CN108929303A - A method of single tocopherol being separated from mixed tocopherol using poly ion liquid - Google Patents
A method of single tocopherol being separated from mixed tocopherol using poly ion liquid Download PDFInfo
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a kind of method for separating single tocopherol from mixed tocopherol using poly ion liquid, the present invention is using poly ion liquid as adsorbent, the isolated high-purity single tocopherol from mixed tocopherol crude product.Poly ion liquid is due to having many advantages, such as the ionic liquid structure and cellular structure abundant of specificity, thus with tocopherol adsorption capacity is big, monomer selectivity is high, it can be achieved that the Selective Separation of tocopherol monomer.Under optimal conditions, available purity is not less than 80% tocopherol monomer, and the rate of recovery is 85% or more.Suitable for industrialized production.
Description
Technical field
The present invention relates to chemical engineering and polymeric material field, in particular to a kind of poly ion liquid adsorbing separation mixing
The method of tocopherol.
Background technique
Natural VE (Natural Vitamin E), scientific name tocopherol (Tocopherols), also known as mixing fertility
Phenol, it becomes three big pillar products of vitamin series together with vitamin C, vitamin A, has become on international market and use at present
The important vitamin kind that way is wide, volume of production and marketing is big.Mixed tocopherol have strong anti-oxidation and excellent healthcare function, medicine,
The industries such as cosmetics, grease, food and feed are all widely used.There are four types of homologues for natural VE, only on phenyl ring
The number and location of methyl have differences, but they show different characteristic, therefore are in function and suitable application area
It is existing differential, alpha-tocopherol (activity is 100) > betatocopherol (activity is 10~50) > γ-life is followed successively by by bioactivity
Educate phenol (activity is 10) > Delta-Tocopherol (activity is 1).The bioactivity of alpha-tocopherol is maximum, in medicine, food, cosmetics etc.
Industry has important application.In recent years, in order to improve effective utilization, foreign countries have occurred needing the market of tocopherol monomer
It asks, quick up-trend is presented in the demand especially to alpha-tocopherol.From mixed tocopherol, tetra- kinds of separating-purifying α, β, γ, δ
Tocopherol monomer is the inevitable requirement of Market Segmentation.
Tocopherol monomer is further separated from mixed tocopherol, domestic and foreign literature report is less；Generally by chemical anti-
Means should be waited to change molecular structure, non-alpha-tocopherol is made the transition into alpha-tocopherol.For example patent CN1401645A is mixed with high-content
Conjunction tocopherol is base stock, by main chemical processes such as isomerization, plant chromatography purifications, produces high-purity alpha-
Tocopherol (90% or more), and account for 99% or more of total tocopherol content；Although the process flow is simple, it is easy to industrialize,
The structure for changing molecule by force by chemically reacting, can not obtain other monomers.Meanwhile having invention and not passing through chemical reaction
The monomer of tocopherol is separated, patent CN102382095A is using in modified macroporous absorbent resin adsorbing separation mixed tocopherol
Alpha-tocopherol.Patent CN101220018A is then to isolate purity using four-area simulated moving bed chromatographic system and yield is big
In 98% four kinds of tocopherols, the process adsorbent and solvent consumption are low, and entire separation process is not also related to chemically reacting.
For absorption method and ion-exchange, key is the selection of adsorbent.The reported suction for absorption method
Attached dose includes silica gel, absorption resin, such as absorption method (CN11401645A, CN102432584A etc.) etc. by utilizing four kinds of lifes
Educating phenol homologue, absorption property is different on the sorbent, selects eluting solvent appropriate to realize separation, but common adsorbent pair
The selectivity of four kinds of tocopherol monomers is lower, leads to separation costs height.
Summary of the invention
The technical problem to be solved in the present invention is to provide single tocopherols in a kind of poly ion liquid separation mixed tocopherol
Method, this method is easy to operate, at low cost, and low for equipment requirements, gained tocopherol content is high, and overall yield is good；And material
Preparation is simple and recycling can be recycled, environmentally protective, is suitable for industrialized production.
A method of separating single tocopherol from mixed tocopherol, including：Using adsorption separation method, with polyion liquid
Body is adsorbent, and single tocopherol is isolated from mixed tocopherol, and the poly ion liquid is porous poly ion liquid or gathers
Ionic liquid gel.
In the present invention, the purity of the mixed tocopherol crude product be 60~98%, mixed tocopherol can come from as
Using the deodorization distillate of the greases such as soybean oil, rapeseed oil, peanut oil, sunflower oil as raw material, by conventional esterification, cold analysis,
The processes such as crystallization, molecular distillation, absorption obtain, can also be isolated by existing other methods.
The poly ion liquid can be divided into two class of porous poly ion liquid and poly ion liquid gel in the present invention, porous
Poly ion liquid can be copolymerized to obtain by ionic liquid monomer and polymerizable organic monomer, have micropore and meso-hole structure；Polyion
Liquid gel carries out polymerization reaction preparation gained as monomer using ionic liquid or can pass through ionic liquid monomer and organic polymer
Monomer is copolymerized to obtain, and can be non-porous or microcellular structure.
