Method for finely tuning structural color of block copolymer-based structural color material

Abstract

A method for finely tuning the structural color of a block copolymer-based structural color material, relating to the technical field of polymer materials. The method for finely tuning the structural color of a block copolymer-based structural color material comprises the following steps: mixing a monomer 1 and a catalyst solution and then performing a first polymerization reaction, mixing the product and a monomer 2 and then performing a second polymerization reaction to obtain a block copolymer, and self-assembling the block copolymer to obtain the block copolymer-based structural color material. Continuous and efficient preparation of the structural color material can be realized, thereby realizing large-scale production of the structural color material, and the preparation costs of the structural color material can be significantly reduced.

Description

Fine adjustment method of structural color of block copolymer-based structural color materials Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a method for finely adjusting the structural color of block copolymer-based structural color materials. Background Technology

[0002] Structural colors originate from Bragg reflection in periodic nanostructures. These materials possess advantages such as safety, environmental friendliness, vibrant colors, resistance to photobleaching, and stimulus-responsive color changes, making them promising alternatives to traditional toxic pigments in cosmetics, environmentally friendly coatings, safe painting pigments, and anti-counterfeiting inks. Common photonic crystal structures include one-dimensional layered structures, two-dimensional columnar close-packed structures, and three-dimensional spherical stacked structures. Among these, the ordered porous structure of inverted opal has a high refractive index difference, enabling the production of more vibrant structural colors. However, the traditional colloidal particle template method is complex and difficult to scale up for application.

[0003] Block copolymer self-assembly is an effective method for preparing ordered 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-separated structures is generally <100 nm, which cannot generate a photonic bandgap in the visible light region. Therefore, to obtain structural color, it is necessary to synthesize materials with a molecular weight higher than 1 × 10⁻⁶. 6 Block copolymers, especially those with ultra-high molecular weight polymer chains, suffer from severe chain entanglement, slow self-assembly kinetics, and numerous structural defects, making them difficult to apply in practice.

[0004] Bottle-brush block copolymers (BBCPs) are ideal materials for manufacturing photonic crystal pigments. Their polymer side chains are tightly grafted onto a linear framework, reducing entanglement and enabling rapid self-assembly into photonic crystal structures with large periodic sizes exceeding 100 nm. However, the preparation of bottle-brush block copolymer-based structural color materials is currently typically carried out 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 adjust the structural color and poor reproducibility between different batches. Summary of the Invention

[0005] The purpose of this invention is to provide a method for finely adjusting the structural color of block copolymer-based structural color materials, so as to solve the problems existing in the prior art.

[0006] To achieve the above objectives, the present invention provides the following solution:

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

[0008] Monomer 1 and catalyst solution are mixed and subjected to a first polymerization reaction. The product is then mixed with monomer 2 and subjected to a second polymerization reaction to obtain a block copolymer. The block copolymer is then 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: a first T-shaped mixer for mixing the catalyst and solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and monomer 1, a first microreactor for carrying out a first polymerization reaction, a third T-shaped mixer for mixing the product and monomer 2, a second microreactor for carrying out a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and solvent, a diluent for diluting the block copolymer, and an adsorption column for removing the catalyst.

[0010] Furthermore, monomer 1 and monomer 2 are different cyclic olefin polymerization monomers;

[0011] The molecular weight of the cyclic olefin polymer monomer is 500-10000 Da;

[0012] The block copolymer has a bottle brush-like topology.

[0013] The temperatures for the first and second polymerization reactions are 15–100°C.

[0014] The pore inner diameter of the series-connected microreactors is 0.5–5 mm.

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

[0016] Furthermore, monomer 1 and monomer 2 are each independently selected from any one of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polypropylene oxide, polystyrene, polydimethylsiloxane, polycaprolactone, polylactide, tert-butyl polyacrylate, and polymethyl methacrylate containing norbornene groups.

[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 either emulsion assembly or bulk assembly.

[0019] Further, the emulsion assembly includes:

[0020] The block copolymer solution and PVA aqueous solution were mixed and emulsified. After the solvent evaporated, the block copolymer-based structural color material was obtained.

