CN106243343B - A kind of synthesis and application of phenyl boric acid functionalization block polymer - Google Patents
A kind of synthesis and application of phenyl boric acid functionalization block polymer Download PDFInfo
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Abstract
The present invention relates to a kind of temperature sensitive block polymer of phenyl boric acid functionalization and its synthetic method, and it is used for adsorbing separation o-dihydroxy compound；The present invention surrounds the affine principle of boron, using temperature sensitive block polymer L64 as matrix, Carboxybenzeneboronic acid group between being introduced by acyl chloride reaction into temperature sensitive block copolymer template, synthesize a kind of new temperature sensitive block polymer of phenyl boric acid functionalization, to the correlated performances of resulting polymers after such as cloud point, solubility are studied, it was demonstrated that be successfully made modification to polymer；The method of the present invention is simple to operate efficiently, greatly reduces time and cost；The present invention is by the prepared temperature sensitive block polymer PEO of phenyl boric acid functionalization20PPO60PEO20For affine adsorbing separation alizarin red, reach 98% for the rate of recovery of alizarin red, it is shown that good affine adsorbing separation effect.
Description
Technical field
The present invention relates to a kind of temperature sensitive block polymer of phenyl boric acid functionalization and its synthetic method, and it is adjacent for adsorbing separation
Dihydroxy compounds.
Background technology
Include a trivalent boron atom, an alkyl or aryl substituent, and two hydroxyls in boric acid base group.As
For one kind tool compared with the non-natural organic acid of stiff stability and numerous characteristic reactions, boric acid and its derivative have been successfully applied C-C
Synthesis, sugar detection and insoluble drug release of key etc..But for boric acid and its derivative, its most important property is no more than
Itself and a kind of critically important material --- characteristic reactions between o-dihydroxy compound, by means of the progress of the reaction, boric acid
Borate can be combined to form with o-dihydroxy compound and causes the steric configuration of boric acid and physicochemical property that significant become occurs
Change.And a kind of reversible reaction is used as, the change of system environment can cause significant impact to the generation of borate, and cause boric acid
The significant change of physicochemical property, indicate the good response of boric acid and its derivative for system environmental change.In recent years, will
It is adsorbing separation neighbour's dihydroxy that the part of boric acid functional group, which is bonded to the affine sorbing material of boron that insoluble stromal surface synthesizes,
One of based compound specificity highest method, has widely been applied to separation and enrichment containing o-dihydroxy material
In.These matrix are mainly magnetic nano-particle, silica gel, integral post, graphene etc., but the usual surface binding site of these materials
Limited, adsorption capacity is not generally high；Practical application need to consume a large amount of adsorbents, and cost is higher；Building-up process complexity wastes time and energy.
Therefore, find a kind of low cost and efficient adsorbent matrix seems extremely important.
Stimuli responsive polymers refer to the change with external environment condition（Such as：Temperature, pH, magnetic etc.）, the reason of its own
Some significant changes can be occurred by changing property, and thus the change to external environment condition produces the polymer of response.Triblock polymer
PEO20PPO60PEO20（L64）It is exactly a kind of stimuli responsive polymers, using hydrophobic PPO groups as outer core and hydrophilic
PEO groups are core center, its Thermo-sensitive of this special structures shape, i.e., as the rising of temperature, micella can assemble shape
Into greater compactness of spherical structure, hydrophobicity enhancing, so as to be separated out from water.But the polymer is not employed for the affine adsorption material of boron
In the adsorbing separation of material and o-dihydroxy compound, this is undoubtedly a kind of sorry..And it is used for point of o-dihydroxy material at this stage
Include boron affinity chromatography and the affine related separation method of boron from enrichment method, still there are many drawbacks, such as specificity is not good enough, inhales
Attached capacity is relatively low, separation process is complicated, time-consuming too long, big etc. using limitation.
