CN102660003A - Hyperbranched water-soluble conjugated polymer and preparation method thereof - Google Patents
Hyperbranched water-soluble conjugated polymer and preparation method thereof Download PDFInfo
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- CN102660003A CN102660003A CN2012101594597A CN201210159459A CN102660003A CN 102660003 A CN102660003 A CN 102660003A CN 2012101594597 A CN2012101594597 A CN 2012101594597A CN 201210159459 A CN201210159459 A CN 201210159459A CN 102660003 A CN102660003 A CN 102660003A
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Abstract
The invention relates to a hyperbranched water-soluble conjugated polymer and a preparation method thereof, wherein a hyperbranched reaction method of A2+A2'+B3 is adopted for the polymer, and aromatic structure units such as intermediate tribromobenzene and derivatives thereof are taken as the core (B3) of the hyperbranched polymer to carry out organic metal catalytic reaction with monomers (A2 and A2') containing phenyl, 9, 9-bireplacing fluorenyl and other aromatic structures, so as to synthesize a series of hyperbranched conjugated polymers containing water soluble groups in the side chain.. The synthesizing method is simple, furthermore, the cores of the polymers, a connecting group and the hydrophilic side chains of the polymers can be controlled respectively, so as to obtain the hyperbranched water-soluble conjugated polymers having different spatial structures. The polymer is a fluorescent sensing material having high sensitivity and can make up the deficiency that the detection sensitivity is reduced as fluorescent extinguishes automatically due to easy gathering of the conventional linear water-soluble conjugated polymer in water; furthermore, the branched structure is beneficial for sufficient interaction with biomolecules to be detected; therefore, the hyperbranched water-soluble conjugated polymer and the preparation method are expected to be well applied in chemical/biological sensing.
Description
Technical field
The invention belongs to chemical/biological sensing material technical field, be specifically related to a kind of water miscible hyperbranched conjugated polymer and preparation method thereof.
Background technology
Soluble conjugated polymer mainly is meant the conjugated polymers that contains the ionic functional group side chain; Caused the concern that People more and more is extensive and fervent in recent ten years, this mainly is because some unique photoelectric properties that they demonstrate can obtain diversified application in areas of information technology such as chemical/biological fluorescence senses of new generation.This compounds combines the excellent photoelectric property of traditional conjugated polymers and water solubility of polyelectrolyte characteristics.On the one hand, as conjugated polymers, they generally have very strong photo absorption performance in the ultraviolet-visible district, and have the character of " molecular wire ", promptly electronics or energy can be on conjugated main chain fast transferring.On the other hand; They mainly realize water-soluble through on the side chain of conjugated system, articulating the wetting ability ionic functional group; Ionic functional group can with other charge species generation electrostatic interaction; Therefore can detect micro substance in the surrounding environment through electronics between polymkeric substance and the oppositely charged quencher or energy transfer, and electronics or energy delocalization on whole polymer chain very easily, the quenching of fluorescence signal is exaggerated.Utilize these characteristics, on quencher, introduce the specific recognition group of various materials to be detected, through observe Quenching of fluorescence or recover just can be easy realization to the highly sensitive detection of multiple organic and inorganic and biomolecules.Nobel chemistry Prize winner A. J. Heeger in 2000, it is that sensing material has been carried out preliminary exploration in the bio-sensing field that the research group of G. C. Bazan and F. Wudl etc. has begun with the soluble conjugated polymer.
The soluble conjugated polymer of now having developed mostly is a thread-like molecule with regard to the main chain configuration.In the aqueous solution, because the hydrophobic interaction of conjugated main chain and the acting in conjunction of these two kinds of power of flexible side-chains hydrophilic interaction, the thread-like molecule of rigid structure forms the state of aggregation configuration easily, thereby causes fluorescence self quencher; Its one dimension rigid structure has not only limited to their solubleness in water, and has limited and material to be detected, particularly has the abundant interaction of the biomolecules of multilevel hierarchy, and detection sensitivity is descended.Therefore, further optimizing the structure of soluble conjugated polymer, and improve practicality indexs such as material tests sensitivity, range of application, is the hot research problem in present this field.
Multi-branch polymer with three-dimensional tree branched structure is representing one type rising, and has very novel character and a type material that is rich in application prospect, has become the 4th type of main polymkeric substance configuration after line style, crosslinked and branch configurations in recent years.Be divided into three parts on this quasi-molecule structure: nuclear, highly branched branch and a large amount of outermost layer groups.Can be through the chemically modified of different piece be realized better water-solubility, effectively improve the linear conjugated polymkeric substance because fluorescence self quencher that gathering causes, the luminescent properties of material is carried out independent regulation and control; And this quasi-molecule specific surface area is big, and effectively contact range is wide, sees from the angle of Application in Sensing, helps realizing signal transmission more rapidly and effectively, the extraordinary shortcoming that remedies thread-like molecule.Hyperbranched reaction is as a kind of important method of preparation multi-branch polymer, and synthesis step is simpler with respect to other preparation method.Therefore, design synthesis of super branched soluble conjugated polymer will be one of more satisfactory method that improves the sensing material performance.
