A method for finely adjusting the structural color of block copolymer-based structural color materials

Abstract

The present invention discloses a method for finely adjusting the structural color of a block copolymer-based structural color material, belonging to the technical field of polymer materials. The method comprises the following steps: mixing monomer 1 and a catalyst solution, conducting a first polymerization reaction, mixing the product with monomer 2, conducting a second polymerization reaction to obtain a block copolymer, and self-assembling the block copolymer to obtain the block copolymer-based structural color material. The method can achieve continuous and efficient preparation of structural color materials, thereby enabling large-scale production of structural color materials, and can significantly reduce the preparation cost of structural color materials.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a method for finely adjusting the structural color of a block copolymer-based structural color material. Background Art

[0002] Structural color originates from Bragg reflection within periodic nanostructures. These materials offer advantages such as safety, environmental friendliness, excellent visual quality, resistance to photobleaching, and stimuli-responsive color change. They are expected to replace traditional toxic pigments in cosmetics, environmentally friendly coatings, safety paints, and anti-counterfeiting inks. Common photonic crystal structures include one-dimensional layered structures, two-dimensional columnar close-packed structures, and three-dimensional spherical stacking structures. Among these, the ordered porous structure of inverse opal exhibits a high refractive index contrast, resulting in even more vibrant structural color. However, the complex preparation process of traditional colloidal particle template methods has hindered large-scale application.

[0003] Block copolymer self-assembly is an effective method for preparing ordered structural polymer materials. In 1999, Thomas's group first reported structural color materials based on linear block copolymers, obtaining a rich variety of phase structures. However, the periodic size of conventional phase separation structures is generally less than 100nm, which cannot produce a photonic band gap in the visible light region. Therefore, in order to obtain structural colors, it is necessary to synthesize molecular weights higher than 1×10 6 The block copolymers of ultra-high molecular weight polymer chains are severely entangled, the self-assembly kinetics are slow, and there are many structural defects, which makes it difficult to apply them in practice.

[0004] Bottlebrush block copolymers (BBCPs) are ideal materials for making photonic crystal pigments. Their polymer side chains are tightly grafted onto a linear backbone, reducing entanglement and allowing for rapid self-assembly into photonic crystal structures with large periodicity exceeding 100 nm. However, the preparation of bottlebrush block copolymer-based structural color materials is currently typically performed in small-scale batches in the laboratory. Large-scale production still faces many challenges, including poor control of polymer molecular weight and molecular weight distribution, which makes it difficult to finely tune the structural color and poor reproducibility between different batches. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for finely adjusting the structural color of a block copolymer-based structural color material to solve the problems existing in the above-mentioned prior art.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] One of the technical solutions of the present invention is a method for preparing a block copolymer-based structural color material, comprising the following steps:

[0008] The monomer 1 and the catalyst solution are mixed to carry out a first polymerization reaction, the product is mixed with the monomer 2 to carry out a second polymerization reaction to obtain a block copolymer, and the block copolymer is self-assembled to obtain the block copolymer-based structural color material.

[0009] Furthermore, the preparation process of the block copolymer is carried out in a series of microreactors, which include the following devices connected in series in sequence: a first T-shaped mixer for mixing a catalyst and a solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and monomer 1, a first microreactor for performing a first polymerization reaction, a third T-shaped mixer for mixing the product and monomer 2, a second microreactor for performing a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and the solvent, a diluter for diluting the block copolymer, and an adsorption column for removing the catalyst.

[0010] Furthermore, the monomer 1 and monomer 2 are different cycloolefin polymerization monomers;

[0011] The molecular weight of the cycloolefin polymerization monomer is 500 to 10,000 Da;

[0012] The topology of the block copolymer is bottle brush type;

[0013] The temperature of the first polymerization reaction and the second polymerization reaction is 15 to 100° C.;

[0014] The inner diameter of the pores of the serially connected microreactors is 0.5 to 5 mm.

[0015] Furthermore, the microreactor is a circular tube type (made of stainless steel) or a special channel type reactor (enhanced straight tube type, Z-shaped, S-shaped, etc.).

[0016] Furthermore, the monomer 1 and monomer 2 are independently selected from any one of polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polypropylene oxide, polystyrene, polydimethylsiloxane, polycaprolactone, polylactide, polytert-butyl acrylate and polymethyl methacrylate having a norbornene group.

[0017] Furthermore, the solvent includes any one of toluene, dichloromethane, chloroform, ethyl acetate, butyl acetate, anisole and phenethyl ether.

[0018] Furthermore, the self-assembly is emulsion assembly or bulk assembly.

[0019] Furthermore, the emulsion assembly comprises:

[0020] The block copolymer solution and the PVA aqueous solution are mixed and emulsified, and the block copolymer-based structural color material is obtained after the solvent is evaporated.

[0021] Furthermore, the body assembly includes:

[0022] The block copolymer solution is coated on the surface of a substrate, and the block copolymer-based structural color material is obtained after the solvent evaporates.

[0023] The second technical solution of the present invention: a block copolymer-based structural color material prepared by the above preparation method.

[0024] The third technical solution of the present invention: an application of the above-mentioned block copolymer-based structural color material in the preparation of pigments.

[0025] Technical solution 4 of the present invention: A method for finely adjusting the structural color of a block copolymer-based structural color material, comprising the following steps:

[0026] The monomer 1 and the catalyst solution are mixed to carry out a first polymerization reaction, the product is mixed with the monomer 2 to carry out a second polymerization reaction to obtain a block copolymer, and the block copolymer is self-assembled to obtain a block copolymer-based structural color material.

[0027] Furthermore, the reflection wavelength of the block copolymer-based structural color material is 400 to 700 nm.

[0028] Furthermore, the preparation process of the block copolymer is carried out in a series of microreactors, which include the following devices connected in series in sequence: a first T-shaped mixer for mixing a catalyst and a solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and monomer 1, a first microreactor for performing a first polymerization reaction, a third T-shaped mixer for mixing the product and monomer 2, a second microreactor for performing a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and the solvent, a diluter for diluting the block copolymer, and an adsorption column for removing the catalyst.