[0021] Furthermore, the body assembly includes:

[0022] A solution of the block copolymer is coated onto 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: the application of the above-mentioned block copolymer-based structural color material in pigment preparation.

[0025] The fourth technical solution 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] Monomer 1 and catalyst solution are mixed and subjected to a first polymerization reaction. The product is then mixed with monomer 2 and subjected to a second polymerization reaction to obtain a block copolymer. The block copolymer self-assembles to obtain a block copolymer-based structural color material.

[0027] Furthermore, the reflection wavelength of the block copolymer-based structural color material is 400–700 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: a first T-shaped mixer for mixing the catalyst and solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and monomer 1, a first microreactor for carrying out a first polymerization reaction, a third T-shaped mixer for mixing the product and monomer 2, a second microreactor for carrying out a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and solvent, a diluent for diluting the block copolymer, and an adsorption column for removing the catalyst.

[0029] Furthermore, monomer 1 and monomer 2 are different cyclic olefin polymerization monomers;

[0030] The molecular weight of the cyclic olefin polymer monomer is 500-10000 Da;

[0031] The block copolymer has a bottle brush-like topology.

[0032] The temperatures for the first and second polymerization reactions are 15–100°C.

[0033] The pore inner diameter of the series-connected microreactors is 0.5–5 mm.

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

[0035] Furthermore, monomer 1 and monomer 2 are each independently selected from any one of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polypropylene oxide, polystyrene, polydimethylsiloxane, polycaprolactone, polylactide, tert-butyl polyacrylate, and polymethyl methacrylate containing norbornene groups.

[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 either emulsion assembly or bulk assembly.

[0038] Further, the emulsion assembly includes:

[0039] The block copolymer solution and PVA aqueous solution were mixed and emulsified. After the solvent evaporated, the block copolymer-based structural color material was obtained.

[0040] Furthermore, the body assembly includes:

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

[0042] This invention allows for precise control of key reaction parameters during the preparation process, enabling the large-scale production of block copolymer-based structural color materials with vibrant structural colors and achieving fine control over the structural color. The method of this invention overcomes the technical bottlenecks of traditional batch preparation methods, which limit the color of structural color materials to fine adjustments and the gram-scale synthesis, providing a feasible solution for the industrial production of bottle brush 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 precisely control the molecular weight of block copolymer-based structural color materials, thereby achieving fine adjustment of structural color, and can make structural color materials 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 compatible with automated production, which makes it possible to build a color library of efficient and low-cost structural color materials. At the same time, it promotes the transformation from laboratory research to commercial products and provides a new way for the development of environmentally friendly and health-friendly pigments.

[0047] Furthermore, the synthesis strategy of this invention has broad application prospects and can be extended to a variety of block copolymer-based assembly materials, covering multiple fields such as ultrasoft elastomers, organic optoelectronics, photolithography, energy storage, and biomedical devices. It provides a blueprint for industrial production, significantly reduces production costs, and promotes the development of block copolymer-based assembly materials. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

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

[0050] Figure 2 is a schematic diagram of a special pore reactor. Detailed Implementation

[0051] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0052] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0053] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0054] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0055] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0056] In a first aspect, the present invention provides a method for preparing a block copolymer-based structural color material, comprising the following steps:

[0057] The outlets of the continuous delivery pumps for the solvent and catalyst solutions are connected to the two inlets of the first T-shaped mixer, respectively.

[0058] Connect the outlet of the first T-shaped mixer to one inlet of the second T-shaped mixer;

[0059] Connect the outlet of the continuous delivery pump of the solution of cyclic olefin monomer 1 to another inlet of the second T-shaped mixer;

[0060] Connect the outlet of the second T-shaped mixer to the inlet on one side of the first microreactor;

[0061] Connect the outlet on the other side of the first microreactor to one inlet of the third T-shaped mixer;

[0062] Connect the outlet of the continuous delivery pump of the solution of cyclic olefin monomer 2 to another inlet of the third T-shaped mixer;

[0063] Connect the outlet of the third T-shaped mixer to the inlet on one side of the second microreactor;

[0064] Connect the outlet on the other side of the second microreactor to one inlet of the fourth T-shaped mixer;

[0065] Connect the solvent to another inlet of the fourth T-shaped mixer, and connect the outlet of the fourth T-shaped mixer to the inlet of the diluent;

[0066] The outlet of the diluent is connected to the inlet of an adsorption column packed with metal scavenging agent, and the purified block copolymer solution is collected at the outlet of the adsorption column packed with metal scavenging agent.

