CN106243343A - The synthesis of a kind of phenylboric acid functionalization block polymer and application - Google Patents

The synthesis of a kind of phenylboric acid functionalization block polymer and application Download PDF

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CN106243343A
CN106243343A CN201610653703.3A CN201610653703A CN106243343A CN 106243343 A CN106243343 A CN 106243343A CN 201610653703 A CN201610653703 A CN 201610653703A CN 106243343 A CN106243343 A CN 106243343A
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peo
ppo
phenylboric acid
block polymer
solution
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CN106243343B (en
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李媛媛
韩娟
杨晓洁
王赟
陈桐
唐旭
倪良
高蒙蒙
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04—End-capping
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics

Abstract

The present invention relates to a kind of temperature sensitive block polymer of phenylboric acid functionalization and synthetic method thereof, and for adsorbing separation o-dihydroxy compound；The present invention is around the affine principle of boron, with temperature sensitive block polymer L64 as substrate, Carboxybenzeneboronic acid group between being introduced in temperature sensitive block copolymer template by acyl chloride reaction, synthesize a kind of new temperature sensitive block polymer of phenylboric acid functionalization, after the correlated performance of resulting polymers is studied such as cloud point, dissolubility etc., it was demonstrated that polymer is successfully made modification；The method of the present invention is simple to operate efficiently, greatly reduces time and cost；The present invention is by prepared phenylboric acid functionalization temperature sensitive block polymer PEO20PPO60PEO20For affine adsorbing separation alizarin red, the response rate for alizarin red reaches 98%, it is shown that good affine adsorbing separation effect.

Description

The synthesis of a kind of phenylboric acid functionalization block polymer and application
Technical field
The present invention relates to a kind of temperature sensitive block polymer of phenylboric acid functionalization and synthetic method thereof, and adjacent for adsorbing separation Dihydroxy compounds.
Background technology
Boric acid base group includes a trivalent boron atom, an alkyl or aryl substituent group, and two hydroxyls.As One class tool is compared with the non-natural organic acid of stiff stability and numerous characteristic reactions, and boric acid and derivant thereof have been successfully applied C-C The aspects such as the synthesis of key, sugar detection and drug release.But for boric acid and derivant thereof, its most important character is no more than Characteristic reactions between the material o-dihydroxy compound that itself and a class are critically important, by means of the carrying out of this reaction, boric acid Can be combined with o-dihydroxy compound and form borate and make the steric configuration of boric acid and physicochemical property occur significantly to become Change.And as a kind of reversible reaction, the generation of borate can be caused significant impact by the change of system environment, and cause boric acid The significant change of physicochemical property, indicates boric acid and derivant thereof the good response for system environmental change.In recent years, will It is adsorbing separation neighbour's dihydroxy that the part of boric acid functional group is bonded to the affine adsorbing material of boron that insoluble stromal surface synthesizes One of method that based compound specificity is the highest, is applied to the separation containing o-dihydroxy material and enrichment the most widely In.These substrate are mainly magnetic nanoparticle, silica gel, integral post, Graphene etc., but the usual surface binding site of these materials Limited, adsorption capacity is the highest；Actual application need to consume a large amount of adsorbent, relatively costly；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 refers to the change (such as: temperature, pH, magnetic etc.) along with external environment condition, the reason of himself Changing character can occur some significantly to change, and external environment condition thus changes the polymer producing response.Triblock polymer PEO20PPO60PEO20(L64) it is exactly a kind of stimuli responsive polymers, with hydrophobic PPO group as outer core with hydrophilic PEO group is core center, and its Thermo-sensitive of this special structures shape, i.e. along with the rising of temperature, micelle can assemble shape Becoming greater compactness of spherical structure, hydrophobicity strengthens, thus separates out from water.But this polymer is not employed for the affine adsorption material of boron In the adsorbing separation of material and o-dihydroxy compound, this is a kind of sorry..And dividing for o-dihydroxy material present stage Include boron affinity chromatography and the affine relevant separation method of boron from enrichment method, still have many drawbacks, as the best in specificity, suction Attached capacity is relatively low, separation process is complicated, the most long, use limitation is big.
