CN103333283A - Two pH response regeneration polymers capable of forming slightly alkaline aqueous two-phase system, and preparation method and application of slightly alkaline aqueous two-phase system - Google Patents
Two pH response regeneration polymers capable of forming slightly alkaline aqueous two-phase system, and preparation method and application of slightly alkaline aqueous two-phase system Download PDFInfo
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Abstract
The invention relates to two pH response regeneration polymers PADB6.29 and PMDM7.19 which can form a slightly alkaline aqueous two-phase system, the slightly alkaline aqueous two-phase system, and a preparation method and an application of the slightly alkaline aqueous two-phase system. PADB6.29 is formed by random copolymerization of AA (Acrylic Acid), DMAEMA (Methacrylic Acid-N,N-Dimethylamino Ethyl Ester) and BMA (Buthyl Methacrylate) at a feeding mole ratio of 23.15:18.88:1; an isoelectric point of PADB6.29 is 6.29; and the intrinsic viscosity of PADB6.29 is 213.0mL/mg. PMDM7.19 is formed by random copolymerization of MAA (Methyl Acrylic Acid), DMAEMA and MMA (Methl Methacrylate) at a feeding mole ratio of 3.24:3.78:1; an isoelectric point of PMDM7.19 is 7.19; and the intrinsic viscosity of PMDM7.19 is 215.6mL/mg. According to the polymers, the preparation method and the application, structures of the two polymers are characterized, a result shows that monomer categories and proportions are similar to the feeding rates, and the two polymers are reversible in pH dissolution and high in recovery rate, so that the industrial cost is lowered greatly, popularization of an aqueous two-phase technology is facilitated, and large-scale popularization and application are suitable.
Description
Technical field
The present invention relates to the dissolution invertible polymer technical field, relate in particular to pH response regeneration type technical field of polymer, two kinds of pH that particularly can form the meta-alkalescence aqueous two-phase system respond regeneration type polymkeric substance and preparation method thereof and application.
Background technology
Aqueous two-phase system refers to the mixed solution of two kinds of hydrophilic polymers or a kind of hydrophilic polymer and a kind of inorganic salt, form mutual exclusive two-phase water solution system under certain condition, can be widely used in product separation and the purification in fields such as biological chemistry, cytobiology and biochemical industry, be a kind of extremely promising separation unit operation in the biological downstream engineering, have wide prospect in industrial application.The formation of aqueous two-phase system mainly is because the hydrophobicity difference between the superpolymer can be divided into two-phase when hydrophobic difference acquires a certain degree.Yet, owing to existing, the polymkeric substance that is used for two aqueous phase separation systems is difficult to the recovery problem, hindered the application of two water extraction and separation technologies to a certain extent.Therefore, the polymkeric substance that solve to be used for two aqueous phase separation systems recycles problem becomes key.
Johansson etc. use oxyethane (EO), propylene oxide (PO) synthetic polymer, and at the C14H29-group of this polymkeric substance afterbody combining fat family, form HM-EOPO superpolymer (Biotechnology and Bioengineering, 1999,66(4): 247-257), this superpolymer can form two-phase system with water, and can be only temperature to 14 by regulation system ℃ locate to be reclaimed.
Mos van Berlo etc. under 25 ℃, one normal atmosphere, the ammonium carbamate (NH of working pressure response type
2COONH
4) form aqueous two-phase system (Journal of Chromatography B with PEG2000, PEG4000, PEG10000,1998,711(1-2): 61-68), wherein ammonium carbamate very easily is decomposed into carbonic acid gas and the ammonia of gaseous state under the situation of pressurization, and carbonic acid gas and ammonia can generate ammonium carbamate again after water-soluble under certain pressure, so can form the application system of a circulation by the pressure of regulation system.
Patrickios etc. then utilize methacrylic acid (MAA), methacrylic acid-N, N-dimethylaminoethyl (DMAEMA), methyl methacrylate (MMA) are as monomer, copolyreaction has generated a kind of polymkeric substance (Fluid Phase Equilibria of pH response through group, 1995,108(1-2): 243-254), this polymkeric substance can form aqueous two-phase system with polyvinyl alcohol (PVA).