[0029] Furthermore, the monomer 1 and monomer 2 are different cycloolefin polymerization monomers;

[0030] The molecular weight of the cycloolefin polymerization monomer is 500 to 10000 Da;

[0031] The topology of the block copolymer is bottle brush type;

[0032] The temperature of the first polymerization reaction and the second polymerization reaction is 15 to 100° C.;

[0033] The inner diameter of the pores of the serially connected microreactors is 0.5 to 5 mm.

[0034] Furthermore, the microreactor is a circular tube type (made of stainless steel) or a special channel type reactor (enhanced straight tube type, Z-shaped, S-shaped, etc.).

[0035] Furthermore, the monomer 1 and monomer 2 are independently selected from any one of polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polypropylene oxide, polystyrene, polydimethylsiloxane, polycaprolactone, polylactide, polytert-butyl acrylate and polymethyl methacrylate having a norbornene group.

[0036] Furthermore, the solvent includes any one of toluene, dichloromethane, chloroform, ethyl acetate, butyl acetate, anisole and phenethyl ether.

[0037] Furthermore, the self-assembly is emulsion assembly or bulk assembly.

[0038] Furthermore, the emulsion assembly comprises:

[0039] The block copolymer solution and the PVA aqueous solution are mixed and emulsified, and the block copolymer-based structural color material is obtained after the solvent is evaporated.

[0040] Furthermore, the body assembly includes:

[0041] The block copolymer solution is coated on the surface of a substrate, and the block copolymer-based structural color material is obtained after the solvent evaporates.

[0042] The present invention allows precise control of key reaction parameters during the preparation process, enabling large-scale production of block copolymer-based structural color materials with vibrant structural colors and enabling fine-tuning of structural color. This method overcomes the technical bottlenecks of traditional batch preparation methods, which limit the color of structural color materials to fine tuning and the gram-scale synthesis scale. It provides a viable solution for the industrialized production of bottlebrush block copolymer-based structural color materials.

[0043] The present invention discloses the following technical effects:

[0044] (1) The method of the present invention can realize the continuous and efficient preparation of structural color materials, thereby realizing the large-scale production of structural color materials, and the method of the present invention can significantly reduce the preparation cost of structural color materials.

[0045] (2) The preparation method of the present invention can accurately control the molecular weight of the block copolymer-based structural color material, thereby achieving fine adjustment of the structural color, and can make the structural color material have strong and bright colors, excellent brightness and rich color saturation.

[0046] (3) The preparation method of the present invention is simple and safe to operate, and is compatible with automated production. It makes it possible to construct an efficient and low-cost color library of structural color materials, while promoting the transformation from laboratory research to commercial products, and provides a new path for the development of environmentally and health-friendly pigments.

[0047] Moreover, the synthetic strategy of the present invention has broad application prospects and can be extended to a variety of block copolymer-based assembly materials, covering multiple fields such as ultra-soft elastomers, organic optoelectronics, lithography, energy storage and biomedical equipment. It provides a blueprint for industrial production, greatly reduces production costs, and promotes the development of block copolymer-based assembly materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0049] Figure 1 Schematic diagram of the continuous preparation process of block copolymer-based structural color materials;

[0050] Figure 2 This is a physical picture of polymer porous microspheres with different structural colors prepared in Example 1;

[0051] Figure 3 This is a macroscopic photograph of the structural color film prepared in Example 7;

[0052] Figure 4 Schematic diagram of the special channel reactor. DETAILED DESCRIPTION

[0053] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0054] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0055] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0056] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0057] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0058] In a first aspect, the present invention provides a method for preparing a block copolymer-based structural color material, comprising the following steps:

[0059] Connecting the outlets of the continuous infusion pump of the solvent and catalyst solution to the two inlets of the first T-shaped mixer respectively;

[0060] Connecting the outlet of the first T-mixer to an inlet of the second T-mixer;

[0061] Connect the outlet of the continuous infusion pump of the solution of cycloolefin polymerization monomer 1 to the other inlet of the second T-shaped mixer;

[0062] Connect the outlet of the second T-shaped mixer to the inlet on one side of the first microreactor;

[0063] Connect the outlet on the other side of the first microreactor to an inlet of the third T-shaped mixer;

[0064] Connect the outlet of the continuous infusion pump of the solution of cycloolefin polymerization monomer 2 to the other inlet of the third T-shaped mixer;

[0065] Connect the outlet of the third T-shaped mixer to the inlet on one side of the second microreactor;

[0066] Connect the outlet on the other side of the second microreactor to an inlet of a fourth T-shaped mixer;

[0067] connecting the solvent to another inlet of the fourth T-shaped mixer, and connecting the outlet of the fourth T-shaped mixer to the inlet of the diluter;

[0068] connecting the outlet of the diluter to the inlet of an adsorption column filled with a metal scavenger, and collecting the purified block copolymer solution at the outlet of the adsorption column filled with the metal scavenger;

[0069] The specific operations are as follows:

[0070] (1) The solvent and catalyst solution are mixed uniformly through a first T-shaped mixer and then mixed uniformly with the cycloolefin polymerization monomer 1 solution through a second T-shaped mixer, and then introduced into a first microreactor for polymerization reaction (ring-opening metathesis polymerization, the polymerization reaction time is 25 to 120 seconds). After the reaction is completed, the solution flows out from the outlet on the other side of the first microreactor to obtain a first effluent.

[0071] (2) The first effluent and the solution of cycloolefin polymerization monomer 2 are mixed evenly through a third T-shaped mixer and introduced into a second microreactor for polymerization reaction (ring-opening metathesis polymerization, the polymerization reaction time is 35 to 120 seconds). After the reaction is completed, the solution flows out from the outlet on the other side of the second microreactor to obtain a block copolymer solution.

[0072] (3) The block copolymer solution and the solvent are mixed through a fourth T-shaped mixer, and passed into a diluter (a stainless steel round tube with an inner diameter of 2.1 to 4 mm) for dilution (online dilution) and cooling to obtain a cooled block copolymer dilution solution.

[0073] (4) Passing the cooled dilute block copolymer solution into an adsorption column filled with a metal scavenger for purification to obtain a purified block copolymer solution.

[0074] (5) Using purified block copolymer solutions for self-assembly, block copolymer-based structural color materials can be prepared continuously and precisely in large quantities.

