CN106117233A - Sorbitol bisacetal class phase selectivity supermolecular gel factor and its preparation method and application - Google Patents
Sorbitol bisacetal class phase selectivity supermolecular gel factor and its preparation method and application Download PDFInfo
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- CN106117233A CN106117233A CN201610458621.3A CN201610458621A CN106117233A CN 106117233 A CN106117233 A CN 106117233A CN 201610458621 A CN201610458621 A CN 201610458621A CN 106117233 A CN106117233 A CN 106117233A
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- Prior art keywords
- sorbitol
- bisacetal
- oil
- phase selectivity
- class phase
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 title claims abstract description 45
- 239000000600 sorbitol Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 229960002920 sorbitol Drugs 0.000 claims description 60
- 239000003921 oil Substances 0.000 claims description 50
- 235000019198 oils Nutrition 0.000 claims description 50
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000012065 filter cake Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000006184 cosolvent Substances 0.000 claims description 17
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 230000004044 response Effects 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- -1 aliphatic acyl chlorides Chemical class 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 241000220324 Pyrus Species 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000021017 pears Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 2
- 238000001879 gelation Methods 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 22
- 238000013019 agitation Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003292 glue Substances 0.000 description 5
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000003113 dilution method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 0 *C(C1=CC[C@@](*=O)C=C1)O Chemical compound *C(C1=CC[C@@](*=O)C=C1)O 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- 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
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor and its preparation method and application, this gelator is with shown in formula I:Wherein R=(CH2)4CH3Or (CH2)10CH3.The low molecular weight organic compound that a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor of the present invention is simple in construction, be readily synthesized, use and also be able to show the ability of oil phase in selective gel carburetion/aqueous mixtures on a small quantity, and gelator can recycle.The present invention solves existing similar phase selectivity supermolecular gel factor preparation process inconvenience complicated, actually used and the problem such as gelation efficacy is low, and in industrial wastewater, there is preferable application prospect in the field such as the recovery of oil based solvent and marine oil overflow recovery.
Description
Technical field
The invention belongs to technical field of fine, be specifically related to a kind of sorbitol bisacetal class phase selectivity supermolecule and coagulate
Glue factor and preparation method thereof and the application in oil product gel.
Background technology
The discharge of oil oil spilling and industrial oily waste water may result in serious environmental pollution, processes oil product the most both at home and abroad
The method polluted mainly has solvent dilution method, adsorbent method, Macromolecule oil preparation etc..Although solvent dilution method is simple, but
The most fundamentally solve pollution problem.Carry out separating with adsorbent, make oil product be difficult to reclaim, and cost is the highest.
Owing to Macromolecule oil preparation is difficult to miscible with stickiness oil product so that gelatinizing process is complicated, time-consuming, inefficiency.Development in recent years
Based on the high efficiency, low cost oil-water separation technique that the phase selectivity supermolecular gel factor is technical characterstic, administer at oil pollution
With fields such as water body purifications, there is good using value.
The phase selectivity supermolecular gel factor is the self assembly performance utilizing organic micromolecule gel factor, optionally coagulates
Oil phase in glue oil/water mixed system and not gel aqueous phase, thus by oil-water separation.Its dominant mechanism is: gelator passes through
The non-covalent interactions such as hydrogen bond, electrostatic interaction, Van der Waals force, pi-pi accumulation, Van der Waals force, in one-dimensional square upwards self assembly
Forming the fibre structures such as banding, tubulose or helical form, these fibers the most mutually tangle and form three-dimensional net structure, and then utilize table
Substantial amounts of oil molecule is fixed in network by surface tension, capillary force etc., makes oil phase be formed and has viscoelastic semisolid half
Liquid and the physical gel of thermal reversibility.Different from traditional chemical gel, physical gel is energy under certain outside stimulus
Realizing the reversible phase in version of dissolved colloidal state and gel state, this oleogel formed after making addition gelator reversibly becomes molten
Glue, uses the recyclable gelator of method and the oil of gel such as distillation.
Design the novel sorbitol bisacetal class phase selectivity supermolecular gel factor, oil pollution under actual environment can be met
The widespread demand administered, expands the research of phase selectivity gelling performance and application simultaneously and provides bright prospects.
Summary of the invention
For problems of the prior art, the present invention provides a kind of sorbitol bisacetal class phase selectivity supermolecule to coagulate
Glue factor and preparation method thereof, the invention discloses this sorbitol bisacetal class phase selectivity supermolecular gel factor can make simultaneously
The method processing oil pollution for fuel thickener, and can recycle.
