CN110016111B - A kind of self-assembly based on brush-like block polymer and its synthesis method and application - Google Patents
A kind of self-assembly based on brush-like block polymer and its synthesis method and application Download PDFInfo
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Abstract
本发明公开了一种基于刷状嵌段聚合物的自组装物及其合成方法和应用，所述自组装物的合成方法，包括以下步骤：将刷状嵌段共聚物PNBPM‑b‑PNDM均匀分散在四氢呋喃中，将混合液涂布在玻璃片上，室温下溶剂挥发以后得到聚合物薄膜。本发明使得光子晶体材料可以应用于光传感器、光阀及颜料和染料等方面，具有极大的实用价值。
The invention discloses a brush-shaped block polymer-based self-assembly, a synthesis method and application thereof, and the synthesis method of the self-assembly comprises the following steps: uniformly distributing the brush-shaped block copolymer PNBPM-b-PNDM Disperse in tetrahydrofuran, apply the mixed solution on a glass sheet, and obtain a polymer film after the solvent is evaporated at room temperature. The invention enables the photonic crystal material to be applied to optical sensors, light valves, pigments and dyes, etc., and has great practical value.
Description
Technical Field
The invention relates to the technical field of preparation of brush-shaped block copolymers, in particular to a self-assembly based on brush-shaped block polymers and a synthesis method and application thereof.
Background
The photonic crystal can regulate and control the propagation of light waves due to the existence of an internal photon forbidden band structure, so that the photonic crystal has great application value, such as special pigment, waveguide, reflective coating and the like. Responsive photonic crystals are a class of materials whose reflected wavelength can change with changes in external physical or chemical conditions. Such materials must have a responsive group present in addition to the periodic structure necessary for conventional photonic crystals. Two methods are common for introducing responsive groups: (1) the photonic crystal structure is directly constructed by using a responsive material as a matrix, for example, a one-dimensional photonic crystal is prepared by using block polymer self-assembly, and a chain segment swells in a solvent atmosphere so as to show the change of reflection wavelength. (2) Firstly, a photonic crystal structure is prepared, and then a responsive material is doped into a matrix to form a stable photonic crystal composite material. According to the requirements, the photonic crystal materials with different responsivities such as Ph, temperature, chemical solvents, electric fields, magnetic fields and the like can be designed and prepared by the two methods.
The temperature sensitive photonic crystal is a responsive photonic crystal material which is widely researched. Since the pioneering work of Asher (a.asher, et al Science 1996,274,959.), numerous temperature sensitive photonic crystal materials with similar structures have been reported. Most of the photonic crystals are temperature-sensitive hydrogel photonic crystals prepared by embedding colloidal crystals into poly (N-isopropylacrylamide) (PNIPAM). Since PNIPAM is a thermosensitive polymer having a lower critical solution temperature (LCST, about 32 ℃), when the temperature is increased, the polymer changes from hydrophilic to hydrophobic, drains water and shrinks in volume, so that the inter-particle distance in the colloidal crystal decreases, resulting in blue-shift of the reflection wavelength. When the temperature is reduced, the state can be restored. Although the photonic crystal material prepared by the method has obvious temperature response behavior, the process is complex, and a large range of photonic crystal materials are difficult to prepare. Therefore, it is important to invent a simple and feasible low-cost technology for preparing the temperature-responsive one-dimensional photonic crystal material.
The patent discloses a novel brush-shaped block copolymer (PNBPM-b-PNDM), which is a series of one-dimensional photonic crystal materials obtained by self-assembly of simple low-boiling-point solvent films and has obvious temperature response behavior under heating conditions. Is expected to be practically applied to optical sensors and the like.
Disclosure of Invention
The invention aims to provide a brush-shaped block polymer-based self-assembly material, a synthesis method and application thereof aiming at the technical defects in the prior art, and is expected to be practically applied to optical sensors, light valves, pigments and dyes.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the brush block polymer-based self-assembly object is formed by self-assembling the brush block polymer, wherein the brush block copolymer is marked as PNBPM-b-PNDM, and the structural formula of the brush block copolymer is as follows:
wherein m is the polymerization degree of NBPM, and m is 100-; n is the polymerization degree of NDM, and n is 100-1500; the polymerization degree of the main chain is 200-3000;
wherein: the structural formula of NBPM is:
the structural formula of NDM is:
preferably, m is n.
Preferably, when the polymerization degree m of the NBPM is 180-220 and the polymerization degree n of the NDM is 180-220, the self-assembly substance is dark purple before heating and blue after heating, and preferably, m is 200 and n is 200.