Cao Xuejun and Yan Bo etc. have synthesized two kinds of novel pH response type polymer P
ADB2.79With P
ADBA4.01(Journal of Chromatography A, 2012,1245(0): 39-45), polymer P wherein
ADB2.79Be with vinylformic acid (AA), methacrylic acid-N, N-dimethylaminoethyl (DMAEMA), butyl methacrylate (BMA) are synthesized as monomer, and polymer P
ADBA4.01Then be to compare P
ADB2.79Add into this monomer of vinylcarbinol (Aal), and these two kinds of polymkeric substance can form aqueous two-phase system in the scope of pH=4.8-6.2, and all have the higher rate of recovery (polymer P
ADB2.79With P
ADBA4.01The rate of recovery be respectively 97.18% and 98.87%).
Aforesaid method has solved the recovery problem of slant acidity aqueous two-phase system polymkeric substance to a certain extent.And some material adapts to alkaline environment, is not suitable for separating under the slant acidity condition.Therefore, the research and development polymkeric substance that can recycling utilization can form aqueous two-phase system again under the meta-alkalescence condition becomes problem demanding prompt solution.
Summary of the invention
Main purpose of the present invention is the deficiency at above-mentioned prior art existence, a kind of two kinds of pH response regeneration type polymkeric substance that form the meta-alkalescence aqueous two-phase system and preparation method thereof and application are provided, this can form two kinds of pH response regeneration type polymkeric substance pH invertible dissolutions of meta-alkalescence aqueous two-phase system, rate of recovery height, thereby greatly reduce industrial cost, be beneficial to the popularization of two water technology, be suitable for large-scale promotion application.
To achieve these goals, a first aspect of the present invention provides a kind of pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29
A kind of pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29, be that compound obtains through random copolymerization shown in compound shown in compound, the formula (2) shown in the formula (1) of 23.15:18.88:1 and the formula (3) by molar ratio, its molecular weight distribution is as follows: M
nBe 1.499 * 10
5D, M
wBe 2.942 * 10
5D, M
νBe 3.136 * 10
5D, M
zBe 6.429 * 10
5D, molecular weight polymolecularity M
w/ M
nBe 1.962, limiting viscosity is 213.0mL/mg, and iso-electric point is 6.29.
Further, the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29Particle diameter be 3.747nm, maximum recovery is 98.8%.
A second aspect of the present invention provides the pH response regeneration type polymer P of above-mentioned formed meta-alkalescence aqueous two-phase system
ADB6.29The preparation method.
A kind of pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29The preparation method, comprise the steps: that compound shown in compound shown in compound shown in the described formula (1), the described formula (2) and the described formula (3) is pressed molar ratio 23.15:18.88:1 to add in the solvent, add initiator again, in the presence of rare gas element, carry out polyreaction and obtain the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29
Preferably, described solvent is deionized water; Described initiator is sodium bisulfite and ammonium persulphate, and the initiator additional proportion is 1.3%(w/w) (this ratio 1.3%(w/w) for formula (1), formula (2) and formula (3) total mass 1.3%), described rare gas element is nitrogen; The oscillatory reaction under 55 ℃ temperature, condition that rotating speed is 200rpm of described polyreaction realized in 24 hours.
A third aspect of the present invention provides a kind of pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19
A kind of pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19, be that compound obtains through random copolymerization shown in compound shown in compound, the formula (4) shown in the formula (2) of 3.24:3.78:1 and the formula (5) by molar ratio, its molecular weight distribution is as follows: M
nBe 6.224 * 10
5D, M
wBe 7.714 * 10
5D, M
ν(this symbolic representation viscosity-average molecular weight) is 3.205 * 10
5D, M
zBe 1.131 * 10
6D, molecular weight polymolecularity M
w/ M
nBe 1.239, limiting viscosity is 215.6mL/mg, and iso-electric point is 7.19.