[0075] The solvent, the catalyst solution, the cycloolefin polymerization monomer 1 solution, and the cycloolefin polymerization monomer 2 solution are respectively placed in a liquid reservoir equipped with a continuous infusion pump; the first microreactor and the second microreactor are respectively placed in an oil bath for temperature control;

[0076] In a specific embodiment of the present invention, the catalyst in the catalyst solution is a third-generation Grubbs catalyst.

[0077] In a specific embodiment of the present invention, the maximum reflection wavelength of the block copolymer-based structural color material is 400-700 nm (the method of the present invention can achieve fine adjustment of the structural color, such as preparing structural color materials with maximum reflection wavelengths of 500 nm, 505 nm, 510 nm, etc. and with extremely small changes in reflection wavelength).

[0078] In a specific embodiment of the present invention, the topology of the block copolymer is bottle-brush type;

[0079] The polymerization temperature is 15 to 100°C;

[0080] The inner diameter of the pipe of the first microreactor and the second microreactor is 0.5-5 mm; the first microreactor and the second microreactor are both circular tube type or special channel type reactors (enhanced straight tube type, Z-shaped, S-shaped, etc.); the schematic diagram of the special channel reactor is shown in Figure 4 .

[0081] In a specific embodiment of the present invention, the molecular weight of the cycloolefin polymerization monomer is 500 to 10,000 Da;

[0082] The cycloolefin polymerization monomer 1 and the cycloolefin polymerization monomer 2 are each independently selected from any one of polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polypropylene oxide, polystyrene, polydimethylsiloxane, polycaprolactone, polylactide, polytert-butyl acrylate and polymethyl methacrylate having a norbornene group, and the cycloolefin polymerization monomer 1 and the cycloolefin polymerization monomer 2 are different substances;

[0083] The solvent used in preparing the solution of cycloolefin polymerization monomer 1, the solution of cycloolefin polymerization monomer 2 and the solution of the catalyst includes any one of toluene, dichloromethane, chloroform, ethyl acetate, butyl acetate, anisole and phenethyl ether.

[0084] In a specific embodiment of the present invention, the self-assembly is emulsion assembly or bulk assembly.

[0085] In a specific embodiment of the present invention, the emulsion assembly comprises:

[0086] The purified block copolymer solution and the PVA aqueous solution are mixed and emulsified, and the block copolymer-based structural color material (structural color microspheres) is obtained after the solvent is evaporated.

[0087] In a specific embodiment of the present invention, the body assembly includes:

[0088] The purified block copolymer solution is coated on the surface of a substrate, and the block copolymer-based structural color material (structural color film) is obtained after the solvent evaporates.

[0089] Furthermore, the coating method is selected from any one of spraying, scraping and brushing.

[0090] In a specific embodiment of the present invention, the concentration of the solution of cycloolefin polymerization monomer 1 is 40 to 86 mmol / L, and the flow rate is 0.75 to 12 mL / min; the concentration of the solution of cycloolefin polymerization monomer 2 is 40 to 300 mmol / L, and the flow rate is 0.58 to 28.8 mL / min; the concentration of the catalyst solution is 0.1 to 4.0 mmol / L, and the flow rate is 0.35 to 8.10 mL / min; in the first T-shaped mixer, the flow rate of the pure solvent mixed with the catalyst is 0.31 to 9.43 mL / min.

[0091] The schematic diagram of the continuous preparation process of block copolymer-based structural color materials is shown in Figure 1 .

[0092] In a second aspect, the present invention provides a block copolymer-based structural color material prepared by the above preparation method.

[0093] In a third aspect, the present invention provides a use of the above-mentioned block copolymer-based structural color material in the preparation of pigments.

[0094] In a fourth aspect, the present invention provides a method for finely adjusting the structural color of a block copolymer-based structural color material, and a method for preparing the block copolymer-based structural color material.

[0095] Example 1

[0096] A method for finely adjusting the structural color of a block copolymer-based structural color material:

[0097] (1) Setting up the reaction system: Connect the outlets of the continuous infusion pumps for the solvent and catalyst solutions to the two inlets of the first T-shaped mixer, respectively;

[0098] Connecting the outlet of the first T-mixer to an inlet of the second T-mixer;

[0099] Connect the outlet of the continuous infusion pump of the solution of cycloolefin polymerization monomer 1 to the other inlet of the second T-shaped mixer;

[0100] Connect the outlet of the second T-shaped mixer to the inlet on one side of the first microreactor;

[0101] Connect the outlet on the other side of the first microreactor to an inlet of the third T-shaped mixer;

[0102] Connect the outlet of the continuous infusion pump of the solution of cycloolefin polymerization monomer 2 to the other inlet of the third T-shaped mixer;

[0103] Connect the outlet of the third T-shaped mixer to the inlet on one side of the second microreactor;

[0104] Connect the outlet on the other side of the second microreactor to an inlet of a fourth T-shaped mixer;

[0105] connecting the solvent to another inlet of the fourth T-shaped mixer, and connecting the outlet of the fourth T-shaped mixer to the inlet of the diluter;

[0106] The outlet of the diluter is connected to the inlet of an adsorption column filled with a metal scavenger, and the purified block copolymer solution is collected at the outlet of the adsorption column filled with a metal scavenger.

[0107] (2) Solution preparation: NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight of 3000 Da, molecular weight distribution index of 1.10), NB-PEG (norbornene-terminated polyethylene glycol) macromonomer (molecular weight of 2000 Da, molecular weight distribution index of 1.09), and Grubbs third-generation catalyst (relative molecular weight of 884.53 Da) were prepared into 86 mmol / L, 86 mmol / L, and 2.5 mmol / L NB-PCL ultra-dry toluene solution, NB-PEG ultra-dry toluene solution, and Grubbs third-generation catalyst ultra-dry toluene solution, respectively;

[0108] The NB-PCL ultra-dry toluene solution, the NB-PEG ultra-dry toluene solution, the Grubbs third-generation catalyst ultra-dry toluene solution (catalyst solution) and the pure toluene solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0109] (3) Polymer synthesis: The catalyst solution (flow rate set to 0.64 mL / min) and pure toluene solvent (flow rate set to 0.41 mL / min) were mixed evenly in the first T-shaped mixer, and then mixed evenly with NB-PCL ultra-dry toluene solution (solution of cycloolefin polymerization monomer 1, flow rate set to 0.75 mL / min) through the second T-shaped mixer, and then passed into the first microreactor (stainless steel circular tube reactor, the inner diameter of the tube is 500 μm, the reactor is placed in a constant temperature oil bath at 70°C) for polymerization reaction (ring-opening metathesis polymerization), with a residence time of 25 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactants in the first microreactor is 25 s). After the reaction is completed, the first effluent is obtained from the outlet on the other side of the first microreactor;

[0110] The first effluent and the NB-PEG ultra-dry toluene solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 1.05 mL / min) were mixed uniformly by a third T-shaped mixer and passed into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 500 μm, heated in a constant temperature oil bath at 70°C) for polymerization (ring-opening metathesis polymerization) with a residence time of 35 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 35 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain.

