CN109180986A - A kind of building of solid fabric element base ionic liquid, preparation method and applications - Google Patents
A kind of building of solid fabric element base ionic liquid, preparation method and applications Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C—CHEMISTRY; METALLURGY
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Abstract
The building of the present invention relates to a kind of solid fabric element base ionic liquid material containing carboxylic acid group, preparation method and applications.To solve the problems, such as that traditional solid-carrying type ionic liquid preparation method can dissolve cellulose carrier, acid imidazolium ionic liquid containing carboxylic acid group is synthesized in the surface of porous cellulose microballoon and hole using substep Graft Method, is prepared for a series of acid solid fabric element base ionic liquid of alkyl chains containing different length and variety classes acidic anionic.Solid fabric element base ionic liquid prepared by the present invention has the characteristics that environmental-friendly, renewable, low corrosion, low cost, stable structure, good biocompatibility and catalytic activity are higher, it can be applied to auxiliary plant resources constituents extraction or conversion, be a kind of multi-functional bio-based materials.
Description
Technical field
This research is related to a kind of building of solid fabric element base ionic liquid, preparation method and applications, belongs to biomass
Material Field.
Background technique
" ionic liquid " is because it is with green safe, not volatile, pH value is adjustable, good chemical and thermal stability etc.
Advantage become world today's research hotspot, be widely used in extraction and separation, organic synthesis, green catalysis, analysis detection and
The fields such as functional material.But there are some defects in conventional liquid ionic liquid, as viscosity is larger, price is high in actual use
It is expensive, recycling is cumbersome etc., these defects limit its large-scale use in production.And ionic liquid is fixed on some specific
Matrix, can not only effectively solve these problems, the good characteristic of ionic liquid can also be retained.Current reported ion
Up to tens kinds of liquid-carrier, such as active carbon, molecular sieve, ferroso-ferric oxide, graphene and metal organic framework.These carriers
Although preferable support can be provided for the immobilization of ionic liquid, due to generally lacking biocompatibility so that solid-state from
Development of the sub- liquid in the fields such as biology and medical treatment is restricted to a certain extent.
Cellulose has from a wealth of sources, cheap, plastic as biology base high molecular polymer the most abundant on the earth
Property strong, stable structure, green is renewable and has the characteristics that good biocompatibility, be the new type functional material of great potential
Material.In addition, cellulose crystallinity, rigidity, organic solvent resistance and resistance to acid and alkali also with higher, and contained by cellulose
For abundant hydroxyl group but also cellulose surface is easy to be modified by chemical group, these characteristics make cellulose become ideal raw
Object base carrier.The immobilized matrix as multiple material currently, cellulose has been reported, but still without by ionic liquid supported in fibre
Tie up the relevant report of plain matrix.This is because conventional solid support method is usually that carrier is directly mixed with ionic liquid,
Physically or chemically effect is made it through to be connected to each other, but when cellulose and ionic liquid directly contact, between cellulosic molecule
Hydrogen bond be soon weakened, be quickly soluble in cellulose in ionic liquid, so as to cause ionic liquid in cellulose matrix
The immobilized failure in surface.
Therefore, it is the technology that the integrality of carrier matrix how is kept in the preparation process of cellulose base ionic liquid
It is crucial.
Summary of the invention
The object of the present invention is to provide a kind of buildings of solid fabric element base ionic liquid, preparation method and applications.It is logical
The progress substep graft reaction in porous cellulose microsphere surface and hole is crossed, is prepared for a series of containing different length alkyl chain
Imidazolium-based cations and variety classes anion solid fabric element base ionic liquid, solve the research field all the time
Ionic liquid can not be immobilized in the cellulose matrix the problem of.Meanwhile the solid fabric element base ionic liquid is provided in plant
The method applied in the extraction or conversion of resource.