[0067] The specific steps are as follows:

[0068] (1) The solvent and catalyst solution are mixed evenly through the first T-shaped mixer and then mixed evenly with the cyclic olefin polymerization monomer 1 solution through the second T-shaped mixer. The mixture is then introduced into the first microreactor for polymerization reaction (ring-opening metathesis polymerization, the polymerization reaction time is 25-120s). After the reaction is completed, the mixture flows out from the outlet on the other side of the first microreactor to obtain the first effluent.

[0069] (2) The first effluent and the solution of cyclic olefin monomer 2 are mixed evenly through the third T-shaped mixer and then introduced into the second microreactor for polymerization reaction (ring-opening metathesis polymerization, the polymerization reaction time is 35-120s). After the reaction is completed, the solution flows out from the outlet on the other side of the second microreactor to obtain the block copolymer solution.

[0070] (3) The block copolymer solution and solvent are mixed through a fourth T-shaped mixer, and then passed into a diluent (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 diluted solution.

[0071] (4) The cooled block copolymer dilution solution is passed through an adsorption column packed with metal scavenger for purification to obtain a purified block copolymer solution.

[0072] (5) Block copolymer-based structural color materials are continuously and precisely prepared in large quantities by self-assembly using purified block copolymer solutions.

[0073] The solvent, catalyst solution, cyclic olefin polymerization monomer 1 solution, and cyclic olefin polymerization monomer 2 solution are respectively placed in a storage tank equipped with a continuous infusion pump; the first microreactor and the second microreactor are respectively placed in an oil bath for temperature control;

[0074] In a specific embodiment of the present invention, the catalyst in the catalyst solution is a third-generation Grubbs catalyst.

[0075] 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 minimal changes in reflection wavelength, such as 500 nm, 505 nm, 510 nm, etc.).

[0076] In a specific embodiment of the present invention, the topology of the block copolymer is bottle brush type;

[0077] The polymerization reaction temperature is 15–100℃;

[0078] The inner diameter of the pipes in both the first and second microreactors is 0.5–5 mm; both the first and second microreactors are circular tube type or special channel type reactors (enhanced straight tube type, Z-shaped, S-shaped, etc.); a schematic diagram of the special channel reactor is shown in Figure 2.

[0079] In a specific embodiment of the present invention, the molecular weight of the cyclic olefin polymer monomer is 500 to 10000 Da;

[0080] Cyclic olefin monomer 1 and cyclic olefin monomer 2 are each independently selected from any one of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polypropylene oxide, polystyrene, polydimethylsiloxane, polycaprolactone, polylactide, tert-butyl polyacrylate and polymethyl methacrylate containing norbornene groups, and cyclic olefin monomer 1 and cyclic olefin monomer 2 are different substances;

[0081] The solvents used in preparing the solutions of cyclic olefin monomer 1, cyclic olefin monomer 2, and catalyst include any one of toluene, dichloromethane, chloroform, ethyl acetate, butyl acetate, anisole, and phenethyl ether.

[0082] In a specific embodiment of the present invention, self-assembly is either emulsion assembly or bulk assembly.

[0083] In a specific embodiment of the present invention, emulsion assembly includes:

[0084] The purified block copolymer solution and PVA aqueous solution were mixed and emulsified. After the solvent evaporated, the block copolymer-based structural color material (structural color microspheres) was obtained.

[0085] In a specific embodiment of the present invention, the body assembly includes:

[0086] The purified block copolymer solution was coated onto the substrate surface, and after the solvent evaporated, the block copolymer-based structural color material (structural color film) was obtained.