The porous poly ion liquid has general structure as shown in formula (i) or formula (ii)：
Wherein the ratio of x and y is 1:40~5:1.The ratio of x and y is further preferably 1:20~2:1.Polyion liquid
Body is porous poly ion liquid, has micropore and meso-hole structure, and general structure is also referred to as (M+N-)xCy。
It is further preferred that the porous poly ion liquid is copolymerized by ionic liquid monomer and polymerizable organic monomer C
It arrives, the ionic liquid monomer includes cation M+And anion N-。
Preferably, the poly ion liquid gel is prepared by ionic liquid monomer progress polymerization reaction, and structure is such as
Shown in following formula (III)；Or be copolymerized to obtain by ionic liquid monomer and polymerizable organic monomer C, shown in structure such as following formula (IV)；
The ionic liquid monomer includes cation M+And anion N-；
Wherein, the R in formula (III) and formula (IV) is one of alkyl or aryl, and n is 10~3000, x's and y
Ratio is 10:1~100:1.
For porous poly ion liquid and poly ion liquid gel, it is preferable that
The cation M+For glyoxaline cation, structure is shown below：
Or quaternary ammonium cation, structure are shown below：
Or season phosphine cation, structure are shown below：
Or pyridylium, structure are shown below：
Wherein, cationic M+Middle substituent R1,R2,R3,R4,R5It is independently selected from hydrogen, alkyl, aryl contains hydroxyl
One of base, halogen, amino or alkyl of carbonyl substituent group, and each cation M+Substituent group at least one take
Dai Ji contains polymerizable groups, remaining substituent group is hydrogen；Each cation M+Middle polymerizable groups are independently selected from vinyl
Class, styrene base class, acrylic amide, acrylic compounds, vinyl ethers；
Polymerizable groups (1) are vinyl-based, (2) styrene base class, (3) acrylic amide, (4) acrylic compounds, (5) second
The structural formula difference of alkenyl ethers is as follows：
Anion N-For halide ion (Cl-、Br-、I-Deng), dihydrogen phosphate ions (H2PO4 -), hydrogen sulfate ion
(HSO4 -), carboxylic acid ion (CnH2n+1COO-), sulfonate ion (CnH2n+1SO3 -) and amino acid ion (R1(NH)(CH)
R2COO-One of), wherein 1≤n<18, amino acid ion (R1(NH)(CH)R2COO-) in substituent R1,R2Respectively solely
It is vertical in hydrogen, alkyl, the alkyl containing amino-substituent, aryl or nitrogen heterocycle.
Preferably, the porous poly ion liquid and poly ion liquid gel preparation in polymerizable organic monomer C be (1)
Divinylbenzene, (2) N, N '-methylene-bisacrylamide, (3) N, N '-di-2-ethylhexylphosphine oxide methyl-prop enamine, (4) diacrylate second
One or more of diol ester, (5) ethylene glycol dimethacrylate：Structural formula difference is as follows：
It is further preferred that the polymerizable organic monomer C is divinylbenzene.
The study found that the structure of ionic liquid plays a key effect to the separation selectivity and capacity of tocopherol monomer, have
The structure of machine polymerized monomer C then influences the cellular structure of synthesized poly ion liquid, also influences adsorption capacity.
It is further preferred that preparing cation M in the ionic liquid monomer of porous poly ion liquid+For 1- vinyl -3-
Alkyl imidazole, 1- (4- methyl styrene) -3- alkyl imidazole, (methyl) acrylamide (alkyl imidazole), (4- methyl styrene)
Trialkyl ammonium, (methyl) acrylic acid (trialkyl ammonium), (4- methyl styrene) trialkyl phosphine, vinylpyridine, vinylpyridine
It coughs up, one of vinylpiperidine；Anion N-For halide ion (Cl-、Br-、I-Deng), carboxylic acid ion (CnH2n+1COO-)、
Sulfonate ion (CnH2n+1SO3 -) and amino acid ion (R1(NH)(CH)R2COO-One of), wherein 1≤n<18, amino
Acid ion (R1(NH)(CH)R2COO-) in substituent R1,R2It is independently selected from hydrogen, alkyl, the alkane containing amino-substituent
Base, aryl or nitrogen heterocycle.
It is further preferred that the ionic liquid monomer for preparing porous poly ion liquid is 1- vinyl -3- ethyl imidazol(e)
Laruate, N- (1- ethyl -3- ethyl imidazol(e)) Methacrylamide laruate, 1- vinyl -3- decyl imidazole-alanine
One of salt, (4- methyl styrene) tributylphosphine acetate, N- butylethylene yl pyridines caproate, the organic polymer list
Body is divinylbenzene.