Summary of the invention
Technical problem:The objective of the invention is to disclose a kind of hyperbranched soluble conjugated polymer, can be used as the chemical/biological sensing material.
The present invention also aims to provide a kind of novel preparation method of above-mentioned polymkeric substance.
Technical scheme:The present invention adopts catalytic Sonogashira of organo-metallic or Suzuki polyreaction, through A
2+ A
2'+B
3The earlier synthetic neutral conjugation polymkeric substance of hyperbranched reaction method, synthesized said hyperbranched water-soluble polymers through quaterisation again, its molecular structure is following:
Wherein, the nuclear of hyperbranched polymer is phenyl, and Ar on the hyperbranched polymer branch and Ar ' are that phenyl, 9,9 two replaces a kind of in the fluorenyls, and the square of described nuclear, Ar and Ar ' junction is represented the mode of connection of the two to be specially triple bond or singly-bound; Polymerization degree x, y, z, k, l, m, n are the natural number greater than 1; R, R
1And R
2Be selected from a kind of in the following groups: R respectively
aR
bR
cR
dN
+, Wasserstoffatoms H; The R here
a, R
b, R
c, R
dBe respectively a kind of among alkyl, alkoxyl group, alcoxyl long chain alkyl group or the Wasserstoffatoms H.
When Ar or Ar ' are phenyl, R
1Or R
2All be positioned at the C of phenyl
2And C
5On the position, the connecting key of described nuclear, Ar and Ar ' all is positioned at the C of phenyl
1And C
4On the position.
When Ar or Ar ' are 9,9 two when replacing fluorenyls, R
1Or R
2All be positioned on 9 of fluorenyl, the connecting key of described nuclear, Ar and Ar ' all is positioned on 2,7 of fluorenyl.
The preparation method of hyperbranched soluble conjugated polymer is to adopt catalytic Sonogashira of organo-metallic or Suzuki polyreaction, through A
2+ A
2'+B
3The earlier synthetic neutral conjugation polymkeric substance of hyperbranched reaction method; Wherein, B
3Contain phenyl monomer, A for what form hyperbranched polymer nuclear
2And A
2' for forming two reaction monomers of hyperbranched polymer branch, the neutral conjugation polymkeric substance obtains hyperbranched soluble conjugated polymer through quaterisation again.
Beneficial effect:The present invention prepares the many branched water-solubles conjugated polymers with three-dimensional tree branched structure through the method for hyperbranched reaction, and nuclear, linking group and hydrophilic side chain thereof that this method is convenient to polymkeric substance are regulated and control respectively, obtain different many branching space structures.Material of the present invention can remedy and traditional line style soluble conjugated polymer easy gathering in water cause fluorescence self quencher, the deficiency that detection sensitivity is descended, and help fully interacting with biomolecules to be detected, can be used as the high-performance fluorescent sensing material.
Description of drawings
Fig. 1. be the hyperbranched soluble conjugated polymer of the present invention preparation and neutral conjugation polymkeric substance thereof the uv-visible absorption spectra in methyl alcohol and methylene dichloride respectively.
Fig. 2. be the hyperbranched soluble conjugated polymer of the present invention preparation and neutral conjugation polymkeric substance thereof the fluorescence emission spectrum in methyl alcohol and methylene dichloride respectively.
Embodiment
In order to understand content of the present invention better, further specify technical scheme of the present invention through concrete embodiment below, but can not limit scope of the present invention with this.
Embodiment 1:
Prepare monomer (1), (2) and (3), the monomer A in the promptly hyperbranched reaction through following method
2, A
2', and B
3(1), (2) are fed intake in different ratios with (3), and like 10:11:1, the 20:22:1 equal proportion is then at Pd (PPh
3)
4With the Sonogashira reaction three's coupling is got up under/CuI the catalysis, react after 3 days, drop into
A certain proportion of bromobenzene reacted 1 day again, promptly obtained neutral hyperbranched conjugated polymer P1, further carried out quaterisation with Trimethylamine 99, obtained hyperbranched soluble conjugated polymer P1 '.
Embodiment 2:
With embodiment 1, preparation monomer (2) and (3) obtains monomer (4) with following method is synthetic, and (4), (2) are fed intake in different ratios with (3), and like 10:11:1, the 20:22:1 equal proportion is then at Pd (PPh
3)
4With the Sonogashira reaction three's coupling is got up under/CuI the catalysis, react after 3 days, drop into a certain proportion of bromobenzene; Reacted again 1 day; Promptly obtain neutral hyperbranched conjugated polymer P2, further carry out quaterisation, obtain hyperbranched soluble conjugated polymer P2 ' with Trimethylamine 99.