In view of above 2 points, the present invention utilizes stimuli responsive polymers PEO first20PPO60PEO20Temperature-sensing property with And the affinity characteristic that phenylboric acid group is to o-dihydroxy compound, Carboxybenzeneboronic acid between introducing in polymer with acyl chloride reaction Group prepares phenylboric acid functionalization PEO20PPO60PEO20, this novel modified polymer is used for affine absorption system.This newly Type polymer absorbant have synthesis step simply efficiently, temperature-responsive is sensitive, adsorption efficiency is high and low cost and other advantages.
Summary of the invention
The phenylboric acid functionalization of the absorption o-dihydroxy compound that it is an object of the invention to provide a kind of high power capacity is temperature sensitive Block polymer and synthetic method thereof.
For achieving the above object, the technical solution used in the present invention is:
Around the affine principle of boron, with temperature sensitive block polymer PEO20PPO60PEO20(L64) be substrate, by acyl chloride reaction to Carboxybenzeneboronic acid group between introducing in temperature sensitive block copolymer template, synthesizes a kind of new temperature sensitive block polymerization of phenylboric acid functionalization Thing, after studying such as cloud point, dissolubility etc. the correlated performance of resulting polymers, it was demonstrated that be successfully made polymer and change Property.
And with the alizarin red containing adjacent hydroxyl as model compound, the prepared temperature sensitive block of phenylboric acid functionalization is gathered Compound PEO20PPO60PEO20For affine adsorbing separation alizarin red.
Described boric acid functionalization PEO20PPO60PEO20Synthetic method carry out in accordance with the following steps:
During Carboxybenzeneboronic acid adds a certain amount of dichloromethane between Jiang, it is added thereto to oxalyl chloride after fully dissolving, and drips few Amount N,N-dimethylformamide is with initiation reaction；Gained solution stirs reaction a period of time, rotation of then reducing pressure under fixed temperature Turn and solvent is distilled off obtains yellow liquid product, i.e. 3-formyl chloride phenylboric acid；Whole product 3-formyl chloride phenylboric acids are dissolved in A certain amount of dichloromethane obtains solution A；By PEO20PPO60PEO20It is dissolved in a certain amount of dichloromethane, and adds wherein Enter triethylamine and obtain solution B；Then, under ice-water bath cools down, solution A is instilled in solution B；Ice-water bath is removed in dropping recession completely, Mixed solution system stirs reaction a period of time under fixed temperature；Then decompression rotary distillation is except removing solvent, in system Add water, and heat split-phase, be dried mutually under collection and can obtain product.
Wherein, between described, Carboxybenzeneboronic acid is 0.12g:5-30mL with the consumption of dichloromethane；
Described Carboxybenzeneboronic acid is that 0.12g:124 μ L:1-20 drips with the usage ratio of oxalyl chloride, N,N-dimethylformamide；
The reaction of described solution stirring, for 15-40 DEG C, reacts 2-13 h；
The dichloromethane of described dissolving 3-formyl chloride phenylboric acid for 5-30mL, preferably 3-formyl chloride phenylboric acid and dichloromethane Consumption is 0.12g:17.5mL；
Described dissolving PEO20PPO60PEO20Dichloromethane and PEO20PPO60PEO20, the consumption of triethylamine be 5-60mL:0.50 G:150 μ L；
Described solution A is 1:2 with the volume ratio of solution B；
The stirring reaction of described mixed solution system is 15-40 DEG C of reaction 2-13 h.
Obtained phenylboric acid functionalization PEO20PPO60PEO20Carry out Performance Testing by the following method:
Cloud point measures: add the PEO of 0.10 g respectively in two 25.00 mL color comparison tubes20PPO60PEO20With 0.10 g function Change PEO20PPO60PEO20With a certain amount of sorbitol (a kind of o-dihydroxy compound), in color comparison tube, add a certain amount of steaming Distilled water, the system gross mass of making reaches 20 g.Solution is sufficiently mixed after shaking up, then regulates pH value of solution to desired value.Respectively with turbid Degree method and ultraviolet method measure the cloud point of sample solution.
Saltout experiment: in two 5.00 mL colorimetric bottles, add 0.20 g PEO respectively20PPO60PEO20With 0.20 g merit PEO can be changed20PPO60PEO20, and add appropriate distilled water and make system gross mass reach 2.00 g.Then add certain in system The K of amount2HPO4, fully shake system, treat K2HPO4After being completely dissolved, system is stood 15min to observe effect of saltouing.