[0111] (4) Dilution and Cooling: The block copolymer solution was piped into a fourth T-shaped mixer and mixed with pure toluene solvent (flow rate set at 15.2 mL / min). The mixed solution then flowed into a stainless steel circular tube with an inner diameter of 2.1 mm for further dilution and cooling. During this process, the concentration of the block copolymer solution decreased from 127 mg / mL to 20 mg / mL. Simultaneously, the temperature of the solution was lowered from 70°C during the polymerization reaction to room temperature by air cooling in the pipe, resulting in a cooled dilute block copolymer solution.

[0112] (5) Purification: The cooled block copolymer dilute solution is passed through a column containing Silicycle DMT metal scavenger (column capacity is 8 mL) to remove the residual catalyst online to ensure that the final product is environmentally friendly and non-toxic, thereby obtaining a purified block copolymer solution.

[0113] (6) Self-assembly (emulsion assembly): 100 mL of the purified block copolymer solution was collected into a 2-L beaker containing 1 L of PVA aqueous solution. The mixture was then stirred at 6000 rpm for 30 s using a high-speed homogenizer to form an oil-in-water (O / W) emulsion due to shear force. The emulsion was then immediately placed in a constant temperature and humidity chamber at 25°C and 50% humidity. After the solvent slowly evaporated, porous polymer microspheres were formed, resulting in a blue block copolymer-based structural color material with a polymer molecular weight of 181 kDa and a maximum reflection wavelength of 461 ± 5 nm.

[0114] Under these conditions, the output of block copolymer-based structural color materials can reach 0.52 kg / day.

[0115] Preparation of PVA aqueous solution: Dissolve polyvinyl alcohol (molecular weight 20,000-30,000 Da) in Milli-Q water and heat to 95°C to form a clear PVA aqueous solution with a concentration of 20 mg / mL.

[0116] (7) Fine adjustment of structural color: With other conditions unchanged, by adjusting the flow rate ratio of catalyst and solvent (0.74 mL / min: 0.31 mL / min, 0.70 mL / min: 0.35 mL / min, 0.66 mL / min: 0.39 mL / min, 0.63 mL / min: 0.42 mL / min, 0.60 mL / min: 0.45 mL / min), polymer porous microspheres with different structural colors were obtained. The polymer molecular weights were 154 kDa, 169 kDa, 189 kDa, 198 kDa and 211 kDa, respectively, and the maximum reflection wavelengths were 411 nm, 428 nm, 452 nm, 477 nm and 486 nm, respectively. The actual pictures of polymer porous microspheres with different structural colors are shown in Figure 2. Figure 2(Showing macroscopic photos and reflection optical micrographs of microspheres dispersed in water), from left to right this time are samples with maximum reflection wavelengths of 411 nm, 428 nm, 452 nm, 477 nm, and 486 nm.

[0117] Figure 2 The polymer porous microspheres with different structural colors were clearly displayed, further demonstrating the effectiveness and accuracy of the method of the present invention.

[0118] Example 2

[0119] The same as Example 1, except that step (2) is specifically as follows: NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight 3000 Da, molecular weight distribution index 1.10), NB-PEO (norbornene-terminated polyethylene glycol) macromonomer (molecular weight 2000 Da, molecular weight distribution index 1.09), and Grubbs third-generation catalyst (relative molecular mass 884.53 Da) are respectively prepared into 86 mmol / L, 86 mmol / L, and 2.5 mmol / L NB-PCL ultra-dry butyl acetate solution, NB-PEG ultra-dry butyl acetate solution, and Grubbs third-generation catalyst ultra-dry butyl acetate solution;

[0120] NB-PCL ultra-dry butyl acetate solution, NB-PEG ultra-dry butyl acetate solution, Grubbs third-generation catalyst ultra-dry butyl acetate solution (catalyst solution) and pure butyl acetate solvent were placed in reservoirs with continuous infusion pumps, respectively.

[0121] A blue block copolymer-based structural color material was obtained, with a polymer molecular weight of 180 kDa and a reflection wavelength of 459±4 nm.

[0122] Under these conditions, the output of block copolymer-based structural color materials can reach 0.52 kg / day.

[0123] Step (7) is specifically as follows: when other conditions remain unchanged, fine adjustment of the structural color: when other conditions remain unchanged, by adjusting the flow rate ratio of the catalyst and the solvent (0.74mL / min:0.31mL / min, 0.70mL / min:0.35mL / min, 0.66mL / min:0.39mL / min, 0.63mL / min:0.42mL / min, 0.60mL / min:0.45mL / min), polymer porous microspheres with different structural colors are obtained, and the polymer molecular weights are 151kDa, 166kDa, 186kDa, 194kDa and 206kDa, respectively, and the maximum reflection wavelengths are 413nm, 430nm, 447nm, 472nm and 481nm, respectively. When only the solvent is changed and other conditions remain unchanged, the structural color of the obtained structural color material does not change significantly, indicating good repeatability of the method.