Preferably, when the polymerization degree m of the NBPM is 280-320 and the polymerization degree n of the NDM is 280-320, the self-assembly substance is blue before heating and bright green after heating, and preferably, m is 300 and n is 300.
Preferably, when the polymerization degree m of the NBPM is 380-420 and the polymerization degree n of the NDM is 380-420, the self-assembly substance is green and red after heating, and preferably, m is 400 and n is 400.
Preferably, when the polymerization degree m of the NBPM is 480-520 and the polymerization degree n of the NDM is 480-520, the self-assembly material is red before heating and grey brown after heating, and preferably, m is 500 and n is 500.
In another aspect of the present invention, there is also included a method of synthesizing a brush block polymer-based self-assembly, comprising the steps of: uniformly dispersing the brush block copolymer PNBPM-b-PNDM in tetrahydrofuran, coating the mixed solution on a glass sheet, and volatilizing the solvent at room temperature to obtain the polymer film.
Preferably, the self-assembly method further comprises a thermal quenching step, specifically, the polymer film is placed on a flat heating table and kept for 1-24 hours at 50-300 ℃.
Preferably, the preparation method of the brush block copolymer PNBPM-b-PNDM comprises the following steps: dissolving norbornene monomer NBPM with a biphenyl structure into an organic solvent, adding a G-3 catalyst, stirring at 20-40 ℃ for reaction to homopolymerize the monomer NBPM, then adding the dissolved norbornene monomer NDM with a decyl structure into the reaction solution for continuous reaction to realize copolymerization of the NBPM and the NDM, adding a terminator after the reaction is finished for quenching reaction, and finally obtaining a target brush block copolymer (PNBPM-b-PNDM);
preferably, the molar ratio of G-3, NBPM and NDM is: 1:(100-1500):(100-1500).
In another aspect of the invention, the application of the brush block copolymer self-assembly method in regulating and controlling the color of a polymerization product is also included.
Preferably, when the polymerization degree m of the NBPM is 180-220 and the polymerization degree n of the NDM is 180-220, the self-assembly substance is dark purple before heating and blue after heating, and preferably, m is 200 and n is 200; when the polymerization degree m of the NBPM is 280-320 and the polymerization degree n of the NDM is 280-320, the self-assembly substance is blue before heating and bright green after heating, preferably, m is 300, and n is 300; when the polymerization degree m of the NBPM is 380-420 and the polymerization degree n of the NDM is 380-420, the self-assembly substance is green and red after heating, preferably, m is 400, and n is 400; when the polymerization degree m of the NBPM is 480-520 and the polymerization degree n of the NDM is 480-520, the self-assembly material is red before heating and grey brown after heating, and preferably, m is 500 and n is 500.
The invention also comprises the application of the self-assembly based on the brush-shaped block copolymer as a temperature-sensitive one-dimensional photonic crystal material in the aspects of optical sensors, light valves, pigments, dyes and the like.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis of the brush-shaped block copolymer is obtained by a series of ring-opening metathesis polymerization (ROMP) methods with controllable activity, firstly, a one-dimensional photonic crystal film is prepared by self-assembly of a low-boiling-point solvent, and then, the temperature-sensitive characteristic of the one-dimensional photonic crystal film is researched by heating treatment. Reflection spectrum tests show that the reflection wavelength has obvious red shift after heat treatment, and the reflectivity is reduced to a certain extent, which shows that the material has obvious temperature responsiveness. In addition, a linear relation graph between the main chain polymerization degree and the main reflection wavelength is obtained, and the relation between the material structure and the performance is well combined. The invention can be used in light sensor, light valve, pigment and dye, with high application value.
Drawings
FIG. 1 example 1 synthetic route for brush block copolymer (PNBPM-b-PNDM).
FIG. 2 nuclear magnetic spectrum of brush block copolymer of example 1 (PNBPM-b-PNDM).
FIG. 3 comparative pictures before and after self-assembly heat treatment of brush block copolymer (PNBPM-b-PNDM) of example 2.