Wherein, the sorbitol quality that cloud point adds when measuring is 0-20 mg；Solution ph is 4-12, by 0.1 M's The NaOH regulation of HCl and 0.1 M.Saltout the final K of system in testing2HPO4Mass concentration is 10-50%.
Obtained phenylboric acid functionalization PEO20PPO60PEO20For affine adsorbing separation alizarin red:
Adsorbing separation experiment to alizarin red (a kind of o-dihydroxy compound): add one in 10.00 mL plastic centrifuge tubes Quantitative alizarin red and phenylboric acid functionalization PEO20PPO60PEO20, then it is added thereto to appropriate water and makes system gross mass Reach 2.00 g.By gained solution ultrasonic vibration 15min so that after system mix homogeneously, adding a certain amount of in system K2HPO4, and fully rock and make it be completely dissolved.After standing adsorption a period of time, isolating polymer is also dissolved mensuration wherein The amount of contained alizarin red, and calculate the alizarin red response rate.
Wherein, alizarin red addition is 0.05-0.4 mg；Phenylboric 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；In solution, alizarin red content is purple Outward-visible spectrophotometry measures, and i.e. measures its absorbance at 424nm and obtains content；Alizarin red response rate E1Calculate As follows:
E1=Ma/Mb
M in formulaaThe amount of the alizarin red in absorption post-consumer polymer；
MbThe amount of the alizarin red added in system.
Present invention have the advantage that
(1) present invention uses temperature sensitive block polymer PEO20PPO60PEO20(L64) it is substrate, and by acyl chloride reaction to it Carboxybenzeneboronic acid group between middle introducing, obtains a kind of novel temperature sensitive block polymer of phenylboric acid functionalization.With block polymer PEO20PPO60PEO20As the substrate of boron affinitive material, relative to general magnetic nano-particle, integral post substrate etc., cost is relatively Low, chemical stability is preferable；This adsorbent synthesis utilize acyl chloride reaction, simple to operate efficiently, greatly reduce the time and Cost.
(2) present invention takes full advantage of stimuli responsive polymers PEO20PPO60PEO20Temperature-sensing property, can by rise High-temperature strengthens its hydrophobicity, it is thus possible to separate out in a large number from solution, the highest to the adsorption efficiency of object, therefore need not make High adsorption effect is i.e. can reach with substantial amounts of adsorbent.
(3) present invention is by phenylboric acid functionalization PEO of preparation20PPO60PEO20For o-dihydroxy compound alizarin red Affine adsorbing separation, the response rate for alizarin red reaches 98%, it is shown that good affine adsorbing separation effect.
Accompanying drawing explanation
Fig. 1 is phenylboric acid functionalization PEO20PPO60PEO20Synthetic route chart；
Fig. 2 is phenylboric acid functionalization PEO20PPO60PEO20 H1NMR schemes；
Fig. 3 is phenylboric acid functionalization PEO20PPO60PEO20Adsorption effect to alizarin red, in figure (a) be alizarin red+ PEO20PPO60PEO20；B () is alizarin red+phenylboric acid functionalization PEO20PPO60PEO20。
Detailed description of the invention:
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, illustrate the present invention below in conjunction with accompanying drawing Technical scheme in embodiment is clearly and completely described, it is clear that described embodiment is that a part of the present invention is implemented Example rather than whole embodiments, based on the embodiment in the present invention, those of ordinary skill in the art are not making creativeness The every other embodiment obtained on the premise of work, broadly falls into 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, after fully dissolving, is added thereto to 124 μ L oxalyl chlorides, And drip 1 N,N-dimethylformamide with initiation reaction.Gained solution stirs reaction 2 h, rotation of then reducing pressure at 15 DEG C Solvent is distilled off and obtains yellow liquid product, i.e. 3-formyl chloride phenylboric acid 0.08 g.By 0.08 g product 3-formyl chlorobenzene boron Acid is dissolved in 5 mL dichloromethane and obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 5 mL dichloromethane, and to it Middle addition 150 μ L triethylamine obtains solution B.Then, under ice-water bath cools down, all of solution A is instilled in solution B.Dropping Ice-water bath is removed in recession completely, and system stirs reaction 2 h at 15 DEG C.Then decompression rotary distillation is except removing solvent, in system Adding 5 mL water, and heat split-phase, be dried to obtain product 0.21 g under collection mutually, productivity is about 40%.