In view of 2 points above, the present invention utilizes stimuli responsive polymers PEO first20PPO60PEO20Temperature-sensing property with
And phenyl boric acid group is to the affinity characteristic of o-dihydroxy compound, Carboxybenzeneboronic acid between being introduced with acyl chloride reaction into polymer
Group prepares phenyl boric acid functionalization PEO20PPO60PEO20, the novel modified polymer is used for affine absorption system.It is this new
Type polymer absorbant has that synthesis step is simple efficiently, temperature-responsive is sensitive, adsorption efficiency is high and low cost and other advantages.
The content of the invention
It is an object of the invention to provide a kind of phenyl boric acid functionalization of the absorption o-dihydroxy compound of high power capacity is temperature sensitive
Block polymer and its synthetic method.
To achieve the above object, the technical solution adopted by the present invention is：
Around the affine principle of boron, with temperature sensitive block polymer PEO20PPO60PEO20（L64）It is anti-by chloride for matrix
Carboxybenzeneboronic acid group between should being introduced into temperature sensitive block copolymer template, synthesize a kind of new temperature sensitive block of phenyl boric acid functionalization
Polymer, to the correlated performances of resulting polymers after such as cloud point, solubility are studied, it was demonstrated that be successfully made to polymer
It is modified.
And using the alizarin red containing adjacent hydroxyl as model compound, the prepared temperature sensitive block of phenyl boric acid functionalization is gathered
Compound PEO20PPO60PEO20For affine adsorbing separation alizarin red.
The boric acid functionalization PEO20PPO60PEO20Synthetic method carry out in accordance with the following steps：
Carboxybenzeneboronic acid is added in a certain amount of dichloromethane by between, fully adds oxalyl chloride thereto after dissolving, and drip
Add a small amount of N,N-dimethylformamide with initiation reaction；Resulting solution stirring reaction under fixed temperature for a period of time, then subtracts
Pressure rotary distillation removes solvent and obtains yellow liquid product, i.e. 3- formyls chlorophenylboronic acid；By whole product 3- formyl chlorophenylboronic acids
It is dissolved in a certain amount of dichloromethane and obtains solution A；By PEO20PPO60PEO20Be dissolved in a certain amount of dichloromethane, and to its
Middle addition triethylamine obtains solution B；Then under ice-water bath cooling, solution A is instilled in solution B；Recession deicing completely is added dropwise
Water-bath, stirring reaction is for a period of time under fixed temperature for mixed solution system；Then rotary distillation is depressurized except removing solvent, Xiang Ti
Water is added in system, and heats split-phase, product can be obtained by collecting lower phase drying.
Wherein, the dosage of Carboxybenzeneboronic acid and dichloromethane is 0.12g between described：5-30mL；
Described Carboxybenzeneboronic acid is 0.12g with oxalyl chloride, the usage ratio of N,N-dimethylformamide：124μL：1-20
Drop；
The solution stirring reaction is 15-40 DEG C, reaction 2-13 h；
The dichloromethane of the dissolving 3- formyl chlorophenylboronic acids for 5-30mL, preferably 3- formyls chlorophenylboronic acid and dichloro
Methane dosage is 0.12g：17.5mL；
The dissolving PEO20PPO60PEO20Dichloromethane and PEO20PPO60PEO20, triethylamine dosage be 5-60mL：
0.50 g：150 μL；
The volume ratio of the solution A and solution B is 1:2；
The mixed solution system stirring reaction is 15-40 DEG C of reaction 2-13 h.
Resulting phenyl boric acid functionalization PEO20PPO60PEO20Carry out Performance Testing by the following method：
Cloud point determines：0.10 g PEO is added into two 25.00 mL colorimetric cylinders respectively20PPO60PEO20With 0.10 g
Functionalization PEO20PPO60PEO20With a certain amount of sorbierite（A kind of o-dihydroxy compound）, added into colorimetric cylinder a certain amount of
Distilled water, system gross mass is reached 20 g.Solution is sufficiently mixed after shaking up, then adjusts pH value of solution to desired value.Respectively
With the cloud point of nephelometry and ultraviolet method determination sample solution.
