CN108997542A - A kind of preparation method and applications of amphiphilic temperature sensitive block polymer - Google Patents
A kind of preparation method and applications of amphiphilic temperature sensitive block polymer Download PDFInfo
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention belongs to technical field of polymer, are related to a kind of preparation method and applications of amphiphilic temperature sensitive block polymer, which is made of water-soluble PEG block and the PNIPAM block with Thermo-sensitive.The present invention provides a kind of block polymer materials of temperature response type, the material is that three monothioesters containing carboxyl are first prepared, it is prepared for polyethylene glycol Macromolecular chain transfer agent by esterification with poly glycol monomethyl ether again, finally by RAFT polymerization by n-isopropyl acrylamide monomer polymerization to polyethylene glycol Macromolecular chain transfer agent, the temperature sensitive block polymer of narrow, the suitable low critical inversion temperature of Distribution Breadth Index has been synthesized.Polymer prepared by the present invention has many advantages, such as that Distribution Breadth Index is narrow, low critical inversion temperature is suitable；By the double-aqueous phase system of temperature sensitive block polymer and organic salt building regenerative, have the characteristics that phase separation temperature is low, operating condition is mild, polymer is easily recycled.
Description
Technical field
The invention belongs to technical field of polymer, are related to the preparation method of the amphiphilic temperature sensitive block polymer of one kind and its answer
With.
Background technique
There is wide application in fields such as the extraction and separation of medicine, food, natural active matter based on double-aqueous phase system
Prospect and its own excellent characteristic, such as have the characteristics that water content is big, split-phase speed is fast, at low cost and easy to operate, it is
Widely used method for separating and concentrating in recent years.What double-aqueous phase system grew up first is polymer-polymer systems, should
Most of system is at high cost using glucan as phase formation agent, large viscosity, has then developed polymer-instead of glucan with salt
Salt system, hydrophilic organic solvent-salt system and ionic liquid-salt system, although these three systems reduce costs and viscosity,
But still it cannot achieve into the recycling of phase object.With the development of temperature sensitive polymer, temperature sensitive polymer is introduced aqueous two-phase by people
System realizes the recycling of polymer using simple temperature control.
It is few to be commercialized temperature sensitive polymer type, low critical inversion temperature is high, it is difficult to meet diversified practical application.Such as
The present has obtained significant progress by the polymeric system that RAFT polymerize design synthesizing new temperature response type, but will preparation
The double-aqueous phase system of obtained temperature response type polymer construction regenerative, the research of this aspect are also less common.Therefore, it adopts
Synthesize that Distribution Breadth Index is narrow, molecular weight is controllable, the temperature sensitive block of suitable low critical inversion temperature is poly- with RAFT
It is particularly significant to close object.The temperature sensitive block polymer of preparation and organic salt are constructed into regenerative double-aqueous phase system, determine system liquid
The data of liquid equilibrium establish in system the material composition of phase up and down, and have studied into the phase separation ability of phase salt.By right
The research of above-mentioned double-aqueous phase system phasor has further established good theoretical base for isolating and purifying for double-aqueous phase system
Plinth.
Summary of the invention
The present invention is directed to overcome commercialization temperature sensitive polymer at the limitation of phase species, quantity, and it is an object of the present invention to provide one kind
Distribution Breadth Index is narrow, molecular weight is controllable, the preparation method of the temperature sensitive polymer material of suitable low critical inversion temperature and
It is applied, polymer material of the present invention-organic salt building regenerative double-aqueous phase system, behaviour low with phase separation temperature
Make mild condition, the features such as polymer is easily recycled.
The technical solution adopted by the present invention:
The present invention provides a kind of block polymer material of temperature response type, the material is first prepared containing carboxylic
Three monothioesters of base, then it is prepared for polyethylene glycol Macromolecular chain transfer agent by esterification with poly glycol monomethyl ether,
It polymerize finally by RAFT by n-isopropyl acrylamide monomer polymerization to polyethylene glycol Macromolecular chain transfer agent, has synthesized distribution
The temperature sensitive block polymer of narrow, the suitable low critical inversion temperature of breadth index.