(2) phenylboric acid functionalization PEO20PPO60PEO20Performance Testing:
Cloud point measures: add the PEO of 0.10 g respectively in two 25.00 mL color comparison tubes20PPO60PEO20With 0.10 g function Change PEO20PPO60PEO20, in color comparison tube, adding a certain amount of distilled water, the system gross mass of making reaches 20 g.Solution is abundant After mixing shakes up, then regulate pH value of solution to 4.PEO is recorded with nephelometry20PPO60PEO20Cloud point is 58.2 DEG C, with nephelometry and Ultraviolet method records functionalization PEO respectively20PPO60PEO20Cloud point be 23.4 DEG C and 24.1 DEG C.It is found that two kinds of cloud points are surveyed Metering method result is basically identical, all show modified phenylboric acid functionalization PEO20PPO60PEO20Cloud point relative to PEO20PPO60PEO20Substantially reducing, polymer hydrophilicity and cloud point change, and this result confirms that the success of boric acid base group is drawn Enter.
Saltout experiment: in two 5.00 mL colorimetric bottles, add 0.20 g PEO respectively20PPO60PEO20With 0.20 g merit PEO can be changed20PPO60PEO20, and add appropriate distilled water and make system gross mass reach 2.00 g.Then add certain in system The K of amount2HPO4, make K in system2HPO4Final concentration of 10%, fully shake 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 differences separate out situation and also demonstrate benzene Boric acid functionalization PEO20PPO60PEO20Successful modification.
(3) the adsorbing separation experiment to alizarin red (a kind of o-dihydroxy compound): in 10.00 mL plastic centrifuge tubes Add the alizarin red of 0.05 mg, a certain amount of phenylboric acid functionalization PEO20PPO60PEO20, then it is added thereto to appropriate water And the system gross mass of making reaches 2.00 g, phenylboric acid functionalization PEO in system20PPO60PEO20Final concentration of 0.5%.Gained is molten After liquid ultrasonic vibration 15min mix homogeneously, in system, add a certain amount of K2HPO4So that it is final concentration of 10%, and fully shake Rolling makes it be completely dissolved.After standing adsorption 0.5 h, isolating polymer is also dissolved the amount measuring alizarin red contained therein, And to calculate the alizarin red response rate be 30%.
Embodiment 2:
(1) boric acid functionalization PEO20PPO60PEO20Synthesis:
Carboxybenzeneboronic acid between 0.12 g is added in 30 mL dichloromethane, after fully dissolving, is added thereto to 124 μ L oxalyl chlorides, And drip 10 N,N-dimethylformamides with initiation reaction.Gained solution stirs reaction 13 h, rotation of then reducing pressure at 40 DEG C Turn and solvent is distilled off obtains yellow liquid product, i.e. 3-formyl chloride phenylboric acid 0.12 g.By 0.12 g product 3-formyl chlorobenzene Boric acid is dissolved in 30 mL dichloromethane and obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 60 mL dichloromethane, and It is added thereto to 150 μ L triethylamines and obtains solution B.Then, under ice-water bath cools down, all of solution A is instilled in solution B. Ice-water bath is removed in dropping recession completely, and system stirs reaction 13 h at 40 DEG C.Then decompression rotary distillation is except removing solvent, to Adding 5 mL water in system, and heat split-phase, be dried mutually and can obtain product 0.44 g under collection, productivity is about 84%.
(2) phenylboric acid functionalization PEO20PPO60PEO20Performance Testing:
Cloud point measures: add the PEO of 0.10 g respectively in two 25.00 mL color comparison tubes20PPO60PEO20With 0.10 g function Change PEO20PPO60PEO20, in color comparison tube, adding a certain amount of distilled water, the system gross mass of making reaches 20 g.Solution is abundant After mixing shakes up, then regulate pH value of solution to 12.PEO is recorded with nephelometry20PPO60PEO20Cloud point is 58.2 DEG C, with nephelometry and Ultraviolet method records functionalization PEO respectively20PPO60PEO20Cloud point be 44.2 DEG C and 44.1 DEG C.It is found that PEO20PPO60PEO20Cloud point is not affected by pH；And two kinds of cloud point measuring method results are basically identical, all show modified benzene Boric acid functionalization PEO20PPO60PEO20Cloud point raises with pH value and substantially increases；Acquired results also confirms benzene boron from side Acid functionalization PEO20PPO60PEO20Successful modification.