The present invention provides a kind of solid fabric element base ionic liquid (Fig. 1) and its synthetic routes (Fig. 2), specifically according to such as
Lower step carries out:
(i) grafting of epoxy group: porous cellulose microballoon (b), epoxychloropropane and sodium hydroxide solution are mixed equal
It is even, it is placed in 4~6h of concussion in shaking table at room temperature, filters, is washed three times with dehydrated alcohol, 40~50 after reaction
The porous cellulose microballoon (c) of epoxy group modification can be obtained in DEG C drying；Its epoxychloropropane dosage is that every gram of cellulose is micro-
Ball 1.1 × 10-2~1.3 × 10-2mol；Sodium hydroxide concentration is every gram of cellulose microsphere 2.5 × 10-2~3.2 × 10-2mol；Hydrogen
Sodium hydroxide solution concentration is 1.25 × 10-2~1.55 × 10-2mol/mL；
The grafting of (II) imidazole group: sample c obtained in step (i) is added to the N,N-dimethylformamide of imidazoles
(DMF) in solution, 7~9h is reacted under conditions of 75~85 DEG C, filters, is washed three times with dehydrated alcohol, 40 after reaction
The porous cellulose microballoon (d) of imidazole group modification can be obtained in~50 DEG C of dryings；Its imidazoles dosage is that every gram of cellulose is micro-
Ball 0.9 × 10-2~1.2 × 10-2mol；The DMF solution concentration of imidazoles is 1.5 × 10-4~1.9 × 10-4mol/mL；
The grafting of (III) carboxylic acid group: by step (II) to sample d be fitted into reaction flask, low whipping speed is
Under conditions of 200~400rpm, the DMF solution of the carboxylic acid of halogen substituent is added drop-wise in reaction flask, at 65~75 DEG C
Under the conditions of react 8~10h, filter, wash three times with dehydrated alcohol after reaction, 40~50 DEG C of dryings, can be obtained it is negative from
Son is the solid fabric element base ionic liquid (e) of halide ion；Carboxylic acid used is chlorine (bromine) acetic acid, 3- chlorine (bromine) propionic acid, 4- chlorine
(bromine) butyric acid or 5- chlorine (bromine) valeric acid；Its carboxylic acid dosage is every gram of cellulose microsphere 0.6 × 10-2~0.85 × 10-2mol；Carboxylic acid
DMF solution concentration be 0.9 × 10-4~1.4 × 10-4mol/mL；
The grafting of (IV) acidic anionic: inorganic acids anion, heteropllyacids anion and organic acid are chosen respectively
Anionic grafting sample e obtained in step (III) is specifically divided into following three kinds of methods because the type for being grafted acid is different:
1) grafting of inorganic acids anion: under conditions of low whipping speed is 200~400rpm, slowly into sample e
The aqueous solution of inorganic acid is added dropwise, after completion of dropwise addition, 8~12h is reacted under the conditions of 50~60 DEG C, is filtered after reaction, with steaming
Distilled water cleaning sample to surface is in neutrality, dry after 40~50 DEG C, and the solid fabric containing inorganic acids anion can be obtained
Plain base ionic liquid；Inorganic acid used is sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid；The dosage of inorganic acid is every gram of cellulose microsphere
0.4×10-2~0.6 × 10-2mol；The concentration of aqueous solution of inorganic acid is 0.15 × 10-2~0.3 × 10-2mol/mL；
2) grafting of heteropllyacids anion: under conditions of low whipping speed is 200~400rpm, slowly into sample e
The ethanol solution of heteropoly acid is added dropwise, after completion of dropwise addition, reacts 36~48h at room temperature, filters after reaction, with distillation
Water cleaning sample to surface is in neutrality, dry after 40~50 DEG C, and the solid fabric containing heteropllyacids anion can be obtained
Plain base ionic liquid；Heteropoly acid used is phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid；The dosage of heteropoly acid is every gram of cellulose microsphere
0.1×10-3~0.2 × 10-3mol；The ethanol solution concentration of heteropoly acid is 0.4 × 10-4~0.1 × 10-3mol/mL；
3) grafting of organic acid anion: under conditions of low whipping speed is 200~400rpm, slowly into sample e