For solve above-mentioned technical problem, the present invention by the following technical solutions:
A kind of sorbitol bisacetal class phase selectivity supermolecular gel factor, structural formula is as follows:
Wherein, R=(CH2)4CH3Or (CH2)10CH3。
The preparation method of the described sorbitol bisacetal class phase selectivity supermolecular gel factor, comprises the steps:
(1) in reaction vessel, sorbitol, organic solvent and catalyst are added, more logical N in reactor2To reactor completely
For inert atmosphere, being subsequently adding p formylbenzoic acid methyl ester, heating-up temperature, to 50-80 DEG C, in 1-5 hour response time, filters
Collect filter cake, use acetone recrystallization filter cake, be dried 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol；
(2) in reaction vessel, 1,3:2,4-bis-(4-methyl formate base the benzylidene)-D-mountain that step (1) prepares is added
Pears alcohol, methanol or oxolane are solvent, add hydrazine hydrate, heating-up temperature to 30-70 DEG C, 5-10 hour response time, mistake
Filter collect filter cake, be dried 1,3:2,4-bis-(4-formohydrazide group benzylidene)-D-glucitol；
(3) in reaction vessel, 1,3:2,4-bis-(4-formohydrazide group the benzylidene)-D-Pyrusussuriensis that step (2) prepares is added
Alcohol, methanol or oxolane are solvent, and acid binding agent adds aliphatic acyl chlorides, react 5-10 hour under conditions of 0-30 DEG C,
Filter cake, more in ethanol recrystallization filter cake are collected by filtration, be dried to obtain sorbitol bisacetal class phase selectivity supermolecular gel because of
Son.
In described step (1), sorbitol is 1:(1-5 with the mol ratio of p formylbenzoic acid methyl ester), sorbitol and catalysis
The mass ratio of agent is 1:(0.01-0.15).
Organic solvent in described step (1) is one or both mixture in methanol, hexamethylene, toluene；Described step
Suddenly the catalyst in (1) is dodecyl sodium sulfonate or p-methyl benzenesulfonic acid.
1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol and the quality of hydrazine hydrate in described step (2)
Ratio is 1:(1-9).
In described step (3), 1,3:2,4-bis-(4-formohydrazide group benzylidene)-D-glucitol rubs with aliphatic acyl chlorides
Your ratio is 1:(1-5), aliphatic acyl chlorides is 1:(1-20 with the mass ratio of acid binding agent).
Acid binding agent in described step (3) is pyridine or triethylamine, and aliphatic acyl chlorides is positive caproyl chloride or lauroyl chloride.
The described sorbitol bisacetal class phase selectivity supermolecular gel factor as fuel thickener in selective gel oils
Or the application in organic solvent, comprise the steps:
A, the mass ratio utilizing cosolvent that gelator dissolving is obtained oil/water mixed system, gelator and cosolvent are 1:
(1-20)；
B, the cosolvent containing gelator step A prepared join in oil/water mixed system and are sufficiently mixed, at room temperature
Stand no less than 10min, obtain organogel and water layer, wherein gelator and the quality of oil solvent in oil/water mixed system
Ratio is 1:(50-200)；
C, by filter or tilt, organogel step B obtained separates with water layer；
D, isolated for step C organogel is distilled under normal or reduced pressure, make gelator divide with oil solvent and cosolvent
From, it is achieved the recycling of gelator.
Described cosolvent is methanol, ethanol, propanol, isopropanol, n-butyl alcohol, benzyl alcohol, petroleum ether, normal hexane, hexamethylene
Alkane, normal octane, heptane, dichloromethane, chloroform, carbon tetrachloride, acetone, butanone, ether, butyl ether, benzene,toluene,xylene, chlorine
Benzene, Nitrobenzol, ethyl acetate, methyl acetate, acetonitrile, oxolane, N,N-dimethylformamide or dimethyl sulfoxide.
Described oil solvent is vegetable oil, lubricating oil, gasoline, diesel oil, kerosene, crude oil, pump oil, hexamethylene, normal hexane, just
Octane, toluene or dimethylbenzene.