Saltout experiment: in two 5.00 mL colorimetric bottles, add 0.20 g PEO respectively20PPO60PEO20With 0.20 g merit PEO can be changed20PPO60PEO20, and add appropriate distilled water and make system gross mass reach 2.00 g.Then add certain in system The K of amount2HPO4, make K in system2HPO4Final concentration of 20%, fully shake 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 PEO20PPO60PEO20Being affected by salinity, separate out effect preferable, hydrophobicity is stronger；Two kinds of polymer differences separate out feelings Condition also demonstrates phenylboric acid functionalization PEO20PPO60PEO20Successful modification.
(3) the adsorbing separation experiment to alizarin red (a kind of o-dihydroxy compound): in 10.00 mL plastic centrifuge tubes Add the alizarin red of 0.1 mg, a certain amount of phenylboric acid functionalization PEO20PPO60PEO20, then it is added thereto to appropriate water also The system gross mass of making reaches 2.00 g, phenylboric acid functionalization PEO in system20PPO60PEO20Final concentration of 1%.Gained solution is surpassed After 15min mix homogeneously is swung in acoustic shock, in system, add a certain amount of K2HPO4So that it is final concentration of 40%, and fully rock and make It is completely dissolved.After standing adsorption 5 h, isolating polymer is also dissolved the amount measuring alizarin red contained therein, and calculate The alizarin red response rate is 79%.
Embodiment 3:
(1) boric acid functionalization PEO20PPO60PEO20Synthesis:
Carboxybenzeneboronic acid between 0.12 g is added in 15 mL dichloromethane, after fully dissolving, is added thereto to 124 μ L oxalyl chlorides, And drip 5 N,N-dimethylformamides with initiation reaction.Gained solution stirs reaction 5 h, rotation of then reducing pressure at 25 DEG C Solvent is distilled off and obtains yellow liquid product i.e. 3-formyl chloride phenylboric acid 0.1 g.By molten for 0.1 g product 3-formyl chloride phenylboric acid Solution A is obtained in 15 mL dichloromethane；By 0.50 g PEO20PPO60PEO20It is dissolved in 30 mL dichloromethane, and wherein Add 150 μ L triethylamines and obtain solution B.Then, under ice-water bath cools down, all of solution A is instilled in solution B.Drip Ice-water bath is removed in full recession, and system stirs reaction 5 h at 25 DEG C.Then decompression rotary distillation is except removing solvent, adds in system Entering 5 mL water, and heat split-phase, be dried mutually and can obtain product about 0.38 g under collection, productivity is about 72%.
(2) phenylboric acid functionalization PEO20PPO60PEO20Performance Testing:
Cloud point measures: add the PEO of 0.10 g respectively in two 25.00 mL color comparison tubes20PPO60PEO20With 0.10 g function Change PEO20PPO60PEO20, with 20 mg sorbitol (a kind of o-dihydroxy compound), in color comparison tube, add a certain amount of distillation Water, the system gross mass of making reaches 20 g.Solution is sufficiently mixed after shaking up, then regulates pH value of solution to 12.Record with nephelometry PEO20PPO60PEO20Cloud point is 58.2 DEG C, records functionalization PEO respectively with nephelometry and ultraviolet method20PPO60PEO20Cloud point It it is 50.3 DEG C and 50.2 DEG C.It is found that PEO20PPO60PEO20Cloud point do not affected by sorbitol addition, and two kinds Cloud point measuring method result is basically identical, all show modified phenylboric acid functionalization PEO20PPO60PEO20Cloud point along with The increase of sorbitol addition and increase；This result confirms being successfully introduced into of boric acid base group.
Saltout experiment: in two 5.00 mL colorimetric bottles, add 0.20 g PEO respectively20PPO60PEO20With 0.20 g merit PEO can be changed20PPO60PEO20, and add appropriate distilled water and make system gross mass reach 2.00 g.Then add certain in system The K of amount2HPO4, make K in system2HPO4Final concentration of 50%, fully shake 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 PEO20PPO60PEO20Affected by salinity, had certain precipitation effect and hydrophobicity；Two kinds of polymer differences separate out feelings Condition also demonstrates phenylboric acid functionalization PEO20PPO60PEO20Successful modification.