Saltout experiment：Respectively 0.20 g PEO are added into two 5.00 mL colorimetric bottles20PPO60PEO20With 0.20 g work(
PEO can be changed20PPO60PEO20, and adding appropriate distilled water makes system gross mass reach 2.00 g.Then added into system certain
The K of amount2HPO4, fully shaking system, treat K2HPO4After being completely dissolved, system is stood into 15min to observe effect of saltouing.
Wherein, the sorbierite quality added when cloud point determines is 0-20 mg；Solution ph is 4-12, passes through 0.1 M's
HCl and 0.1 M NaOH are adjusted.Saltout the final K of system in testing2HPO4Mass concentration is 10-50%.
Resulting phenyl boric acid functionalization PEO20PPO60PEO20For affine adsorbing separation alizarin red：
To with alizarin red（A kind of o-dihydroxy compound）Adsorbing separation experiment：Add into 10.00 mL plastic centrifuge tubes
Enter a certain amount of alizarin red and phenyl boric acid functionalization PEO20PPO60PEO20, appropriate water is then added thereto and makes system total
Quality reaches 2.00 g.By resulting solution ultrasonic vibration 15min so that after system is well mixed, added into system a certain amount of
K2HPO4, and fully rocking is completely dissolved it.Standing adsorption for a period of time after, isolating polymer simultaneously dissolved measure wherein
The amount of contained alizarin red, and calculate the alizarin red rate of recovery.
Wherein, alizarin red addition is 0.05-0.4 mg；Phenyl boric acid functionalization PEO in absorption system20PPO60PEO20Eventually
Concentration is 0.5-2.5%, K2HPO4Final concentration of 10-50%；The standing adsorption time is 0.5-5 h；Alizarin red content is purple in solution
Outside-visible spectrophotometry measure, that is, measure its absorbance at 424nm and obtain content；Alizarin red rate of recovery E1Calculate
It is as follows：
E1=Ma/Mb
M in formulaa--- the amount of the alizarin red in absorption post-consumer polymer；
Mb--- the amount of the alizarin red added into system.
The invention has the advantages that：
（1）The present invention uses temperature sensitive block polymer PEO20PPO60PEO20(L64) it is matrix, and passes through acyl chloride reaction
Carboxybenzeneboronic acid group between introducing thereto, obtains a kind of new temperature sensitive block polymer of phenyl boric acid functionalization.Gathered with block
Compound PEO20PPO60PEO20As the matrix of boron affinitive material, relative to general magnetic nano-particle, integral post matrix etc., into
This is relatively low, and chemical stability is preferable；The acyl chloride reaction that adsorbent synthesis utilizes, it is simple to operate efficient, when greatly reducing
Between and cost.
（2）The present invention takes full advantage of stimuli responsive polymers PEO20PPO60PEO20Temperature-sensing property, liter can be passed through
High-temperature strengthens its hydrophobicity, very high to the adsorption efficiency of object so as to largely be separated out from solution, therefore need not make
High adsorption effect is can reach with substantial amounts of adsorbent.
（3）Phenyl boric acid functionalization PEO of the invention by preparation20PPO60PEO20For o-dihydroxy compound alizarin red
Affine adsorbing separation, reach 98% for the rate of recovery of alizarin red, it is shown that good affine adsorbing separation effect.
