferably an integer of 1 to 10), and Z-is XZ-The number of charges of the group, z is selected from 1, 2 or 3; n XZ-The absolute value of the total number of charges of the radical being equal to n0；
In formula (I), b A groups, which are identical or different from each other, are each independently selected from hydrogen, optionally substituted C1～20A linear or branched alkyl group and a group of formula (II), at least one A group being selected from the group of formula (II); b is an integer of 1 to 20 (preferably an integer of 2 to 10, more preferably 2, 3, 4, 5 or 6);
in the group of formula (II), the L 'group is selected from optionally substituted n' -valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r of n' repeating units0Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Straight or branched heteroalkyl (preferably selected from C)1～20Straight or linear alkyl); each of the m ' repeating units a ', b ', c ', d ', which are the same or different from each other, is independently selected from an integer of 0 to 5 (preferably 0, 1 or 2), and at least one a ' is an integer of 1 to 5 and at least one d ' is an integer of 1 to 5; each R of m' repeating units1Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III); each R of m' repeating units2Each independently selected from optionally substituted C1～20Straight or branched alkylene and optionally substituted C3～20M' is an integer of 1 to 20 (preferably an integer of 1 to 10), represents a bonding end of the group of formula (II) to the group L of formula (I), △ represents a bonding end of the group of formula (II) to the group R of formula (I);
in the formula (III), the groups and symbols are as defined in the formula (II), and R's in the m' repeating units1' each is independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III) (preferably each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Linear or linear heteroalkyl);
c R groups are each independently selected from optionally substituted mbC of valence1～50Hydrocarbyl or C3～50Heterocarbyl (preferably optionally substituted m)bC of valence1～20Straight or branched alkyl and C3～20Linear or branched heteroalkyl), mbIs an integer of 1 to 20 (preferably an integer of 1 to 10); c is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1, 2, 3, 4 or 5);
the number of (hydrocarbyl) bonded ends present in the a L groups is the same as the number of (carbonyl) bonded ends present in the b a groups, the a L groups being bonded to each other via their (hydrocarbyl) bonded ends to the (carbonyl) bonded ends of the b a groups;
the number of tertiary amine nitrogen atoms present in the b a groups is greater than the number of (hydrocarbyl) bound ends present in the c R groups, the number of (tertiary amine) bound ends present in the b a groups, as represented by △, is equal to the number of (hydrocarbyl) bound ends present in the c R groups, and the b a groups are bonded to each other through the (tertiary amine) bound ends present therein, as represented by △, and the (hydrocarbyl) bound ends of the c R groups;
said optionally substituted means optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, mercapto, halogen and C1-5Linear or branched alkoxy;
the structure shown in formula (I) conforms to the bonding rule.
According to the invention, preferably, the quaternary ammonium salt surfactant has a structure shown in formula (I-I):
wherein a L groups, equal to or different from each other, are each independently selected from optionally substituted m-valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group, m is an integer of 1 to 20 (preferably an integer of 1 to 10), a is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1, 2 or 3); n is0Is composed of
Number of charges of group, n0Is an integer of 1 to 20 (preferably an integer of 1 to 10); n XZ-The radicals, equal to or different from each other, are each independently selected from F-、Cl-、Br-、I-And OH-N is an integer of 1 to 20 (preferably an integer of 1 to 10), and Z-is XZ-The number of charges of the group, z is selected from 1, 2 or 3; n XZ-The absolute value of the total number of charges of the radical being equal to n0；
In the formula (I-I), b A groups are the same or different and are independently selected from hydrogen and optionally substituted C1～20A linear or branched alkyl group and a group of formula (II-I), at least one A group being selected from the group of formula (II-I); b is an integer of 1 to 20 (preferably an integer of 2 to 10, more preferably 2, 3, 4, 5 or 6);
in the group of formula (II-I), the L 'group is selected from optionally substituted n' valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r of n' repeating units0Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Straight or branched heteroalkyl (preferably selected from C)1～20Straight or linear alkyl); each of the m ' repeating units a ', b ', c ', d ', which are the same or different from each other, is independently selected from an integer of 0 to 5 (preferably 0, 1 or 2), and at least one a ' is an integer of 1 to 5 and at least one d ' is an integer of 1 to 5; each R of m' repeating units1Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III-I); each R of m' repeating units2Each independently selected from optionally substituted C1～20Straight or branched alkylene and optionally substituted C3～20Linear or linear heteroalkylene; each R of m' repeating units3Each independently selected from optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20A linear or linear heteroalkyl group; m' is an integer of 1 to 20 (preferably an integer of 1 to 10); represents the binding end of the group of formula (II-I) to which the group L of formula (I-I) is bonded;
in the formula (III-I), each group and each symbol are as defined in the formula (II-I), and each R in m' repeating units1' each is independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III-I) (preferably each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Linear or linear heteroalkyl);
the number of (hydrocarbyl) bonded ends present in the a L groups is the same as the number of (carbonyl) bonded ends present in the b a groups, the a L groups being bonded to each other via their (hydrocarbyl) bonded ends to the (carbonyl) bonded ends of the b a groups;
said optionally substituted means optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, mercapto, halogen and C1-5Linear or branched alkoxy;
the structure shown in the formula (I-I) conforms to the bonding rule.
According to the invention, the quaternary ammonium salt surfactant is selected from quaternary ammonium salt surfactants with the following specific structures or a mixture thereof in any proportion:
the invention provides a preparation method of a quaternary ammonium salt surfactant, which comprises the steps of reacting a compound shown in a formula (X), a compound shown in a formula (Y) and a compound shown in a formula (Z);
in formula (X), the L 'group is selected from optionally substituted n' valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r in n' repeating units0Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Straight or branched heteroalkyl (preferably selected from C)1～20Straight or linear alkyl); each a 'of the m' repeating units is the same or different from each other, and is independently selected from an integer of 1 to 5 (preferably 1, 2 or 3); each R of m' repeating units1Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (X-I); each R of m' repeating units2Each independently selected from optionally substituted C1～20Straight or branched alkylene and optionally substituted C3～20Linear or linear heteroalkylene; m' is an integer of 1 to 20 (preferably an integer of 1 to 10);
in the formula (X-I), R0、R2A ' and m ' are as defined in formula (X), each R in m ' repeating units1' each is independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (X-I) (preferably each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Linear or linear heteroalkyl) in which at least one R is1' is hydrogen;
in formula (Y), the R' group is optionally substituted maC of valence1～50Hydrocarbyl or C3～50Heterocarbyl (preferably optionally substituted m)aC of valence1～20Straight or branched alkyl and C3～20Linear or branched heteroalkyl); m isaThe Y groups in the repeating units are the same or different from each other and are each independently selected from F, Cl, Br, I, OH and optionally substituted C1～5Straight or branched chain alkyl (preferably methyl); m isaIs an integer of 1 to 20 (preferably an integer of 1 to 10);
in formula (Z), the R group is optionally substituted mbC of valence1～50Hydrocarbyl or C3～50Heterocarbyl (preferably optionally substituted m)bC of valence1～20Straight or branched alkyl and C3～20Linear or branched heteroalkyl); m isbThe X groups in the repeating units are the same or different from each other and are each independently selected from F, Cl, Br, I and OH; m isbIs an integer of 1 to 20 (preferably an integer of 1 to 10).