FIG. 4 is a reflection spectrum of a photonic crystal film of example 2. A1-A6 and B1-B6 represent the reflectance spectra before and after thermal assembly of BCP1-BCP6, respectively.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the brush-shaped block copolymer BCP1-6 comprises the following steps: the preparation route is shown in figure 1,
the general structural formula of BCP1-6 is:
the synthesis steps of BCP1(m 200, n 200) are as follows:
NBPM (57.6mg, 91.2. mu. mol), 1mL dry methylene chloride, and G-3(0.41mg, 0.46X 10. mu. mol) were added to a 10mL polymerization flask-3mmol) of dichloromethane solution, stirring the reaction solution at room temperature for 30 minutes, adding 1.1mL of dichloromethane solution containing NDM (72.2mg, 91.2. mu. mol) into the reaction solution, and continuing the reaction for 1 hour, wherein the whole addition and reaction process are carried out in a glove box. After the reaction was complete, 1mL of ethyl vinyl ether was added to quench the reaction. Removing the glove box, precipitating in anhydrous methanol, centrifuging, and vacuum drying to obtain the final product with main chain polymerization degree of 400, wherein the polymerization degree of NBPM is 200 and the polymerization degree of NDM is 200.
The synthesis of BCP2(m 300, n 300) was as follows:
NBPM (57.6mg, 91.2. mu. mol), 1mL dry methylene chloride, and G-3(0.27mg, 0.31X 10) were added to a 10mL polymerization flask-3mmol) of dichloromethane solution, stirring the reaction solution at room temperature for 30 minutes, adding 1.1mL of dichloromethane solution containing NDM (72.2mg, 91.2. mu. mol) into the reaction solution, and continuing the reaction for 1 hour, wherein the whole addition and reaction process are carried out in a glove box. After the reaction was complete, 1mL of ethyl vinyl ether was added to quench the reaction. The mixture was taken out of the glove box, precipitated in anhydrous methanol, centrifuged, and vacuum-dried to obtain a brush-like block copolymer BCP2 having a polymerization degree of 600 in the main chain of NBPM of 300 and NDM of 300.
The synthesis steps of BCP3(m 400, n 400) are as follows:
NBPM (57.6mg, 91.2. mu. mol), 1mL dry methylene chloride, and G-3(0.21mg, 0.23X 10) were added to a 10mL polymerization flask-3mmol) of dichloromethane solution, stirring the reaction solution at room temperature for 30 minutes, adding 1.1mL of dichloromethane solution containing NDM (72.2mg, 91.2. mu. mol) into the reaction solution, and continuing the reaction for 1 hour, wherein the whole addition and reaction process are carried out in a glove box. After the reaction was complete, 1mL of ethyl vinyl ether was added to quench the reaction. The mixture was taken out of the glove box, precipitated in anhydrous methanol, centrifuged, and vacuum-dried to obtain a brush-like block copolymer BCP3 having a backbone polymerization degree of 800, wherein the polymerization degree of NBPM was 400 and the polymerization degree of NDM was 400.
The synthesis of BCP4(m 500, n 500) was as follows:
NBPM (57.6mg, 91.2. mu. mol), 1mL dry methylene chloride, and G-3(0.16mg, 0.18X 10) were added to a 10mL polymerization flask-3mmol) of dichloromethane solution, stirring the reaction solution at room temperature for 30 minutes, adding 1.1mL of dichloromethane solution containing NDM (72.2mg, 91.2. mu. mol) into the reaction solution, and continuing the reaction for 1 hour, wherein the whole addition and reaction process are carried out in a glove box. After the reaction was complete, 1mL of ethyl vinyl ether was added to quench the reaction. Moving out of the glove box in anhydrous methanolAnd (3) performing precipitation, centrifuging and vacuum drying to obtain a brush-shaped block copolymer BCP4 with the main chain polymerization degree of 1000, wherein the polymerization degree of NBPM is 500, and the polymerization degree of NDM is 500.
The synthesis of BCP5(m 700, n 700) was as follows:
NBPM (57.6mg, 91.2. mu. mol), 1mL dry methylene chloride, and G-3(0.12mg, 0.13X 10) were added to a 10mL polymerization flask-3mmol) of dichloromethane solution, stirring the reaction solution at room temperature for 30 minutes, adding 1.1mL of dichloromethane solution containing NDM (72.2mg, 91.2. mu. mol) into the reaction solution, and continuing the reaction for 1 hour, wherein the whole addition and reaction process are carried out in a glove box. After the reaction was complete, 1mL of ethyl vinyl ether was added to quench the reaction. The mixture was taken out of the glove box, precipitated in anhydrous methanol, centrifuged, and vacuum-dried to obtain a brush-like block copolymer BCP5 having a backbone polymerization degree of 1400, wherein the polymerization degree of NBPM was 700 and the polymerization degree of NDM was 700.