The present invention provides a kind of preparation methods of temperature sensitive block polymer, the specific steps are as follows:
(1) preparation of RAFT reagent (BTPA)
In potassium hydroxide aqueous solution (104mg/mL, 31.25mL), dropwise be added dropwise 3- mercaptopropionic acid (2.5mL,
28.75mmol), carbon disulfide (3.75mL, 28.75mmol) then is added dropwise dropwise, is placed in and reacts 5h at room temperature.Cylite is added
(4.95g, 28.75mmol), 85 DEG C of back flow reaction 12h.After reaction, mixed liquor is cooled to room temperature, and chloroform is added
(70.0mL) adds excessive salt acid for adjusting pH value, and washs organic layer repeatedly with a large amount of distilled water, and rotary evaporation is organic
Layer, obtains the solid of yellow.
(2) preparation of the Macromolecular chain transfer agent based on poly glycol monomethyl ether
Dry poly glycol monomethyl ether (15.0g, 3.0mmol) is dissolved in the dry toluene of 30.0mL, in 50 DEG C of conditions
Lower azeotropic distillation removes a large amount of solvent.Then dry BTPA (1.635g, 6.0mmol) and anhydrous methylene chloride is added
(120.0mL) is placed in 0 DEG C of ice-water bath and is stirred.It is added dropwise N, N '-dicyclohexylcarbodiimide (DCC, 1.245g,
6.0mmol), the mixed liquor of 4-dimethylaminopyridine (DMAP, 0.0735g, 0.6mmol) and anhydrous methylene chloride (30.0mL),
It is dripped off in 1h.Mixture reacts 48h at room temperature.After reaction, insoluble salt, rotary evaporation filtrate are filtered to remove.Then
It is precipitated in excessive ether, dissolution-precipitating circulation is repeatedly for three times.It at last one night of drying at room temperature in a vacuum drying oven, obtains
Flaxen solid powder.
(3) preparation of temperature sensitive block polymer PEG-b-PNIPAM
By the Macromolecular chain transfer agent of poly glycol monomethyl ether, n-isopropyl acrylamide and azodiisobutyronitrile are dissolved in 1,
4- dioxane is simultaneously added in single-necked flask, and mixed liquor seals under vacuum after " freezing-pump-thaw " three times circulation,
After being reacted in oil bath, polymerization is quenched with liquid nitrogen, opens tube sealing, with Isosorbide-5-Nitrae-dioxane dilution dissolution, the excessive second of mixture
Ether precipitating, takes out sediment, repeats above-mentioned dilution dissolution-precipitating circulation three times, obtains lurid temperature sensitive block polymer
PEG-b-PNIPAM。
In step (3), the Macromolecular chain transfer agent of the poly glycol monomethyl ether, n-isopropyl acrylamide, azo two
The usage ratio of isobutyronitrile and 1,4- dioxane is 0.105-0.315g:0.2225-0.6675g:2-4mg:1-3mL.
In step (3), reaction temperature is 70-80 DEG C in the oil bath, reaction time 2-22h.
The amphiphilic temperature sensitive block polymer is the PNIPAM block group by water-soluble PEG block and with Thermo-sensitive
At chemical formula isWherein, m 50-150, n 20-200.
The present invention also provides a kind of amphiphilic temperature sensitive block polymer PEG-b-PNIPAM and organic salt to construct aqueous two-phase
System establishes phasor, the separation and recovery for protein.
Detailed description of the invention
Fig. 1 is the synthesis process schematic diagram (a) of RAFT reagent (BTPA) prepared by embodiment 1, prepared by embodiment 1
The synthesis process schematic diagram (b) of Macromolecular chain transfer agent based on poly glycol monomethyl ether, temperature sensitive block prepared by embodiment 3
The synthesis process schematic diagram (c) of polymer P EG-b-PNIPAM.
Fig. 2 is the infrared spectrogram (a) of RAFT reagent (BTPA) prepared by embodiment 1, prepared by embodiment 1 based on
The infrared spectrogram (b) of the Macromolecular chain transfer agent of poly glycol monomethyl ether, temperature sensitive block polymer prepared by embodiment 3
The infrared spectrogram (c) of PEG-b-PNIPAM.