Beneficial effects of the present invention: 1, a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor of the present invention is
Simple in construction, the low molecular weight organic compound being readily synthesized, use and also be able on a small quantity show the mixing of selective gel oil/water
The ability of oil phase in thing；2, the sorbitol bisacetal class phase selectivity supermolecular gel factor prepared by the present invention can be in room temperature
Under the conditions of selective gel carburetion class or organic solvent, such as vegetable oil, gasoline, diesel oil, hexamethylene, normal octane or toluene etc., solidifying
Glue process can complete within 2-10min, thus realizes easily separating oil based solvent with water, is easy to by distillation
Oil based solvent is reclaimed, and obtained gelator can be reused；3, the present invention solves the selection of existing class patibhaga-nimitta
Property supermolecular gel factor preparation process inconvenience complicated, actually used and problem, the oil in industrial wastewater such as gelation efficacy is low
There is preferable application prospect in the fields such as the recovery of kind solvent and marine oil overflow recovery.
Accompanying drawing explanation
Fig. 1 is the picture (figure a) of compound A selective gel normal octane in normal octane/aqueous systems and xerogel is micro-
Seeing shape appearance figure (figure b), in figure, the concentration of fuel thickener A is 1% w/w.
Fig. 2 is the picture (figure a) of compound B selective gel normal octane in normal octane/aqueous systems and xerogel is micro-
Seeing shape appearance figure (figure b), in figure, the concentration of fuel thickener B is 1% w/w.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following example are merely to illustrate this
Inventing not for limiting the scope of the present invention, the person skilled in the art in this field can make one according to the content of foregoing invention
A little nonessential improvement and adjustment.
Embodiment 1
The preparation method of a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor, comprises the steps:
(1) in the four-hole bottle equipped with water knockout drum, mechanical agitation, thermometer and airway, sorbitol 9.1 grams is added
(0.05mol), methanol 30 grams, hexamethylene 100 grams, stirring makes sorbitol be completely dissolved.N it is passed through again in airway2, treat N2Fill
After full reaction vessel, add p formylbenzoic acid methyl ester 8.2 grams (0.05mol) and dodecyl sodium sulfonate 0.091 gram, heating temperature
Degree is to 60 DEG C, and after reacting 1 hour, system starts to become viscous, and continues stirring reaction 3 hours, and sucking filtration after completion of the reaction, filter cake is with third
Ketone is recrystallized to give product, dries to obtain 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol 5.3 grams.Productivity is
45%；
(2) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 3.3 grams obtained by step (1), methanol 60
Gram, hydrazine hydrate 3.3 grams, heating-up temperature to 65 DEG C, in 10 hours response time, filter cake is collected by filtration, is dried to obtain 1,3:2,4-bis-
(4-formohydrazide group benzylidene)-D-glucitol is 2.3 grams, and productivity is 70%；
(3) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 1.0 grams obtained by step (2)
(0.002mol), methanol 30 grams, pyridine 0.27 gram, positive caproyl chloride 0.27 gram (0.002mol), reaction temperature is 5 DEG C, during reaction
Between 10 hours, filter cake, more in ethanol recrystallization filter cake are collected by filtration, being dried to obtain compound A is 0.47 gram.Productivity is 70%,
Fusing point is 208-210 DEG C.The structural formula of compound A is as follows:。
1H-NMR (600MHz, DMSO-d6): δ 10.37 (s, 4H, CO-NH-NH-CO), 7.98-8.01 (d, 4H,
Ar-H), 7.59-7.61 (d, 4H, Ar-H), 5.76 (s, 2H, OCHO), 4.97-4.98 (d, 1H, OH),
4.50-4.51 (d, 1H, OH), 4.02-4.21 (m, 4H, 2CH2), 3.90 (m, 1H, CH), 3.79 (m,
1H, CH), 3.61 (m, 1H, CH), 3.46 (m, 1H, CH),1.32-2.33 (m, 22H, 2C5H11)。
Embodiment 2
The preparation method of a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor, comprises the steps:
(1) in the four-hole bottle equipped with water knockout drum, mechanical agitation, thermometer and airway, sorbitol 9.1 grams is added
(0.05mol), methanol 30 grams, hexamethylene 100 grams, stirring makes sorbitol be completely dissolved.N it is passed through again in airway2, treat N2Fill
After full reaction vessel, add p formylbenzoic acid methyl ester 16.4 grams (0.10mol) and dodecyl sodium sulfonate 1.36 grams, heating temperature
Degree is to 60 DEG C, and after reacting 1 hour, system starts to become viscous, and continues stirring reaction 3 hours, and sucking filtration after completion of the reaction, filter cake is with third
Ketone is recrystallized to give product, dries to obtain 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol 13.1 grams.Productivity is
55%；
(2) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 3.3 grams obtained by step 1, methanol 60 grams,
Hydrazine hydrate 6 grams, heating-up temperature to 65 DEG C, in 10 hours response time, filter cake is collected by filtration, is dried to obtain 1,3:2,4-bis-(4-first
Hydrazide group benzylidene)-D-glucitol is 3.0 grams, productivity is 91%；
(3) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 1.0 grams (0.002mol) obtained by step 2,
Methanol 30 grams, pyridine 5 grams, positive caproyl chloride 0.54 gram (0.004mol), reaction temperature is 5 DEG C, 10 hours response time, filters and receives
Collection filter cake, then recrystallization filter cake in ethanol, being dried to obtain compound A is 0.9 gram.Productivity is 67%.
