CN106422410B - A kind of preparation method and application of antenna type amino acid pattern immobilization ionic liquid - Google Patents
A kind of preparation method and application of antenna type amino acid pattern immobilization ionic liquid Download PDFInfo
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- CN106422410B CN106422410B CN201610827512.4A CN201610827512A CN106422410B CN 106422410 B CN106422410 B CN 106422410B CN 201610827512 A CN201610827512 A CN 201610827512A CN 106422410 B CN106422410 B CN 106422410B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The present invention is prepared for a kind of immobilization ionic liquid in a manner of being chemically bonded, using silica gel, polyvinyl alcohol, N- methylimidazoles and L-PROLINE, and this approach includes the following steps：（1）It is reacted using γ-r-chloropropyl trimethoxyl silane as coupling agent with N- methylimidazoles, the anion of product is then replaced with by hydroxide ion by chlorion using ion exchange resin；（2）Product is reacted with L-PROLINE, hydroxide radical anion is replaced with into amino acid anion；（3）Polyvinyl alcohol long-chain is bonded to Silica Surface and obtains the silica gel with polyhydroxy feeler；（4）Amino acid pattern methylimidazole ionic liquid with coupling agent side chain is bonded on silica gel feeler.This method provides a kind of new method to prepare the immobilization ionic liquid with suction-operated.
Description
Technical field
The present invention relates to a kind of preparation methods of immobilization ionic liquid, and in particular to a kind of using silica gel, N- methyl miaows
The method that azoles and L-PROLINE prepare antenna type immobilization ionic liquid, belongs to chemical synthesis and separation field.
Background technology
Ionic liquid be it is a kind of in room temperature and environment close to room temperature completely with liquid existing for ionic condition, phase
Be compared to traditional chemical medium its with structure designability, low-steam pressure, high polarization potentiality, excellent solubility property, high temperature
Stability and be conducive to the advantages such as dynamics Controlling, be widely used in the fields such as organic synthesis and separation science,
It is found in some Separation Research and application, and there are stronger interactions between natural activity molecule.
Immobilization ionic liquid refers to that ionic liquid is fixed on certain solid carrier by physics or chemical method
Obtained from load-type ion liquid or surface there is the solid matter of ionic liquid structure, usual chemical method to be fixed than Physical
It is more secured.It not only remains the characteristic of carrier, and can play the advantage of ionic liquid well, and by changing ion
Liquid structure and bonding pattern can obtain more new materials of different nature.Free state ionic liquid exists in use to be used
The shortcomings of measuring big, mass transfer difficulty, being difficult to detach with target substance, is unfavorable for industrializing large-scale application.By by ionic liquid
It is immobilized that on different inorganic or organic carriers, ionic liquid can more stablized, specific surface bigger, dosage significantly reduces,
Utilization rate and rate of recovery higher；Separation, recycling after use is also easy to implement, will be had more in terms of industrial continuous application excellent
Gesture.The general carrier for requiring immobilization has larger porosity and specific surface area, is capable of providing enough interaction forces or life
At the functional group of chemical bond.In addition, carrier should have enough heat, chemical stability and mechanical strength.Common fixing from
Sub- liquid carrier materials have silica gel, molecular sieve, activated carbon and diatomite and Fe3O4Etc. inorganic material (be wherein with silica gel
It is main).It is existing research by immobilization ionic liquid be used in active skull cap components separation process (Nie LR, Lu J, Zhang W,
He A,Yao S,Ionic liquid-modified silica gel as adsorbents for adsorption and
separation of water-soluble phenolic acids from Salvia militiorrhiza Bunge
[J].Separation and Purification Technology,2015,155:2-12. Juanjuan ZHANGs, Cao Shuwen, Yu Yan
Shadow, immobilization ionic liquid adsorb flavone compound performance study [J],《Analytical chemistry》,2009,37(12):1810-
1814).But what current ionic liquid was all made of is the fixed mode of single layer, the finite surface area of carrier, and supported quantity is needed into one
Step improves.