Fig. 3 is RAFT reagent (BTPA) prepared by embodiment 11H NMR schemes (a), based on poly- prepared by embodiment 1
The Macromolecular chain transfer agent of glycol monoethyl ether1H NMR schemes (b), temperature sensitive block polymer PEG-b- prepared by embodiment 3
PNIPAM's1H NMR schemes (c).Wherein solvent is CDCl3。
Fig. 4 is RAFT reagent (BTPA) prepared by embodiment 113C NMR figure, wherein solvent is CDCl3。
Fig. 5 is mass spectrum (MS) figure of RAFT reagent (BTPA) prepared by embodiment 1.
Fig. 6 is the gel permeation chromatography of the Macromolecular chain transfer agent based on poly glycol monomethyl ether prepared by embodiment 1
(GPC) figure (a), gel permeation chromatography (GPC) figure (b) of temperature sensitive block polymer PEG-b-PNIPAM prepared by embodiment 3.
Mobile phase is THF.
Fig. 7 is temperature sensitive block polymer PEG-b-PNIPAM prepared by embodiment 3 under 25 DEG C (a) and 40 DEG C (b)
TEM figure.
Fig. 8 is the light transmission rate of the temperature dependency of temperature sensitive block polymer PEG-b-PNIPAM prepared by embodiment 3
Scheme (a) and dynamic laser light scattering figure (b).
Fig. 9 is cloud point gram of the temperature sensitive block polymer PEG-b-PNIPAM under various concentration prepared by embodiment 3.
Figure 10 is that there are different monovalent cations to have by temperature sensitive block polymer PEG-b-PNIPAM prepared by embodiment 3
Influence (b) of the machine salt to the influence (a) of its cloud point and there are different multivalent anions organic salt to its cloud point.
Figure 11 is temperature sensitive block polymer PEG-b-PNIPAM+Na prepared by embodiment 32C4H4O6/K2C4H4O6/
(NH4)2C4H4O6+H2The dual-node data (T=298.15K) of O ATPS.
Figure 12 is temperature sensitive block polymer PEG-b-PNIPAM+K prepared by embodiment 33C6H5O7/K2C4H4O6/K2C2O4+
H2The dual-node data (T=298.15K) of O ATPS.
Figure 13 is temperature sensitive block polymer PEG-b-PNIPAM+Na prepared by embodiment 32C4H4O6+H2In O ATPS not
The synthermal influence (T=288.15-298.15K) to its dual-node data.
Figure 14 is temperature sensitive block polymer PEG-b-PNIPAM+K prepared by embodiment 33C6H5O7/K2C4H4O6/K2C2O4/
Na2C4H4O6/(NH4)2C4H4O6+H2The Liquid-liquid equilibrium data (T=288.15-298.15K) of O ATPS.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with Detailed description of the invention to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments, based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1:
Step (1): the preparation of RAFT reagent (BTPA)
In potassium hydroxide aqueous solution (104mg/mL, 31.25mL), dropwise be added dropwise 3- mercaptopropionic acid (2.5mL,
28.75mmol), carbon disulfide (3.75mL, 28.75mmol) then is added dropwise dropwise, is placed in and reacts 5h at room temperature.Cylite is added
(4.95g, 28.75mmol), 85 DEG C of back flow reaction 12h.After reaction, mixed liquor is cooled to room temperature, and chloroform is added
(70.0mL) adds excessive salt acid for adjusting pH value, and washs organic layer repeatedly with a large amount of distilled water, and rotary evaporation is organic
Layer, obtains the solid of yellow.