According to the preparation method of the present invention, the molar ratio between the compound represented by the formula (X) (in terms of amine group) and the compound represented by the formula (Y) (in terms of carbonyl group) and the compound represented by the formula (Z) (in terms of X group) is preferably 1: 0.1-10: 0.1 to 10 (more preferably 1: 0.25 to 1: 0.5 to 5).
According to the present invention, the production method may comprise a step of reacting the compound represented by the formula (X) with the compound represented by the formula (Y) or the compound represented by the formula (Z), a step A of reacting the compound represented by the formula (X) with the compound represented by the formula (Y) first and a step B of reacting the product of the step A with the compound represented by the formula (Z), or a step B of reacting the compound represented by the formula (X) with the compound represented by the formula (Z) first and a step A of reacting the product of the step B with the compound represented by the formula (Y).
According to the production method of the present invention, a solvent may or may not be added, and preferably a solvent is added, in the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z). The solvent is preferably selected from sulfone, sulfoxide, furan, C1～6Alcohol of (1), C1～6The ketone (b) may be, for example, one or more selected from dimethyl sulfoxide, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone and methyl ethyl ketone. The solvent may be removed by a method known in the art after the completion of the reaction, and is not particularly limited, and examples thereof include distillation and evaporation.
According to the preparation method of the present invention, preferably, an inert gas is introduced into the reaction of the compound represented by the formula (X), the compound represented by the formula (Y), and the compound represented by the formula (Z), and the inert gas is preferably one or more of nitrogen, argon, and helium.
According to the preparation method of the invention, the temperature for the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z) is preferably 0-200 ℃, preferably 20-150 ℃, and more preferably 30-110 ℃; the reaction time is generally 0.5 to 7 days, preferably 0.5 to 72 hours.
According to the production method of the present invention, preferably, the production method comprises a step a of reacting a compound represented by the formula (X) with a compound represented by the formula (Y), and a step B of reacting the product of the step a with a compound represented by the formula (Z).
According to the preparation process of the present invention, preferably, the compound represented by the formula (X) is preferably selected from C1～50And/or C1～50Alkyl alcohol amine (more preferably C)2～20And/or C2～20The alkylol amine) of (a) may be, for example, N-dimethylethylenediamine, N-dimethylpropylenediamine, N,2,2-One or more of tetramethyl-1, 3-propanediamine, 3- (dibutylamino) propylamine, N- (3-aminopropyl) diethanolamine, N-dimethyl-1, 3-cyclohexanediamine, N-diethylethylenediamine, N-dipropylethylenediamine, 2-amino-5-diethylaminopentane and N, N-diisopropylethylenediamine.
According to the preparation method of the present invention, preferably, the compound represented by the formula (Y) is preferably selected from C1～50Polycarboxylic acid esters, polycarboxylic acids and polycarboxylic acid halides (more preferably C)2～30The polycarboxylic acid ester of (a) may be selected from dicarboxylic acid esters, tricarboxylic acid esters, tetracarboxylic acid esters, pentacarboxylic acid esters, and hexacarboxylic acid esters.
According to the preparation method of the present invention, the dicarboxylic acid ester is preferably selected from one or more of the following structures:
wherein, the value of x is preferably selected from integers between 0 and 9, such as 0, 1, 2 or 3; the value of y is preferably selected from integers between 1 and 10, such as 1, 2, 3, 4, 5 or 6; raEach independently selected from C1-12And cycloalkyl groups such as methyl, ethyl, propyl, isopropyl, and the like.
According to the preparation method of the present invention, the tricarboxylic acid ester is preferably selected from one or more of the following structures:
wherein R isaThe definition of (A) is as described above.
According to the preparation method of the present invention, the tetracarboxylic acid ester is preferably selected from one or more of the following structures:
wherein R isaThe value of s is preferably selected from integers between 0 and 9, such as 0,1.2 or 3.
According to the production method of the present invention, the five-membered carboxylic acid ester and six-membered carboxylic acid ester are preferably selected from compounds of the following structures:
wherein R isaThe definition of (A) is as described above.
According to the preparation process of the present invention, preferably, the compound represented by the formula (Z) is preferably selected from C1～50Alkyl halide (preferably selected from C)5～30The alkyl halide of (2) such as 1-bromododecane, 1-bromotetradecane, 1-bromohexadecane, 1-chlorododecane, 1-chlorotetradecane, 1-chlorohexadecane, 1-iodododecane, 1-iodotetradecane, 1-iodohexadecane and the like.
The invention also provides the use of the quaternary ammonium surfactant described above. The quaternary ammonium salt surfactant can be used as a high-efficiency low-consumption wetting agent for the field of tertiary oil recovery. In the tertiary oil recovery process, the quaternary ammonium salt surfactant can effectively convert the surface of a carbonate reservoir wrapped by crude oil into water wettability or neutral wettability to realize wettability reversal, thereby being beneficial to the improvement of oil washing efficiency.
Technical effects
The preparation method is simple, the reaction condition is mild, and the yield is high.
The preferable preparation method of the invention does not use acyl halide, can avoid the toxic action brought by acyl halide, simultaneously avoids the limitation of anhydrous and anaerobic conditions, and simplifies the reaction conditions.
The preferable preparation method of the invention uses the polycarboxylic acid ester which is widely available, green and cheap, and is suitable for industrial production.