[0124] Example 3

[0125] The same as Example 1, except that step (2) specifically comprises: preparing NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight of 3000 Da, molecular weight distribution index of 1.10), NB-PEG (norbornene-terminated polyethylene glycol) macromonomer (molecular weight of 2000 Da, molecular weight distribution index of 1.09), and Grubbs third-generation catalyst (relative molecular mass of 884.53 Da) into 86 mmol / L, 86 mmol / L, and 2.5 mmol / L NB-PCL ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, and Grubbs third-generation catalyst ultra-dry anisole solution, respectively;

[0126] The NB-PCL ultra-dry anisole solution, the NB-PEG ultra-dry anisole solution, the Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution) and the pure anisole solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0127] Step (3) is specifically as follows: the catalyst solution (flow rate is set to 2.73 mL / min) and the pure anisole solvent (flow rate is set to 1.48 mL / min) are mixed uniformly in a first T-shaped mixer and then mixed uniformly with the NB-PCL ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 1, flow rate is set to 3.00 mL / min) through a second T-shaped mixer, and then introduced into a first microreactor (stainless steel circular tube reactor, the inner diameter of the tube is 1 mm, and the reactor is placed in a 70 ° C constant temperature oil bath for heating) to carry out polymerization reaction (ring-opening metathesis polymerization), the residence time is 35 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactant in the first microreactor is 35 s), and after the reaction is completed, the first effluent is obtained by flowing out from the outlet on the other side of the first microreactor;

[0128] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 4.20 mL / min) were uniformly mixed in a third T-shaped mixer and passed into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 1 mm, heated in a constant temperature oil bath at 70° C.) for polymerization (ring-opening metathesis polymerization) with a residence time of 45 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 45 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain.

[0129] Step (4) is specially: the block copolymer solution is introduced into the fourth T-shaped mixer through a pipeline and mixed with a pure anisole solvent (flow velocity is set to 60.1mL / min), and the mixed solution flows into a stainless steel round tube with an internal diameter of 2.1mm, to further dilute and cool. In this process, the concentration of the block copolymer solution is reduced to 20mg / mL from 127mg / mL, and the air cooling effect of the pipeline is simultaneously applied to reduce the temperature of the solution from 70°C during the polymerization reaction to room temperature, thereby obtaining a cooled block copolymer dilute solution.

[0130] A blue block copolymer-based structural color material was obtained, with a polymer molecular weight of 169 kDa and a reflection wavelength of 420 ± 7 nm.

[0131] Under these conditions, the output of block copolymer-based structural color materials can reach 2.08 kg / day.

[0132] Step (7) is specifically as follows: when other conditions remain unchanged, by adjusting the flow rate ratio of the catalyst and the solvent (2.64mL / min:1.55mL / min, 2.58mL / min:1.62mL / min, 2.52mL / min:1.68mL / min, 2.46mL / min:1.74mL / min, 2.40mL / min:1.80mL / min), polymer porous microspheres with different structural colors are obtained, and the polymer molecular weights are 185kDa, 189kDa, 194kDa, 199kDa and 205kDa, and the maximum reflection wavelengths are 445nm, 452nm, 464nm, 471nm and 480nm, respectively.

[0133] Example 4

[0134] The same as Example 1, except that step (2) specifically comprises: preparing NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight of 3000 Da, molecular weight distribution index of 1.10), NB-PEG (norbornene-terminated polyethylene glycol) macromonomer (molecular weight of 2000 Da, molecular weight distribution index of 1.09), and Grubbs third-generation catalyst (relative molecular mass of 884.53 Da) into 86 mmol / L, 86 mmol / L, and 2.5 mmol / L NB-PCL ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, and Grubbs third-generation catalyst ultra-dry anisole solution, respectively;

[0135] The NB-PCL ultra-dry anisole solution, the NB-PEG ultra-dry anisole solution, the Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution) and the pure anisole solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0136] Step (3) is specifically as follows: the catalyst solution (flow rate is set to 8.10 mL / min) and the pure anisole solvent (flow rate is set to 8.71 mL / min) are mixed uniformly in a first T-shaped mixer, and then mixed uniformly with the NB-PCL ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 1, with a flow rate set to 12.00 mL / min) through a second T-shaped mixer, and then introduced into a first microreactor (a stainless steel circular tube reactor with an inner diameter of 4 mm, and the reactor is placed in a 70°C constant temperature oil bath for heating) to carry out a polymerization reaction (ring-opening metathesis polymerization) with a residence time of 90 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactants in the first microreactor is 90 s). After the reaction is completed, the first effluent is obtained by flowing out from the outlet on the other side of the first microreactor;

[0137] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 28.80 mL / min) were mixed uniformly in a third T-shaped mixer and introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 4 mm, heated in a constant temperature oil bath at 70° C.) for polymerization (ring-opening metathesis polymerization) with a residence time of 90 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 90 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain the block copolymer solution.

[0138] Step (4) is specially: the block copolymer solution is introduced into the fourth T-shaped mixer through a pipeline and mixed with a pure anisole solvent (flow velocity is set to 253.1mL / min), and the mixed solution flows into a stainless steel round tube with an internal diameter of 5mm, to further dilute and cool. In this process, the concentration of the block copolymer solution is reduced to 20mg / mL from 131mg / mL, and the air cooling effect of the pipeline is simultaneously applied to reduce the temperature of the solution from 70°C during the polymerization reaction to room temperature, thereby obtaining a cooled block copolymer dilute solution.

[0139] A blue block copolymer-based structural color material was obtained, with a polymer molecular weight of 175 kDa and a reflection wavelength of 431 ± 7 nm.

[0140] Under these conditions, the output of block copolymer-based structural color materials can reach 8.62 kg / day.

[0141] Step (7) is specifically as follows: when other conditions remain unchanged, by adjusting the flow rate ratio of the catalyst and the solvent (7.94mL / min:8.86mL / min, 7.79mL / min:9.01mL / min, 7.64mL / min:9.15mL / min, 7.51mL / min:9.29mL / min, 7.37mL / min:9.43mL / min), polymer porous microspheres with different structural colors are obtained, and the polymer molecular weights are 182kDa, 185kDa, 191kDa, 195kDa and 203kDa, and the maximum reflection wavelengths are 444nm, 451nm, 462nm, 470nm and 479nm, respectively.