The aqueous solution of organic acid is added dropwise, 12~16h is reacted under conditions of 70~90 DEG C, during sample to surface is in wash with distilled water
Property, it is dry after 40~50 DEG C, the solid fabric element base ionic liquid containing organic acid anion can be obtained；It is used organic
Acid is Loprazolam, trifluoromethanesulfonic acid, p-aminobenzene sulfonic acid or p-methyl benzenesulfonic acid.The dosage of organic acid is that every gram of cellulose is micro-
Ball 0.4 × 10-2~0.6 × 10-2mol；The amount of aqueous solution used of organic acid is 0.15 × 10-2~0.3 × 10-2mol/mL。
A kind of solid fabric element base ionic liquid (CM-IL) of the present invention can be applied to plant resources ingredient extraction or
Conversion.In terms of being specifically divided into following two:
(1) for being catalyzed the transesterification preparation biodiesel of natural oil, method particularly includes: CM-IL, grease and methanol are added
Enter in microwave bottle, controls reaction condition are as follows: molar ratio n (methanol)/n (oil)=6~14；Mass ratio m (CM-IL)/m (oil)=
0.03~0.2 (CM-IL additional amount depends on its type)；Mixing speed is 300~500rpm；Microwave reactor power is 400
~600W；Reaction temperature is 65~85 DEG C；Reaction time is 20~40min.After reaction, room is down to after microwave bottle being taken out
A small amount of distilled water is added into reaction mixture system, pours the mixture into centrifuge tube for temperature, revolving speed be 7000~
10~20min is centrifuged under conditions of 12000rpm.Mixture in centrifuge tube is divided into 3 layers, and upper layer is oil reservoir, as fatty acid methyl
Ester (biodiesel)；Middle layer is water layer, as the mixture of water, methanol, glycerol and other impurities；Lower layer is solid layer, i.e.,
For the CM-IL after reaction, by the CM-IL of recycling after ethyl alcohol cleans 3 times, drying is used next time to the utmost.
(2) it is used for natural products contained in assisted extraction plant, method particularly includes: by solid fabric element base ionic liquid
Body, vegetable material and Extraction solvent are added in microwave bottle, control extraction conditions are as follows: liquid-solid ratio v (Extraction solvent)/m (plant material
Material)=10~15mL/g；(CM-IL additional amount depends on its kind to mass ratio (CM-IL)/m (vegetable material)=0.02~0.05
Class and vegetable material type)；Mixing speed is 300~500rpm；Microwave reactor power is 300~600W；Extracting temperature 50
~70 DEG C；Extraction time is 3~17min.After extraction, mixture is handled through vacuum filtration, is respectively obtained extracting solution and is consolidated
Body mixture, extracting solution remove Extraction solvent by Rotary Evaporators (30~45 DEG C of bath temperature), obtain the extraction in plant
Object；Solid residue sieves with 100 mesh sieve son after oven drying (40~50 DEG C of drying temperature), respectively obtains the CM-IL of recycling and mentions
Plant material residues after taking, after ethyl alcohol cleans 3 times, drying uses next time to the utmost the CM-IL of recycling.Afore-mentioned plants material is
After crushed, the powder obtained after 300 mesh sieve is crossed；Extraction solvent is water, ethyl alcohol or 50~80% ethanol solutions.
Present invention has an advantage that
1. having captured ionic liquid for a long time can not be immobilized in this technological difficulties of cellulose-based carrier, one is synthesized for the first time
Acid solid fabric element base ionic liquid material of the series containing carboxylic acid group；
2. solid fabric element base ionic liquid prepared by the present invention be a kind of efficient, renewable, low corrosion, low cost and
Functional material with biocompatibility；
3. extraction and conversion field that solid fabric element base ionic liquid prepared by the present invention can be applied to living resources
And obtain better effects.