The quaternary ammonium salt surfactant has excellent surface activity and aggregation capacity, and can be used as a high-efficiency and low-consumption wetting agent in the field of tertiary oil recovery. The quaternary ammonium salt surfactant can achieve an excellent wetting effect at a lower concentration.
Drawings
FIG. 1 is an ESI mass spectrum of a quaternary ammonium surfactant intermediate prepared in example 1 of the present invention.
FIG. 2 shows NMR of intermediate of quaternary ammonium salt surfactant prepared in example 1 of the present invention1H NMR spectrum.
FIG. 3 is an ESI mass spectrum of the quaternary ammonium salt surfactant prepared in example 1 of the present invention.
FIG. 4 shows NMR spectra of quaternary ammonium salt surfactant prepared in example 1 of the present invention1H NMR spectrum.
FIG. 5 is an ESI mass spectrum of a quaternary ammonium surfactant intermediate prepared in example 2 of the present invention.
FIG. 6 shows NMR of intermediate of quaternary ammonium salt surfactant prepared in example 2 of the present invention1H NMR spectrum.
FIG. 7 is a high resolution ESI mass spectrum of the quaternary ammonium surfactant prepared in example 2 of the present invention.
FIG. 8 shows NMR spectra of quaternary ammonium salt surfactant prepared in example 2 of the present invention1H NMR spectrum.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, steps, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently used, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
In the context of the present invention, the expression "halo" refers to fluoro, chloro, bromo or iodo.
In the context of the present invention, the term "hydrocarbyl" has the meaning conventionally known in the art and includes straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, or combinations thereof, wherein straight or branched chain alkyl, straight or branched chain alkenyl, cycloalkyl, cycloalkenyl, aryl, or combinations thereof are preferred. Specific examples of the hydrocarbon group include C1-50A hydrocarbon radical comprising C1-50Straight or branched alkyl, C2-50Straight-chain or branched alkenyl, C2-50Straight-chain or branched alkynyl, C3-50Cycloalkyl radical, C3-50Cycloalkenyl radical, C3-50Cycloalkynyl group, C6-50Aryl or a combination thereof, wherein C is preferred1-50Straight or branched alkyl, C2-50Straight-chain or branched alkenyl, C3-50Cycloalkyl radical, C3-50Cycloalkenyl radical, C6-50Aryl or a combination thereof. As said combination group, for example, there may be mentioned one or more C1-50Straight or branched chain alkyl (preferably one or more C)1-20Straight or branched alkyl) with one or more C6-50Radicals obtained by direct substitution or bonding of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C1-50Straight or branched alkenyl (preferably one or more C)1-20Straight or branched alkenyl) with one or more C6-50A group obtained by directly substituting or bonding an aryl group (preferably one or more phenyl groups or naphthyl groups),One or more C1-50Straight or branched chain alkyl (preferably one or more C)1-20Straight or branched alkyl) with one or more C3-50A group obtained by direct substitution or bonding of cycloalkyl (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl), one or more C1-50Straight or branched alkenyl (preferably one or more C)1-20Straight or branched alkenyl) with one or more C3-50A group obtained by direct substitution or bonding of cycloalkyl (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl), one or more C1-50Straight or branched chain alkyl (preferably one or more C)1-20Straight or branched alkyl) with one or more C3-50A group obtained by direct substitution or bonding of cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl), one or more C1-50Straight or branched alkenyl (preferably one or more C)1-20Straight or branched alkenyl) with one or more C3-50Cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl) groups obtained by direct substitution or bonding. The substitution refers to one group as a substituent to replace a hydrogen atom in another group. The total number of carbon atoms in the combined group is an integer of 3 to 50 (preferably 3 to 20). As the above-mentioned combination group, there may be mentioned, for example, one or more C1-20Straight or branched alkylphenyl, phenyl C1-20Straight or branched chain alkyl or mono-or poly-C1-20Straight-chain or branched alkylphenyl C1-20Straight or branched chain alkyl, etc., of which C is more preferable1-10Straight or branched alkylphenyl radicals, e.g. tert-butylphenyl, phenyl C1-10Straight or branched alkyl (e.g. benzyl) or C1-10Straight-chain or branched alkylphenyl C1-10Straight or branched chain alkyl (such as t-butylbenzyl).
In the context of the present invention, by "heterohydrocarbyl" is meant one or more (ratios) within the hydrocarbyl molecular structure (excluding the ends of the backbone or any side chains in the hydrocarbyl molecular structure)Such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH2The radicals-being selected from-O-, -S-, -N ═ N-and-NR '- (R' is H or C1-4Straight or branched chain alkyl), or one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH inside the hydrocarbon-based molecular structure (excluding the end of the main chain or any side chain in the hydrocarbon-based molecular structure)<Radical substituted by radical-N<A group obtained by direct substitution. As said substituent, it is preferably-O-or-S-. It is apparent that, from the viewpoint of structural stability, a plurality of-O-, -NR' -, -N-or-N-groups are present<When used, these substituent groups are not directly bonded to each other; where multiple-S-groups are present, these substituent groups may be bonded directly to one another. The number of carbon atoms of the hydrocarbon group is represented by the group-CH2-or a group-CH<Substituted with a corresponding decrease, but for the sake of simplicity, the number of carbon atoms of the hydrocarbon group before the substitution is still used to refer to the number of carbon atoms of the heterohydrocarbon group. By "heteroalkyl" is meant a straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heteroalkynyl, straight or branched heterocyclyl, straight or branched heterocyclenyl, straight or branched heterocycloalkynyl, straight or branched heteroaryl, or combinations thereof, with straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heterocyclyl, straight or branched heterocycloalkenyl, straight or branched heteroaryl, or combinations thereof being preferred. The total number of carbon atoms in the combined group is an integer of 3 to 50 (preferably 3 to 20).
As the heterohydrocarbyl group, specifically exemplified is C4Straight chain alkyl radicals such as
(the group indicated by the arrow in the formula is not located within the molecular structure but at the end of the main chain) direct substitution with a substituent-O-will give-CH2-O-CH2-CH3or-CH2-CH2-O-CH3Is called C4A linear heteroalkyl group; c4Straight chain alkyl radicals such as
(the group indicated by the arrow in the formula is not located within the molecular structure but at the end of the main chain) direct substitution with a substituent-NH-will give-CH2-NH-CH2-CH3or-CH2-CH2-NH-CH3Also known as C4A linear heteroalkyl group. Or, C4Branched alkyl radicals such as
(the groups indicated by the arrows are not located within the molecular structure but at the ends of the main and side chains) by a substituent-N<Direct substitution will result in
Is called C4A branched heteroalkyl group. According to the invention, as the heterohydrocarbyl group, there may be mentioned, for example, C3-50Straight or branched heterohydrocarbyl, of which C is preferred3-20Straight or branched heterohydrocarbyl radicals or C3-6Straight or branched heterohydrocarbyl.