Preferably, in porous poly ion liquid preparation, the proportion of ionic liquid monomer and polymerizable organic monomer is 20:1~
1:5。
The molar ratio of ionic liquid monomer and polymerizable organic monomer has significantly the structural behaviour of porous poly ion liquid
It influences.It is pore-free material in gained poly ion liquid when molar ratio is excessively high；When molar ratio is too low, porous poly ion liquid
In ionic liquid content can be very few, the Optimality of ionic liquid itself cannot be made full use of in adsorption separation process later
Energy.It include ionic liquid monomer, polymerizable organic monomer C, pore-foaming agent and initiation in the copolymerization system of porous poly ion liquid
Agent.
Preferably, the pore-foaming agent is dimethylformamide, methanol, acetonitrile, acetone, ethyl alcohol, ethyl acetate, tetrahydro furan
It mutters, one or more of toluene and chloroform；Further, the pore-foaming agent is one of methanol, acetonitrile, ethyl alcohol or several
Kind.The initiator is normal starter, such as azodiisobutyronitrile.Select suitable solvent that can effectively adjust as pore-foaming agent more
The structural behaviour of hole poly ion liquid, if pore-foaming agent selection is not proper, obtained poly ion liquid is pore-free material.
Preferably, reaction temperature when copolyreaction be 60~120 DEG C, the time be 12~for 24 hours.To reaction in copolyreaction
System is stirred.
Porous poly ion liquid of the invention shows very high separation selectivity, such as 1- ethylene to tocopherol monomer
The polymer P (DVB-EVIMC8) that base -3- ethyl imidazol(e) caprylate and divinylbenzene are copolymerized is to Delta-Tocopherol/α-life
The separation selectivity for educating phenol is up to 8.24, and betatocopherol/alpha-tocopherol separation selectivity is up to 4.05, in contrast, conventional
717 adsorbent of Amberlite selectivity only be respectively 1.02 and 1.01, illustrate the splendid separation of porous poly ion liquid
Selectivity.
It is further preferred that the ionic liquid monomer of the poly ion liquid gel is Gemini type ionic liquid, structure
Formula is as follows：
Further preferably, cation M in Gemini type ionic liquid+Middle polymerizable groups R1For vinyl-based, styryl
Class, acrylic amide, acrylic compounds or vinyl ethers, further preferably vinyl-based, acrylic amide or acrylic acid
Class, substituent R in Gemini type ionic liquid2For the alkyl of carbon number 1~25；Cation M in Gemini type ionic liquid+For miaow
One of azoles, quaternary ammonium, season phosphine or pyridine；Anion N in Gemini type ionic liquid-For carboxylic acid ion (CnH2n+ 1COO-), sulfonate ion (CnH2n+1SO3 -) and amino acid ion (R1(NH)(CH)R2COO-One of), wherein 1≤n<
18, amino acid ion (R1(NH)(CH)R2COO-) in substituent R1,R2It is independently selected from hydrogen, alkyl, replaces containing amino
Alkyl, aryl, the nitrogen heterocycle of base.
It is further preferred that the ionic liquid monomer for preparing ionic liquid gel is bis- (vinyl imidazole) hexyls of 1,6-
Bromide；The polymerization system includes ionic liquid monomer, initiator and water, and in the case where wavelength is the light of 365nm, irradiation 20min is
?.
Preferably, the adsorption separating method is one of ADSORPTION IN A FIXED BED separates or moving-bed adsorption separates.
It is further preferred that the adsorption separating method is ADSORPTION IN A FIXED BED partition method, include the following steps：
(1) poly ion liquid is packed into chromatographic column；
(2) mixed tocopherol crude product is substantially soluble in eluting solvent I, is made into upper prop liquid；
(3) it sets under adsorption temp and the upper prop liquid is passed through chromatographic column；
(4) it sets and is passed through eluting solvent II under desorption temperature into chromatographic column, Fractional Collections efflux merges with identical
The eluent of component, vacuum distillation, successively respectively obtains alpha-tocopherol, betatocopherol and Gamma-Tocopherol mixture, δ-fertility
Phenol；
(5) continued to rinse chromatographic column with eluting solvent I, regenerate poly ion liquid, into next adsorbing separation
Circulation.
Sequentially first obtain is alpha-tocopherol in step (4), and second obtain is betatocopherol and γ-fertility
Phenol mixture, what third obtained is Delta-Tocopherol.The method of the present invention respectively obtains α-tocopherol, betatocopherol and Gamma-Tocopherol
Mixture, Delta-Tocopherol, respective purity is 80~95%.
It is further preferred that mobile phase described in step (2) is eluting solvent I, eluting solvent I is methanol, volume is dense
The one or more of ethanol water, dehydrated alcohol, isopropanol that degree is 95%.
It is further preferred that in step (2) in upper prop liquid mixed tocopherol crude product concentration be 10 mg/mL~
300mg/mL, the content of total tocopherol is between 60-98% in mixed tocopherol crude product.