Detailed description of the invention
Fig. 1 is the general structure of solid fabric element base ionic liquid；Wherein,Represent porous cellulose microballoon； n
=1~4；R is [HSO4]-、[H2PO4]-、Cl-、[NO3]-、[H2PW12O40]-、[H4PMo12O40]-、[H3Si(W3O10)4]-、
[CH3SO3]-、[CF3SO3]-、One of；
Fig. 2 is the synthetic route of solid fabric element base ionic liquid；
Fig. 3 is the infrared spectrogram of porous cellulose matrix, intermediate and acid solid fabric element base ionic liquid；
Fig. 4 is thermogravimetric-weightlessness figure of solid fabric element base ionic liquid；A is differential thermal curve；B figure is thermogravimetric curve；
Fig. 5 is the stereoscan photograph of porous cellulose matrix and solid fabric element base ionic liquid；A is porous cellulose
Matrix (10 μm, 3000 times)；B is CM-IL-1 (10 μm, 3000 times)；C is CM-IL-2 (10 μm, 3000 times)；D is CM-IL-3
(10 μm, 3000 times)；
Fig. 6 is the structural formula of solid fabric element base ionic liquid CM-IL-1 described in embodiment 1；
Fig. 7 is the structural formula of solid fabric element base ionic liquid CM-IL-2 described in embodiment 2；
Fig. 8 is the structural formula of solid fabric element base ionic liquid CM-IL-3 described in embodiment 3.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
[embodiment 1]
(1) anion is the preparation of the CM-IL of inorganic acid: 1g porous cellulose microballoon is fitted into 100mL conical flask, according to
The secondary epoxychloropropane and 10ml concentration 1.25 × 10 that 1.1mol is added-2The sodium hydroxide solution of mol/mL, taper bottleneck is close
Envelope.It is placed in shaking table, shakes 4h at room temperature, filter after reaction, washed three times with dehydrated alcohol, 45 DEG C of conditions
Lower drying obtains the porous cellulose microballoon (b) of epoxy group modification；Sample b is added in reaction flask, it is dense that 10mL is added
Degree is 1.47 × 10-4In imidazoles n,N-Dimethylformamide (DMF) solution of mol/mL, 9h is reacted under conditions of 75 DEG C, instead
It filters after answering, is washed three times with dehydrated alcohol, dry under the conditions of 45 DEG C, the porous cellulose for obtaining imidazole group modification is micro-
Ball (c)；Sample c is added in reaction flask, under conditions of low whipping speed is 300rpm, 10mL concentration is added dropwise into reaction flask
It is 0.9 × 10-4The monoxone DMF solution of mol/mL after completion of dropwise addition, reacts 8h under conditions of 70 DEG C, after reaction mistake
Filter, is washed three times with dehydrated alcohol, dry under the conditions of 40 DEG C, and obtaining anion is Cl-Solid fabric element base ionic liquid；?
Under conditions of mixing speed is 300rpm, the aqueous sulfuric acid that 10mL concentration is 0.15 mol/mL is slowly added dropwise into sample d,
After completion of dropwise addition, 8h reacting under the conditions of 50 DEG C, is filtered after reaction, sample to surface is in neutrality wash with distilled water, and 40
Dry under the conditions of DEG C, obtaining anion is [HSO4]-Solid fabric element base ionic liquid (CM-IL-1).
Fig. 3 shows the infrared spectrogram of CM-IL-1,913cm-1Place is epoxy group characteristic peak, 1768cm-1With
1571cm-1The infrared peak at place is imidazoles five-membered ring characteristic peak, 1780cm-1The infrared peak that place occurs is carboxylic acid group characteristic peak, with
Above results showed that successful grafting of the ionic liquid on cellulose matrix；613cm-1And 1104cm-1The infrared peak that place occurs is
The characteristic peak of sulfate radical illustrates acidic anionic [HSO4]-Successful grafting.
(2) for being catalyzed the transesterification preparation biodiesel of shiny-leaved yellowhorn seed kernel oil: by molar ratio be 8 shiny-leaved yellowhorn seed kernel oil with
Methanol is added in microwave bottle, adds the CM-IL-1 for being 0.05 with shiny-leaved yellowhorn seed kernel oil mass ratio, and microwave bottle is placed in microwave
In reactor, low whipping speed 500rpm, microwave reaction power 500W, reaction temperature react 30min under conditions of being 65 DEG C.