In the context of the present invention, said optionally substituted hydrocarbyl and heterohydrocarbyl are optionally substituted by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) hydrogens selected from the group consisting of hydroxyl, amino, mercapto, halogen and C1-5Straight or branched alkoxy-substituted hydrocarbyl and heterohydrocarbyl.
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
According to the invention, preferably, the L group is selected from the following groups: c having a valence of 2 to 6 (preferably 1, 2 or 3)1-50Straight chain or branched alkyl, C of 2 to 6 valences (preferably 1, 2 or 3 valences)2-50Straight chain or branched alkenyl, C substituted with one or more (preferably one, two, three or four) hydroxy groups having 2 to 6 valences (preferably 1, 2 or 3 valences)1-50Straight chain or branched alkyl, C substituted by one or more (preferably one, two, three or four) hydroxy groups having 2 to 6 valences (preferably 1, 2 or 3 valences)2-50Straight or branched alkenyl, C having a valence of 1 to 6 (preferably 1, 2 or 3)3-50Cycloalkyl or cycloheteroalkyl, 1-6 (preferably 1, 2 or 3) valent C3-50Cycloalkenyl or cycloheteroalkenyl, 1-6 (preferably 1, 2 or 3) valent C6-50Aryl or heteroaryl.
According to the invention, preferably the L group is selected from the group consisting of a cyclobutyl group having a valence of 1 to 4 (preferably 1, 2 or 3), a cyclopentyl group having a valence of 1 to 5 (preferably 1, 2 or 3), a cyclohexyl group having a valence of 1 to 6 (preferably 1, 2 or 3), a cyclobutenyl group having a valence of 1 to 4 (preferably 1, 2 or 3), a cyclopentenyl group having a valence of 1 to 5 (preferably 1, 2 or 3), a cyclopentadienyl group having a valence of 1 to 5 (preferably 1, 2 or 3), a cyclohexenyl group having a valence of 1 to 6 (preferably 1, 2 or 3), a cyclohexadienyl group having a valence of 1 to 6 (preferably 1, 2 or 3), a furyl group having a valence of 1 to 4 (preferably 1, 2 or 3), a thienyl group having a valence of 1 to 4 (preferably 1, 2 or 3), a pyrrolyl group having a valence of 1 to 4 (preferably 1 to 6), and a pyrrolyl group having a valence of 1 to 4 (preferably 1 to 6), 2-or 3-valent) indolyl group, 1-to 3-valent (preferably 1-or 2-valent) pyrazolyl group, 1-to 3-valent (preferably 1-or 2-valent) imidazolyl group, 1-to 2-valent thiazolyl group, 1-to 3-valent (preferably 1-or 2-valent) oxazolyl group, 1-to 5-valent (preferably 1-valent, 2-valent or 3-valent) pyridyl group, 1-to 7-valent (preferably 1-valent, 2-valent or 3-valent) quinolyl group, 1-to 6-valent (preferably 1-valent, 2-valent, 3-valent, 4-valent or 5-valent) phenyl group, 1-to 8-valent (preferably 1-valent, 2-valent, 3-valent, 4-valent or 5-valent) naphthyl group, group represented by formula (L-I), group represented by formula (L-II), group represented by formula (L-III), group represented by formula (L-IV),
in formula (L-I), j represents the number of phenyl-bound ends, each j is independently selected from an integer between 0 and 5 (preferably 1, 2 or 3), and at least one j is an integer between 1 and 5;
in the formula (L-II), RjEach independently selected from C1-10Linear or branched alkylene of (C)1-10Linear or branched heteroalkylene of (C)1-10And C is a linear or branched alkyleneoxy group1-10Is a linear or branched heteroalkyleneoxy group (i.e., C having a valence of 2)1-10Straight or branched alkyl of (2), C1-10Linear or branched heteroalkyl, 2-valent C1-10And C having a valence of 21-10Linear or branched heteroalkyloxy) represents RjAt the bound end of the radical, j being RjThe number of the bonding ends of the groups, each j is independently selected from an integer of 0-5 (preferably 1, 2 or 3), and at least one j is an integer of 1-5;
in the formula (L-III), each RjEach independently selected from C1-10Linear or branched alkylene and C1-10Represents RjBound end of a radical, j being R to which it belongsjThe number of bound ends of the groups, each j is independently selected from 0, 1 or 2 (preferably 1 or 2), at least one j is 1 or 2; each R isj' the groups are each independently selected from C1-10Is straight-chain or branched alkyl, j' is R to which it belongsj'the number of groups, each j' is independently selected from 0, 1 or 2 (preferably 1 or 2); for R bound to the same N atomjGroup and Rj'for the group, the sum of j and j' is 2; j' is an integer between 0 and 5 (preferably 1, 2, 3 or 4); in formula (L-IV), the Ar ring group is selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, phenyl and naphthyl (preferably selected from the group consisting of cyclobutyl, cyclopentyl, cyclohexyl, cyclopentadienyl, phenyl and naphthyl); each R isjEach independently selected from C1-10Linear or branched alkylene and C1-10Represents RjBound end of a radical, j being R to which it belongsjThe number of bound ends of the groups, each j is independently selected from 0, 1 or 2 (preferably 1 or 2), at least one j is 1 or 2; each R isj' the groups are each independently selected from C1-10Is straight-chain or branched alkyl, j' is R to which it belongsj'the number of groups, each j' is independently selected from 0, 1 or 2 (preferably 1 or 2); for R bound to the same N atomjGroup and Rj'for the group, the sum of j and j' is 2; j' is an integer between 0 and 5 (preferably 1, 2, 3 or 4).
According to the present invention, in the method for preparing the quaternary ammonium salt surfactant, the reaction product may be a single quaternary ammonium salt surfactant or a mixture containing a plurality of quaternary ammonium salt surfactants. These reaction products are all intended for the present invention, and the difference in the form of their existence does not affect the achievement of the effects of the present invention. Thus, the reaction products are collectively referred to herein, without distinction, as the quaternary ammonium surfactants of the present invention. In view of this, there is no absolute necessity for further purification of these reaction products, or for further isolation of quaternary ammonium surfactants of a specific structure from these reaction products, according to the present invention. Of course, such purification or isolation is sometimes preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. As the purification or separation method, for example, the reaction product may be purified or separated by a column chromatography method, a preparative chromatography method or the like.