It is further preferred that the ethyl alcohol that eluting solvent II described in step (4) is methanol, volumetric concentration is 95% is water-soluble
One kind or mixed system of liquid, dehydrated alcohol, isopropanol, acetone, n-hexane, normal heptane, ethyl acetate and petroleum ether.
It is further preferred that adsorption temp is 10~60 DEG C in step (3), adsorption flow rate is controlled in 0.5~3 times of bed
Volume/hour；Desorption temperature in step (4) is 10~60 DEG C, and flow control is desorbed in 0.5~3 times of bed volume/hour.
Absorption and desorption temperature are 10~60 DEG C described in step (3) and (4), and outer loop water-bath is used to constant temperature.
Operation temperature is too low, is unfavorable for actual operation and production application；Temperature is excessively high, and excessively high or too low temperature is required by more
Big energy consumption is realized, leads to the increase of production cost.Absorption and desorption flow control are in 0.5~3 times of bed volume/small
When, flow velocity should not be excessively slow, otherwise can make that the production cost increases；Flow velocity is unsuitable too fast, otherwise can reduce the effect of absorption and elution
Rate.
Compared with prior art, the invention has the advantages that：
(1) poly ion liquid used in the present invention has very high tocopherol monomer separation selectivity, is provided simultaneously with height
Adsorption capacity, this make this method have very high tocopherol monomer separation efficiency；
(2) present invention uses the means of physical absorption separation, it is not related to chemically reacting, and selectively obtain high-content
Tocopherol monomer, under optimal conditions, available purity is not less than 80% tocopherol monomer, and the rate of recovery exists
85% or more.
Detailed description of the invention
Fig. 1 is the N of the porous poly ion liquid of carboxylate anion's functionalization prepared in embodiment 12Isollaothermic chart.
Fig. 2 is the mesoporous pore size distribution map of the porous poly ion liquid of carboxylate anion's functionalization prepared in embodiment 1.
Fig. 3 be the scanning electron microscope (SEM) photograph (SEM) of the porous poly ion liquid of carboxylate anion's functionalization prepared in embodiment 1 and
Transmission electron microscope picture (TEM) figure (wherein A and B is SEM figure, and C and D are TEM).
Fig. 4 is the infrared results figure of the porous poly ion liquid of carboxylate anion's functionalization prepared in embodiment 1.
Fig. 5 is the thermogravimetric result figure of the porous poly ion liquid of carboxylate anion's functionalization prepared in embodiment 1.
Fig. 6 is the infrared results figure of the poly ion liquid gel prepared in embodiment 3.
Fig. 7 is the thermogravimetric result figure of the poly ion liquid gel prepared in embodiment 3.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, protection scope of the present invention
It should not be limited by the examples, protection scope of the present invention is determined by claims.Based on the embodiments of the present invention, this field
Those of ordinary skill's every other embodiment obtained without creative efforts, belongs to protection of the present invention
Range.
In the present invention, the purity of the mixed tocopherol is 60~90%, and mixed tocopherol can come from such as with soybean
The deodorization distillate of the greases such as oil, rapeseed oil, peanut oil, sunflower oil is raw material, through over-churning, cold analysis, crystallization, molecular distillation
Etc. processes obtain.
Embodiment 1
Firstly, preparing porous poly ion liquid using 1- vinyl -3- ethyl imidazol(e) laruate as monomer.In 50mL
In Schlenk holding bottle, by 1.00g divinylbenzene, 1.24g 1- vinyl -3- ethyl imidazol(e) laruate and 44.8mg
Azodiisobutyronitrile is dissolved in 20mL acetonitrile, under the conditions of 100 DEG C, is stirred to react for 24 hours.After room temperature is cooling, with ethanol washing,
And be dried in vacuo at 60 DEG C for 24 hours, grinding is stand-by.It is measured through nitrogen adsorption instrument, product shows as apparent meso pore characteristics, compares table
Area is 247m2g-1, Kong Rongwei 0.36cm3g-1, aperture 6.1nm.Porous poly ion liquid structure intermediate ion content liquid by
Elemental analysis result is calculated, and ionic liquid content is 1.01 mmol/g.
It is the porous poly ion liquid of carboxylate anion's functionalization that poly ion liquid, which is prepared, in the embodiment, and structural formula is as follows
Shown in formula：
Its N2Isollaothermic chart is as shown in Figure 1；Mesoporous pore size distribution map is as shown in Figure 2；A in scanning electron microscope (SEM) photograph (SEM) such as Fig. 3
With shown in B, transmission electron microscope picture (TEM) is as shown in C and D in Fig. 3；Infrared results figure is as shown in figure 4,1160cm-1The peak at place is miaow
Azoles cation may replace the characteristic peak of C-N covalent bond at N, 1630cm-1And 1654cm-1The peak at place is imidazole ring framework characteristic
Peak, 1560cm-1The peak at place is carboxylate anion COO-Characteristic peak, 2922cm-1And 2853cm-1The peak at place is carboxylate anion
C-H group stretching vibration peak, 3050cm are saturated with alkyl chain in porous poly ion liquid structure-1~3140cm-1Peak is imidazole ring
C-H group stretching vibration peak, these results, which clearly show that in polymer architecture, 1- vinyl -3- ethyl imidazol(e) laruate；
Thermogravimetric result figure is as shown in figure 5, the initial decomposition at 200 DEG C of temperature is the decomposition of ionic liquid, later in 350 DEG C of point
Solution is the decomposition of organic copolymer monomer divinylbenzene.