(3) the adsorbing separation experiment to alizarin red (a kind of o-dihydroxy compound): in 10.00 mL plastic centrifuge tubes Add the alizarin red of 0.4 mg, a certain amount of phenylboric acid functionalization PEO20PPO60PEO20, then it is added thereto to appropriate water also The system gross mass of making reaches 2.00 g, phenylboric acid functionalization PEO in system20PPO60PEO20Final concentration of 2.5%.By gained solution After ultrasonic vibration 15min mix homogeneously, in system, add a certain amount of K2HPO4So that it is final concentration of 50%, and fully rock Make it be completely dissolved.After standing adsorption 5 h, isolating polymer is also dissolved the amount measuring alizarin red contained therein, and count Calculating the alizarin red response rate is 95%.
Embodiment 4:
(1) boric acid functionalization PEO20PPO60PEO20Synthesis:
Carboxybenzeneboronic acid between 0.12 g is added in 17.50 mL dichloromethane, after fully dissolving, be added thereto to 124 μ L oxalyl Chlorine, and drip 4 DMFs with initiation reaction.Gained solution is stirred at room temperature reaction 12 h, then reduces pressure Rotary distillation removes solvent and obtains yellow liquid product i.e. 3-formyl chloride phenylboric acid 0.12 g.By 0.12 g product 3-formyl chlorobenzene Boric acid is dissolved in 17.50 mL dichloromethane and obtains solution A；By 0.50 g PEO20PPO60PEO20It is dissolved in 35.00 mL dichloromethanes In alkane, and it is added thereto to 150 μ L triethylamines and obtains solution B.Then under ice-water bath cools down, by whole 17.50 mL solution A Instill in 35.00 mL solution B.Dropping recession completely goes ice-water bath, system to be stirred at room temperature reaction 12 h.Then reduce pressure rotation Turn distillation and remove solvent, in system, add 5 mL water, and heat split-phase.Product 0.46 g, productivity it is dried to obtain mutually under collection It is about 88%, the product H obtained under this embodiment1As in figure 2 it is shown, as seen from the figure, the hydrogen that phenylboric acid group is corresponding confirms NMR figure Being successfully introduced into of phenylboric acid group.
(2) phenylboric acid functionalization PEO20PPO60PEO20Performance Testing:
Cloud point measures: add the PEO of 0.10 g respectively in two 25.00 mL color comparison tubes20PPO60PEO20With 0.10 g function Change PEO20PPO60PEO20, with 10 mg sorbitol (a kind of o-dihydroxy compound), in color comparison tube, add a certain amount of distillation Water, the system gross mass of making reaches 20 g.Solution is sufficiently mixed after shaking up, then regulates pH value of solution to 8.Record with nephelometry PEO20PPO60PEO20Cloud point is 58.1 DEG C, records functionalization PEO respectively with nephelometry and ultraviolet method20PPO60PEO20Cloud point It it is 42.4 DEG C and 41.8 DEG C.It is found that PEO20PPO60PEO20Cloud point do not affected by sorbitol addition, and two kinds Cloud point measuring method result is basically identical, all show modified phenylboric acid functionalization PEO20PPO60PEO20Cloud point with mountain The increase of pears alcohol addition there occurs significantly rising；This result also demonstrate that being successfully introduced into of boric acid base group.
Saltout experiment: in two 5.00 mL colorimetric bottles, add 0.20 g PEO respectively20PPO60PEO20With 0.20 g merit PEO can be changed20PPO60PEO20, and add appropriate distilled water and make system gross mass reach 2.00 g.Then add certain in system The K of amount2HPO4, make K in system2HPO4Final concentration of 30%, fully shake system, treat K2HPO4After being completely dissolved, system is stood After 15min, it was observed that PEO20PPO60PEO20Do not separate out, and functionalization PEO20PPO60PEO20There is a large amount of precipitation.Illustrate now Functionalization PEO20PPO60PEO20Being affected by salinity, separate out effect fine, hydrophobicity is the strongest；Two kinds of polymer differences separate out feelings Condition also demonstrates phenylboric acid functionalization PEO20PPO60PEO20Successful modification.