The main raw materials used in the embodiment are as follows:
| name of article | Origin of origin | Purity of |
| DL-malic acid dimethyl ester | Alfa Aesar | >97％ |
| Citric acid trimethyl ester | Alfa Aesar | >97％ |
| Azobenzene-3, 3' -dicarboxylic acids | TCI | >95％ |
| 2, 5-Furanedicarboxylic acid | TCI | >98％ |
| N, N-dimethylethylenediamine | Alfa Aesar | >98％ |
| 1-bromododecane | TCI | >98％ |
| Organic solvent | Beijing chemical plant | AR |
EXAMPLE 1 preparation of dimeric quaternary ammonium surfactant
The preparation method of the dimeric quaternary ammonium salt surfactant is as follows:
the specific method comprises the following steps:
(1) the synthesis steps of intermediate product diamide: 14.1g (160.0mmol) of N, N-dimethylethylenediamine was added to 3.2g (20.0mmol) of DL-malic acid dimethyl ester and refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
ESI-MS characterization of the intermediates: 275.2(M + H), 297.2(M + Na).
1H NMR(CDCl 3400 MHz): δ 2.24 (singlet, 12H, -N (CH)3)2) 2.44 (multiplet, 4H, -NH-CH)2-CH2-N(CH3)2) 2.51, 2.82 (multiplet, 2H, -NH-CO-CH)2-CH (OH) -CO-NH-), 3.25 (multiplet, 4H, -NH-CH2-CH2-N(CH3)2) 4.42 (singlet, 1H, -CH-OH), 5.95 (singlet, 1H, -CH-OH), 7.04, 7.49 (singlet, 2H, -NH-CO-CH)2-CH(OH)-CO-NH-)。
(2) Preparation of dimeric quaternary ammonium salt surfactant:
1.6g (6.0mmol) of the intermediate and 6.0g (24.0mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone, and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give the product as a powder with a yield of 90%.
Pattern results for dimeric quaternary ammonium surfactant:1H NMR(CD3OD, 400 MHz): δ is 0.87 (triplet, 6H, -CH)3) 1.29-1.80 (multiplet, 40H, CH)3-(CH2)10-CH2-N+-), 2.71-2.85 (multiplet, 4H, CH)3-(CH2)10-CH2-N+-), 3.13-3.20 (multiplet, 12H, -N+(CH3)2) 3.45-3.52 (multiplet, 7H, -CO-NH-CH)2-CH2-N+-，-NH-CO-CH2-CH (OH) -CO-NH-), 3.55-3.76 (multiplet, 4H, -CO-NH-CH2-CH2-N+-, 4.46 (triplet, 1H, -NH-CO-CH)2-CH (OH) -CO-NH-. MS-ESI (m/z): theoretical value 772.82; and (3) testing results: 306.6([ M-2 Br)]2+/2)。1The results of H NMR and MS-ESI show that the product is consistent with the target product. Elemental analysis results: theoretical value: c36H76N4O3Br2: c, 55.95; h, 9.91; and N, 7.25. And (3) testing results: c, 55.90; h, 9.88; and N, 7.20.
These spectrum results show that the compound prepared in this example is a dimeric quaternary ammonium salt surfactant product.
EXAMPLE 2 preparation of Triquaternary ammonium salt surfactant
The preparation method of the trimeric quaternary ammonium salt surfactant is as follows:
the specific method comprises the following steps:
(1) synthesis of intermediate tripolyamide: 10.6g (120.0mmol) of N, N-dimethylethylenediamine was added to 2.3g (10.0mmol) of trimethyl citrate, and the mixture was refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
ESI-MS characterization of the intermediates: 403.2(M + H), 425.3(M + Na).
1H NMR(CDCl 3400 MHz): δ 2.24 (singlet, 18H, -N (CH)3)2) 2.41 (multiplet, 6H, -NH-CH)2-CH2-N(CH3)2) 2.60-2.73 (multiplet, 4H, -NH-CO-CH)2-CH (OH) -, 3.32 (multiplet, 6H, -NH-CH2-CH2-N(CH3)2) 5.20 (singlet, 1H, -CH-OH), 7.10, 7.47 (singlet, 3H, -NH-CH)2-CH2-N(CH3)2)。
(2) Preparation of trimeric quaternary ammonium salt surfactant: 4.0g (6.4mmol) of the intermediate and 16.0g (63.7mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give the product as a powder in 85% yield.
Map results for the trimeric quaternary surfactant:1H NMR(CD3OD, 400 MHz): δ is 0.88 (triplet, 9H, -CH)3) 1.29-1.39 (multiplet, 54H, CH)3-(CH2)9-CH2-CH2-N+-, 1.80 (singlet, 6H, CH)3-(CH2)9-CH2-CH2-N+-, 2.64-2.91 (multiplet, 6H, CH)3-(CH2)9-CH2-CH2-N+-), 3.16-3.25 (multiplet, 18H, -N+(CH3)2) 3.45-3.55 (multiplet, 11H, -CO-NH-CH)2-CH2-N+-，-NH-CO-CH2-OH), 3.65-3.72 (multiplet, 6H, -CO-NH-CH)2-CH2-N+-). MS-ESI (m/z): theoretical value 1146.64; and (3) testing results: 495.40([ M-2 Br)]2+/2)。1The results of H NMR and MS-ESI show that the product is consistent with the target product. Elemental analysis results: theoretical value: c54H113N6O4Br3: c, 56.39; h, 9.90; and N, 7.31. And (3) testing results: c, 56.26; h, 9.82; and N, 7.29.
The results of these spectra show that the compound prepared in this example is a trimeric quaternary ammonium salt surfactant product.
EXAMPLE 3 preparation of gemini surfactants with linking group containing aromatic rings
The preparation method of the gemini surfactant with the connecting group containing aromatic rings is as follows:
the specific method comprises the following steps:
(1) synthesis of intermediate dimethyl ester: 2.7g (10.0mmol) of azobenzene-3, 3' -dicarboxylic acid was added to 50mL of methanol, and a catalytic amount of concentrated sulfuric acid was added thereto and refluxed for 3 hours. After the reaction is finished, the solvent is removed by a rotary evaporator, and the intermediate dimethyl ester can be obtained with the yield of 99%.