Further, the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19Particle diameter be 3.930nm, maximum recovery is 96.7%.
A fourth aspect of the present invention provides the pH response regeneration type polymer P of above-mentioned formed meta-alkalescence aqueous two-phase system
MDM7.19The preparation method.
A kind of pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19The preparation method, comprise the steps: that compound shown in compound shown in compound shown in the described formula (4), the formula (2) and the formula (5) is pressed molar ratio 3.24:3.78:1 to add in the solvent, add initiator again, in the presence of rare gas element, carry out polyreaction and obtain the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19
Preferably, described solvent is deionized water; Described initiator is sodium bisulfite and ammonium persulphate, and the initiator additional proportion is 1.3%(w/w), described rare gas element is nitrogen; The oscillatory reaction under 55 ℃ temperature, condition that rotating speed is 200rpm of described polyreaction realized in 24 hours.
A fifth aspect of the present invention provides a kind of meta-alkalescence aqueous two-phase system.
A kind of meta-alkalescence aqueous two-phase system, its pH scope is 8.4-8.7, and comprises the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29With the pH response regeneration type polymer P that can form the meta-alkalescence aqueous two-phase system
MDM7.19
Further, the described pH scope meta-alkalescence aqueous two-phase system that is 8.4-8.7 comprises the pH response regeneration type polymer P according to above-mentioned formed meta-alkalescence aqueous two-phase system
ADB6.29Or the pH of above-mentioned formed meta-alkalescence aqueous two-phase system response regeneration type polymer P
ADB6.29The pH response regeneration type polymer P of the formed meta-alkalescence aqueous two-phase system that the preparation method makes
ADB6.29, and the pH response regeneration type polymer P of above-mentioned formed meta-alkalescence aqueous two-phase system
MDM7.19Or the pH of above-mentioned formed meta-alkalescence aqueous two-phase system response regeneration type polymer P
MDM7.19The pH response regeneration type polymer P of the formed meta-alkalescence aqueous two-phase system that the preparation method makes
MDM7.19
The 6th aspect of invention provides the preparation method of above-mentioned meta-alkalescence aqueous two-phase system.
A kind of preparation method of meta-alkalescence aqueous two-phase system comprises the steps: the pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system with described
ADB6.29And the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19Proportional being dissolved in the sodium hydroxide solution at room temperature settles into phase, and the pH scope that obtains into phase is the described meta-alkalescence aqueous two-phase system of 8.4-8.7.
A seventh aspect of the present invention provides the above-mentioned application of meta-alkalescence aqueous two-phase system in the separating bio product.
More preferably, described biological product is microbiotic or VITAMIN.
The example that separates VITAMIN can be the above-mentioned application of meta-alkalescence aqueous two-phase system in the vitamin B12 separation and purification.Microbiotic can be lincomycin or Spiramycin Base.Specific practice is: add microbiotic or VITAMIN in above-mentioned aqueous two-phase system, settle into phase after mixing, enrichment during microbiotic will or descend mutually in last phase.By regulating above-mentioned two aqueous phase polymer Ps
ADB6.29And P
MDM7.19Concentration ratio, the pH of phase system, the kind of salt ion and concentration are regulated and control microbiotic or the distribution of VITAMIN in aqueous two-phase system in the phase system, and just can not form two-phase when system pH exceeds into the pH=8.4-8.7 scope of phase.
In the present invention: vinylformic acid, methacrylic acid, methyl methacrylate and butyl methacrylate are commercially available product, methacrylic acid-N, and the N-dimethylaminoethyl can be by N, and N-dimethylethanolamine and methacrylic chloride reaction make.
The present invention use IR with
1H NMR is to the responsive regeneration type of two kinds of pH polymer P
ADB6.29And P
MDM7.19Structure characterize, the result shows that monomer whose kind and ratio are all similar to feed ratio.
