CN103254371A - Synthetic method of amphiphilic block polymer with near-infrared fluorescence characteristic - Google Patents
Synthetic method of amphiphilic block polymer with near-infrared fluorescence characteristic Download PDFInfo
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- CN103254371A CN103254371A CN2012102704787A CN201210270478A CN103254371A CN 103254371 A CN103254371 A CN 103254371A CN 2012102704787 A CN2012102704787 A CN 2012102704787A CN 201210270478 A CN201210270478 A CN 201210270478A CN 103254371 A CN103254371 A CN 103254371A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 238000010189 synthetic method Methods 0.000 title claims description 12
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- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
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- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
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- 239000000126 substance Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 14
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- 238000010671 solid-state reaction Methods 0.000 claims description 6
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- 239000012987 RAFT agent Substances 0.000 abstract 1
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- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
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- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- PAOHHYDZFURJKA-UHFFFAOYSA-N 2-naphthalen-1-yl-1h-benzimidazole Chemical compound C1=CC=C2C(C=3NC4=CC=CC=C4N=3)=CC=CC2=C1 PAOHHYDZFURJKA-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种有近红外荧光特性两亲性嵌段聚合物的合成方法，萘甲酸与邻苯二胺的固相反应合成含2-苯并咪唑基-β-萘基团的功能性单体VDHBI，分别以N-异丙基丙烯酰胺（NIPAM）和所述VDHBI为单体，以α-二硫代萘甲酸异丁腈酯(CPDN)为RAFT试剂，进行RAFT聚合后得到均聚物PNIPAM，以所述PNIPAM为大分子RAFT试剂，以所述VDHBI为第二单体进行RAFT聚合，合成了两亲性嵌段聚合物PNIPAM-b-PVDHBI。采用本发明方案，提供了一种通过“活性”/可控自由基聚合方法，制备分子量可控和分子量分布窄的结构精致的近红外荧光两亲性嵌段聚合物，也提供了一种具有多重刺激响应性近红外荧光两亲性嵌段聚合物合成的新方法。
The invention discloses a method for synthesizing amphiphilic block polymers with near-infrared fluorescence characteristics. The solid phase reaction of naphthoic acid and o-phenylenediamine synthesizes a functional compound containing 2-benzimidazolyl- β -naphthalene groups. Monomer VDHBI, using N-isopropylacrylamide (NIPAM) and the VDHBI as monomers, and α-dithionaphthoic acid isobutyronitrile (CPDN) as RAFT reagent, after RAFT polymerization to obtain homopolymer PNIPAM, using the PNIPAM as a macromolecular RAFT agent, and using the VDHBI as the second monomer to carry out RAFT polymerization, synthesized the amphiphilic block polymer PNIPAM- b -PVDHBI. By adopting the solution of the present invention, a kind of near-infrared fluorescent amphiphilic block polymer with controllable molecular weight and narrow molecular weight distribution can be prepared by "living"/controllable free radical polymerization method, and a kind of amphiphilic block polymer with A new method for the synthesis of multiple stimuli-responsive near-infrared fluorescent amphiphilic block polymers.
Description
Technical field
The invention belongs to the high molecular polymer field, be specifically related to a kind of synthetic method that the Amphipathilic block polymer of near-infrared fluorescent characteristic is arranged.
Background technology
The stimulating responsive compound becomes the focus that people pay close attention in recent years, it mainly is a class in the small stimulus of external environment (as light, temperature, pH, ionic strength, electric field and magnetic field etc.) effect down, and the compound of reversible or irreversible change accordingly can take place for some physics of self or chemical property.When these stimulus signals changed, the self property of compound such as phase, shape, surface energy, speed of reaction, infiltration rate or recognition performance etc. can change thereupon.Based on physics and the chemical property behavior of responsiveness compound uniqueness, they play a significant role at detection and sensory field.
The small molecules chemical sensor of stimulating responsive has low consumption, high sensitivity and advantages of simple operation, but the small molecules chemical sensor also has many defectives, as poorly water-soluble, structural stability is relatively poor and back functionalization difficulty etc. relatively.Be that the macromolecular material that elementary cell obtains stimulating responsive is a focus of current research with the amphipathic nature block polymer.If will have the fluorescent signal primitive of sensitive response is incorporated in the polymkeric substance, the subtle change of environment then can change the noticeable change of polymer fluorescent signal into, based on this mechanism, just can construct the fluorescence response sensor of microenvironment sensitivity, wherein more common to the fluorescence response sensor of temperature, pH, light and metal ion microenvironment sensitivity.