Polyvinyl alcohol (PVA) is that appearance is white powder, is that a kind of quite extensive water soluble polymer long-chain of purposes is more
First alcohols polymer, performance between plastics and rubber, application range throughout weaving, food, medicine, building, timber process,
The industries such as papermaking, printing, agricultural, steel, macromolecule chemical industry.The high polymer long chain in the polymer mutually twines under anhydrous conditions
Around curling, chain forms the cross-linked structure of cubic network shape with interchain.Macromolecular chain fully extends after meeting water, as big in opened one
Mesh bag, cubic network expand manyfold.These long-chains shaped like feeler also have certain shape memory, active alcohol on chain
A variety of chemical reactions such as esterification, etherificate, acetalation can occur for hydroxyl, can carry different functional groups whereby.Based on this, I
Polyvinyl alcohol, silica gel combined with corresponding anion/cation structure prepare a kind of novel antenna type immobilization ion
Liquid, it is intended to improve the adsorbance in supported quantity and separation application.
Invention content
The purpose of the present invention is to provide it is a kind of using silica gel, methylimidazole and L-PROLINE prepare antenna type immobilization from
The method of sub- liquid first passes through polyvinyl alcohol and forms the cubic network with multiple feelers on silica-gel carrier, then passes through chemistry
Bonding allows these feelers to carry a considerable amount of ionic liquids, inclined with the supported quantity caused by improvement at present direct single layer immobilization
Low problem.
The present invention is realized by following technology path (Fig. 1), including following four step：(1) with γ-chloropropyl
Trimethoxy silane is that coupling agent is reacted with methylimidazole, then uses ion exchange resin by the anion of product by chlorion
Replace with hydroxide ion；(2) product is reacted with L-PROLINE, by hydroxide radical anion replace with amino acid the moon from
Son；(3) polyvinyl alcohol long-chain is bonded to Silica Surface and obtains the silica gel with polyhydroxy feeler；(4) coupling agent side will be carried
The amino acid pattern methylimidazole ionic liquid of chain is fixed to by chemical reaction on silica gel feeler.Using Fourier infrared spectrograph
(FT-IR) immobilization ionic liquid particle is characterized with thermogravimetric analysis (TGA), it is as a result as follows：
(1) functional group characterizes
It is characterized using Spectrum Two L1600300 types Fourier infrared spectrograph (Perkin Elmer companies of the U.S.)
The variation (Fig. 2) of important functional group, 3448cm in preparation process-1For the stretching vibration peak of O-H；2923.80 and
2860.49cm-1For the asymmetry and symmetrical stretching vibration peak of methyl C-H；1735.87cm-1For the feature of carboxylic acid carbonyl C=O
Peak；1572.23cm-1It, can be as the spy of ionic liquid methyl imidazolium cation segment for the stretching vibration peak of imidazole ring C=N
Levy peak；1096.37cm-1For the antisymmetric stretching vibration absorption peak of Si-O-Si；804.13cm-1It shakes for the in-plane bending of Si-H
It is dynamic.Wherein 1572.23cm-1The peak at place is peculiar for immobilization ionic liquid.It can illustrate to touch according to the above spectroscopic signal feature
Angie type L-PROLINE type immobilization methylimidazole ionic liquid is finally synthesized.
(2) supported quantity characterizes
The ion of antenna type immobilization ionic liquid is measured using TG209F1 thermogravimetric analyzers (German NETZSCH companies)
Liquid supported quantity, heating rate are 10 DEG C/min, and temperature range is 20~790 DEG C.It can by weight loss on heating ratio shown in Fig. 3
Know that its supported quantity is 0.32g/g carriers.By with recent literature (Liu J, Yao S, Wang L, et al, Adsorption of
bromophenol blue from aqueous samples by novel supported ionic liquids[J]
.Journal of Chemical Technology&Biotechnology,2014,89(89):230-238.) report compares
It can be seen that supported quantity significantly improves.
Compared with the conventional method, the advantage of the invention is that：Using polyvinyl alcohol cheap and easy to get as raw material, its long-chain is utilized
Forming quantity considerable feeler is carried by the method for chemical bonding on feeler cloudy with methyl imidazolium cation and L-PROLINE
The ionic liquid functional group of ion, the immobilization ionic liquid have larger adsorption capacity, can be used as new adsorbent.
Description of the drawings
Fig. 1 is the synthetic method schematic diagram of antenna type immobilization ionic liquid
Fig. 2 is infrared spectrogram
Fig. 3 is thermogravimetric analysis figure
Specific implementation mode
The technical solution further illustrated the present invention with reference to specific implementation example.It is necessarily pointed out that following
Example should not be understood as limiting the scope of the invention, if the person skilled in the art in the field is according to foregoing invention content
Some nonessential modifications and adaptations are made to the present invention, still fall within protection scope of the present invention.