[0142] Example 5

[0143] The same as Example 1, except that step (2) specifically comprises: preparing 40 mmol / L, 300 mmol / L, and 2.5 mmol / L NB-PS ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, and Grubbs third-generation catalyst ultra-dry anisole solution of 40 mmol / L, 300 mmol / L, and 2.5 mmol / L, respectively, of NB-PS (norbornene-terminated polystyrene) macromonomer (molecular weight 8000 Da, molecular weight distribution index 1.20), NB-PEG (norbornene-terminated polyvinylpyrrolidone) macromonomer (molecular weight 500 Da, molecular weight distribution index 1.07), and Grubbs third-generation catalyst (relative molecular weight 884.53 Da);

[0144] The NB-PS ultra-dry anisole solution, the NB-PEG ultra-dry anisole solution, the Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution) and the pure anisole solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0145] Step (3) is specifically as follows: the catalyst solution (flow rate is set to 1.78 mL / min) and the pure anisole solvent (flow rate is set to 2.42 mL / min) are mixed uniformly in a first T-shaped mixer, and then mixed uniformly with the NB-PS ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 1, flow rate is set to 3.00 mL / min) through a second T-shaped mixer, and then introduced into a first microreactor (stainless steel circular tube reactor, the inner diameter of the tube is 1 mm, and the reactor is placed in a 70°C constant temperature oil bath for heating) to carry out polymerization reaction (ring-opening metathesis polymerization), with a residence time of 60 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactant in the first microreactor is 60 s), and after the reaction is completed, the outlet on the other side of the first microreactor flows out to obtain a first effluent;

[0146] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 6.00 mL / min) were uniformly mixed in a third T-shaped mixer and passed into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 1 mm, heated in a constant temperature oil bath at 70° C.) for polymerization (ring-opening metathesis polymerization) with a residence time of 90 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 90 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain.

[0147] Step (4) is specially: the block copolymer solution is entered into the 4th T-shaped mixer by pipeline and mixed with pure anisole solvent (flow velocity is set to 79.2mL / min), and the mixed solution flows into the stainless steel round tube with an internal diameter of 2.1mm, to further dilute and cool. In this process, the concentration of the block copolymer solution is reduced to 20mg / mL from 140mg / mL, and the air cooling effect of the pipeline is simultaneously applied to reduce the temperature of the solution from 70°C during the polyreaction to room temperature, thereby obtaining a cooled block copolymer dilute solution.

[0148] A red block copolymer-based structural color material was obtained, with a polymer molecular weight of 370 kDa and a reflection wavelength of 661 ± 6 nm.

[0149] Under these conditions, the output of block copolymer-based structural color materials can reach 2.68 kg / day.

[0150] Step (7) is specifically as follows: when other conditions remain unchanged, by adjusting the flow rate ratio of the catalyst and the solvent (1.71mL / min:2.49mL / min, 1.65mL / min:2.54mL / min, 1.60mL / min:2.60mL / min, 1.55mL / min:2.65mL / min, 1.50mL / min:2.70mL / min), polymer porous microspheres with different structural colors are obtained, and the polymer molecular weights are 310kDa, 325kDa, 341kDa, 356kDa and 372kDa, and the maximum reflection wavelengths are 621nm, 632nm, 640nm, 647nm and 658nm, respectively.

[0151] Example 6

[0152] A method for finely adjusting the structural color of a block copolymer-based structural color material:

[0153] (1) Setting of reaction system: same as in Example 1.

[0154] (2) Solution preparation: NB-PS (norbornene-terminated polystyrene) macromonomer (molecular weight 4000 Da, molecular weight distribution index 1.16), NB-PEG (norbornene-terminated polyethylene glycol) macromonomer (molecular weight 4000 Da, molecular weight distribution index 1.13), and Grubbs third-generation catalyst (relative molecular weight 884.53 Da) were prepared into 40 mmol / L, 40 mmol / L, and 0.2 mmol / L NB-PS ultra-dry ethyl acetate solution, NB-PEG ultra-dry ethyl acetate solution, and Grubbs third-generation catalyst ultra-dry ethyl acetate solution, respectively;

[0155] The NB-PS ultra-dry ethyl acetate solution, the NB-PEG ultra-dry ethyl acetate solution, the Grubbs third-generation catalyst ultra-dry ethyl acetate solution (catalyst solution) and the pure ethyl acetate solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0156] (3) Polymer synthesis: The catalyst solution (flow rate set to 2.36 mL / min) and pure ethyl acetate solvent (flow rate set to 1.84 mL / min) were mixed evenly in the first T-shaped mixer, and then mixed evenly with NB-PCL ultra-dry ethyl acetate solution (solution of cycloolefin polymerization monomer 1, flow rate set to 3.00 mL / min) through the second T-shaped mixer, and then passed into the first microreactor (stainless steel circular tube reactor, the inner diameter of the tube is 2 mm, the reactor is placed in a constant temperature oil bath at 70 ° C) for polymerization reaction (ring-opening metathesis polymerization), with a residence time of 100 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactants in the first microreactor is 100 s). After the reaction is completed, the first effluent is obtained from the outlet on the other side of the first microreactor;

[0157] The first effluent and the NB-PEG ultra-dry ethyl acetate solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 3.00 mL / min) were mixed uniformly through a third T-shaped mixer and introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 2 mm, heated in a constant temperature oil bath at 70°C) for polymerization (ring-opening metathesis polymerization) with a residence time of 120 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 120 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain the block copolymer solution.

[0158] (4) Dilution and Cooling: The block copolymer solution was piped into a fourth T-shaped mixer and mixed with pure ethyl acetate (flow rate set at 37.7 mL / min). The mixed solution then flowed into a stainless steel tube with an inner diameter of 4 mm for further dilution and cooling. During this process, the concentration of the block copolymer solution decreased from 94 mg / mL to 20 mg / mL. Simultaneously, the temperature of the solution was lowered from 70°C during the polymerization reaction to room temperature by air cooling in the pipe, resulting in a cooled dilute block copolymer solution.

[0159] (5) Purification: The cooled block copolymer dilute solution was passed through a column containing Silicycle DMT metal scavenger (column capacity was 20 mL) to remove the residual catalyst online, ensuring that the final product was environmentally friendly and non-toxic, and a purified block copolymer solution was obtained with a polymer molecular weight of 2010 kDa.

[0160] (6) Self-assembly (bulk assembly): The purified block copolymer solution was scraped onto a polyethylene terephthalate (PET) film. After the solvent evaporated, a structural color film with a thickness of 5 μm and a wavelength of 521 ± 5 nm was obtained.