N-N-isopropylacrylamide (NIPAM) molecule is 32
oHave near the C a minimum critical phase transition temperature (Lower Critical Solution Temperature, LCST).Be lower than this temperature, the NIPAM molecule because and water molecules between hydrogen bond action, present wetting ability.Be higher than this temperature, hydrogen bond action is destroyed, and NIPAM then presents hydrophobicity.Detect analytical technology with respect to other, the fluorescence sense technology is combined with the temperature sensitive property of NIPAM, have more susceptibility and selectivity.People such as Li (referring to: Li, C. H.; Liu, S. Y.
J. Mater. Chem. 2010, 20,10716 – 10723) reported that the letex polymerization by NIPAM has obtained near monodispersed temperature-sensitive nano gel, and load can with Hg
2+The fluorescent monomer (NPTUA) of reaction.During room temperature, this nanogel is as just the Hg of proportional-type
2+Detector, when temperature is higher than phase transition temperature, Hg
2+The susceptibility that detects can be much improved.Jo W. H. etc. (referring to: Hong S. W., Kim D. Y., Lee J. U., Jo W. H.
Macromolecules 2009, 42,2756 – 2761) and use pyrene and C respectively at PNIPAM chain two ends
60Fluorescent chromophore is modified, and has synthesized temperature sensing polymer Py-PNIPAM-C
60, when temperature was lower than its critical phase transition temperature (LCST), two fluorophors distance was far away, and cancellation efficient is lower; And when temperature was higher than LCST, it is folding that polymer chain takes place, and terminal fluorophor space length reduces, and cancellation efficient increases greatly, and fluorescence intensity obviously reduces.People such as Li (referring to: Li C. H., Zhang Y. X., Hu J.M., Cheng J. J., Liu S. Y.
Angew. Chem. Int. Ed. 2010, 49,5120 – 5124) reported that the stimulating responsive amphiphilic block copolymer based on many chromic systems, this polymkeric substance are proved and can realize the reversible three grade conversions of fluorescent emission (green, yellow, orange and red) under temperature, pH and illumination.
At biological field, the stimulating responsive polymer that contains the PNIPAM segment also has good application.People such as Liu (referring to: Zhang J. Y., Jiang X., Zhang Y. F., Li Y. T., Liu S. Y.
Macromolecules 2007, 9125 – 9132) and reported that use shell/crosslinked method of nuclear has obtained structural stability Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (PEO-preferably
b-P (NIPAM-
Co-NAS)).That this polymkeric substance can carry out the shell nuclear of completely reversibility is crosslinked/separate crosslinkedly, and have the swelling/deswelling behavior of thermal control, thereby in drug delivery, biological detection potential application is arranged.
It is not enough etc. that the many problems that exist when using organic fluorescent dye (operation interval mostly is in the UV, visible light district) widely to be used for fluoroscopic examination in the organism at present, the background interference that is difficult to enter some composition in biological tissue inside, the biological sample as: light make that fluoroscopic examination efficient reduces greatly, ultraviolet-visible enters the degree of depth in the organism.The existence of these problems makes fluorescence imaging method application in vivo become especially difficult.Yet, the fluoroscopic examination near infrared spectrum district (700-900 nm) can be avoided self disturbing of biomolecules, luminous energy is penetrated into organization internal and obtains higher sensitivity for analysis, is fit to the analysis of biological tissue's radiography more, thereby carries out biological detection and medical diagnosis on disease.Therefore, the responsiveness compound based on the near-infrared fluorescent mark more is applicable to the biological tissue imaging, has unique advantage at biological field.