Step (2): the preparation of the Macromolecular chain transfer agent based on poly glycol monomethyl ether
Dry poly glycol monomethyl ether (15.0g, 3.0mmol) is dissolved in the dry toluene of 30.0mL, in 50 DEG C of conditions
Lower azeotropic distillation removes a large amount of solvent.Then dry BTPA (1.635g, 6.0mmol) and anhydrous methylene chloride is added
(120.0mL) is placed in 0 DEG C of ice-water bath and is stirred.It is added dropwise N, N '-dicyclohexylcarbodiimide (DCC, 1.245g,
6.0mmol), the mixed liquor of 4-dimethylaminopyridine (DMAP, 0.0735g, 0.6mmol) and anhydrous methylene chloride (30.0mL),
It is dripped off in 1h.Mixture reacts 48h at room temperature.After reaction, insoluble salt, rotary evaporation filtrate are filtered to remove.Then
It is precipitated in excessive ether, dissolution-precipitating circulation is repeatedly for three times.It at last one night of drying at room temperature in a vacuum drying oven, obtains
Flaxen solid powder.
Step (3): the preparation of temperature sensitive block polymer PEG-b-PNIPAM
By the Macromolecular chain transfer agent (0.105g, 0.02mmol) of poly glycol monomethyl ether, n-isopropyl acrylamide
(NIPAM, 0.2225g, 6mmol) and azodiisobutyronitrile (AIBN, 2mg, 12 μm of ol) are dissolved in 1,4- dioxane (1.0mL) and add
Enter in single-necked flask.Mixed liquor by freeze three times-pump-thaw circulation after seal under vacuum.2h is reacted in 70 DEG C of oil baths,
Polymerization is quenched with liquid nitrogen, opens tube sealing, is diluted with Isosorbide-5-Nitrae-dioxane, mixture is precipitated with excessive ether.It repeats above-mentioned molten
Solution-precipitating circulation three times, obtains lurid temperature sensitive block polymer PEG-b-PNIPAM.
Embodiment 2:
Step (1) and step (2) are the same as embodiment 1；
Step (3): the preparation of temperature sensitive block polymer PEG-b-PNIPAM
By the Macromolecular chain transfer agent (0.315g, 0.06mmol) of poly glycol monomethyl ether, n-isopropyl acrylamide
(NIPAM, 0.6675g, 6mmol) and azodiisobutyronitrile (AIBN, 4mg, 24 μm of ol) are dissolved in 1,4- dioxane (3.0mL) and add
Enter in single-necked flask.Mixed liquor by freeze three times-pump-thaw circulation after seal under vacuum.It is reacted in 80 DEG C of oil baths
12h is quenched polymerization with liquid nitrogen, opens tube sealing, diluted with Isosorbide-5-Nitrae-dioxane, and mixture is precipitated with excessive ether.In repetition
It states dissolution-precipitating circulation three times, obtains lurid temperature sensitive block polymer PEG-b-PNIPAM.
Embodiment 3:
Step (1) and step (2) are the same as embodiment 1；
Step (3): the preparation of temperature sensitive block polymer PEG-b-PNIPAM
By the Macromolecular chain transfer agent (0.21g, 0.04mmol) of poly glycol monomethyl ether, n-isopropyl acrylamide
(NIPAM, 0.445g, 4mmol) and azodiisobutyronitrile (AIBN, 3mg, 18 μm of ol) are dissolved in 1,4- dioxane (2.0mL) and add
Enter in single-necked flask.Mixed liquor by freeze three times-pump-thaw circulation after seal under vacuum.It is reacted in 75 DEG C of oil baths
22h is quenched polymerization with liquid nitrogen, opens tube sealing, diluted with Isosorbide-5-Nitrae-dioxane, and mixture is precipitated with excessive ether.In repetition
It states dissolution-precipitating circulation three times, obtains lurid temperature sensitive block polymer PEG-b-PNIPAM.
It is the synthesis process schematic diagram (a) of RAFT reagent (BTPA) prepared by embodiment 1,1 institute of embodiment as shown in Figure 1
The synthesis process schematic diagram (b) of the Macromolecular chain transfer agent based on poly glycol monomethyl ether of preparation, temperature prepared by embodiment 3
The synthesis process schematic diagram (c) of quick block polymer PEG-b-PNIPAM.