After reaction, it is down to room temperature after microwave bottle being taken out, a small amount of distilled water is added into reaction mixture system, is poured the mixture into
In centrifuge tube, 15min is centrifuged under conditions of revolving speed is 8000rpm.The oil reservoir for taking centrifuge tube upper layer, after GC-MS is detected
Biodiesel production rate is 96.3% out.Take the solid layer of centrifuge tube lower layer after ethyl alcohol cleaning three times, the CM-IL- recycled
1。
(3) for the natural component in assisted extraction green tea: the CM-IL-1, green tea powder and distilled water of preparation are added
In microwave bottle, extraction conditions are controlled are as follows: liquid-solid ratio v (water)/m (green tea powder)=10mL/g；Mass ratio (CM-IL-1)/m is (dry
Green tea powder)=0.03；Mixing speed is 300rpm；Microwave reactor power is 500W；55 DEG C of Extracting temperature；Extraction time is
7min.After extraction, mixture is handled through vacuum filtration, respectively obtains extracting solution and solid mixture, and solid mixture exists
Under conditions of 40 DEG C after drying, son is sieved with 100 mesh sieve, the CM-IL-1 of the CM-IL-1 recycled, recycling are cleaned 3 times through ethyl alcohol
Afterwards, drying uses next time to the utmost.Extracting solution removes Extraction solvent by Rotary Evaporators (35 DEG C of bath temperature), obtains in green tea
Extract, extract after HPLC is detected, the method extract green tea natural component in several representative compounds extraction
Rate are as follows: nutgall catechin 35.7mg/g, Epigallo-catechin gallate (EGCG) 73.2mg/g and 11.8 mg/ of epicatechin
g。
[embodiment 2]
(1) anion is the preparation of the CM-IL of heteropoly acid: 1g porous cellulose microballoon is fitted into 100mL conical flask, according to
The secondary epoxychloropropane and 10ml concentration 1.37 × 10 that 1.2mol is added-2The sodium hydroxide solution of mol/mL, taper bottleneck is close
Envelope.It is placed in shaking table, shakes 6h at room temperature, filter after reaction, washed three times with dehydrated alcohol, 50 DEG C of conditions
Lower drying obtains the porous cellulose microballoon (b) of epoxy group modification；Sample b is added in reaction flask, it is dense that 10mL is added
Degree is 1.5 × 10-4In imidazoles n,N-Dimethylformamide (DMF) solution of mol/mL, 8h is reacted under conditions of 80 DEG C, instead
It filters after answering, is washed three times with dehydrated alcohol, dry under the conditions of 50 DEG C, the porous cellulose for obtaining imidazole group modification is micro-
Ball (c)；Sample c is added in reaction flask, under conditions of low whipping speed is 400rpm, 10mL concentration is added dropwise into reaction flask
It is 1.1 × 10-4The bromo-propionic acid DMF solution of mol/mL after completion of dropwise addition, reacts 9h under conditions of 75 DEG C, after reaction mistake
Filter, is washed three times with dehydrated alcohol, dry under the conditions of 45 DEG C, and obtaining anion is Br-Solid fabric element base ionic liquid
(d)；Under conditions of low whipping speed is 400rpm, the phosphotungstic acid that 10mL concentration is 0.35mol/mL is slowly added dropwise into sample d
Ethanol solution after completion of dropwise addition, reacts 48h at room temperature, filters after reaction, wash with distilled water sample to surface
It is in neutrality, dry under the conditions of 50 DEG C, obtaining anion is [H2PW12O40]-Solid fabric element base ionic liquid (CM-IL-2).
The infrared spectrogram of CM-IL-2 is shown in Fig. 3, in 1079cm-1、981cm-1And 892cm-1Place occurs infrared
Peak is that there is 3 main characteristic peaks for the phosphotungstic acid of Keggin-type, it was demonstrated that anion [H2PW12O40]–Successful grafting.
(2) for being catalyzed the transesterification preparation biodiesel of Chinese pistache seed oil: the Chinese pistache seed oil for being 12 by molar ratio
It is added in microwave bottle with methanol, the CM-IL-2 for being 0.1 with Chinese pistache seed oil mass ratio is added, microwave bottle is placed in microwave
In reactor, low whipping speed 300rpm, microwave reaction power 600W, reaction temperature react 20min under conditions of being 80 DEG C.