Embodiment 2
For fixed bed separation process, the porous poly ion liquid prepared in 20g embodiment 1 is packed into chromatographic column (φ
20mm × 500mm), and rinsed and be compacted with dehydrated alcohol.By 5g mixed tocopherol crude product (content 80%, wherein Delta-Tocopherol
11.6%, betatocopherol and Gamma-Tocopherol sample totally 55.0%, alpha-tocopherol 13.4%) it is completely dissolved in 20mL dehydrated alcohol
In, it is made into the material liquid that concentration is 250 mg/mL.Operation temperature is at 15 DEG C, by upper prop liquid with 1.5 times of bed volume/hours
It is passed through chromatographic column；It is rinsed with n-hexane, flow control is in 1.5 times of bed volume/hours, Fractional Collections efflux, using efficient
Liquid chromatographic detection, merges the eluent with same composition, and vacuum distillation successively respectively obtains 0.59g Delta-Tocopherol (content
89.4%), 2.78g betatocopherol and Gamma-Tocopherol mixture (content 90.1%), 0.67g alpha-tocopherol (content 91.3%),
Overall recovery is 91.0%.Continued to rinse chromatographic column with dehydrated alcohol, flow control makes porous poly- in 3 times of bed volume/hours
Ionic liquid is regenerated, and is recycled into next adsorbing separation.
Embodiment 3
With bis- (vinyl imidazole) the hexyl bromides of 1,6- for monomer, poly ion liquid gel is prepared.By the bis- (second of 2g 1,6-
Alkenyl imidazoles) hexyl bromide and 10mg azo diisobutyl amidine hydrochloride, it is dissolved in 2mL water, in the light that wavelength is 365nm
Lower irradiation 20min, repeatedly freeze-drying water removal grinding is stand-by after washing.
The poly ion liquid gel structure formula that the embodiment is prepared is as follows：
Infrared results figure is as shown in fig. 6,1153cm-1The peak at place is the spy that glyoxaline cation may replace C-N covalent bond at N
Levy peak, 1620cm-1、1570cm-1、1550cm-1、1455cm-1The peak at place is imidazole ring framework characteristic peak, 2934cm-1With
2856cm-1The peak at place is that alkyl chain is saturated C-H group stretching vibration peak, 3050cm in porous poly ion liquid structure-1~
3140cm-1Peak is imidazole ring C-H group stretching vibration peak, these results clearly show that product is poly ion liquid；Thermogravimetric result
Figure is as shown in fig. 7, the decomposition at 280 DEG C of temperature is the decomposition of ionic liquid.
36g poly ion liquid gel is packed into chromatographic column (φ 20mm × 500mm), and is rinsed and is compacted with dehydrated alcohol.It will
(content 80%, wherein Delta-Tocopherol 12.4%, betatocopherol and Gamma-Tocopherol sample are total for 6g mixed tocopherol crude product
51.6%, alpha-tocopherol 16.0%) it is completely dissolved in 20mL dehydrated alcohol, it is made into the material liquid that concentration is 300mg/mL.Behaviour
Making temperature is that upper prop liquid is passed through chromatographic column with 1.5 times of bed volume/hours at 25 DEG C；It is mixed with n-hexane and ethyl acetate
Solvent (volume ratio 1:1) it rinses, flow control utilizes efficient liquid in 1.5 times of bed volume/hours, Fractional Collections efflux
The detection of phase chromatography, merges the eluent with same composition, and vacuum distillation successively respectively obtains 0.76g Delta-Tocopherol (content
89.2%), 3.17g betatocopherol and Gamma-Tocopherol mixture (content 88.7%), 0.97g alpha-tocopherol (content 90.2%),
Overall recovery is 90.8%.Continued to rinse chromatographic column with dehydrated alcohol, flow control makes polyion in 3 times of bed volume/hours
Liquid gel is regenerated, and is recycled into next adsorbing separation.
Embodiment 4
Firstly, N- (1- ethyl -3- ethyl imidazol(e)) Methacrylamide laruate is monomer, porous polyion liquid is prepared
Body.In 50mL Schlenk holding bottle, by 1.00g divinylbenzene, 1.56g N- (1- ethyl -3- ethyl imidazol(e)) methyl-prop
Acrylamide laruate and 25.6mg azodiisobutyronitrile, are dissolved in acetonitrile, under the conditions of 100 DEG C, are stirred to react for 24 hours.Room temperature
After cooling, it is dried in vacuo for 24 hours with ethanol washing, and at 60 DEG C, grinding is stand-by.It is measured through nitrogen adsorption instrument, product is shown as
Apparent meso pore characteristics, specific surface area 326m2g-1, Kong Rongwei 0.43cm3g-1, aperture 6.0nm.Porous poly ion liquid knot
Structure intermediate ion content liquid is calculated by elemental analysis result, and ionic liquid content is 0.64mmol/g.