[0087] Furthermore, the coating method is selected from any one of spraying, scraping, and brushing.

[0088] In a specific embodiment of the present invention, the concentration of the cyclic olefin monomer 1 solution is 40–86 mmol / L, and the flow rate is 0.75–12 mL / min; the concentration of the cyclic olefin monomer 2 solution is 40–300 mmol / L, and the flow rate is 0.58–28.8 mL / min; the concentration of the catalyst solution is 0.1–4.0 mmol / L, and the flow rate is 0.35–8.10 mL / min; in the first T-shaped mixer, the flow rate of the pure solvent mixed with the catalyst is 0.31–9.43 mL / min.

[0089] Figure 1 shows a schematic diagram of the continuous preparation process of block copolymer-based structural color materials.

[0090] In a second aspect, the present invention provides a block copolymer-based structural color material prepared by the above-described preparation method.

[0091] In a third aspect, the present invention provides an application of the above-mentioned block copolymer-based structural color material in pigment preparation.

[0092] In a fourth aspect, the present invention provides a method for finely adjusting the structural color of a block copolymer-based structural color material, which is the same as the method for preparing the block copolymer-based structural color material.

[0093] Example 1

[0094] A method for finely adjusting the structural color of block copolymer-based structural color materials:

[0095] (1) Setting up the reaction system: Connect the outlet of the continuous delivery pump for the solvent and catalyst solution to the two inlets of the first T-shaped mixer, respectively;

[0096] Connect the outlet of the first T-shaped mixer to one inlet of the second T-shaped mixer;

[0097] Connect the outlet of the continuous delivery pump of the solution of cyclic olefin monomer 1 to another inlet of the second T-shaped mixer;

[0098] Connect the outlet of the second T-shaped mixer to the inlet on one side of the first microreactor;

[0099] Connect the outlet on the other side of the first microreactor to one inlet of the third T-shaped mixer;

[0100] Connect the outlet of the continuous delivery pump of the solution of cyclic olefin monomer 2 to another inlet of the third T-shaped mixer;

[0101] Connect the outlet of the third T-shaped mixer to the inlet on one side of the second microreactor;

[0102] Connect the outlet on the other side of the second microreactor to one inlet of the fourth T-shaped mixer;

[0103] Connect the solvent to another inlet of the fourth T-shaped mixer, and connect the outlet of the fourth T-shaped mixer to the inlet of the diluent;

[0104] The outlet of the diluent is connected to the inlet of an adsorption column packed with metal scavenging agent, and the purified block copolymer solution is collected at the outlet of the adsorption column packed with metal scavenging agent.

[0105] (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 mass 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.

[0106] NB-PCL ultra-dry toluene solution, NB-PEG ultra-dry toluene solution, Grubbs third-generation catalyst ultra-dry toluene solution (catalyst solution) and pure toluene solvent were placed in storage tanks equipped with continuous infusion pumps.

[0107] (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 cyclic olefin polymerization monomer 1, flow rate set to 0.75 mL / min) through the second T-shaped mixer. The mixture was then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter of 500 μm, reactor placed in a 70℃ constant temperature oil bath for heating) to carry out the polymerization reaction (ring-opening metathesis polymerization). The residence time was 25 s (the length of the stainless steel circular tube was adjusted so that the residence time of the reactants in the first microreactor was 25 s). After the reaction was completed, the first effluent flowed out from the outlet on the other side of the first microreactor.

[0108] The first effluent and the NB-PEG ultra-dry toluene solution (a solution of cyclic olefin monomer 2, with a flow rate set at 1.05 mL / min) are mixed evenly through a third T-shaped mixer and then introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 500 μm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time is 35 s (the length of the stainless steel circular tube is adjusted to ensure that the residence time of the reactants in the second microreactor is 35 s). After the reaction is completed, the block copolymer solution flows out from the outlet on the other side of the second microreactor.