(3) the adsorbing separation experiment to alizarin red (a kind of o-dihydroxy compound): in 10.00 mL plastic centrifuge tubes Add the alizarin red of 0.3 mg, a certain amount of phenylboric acid functionalization PEO20PPO60PEO20, then it is added thereto to appropriate water also The system gross mass of making reaches 2.00 g, phenylboric acid functionalization PEO in system20PPO60PEO20Final concentration of 2%.Gained solution is surpassed After 15min mix homogeneously is swung in acoustic shock, in system, add a certain amount of K2HPO4So that it is final concentration of 40%, and fully rock and make It is completely dissolved.After standing adsorption 4 h, isolating polymer is also dissolved the amount measuring alizarin red contained therein, and calculate The alizarin red response rate is 98%.Therefore, under the conditions of being somebody's turn to do, the adsorption effect of alizarin red is fine, simultaneously takes account of material consumption, so determining this Condition is optimal adsorption condition.In the present embodiment, adsorption effect is as shown in Figure 3: (a) alizarin red+PEO20PPO60PEO20； (b) alizarin red+phenylboric acid functionalization PEO20PPO60PEO20.Can substantially observe PEO in the drawings20PPO60PEO20To alizarin Red almost without absorption, and phenylboric acid functionalization PEO20PPO60PEO20Adsorb most alizarin red, it is shown that phenylboric acid function Change PEO20PPO60PEO20And combination effect good between o-dihydroxy compound.

Claims (9)

1. a phenylboric acid functionalization block polymer, it is characterised in that described polymer is with temperature sensitive block polymer PEO20PPO60PEO20For substrate, Carboxybenzeneboronic acid group between being introduced in temperature sensitive block copolymer template by acyl chloride reaction.
2. the synthetic method of a phenylboric acid functionalization block polymer, it is characterised in that described polymer is in accordance with the following steps Carry out:
During Carboxybenzeneboronic acid adds a certain amount of dichloromethane between Jiang, it is added thereto to oxalyl chloride after fully dissolving, and drips few Amount N,N-dimethylformamide is with initiation reaction；Gained solution stirs reaction a period of time, rotation of then reducing pressure under fixed temperature Turn and solvent is distilled off obtains yellow liquid product, i.e. 3-formyl chloride phenylboric acid；Whole product 3-formyl chloride phenylboric acids are dissolved in A certain amount of dichloromethane obtains solution A；By PEO20PPO60PEO20It is dissolved in a certain amount of dichloromethane, and adds wherein Enter triethylamine and obtain solution B；Then, under ice-water bath cools down, solution A is instilled in solution B；Ice-water bath is removed in dropping recession completely, Mixed solution system stirs reaction a period of time under fixed temperature；Then decompression rotary distillation is except removing solvent, in system Add water, and heat split-phase, be dried mutually under collection and can obtain product.
The synthetic method of a kind of phenylboric acid functionalization block polymer the most according to claim 2, it is characterised in that described Between adding in dichloromethane, Carboxybenzeneboronic acid is 0.12g:5-30mL with the consumption of dichloromethane.
The synthetic method of a kind of phenylboric acid functionalization block polymer the most according to claim 2, it is characterised in that described Between the usage ratio of Carboxybenzeneboronic acid and oxalyl chloride, N,N-dimethylformamide be that 0.12g:124 μ L:1-20 drips.
The synthetic method of a kind of phenylboric acid functionalization block polymer the most according to claim 2, it is characterised in that described Dissolve 3-formyl chloride phenylboric acid dichloromethane for 5-30mL, preferably 3-formyl chloride phenylboric acid with methylene chloride be 0.12g:17.5mL.
The synthetic method of a kind of phenylboric acid functionalization block polymer the most according to claim 2, it is characterised in that described Dissolve PEO20PPO60PEO20Dichloromethane and PEO20PPO60PEO20, the consumption of triethylamine be 5-60mL:0.50 g:150 μ L。
The synthetic method of a kind of phenylboric acid functionalization block polymer the most according to claim 2, it is characterised in that described Solution A is 1:2 with the volume ratio of solution B.
The synthetic method of a kind of phenylboric acid functionalization block polymer the most according to claim 2, it is characterised in that described Stirring reaction is as 15-40 DEG C, reacts 2-13 h.
9. the phenylboric acid functionalization block polymer application in affine absorption o-dihydroxy compound separation alizarin red.
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