The product structure formula that the present embodiment is prepared is shown below：
The porous poly ion liquid of 20g is packed into chromatographic column (φ 20mm × 500mm), and is rinsed and is compacted with isopropanol.By 10g
Mixed tocopherol crude product (content 80%, wherein Delta-Tocopherol 12.4%, betatocopherol and Gamma-Tocopherol sample totally 51.6%,
Alpha-tocopherol 16.0%) it is completely dissolved in 20mL isopropanol, it is made into the material liquid that concentration is 100mg/mL.Operation temperature is
At 25 DEG C, upper prop liquid is passed through chromatographic column with 1.5 times of bed volume/hours；With isopropanol and normal heptane mixed solvent (volume ratio
It is 1:1) it rinsing, flow control is in 1.5 times of bed volume/hours, Fractional Collections efflux, using high performance liquid chromatography detection,
Merge the eluent with same composition, vacuum distillation successively respectively obtains 0.62g Delta-Tocopherol (content 89.8%), 2.70g
Betatocopherol and Gamma-Tocopherol mixture (content 86.4%), 0.80g alpha-tocopherol (content 90.2%), overall recovery are
90.4%.Continued to rinse chromatographic column with isopropanol, flow control obtains porous poly ion liquid in 3 times of bed volume/hours
Regeneration is recycled into next adsorbing separation.
Embodiment 5
Using 1- vinyl -3- decyl imidazole-alanine salt as monomer, porous poly ion liquid is prepared.In 50mL
In Schlenk holding bottle, by 1.00g divinylbenzene, 0.83g 1- vinyl -3- decyl imidazole-alanine salt and 36.6mg are even
Nitrogen bis-isobutyronitrile, is dissolved in ethyl alcohol, under the conditions of 100 DEG C, is stirred to react for 24 hours.After room temperature is cooling, with ethanol washing, and 60
It is dried in vacuo at DEG C for 24 hours, grinding is stand-by.It is measured through nitrogen adsorption instrument, product shows as apparent meso pore characteristics, and specific surface area is
291m2g-1, Kong Rongwei 0.36cm3g-1, aperture 6.3nm.Porous poly ion liquid structure intermediate ion content liquid is by element point
Analysis result is calculated, and ionic liquid content is 0.80mmol/g.
The product structure formula that the present embodiment is prepared is shown below：
The porous poly ion liquid of 20g is packed into chromatographic column (φ 20mm × 500mm), and is rinsed and is compacted with dehydrated alcohol.It will
(content 80%, wherein Delta-Tocopherol 11.6%, betatocopherol and Gamma-Tocopherol sample are total for 5g mixed tocopherol crude product
55.0%, alpha-tocopherol 13.4%) it is completely dissolved in 20mL dehydrated alcohol, it is made into the material liquid that concentration is 100mg/mL.Behaviour
Making temperature is that upper prop liquid is passed through chromatographic column with 1.5 times of bed volume/hours at 25 DEG C；It is rinsed with n-hexane, flow control exists
1.5 times of bed volume/hours, Fractional Collections efflux, using high performance liquid chromatography detection, merging has washing for same composition
De- liquid, vacuum distillation successively respectively obtain 0.57g Delta-Tocopherol (content 91.8%), 2.89g betatocopherol and Gamma-Tocopherol
Mixture (content 86.1%), 0.67g alpha-tocopherol (content 91.0%), overall recovery 90.6%.Continued with dehydrated alcohol
Chromatographic column is rinsed, flow control regenerates porous poly ion liquid in 3 times of bed volume/hours, into next suction
Fufen is from circulation.
Embodiment 6
Firstly, preparing porous poly ion liquid with (4- methyl styrene) tributylphosphine acetate unit.In 50mL
In Schlenk holding bottle, by 1.00g divinylbenzene, 1.91g N- acrylic acid ethyl-N- hydroxyethyl dimethyl ammonium chloride and
87.3mg azodiisobutyronitrile, is dissolved in n,N-Dimethylformamide, under the conditions of 100 DEG C, is stirred to react for 24 hours.Room temperature is cooling
Afterwards, it with ethanol washing, and is dried in vacuo for 24 hours at 60 DEG C, grinding is stand-by.It is measured through nitrogen adsorption instrument, product is shown as obviously
Meso pore characteristics, specific surface area 374m2g-1, Kong Rongwei 0.44cm3g-1, aperture is 6.1 nm.Porous poly ion liquid structure
Intermediate ion content liquid is calculated by elemental analysis result, and ionic liquid content is 1.22mmol/g.