The present invention compared with prior art has following beneficial effect:
The responsive regeneration type of the two kinds of pH polymer P that designs and synthesizes of the present invention
ADB6.29And P
MDM7.19, these two kinds of mixed with polymers can form aqueous two-phase system, P in the meta-alkalescence scope
ADB6.29With vinylformic acid, methacrylic acid-N, N-dimethylaminoethyl, butyl methacrylate are monomer, and P
MDM7.19With methacrylic acid, methacrylic acid-N, N-dimethylaminoethyl, methyl methacrylate are monomer, be solvent with the deionized water, sodium bisulfite, ammonium persulphate are initiator, the employing solution polymerization forms, and two polymkeric substance can both reach the recovery of polymkeric substance by the pH value of regulating its solution; Polymer P
ADB6.29Iso-electric point be 6.29, the rate of recovery reaches 98.8%, and polymer P
MDM7.19Iso-electric point be 7.19, the rate of recovery reaches 96.7%.Therefore, can form two kinds of pH response regeneration type polymkeric substance pH invertible dissolutions of meta-alkalescence aqueous two-phase system, rate of recovery height, thus reduce industrial cost greatly, be beneficial to the popularization of two water technology, be suitable for large-scale promotion application.
Description of drawings
Fig. 1 is pH response regeneration type polymer P of the present invention
ADB6.29The reaction equation of preparation.
Fig. 2 is pH response regeneration type polymer P of the present invention
MDM7.19The reaction equation of preparation.
Fig. 3 is pH response regeneration type polymer P of the present invention
ADB6.29With P
MDM7.19The phasor of the meta-alkalescence pH response regenerative aqueous two-phase system that constitutes.
Embodiment
Content for a better understanding of the present invention is described further below in conjunction with specific embodiment.
Embodiment 1pH response regeneration type polymer P
ADB6.29Preparation, its reaction equation as shown in Figure 1:
Adding 120mLpH is 7.0 deionized water in the tool plug Erlenmeyer flask of 250ml, 5mL vinylformic acid, 10mL methacrylic acid-N, N-dimethylaminoethyl, 0.5mL butyl methacrylate (three's mol ratio is 23.15:18.88:1), add initiator sodium bisulfite, each 0.208g of ammonium persulphate, shake up and make its dissolving.Feed nitrogen 15min, to guarantee having only rare gas element in the triangular flask.With the mouth of self-styled band sealing Erlenmeyer flask, and be placed in 55 ℃ the shaking bath, 24h vibrates under the 200rpm rotating speed.After reaction finishes, with the white colloidal solid taking-up of triangular flask bottom, clean with ethanol, acetone, be put in the vacuum drying oven drying.The white solid of dry gained is pH response regeneration type polymer P of the present invention
ADB6.29
Embodiment 2pH response regeneration type polymer P
MDM7.19Preparation, its reaction equation as shown in Figure 2:
Adding 40mLpH is 7.0 deionized water in the tool plug Erlenmeyer flask of 100mL, add 1.3mL methacrylic acid, 3mL methacrylic acid-N, N-dimethylaminoethyl, 0.5mL methyl methacrylate (mol ratio is 3.24:3.78:1), add initiator sodium bisulfite, each 0.0623g of ammonium persulphate, shake up and make its dissolving.Feed nitrogen 10min, to guarantee having only rare gas element in the triangular flask.With the mouth of self-styled band sealing Erlenmeyer flask, and be placed in 55 ℃ the shaking bath, 24h vibrates under the 200rpm rotating speed.After reaction finishes, with the white colloidal solid taking-up of triangular flask bottom, clean with ethanol, acetone, be put in the vacuum drying oven drying.The white solid of dry gained is pH response regeneration type polymer P of the present invention
MDM7.19
The isoelectric point determination of embodiment 3pH response regeneration type polymkeric substance:
Prepare the polymer P of 0.01mg/mL respectively
ADB6.29With polymer P
MDM7.19Some parts of solution, solvent is deionized water.Regulate two kinds of polymers solns respectively to different pH values (from pH=5.5 to pH=8.5, every 1.0 1 pH values) with 3M hydrochloric acid or sodium hydroxide.Utilize Zeta potential nano particle size analyser to measure the polymerization P of different pH values respectively
ADB6.29With polymer P
MDM7.19The Zeta potential of solution according to measurement result, is that X-coordinate, Zeta potential are ordinate zou with the pH value, makes broken line graph, on the figure shown in Zeta potential when being zero corresponding pH value be to the iso-electric point of emergencing copolymer.The result is: polymer P
MDM7.19Iso-electric point be 7.19, and polymer P
ADB6.29Iso-electric point be 6.29.