[0161] Under these conditions, the output of block copolymer-based structural color materials can reach 1.38 kg / day.

[0162] (7) Fine adjustment of structural color: With other conditions unchanged, by adjusting the flow rate ratio of catalyst and solvent (2.34mL / min:1.86mL / min, 2.32mL / min:1.88mL / min, 2.30mL / min:1.90mL / min, 2.28mL / min:1.92mL / min, 2.26mL / min:1.94mL / min), polymer structural color films with different structural colors were obtained. The molecular weights of the polymers were 2026kDa, 2042kDa, 2058kDa, 2074kDa and 2089kDa, and the maximum reflection wavelengths were 526nm, 532nm, 540nm, 547nm and 558nm, respectively.

[0163] Example 7

[0164] A method for finely adjusting the structural color of a block copolymer-based structural color material:

[0165] (1) Setting of reaction system: same as in Example 1.

[0166] (2) Solution preparation: NB-PMMA (norbornene-terminated polymethyl methacrylate) macromonomer (molecular weight of 4000 Da, molecular weight distribution index of 1.16), NB-PS (norbornene-terminated polystyrene) macromonomer (molecular weight of 4000 Da, molecular weight distribution index of 1.13), and Grubbs third-generation catalyst (relative molecular weight of 884.53 Da) were prepared into 40 mmol / L, 40 mmol / L, and 0.2 mmol / L NB-PMMA ultra-dry ethyl acetate solution, NB-PS ultra-dry ethyl acetate solution, and Grubbs third-generation catalyst ultra-dry ethyl acetate solution, respectively;

[0167] The NB-PMMA ultra-dry ethyl acetate solution, the NB-PS ultra-dry ethyl acetate solution, the Grubbs third-generation catalyst ultra-dry ethyl acetate solution (catalyst solution) and the pure ethyl acetate solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0168] (3) Polymer synthesis: The catalyst solution (flow rate set to 2.94 mL / min) and pure ethyl acetate solvent (flow rate set to 1.26 mL / min) were mixed evenly in the first T-shaped mixer, and then mixed evenly with NB-PCL ultra-dry ethyl acetate solution (solution of cycloolefin polymerization monomer 1, flow rate set to 3.00 mL / min) through the second T-shaped mixer, and then passed into the first microreactor (stainless steel circular tube reactor, the inner diameter of the tube is 2 mm, the reactor is placed in a constant temperature oil bath at 70 ° C) for polymerization reaction (ring-opening metathesis polymerization), with a residence time of 120 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactants in the first microreactor is 120 s). After the reaction is completed, the first effluent is obtained from the outlet on the other side of the first microreactor;

[0169] The first effluent and the NB-PS ultra-dry ethyl acetate solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 3.00 mL / min) were mixed uniformly in a third T-shaped mixer and introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 2 mm, heated in a constant temperature oil bath at 70°C) for polymerization (ring-opening metathesis polymerization) with a residence time of 120 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 120 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain a block copolymer solution.

[0170] (4) Dilution and Cooling: The block copolymer solution was piped into a fourth T-shaped mixer and mixed with pure ethyl acetate (flow rate set at 37.7 mL / min). The mixed solution then flowed into a stainless steel tube with an inner diameter of 4 mm for further dilution and cooling. During this process, the concentration of the block copolymer solution decreased from 94 mg / mL to 20 mg / mL. Simultaneously, the temperature of the solution was lowered from 70°C during the polymerization reaction to room temperature by air cooling in the pipe, resulting in a cooled dilute block copolymer solution.

[0171] (5) Purification: The cooled block copolymer dilute solution was passed through a column containing Silicycle DMT metal scavenger (column capacity was 20 mL) to remove the residual catalyst online to ensure that the final product was environmentally friendly and non-toxic, and a purified block copolymer solution was obtained with a polymer molecular weight of 1632 kDa.

[0172] (6) Self-assembly (bulk assembly): The purified block copolymer solution was scraped onto a polyethylene terephthalate (PET) film. After the solvent evaporated, a structural color film with a thickness of 5 μm and a wavelength of 425 ± 5 nm was obtained.

[0173] Under these conditions, the output of block copolymer-based structural color materials can reach 1.38 kg / day.

[0174] (7) Fine adjustment of structural color: When other conditions remain unchanged, by adjusting the flow rate ratio of catalyst and solvent (2.91mL / min:1.29mL / min, 2.88mL / min:1.32mL / min, 2.85mL / min:1.35mL / min, 2.82mL / min:1.38mL / min, 2.79mL / min:1.41mL / min), polymer structural color films with different structural colors are obtained. The polymer molecular weights are 1648kDa, 1664kDa, 1680kDa, 1696kDa and 1712kDa, respectively, and the maximum reflection wavelengths are 432nm, 439nm, 446nm, 452nm and 461nm, respectively. The actual pictures of these five polymer structural color films with different structural colors are shown in Figure 3 , from left to right, the corresponding maximum reflection wavelengths are 432nm, 439nm, 446nm, 452nm and 461nm respectively. Figure 3 The polymer structural color films with different structural colors are clearly displayed, further demonstrating the effectiveness and accuracy of the method of the present invention.

[0175] Comparative Example 1

[0176] The same as Example 1, except that step (2) specifically comprises: preparing NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight of 3000 Da, molecular weight distribution index of 1.10), NB-PEG (norbornene-terminated polyethylene glycol) macromonomer (molecular weight of 2000 Da, molecular weight distribution index of 1.09), and Grubbs third-generation catalyst (relative molecular mass of 884.53 Da) into 86 mmol / L, 86 mmol / L, and 2.5 mmol / L NB-PCL ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, and Grubbs third-generation catalyst ultra-dry anisole solution, respectively;

[0177] The NB-PCL ultra-dry anisole solution, the NB-PEG ultra-dry anisole solution, the Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution) and the pure anisole solvent were placed in a reservoir with a continuous infusion pump, respectively.