It is the infrared spectrogram (a) of RAFT reagent (BTPA) prepared by embodiment 1, FTIR (KBr, cm as shown in Figure 2-1):3029,2915,1701,1598,1494,1453,1250,1072,815,798,777,710cm-1；Prepared by embodiment 1
The Macromolecular chain transfer agent based on poly glycol monomethyl ether infrared spectrogram (b), FTIR (KBr, cm-1):2888,1469,
1345,1281,1242,1113,962,843；The infrared light of temperature sensitive block polymer PEG-b-PNIPAM prepared by embodiment 3
Spectrogram (c), FTIR (KBr, cm-1):3291,3070,2973,2882,1650,1548,1463,1366,1281,1242,1114,
960,843。
It is RAFT reagent (BTPA) prepared by embodiment 1 as shown in Figure 31H NMR schemes (a),1H NMR(CDCl3)δ
(ppm)2.88(2H,CH2- C=O), 3.65 (2H, CH2-S),4.64(2H,CH2-Ar),7.33(5H,ArH)；Embodiment 1 is made
The standby Macromolecular chain transfer agent based on poly glycol monomethyl ether1H NMR schemes (b),1H NMR(400MHz,CDCl3)δ(ppm)
7.31(5H,ArH),4.59(2H,ArCH2-),4.25(2H,-CH2OCO-),3.63(452H,-CH2CH2O-),3.37(3H,
CH3O-),2.80(2H,-CH2SC- (=S) -)；Temperature sensitive block polymer PEG-b-PNIPAM prepared by embodiment 31H
NMR schemes (c),1H NMR(400MHz,CDCl3) δ (ppm) 3.94 (152H ,-C=O-NH-), 3.66 (452H ,-CH2CH2O-)。
It is RAFT reagent (BTPA) prepared by embodiment 1 as shown in Figure 413C NMR figure.13C NMR(101MHz,
CDCl3)δ(ppm)177.26,134.83,129.52,129.27,128.74,128.64,127.85,41.56,32.94,
30.89。
It is RAFT reagent (BTPA, C prepared by embodiment 1 as shown in Figure 511H12O2S3) mass spectrogram, theoretical values:
580.82, actual numerical value: 580.76 [M]+。
It is the gel infiltration of the Macromolecular chain transfer agent prepared by embodiment 1 based on poly glycol monomethyl ether as shown in Figure 6
Saturating chromatography (GPC) figure (a), Mn=6.1KDa, Mw/Mn=1.06；Temperature sensitive block polymer PEG-b- prepared by embodiment 3
Gel permeation chromatography (GPC) figure (b) of PNIPAM, Mn=23KDa, Mw/Mn=1.20.
Embodiment 4: the research of the temperature sensitive performance of temperature sensitive block polymer (PEG-b-PNIPAM)
(1) influence of the research temperature to polymersome pattern, as shown in Figure 7.In Fig. 7 (a), PEG-b-PNIPAM
Aqueous solution exist at 25 DEG C with the state of single-stranded dissolution；And in Fig. 7 (b), when temperature reaches 40 DEG C, polymer can be certainly
It is the spherical micelle of shell that assembling, which is formed by core, PEG of PNIPAM,.
(2) the temperature-induced behavior of polymer P EG-b-PNIPAM passes through ultraviolet specrophotometer (UV) and dynamic laser light
(DLS) is scattered to probe into.Shown in the dependence of light transmission rate and temperature such as Fig. 8 (a), the light transmission rate test of temperature dependency
Show low critical inversion temperature (LCST) behavior of PEG-b-PNIPAM due to PNIPAM block, it is higher than 34 DEG C of hairs in temperature
Raw aggregation.Shown in dynamic laser light scattering such as Fig. 8 (b), dynamic laser light scattering as shown, PEG-b-PNIPAM aqueous solution
At 25 DEG C, partial size 36.32nm, the polydispersity coefficient 0.059 of partial size.And self assembly obtains aggregation at 40 DEG C,
Partial size is increased to 191.9nm, the polydispersity coefficient 0.1 of partial size.
Embodiment 5: the analysis and research of temperature sensitive block polymer PEG-b-PNIPAM cloud point
(1) cloud point of the temperature sensitive block polymer (PEG-b-PNIPAM) of various concentration is determined, as shown in Figure 9.From figure
In it can be concluded that, cloud point can be reduced with the increase of temperature sensitive block polymer concentration.When the concentration of temperature sensitive block polymer increases
When being added to 0.065g/mL, cloud point is no longer reduced.Therefore, the minimum critical point temperature (LCST) of temperature sensitive block polymer is 28.6
℃.When the concentration of temperature sensitive block polymer continues growing, cloud point is also continued growing.