Brief description of the drawings
Fig. 1 is phenyl boric acid functionalization PEO20PPO60PEO20Synthetic route chart；
Fig. 2 is phenyl boric acid functionalization PEO20PPO60PEO20 H1NMR schemes；
Fig. 3 is phenyl boric acid functionalization PEO20PPO60PEO20To the adsorption effect of alizarin red, in figure (a) be alizarin red+
PEO20PPO60PEO20；(b) it is alizarin red+phenyl boric acid functionalization PEO20PPO60PEO20。
Embodiment：
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with brief description of the drawings to this
Technical scheme in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example, rather than whole embodiments are applied, based on the embodiment in the present invention, those of ordinary skill in the art are not making creation
Property work on the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
Embodiment 1：
（1）Boric acid functionalization PEO20PPO60PEO20Synthesis：
Carboxybenzeneboronic acid between 0.12 g is added in 5 mL dichloromethane, fully adds 124 μ L oxalyl thereto after dissolving
Chlorine, and 1 drop DMF is added dropwise with initiation reaction.Resulting solution h of stirring reaction 2 at 15 DEG C, is then depressurized
Rotary distillation removes solvent and obtains yellow liquid product, the i.e. g of 3- formyls chlorophenylboronic acid 0.08.By 0.08 g product 3- formyl chlorides
Phenyl boric acid, which is dissolved in 5 mL dichloromethane, obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 5 mL dichloromethane, and
150 μ L triethylamines are added thereto obtains solution B.Then under ice-water bath cooling, all solution As are instilled in solution B.
Recession completely is added dropwise and removes ice-water bath, system h of stirring reaction 2 at 15 DEG C.Then rotary distillation is depressurized except removing solvent, Xiang Ti
5 mL water are added in system, and heat split-phase, are collected lower mutually dry that the g of product 0.21, yield are about 40%.
（2）Phenyl boric acid functionalization PEO20PPO60PEO20Performance Testing：
Cloud point determines：0.10 g PEO is added into two 25.00 mL colorimetric cylinders respectively20PPO60PEO20With 0.10 g
Functionalization PEO20PPO60PEO20, a certain amount of distilled water is added into colorimetric cylinder, system gross mass is reached 20 g.By solution
It is sufficiently mixed after shaking up, then adjusts pH value of solution to 4.PEO is measured with nephelometry20PPO60PEO20Cloud point is 58.2 DEG C, uses turbidity
Method and ultraviolet method measure functionalization PEO respectively20PPO60PEO20Cloud point be 23.4 DEG C and 24.1 DEG C.It can be found that two kinds turbid
Point measuring method result is basically identical, all show modified phenyl boric acid functionalization PEO20PPO60PEO20Cloud point relative to
PEO20PPO60PEO20Obvious to reduce, polymer hydrophilicity and cloud point change, and the result confirms that the success of boric acid base group is drawn
Enter.
Saltout experiment：Respectively 0.20 g PEO are added into two 5.00 mL colorimetric bottles20PPO60PEO20With 0.20 g work(
PEO can be changed20PPO60PEO20, and adding appropriate distilled water makes system gross mass reach 2.00 g.Then added into system certain
The K of amount2HPO4, make K in system2HPO4Final concentration of 10%, fully shaking system, treat K2HPO4After being completely dissolved, system is stood
After 15min, it was observed that PEO20PPO60PEO20Do not separate out, and functionalization PEO20PPO60PEO20There is a small amount of precipitation.Illustrate now
Functionalization PEO20PPO60PEO20There are certain precipitation effect and hydrophobicity；Two kinds of polymer difference precipitation situation also demonstrates benzene
Boric acid functionalization PEO20PPO60PEO20Successful modification.
（3）To alizarin red（A kind of o-dihydroxy compound）Adsorbing separation experiment：Into 10.00 mL plastic centrifuge tubes
Add 0.05 mg alizarin red, a certain amount of phenyl boric acid functionalization PEO20PPO60PEO20, appropriate water is then added thereto
And system gross mass is reached 2.00 g, phenyl boric acid functionalization PEO in system20PPO60PEO20Final concentration of 0.5%.Gained is molten
After liquid ultrasonic vibration 15min is well mixed, a certain amount of K is added into system2HPO4, make its final concentration of 10%, and fully shake
Rolling is completely dissolved it.After the h of standing adsorption 0.5, isolating polymer is simultaneously dissolved the amount for determining alizarin red contained therein,
And the alizarin red rate of recovery is calculated as 30%.