(2) Synthesis of intermediate diamine: 3.5g (40.0mmol) of N, N-dimethylethylenediamine was added to 3.0g (10.0mmol) of intermediate dimethyl ester and refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
(3) Preparation of dimeric quaternary ammonium salt surfactant with aromatic ring-containing linking group: 4.1g (10.0mmol) of the intermediate and 10.0g (40.0mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give the product as a powder with a yield of 80%.
EXAMPLE 4 preparation of dimeric surfactants in which the linking group contains heterocycles
The preparation method of the dimeric surfactant with the connecting group containing the heterocycle is as follows:
the specific method comprises the following steps:
(1) synthesis of intermediate dimethyl ester: 1.6g (10.0mmol) of 2, 5-furandicarboxylic acid was added to 50mL of methanol, and a catalytic amount of concentrated sulfuric acid was added thereto and refluxed for 3 hours. After the reaction is finished, the solvent is removed by a rotary evaporator, and the intermediate dimethyl ester can be obtained with the yield of 99%.
(2) Synthesis of intermediate diamine: 3.5g (40.0mmol) of N, N-dimethylethylenediamine was added to 1.8g (10.0mmol) of intermediate dimethyl ester and refluxed at 106 ℃ for 3 hours. After the reaction was completed, excess N, N-dimethylethylenediamine was removed by a rotary evaporator to obtain an intermediate with a yield of 99%.
(3) Preparation of dimeric quaternary ammonium salt surfactant with heterocyclic ring-containing linking group: 3.0g (10.0mmol) of the intermediate and 10.0g (40.0mmol) of 1-bromododecane were dissolved in a mixed solvent of methanol and acetone, and reacted at 40 ℃ for 72 hours. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/ethyl acetate to give a powder product with 86% yield.
Example 5 measurement of surface tension and measurement of critical aggregation concentration
The surface tension of aqueous surfactant solutions of different concentrations was measured using a K100 surface tension meter from KRUSS, germany, using a flying ring. Each surface tension value (γ) is repeated five or more times and each surface tension curve is repeated three times. The test temperature was controlled at 25.0. + -. 0.1 ℃. Respectively measuring the surface tension values of the dimeric and trimeric quaternary ammonium salt surfactants with different concentrations, defining the turning point of the obtained surface tension-concentration logarithm (gamma-logC) curve as the critical aggregation concentration of the surfactant, and defining the surface tension value of the curve in a platform region as the gamma-concentration of the surfactantCAC。
Example 6 determination of critical aggregation concentration of surfactant by conductivity method
Conductivity values of the surfactant at different concentrations were measured using a DDS-11A type laboratory conductivity meter of shanghai wisdom photo instruments ltd. In the experimental process, a high-concentration surfactant solution is continuously added into 10.00mL of water, and the reading of a conductivity meter is carried out after the system is completely balanced. In the experimental process, the surfactant solution is placed in a constant-temperature water bath, so that the temperature of the solution in the experimental process is constant at (25.0 +/-0.1). Conductivity values of the quaternary ammonium salt surfactants of examples 1-4 at different concentrations were measured, respectively, and the turning point of the conductivity-concentration (κ -C) curve obtained was the critical aggregation concentration of the surfactant.
TABLE 1 Critical aggregation concentration of Quaternary ammonium surfactants in aqueous solution (25 ℃ C.)
Table 1 shows the Critical Aggregation Concentration (CAC) and the average value (CAC) of the quaternary ammonium salt surfactant obtained by the surface tension and electric conductivity methoda) And gammaCAC. Meanwhile, the corresponding data of the conventional single-chain Quaternary ammonium salt surfactant Dodecyl Trimethyl Ammonium Bromide (DTAB) reported in the literature (Esumi K., Taguma K., KoideY. aqueous Properties of Multi-chain Quaternary ammonium surfactants Langmuir1996,12: 4039-4041) are also given in the table. Compared with the traditional quaternary ammonium salt surfactant DTAB, the quaternary ammonium salt surfactant disclosed by the invention has extremely low critical aggregation concentration. At the same time, the surface tension (gamma) of the quaternary ammonium surfactants of the invention is comparable to DTABCAC) The values are lower, indicating that they have a stronger surface activity.
On the other hand, the surface tension (. gamma.) of the trimeric surfactant obtained in example 2 of the present inventionCAC) Is 33.0mN/m, and under the condition that the alkyl chain length is the same, the value is obviously lower than that of two trimeric cationic quaternary ammonium salt surfactants (45.0mN/m and 42.0mN/m) in the document (Langmuir,2010,26,7922-7927) and a star-shaped trimeric cationic quaternary ammonium salt surfactant (41.8mN/m) in the document (Colloids surf. A,2014,457,374-381), and the result shows that the quaternary ammonium salt surfactant disclosed by the invention has more excellent surface activity. When the micro-pore structure is applied to crude oil exploitation, the capillary resistance of the carbonate micro-pores to oil drops is reduced, and therefore the oil washing efficiency is improved.
Example 7 wettability test
A mica sheet is used for simulating reservoir rock, Tahe thick oil, Chunguang thick oil, Shenglichen 25 thick oil, Yong8 thick oil and Shengliqian offshore thick oil are respectively used as oil phases, 0.5mM or 5.0mM quaternary ammonium salt surfactant solution in the embodiment 1-4 is respectively used as a water phase, and a three-phase method is used for measuring a contact angle on a DSA100 contact angle measuring instrument. The contact angle results are shown in table 2.
TABLE 2 results of wettability tests
(continuation table 2)
From the results of Table 2, it can be seen that at fixed concentrations of 0.5mM and 5.0mM, the contact angle of the quaternary ammonium salt surfactant of the present invention is smaller than that of the single-chain quaternary ammonium salt surfactant DTAB, indicating that it has stronger wettability. At the same time, the contact angle of DTAB at 0.5mM was very large (over 110 ℃ C.), indicating that the interface was still an oil-wet interface at this time. When the quaternary ammonium salt surfactant is 0.5mM, the contact angle is respectively reduced to about 80 degrees or 50 degrees, the quaternary ammonium salt surfactant is neutral-wetting and weak-water-wetting, and the oil displacement recovery rate of rock sample water in the wetting state is highest. Therefore, the quaternary ammonium salt surfactant obtained by the invention can realize wetting reversion at a lower concentration, thereby being beneficial to the improvement of the recovery ratio of crude oil.