(2) different monovalent cation Na+、K+、NH4 +Shown in influence such as Figure 10 (a) to cloud point, the suitable of cloud point is reduced
Sequence are as follows: Na+>K+>NH4 +.Cation radius is smaller, easier to carry out hydration left and right, and the influence to cloud point is also bigger.(Na+=
102pm<K+=138pm < NH4 +=143pm).
(3) shown in influence of the multivalent anions to cloud point such as Figure 10 (b), the sequence of cloud point is reduced are as follows: C6H5O7 3->
C4H4O6 2->C2O4 2-.Mainly since ionic valence condition is higher, with the stronger ability of saltouing, can be good in aqueous solution
Bound water molecule.This result and gibbs hydration free (Δ Ghyd) it is the sequence consensus that parameter obtains.Gibbs aquation is certainly
By energy (Δ Ghyd):ΔGhyd(C6H5O7 3-)=- 2763KJ/mol > Δ Ghyd(C4H4O6 2-)=- 1090KJ/mol > Δ Ghyd
(C2O4 2-)=- 673KJ/mol.So the Δ G of anionhydBigger, hydratability is stronger, and then reduces the ability of cloud point
Also stronger.
Embodiment 6: temperature sensitive block polymer (PEG-b-PNIPAM)+organic salt (K3C6H5O7/Na2C4H4O6/K2C4H4O6/
(NH4)2C4H4O6/K2C2O4)+H2The data and association of O double-aqueous phase system phasor
(1) in T=298.15K, PEG-b-PNIPAM+Na2C4H4O6/K2C4H4O6/(NH4)2C4H4O6+H2O ATPS's
Binode is as shown in figure 11.In binode phasor, the binodal line the close to axis, illustrates that the ability of saltouing of split-phase salt is stronger.
Binodal line is moved to the left, corresponding monophase field range shorter, that is to say, that the salt content of ATPS is reduced, so that the salt of salt
The enhancing of analysis ability；Meanwhile binodal line is more moved to the left, it is meant that reaches polymer needed for split-phase in the identical situation of salinity
Dosage it is fewer.Gibbs hydration free (the Δ G of the saltout ability and composition ion of salthyd) related, with ion hydration freedom
It can be carried out the thermodynamics method compared and think ion Δ GhydSmaller, ability of saltouing is stronger.Gibbs free energy (Δ Ghyd):Δ
Ghyd(Na+)=- 365KJ/mol > Δ Ghyd(K+)=- 295KJ/mol > Δ Ghyd(NH+)=- 285KJ/mol.Three kinds of organic salt
Anion (C4H4O6 2-) identical, but cation is different, three kinds of cationic abilities of saltouing: Na+>K+>NH+.This sequentially with lucky cloth
This hydration free (Δ Ghyd) it is that the sequence that parameter obtains is identical.
(2) in T=298.15K, PEG-b-PNIPAM+K3C6H5O7/K2C4H4O6/K2C2O4+H2The binode of O ATPS
As shown in figure 12.Cation (the K of three kinds of organic salt+) identical, but anion is different, the ability of saltouing of three kinds of anion:
C6H5O7 3->C4H4O6 2-≈C2O4 2-。C4H4O6 2-And C2O4 2-Ability of saltouing it is essentially identical, but C6H5O7 3-Ability ratio of saltouing
The above two are eager to excel, it may be possible to since the ion of high-valence state can be in conjunction with more hydrones, so the ion with higher chemical valence
The relatively low chemical valence of ability of saltouing ion ability of saltouing.This result and gibbs hydration free (Δ Ghyd) it is ginseng
The sequence that number obtains is not much different.Gibbs free energy (Δ Ghyd):ΔGhyd(C6H5O7 3-)=- 2763KJ/mol > Δ Ghyd
(C4H4O6 2-)=- 1090KJ/mol > Δ Ghyd(C2O4 2-)=- 673KJ/mol.