The recovery experiment embodiment of embodiment 4 polymkeric substance
The weight of the centrifuge tube sleeve pipe of weighing sky at first.Add the polymers soln of 5% (w/w) (solvent is water for the w/w of this unit representation quality per-cent, the i.e. total mass of polymer quality/solution) in the centrifuge tube sleeve pipe, the NaOH aqueous solution that drips 0.3M is regulated pH, up to there being solid to separate out, and the solution becomes muddiness.Continuation dropping NaOH liquid is separated out fully up to precipitating, sedimentation, and supernatant liquor becomes clarification.Regulate pH to the iso-electric point place (polymer P of above-mentioned polymkeric substance
MDM7.19Iso-electric point is 7.19, and polymer P
ADB6.29Iso-electric point is 6.29).The centrifuge tube sleeve pipe is put into the centrifugal 30min of whizzer, and revolution is 4000rpm.Centrifugal later supernatant liquor being outwelled put into vacuum drying oven and is dried to constant weight.The dry weight that finishes to measure again the centrifuge tube sleeve pipe just is the quality of the polymkeric substance that reclaims with before difference.Polymer P
MDM7.19Maximum recovery reach 98.8%, and polymer P
ADB6.29Maximum recovery reach 96.7%.
Embodiment 5pH response regeneration type polymericular weight and viscosimetric analysis example:
K with ultrapure water preparation pH=3.5
2HPO
4/ H
3PO
4Damping fluid 1000mL, and get 1000mL ultrapure water (all being added with 0.02% sodium azide (this 0.02% for adding the mass percent of material) in the above-mentioned solution, for the protection of chromatographic column), the filter membrane with 0.22 μ m filters respectively.With above-mentioned damping fluid prepare respectively 0.2%(this 0.2% for mass percent) polymer P
ADB6.29With P
MDM7.19Each 10mL of solution.
Adopt gel chromatographic columns and the coupling of multi-angle scatterometer to measure polymer P
ADB6.29With polymer P
MDM7.19Molecular weight distribution.The result is: polymer P
ADB6.29The molecular weight situation be: M
nBe 1.499 * 10
5D, M
wBe 2.942 * 10
5D, M
zBe 6.429 * 10
5D, molecular weight polymolecularity M
w/ M
nBe 1.962.Polymer P
MDM7.19The molecular weight situation be: M
nBe 6.224 * 10
5D, M
wBe 7.714 * 10
5D, M
zBe 1.131 * 10
6D, molecular weight polymolecularity M
w/ M
nBe 1.239.
Adopt the determination of ubbelohde viscometer polymer P
ADB6.29With P
MDM7.19Limiting viscosity and viscosity-average molecular weight, wherein the starting point concentration of polymeric solution is 10mg/mL, measure after the 2.5mL solvent dilutes follow-up the adding one by one again, dilutes 4 times, solvent is the NaOH aqueous solution of 125mM.The result is: polymer P
ADB6.29Limiting viscosity be 213.0mL/mg, viscosity-average molecular weight M
νBe 3.136 * 10
5D.Polymer P
MDM7.19Limiting viscosity be 215.6mL/mg, viscosity-average molecular weight M
νBe 3.205 * 10
5D.