Embodiment 3
The preparation method of a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor, comprises the steps:
(1) in the four-hole bottle equipped with water knockout drum, mechanical agitation, thermometer and airway, sorbitol 9.1 grams is added
(0.05mol), methanol 30 grams, toluene 100 grams, stirring makes sorbitol be completely dissolved.N it is passed through again in airway2, treat N2It is full of
After reaction vessel, add p formylbenzoic acid methyl ester 41.0 grams (0.25mol) and dodecyl sodium sulfonate 1.36 grams, heating-up temperature
To 60 DEG C, after reacting 1 hour, system starts to become viscous, and continues stirring reaction 3 hours, sucking filtration after completion of the reaction, filter cake acetone
It is recrystallized to give product, dries to obtain 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol 14.3 grams.Productivity is
73%；
(2) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 3.3 grams obtained by step 1, oxolane 60
Gram, hydrazine hydrate 29.7 grams, heating-up temperature to 65 DEG C, in 10 hours response time, filter cake is collected by filtration, is dried to obtain 1,3:2,4-bis-
(4-formohydrazide group benzylidene)-D-glucitol is 3.1 grams, and productivity is 94%；
(3) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 1.0 grams (0.002mol) obtained by step 2,
Oxolane 30 grams, triethylamine 26.8 grams, positive caproyl chloride 1.34 grams (0.010mol), reaction temperature is 5 DEG C, and the response time 10 is little
Time, filter cake, more in ethanol recrystallization filter cake are collected by filtration, being dried to obtain compound A is 1.1 grams.Productivity is 82%.
Embodiment 4
(1) in the four-hole bottle equipped with water knockout drum, mechanical agitation, thermometer and airway, sorbitol 9.1 grams is added
(0.05mol), methanol 30 grams, toluene 100 grams, stirring makes sorbitol be completely dissolved.N it is passed through again in airway2, treat N2It is full of
After reaction vessel, add p formylbenzoic acid methyl ester 41.0 grams (0.25mol) and dodecyl sodium sulfonate 1.36 grams, heating-up temperature
To 60 DEG C, after reacting 1 hour, system starts to become viscous, and continues stirring reaction 3 hours, sucking filtration after completion of the reaction, filter cake acetone
It is recrystallized to give product, dries to obtain 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol 14.3 grams.Productivity is
73%；
(2) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 3.3 grams obtained by step 1, oxolane 60
Gram, hydrazine hydrate 6 grams, heating-up temperature to 65 DEG C, in 10 hours response time, filter cake is collected by filtration, is dried to obtain 1,3:2,4-bis-(4-
Formohydrazide group benzylidene)-D-glucitol is 3.0 grams, productivity is 91%；
(3) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 1.0 grams (0.002mol) obtained by step 2,
Methanol 30 grams, pyridine 0.44 gram, lauroyl chloride 0.44 gram (0.002mol), reaction temperature is 5 DEG C, 10 hours response time, mistake
Filter cake, then recrystallization filter cake in ethanol are collected in filter, and being dried to obtain compound B is 0.7 gram.Productivity is 83%, and fusing point is 213-
215℃。1H-NMR (600MHz, DMSO-d6): δ 10.35 (s, 4H, CONHNHCO), 7.98-7.99 (d, 4H, Ar-
H), 7.59-7.62 (d, 4H, Ar-H), 5.76 (s, 2H, OCHO), 4.97-4.99 (d, 1H, OH), 4.51-
4.52 (d, 1H, OH), 4.21 (m, 4H, 2CH2), 4.02 (m, 1H, CH), 3.79 (m, 1H, CH),
3.60 (m, 1H, CH), 3.44 (m, 1H, CH),0.84-2.32 (m, 46H, 2C11H23)。
Embodiment 5
The preparation method of a kind of sorbitol bisacetal class phase selectivity supermolecular gel factor, comprises the steps:
(1) in the four-hole bottle equipped with water knockout drum, mechanical agitation, thermometer and airway, sorbitol 9.1 grams is added
(0.05mol), methanol 30 grams, hexamethylene 100 grams, stirring makes sorbitol be completely dissolved.N it is passed through again in airway2, treat N2Fill