After reaction, it is down to room temperature after microwave bottle being taken out, a small amount of distilled water is added into reaction mixture system, is poured the mixture into
In centrifuge tube, 20min is centrifuged under conditions of revolving speed is 7000rpm.The oil reservoir for taking centrifuge tube upper layer, after GC-MS is detected
Biodiesel production rate is 94.7% out.Take the solid layer of centrifuge tube lower layer after ethyl alcohol cleaning three times, the CM-IL- recycled
2。
(3) for the natural component in assisted extraction honeysuckle: by the CM-IL-2, Honeysuckle Flower and distilled water of preparation
It is added in microwave bottle, controls extraction conditions are as follows: liquid-solid ratio v (water)/m (Honeysuckle Flower)=15mL/g；Mass ratio (CM-IL-
2)/m (Honeysuckle Flower)=0.02；Mixing speed is 400rpm；Microwave reactor power is 600W；65 DEG C of Extracting temperature；It mentions
Taking the time is 9min.After extraction, mixture is handled through vacuum filtration, respectively obtains extracting solution and solid mixture, solid-state
After mixture is dry under conditions of 50 DEG C, son is sieved with 100 mesh sieve, the CM-IL-2 recycled, the CM-IL-2 of recycling is through ethyl alcohol
After cleaning 3 times, drying is used next time to the utmost.Extracting solution removes Extraction solvent by Rotary Evaporators (40 DEG C of bath temperature), obtains
Extract into honeysuckle, extract is after HPLC is detected, several representativenesses in the honeysuckle natural component that the method is extracted
The recovery rate of compound are as follows: neochlorogenic acid 1.4mg/g, chlorogenic acid 40.2mg/g, caffeic acid 0.5mg/g, 3,5-Dicaffeoylquinic acid 1.1
Mg/g and 4,5-Dicaffeoylquinic acid 8.6mg/g.
[embodiment 3]
(1) anion is the preparation of the CM-IL of organic acid: 1g porous cellulose microballoon is fitted into 100mL conical flask, according to
The secondary epoxychloropropane and 10ml concentration 1.55 × 10 that 1.25mol is added-2The sodium hydroxide solution of mol/mL, taper bottleneck is close
Envelope.It is placed in shaking table, shakes 5h at room temperature, filter after reaction, washed three times with dehydrated alcohol, 50 DEG C of conditions
Lower drying obtains the porous cellulose microballoon (b) of epoxy group modification；Sample b is added in reaction flask, it is dense that 10mL is added
Degree is 1.6 × 10-4In imidazoles n,N-Dimethylformamide (DMF) solution of mol/mL, 9h is reacted under conditions of 85 DEG C, instead
It filters after answering, is washed three times with dehydrated alcohol, dry under the conditions of 40 DEG C, the porous cellulose for obtaining imidazole group modification is micro-
Ball (c)；Sample c is added in reaction flask, under conditions of low whipping speed is 300rpm, 10mL concentration is added dropwise into reaction flask
It is 1.2 × 10-4The bromo-butyric acid DMF solution of mol/mL after completion of dropwise addition, reacts 8h under conditions of 70 DEG C, after reaction mistake
Filter, is washed three times with dehydrated alcohol, dry under the conditions of 40 DEG C, and obtaining anion is Br-Solid fabric element base ionic liquid
(d)；Under conditions of low whipping speed is 300rpm, it is 0.25mol/mL to methyl that 10mL concentration is slowly added dropwise into sample d
Benzene sulfonic acid aqueous solution after completion of dropwise addition, reacts 15h under the conditions of 80 DEG C, filters after reaction, and sample is extremely wash with distilled water
Surface is in neutrality, and dry under the conditions of 50 DEG C, obtaining anion isSolid fabric element base ionic liquid (CM-IL-3).
The infrared spectrogram of CM-IL-3, sulfonic characteristic peak in p-methyl benzenesulfonic acid shown in figure are shown in Fig. 3
In 1260cm-1Place, phenyl ring characteristic peak is in 1550~1600cm-1, methyl characteristic peak is in 1380~1430cm-1, these infrared spies
The interaction at sign peak causes in the infrared spectroscopy of sample CM-IL-3 in 1200~1600cm-1There is a broad peak.