The advantage of micromolecular near infrared fluorescent probe in biological tissue's radiography clearly but also exists many deficiencies, and as the light of these compounds, heat, unstable chemcial property etc., and kind is few, synthetic also difficulty relatively.Compare with small molecules, the near infrared fluorescent probe polymkeric substance has low toxicity, unique advantage such as good solubility and stability, and by synthetic different water miscible block polymers, can implement the self-assembly of polymkeric substance, thereby chain conformation and the configuration of regulating and control polymkeric substance make it have response performance widely simple and effectively.Relative ripe small molecules probe with development is compared, detection system based on polymer probe still is in the early stage of development, therefore, the responsive polymer based near infrared fluorescent probe that processability is good, futuramic and detection architecture efficiently, with the important research work that realizes accurate detection and the examination to the subtle change of the concentration of glucose, biological activity small molecules and other biomacromolecule and gradient, become detecting and sensory field is paid close attention to.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic method that the Amphipathilic block polymer of near-infrared fluorescent characteristic is arranged.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
A kind of synthetic method that the Amphipathilic block polymer of near-infrared fluorescent characteristic is arranged, the Amphipathilic block polymer PNIPAM-that adopts the preparation of RAFT synthetic method to have the near-infrared fluorescent performance
b-PVDHBI, the structural formula of described polymkeric substance is:
Described Amphipathilic block polymer PNIPAM-
bThe molecular weight distribution of-PVDHBI (
M w/
M n) below 1.4, specifically may further comprise the steps:
The synthetic 2-benzimidazolyl-of the solid state reaction of step 1) by O-Phenylene Diamine and naphthoic acid-
β-naphthalene (VNBI)
Intermediate, use again p-chloromethyl styrene (VBC) and VNBI the reaction obtain monomer 1-(4-vinyl benzyl)-2-benzimidazolyl--
β-naphthalene (VDHBI)
Step 2) being monomer with NIPAM, is RAFT reagent with CPDN, obtains homopolymer PNIPAM by RAFT active free radical polymerization method;
Step 3) is macromole RAFT reagent with PNIPAM, is that second monomer carries out the RAFT polymerization with VDHBI, synthetic above-mentioned Amphipathilic block polymer PNIPAM-
b-PVDHBI.
The building-up reactions formula of step (1), (2), (3):
Further, described intermediate VNBI in the described step (1) is to be that the solid state reaction by 20 minutes is synthetic under 180 ℃ the situation in temperature, described homopolymer PNIPAM in the described step (2) is to be synthetic under 70 ℃ the situation in temperature, the Amphipathilic block polymer PNIPAM-in the described step (3)
b-PVDHBI also is synthetic under 70 ℃ situation.
The invention has the beneficial effects as follows:
Adopt technical solution of the present invention, provide a kind of by " activity "/controllable free radical polymerization process, the near-infrared fluorescent polymkeric substance of the structure exquisiteness of the controlled and narrow molecular weight distribution of preparation molecular weight, the CH of synthetic Amphipathilic block polymer
2Cl
2(near the 380nm) and near-infrared region (near the 750nm) all has stronger fluorescent emission in the ultraviolet region for solution or the aqueous solution, environmental change to external world simultaneously, all have certain responsiveness as temperature and pH variation, a kind of synthetic novel method of multiple stimulation responsiveness near-infrared fluorescent polymkeric substance that has also is provided.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, preferred embodiment of the present invention and conjunction with figs. describe in detail as after.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not constitute improper restriction of the present invention.In the accompanying drawings:
Fig. 1 is block polymer PNIPAM-among the embodiment two
bThe tetrahydrofuran (THF) of-PVDHBI (THF) solution (starting point concentration of polymkeric substance is 0.5mg/mL) is along with the fluorescence of the deionized water that adds different ratios strengthens collection of illustrative plates (laser wavelength lambda
Ex =303nm);
Fig. 2 is block polymer PNIPAM-among the embodiment two
bThe tetrahydrofuran (THF) of-PVDHBI (THF) solution (starting point concentration of polymkeric substance is 0.5mg/mL) is along with the fluorescence of the deionized water that adds different ratios strengthens collection of illustrative plates (laser wavelength lambda
Ex =600nm);
Fig. 3 is block polymer PNIPAM-among the embodiment two
bThe tetrahydrofuran (THF) of-PVDHBI (THF) solution (starting point concentration of polymkeric substance is 0.5mg/mL) is along with the fluorescence of the deionized water that adds different ratios strengthens collection of illustrative plates and dynamic light scattering (DLS) graphic representation;
Fig. 4 is block polymer PNIPAM-among the embodiment three
bThe THF/ aqueous solution of-PVDHBI (starting point concentration of polymkeric substance is 0.3mg/mL), the fluorescent emission collection of illustrative plates (excitation wavelength lambda under different pH values
Ex =303nm);
Fig. 5 is block polymer PNIPAM-among the embodiment three
bThe THF/ aqueous solution of-PVDHBI (starting point concentration of polymkeric substance is 0.3mg/mL), pH=3 and pH=9 exchange become for the time fluorescence intensity reply figure;
Fig. 6 is the block polymer PNIPAM-of different concns among the embodiment four
bThe transmittance of-PVDHBI the aqueous solution is with the variation of temperature collection of illustrative plates;
Fig. 7 is the block polymer PNIPAM-of different pH among the embodiment four
b((concentration of polymkeric substance is 0.1mg/mL to the fluorescence intensity of-PVDHBI aqueous solution, λ with the variation of temperature collection of illustrative plates
Ex =303nm).