After full reaction vessel, add p formylbenzoic acid methyl ester 16.4 grams (0.10mol) and dodecyl sodium sulfonate 1.36 grams, heating temperature
Degree is to 60 DEG C, and after reacting 1 hour, system starts to become viscous, and continues stirring reaction 3 hours, and sucking filtration after completion of the reaction, filter cake is with third
Ketone is recrystallized to give product, dries to obtain 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol 13.1 grams.Productivity is
55%；
(2) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 3.3 grams obtained by step 1, methanol 60 grams,
Hydrazine hydrate 6 grams, heating-up temperature to 65 DEG C, in 10 hours response time, filter cake is collected by filtration, is dried to obtain 1,3:2,4-bis-(4-first
Hydrazide group benzylidene)-D-glucitol is 3.0 grams, productivity is 91%；
(3) equipped with mechanical agitation, thermometer four-hole bottle in add the compound 1.0 grams (0.002mol) obtained by step 2,
Methanol 30 grams, pyridine 44 grams, lauroyl chloride 2.18 grams (0.010mol), reaction temperature is 5 DEG C, 10 hours response time, filters
Collecting filter cake, then recrystallization filter cake in ethanol, being dried to obtain compound B is 1.5 grams.Productivity is 89%.The structure of compound B
Formula is as follows:。
Embodiment 6
In tool plug test tube, add 0.01 g of compound A, cosolvent oxolane 0.13 gram is joined in test tube, by concussion
Or ultrasonic make it be completely dissolved.1 gram of vegetable oil and 1 gram of water is added, by the hydrotropy containing gelator in another tool plug test tube
Agent joins in test tube, and left at room temperature 3min can form gel, is inverted by test tube, does not observes and have solution to ooze out or flow
Under.
Make gel and water layer separately by the method for simple filtration or inclination, obtained organogel is utilized normal pressure or
The method of decompression distillation, heats gel in flask, oil solvent can be steamed recovery, and in flask, remaining being coagulates oil
Agent (gelator).
Embodiment 7
The organic gel agent used is the compound A that the oil solvent steamed in embodiment 6 reclaims, and other conditions are with embodiment 6, same
Sample can obtain the effect of embodiment 6.
Embodiment 8
The gelator used is compound B, and cosolvent, oil solvent and other operating condition are with embodiment 6, it is possible to obtain with real
Execute the same effect of example 6.
Embodiment 9
The oil solvent used is gasoline, and gelator, cosolvent and other operating condition are with embodiment 6, it is possible to obtain with implementing
The same effect of example 6.
Embodiment 10
The oil solvent used is diesel oil, and gelator, cosolvent and other operating condition are with embodiment 6, it is possible to obtain with implementing
The same effect of example 6.
Embodiment 11
The oil solvent used is hexamethylene, and gelator, cosolvent and other operating condition are with embodiment 6, it is possible to obtain with real
Execute the same effect of example 6.
Embodiment 12
The oil solvent used is normal octane, and gelator, cosolvent and other operating condition are with embodiment 6, it is possible to obtain with real
Execute the same effect of example 6.
Embodiment 13
The oil solvent used is toluene, and gelator, cosolvent and other operating condition are with embodiment 6, it is possible to obtain with implementing
The same effect of example 6.
All raw materials can be self-control or commercially available.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.The skill of the industry
The art personnel simply explanation it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements both fall within scope of the claimed invention.Claimed scope by appending claims and
Its equivalent defines.