In conclusion, compared with the traditional surfactant, the quaternary ammonium salt surfactant prepared by the invention has stronger surface activity and aggregation capability, thereby showing the characteristics of high efficiency and low consumption. And the quaternary ammonium salt surfactant is also superior to the traditional surfactant in the aspect of wettability to crude oil, can realize wetting reversal at lower concentration, and is favorable for improving the oil washing efficiency.
Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.
Claims (19)
1. A quaternary ammonium salt surfactant has a structure shown in a formula (I):
wherein a L groups, equal to or different from each other, are each independently selected from optionally substituted m-valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group, m is an integer of 1 to 20 (preferably an integer of 1 to 10), a is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1, 2 or 3); n is0Is composed of
Number of charges of group, n0Is an integer of 1 to 20 (preferably an integer of 1 to 10); n XZ-The radicals, equal to or different from each other, are each independently selected from F-、Cl-、Br-、I-And OH-N is an integer of 1 to 20 (preferably an integer of 1 to 10), and Z-is XZ-The number of charges of the group, z is selected from 1, 2 or 3; n XZ-The absolute value of the total number of charges of the radical being equal to n0；
In formula (I), b A groups, which are identical or different from each other, are each independently selected from hydrogen, optionally substituted C1～20A linear or branched alkyl group and a group of formula (II), at least one A group being selected from the group of formula (II); b is an integer of 1 to 20 (preferably an integer of 2 to 10, more preferably 2, 3, 4, 5 or 6);
in the group of formula (II), the L 'group is selected from optionally substituted n' -valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r of n' repeating units0Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Straight or branched heteroalkyl (preferably selected from C)1～20Straight or linear alkyl); each of the m ' repeating units a ', b ', c ', d ', which are the same or different from each other, is independently selected from an integer of 0 to 5 (preferably 0, 1 or 2), and at least one a ' is an integer of 1 to 5 and at least one d ' is an integer of 1 to 5; each R of m' repeating units1Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III); each R of m' repeating units2Each independently selected from optionally substituted C1～20Straight or branched alkylene and optionally substituted C3～20M' is an integer of 1 to 20 (preferably an integer of 1 to 10), represents a bonding end of the group of formula (II) to the group L of formula (I), △ represents a bonding end of the group of formula (II) to the group R of formula (I);
in the formula (III), the groups and symbols are as defined in the formula (II), and R's in the m' repeating units1' each is independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III) (preferably each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Linear or linear heteroalkyl);
c R groups are each independently selected from optionally substituted mbC of valence1～50Hydrocarbyl or C3～50Heterocarbyl (preferably optionally substituted m)bC of valence1～20Straight or branched alkyl and C3～20Linear or branched heteroalkyl), mbIs an integer of 1 to 20 (preferably an integer of 1 to 10); c is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1, 2, 3, 4 or 5);
the number of (hydrocarbyl) bonded ends present in the a L groups is the same as the number of (carbonyl) bonded ends present in the b a groups, the a L groups being bonded to each other via their (hydrocarbyl) bonded ends to the (carbonyl) bonded ends of the b a groups;
the number of tertiary amine nitrogen atoms present in the b a groups is greater than the number of (hydrocarbyl) bound ends present in the c R groups, the number of (tertiary amine) bound ends present in the b a groups, as represented by △, is equal to the number of (hydrocarbyl) bound ends present in the c R groups, and the b a groups are bonded to each other through the (tertiary amine) bound ends present therein, as represented by △, and the (hydrocarbyl) bound ends of the c R groups;
said optionally substituted means optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, mercapto, halogen and C1-5Linear or branched alkoxy;
the structure shown in formula (I) conforms to the bonding rule.
2. The quaternary ammonium salt surfactant according to claim 1, wherein the quaternary ammonium salt surfactant has a structure represented by formula (I-I):
wherein a L groups, equal to or different from each other, are each independently selected from optionally substituted m-valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group, m is an integer of 1 to 20 (preferably an integer of 1 to 10), a is an integer of 1 to 20 (preferably an integer of 1 to 10, more preferably 1, 2 or 3); n is0Is composed of
Number of charges of group, n0Is an integer of 1 to 20 (preferably an integer of 1 to 10); n XZ-The radicals, equal to or different from each other, are each independently selected from F-、Cl-、Br-、I-And OH-N is an integer of 1 to 20 (preferably 1 to 20)An integer of 1 to 10), Z-is XZ-The number of charges of the group, z is selected from 1, 2 or 3; n XZ-The absolute value of the total number of charges of the radical being equal to n0；
In the formula (I-I), b A groups are the same or different and are independently selected from hydrogen and optionally substituted C1～20A linear or branched alkyl group and a group of formula (II-I), at least one A group being selected from the group of formula (II-I); b is an integer of 1 to 20 (preferably an integer of 2 to 10, more preferably 2, 3, 4, 5 or 6);
in the group of formula (II-I), the L 'group is selected from optionally substituted n' valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r of n' repeating units0Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Straight or branched heteroalkyl (preferably selected from C)1～20Straight or linear alkyl); each of the m ' repeating units a ', b ', c ', d ', which are the same or different from each other, is independently selected from an integer of 0 to 5 (preferably 0, 1 or 2), and at least one a ' is an integer of 1 to 5 and at least one d ' is an integer of 1 to 5; each R of m' repeating units1Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III-I); each R of m' repeating units2Each independently selected from optionally substituted C1～20Straight or branched alkylene and optionally substituted C3～20Linear or linear heteroalkylene; each R of m' repeating units3Each independently selected from optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20A linear or linear heteroalkyl group; m' is an integer of 1 to 20 (preferably an integer of 1 to 10); is represented by(II-I) the binding end of the group to which the L group in formula (I-I) is bonded;
in the formula (III-I), each group and each symbol are as defined in the formula (II-I), and each R in m' repeating units1' each is independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (III-I) (preferably each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Linear or linear heteroalkyl);
the number of (hydrocarbyl) bonded ends present in the a L groups is the same as the number of (carbonyl) bonded ends present in the b a groups, the a L groups being bonded to each other via their (hydrocarbyl) bonded ends to the (carbonyl) bonded ends of the b a groups;
said optionally substituted means optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, mercapto, halogen and C1-5Linear or branched alkoxy;
the structure shown in the formula (I-I) conforms to the bonding rule.