More than all figure all be at block polymer PNIPAM-
b-PVDHBI's
M N, GPC=14200 g/mol,
M w/
M nProduce under=1.31 the situation.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
A kind of synthetic method that the Amphipathilic block polymer of near-infrared fluorescent characteristic is arranged, the Amphipathilic block polymer PNIPAM-that adopts the preparation of RAFT synthetic method to have the near-infrared fluorescent performance
b-PVDHBI, the structural formula of described polymkeric substance is:
Described Amphipathilic block polymer PNIPAM-
bThe molecular weight distribution of-PVDHBI (
M w/
M n) below 1.4, specifically may further comprise the steps:
The synthetic 2-benzimidazolyl-of the solid state reaction of step 1) by O-Phenylene Diamine and naphthoic acid-
β-naphthalene (VNBI)
Intermediate, use again p-chloromethyl styrene (VBC) and VNBI the reaction obtain monomer 1-(4-vinyl benzyl)-2-benzimidazolyl--
β-naphthalene (VDHBI)
Step 2) being monomer with NIPAM, is RAFT reagent with CPDN, obtains homopolymer PNIPAM by RAFT active free radical polymerization method;
Step 3) is macromole RAFT reagent with PNIPAM, is that second monomer carries out the RAFT polymerization with VDHBI, synthetic above-mentioned Amphipathilic block polymer PNIPAM-
b-PVDHBI.
The building-up reactions formula of step (1), (2), (3):
Further, described monomer VNBI in the described step (1) is to be that the solid state reaction by 20 minutes is synthetic under 180 ℃ the situation in temperature, described homopolymer PNIPAM in the described step (2) is to be synthetic under 70 ℃ the situation in temperature, the Amphipathilic block polymer PNIPAM-in the described step (3)
b-PVDHBI also is synthetic under 70 ℃ situation.
The embodiment of present embodiment is as follows:
Embodiment one:
1, monomer VDHBI synthetic mainly contains two steps:
(1) with O-Phenylene Diamine with
βAfter-naphthoic acid mixes, pack in the 10mL ampere bottle, add polyphosphoric acid again.In the oil bath about 180 ℃, vacuumize the about 30min of reaction.Reaction finishes the back naturally cooling, adds the DMSO dissolving.Solution is poured in the deionized water, stirs, and precipitation occurs.Suction filtration gets filter cake, and washing back suction filtration gets pure product with the dehydrated alcohol recrystallization.
(2) in three neck round-bottomed flasks, add DMF, intermediate
α-benzimidazolyl-naphthalene, K
2CO
3(grinding thin) stirs about 20min until whole dissolvings.Add p-chloromethyl styrene (VBC), be heated to 38 ℃～42 ℃, more than reaction 48h under this temperature.Point plate control reaction end, column chromatography is purified.
2, the RAFT method of polymkeric substance is synthetic
(1) the RAFT polymerization of PNIPAM
By proportioning [NIPAM]
0: [AIBN]
0: [CPDN]
0=100:1:3 adds NIPAM, CPDN and AIBN, and adds the DMF dissolving, and argon gas bubbling 15 minutes to be to remove oxygen, then tube sealing.Place 70 ℃ oil bath to carry out polymerization in the ampere bottle.Reaction was taken out after the scheduled time, placed to open after the ice-water bath cooling to seal, and with a small amount of THF dissolve polymer, polymers soln is poured in a large amount of anhydrous diethyl ethers precipitated then, suction filtration collection filter cake.Polymkeric substance is dried to constant weight in 50 ℃ of baking ovens.
(2) PNIPAM-
bThe RAFT polymerization of-PVDHBI
Be monomer with VDHBI, PNIPAM is RAFT reagent, and AIBN is initiator, RAFT polymerization in DMF solution, and the RAFT solution polymerization of its operating process and NIPAM is similar, and typical proportioning is [VDHBI]
0: [AIBN]
0: [PNIPAM]
0=15:1:3.