(3) for polymer-salt double-aqueous phase system (ATPS), many studies have shown that, temperature change is to binodal line position
Be affected.Temperature reduces, and binodal line moves right far from coordinate origin；Temperature increases, and binodal line is moved to the left, to seat
It is close to mark origin.As shown in figure 13, for PEG-b-PNIPAM+Na2C4H4O6+H2O ATPS, as the temperature rises, binodal line
It is moved to the left, equal phase region reduces, and two-phase section increases.Illustrate the raising with system temperature, system enhances at phase ability.This
Conclusion is consistent with other polymers-salt ATPS, it may be possible to due to as the temperature rises, reducing the combination energy of polymer and water
Power, to push the split-phase of system.
(4) temperature sensitive block polymer (PEG-b-PNIPAM)+organic salt (K is had studied3C6H5O7/Na2C4H4O6/K2C4H4O6/
(NH4)2C4H4O6/K2C2O4)+H2The Liquid-liquid equilibrium of O double-aqueous phase system, as shown in figure 14.It can be seen from the figure that various bodies
The absolute value of the slope of system increases with temperature and is increased.This is because slope (STL) is represented by │ STL │=│ Δ Y/ Δ X │,
Δ X and Δ Y respectively indicates the concentration difference of salt and PEG-b-PNIPAM in two-phase, i.e. │ Δ X │=│ xb-xt│, │ Δ Y │=│ yb-
yt│, wherein xtAnd xbRespectively indicate concentration of the salt in upper phase (Top) and lower phase (Bottom), ytAnd ybRespectively indicate PEG-b-
Concentration of the PNIPAM in upper phase (Top) and lower phase (Bottom).As the temperature rises, the hydrophobicity of PEG-b-PNIPAM increases
By force, part water is caused to return to lower phase from upper phase, at this point, the concentration of the PEG-b-PNIPAM and salt in upper phase increase, xtAnd ytIncrease
Greatly；The concentration of PEG-b-PNIPAM and salt reduces in lower phase, xbAnd ybReduce.Therefore, Δ X reduces while Δ Y increases, finally
The absolute value of STL is caused to increase.
Claims (5)
1. a kind of preparation method of amphiphilic temperature sensitive block polymer, which comprises the steps of:
(1) Macromolecular chain transfer agent of poly glycol monomethyl ether, n-isopropyl acrylamide and azodiisobutyronitrile are dissolved in 1,
4- dioxane is simultaneously added in single-necked flask, and mixed liquor seals under vacuum after " freezing-pump-thaw " three times circulation；
After being reacted in oil bath, polymerization is quenched with liquid nitrogen, opens tube sealing, with Isosorbide-5-Nitrae-dioxane dilution dissolution, the excessive second of mixture
Ether precipitating, takes out sediment, repeats above-mentioned dilution dissolution-precipitating circulation three times, obtains lurid temperature sensitive block polymer
PEG-b-PNIPA。
2. the preparation method of the amphiphilic temperature sensitive block polymer of one kind according to claim 1, which is characterized in that described poly-
Macromolecular chain transfer agent, n-isopropyl acrylamide, the use of azodiisobutyronitrile and 1,4- dioxane of glycol monoethyl ether
Amount ratio is 0.105-0.315g:0.2225-0.6675g:2-4mg:1-3mL.
3. the preparation method of the amphiphilic temperature sensitive block polymer of one kind according to claim 1, which is characterized in that the oil
Reaction temperature is 70-80 DEG C in bath, reaction time 2-22h.
4. a kind of amphiphilic temperature sensitive block polymer, which is characterized in that be by any one of claims 1 to 3 preparation side
Made from method, it is made of water-soluble PEG block and the PNIPAM block with Thermo-sensitive, chemical formula isWherein, m 50-150, n 20-200.
5. a kind of purposes of amphiphilic temperature sensitive block polymer as claimed in claim 4, which is characterized in that will be described amphiphilic
Temperature sensitive block polymer PEG-b-PNIPAM and organic salt construct double-aqueous phase system, establish phasor, and the separation for protein is returned
It receives.
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