The product structure formula that the present embodiment is prepared is shown below：
The porous poly ion liquid of 25g is packed into chromatographic column (φ 20mm × 500mm), and is rinsed and is compacted with dehydrated alcohol.It will
(content 80%, wherein Delta-Tocopherol 11.6%, betatocopherol and Gamma-Tocopherol sample are total for 10g mixed tocopherol crude product
55.0%, alpha-tocopherol 13.4%) it is completely dissolved in 100mL dehydrated alcohol, it is made into the material liquid that concentration is 100mg/mL.
Operation temperature is after residence time of the upper prop liquid in chromatographic column is 5h, to be rinsed with n-hexane, flow control is 1.5 at 15 DEG C
Times bed volume/hour, Fractional Collections efflux merge the eluent with same composition using high performance liquid chromatography detection,
Vacuum distillation successively respectively obtains 0.58g Delta-Tocopherol (content 90.8%), 2.80g betatocopherol and Gamma-Tocopherol mixing
Object (content 88.9%), 0.66g alpha-tocopherol (content 92.0%), overall recovery 90.6%.Continue to rinse with dehydrated alcohol
Chromatographic column, flow control regenerate porous poly ion liquid in 3 times of bed volume/hours, into next absorption point
From circulation.
Embodiment 7
Firstly, preparing porous poly ion liquid using N- butylethylene yl pyridines caproate as monomer.In 50mL Schlenk
In holding bottle, by 1.00g divinylbenzene, 0.86g N- butylethylene yl pyridines caproate and 55.8mg azodiisobutyronitrile,
It is dissolved in acetonitrile, under the conditions of 80 DEG C, is stirred to react for 24 hours.After room temperature is cooling, with ethanol washing, and it is dried in vacuo at 60 DEG C
For 24 hours, grinding is stand-by.It is measured through nitrogen adsorption instrument, product shows as apparent meso pore characteristics, and specific surface area is 393 m2g-1, hole
Holding is 0.51cm3g-1, aperture 5.9nm.Porous poly ion liquid structure intermediate ion content liquid is calculated by elemental analysis result
It obtains, ionic liquid content is 0.74mmol/g.
The product structure formula that the present embodiment is prepared is shown below：
The porous poly ion liquid of 20g is packed into chromatographic column (φ 20mm × 500mm), and is rinsed and is compacted with dehydrated alcohol.It will
(content 80%, wherein Delta-Tocopherol 12.4%, betatocopherol and Gamma-Tocopherol sample are total for 10g mixed tocopherol crude product
51.6%, alpha-tocopherol 16.0%) it is completely dissolved in 100mL dehydrated alcohol, it is made into the material liquid that concentration is 100mg/mL.
Operation temperature is at 25 DEG C, after residence time of the upper prop liquid in chromatographic column is 5h, with n-hexane and ethyl acetate mixed solvent
(volume ratio 1:1) it rinses, flow control utilizes high-efficient liquid phase color in 1.5 times of bed volume/hours, Fractional Collections efflux
Spectrum detection, merges the eluent with same composition, and vacuum distillation successively respectively obtains 0.62g Delta-Tocopherol (content
90.8%), 2.73g betatocopherol and Gamma-Tocopherol mixture (content 86.9%), 0.80g alpha-tocopherol (content 91.0%),
Overall recovery is 91.5%.Continued to rinse chromatographic column with dehydrated alcohol, flow control makes porous poly- in 3 times of bed volume/hours
Ionic liquid is regenerated, and is recycled into next adsorbing separation.
Claims (13)
1. a kind of method for separating single tocopherol from mixed tocopherol using poly ion liquid, which is characterized in that including：It adopts
Single tocopherol, the polyion liquid are isolated from mixed tocopherol using poly ion liquid as adsorbent with adsorption separation method
Body is porous poly ion liquid or poly ion liquid gel.
2. method according to claim 1, which is characterized in that the porous poly ion liquid is prepared by the following method：It is causing
In the agent of hole, reaction temperature is controlled, is copolymerized to obtain by ionic liquid monomer and polymerizable organic monomer C, the ionic liquid monomer
Including cationic M+And anion N-；The general structure of porous poly ion liquid is as shown in formula (i) or formula (ii)：
Wherein the ratio of x and y is 1 in formula (I) and formula (II):40~5:1.
3. method according to claim 1, which is characterized in that the poly ion liquid gel is carried out by ionic liquid monomer
Polymerization reaction is prepared, shown in structure such as following formula (III)；Or it is copolymerized by ionic liquid monomer and polymerizable organic monomer C
It arrives, shown in structure such as following formula (IV)；The ionic liquid monomer includes cation M+And anion N-；
Wherein, the R in formula (III) and formula (IV) is one of alkyl or aryl, and n is that the ratio of 10~3000, x and y is
10:1~100:1.