Homopolymer PVDHBI, PNIPAM and block polymer PNIPAM-that table 1. uses gel chromatography (GPC) test to obtain
bThe number-average molecular weight of-PVDHBI (
M N, GPC) and molecular weight distribution (
M w/
M n)
| Sample | M n, GPC (g.mol -1) | M w/ M n |
| PNIPAM | 11620 | 1.16 |
| PNIPAM 102- b-PVDHBI 7 | 14200 | 1.31 |
Embodiment two: block polymer PNIPAM-
bThe self-assembly performance test of-PVDHBI
At block polymer PNIPAM-
bIn-PVDHBI the structure, the VDHBI segment is hydrophobic, and the NIPAM segment is hydrophilic.As can be seen, in the THF of block polymer solution, along with the volume of the water that adds increases gradually, the fluorescence intensity of polymers soln also strengthens gradually from Fig. 1, Fig. 2 and Fig. 3, and this is because polymkeric substance in the mixing solutions of water and THF self-assembly has taken place.When the volume of water be the THF volume 70% the time fluorescence intensity reach maximum value.Simultaneously, from the DLS graphic representation (Fig. 3) as can be seen, the polymer particles particle size increases and increases along with amount of water, has confirmed that polymkeric substance assembles in solution.
Embodiment three: block polymer PNIPAM-
bThe pH sensitivity tests of-PVDHBI
Since nitrogen atom on the benzoglyoxaline, when changing the pH of polymkeric substance THF solution, its fluorescence intensity generation obvious variation.As can be seen, block polymer solution is along with the increase of pH or reduce from Fig. 4 and Fig. 5, and its fluorescence intensity changes obviously, and can be by strong to the weak or repeatedly variation repeatedly that grows from weak to strong.When solution became alkalescence by neutrality, the change in fluorescence of polymers soln was little.Solution be acidity namely when the pH value reduces gradually, the nitrogen-atoms on the benzoglyoxaline cause the fluorescence emission peak red shift gradually of polymers soln, and fluorescence intensity increases gradually gradually by protonated.When the pH value was 3 left and right sides, fluorescence intensity reached maximum value.
Embodiment four: block polymer PNIPAM-
bThe temperature sensitive property testing of-PVDHBI
Since the temperature sensitive property of NIPAM, along with the rising of temperature, block polymer PNIPAM-
b-PVDHBI aqueous solution transmittance descend gradually (Fig. 6).This is because the NIPAM segment is in extended configuration when temperature is low, and temperature is in contraction schedule when higher.After temperature raise, the hydrogen bond that forms between NIPAM segment and water molecules was destroyed, causes polymkeric substance to be assembled in solution, thereby had taken place to change mutually.Therefore, aqueous solutions of polymers is because the scattering of light effect of aggregate becomes muddy gradually.When temperature retrieval after room temperature, solution becomes clarification again.
Along with the rising of temperature, the block polymer PNIPAM-under the condition of different pH
bThe fluorescence intensity of-PVDHBI the aqueous solution all presents and reduces the trend (Fig. 7) that afterwards increases earlier.As we can see from the figure, when temperature by 25
oC is heated to 35
oIn the process of C, the fluorescence intensity of aqueous solutions of polymers reduces slowly.This may be because block polymer has formed PVDHBI for nuclear, PNIPAM is the micella of shell in the aqueous solution, the NIPAM segment shrinks in temperature-rise period gradually, causes PVDHBI nuclear to be exposed in the bigger water of polarity, and polymers soln fluorescence reduces.When temperature is higher than 35
oDuring C, surround the further contraction of NIPAM segment of PVDHBI nuclear and become hydrophobic, polarity reduces around causing examining, thereby the fluorescence intensity of polymers soln strengthens.