(2) for being catalyzed the transesterification preparation biodiesel of camptotheca seed oil: by molar ratio be 14 Chinese pistache seed oil with
Methanol is added in microwave bottle, is added with camptotheca seed oil quality than the CM-IL-3 for 0.2, and microwave bottle merging microwave is anti-
It answers in device, low whipping speed 400rpm, microwave reaction power 600W, reaction temperature reacts 40min under conditions of being 75 DEG C.Instead
After answering, will microwave bottle take out after be down to room temperature, into reaction mixture system plus a small amount of distilled water, pour the mixture into from
In heart pipe, 10min is centrifuged under conditions of revolving speed is 10000rpm.The oil reservoir for taking centrifuge tube upper layer obtains after GC-MS is detected
Biodiesel production rate is 97.8%.Take the solid layer of centrifuge tube lower layer after ethyl alcohol cleaning three times, the CM-IL-3 recycled.
(3) for the natural component in assisted extraction mulberry leaf: by the CM-IL-3 of preparation, Mulberry Leaf and 70% ethanol water
Solution is added in microwave bottle, controls extraction conditions are as follows: liquid-solid ratio v (water)/m (Mulberry Leaf)=12mL/g；Mass ratio (CM-IL-
3)/m (Mulberry Leaf)=0.05；Mixing speed is 500rpm；Microwave reactor power is 300W；60 DEG C of Extracting temperature；It extracts
Time is 8min.After extraction, mixture is handled through vacuum filtration, respectively obtains extracting solution and solid mixture, and solid is mixed
It closes object and after drying, sieves with 100 mesh sieve son, the CM-IL-3 of the CM-IL-3 recycled, recycling are clear through ethyl alcohol under conditions of 50 DEG C
After washing 3 times, drying is used next time to the utmost.Extracting solution removes Extraction solvent by Rotary Evaporators (45 DEG C of bath temperature), obtains
Extract in mulberry leaf, extract is after HPLC is detected, several representative compounds in the mulberry leaf natural component that the method is extracted
Recovery rate are as follows: 1-DNJ 1.4mg/g, Quercetin 4.1mg/g and rutin 1.7mg/g.
Claims (5)
1. a kind of building of solid fabric element base ionic liquid, preparation method and applications, it is characterised in that: be grafted by substep
Method the acid imidazolium ionic liquid containing carboxylic acid group is synthesized in the surface of porous cellulose microballoon and hole；
Wherein,Represent porous cellulose microballoon；
N=1~4；
R is [HSO4]-、[H2PO4]-、Cl-、[NO3]-、[H2PW12O40]-、[H4PMo12O40]-、[H3Si(W3O10)4]-、
[CH3SO3]-、[CF3SO3]-、One of.
2. the preparation method of solid fabric element base ionic liquid according to claim 1, it is characterised in that:
Specifically comprise the following steps:
The grafting of (I) epoxy group: porous cellulose microballoon (b), epoxychloropropane and sodium hydroxide solution are uniformly mixed,
It is placed in 4~6h of concussion in shaking table under room temperature, filters, is washed three times with dehydrated alcohol after reaction, 40~50 DEG C dry
It is dry, the porous cellulose microballoon (c) of epoxy group modification can be obtained；Its epoxychloropropane dosage is every gram of cellulose microsphere
1.1×10-2~1.3 × 10-2mol；Sodium hydroxide concentration is every gram of cellulose microsphere 2.5 × 10-2~3.2 × 10-2mol；Hydrogen-oxygen
Changing sodium solution concentration is 1.25 × 10-2~1.55 × 10-2mol/mL；
The grafting of (II) imidazole group: sample c obtained in step (I) is added to the N,N-dimethylformamide of imidazoles
(DMF) in solution, 7~9h is reacted under conditions of 75~85 DEG C, filters, is washed three times with dehydrated alcohol, 40 after reaction
The porous cellulose microballoon (d) of imidazole group modification can be obtained in~50 DEG C of dryings；Its imidazoles dosage is every gram of cellulose microsphere
0.9×10-2~1.2 × 10-2mol；The DMF solution concentration of imidazoles is 1.5 × 10-4~1.9 × 10-4mol/mL；