Embodiment 6pH response regeneration type polymkeric substance particle diameter is measured example:
Prepare the polymer P of 10mg/mL respectively
ADB6.29With polymer P
MDM7.19Solution, solvent is ultrapure water, and through the water system membrane filtration of 0.45 μ m, adopts the multi-angle scatterometer to measure the particle diameter of two kinds of polymkeric substance.The result is: polymer P
ADB6.29Particle diameter concentrate on 3.747nm, and polymer P
MDM7.19Particle diameter concentrate on 3.930nm.
Embodiment 7pH response regeneration type polymers soln becomes experiment mutually:
With the 1.8g polymer P
ADB6.29With the 1.8g polymer P
MDM7.19Mixed dissolution configures 6%(w/w in the NaOH of the 30mL150mM aqueous solution) P of mass percent
ADB6.29And 6%(w/w) P of mass percent
MDM7.19Mixing solutions, stir.Get uniform mixing solutions in the 2mL graduated centrifuge tube, static 5h at room temperature, get final product the meta-alkalescence aqueous two-phase system, and to become the pH scope of phase be 8.4-8.7.
Embodiment 8P
ADB6.29/ P
MDM7.19The phasor example of aqueous two-phase system:
Prepare each polymers soln of 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 100mg/mL respectively, regulate each pH value of solution (solution just becomes clarification) to the scope of 8.4-8.7 with the NaOH aqueous solution of 3M, with the polymer P of 100 μ L liquid-transfering guns toward 20mg/mL
ADB6.29The polymer P that dropwise adds 100mg/mL in the solution
MDM7.19Solution just becomes muddy to the solution of clear, calculates the concentration of two polymkeric substance, is a cloud point on the binodal line.Add the deionized water with the pH value then, become clarification again to turbid solution, continue dropwise to add with 100 μ L liquid-transfering guns the polymer P of 100mg/mL
MDM7.19Solution, the solution to clear just becomes muddy again, obtains second cloud point.Repeat aforesaid operations with different concns, obtain a series of cloud point, these cloud points can be formed the binodal line of phasor.Polymer P in the two-phase about after adopting HPLC to be detected as mutually respectively
ADB6.29With polymer P
MDM7.19Concentration, obtain two points, be linked to be straight line with these 2, be an anchor line (string) of phasor.
Above-mentioned P
ADB6.29-P
MDM7.19The phasor of aqueous two-phase system as shown in Figure 3, wherein X-axis is represented the down composition of phase, and Y-axis is represented the composition of phase, from the figure as can be seen, as use 5%(w/w) polymer P
ADB6.29With 5%(w/w) polymer P
MDM7.19After becoming mutually, with HPLC detect anchor line (string) (seeing the straight line AB in the accompanying drawing 3), and the length ratio of line segment MB and AM is about 3:1, with the Cheng Xianghou volume ratio basically identical of two-phase up and down, this moment is detected, and to go up phase component be 3.487% P
ADB6.29With 1.293% P
MDM7.19, following phase component is 0.354% P
ADB6.29With 5.485% P
MDM7.19And when adopting 6%(w/w) P
ADB6.29With 6%(w/w) polymer P
MDM7.19After becoming mutually, with HPLC detect anchor line (string) (seeing the straight line CD in the accompanying drawing 3), contain 5.347% P in mutually on Cheng Xianghou is detected
ADB6.29With 0.431% P
MDM7.19, down contain 0.258% P in mutually
ADB6.29With 5.802% P
MDM7.19, i.e. polymer P
MDM7.19In mainly being enriched in down mutually, and polymer P
ADB6.29In then mainly being enriched in mutually, and phase volume ratio is tending towards 1:1, and concentration continues to increase, and the separation trend of two polymkeric substance can be more obvious.But along with the increase of polymer concentration, the viscosity of mixed with polymers solution increases, and makes the phase-splitting time also can correspondingly increase, and is 6%(w/w so all select concentration among the present invention for use) P
ADB6.29With 6%(w/w) P
MDM7.19Measure.