In sum, this patent by reversible addition-fracture chain shift (RAFT) active free radical polymerization obtain to contain on the side chain 2-benzimidazolyl--
βThe near-infrared fluorescent polymer P NIPAM-of-naphthylene group
b-PVDHBI.The CH of polymkeric substance
2Cl
2(near the 380nm) and near-infrared region (near the 750nm) all has stronger fluorescent emission to solution in the ultraviolet region, and simultaneously, this polymkeric substance is at THF/H
2Have aggregation inducing fluorescence in the O mixing solutions and strengthen phenomenon.Owing to contain tertiary N atom, PNIPAM-on the benzoglyoxaline
b-PVDHBI is at CH
2Cl
2Fluorescent emission in the solution has pH susceptibility.Because the temperature of NIPAM has responsiveness, polymer P NIPAM-
bThe fluorescent emission of-PVDHBI in the THF/ water mixed solution also can change along with temperature.This patent provides the new synthetic method of a novel near-infrared fluorescent polymkeric substance with multiple stimulation responsiveness.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. the synthetic method with Amphipathilic block polymer of near-infrared fluorescent characteristic adopts the preparation of RAFT synthetic method to have near-infrared fluorescent performance Amphipathilic block polymer PNIPAM-
b-PVDHBI, the structural formula of described polymkeric substance is:
Described Amphipathilic block polymer PNIPAM-
bThe molecular weight distribution of-PVDHBI (
M w/
M n) below 1.4, specifically may further comprise the steps:
The synthetic 2-benzimidazolyl-of the solid state reaction of step 1) by O-Phenylene Diamine and naphthoic acid-
β-naphthalene (VNBI)
Intermediate, use again p-chloromethyl styrene (VBC) and VNBI the reaction obtain monomer 1-(4-vinyl benzyl)-2-benzimidazolyl--
β-naphthalene (VDHBI)
Step 2) being monomer with NIPAM, is RAFT reagent with CPDN, obtains homopolymer PNIPAM by RAFT active free radical polymerization method;
Step 3) is macromole RAFT reagent with PNIPAM, is that second monomer carries out the RAFT polymerization with VDHBI, synthetic above-mentioned Amphipathilic block polymer PNIPAM-
b-PVDHBI.
2. the building-up reactions formula of step (1), (2), (3):
The synthetic method that the Amphipathilic block polymer of near-infrared fluorescent characteristic is arranged according to claim 1, it is characterized in that: the described intermediate VNBI in the described step (1) is to be that the solid state reaction by 20 minutes is synthetic under 180 ℃ the situation in temperature, homopolymer PNIPAM in the described step (2) is to be synthetic under 70 ℃ the situation in temperature, the Amphipathilic block polymer PNIPAM-in the described step (3)
b-PVDHBI also is synthetic under 70 ℃ situation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911896A (en) * | 2015-06-05 | 2015-09-16 | 四川大学 | Anti-ultraviolet aramid fiber III and preparation method thereof |
| CN110003486A (en) * | 2019-03-25 | 2019-07-12 | 江苏大学 | The gold nanoparticle and preparation method and purposes of Thermo-sensitive sugar-containing polymer modification |
| CN110128665A (en) * | 2019-05-13 | 2019-08-16 | 苏州大学 | Amphiphilic block polymer near-infrared fluorescent probe based on azoreductase response and its application |
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| EP1801158A1 (en) * | 2005-12-22 | 2007-06-27 | The Goodyear Tire & Rubber Company | Water-based process for the preparation of polymer-clay nanocomposites |
| CN101775112A (en) * | 2010-02-05 | 2010-07-14 | 苏州大学 | Preparation method of magnetic fluorescence dual functional thermo-sensitive nano particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1801158A1 (en) * | 2005-12-22 | 2007-06-27 | The Goodyear Tire & Rubber Company | Water-based process for the preparation of polymer-clay nanocomposites |
| CN101775112A (en) * | 2010-02-05 | 2010-07-14 | 苏州大学 | Preparation method of magnetic fluorescence dual functional thermo-sensitive nano particle |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911896A (en) * | 2015-06-05 | 2015-09-16 | 四川大学 | Anti-ultraviolet aramid fiber III and preparation method thereof |
| CN104911896B (en) * | 2015-06-05 | 2016-09-28 | 四川大学 | A kind of aramid III fiber of resistance to ultraviolet and preparation method thereof |
| CN110003486A (en) * | 2019-03-25 | 2019-07-12 | 江苏大学 | The gold nanoparticle and preparation method and purposes of Thermo-sensitive sugar-containing polymer modification |
| CN110128665A (en) * | 2019-05-13 | 2019-08-16 | 苏州大学 | Amphiphilic block polymer near-infrared fluorescent probe based on azoreductase response and its application |
| CN110128665B (en) * | 2019-05-13 | 2021-03-26 | 苏州大学 | Azoreductase-responsive near-infrared fluorescent probes based on amphiphilic block polymers and their applications |
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