4. according to Claims 2 or 3 the method, the cation M+For glyoxaline cation, structure is shown below：
Or quaternary ammonium cation, structure are shown below：
Or season phosphine cation, structure are shown below：
Or pyridylium, structure are shown below：
Wherein, cationic M+In substituent R1,R2,R3,R4,R5Be independently selected from hydrogen, alkyl, aryl, containing hydroxyl,
One of halogen, amino or alkyl of carbonyl substituent group, and each cation M+Substituent group at least one substitution
Base contains polymerizable groups, remaining substituent group is hydrogen；
Anion N-For halide ion, H2PO4 -、HSO4 -、CnH2n+1COO-、CnH2n+1SO3 -And R1(NH)(CH)R2COO-In one
Kind, wherein 1≤n<18, R1(NH)(CH)R2COO-Middle substituent R1,R2It is independently selected from hydrogen, alkyl, containing amino-substituent
Alkyl, aryl, nitrogen heterocycle.
5. method according to claim 4, which is characterized in that each cation M+In polymerizable groups be independently selected from
Vinyl-based, styrene base class, acrylic amide, acrylic compounds, vinyl ethers.
6. the method according to Claims 2 or 3, which is characterized in that the polymerizable organic monomer C is divinylbenzene, N, N '-
Methylene-bisacrylamide, N, N '-di-2-ethylhexylphosphine oxide methyl-prop enamine, ethylene glycol diacrylate, ethyleneglycol dimethacrylate
One or more of ester.
7. method according to claim 2, which is characterized in that cationic M+For 1- vinyl -3- alkyl imidazole, 1- (4- methyl
Styrene) -3- alkyl imidazole, (methyl) acrylamide (alkyl imidazole), (4- methyl styrene) trialkyl ammonium, (methyl) propylene
One of sour (trialkyl ammonium), (4- methyl styrene) trialkyl phosphine, vinylpyridine, vinyl pyrrole, vinylpiperidine；
Anion N-For halide ion, CnH2n+1COO-、CnH2n+1SO3 -And R1(NH)(CH)R2COO-One of, wherein 1≤n<18, R1
(NH)(CH)R2COO-Middle substituent R1,R2It is independently selected from hydrogen, alkyl, the alkyl containing amino-substituent, aryl, contains
Azacyclyl.
8. method according to claim 2, which is characterized in that the pore-foaming agent is dimethylformamide, methanol, acetonitrile, third
One or more of ketone, ethyl alcohol, ethyl acetate, tetrahydrofuran, toluene and chloroform.
9. method according to claim 2, which is characterized in that the molar ratio of the ionic liquid monomer and polymerizable organic monomer
It is 20:1~1:5.
10. method according to claim 3, which is characterized in that the ionic liquid monomer of the poly ion liquid gel is
Gemini type ionic liquid, structural formula are as described below：
The cationic M of Gemini type ionic liquid+Middle polymerizable groups R1For vinyl-based, styrene base class, acrylic amide,
Acrylic compounds or vinyl ethers, the substituent R of Gemini type ionic liquid2For the alkyl of carbon number 1~25；Gemini type ion
The cationic M of liquid+For one of imidazoles, quaternary ammonium, season phosphine or pyridine；The anion N of Gemini type ionic liquid-For
CnH2n+1COO-、CnH2n+1SO3 -And R1(NH)(CH)R2COO-One of, wherein 1≤n<18, R1(NH)(CH)R2COO-In take
For base R1,R2It is independently selected from hydrogen, alkyl, containing amino-substituent, aryl, nitrogen heterocycle.
11. method according to claim 1, which is characterized in that the adsorption separating method is ADSORPTION IN A FIXED BED separation or mould
One of quasi- moving bed adsorbing separation；When the adsorption separating method is ADSORPTION IN A FIXED BED partition method, include the following steps：
(1) poly ion liquid is packed into chromatographic column；
(2) mixed tocopherol crude product is substantially soluble in eluting solvent I, is made into upper prop liquid；
(3) it sets under adsorption temp and the upper prop liquid is passed through chromatographic column；
(4) it sets and is passed through eluting solvent II under desorption temperature into chromatographic column, Fractional Collections efflux, merging has same composition
Eluent, vacuum distillation, successively respectively obtain alpha-tocopherol, betatocopherol and Gamma-Tocopherol mixture, Delta-Tocopherol；
(5) continued to rinse chromatographic column with eluting solvent I, regenerate poly ion liquid, recycled into next adsorbing separation.
12. method according to claim 11, which is characterized in that eluting solvent I described in step (2) is methanol, volume is dense
The one or more of ethanol water, dehydrated alcohol, isopropanol that degree is 95%；Mixed tocopherol crude product is dense in upper prop liquid
Degree is 10mg/mL~300mg/mL, and the mass percentage of total tocopherol is between 60~98% in mixed tocopherol crude product.
13. method according to claim 11, which is characterized in that the adsorption temp in step (3) is 10~60 DEG C, absorption stream
Speed control is in 0.5~3 times of bed volume/hour；Desorption temperature in step (4) is 10~60 DEG C, and flow control is desorbed 0.5
~3 times of bed volume/hours.
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