Embodiment 2：
（1）Boric acid functionalization PEO20PPO60PEO20Synthesis：
Carboxybenzeneboronic acid between 0.12 g is added in 30 mL dichloromethane, fully adds 124 μ L grass after dissolving thereto
Acyl chlorides, and 10 drop DMFs are added dropwise with initiation reaction.Resulting solution h of stirring reaction 13 at 40 DEG C, then
Decompression rotary distillation removes solvent and obtains yellow liquid product, the i.e. g of 3- formyls chlorophenylboronic acid 0.12.By 0.12 g product 3- first
Acyl chlorides phenyl boric acid, which is dissolved in 30 mL dichloromethane, obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 60 mL dichloromethanes
In alkane, and 150 μ L triethylamines are added thereto and obtain solution B.Then under ice-water bath cooling, all solution As are instilled molten
In liquid B.Recession completely is added dropwise and removes ice-water bath, system h of stirring reaction 13 at 40 DEG C.Then it is molten except removing to depressurize rotary distillation
Agent, 5 mL water are added into system, and heat split-phase, the g of product 0.44 can be obtained by collecting lower phase drying, and yield is about 84%.
（2）Phenyl boric acid functionalization PEO20PPO60PEO20Performance Testing：
Cloud point determines：0.10 g PEO is added into two 25.00 mL colorimetric cylinders respectively20PPO60PEO20With 0.10 g
Functionalization PEO20PPO60PEO20, a certain amount of distilled water is added into colorimetric cylinder, system gross mass is reached 20 g.By solution
It is sufficiently mixed after shaking up, then adjusts pH value of solution to 12.PEO is measured with nephelometry20PPO60PEO20Cloud point is 58.2 DEG C, uses turbidity
Method and ultraviolet method measure functionalization PEO respectively20PPO60PEO20Cloud point be 44.2 DEG C and 44.1 DEG C.It can be found that
PEO20PPO60PEO20Cloud point is not influenceed by pH；And two kinds of cloud point measuring method results are basically identical, modified benzene all show
Boric acid functionalization PEO20PPO60PEO20Cloud point is raised with pH value and substantially increased；Acquired results are also confirmed to benzene boron from side
Acid functionalization PEO20PPO60PEO20Successful modification.
Saltout experiment：Respectively 0.20 g PEO are added into two 5.00 mL colorimetric bottles20PPO60PEO20With 0.20 g work(
PEO can be changed20PPO60PEO20, and adding appropriate distilled water makes system gross mass reach 2.00 g.Then added into system certain
The K of amount2HPO4, make K in system2HPO4Final concentration of 20%, fully shaking system, treat K2HPO4After being completely dissolved, system is stood
After 15min, it was observed that PEO20PPO60PEO20Do not separate out, and functionalization PEO20PPO60PEO20There is more precipitation.Illustrate now
Functionalization PEO20PPO60PEO20Influenceed by salinity, precipitation effect is preferable, and hydrophobicity is stronger；Two kinds of polymer is different to separate out feelings
Condition also demonstrates phenyl boric acid functionalization PEO20PPO60PEO20Successful modification.
（3）To alizarin red（A kind of o-dihydroxy compound）Adsorbing separation experiment：Into 10.00 mL plastic centrifuge tubes
Add 0.1 mg alizarin red, a certain amount of phenyl boric acid functionalization PEO20PPO60PEO20, then appropriate water is added thereto simultaneously
System gross mass is set to reach 2.00 g, phenyl boric acid functionalization PEO in system20PPO60PEO20Final concentration of 1%.Resulting solution is surpassed
Acoustic shock swing 15min it is well mixed after, a certain amount of K is added into system2HPO4, make its final concentration of 40%, and fully rock and make
It is completely dissolved.After the h of standing adsorption 5, isolating polymer is simultaneously dissolved the amount for determining alizarin red contained therein, and is calculated
The alizarin red rate of recovery is 79%.