3. The quaternary ammonium salt surfactant according to claim 1, wherein the quaternary ammonium salt surfactant is selected from the group consisting of quaternary ammonium salt surfactants having the following specific structures or a mixture thereof in any ratio:
4. a method for producing a quaternary ammonium salt surfactant, comprising the step of reacting a compound represented by the formula (X) with a compound represented by the formula (Y) or a compound represented by the formula (Z);
in formula (X), the L 'group is selected from optionally substituted n' valent C1～50Hydrocarbyl and C3～50A heterohydrocarbyl group; n 'repeating units are the same or different from each other, and n' is an integer of 1 to 20 (preferably an integer of 1 to 10); r in n' repeating units0Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Straight or branched heteroalkyl (preferably selected from C)1～20Straight or linear alkyl); each a 'of the m' repeating units is the same or different from each other, and is independently selected from an integer of 1 to 5 (preferably 1, 2 or 3); each R of m' repeating units1Each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (X-I); each R of m' repeating units2Each independently selected from optionally substituted C1～20Straight or branched alkylene and optionally substituted C3～20Linear or linear heteroalkylene; m' is an integer of 1 to 20 (preferably an integer of 1 to 10);
in the formula (X-I), R0、R2A ' and m ' are as defined in formula (X), each R in m ' repeating units1' each is independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl, optionally substituted C3～20A linear or linear heteroalkyl group and a group of formula (X-I) (preferably each independently selected from hydrogen, optionally substituted C1～20Straight or linear alkyl and optionally substituted C3～20Linear or linear heteroalkyl) in which at least one R is1' is hydrogen;
in formula (Y), the R' group is optionally substituted maC of valence1～50Hydrocarbyl or C3～50Heterocarbyl (preferably optionally substituted m)aOf valueC1～20Straight or branched alkyl and C3～20Linear or branched heteroalkyl); m isaThe Y groups in the repeating units are the same or different from each other and are each independently selected from F, Cl, Br, I, OH and optionally substituted C1～5Straight or branched chain alkyl (preferably methyl); m isaIs an integer of 1 to 20 (preferably an integer of 1 to 10);
in formula (Z), the R group is optionally substituted mbC of valence1～50Hydrocarbyl or C3～50Heterocarbyl (preferably optionally substituted m)bC of valence1～20Straight or branched alkyl and C3～20Linear or branched heteroalkyl); m isbThe X groups in the repeating units are the same or different from each other and are each independently selected from F, Cl, Br, I and OH; m isbIs an integer of 1 to 20 (preferably an integer of 1 to 10).
5. The process according to claim 4, wherein the molar ratio between the compound of formula (X) (calculated as amine group) and the compound of formula (Y) (calculated as carbonyl group) and the compound of formula (Z) (calculated as X group) is preferably 1: 0.1-10: 0.1 to 10 (more preferably 1: 0.25 to 1: 0.5 to 5).
6. The process according to claim 4, wherein the process comprises the step of reacting the compound represented by the formula (X) with the compound represented by the formula (Y) or the compound represented by the formula (Z); or a step B comprising reacting the compound represented by the formula (X) with the compound represented by the formula (Y) and then reacting the product of the step A with the compound represented by the formula (Z); or a step A comprising reacting the compound represented by the formula (X) with the compound represented by the formula (Z) and then reacting the product of the step B with the compound represented by the formula (Y).
7. The process according to claim 4, wherein a solvent (preferably sulfone, sulfoxide, furan, C) is added to the reaction of the compound of formula (X), the compound of formula (Y) or the compound of formula (Z)1～6Alcohol (b) of,C1～6The ketone (b) may be, for example, one or more selected from dimethyl sulfoxide, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone, and methyl ethyl ketone).
8. The process according to claim 4, wherein an inert gas is introduced into the reaction of the compound represented by the formula (X), the compound represented by the formula (Y) or the compound represented by the formula (Z).
9. The process according to claim 4, wherein the reaction temperature of the compound represented by the formula (X), the compound represented by the formula (Y) and the compound represented by the formula (Z) is 0 to 200 ℃ (preferably 20 to 150 ℃).
10. The process according to claim 4, wherein the process comprises the step A of reacting the compound represented by the formula (X) with the compound represented by the formula (Y), and the step B of reacting the product of the step A with the compound represented by the formula (Z).
11. The process according to claim 4, wherein the compound of formula (X) is selected from C1～50And/or C1～50Alkyl alcohol amine (more preferably C)2～20And/or C2～20Alkyl alcohol amine of (a).
12. The process according to claim 4, wherein the compound of formula (Y) is selected from C1～50Polycarboxylic acid esters, polycarboxylic acids and polycarboxylic acid halides (more preferably C)2～30Polycarboxylic acid esters of (1).
13. The process according to claim 4, wherein the compound represented by the formula (Y) is selected from the group consisting of dicarboxylic acid esters, tricarboxylic acid esters, tetracarboxylic acid esters, pentacarboxylic acid esters and hexacarboxylic acid esters.
14. The process according to claim 4, wherein the compound represented by the formula (Y) is selected from one or more of the following structures:
wherein, the value of x is an integer between 0 and 9; the value of y is an integer selected from 1-10; raEach independently selected from C1-12Linear or branched alkyl and cycloalkyl groups.
15. The process according to claim 4, wherein the compound represented by the formula (Y) is selected from one or more of the following structures:
wherein R isaEach independently selected from C1-12Linear or branched alkyl and cycloalkyl groups.
16. The process according to claim 4, wherein the compound represented by the formula (Y) is selected from one or more of the following structures:
wherein R isaEach independently selected from C1-12The value of s is selected from an integer between 0 and 9.
17. The process according to claim 4, wherein the compound represented by the formula (Y) is selected from compounds having the following structures:
wherein R isaEach independently selected from C1-12Linear or branched alkyl and cycloalkyl groups.
18. The process according to claim 4, wherein the compound of formula (Z) is selected from C1～50Alkyl halide (preferably selected from C)5～30Alkyl halides of (a).
19. The quaternary ammonium salt surfactant according to any one of claims 1 to 3 or the quaternary ammonium salt surfactant produced by the method according to any one of claims 4 to 18 is used as a wetting agent (wetting agent in the field of tertiary oil recovery).
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