Embodiment 9 vitamins Bs
12Distribution experiment in above-mentioned two-phase system:
Add the 10mg vitamins B in the 2ml meta-alkalescence aqueous two-phase system in above-described embodiment 7
12With certain density salt ion, dissolving vibration mixing settles into phase.Xiang Gequ 100 μ L solution shine the vitamins B in the known method mensuration supernatant liquor after the dilution up and down
12Concentration, phase vitamins B up and down
12The ratio of concentration be vitamins B
12At meta-alkalescence pH response regeneration type polymer P
ADB6.29And P
MDM7.19Partition ratio in the formed two-phase system.Known to Li
2SO
4When concentration was 10mM, partition ratio reached and is 1.99 to the maximum.
The distribution experiment of embodiment 10 Spiramycin Bases in above-mentioned two-phase system:
Add 5mg Spiramycin Base and certain density salt ion in the 2mL meta-alkalescence aqueous two-phase system in above-described embodiment 7, dissolving vibration mixing settles into phase.Xiang Gequ 50 μ L solution shine the Spiramycin Base concentration in the known method mensuration supernatant liquor after the dilution up and down, and the ratio of the concentration of phase Spiramycin Base is Spiramycin Base at meta-alkalescence pH response regeneration type polymer P up and down
ADB6.29And P
MDM7.19Partition ratio in the formed two-phase system.Known to (NH
4)
2SO
4During concentration 60mM, partition ratio can reach 2.2.
The distribution experiment of embodiment 11 lincomycins in above-mentioned two-phase system:
Add 6mg lincomycin and certain density salt ion in the 2mL meta-alkalescence aqueous two-phase system in above-described embodiment 7, dissolving vibration mixing places thermostat water bath to heat, and settles into phase.Xiang Gequ 50 μ L solution up and down, it is synthermal that lincomycin concentration in the supernatant liquor is measured according to known method in the dilution back down, and the ratio of the concentration of phase lincomycin is lincomycin at meta-alkalescence pH response regeneration type polymer P up and down
ADB6.29And P
MDM7.19Partition ratio in the formed two-phase system.Known to 30 ℃, when KBr concentration was 10mM, it is minimum that partition ratio reaches, and is 0.17.At 40 ℃, Ti (SO
4)
2When concentration was 80mM, it is maximum that partition ratio reaches, and is 5.5.
In sum, two kinds of pH response regeneration type polymer Ps that form the meta-alkalescence aqueous two-phase system of the present invention
ADB6.29With P
MDM7.19, the pH invertible dissolution, rate of recovery height, thus reduce industrial cost greatly, be beneficial to the popularization of two water technology, be suitable for large-scale promotion application.
The above; it only is preferred embodiment of the present invention; be not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the premise of not departing from the present invention, also can make some improvement and replenish, these improvement and replenish and also should be considered as falling into protection scope of the present invention.All those skilled in the art, under the situation that does not break away from the spirit and scope of the present invention, a little change of making when utilizing the above technology contents that discloses, the equivalent variations of modifying and developing are equivalent embodiment of the present invention; Simultaneously, the change of any equivalent variations that all foundations essence technology of the present invention is done above-described embodiment, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (12)
1. the pH that can form the meta-alkalescence aqueous two-phase system responds regeneration type polymer P
ADB6.29, be that compound obtains through random copolymerization shown in compound shown in compound, the formula (2) shown in the formula (1) of 23.15:18.88:1 and the formula (3) by molar ratio, its molecular weight distribution is as follows: M
nBe 1.499 * 10
5D, M
wBe 2.942 * 10
5D, M
νBe 3.136 * 10
5D, M
zBe 6.429 * 10
5D, molecular weight polymolecularity M
w/ M
nBe 1.962, limiting viscosity is 213.0mL/mg, and iso-electric point is 6.29;
2. the pH that forms the meta-alkalescence aqueous two-phase system according to claim 1 responds regeneration type polymer P
ADB6.29, it is characterized in that the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29Particle diameter be 3.747nm, maximum recovery is 98.8%.