Embodiment 3：
（1）Boric acid functionalization PEO20PPO60PEO20Synthesis：
Carboxybenzeneboronic acid between 0.12 g is added in 15 mL dichloromethane, fully adds 124 μ L grass after dissolving thereto
Acyl chlorides, and 5 drop DMFs are added dropwise with initiation reaction.Resulting solution h of stirring reaction 5 at 25 DEG C, then subtracts
Pressure rotary distillation removes solvent and obtains the yellow liquid product i.e. g of 3- formyls chlorophenylboronic acid 0.1.By 0.1 g product 3- formyl chlorobenzenes
Boric acid, which is dissolved in 15 mL dichloromethane, obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 30 mL dichloromethane, and
150 μ L triethylamines are added thereto obtains solution B.Then under ice-water bath cooling, all solution As are instilled in solution B.
Recession completely is added dropwise and removes ice-water bath, system h of stirring reaction 5 at 25 DEG C.Then rotary distillation is depressurized except removing solvent, Xiang Ti
5 mL water are added in system, and heat split-phase, the g of product about 0.38 can be obtained by collecting lower phase drying, and yield is about 72%.
（2）Phenyl boric acid functionalization PEO20PPO60PEO20Performance Testing：
Cloud point determines：0.10 g PEO is added into two 25.00 mL colorimetric cylinders respectively20PPO60PEO20With 0.10 g
Functionalization PEO20PPO60PEO20, with 20 mg sorbierites（A kind of o-dihydroxy compound）, added into colorimetric cylinder a certain amount of
Distilled water, system gross mass is set to reach 20 g.Solution is sufficiently mixed after shaking up, then adjusts pH value of solution to 12.Surveyed with nephelometry
Obtain PEO20PPO60PEO20Cloud point is 58.2 DEG C, and functionalization PEO is measured respectively with nephelometry and ultraviolet method20PPO60PEO20It is turbid
Point is 50.3 DEG C and 50.2 DEG C.It can be found that PEO20PPO60PEO20Cloud point do not influenceed by sorbierite addition, and two
Kind cloud point measuring method result is basically identical, all show modified phenyl boric acid functionalization PEO20PPO60PEO20Cloud point with
The increase of sorbierite addition and increase；The result confirms being successfully introduced into for boric acid base group.
Saltout experiment：Respectively 0.20 g PEO are added into two 5.00 mL colorimetric bottles20PPO60PEO20With 0.20 g work(
PEO can be changed20PPO60PEO20, and adding appropriate distilled water makes system gross mass reach 2.00 g.Then added into system certain
The K of amount2HPO4, make K in system2HPO4Final concentration of 50%, fully shaking system, treat K2HPO4After being completely dissolved, system is stood
After 15min, it was observed that PEO20PPO60PEO20Do not separate out, and functionalization PEO20PPO60PEO20There is a small amount of precipitation.Illustrate now
Functionalization PEO20PPO60PEO20Influenceed by salinity, there is certain precipitation effect and hydrophobicity；Two kinds of polymer is different to separate out feelings
Condition also demonstrates phenyl boric acid functionalization PEO20PPO60PEO20Successful modification.
（3）To alizarin red（A kind of o-dihydroxy compound）Adsorbing separation experiment：Into 10.00 mL plastic centrifuge tubes
Add 0.4 mg alizarin red, a certain amount of phenyl boric acid functionalization PEO20PPO60PEO20, then appropriate water is added thereto simultaneously
System gross mass is set to reach 2.00 g, phenyl boric acid functionalization PEO in system20PPO60PEO20Final concentration of 2.5%.By resulting solution
After ultrasonic vibration 15min is well mixed, a certain amount of K is added into system2HPO4, make its final concentration of 50%, and fully rock
It is completely dissolved it.After the h of standing adsorption 5, isolating polymer is simultaneously dissolved the amount for determining alizarin red contained therein, and is counted
It is 95% to calculate the alizarin red rate of recovery.