The grafting of (III) carboxylic acid group: by step (II) to sample d be fitted into reaction flask, low whipping speed is 200~
Under conditions of 400rpm, the DMF solution of the carboxylic acid of halogen substituent is added drop-wise in reaction flask, under conditions of 65~75 DEG C
8~10h is reacted, filters, is washed three times with dehydrated alcohol after reaction, 40~50 DEG C of dryings, it is halogen that anion, which can be obtained,
The solid fabric element base ionic liquid (e) of plain ion；Carboxylic acid used is chlorine (bromine) acetic acid, 3- chlorine (bromine) propionic acid, 4- chlorine (bromine) fourth
Acid or 5- chlorine (bromine) valeric acid；Its carboxylic acid dosage is every gram of cellulose microsphere 0.6 × 10-2~0.85 × 10-2mol；The DMF of carboxylic acid
Solution concentration is 0.9 × 10-4~1.4 × 10-4mol/mL；
The grafting of (IV) acidic anionic: choose respectively inorganic acids anion, heteropllyacids anion and organic acid yin from
Son grafts on sample e obtained in step (III), because the type for being grafted acid is different, is specifically divided into following three kinds of methods:
1) it the grafting of inorganic acids anion: under conditions of low whipping speed is 200~400rpm, is slowly added dropwise into sample e
The aqueous solution of inorganic acid after completion of dropwise addition, 8~12h is reacted under the conditions of 50~60 DEG C, filters after reaction, uses distilled water
Cleaning sample to surface is in neutrality, dry after 40~50 DEG C, and the solid fabric element base containing inorganic acids anion can be obtained
Ionic liquid；Inorganic acid used is sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid；The dosage of inorganic acid be every gram of cellulose microsphere 0.4 ×
10-2~0.6 × 10-2mol；The concentration of aqueous solution of inorganic acid is 0.15 × 10-2~0.3 × 10-2mol/mL；
2) it the grafting of heteropllyacids anion: under conditions of low whipping speed is 200~400rpm, is slowly added dropwise into sample e
The ethanol solution of heteropoly acid after completion of dropwise addition, reacts 36~48h at room temperature, filters after reaction, clear with distilled water
Sample to surface is washed to be in neutrality, it is dry after 40~50 DEG C, the solid fabric element base containing heteropllyacids anion can be obtained
Ionic liquid；Heteropoly acid used is phosphotungstic acid, phosphomolybdic acid or silico-tungstic acid；The dosage of heteropoly acid be every gram of cellulose microsphere 0.1 ×
10-3~0.2 × 10-3mol；The ethanol solution concentration of heteropoly acid is 0.4 × 10-4~0.1 × 10-3mol/mL；
3) it the grafting of organic acid anion: under conditions of low whipping speed is 200~400rpm, is slowly added dropwise into sample e
The aqueous solution of organic acid reacts 12~16h under conditions of 70~90 DEG C, and sample to surface is in neutrality wash with distilled water,
It is dry after 40~50 DEG C, the solid fabric element base ionic liquid containing organic acid anion can be obtained；Organic acid used is
Loprazolam, trifluoromethanesulfonic acid, p-aminobenzene sulfonic acid or p-methyl benzenesulfonic acid.The dosage of organic acid is every gram of cellulose microsphere
0.4×10-2~0.6 × 10-2mol；The amount of aqueous solution used of organic acid is 0.15 × 10-2~0.3 × 10-2mol。
3. solid fabric element base ionic liquid as described in claim 1, total ionic liquid is in porous cellulose microsphere surface
It is 14.45~44.03% with the grafting rate in hole.
4. the application of solid fabric element base ionic liquid as described in claim 1, it is characterised in that: in catalysis plant origin oil
Application in the transesterification preparation biodiesel of rouge.
5. the application of solid fabric element base ionic liquid as described in claim 1, it is characterised in that: in assisted extraction plant
Application in contained natural products.
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