[0178] Step (3) is specifically as follows: the catalyst solution (flow rate is set to 8.10 mL / min) and the pure anisole solvent (flow rate is set to 8.71 mL / min) are mixed uniformly in a first T-shaped mixer, and then mixed uniformly with the NB-PCL ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 1, with a flow rate set to 12.00 mL / min) through a second T-shaped mixer, and then introduced into a first microreactor (a stainless steel circular tube reactor with an inner diameter of 4 mm, and the reactor is placed in a 70°C constant temperature oil bath for heating) to carry out a polymerization reaction (ring-opening metathesis polymerization) with a residence time of 10 s (the length of the stainless steel circular tube is adjusted so that the residence time of the reactant in the first microreactor is 10 s). After the reaction is completed, the first effluent is obtained by flowing out from the outlet on the other side of the first microreactor;

[0179] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cycloolefin polymerization monomer 2, with a flow rate set at 28.80 mL / min) were mixed uniformly in a third T-shaped mixer and introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 4 mm, heated in a constant temperature oil bath at 70° C.) for polymerization (ring-opening metathesis polymerization) with a residence time of 10 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the second microreactor was 10 s). After the reaction was completed, the block copolymer solution was discharged from the outlet on the other side of the second microreactor to obtain the block copolymer solution.

[0180] Step (4) is specially: the block copolymer solution is introduced into the fourth T-shaped mixer through a pipeline and mixed with a pure anisole solvent (flow velocity is set to 253.1mL / min), and the mixed solution flows into a stainless steel round tube with an internal diameter of 5mm, to further dilute and cool. In this process, the concentration of the block copolymer solution is reduced to 20mg / mL from 131mg / mL, and the air cooling effect of the pipeline is simultaneously applied to reduce the temperature of the solution from 70°C during the polymerization reaction to room temperature, thereby obtaining a cooled block copolymer dilute solution.

[0181] After emulsion assembly, the product has no color. This is because the residence time of the reactants in the microreactor is too short, the monomers are not completely converted, and the first monomer is incorporated into the second block of the block copolymer, resulting in an unclear chain structure and inability to phase separate to produce a structural color material with a good phase separation structure.

[0182] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for preparing a block copolymer-based structural color material, characterized in that: The following steps are involved: The monomer 1 and the catalyst solution are mixed to carry out a first polymerization reaction, the product is mixed with the monomer 2 and then subjected to a second polymerization reaction to obtain a block copolymer, and the block copolymer is self-assembled to obtain the block copolymer-based structural color material; The preparation process of the block copolymer is carried out in a series of microreactors, which include the following devices connected in series in sequence: a first T-shaped mixer for mixing a catalyst and a solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and a solution of monomer 1, a first microreactor for performing a first polymerization reaction, a third T-shaped mixer for mixing a product and a solution of monomer 2, a second microreactor for performing a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and the solvent, a diluter for diluting the block copolymer, and an adsorption column for removing the catalyst; The monomer 1 and monomer 2 are different cycloolefin polymerization monomers; The molecular weight of the cycloolefin polymerization monomer is 500 to 10000 Da; The topology of the block copolymer is bottle brush type; The temperature of the first polymerization reaction and the second polymerization reaction is 15-100° C.; the time of the first polymerization reaction is 25-120 seconds, and the time of the second polymerization reaction is 35-120 seconds; the inner diameter of the pores of the serially connected microreactors is 0.5-5 mm; The concentration of the monomer 1 solution is 40 to 86 mmol / L, and the flow rate is 0.75 to 12 mL / min; The concentration of the monomer 2 solution is 40 to 300 mmol / L, and the flow rate is 0.58 to 28.8 mL / min; The concentration of the catalyst is 0.1 to 4.0 mmol / L, and the flow rate is 0.35 to 8.10 mL / min; The flow rate of the solvent is 0.31 to 9.43 mL / min; The self-assembly is emulsion assembly or bulk assembly.

2. The method for preparing a block copolymer-based structural color material according to claim 1, characterized in that: The emulsion assembly comprises: The block copolymer solution and the PVA aqueous solution are mixed and emulsified, and the block copolymer-based structural color material is obtained after the solvent is evaporated.

3. The method for preparing a block copolymer-based structural color material according to claim 1, characterized in that: The body assembly includes: The block copolymer solution is coated on the surface of a substrate, and the block copolymer-based structural color material is obtained after the solvent evaporates.

4. A block copolymer-based structural color material prepared by the preparation method according to any one of claims 1 to 3.

5. Use of the block copolymer-based structural color material according to claim 4 in the preparation of pigments.

6. A method for finely adjusting the structural color of a block copolymer-based structural color material, characterized in that: The following steps are involved: The monomer 1 and the catalyst solution are mixed to carry out a first polymerization reaction, the product is mixed with the monomer 2 and then a second polymerization reaction is carried out to obtain a block copolymer, and the block copolymer is self-assembled to obtain a block copolymer-based structural color material; The preparation process of the block copolymer is carried out in a series of microreactors, which include the following devices connected in series in sequence: a first T-shaped mixer for mixing a catalyst and a solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and a solution of monomer 1, a first microreactor for performing a first polymerization reaction, a third T-shaped mixer for mixing a product and a solution of monomer 2, a second microreactor for performing a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and the solvent, a diluter for diluting the block copolymer, and an adsorption column for removing the catalyst; The monomer 1 and monomer 2 are different cycloolefin polymerization monomers; The molecular weight of the cycloolefin polymerization monomer is 500 to 10000 Da; The topology of the block copolymer is bottle brush type; The temperature of the first polymerization reaction and the second polymerization reaction is 15-100° C.; the time of the first polymerization reaction is 25-120 seconds, and the time of the second polymerization reaction is 35-120 seconds; the inner diameter of the pores of the serially connected microreactors is 0.5-5 mm; The concentration of the monomer 1 solution is 40 to 86 mmol / L, and the flow rate is 0.75 to 12 mL / min; The concentration of the monomer 2 solution is 40 to 300 mmol / L, and the flow rate is 0.58 to 28.8 mL / min; The concentration of the catalyst is 0.1 to 4.0 mmol / L, and the flow rate is 0.35 to 8.10 mL / min; The flow rate of the solvent is 0.31 to 9.43 mL / min; The self-assembly is emulsion assembly or bulk assembly.

7. The method according to claim 6, characterized in that The reflection wavelength of the block copolymer-based structural color material is 400-700 nm.

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