The synthesis of BCP6(m 1000, n 1000) was as follows:
NBPM (57.6mg, 91.2. mu. mol), 1mL dry methylene chloride, and G-3(0.082 mg, 0.092X 10) were added to a 10mL polymerization flask-3mmol) of dichloromethane solution, stirring the reaction solution at room temperature for 30 minutes, adding 1.1mL of dichloromethane solution containing NDM (72.2mg, 91.2. mu. mol) into the reaction solution, and continuing the reaction for 1 hour, wherein the whole addition and reaction process are carried out in a glove box. After the reaction was complete, 1mL of ethyl vinyl ether was added to quench the reaction. The mixture was taken out of the glove box, precipitated in anhydrous methanol, centrifuged, and vacuum-dried to obtain a brush-like block copolymer BCP6 having a polymerization degree of 2000 in the main chain, wherein the polymerization degree of NBPM was 1000 and the polymerization degree of NDM was 1000.
As shown in FIG. 2, which is a nuclear magnetic hydrogen spectrum of block polymer BCP4, it can be seen that all monomers have been completely converted and that all peaks can be well assigned.
Example 2
The synthesized series of brush-shaped block copolymers (BCP1-BCP6) have the following conditions of solvent self-assembly and heat treatment:
and (3) respectively preparing 10mg/mL tetrahydrofuran solution from the synthesized brush-shaped block copolymer (BCP1-BCP6), dropwise coating the mixed solution on a clean horizontal glass sheet, and volatilizing the solvent completely to obtain 6 different polymer films, namely the prepared one-dimensional photonic crystal material. And then, heating the prepared one-dimensional photonic crystal film for 30min at the temperature of 130 ℃ to research the temperature-sensitive characteristic of the one-dimensional photonic crystal film. As shown in FIG. 2, the self-assembly pictures before and after the heat treatment of BCP1-BCP6 show obvious light reflection phenomenon and temperature-sensitive behavior. The self-assembly of BCP1 appeared dark purple before heating and blue after heating; the self-assembly of BCP2 appeared blue before heating and bright green after heating; the self-assembly of BCP3 was green and red after heating, and the self-assembly of BCP4 was red before heating and grey brown after heating.
FIG. 3 is a reflection spectrogram of BCP1-BCP6 before and after heat treatment, wherein the reflection wavelength has obvious red shift after heating, and the reflectivity is reduced to a certain extent, which indicates that the temperature-sensitive one-dimensional photonic crystal material is successfully prepared.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. A self-assembly based on brush block polymer is characterized by being formed by self-assembly of the brush block polymer, wherein the brush block polymer is marked as PNBPM-b-PNDM and has the structural formula as follows:
wherein m is the polymerization degree of NBPM, and m is 100-; n is the polymerization degree of NDM, and n is 100-1500; the polymerization degree of the main chain is 200-3000;
wherein: the structural formula of NBPM is:
the structural formula of NDM is:
2. the brush block polymer-based self-assembly of claim 1, wherein m ═ n.
3. The brush block polymer-based self-assembly substance of claim 1, wherein the NBPM has a polymerization degree m of 180-220, the NDM has a polymerization degree n of 180-220, and the self-assembly substance is dark purple before heating and blue after heating;
when the polymerization degree m of the NBPM is 280-320 and the polymerization degree n of the NDM is 280-320, the self-assembly substance is blue before heating and bright green after heating;
when the polymerization degree m of the NBPM is 380-420 and the polymerization degree n of the NDM is 380-420, the self-assembly substance is green and is red after being heated;
when the polymerization degree m of the NBPM is 480-520 and the polymerization degree n of the NDM is 480-520, the self-assembly material is red before heating and is grey brown after heating.
4. The brush block polymer-based self-assembly according to claim 3, wherein the degree of polymerization m of NBPM is 200, the degree of polymerization n of NDM is 200, and the self-assembly is dark purple before heating and blue after heating;
when the polymerization degree m of the NBPM is 300 and the polymerization degree n of the NDM is 300, the self-assembly substance is blue before heating and bright green after heating;
when the polymerization degree m of the NBPM is 400 and the polymerization degree n of the NDM is 400, the self-assembly substance is green and is red after being heated;
when the polymerization degree m of the NBPM is 500 and the polymerization degree n of the NDM is 500, the self-assembly substance is red before heating and is grayish brown after heating.
5. The brush block polymer-based self-assembly of claim 1, prepared by the following method: uniformly dispersing the brush block polymer PNBPM-b-PNDM in tetrahydrofuran, coating the mixed solution on a glass sheet, and volatilizing the solvent at room temperature to obtain the polymer film.