Embodiment 4：
（1）Boric acid functionalization PEO20PPO60PEO20Synthesis：
Carboxybenzeneboronic acid between 0.12 g is added in 17.50 mL dichloromethane, fully adds 124 μ L thereto after dissolving
Oxalyl chloride, and 4 drop DMFs are added dropwise with initiation reaction.12 h of reaction are stirred at room temperature in resulting solution, then
Decompression rotary distillation removes solvent and obtains the yellow liquid product i.e. g of 3- formyls chlorophenylboronic acid 0.12.By 0.12 g product 3- formyls
Chlorophenylboronic acid, which is dissolved in 17.50 mL dichloromethane, obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 35.00 mL bis-
In chloromethanes, and 150 μ L triethylamines are added thereto and obtain solution B.Then, will whole 17.50 mL under ice-water bath cooling
Solution A is instilled in 35.00 mL solution Bs.Recession completely is added dropwise and removes ice-water bath, 12 h of reaction are stirred at room temperature in system.Then subtract
Press rotary distillation except solvent is removed, 5 mL water are added into system, and heat split-phase.Lower mutually dry the g of product 0.46 is collected,
Yield is about 88%, the product H obtained under the embodiment1NMR is schemed as shown in Fig. 2 as seen from the figure, hydrogen corresponding to phenyl boric acid group
Confirm being successfully introduced into for phenyl boric acid group.
（2）Phenyl boric acid functionalization PEO20PPO60PEO20Performance Testing：
Cloud point determines：0.10 g PEO is added into two 25.00 mL colorimetric cylinders respectively20PPO60PEO20With 0.10 g
Functionalization PEO20PPO60PEO20, with 10 mg sorbierites（A kind of o-dihydroxy compound）, added into colorimetric cylinder a certain amount of
Distilled water, system gross mass is set to reach 20 g.Solution is sufficiently mixed after shaking up, then adjusts pH value of solution to 8.Measured with nephelometry
PEO20PPO60PEO20Cloud point is 58.1 DEG C, and functionalization PEO is measured respectively with nephelometry and ultraviolet method20PPO60PEO20Cloud point
For 42.4 DEG C and 41.8 DEG C.It can be found that PEO20PPO60PEO20Cloud point do not influenceed by sorbierite addition, and two kinds
Cloud point measuring method result is basically identical, all show modified phenyl boric acid functionalization PEO20PPO60PEO20Cloud point with mountain
There occurs significant rise for the increase of pears alcohol addition；The result also demonstrate that being successfully introduced into for boric acid base group.
Saltout experiment：Respectively 0.20 g PEO are added into two 5.00 mL colorimetric bottles20PPO60PEO20With 0.20 g work(
PEO can be changed20PPO60PEO20, and adding appropriate distilled water makes system gross mass reach 2.00 g.Then added into system certain
The K of amount2HPO4, make K in system2HPO4Final concentration of 30%, fully shaking system, treat K2HPO4After being completely dissolved, system is stood
After 15min, it was observed that PEO20PPO60PEO20Do not separate out, and functionalization PEO20PPO60PEO20There are a large amount of precipitations.Illustrate now
Functionalization PEO20PPO60PEO20Influenceed by salinity, precipitation effect is fine, and hydrophobicity is very strong；Two kinds of polymer is different to separate out feelings
Condition also demonstrates phenyl boric acid functionalization PEO20PPO60PEO20Successful modification.