3. the pH that forms the meta-alkalescence aqueous two-phase system according to claim 1 and 2 responds regeneration type polymer P
ADB6.29The preparation method, comprise the steps: that compound shown in compound shown in compound shown in the described formula (1), the described formula (2) and the described formula (3) is pressed molar ratio 23.15:18.88:1 to add in the solvent, add initiator again, in the presence of rare gas element, carry out polyreaction and obtain the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
ADB6.29
4. the pH that forms the meta-alkalescence aqueous two-phase system according to claim 3 responds regeneration type polymer P
ADB6.29The preparation method, it is characterized in that described solvent is deionized water; Described initiator is sodium bisulfite and ammonium persulphate, and the initiator additional proportion is 1.3%(w/w), described rare gas element is nitrogen; The oscillatory reaction under 55 ℃ temperature, condition that rotating speed is 200rpm of described polyreaction realized in 24 hours.
5. the pH that can form the meta-alkalescence aqueous two-phase system responds regeneration type polymer P
MDM7.19, be that compound obtains through random copolymerization shown in compound shown in compound, the formula (4) shown in the formula (2) of 3.24:3.78:1 and the formula (5) by molar ratio, its molecular weight distribution is as follows: M
nBe 6.224 * 10
5D, M
wBe 7.714 * 10
5D, M
νBe 3.205 * 10
5D, M
zBe 1.131 * 10
6D, molecular weight polymolecularity M
w/ M
nBe 1.239, limiting viscosity is 215.6mL/mg, and iso-electric point is 7.19;
6. the pH that forms the meta-alkalescence aqueous two-phase system according to claim 5 responds regeneration type polymer P
MDM7.19, it is characterized in that the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19Particle diameter be 3.930nm, maximum recovery is 96.7%.
7. according to claim 5 or the 6 described pH response regeneration type polymer Ps that form the meta-alkalescence aqueous two-phase system
MDM7.19The preparation method, comprise the steps: that compound shown in compound shown in compound shown in the described formula (4), the formula (2) and the formula (3) is pressed molar ratio 3.24:3.78:1 to add in the solvent, add initiator again, in the presence of rare gas element, carry out polyreaction and obtain the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19
8. the pH that forms the meta-alkalescence aqueous two-phase system according to claim 7 responds regeneration type polymer P
MDM7.19The preparation method, it is characterized in that described solvent is deionized water; Described initiator is sodium bisulfite and ammonium persulphate; Described rare gas element is nitrogen; The oscillatory reaction under 55 ℃ temperature, condition that rotating speed is 200rpm of described polyreaction realized in 24 hours.
9. meta-alkalescence aqueous two-phase system, its pH scope is 8.4-8.7, and comprises claim 1 or the 2 described pH response regeneration type polymer Ps that form the meta-alkalescence aqueous two-phase system
ADB6.29Or the pH response regeneration type polymer P of the formed meta-alkalescence aqueous two-phase system that makes of claim 3 or 4 described preparation methods
ADB6.29, and claim 5 or the 6 described pH response regeneration type polymer Ps that form the meta-alkalescence aqueous two-phase system
MDM7.19Or the pH response regeneration type polymer P of the formed meta-alkalescence aqueous two-phase system that makes of claim 7 or 8 described preparation methods
MDM7.19
10. the preparation method of meta-alkalescence aqueous two-phase system according to claim 9 comprises the steps: the pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system with described
ADB6.29And the described pH response regeneration type polymer P that forms the meta-alkalescence aqueous two-phase system
MDM7.19Be dissolved in the sodium hydroxide solution, at room temperature settle into phase, becoming the pH scope of phase is 8.4-8.7, can obtain described meta-alkalescence aqueous two-phase system.
11. the application of meta-alkalescence aqueous two-phase system according to claim 10 in the separating bio product.
12. the application of meta-alkalescence aqueous two-phase system according to claim 11 in the separating bio product is characterized in that described biological product is VITAMIN or microbiotic.
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