Embodiment 1：The preparation method of L-PROLINE type methylimidazole ionic liquid
(1) 0.1mol γ-r-chloropropyl trimethoxyl silane is weighed in 100mL round-bottomed flasks, and the N- first of 0.12mol is added
Base imidazoles is warming up to 80 DEG C of back flow reaction 16h under nitrogen protection, generates light yellow viscous liquid.Product washs 4 with ethyl acetate
The secondary complete N- methylimidazoles of removing unreacted, are washed 4 times with anhydrous ether later, and vacuum distillation removes solvent, and product is placed in
60 DEG C of vacuum drying 36h.
(2) the step of weighing 0.05mol (1) product is added 50mL absolute ethyl alcohols and makes it dissolve, after dissolving in beaker
Solution be transferred to equipped in 201 × 7 (717) type strong-base anion-exchange resin packed columns for having anticipated, (packed column
Resin containing 7 times of moles of exchange capacities, a height of 300mm of filler, control outflow flow velocity are no more than 0.1mL per second, constantly add second
Alcohol collects the efflux that pH is more than 8,60 DEG C of vacuum distillation concentrations to ensure that resin is immersed under liquid level.
(3) it takes step (2) product 0.05mol to be placed in 100mL round-bottomed flasks, absolute ethyl alcohol is added and makees solvent, is added
The ethanol solution of 0.15mmol L-PROLINEs.Stirring at normal temperature reacts 10h.60 DEG C of vacuum distillation recycling ethyl alcohol.It is molten with 30mL acetonitriles
Product is solved, cooling at 0 DEG C is placed on, excessive L-PROLINE is precipitated and is simultaneously filtered to remove, 80 DEG C of vacuum distillations of filtrate remove molten
Agent.It is light yellow viscous liquid, yield 83% under product room temperature.
Embodiment 2：The preparation method of antenna type silica gel intermediate
Silica gel 3.0g is weighed, is placed in 100mL round-bottomed flasks.Suitable silica gel water-dispersed is added, uses constant pressure funnel
Hydrochloric acid 15mL is added dropwise successively, the glutaraldehyde water solution 6.0g of mass fraction 50% is in flask, normal-temperature reaction 3h.It is added dropwise later
The degree of polymerization of the polyvinyl alcohol water solution that 20mL mass fractions are 15%, polyvinyl alcohol is 1700, percent alcoholysis 99%.At 35 DEG C
Under be stirred to react 6h.Product is washed with deionized to neutrality, is stored in drier after dry.Product is white antenna type silicon
Rubber powder end.
Embodiment 3：The preparation method of antenna type L-PROLINE type methylimidazole immobilization ionic liquid
It takes antenna type silica gel powder 3.0g to be dispersed in 30mL acetonitriles, step (4) product 0.03mol is added.80 DEG C of reflux
React 12h.Product is washed with deionized 3 times and removes unreacted L-PROLINE type imidazole ion liquid, 60 DEG C of vacuum drying
8h obtains antenna type amino acid pattern immobilization ionic liquid.Final product is faint yellow solid powder, and ionic liquid supported amount is
0.3g ionic liquids/g adsorbents.
Embodiment 4：Antenna type L-PROLINE type methylimidazole immobilization ionic liquid measures the adsorbance of tea polyphenols
250mg antenna type immobilization ionic liquid particles accurately are weighed in 100mL conical flasks, and the certain of 50mL is added
The tea polyphenols solution of 3500mg/L is put into constant temperature oscillation shaking table after vibrating absorption at 45 DEG C 3 hours, takes filtered supernatant
Liquid 0.50mL, is diluted to 25mL, its absorbance, gained standard curve are measured at 273nm with ultraviolet-visible spectrophotometer
For Abs (absorbance)=18.014C (concentration, mg/mL) -0.01 (R2=0.9999) suction then, is calculated according to the curve
Remaining tea polyphenols concentration in attached solution, and then the unit adsorbance of adsorbent can be calculated according to following formula.
Wherein V --- liquor capacity, unit：mL；C0--- initial concentration solution, unit：mg/mL；C1--- it is molten after absorption
The concentration of remaining tea polyphenols, unit in liquid：mg/mL；M --- adsorbent mass, unit：g；qe--- the unit of adsorbent is inhaled
Attached amount, unit：mg/g.
