CN110016111B - Self-assembly based on brush-shaped block polymer and synthesis method and application thereof - Google Patents
Self-assembly based on brush-shaped block polymer and synthesis method and application thereof Download PDFInfo
- Publication number
- CN110016111B CN110016111B CN201810016567.6A CN201810016567A CN110016111B CN 110016111 B CN110016111 B CN 110016111B CN 201810016567 A CN201810016567 A CN 201810016567A CN 110016111 B CN110016111 B CN 110016111B
- Authority
- CN
- China
- Prior art keywords
- self
- polymerization degree
- assembly
- nbpm
- ndm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000001338 self-assembly Methods 0.000 title claims abstract description 58
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 208000003013 permanent neonatal diabetes mellitus Diseases 0.000 claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229920006254 polymer film Polymers 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 56
- 206010028933 Neonatal diabetes mellitus Diseases 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000004038 photonic crystal Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000010791 quenching Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 101150058790 bcp gene Proteins 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 3
- 101150038746 bcp1 gene Proteins 0.000 description 2
- 101150023633 bcpB gene Proteins 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The invention discloses a self-assembly based on brush-shaped block polymers and a synthesis method and application thereof, wherein the synthesis method of the self-assembly comprises the following steps: 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. The invention can be used in light sensor, light valve, pigment and dye, with high application 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810016567.6A CN110016111B (en) | 2018-01-08 | 2018-01-08 | Self-assembly based on brush-shaped block polymer and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810016567.6A CN110016111B (en) | 2018-01-08 | 2018-01-08 | Self-assembly based on brush-shaped block polymer and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110016111A CN110016111A (en) | 2019-07-16 |
| CN110016111B true CN110016111B (en) | 2021-08-13 |
Family
ID=67187494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810016567.6A Expired - Fee Related CN110016111B (en) | 2018-01-08 | 2018-01-08 | Self-assembly based on brush-shaped block polymer and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110016111B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9234985B2 (en) * | 2012-08-01 | 2016-01-12 | California Institute Of Technology | Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization |
-
2018
- 2018-01-08 CN CN201810016567.6A patent/CN110016111B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110016111A (en) | 2019-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luo et al. | Recent progress on photochromic diarylethene polymers | |
| CN110041712B (en) | Preparation method of thermoreversible color-changing composite material based on polydiacetylene and metal organic framework compound | |
| US6506322B1 (en) | Naphthopyrans annelated in C5-C6 with an indene- or dihydronaphthalene-type carbocycle, and compositions and (co)polymer matrices containing them | |
| CN110734527A (en) | thermochromic photonic crystal film in body temperature region and preparation method thereof | |
| Li et al. | Synthesis and characterization of covalently colored polymer latex based on new polymerizable anthraquinone dyes | |
| Sato et al. | Highly transparent benzothiazole-based block and random copolymers with high refractive indices by RAFT polymerization | |
| CN110016111B (en) | Self-assembly based on brush-shaped block polymer and synthesis method and application thereof | |
| Zhang et al. | Multicolor fluorescent supramolecular adhesive gels based on a single molecule with aggregation-induced ratiometric emission | |
| JP5271472B2 (en) | NOVEL PHOTOCHROMIC POLYMER AND METHOD FOR PREPARING THE SAME | |
| CN110016110B (en) | Brush-shaped block polymer and synthesis method and application thereof | |
| Han et al. | Iridium-catalyzed polymerization of benzoic acids and internal diynes: a new route for constructing high molecular weight polynaphthalenes without the constraint of monomer stoichiometry | |
| Liu et al. | Controllable radical polymerization of selenide functionalized vinyl monomers and its application in redox responsive photonic crystals | |
| CN112831066B (en) | Temperature-sensitive photonic crystal gel with wide threshold and high sensitivity and preparation method thereof | |
| JP3931169B2 (en) | Method for producing alkenyl ether star polymer | |
| CN110437573B (en) | Blended self-assembly of brush-shaped block polymer and application | |
| Yun et al. | Electrochromic thin films from a redox active diarylethene by electrochemical polymerization | |
| CN111548455A (en) | Preparation method of thermoreversible color-changing composite material based on PDA and XZn-ZIF | |
| CN110066362A (en) | Visible light and temperature double-response type intelligent tree branched polymer and preparation method thereof | |
| CN114716651B (en) | Alpha-vinyl bridged BODIPY conjugated polymer and preparation method thereof | |
| CN113307908B (en) | Temperature and light dual-responsiveness dendritic polymer microspheres containing DASAs and preparation method thereof | |
| Shen et al. | Synthesis and properties of novel photochromic poly (methyl methacrylate-co-diarylethene) s | |
| TWI818051B (en) | Dispersant composition, coloring composition, and color filter | |
| Nguyen et al. | Synthesis and characterization of the photoswitchable poly (methyl methacrylate-random-methacrylate spirooxazine) | |
| KR101701169B1 (en) | Photo-responsive copolymer and synthesis method of the copolymer, fabrication method of honeycomb-patterned film | |
| Sudhakar et al. | Camouflage fabrics for military protective clothing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210813 |