（3）To alizarin red（A kind of o-dihydroxy compound）Adsorbing separation experiment：Into 10.00 mL plastic centrifuge tubes
Add 0.3 mg alizarin red, a certain amount of phenyl boric acid functionalization PEO20PPO60PEO20, then appropriate water is added thereto simultaneously
System gross mass is set to reach 2.00 g, phenyl boric acid functionalization PEO in system20PPO60PEO20Final concentration of 2%.Resulting solution is surpassed
Acoustic shock swing 15min it is well mixed after, a certain amount of K is added into system2HPO4, make its final concentration of 40%, and fully rock and make
It is completely dissolved.After the h of standing adsorption 4, isolating polymer is simultaneously dissolved the amount for determining alizarin red contained therein, and is calculated
The alizarin red rate of recovery is 98%.Therefore, the adsorption effect of alizarin red is fine under the conditions of being somebody's turn to do, while considers material consumption, so determining to be somebody's turn to do
Condition is optimal adsorption condition.Adsorption effect is as shown in Figure 3 in the present embodiment：(a) alizarin red+PEO20PPO60PEO20；
(b) alizarin red+phenyl boric acid functionalization PEO20PPO60PEO20.PEO can be substantially observed in figure20PPO60PEO20To alizarin
It is red almost without absorption, and phenyl boric acid functionalization PEO20PPO60PEO20Most alizarin red is adsorbed, it is shown that phenyl boric acid function
Change PEO20PPO60PEO20The good combination effect between o-dihydroxy compound.
Claims (10)
1. a kind of phenyl boric acid functionalization block polymer, it is characterised in that the polymer is with temperature sensitive block polymer
PEO20PPO60PEO20For matrix, Carboxybenzeneboronic acid group between being introduced by acyl chloride reaction into temperature sensitive block copolymer template.
2. a kind of synthetic method of phenyl boric acid functionalization block polymer, it is characterised in that the polymer is in accordance with the following steps
Carry out：
Carboxybenzeneboronic acid is added in a certain amount of dichloromethane by between, fully adds oxalyl chloride after dissolving thereto, and be added dropwise less
N,N-dimethylformamide is measured with initiation reaction；Resulting solution under fixed temperature for a period of time, revolve stirring reaction by then decompression
Turn solvent is distilled off to obtain yellow liquid product, i.e. 3- formyls chlorophenylboronic acid；Whole product 3- formyl chlorophenylboronic acids are dissolved in
Solution A is obtained in a certain amount of dichloromethane；By PEO20PPO60PEO20It is dissolved in a certain amount of dichloromethane, and adds thereto
Enter triethylamine and obtain solution B；Then under ice-water bath cooling, solution A is instilled in solution B；Recession completely is added dropwise and removes ice-water bath,
Stirring reaction is for a period of time under fixed temperature for mixed solution system；Then depressurize rotary distillation and remove solvent, add into system
Enter water, and heat split-phase, product can be obtained by collecting lower phase drying.
3. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 2, it is characterised in that described
The dosage of Carboxybenzeneboronic acid and dichloromethane is 0.12g between adding in dichloromethane：5-30mL.
4. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 2, it is characterised in that described
Between Carboxybenzeneboronic acid and oxalyl chloride, the usage ratio of N,N-dimethylformamide be 0.12g：124μL：1-20 drops.
5. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 2, it is characterised in that described
Dissolve the dichloromethane of 3- formyl chlorophenylboronic acids for 5-30mL.
6. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 5, it is characterised in that described
3- formyls chlorophenylboronic acid and methylene chloride are 0.12g：17.5mL.
7. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 2, it is characterised in that described
Dissolve PEO20PPO60PEO20Dichloromethane and PEO20PPO60PEO20, triethylamine dosage be 5-60mL：0.50 g：150 μ
L。
8. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 2, it is characterised in that described
The volume ratio of solution A and solution B is 1:2.
9. the synthetic method of a kind of phenyl boric acid functionalization block polymer according to claim 2, it is characterised in that described
Stirring reaction is 15-40 DEG C, reaction 2-13 h.
10. the phenyl boric acid functionalization block polymer according to claim any one of 1-9 is in affine adsorbing separation alizarin red
In application.
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