It is 236.84mg/g to the adsorbance of tea polyphenols to measure this antenna type immobilization ionic liquid under these conditions, high
In not being bonded common column chromatography silica gel, monolayer ionic liquid bonded silica gel (10~100mg/g) and other common adsorbent such as silicon
(10~80mg/g) such as diatomaceous earth, activated carbon, polyamide, D2301 resins, GS-18 macroporous absorbent resins (Chen Jingchun, Li Yi,
The PRELIMINARY RESULTS of Liu Chunxiu, four kinds of sorbing material separating tea multi-phenols compare [J], Beijing University of Chemical Technology's journal, 2000,27 (2):
95-96；Liu Y,Bai Q,Yi L,et al,Simultaneous purification of tea polyphenols and
caffeine from discarded green tea by macroporous adsorption resins[J]
.European Food Research&Technology,2014,238(1):59-69.)
Claims (3)
1. a kind of preparing antenna type amino acid pattern immobilization ion using silica gel, N- methylimidazoles, polyvinyl alcohol and L-PROLINE
The method of liquid, which is characterized in that carry out according to the following steps：
(1) γ-r-chloropropyl trimethoxyl silane is weighed in 100mL round-bottomed flasks, and the N- methyl miaows of 1.2 times of moles are added
Azoles is warming up to 80~120 DEG C of 8~16h of back flow reaction under nitrogen protection, generates light yellow viscous liquid；Product ethyl acetate
1~4 removing complete N- methylimidazole of unreacted of washing, is washed 1~4 time with anhydrous ether, vacuum distillation removes molten later
Agent, product are placed in 40~60 DEG C of 12~36h of vacuum drying；
(2) for the step of weighing 0.03~0.07mol (1) product in beaker, 30~70mL absolute ethyl alcohol and stirrings, which are added, keeps its molten
Solution, dissolved solution is transferred in 201 × 7 (717) type strong-base anion-exchange resin packed columns, and packed column contains 7 times
The resin of mole exchange capacity, a height of 200~300mm of filler, control outflow flow velocity are no more than 0.1mL per second, constantly add second
Alcohol collects the efflux that pH is more than 8,60~80 DEG C of vacuum distillation concentrations to ensure that resin is immersed under liquid level；
(3) it takes step (2) product 0.05mol to be placed in 100mL round-bottomed flasks, solvent is done with absolute ethyl alcohol, is added a concentration of 0.05
The L-PROLINE ethanol solution of~0.15mmol, stirring at normal temperature react 6~10h；After reaction in 60~80 DEG C of vacuum distillations
Recycle ethyl alcohol；It with 10~30mL acetonitrile lysates, is placed at 0 DEG C cooling, excessive L-PROLINE is precipitated and is crossed filters out
It goes, 60~80 DEG C of vacuum distillations of filtrate remove solvent；
(4) 1.0~3.0g of silica gel is weighed, is placed in 100mL round-bottomed flasks；Suitable silica gel water-dispersed is added, uses constant pressure addition
5~15mL of hydrochloric acid is added dropwise in funnel successively, and 2.0~6.0g of glutaraldehyde water solution of mass fraction 30~70% is in flask, room temperature
React 0.5~3h；Then, the polyvinyl alcohol water solution that 20mL mass fractions are 5~15%, the degree of polymerization of polyvinyl alcohol is added dropwise
It is 1700, percent alcoholysis 99%；Stirring the reaction was continued 2~6h at 15~35 DEG C；Product is washed with deionized to neutrality,
White antenna type silica gel powder is obtained after drying；
(5) 1.0~3.0g of antenna type silica gel powder is taken to be dispersed in 30mL acetonitriles, addition step (4) product 0.01~
0.03mol, 60~80 DEG C of 8~12h of back flow reaction；Product is washed with deionized 1~3 time, and 60~80 DEG C of vacuum drying 4~
8h obtains antenna type amino acid pattern immobilization ionic liquid.
2. a kind of as described in claim 1 prepare antenna type ammonia using silica gel, N- methylimidazoles, polyvinyl alcohol and L-PROLINE
The method of base acid type immobilization ionic liquid, it is characterised in that in step (5) final product be by with PVA feelers silica gel and
L-PROLINE type methylimidazole ionic liquid with γ-r-chloropropyl trimethoxyl silane side chain is in 60~80 DEG C of back flow reactions 8
~12h is obtained.
3. a kind of as described in claim 1 prepare antenna type ammonia using silica gel, N- methylimidazoles, polyvinyl alcohol and L-PROLINE
The method of base acid type immobilization ionic liquid, it is characterised in that the immobilization ionic liquid has specificity with phenolic compound and ties
It closes, can be used as its adsorbent.
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