[0109] (4) Dilution and Cooling: The block copolymer solution was piped into the fourth T-shaped mixer and mixed with pure toluene solvent (flow rate set at 15.2 mL / min). The mixed solution 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. At the same time, the temperature of the solution was lowered from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0110] (5) Purification: The cooled block copolymer dilution solution is passed through a column containing Silicycle DMT metal scavenger (the column capacity is 8 mL) to remove residual catalyst online, ensuring that the final product is environmentally friendly and non-toxic, and obtaining a purified block copolymer solution.

[0111] (6) Self-assembly (emulsion assembly): 100 mL of purified block copolymer solution was collected into a 2 L beaker containing 1 L PVA aqueous solution. Then, the mixture was stirred at 6000 r / min for 30 s using a high-speed homogenizer to form a water-in-oil (O / W) emulsion through 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, and a blue block copolymer-based structural color material was obtained. The polymer molecular weight was 181 kDa and the maximum reflection wavelength was 461 ± 5 nm.

[0112] Under these conditions, the production of block copolymer-based structural color materials can reach 0.52 kg / day.

[0113] Preparation of PVA aqueous solution: Dissolve polyvinyl alcohol (molecular weight of 20,000 to 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.

[0114] (7) Fine adjustment of structural color: Under the condition that other conditions remain 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, and the maximum reflection wavelengths were 411 nm, 428 nm, 452 nm, 477 nm and 486 nm, respectively.

[0115] Example 2

[0116] Same as Example 1, except that step (2) is as follows: NB-PCL (norbornene-terminated polycaprolactone) macromonomer (molecular weight of 3000 Da, molecular weight distribution index of 1.10), NB-PEO (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) 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;

[0117] 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 storage tanks equipped with continuous infusion pumps.

[0118] 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.

[0119] Under these conditions, the production of block copolymer-based structural color materials can reach 0.52 kg / day.

[0120] Step (7) specifically involves fine-tuning the structural color while keeping other conditions constant: By adjusting the flow rate ratios of the 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 151 kDa, 166 kDa, 186 kDa, 194 kDa, and 206 kDa, with maximum reflection wavelengths of 413 nm, 430 nm, 447 nm, 472 nm, and 481 nm, respectively. When only the solvent was changed and other conditions remained constant, the structural color of the obtained structural color materials did not change significantly, indicating good reproducibility of the method.

[0121] Example 3

[0122] Same as Example 1, except that step (2) is specifically as follows: 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) are respectively prepared 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;

[0123] NB-PCL ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution), and pure anisole solvent were placed in storage tanks equipped with continuous infusion pumps.

[0124] Step (3) is as follows: The catalyst solution (flow rate set to 2.73 mL / min) and pure anisole solvent (flow rate set to 1.48 mL / min) are mixed evenly in the first T-shaped mixer and then mixed evenly with NB-PCL ultra-dry anisole solution (solution of cyclic olefin polymerization monomer 1, flow rate set to 3.00 mL / min) through the second T-shaped mixer. The mixture is then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter is 1 mm, reactor is heated in a 70℃ constant temperature oil bath) for polymerization reaction (ring-opening metathesis polymerization). The residence time is 35 s (adjust the length of the stainless steel circular tube so that the residence time of the reactants in the first microreactor is 35 s). After the reaction is completed, the first effluent flows out from the outlet on the other side of the first microreactor.

[0125] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cyclic olefin monomer 2, with a flow rate set at 4.20 mL / min) are mixed evenly through a third T-shaped mixer and then introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 1 mm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time is 45 s (the length of the stainless steel circular tube is adjusted to ensure that the residence time of the reactants in the second microreactor is 45 s). After the reaction is completed, the block copolymer solution flows out from the outlet on the other side of the second microreactor.

[0126] Step (4) specifically involves: introducing the block copolymer solution through a pipe into a fourth T-shaped mixer and mixing it with pure anisole solvent (flow rate set to 60.1 mL / min). The mixed solution then flows 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 decreases from 127 mg / mL to 20 mg / mL, while the temperature of the solution is reduced from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0127] 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.

[0128] Under these conditions, the production of block copolymer-based structural color materials can reach 2.08 kg / day.