Claims (10)
1. a sorbitol bisacetal class phase selectivity supermolecular gel factor, it is characterised in that structural formula is as follows:
Wherein, R=(CH2)4CH3Or (CH2)10CH3。
The preparation method of the sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 1, it is special
Levy and be to comprise the following steps:
(1) in reaction vessel, sorbitol, organic solvent and catalyst are added, more logical N in reactor2To reactor completely
For inert atmosphere, being subsequently adding p formylbenzoic acid methyl ester, heating-up temperature, to 50-80 DEG C, in 1-5 hour response time, filters
Collect filter cake, use acetone recrystallization filter cake, be dried 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol；
(2) in reaction vessel, 1,3:2,4-bis-(4-methyl formate base the benzylidene)-D-mountain that step (1) prepares is added
Pears alcohol, methanol or oxolane are solvent, add hydrazine hydrate, heating-up temperature to 30-70 DEG C, 5-10 hour response time, mistake
Filter collect filter cake, be dried 1,3:2,4-bis-(4-formohydrazide group benzylidene)-D-glucitol；
(3) in reaction vessel, 1,3:2,4-bis-(4-formohydrazide group the benzylidene)-D-Pyrusussuriensis that step (2) prepares is added
Alcohol, methanol or oxolane are solvent, and acid binding agent adds aliphatic acyl chlorides, react 5-10 hour under conditions of 0-30 DEG C,
Filter cake, more in ethanol recrystallization filter cake are collected by filtration, be dried to obtain sorbitol bisacetal class phase selectivity supermolecular gel because of
Son.
The preparation method of the sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 2, it is special
Levy and be: in described step (1), sorbitol is 1:(1-5 with the mol ratio of p formylbenzoic acid methyl ester), sorbitol and catalysis
The mass ratio of agent is 1:(0.01-0.15).
The preparation method of the sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 2, it is special
Levy and be: the organic solvent in described step (1) is one or both mixture in methanol, hexamethylene, toluene；Described step
(1) catalyst in is dodecyl sodium sulfonate or p-methyl benzenesulfonic acid.
The preparation method of the sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 2, it is special
Levy and be: 1,3:2,4-bis-(4-methyl formate base benzylidene)-D-glucitol and the mass ratio of hydrazine hydrate in described step (2)
For 1:(1-9).
The preparation method of the sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 2, it is special
Levy and be: in described step (3) 1,3:2,4-bis-(4-formohydrazide group benzylidene)-D-glucitol and aliphatic acyl chlorides mole
Ratio is 1:(1-5), aliphatic acyl chlorides is 1:(1-20 with the mass ratio of acid binding agent).
The preparation method of the sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 2, it is special
Levying and be: the acid binding agent in described step (3) is pyridine or triethylamine, aliphatic acyl chlorides is positive caproyl chloride or lauroyl chloride.
8. a sorbitol bisacetal class phase selectivity supermolecular gel factor as claimed in claim 1 is being selected as fuel thickener
Application in selecting property gel oils or organic solvent, it is characterised in that comprise the steps:
A, the mass ratio utilizing cosolvent that gelator dissolving is obtained oil/water mixed system, fuel thickener and cosolvent are 1:(1-
20)；
B, the cosolvent containing gelator step A prepared join in oil/water mixed system and are sufficiently mixed, at room temperature
Stand no less than 10min, obtain organogel and water layer, wherein gelator and the quality of oil solvent in oil/water mixed system
Ratio is 1:(50-200)；
C, organogel step B obtained separate with water layer；
D, isolated for step C organogel is distilled under normal or reduced pressure, make gelator divide with oil solvent and cosolvent
From, it is achieved the recycling of gelator.
The sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 8 is selecting as fuel thickener
Application in property gel oils or organic solvent, it is characterised in that: described cosolvent be methanol, ethanol, propanol, isopropanol,
N-butyl alcohol, benzyl alcohol, petroleum ether, normal hexane, hexamethylene, normal octane, heptane, dichloromethane, chloroform, carbon tetrachloride, acetone, fourth
Ketone, ether, butyl ether, benzene,toluene,xylene, chlorobenzene, Nitrobenzol, ethyl acetate, methyl acetate, acetonitrile, oxolane, N, N-
Dimethylformamide or dimethyl sulfoxide.
The sorbitol bisacetal class phase selectivity supermolecular gel factor the most according to claim 8 is being selected as fuel thickener
Application in selecting property gel oils or organic solvent, it is characterised in that: described oil solvent is vegetable oil, lubricating oil, gasoline, bavin
Oil, kerosene, crude oil, pump oil, hexamethylene, normal hexane, normal octane, toluene or dimethylbenzene.
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