Embodiment 3:
With embodiment 1, preparation monomer (1) obtains monomer (5) with (4) with following method reaction, then (1), (5) and a tribromo-benzene is fed intake in different ratios, and like 10:11:1, the 20:22:1 equal proportion is then at Pd (PPh
3)
4/ K
2CO
3With the Suzuki reaction three's coupling is got up under the catalysis, react after 3 days, drop into a certain proportion of bromobenzene; Reacted again 1 day; Promptly obtain neutral hyperbranched conjugated polymer P3, further carry out quaterisation, obtain hyperbranched soluble conjugated polymer P3 ' with Trimethylamine 99.
Claims (4)
1. hyperbranched soluble conjugated polymer is characterized in that having following molecular formula:
Wherein, the nuclear of hyperbranched polymer is phenyl, and Ar on the hyperbranched polymer branch and Ar ' are that phenyl, 9,9 two replaces a kind of in the fluorenyls, and the square of described nuclear, Ar and Ar ' junction is represented the mode of connection of the two to be specially triple bond or singly-bound; Polymerization degree x, y, z, k, l, m, n are the natural number greater than 1; R, R
1And R
2Be selected from a kind of in the following groups: R respectively
aR
bR
cR
dN
+, Wasserstoffatoms H; The R here
a, R
b, R
c, R
dBe respectively a kind of among alkyl, alkoxyl group, alcoxyl long chain alkyl group or the Wasserstoffatoms H.
2. hyperbranched soluble conjugated polymer according to claim 1 is characterized in that, when Ar or Ar ' are phenyl, and R
1Or R
2All be positioned at the C of phenyl
2And C
5On the position, the connecting key of described nuclear, Ar and Ar ' all is positioned at the C of phenyl
1And C
4On the position.
3. hyperbranched soluble conjugated polymer according to claim 1 is characterized in that, when Ar or Ar ' are 9,9 two when replacing fluorenyls, and R
1Or R
2All be positioned on 9 of fluorenyl, the connecting key of described nuclear, Ar and Ar ' all is positioned on 2,7 of fluorenyl.
4. the preparation method like the described hyperbranched soluble conjugated polymer of claim 1 ~ 3 is characterized in that adopting catalytic Sonogashira of organo-metallic or Suzuki polyreaction, through A
2+ A
2'+B
3The earlier synthetic neutral conjugation polymkeric substance of hyperbranched reaction method; Wherein, B
3Contain phenyl monomer, A for what form hyperbranched polymer nuclear
2And A
2' for forming two reaction monomers of hyperbranched polymer branch, the neutral conjugation polymkeric substance obtains hyperbranched soluble conjugated polymer through quaterisation again.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172834A (en) * | 2013-01-28 | 2013-06-26 | 武汉工程大学 | Hyperbranched polymer with 2,4,6-tribromo-1-alkoxybenzene as matrix and preparation method thereof |
| CN104946238A (en) * | 2015-05-04 | 2015-09-30 | 南京邮电大学 | White light conjugated polymer material as well as preparation method and application of white light conjugated polymer material |
| CN105445210A (en) * | 2015-11-12 | 2016-03-30 | 新疆大学 | Method for detecting concentration of trifluoroacetic acid with polymer in acidichromism performance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245131A (en) * | 2008-02-28 | 2008-08-20 | 复旦大学 | Hyperbranched poly-fluorene material containing space steric hindrance group and manufacture method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245131A (en) * | 2008-02-28 | 2008-08-20 | 复旦大学 | Hyperbranched poly-fluorene material containing space steric hindrance group and manufacture method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Macromolecules》 20041027 Xiao-Yu Cao，et al "Novel Blue-Light- Emitting Truxene-Containing Hyperbranched and Zigzag Type Copolymers: Synthesis, Optical Properties, and Investigation of Thermal Spectral Stability" 第8874-8882页 1，3，4 第37卷, 第24期 * |
| XIAO-YU CAO，ET AL: ""Novel Blue-Light- Emitting Truxene-Containing Hyperbranched and Zigzag Type Copolymers: Synthesis, Optical Properties, and Investigation of Thermal Spectral Stability"", 《MACROMOLECULES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172834A (en) * | 2013-01-28 | 2013-06-26 | 武汉工程大学 | Hyperbranched polymer with 2,4,6-tribromo-1-alkoxybenzene as matrix and preparation method thereof |
| CN103172834B (en) * | 2013-01-28 | 2015-03-11 | 武汉工程大学 | Hyperbranched polymer with 2,4,6-tribromo-1-alkoxybenzene as matrix and preparation method thereof |
| CN104946238A (en) * | 2015-05-04 | 2015-09-30 | 南京邮电大学 | White light conjugated polymer material as well as preparation method and application of white light conjugated polymer material |
| CN105445210A (en) * | 2015-11-12 | 2016-03-30 | 新疆大学 | Method for detecting concentration of trifluoroacetic acid with polymer in acidichromism performance |
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Effective date of registration: 20160617 Address after: 163411 Heilongjiang Province, Daqing City Ranghulu District police road No. 13 Patentee after: Daqing create Technology Co., Ltd. Address before: Nanjing City, Jiangsu province 210046 Yuen Road No. 9 Patentee before: Nanjing Post & Telecommunication Univ. |