6. The use of the brush block polymer-based self-assembly of claim 1 as a temperature sensitive one-dimensional photonic crystal material in photosensors, light valves and pigments and dyes.
7. The method of self-assembling brush block polymer-based self-assemblies according to claim 1, comprising the steps of: uniformly dispersing the brush block polymer PNBPM-b-PNDM in tetrahydrofuran, coating the mixed solution on a glass sheet, and volatilizing the solvent at room temperature to obtain the polymer film.
8. The self-assembly method of claim 7, further comprising a thermal quenching step, wherein the polymer film is placed on a flat heating stage and maintained at 50-300 ℃ for 1-24 hours.
9. The self-assembly method of claim 7, wherein the brush block polymer PNBPM-b-PNDM is prepared by a method comprising the steps of: dissolving norbornene monomer NBPM with a biphenyl structure into an organic solvent, adding a G-3 catalyst, stirring at 20-40 ℃ for reaction to homopolymerize the monomer NBPM, then adding the dissolved norbornene monomer NDM with a decyl structure into the reaction solution for continuous reaction to realize copolymerization of the NBPM and the NDM, adding a terminator after the reaction is finished for quenching reaction, and finally obtaining the target brush-shaped block polymer PNBPM-b-PNDM.
10. The self-assembly method of claim 9, wherein the molar ratio of G-3, NBPM and NDM is: 1:(100-1500):(100-1500).
11. The self-assembly method of claim 9, wherein the NBPM has a polymerization degree m of 180-220 and NDM has a polymerization degree n of 180-220, the self-assembly material is dark purple before heating and blue after heating; when the polymerization degree m of the NBPM is 280-320 and the polymerization degree n of the NDM is 280-320, the self-assembly substance is blue before heating and bright green after heating; when the polymerization degree m of the NBPM is 380-420 and the polymerization degree n of the NDM is 380-420, the self-assembly substance is green and is red after being heated; when the polymerization degree m of the NBPM is 480-520 and the polymerization degree n of the NDM is 480-520, the self-assembly material is red before heating and is grey brown after heating.
12. The use of the self-assembly process according to claim 11 for controlling the color of a polymer product, wherein the NBPM has a degree of polymerization m of 200 and the NDM has a degree of polymerization n of 200, and wherein the self-assembly material is dark purple before heating and blue after heating; when the polymerization degree m of the NBPM is 300 and the polymerization degree n of the NDM is 300, the self-assembly substance is blue before heating and bright green after heating; when the polymerization degree m of the NBPM is 400 and the polymerization degree n of the NDM is 400, the self-assembly substance is green and is red after being heated; when the polymerization degree m of the NBPM is 500 and the polymerization degree n of the NDM is 500, the self-assembly substance is red before heating and is grayish brown after heating.
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| JP2009275213A (en) * | 2008-04-17 | 2009-11-26 | Riken Technos Corp | Thermoplastic elastomer composition |
| CN103626905A (en) * | 2013-11-15 | 2014-03-12 | 无锡中科光远生物材料有限公司 | Method for preparing cationic salt response type bottlebrush-shaped polymer |
| CN103992484A (en) * | 2014-05-15 | 2014-08-20 | 长春理工大学 | Brush-like block copolymer with macromolecules at chain ends and preparation method thereof |
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| US9234985B2 (en) * | 2012-08-01 | 2016-01-12 | California Institute Of Technology | Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization |
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| JP2009275213A (en) * | 2008-04-17 | 2009-11-26 | Riken Technos Corp | Thermoplastic elastomer composition |
| CN103626905A (en) * | 2013-11-15 | 2014-03-12 | 无锡中科光远生物材料有限公司 | Method for preparing cationic salt response type bottlebrush-shaped polymer |
| CN103992484A (en) * | 2014-05-15 | 2014-08-20 | 长春理工大学 | Brush-like block copolymer with macromolecules at chain ends and preparation method thereof |
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| Aggregation-induced emission polymer nanoparticles with pH-responsive fluorescence;Zhao, Yuming等;《Polymer chemistry》;20161231;第7卷(第34期);第5386-5395页 * |
| 嵌段树状聚合物刷自组装制备紫外-可见-近红外一维光子晶体;任丽霞等;《中国化学会2017全国高分子学术论文报告会摘要集——主题J：高分子组装与超分子体系》;20171010;第520页 * |
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