[0129] Step (7) specifically involves: under the condition that other conditions remain unchanged, by adjusting the flow rate ratio of the catalyst and solvent (2.64 mL / min: 1.55 mL / min, 2.58 mL / min: 1.62 mL / min, 2.52 mL / min: 1.68 mL / min, 2.46 mL / min: 1.74 mL / min, 2.40 mL / min: 1.80 mL / min), polymer porous microspheres with different structural colors are obtained. The polymer molecular weights are 185 kDa, 189 kDa, 194 kDa, 199 kDa and 205 kDa, and the maximum reflection wavelengths are 445 nm, 452 nm, 464 nm, 471 nm and 480 nm, respectively.

[0130] Example 4

[0131] Same as Example 1, except that step (2) is specifically as follows: 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) are respectively prepared 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;

[0132] NB-PCL ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution), and pure anisole solvent were placed in storage tanks equipped with continuous infusion pumps.

[0133] Step (3) is as follows: The catalyst solution (flow rate set to 8.10 mL / min) and pure anisole solvent (flow rate set to 8.71 mL / min) are mixed evenly in the first T-shaped mixer and then mixed evenly with NB-PCL ultra-dry anisole solution (solution of cyclic olefin polymerization monomer 1, flow rate set to 12.00 mL / min) through the second T-shaped mixer. The mixture is then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter is 4 mm, reactor is heated in a 70℃ constant temperature oil bath) for polymerization reaction (ring-opening metathesis polymerization). The residence time is 90 s (adjust the length of the stainless steel circular tube so that the residence time of the reactants in the first microreactor is 90 s). After the reaction is completed, the first effluent flows out from the outlet on the other side of the first microreactor.

[0134] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cyclic olefin monomer 2, with a flow rate set at 28.80 mL / min) are mixed evenly through a third T-shaped mixer and then fed into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 4 mm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time is 90 s (the length of the stainless steel circular tube is adjusted to ensure that the residence time of the reactants in the second microreactor is 90 s). After the reaction is completed, the block copolymer solution flows out from the outlet on the other side of the second microreactor.

[0135] Step (4) specifically involves: introducing the block copolymer solution through a pipe into a fourth T-shaped mixer and mixing it with pure anisole solvent (flow rate set to 253.1 mL / min). The mixed solution then flows into a stainless steel circular tube with an inner diameter of 5 mm for further dilution and cooling. During this process, the concentration of the block copolymer solution decreases from 131 mg / mL to 20 mg / mL, while the temperature of the solution is reduced from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0136] 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.

[0137] Under these conditions, the production capacity of block copolymer-based structural color materials can reach 8.62 kg / day.

[0138] Step (7) specifically involves: under the condition that other conditions remain unchanged, by adjusting the flow rate ratio of the catalyst and solvent (7.94 mL / min: 8.86 mL / min, 7.79 mL / min: 9.01 mL / min, 7.64 mL / min: 9.15 mL / min, 7.51 mL / min: 9.29 mL / min, 7.37 mL / min: 9.43 mL / min), polymer porous microspheres with different structural colors are obtained. The polymer molecular weights are 182 kDa, 185 kDa, 191 kDa, 195 kDa and 203 kDa, and the maximum reflection wavelengths are 444 nm, 451 nm, 462 nm, 470 nm and 479 nm, respectively.

[0139] Example 5

[0140] Same as Example 1, except that step (2) is specifically as follows: NB-PS (norbornene-terminated polystyrene) macromonomer (molecular weight of 8000 Da, molecular weight distribution index of 1.20), NB-PEG (norbornene-terminated polyvinylpyrrolidone) macromonomer (molecular weight of 500 Da, molecular weight distribution index of 1.07), and Grubbs third-generation catalyst (relative molecular weight of 884.53 Da) are respectively prepared into 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.

[0141] NB-PS ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution), and pure anisole solvent were placed in storage tanks equipped with continuous infusion pumps.

[0142] Step (3) is as follows: The catalyst solution (flow rate set to 1.78 mL / min) and pure anisole solvent (flow rate set to 2.42 mL / min) are mixed evenly in the first T-shaped mixer and then mixed evenly with NB-PS ultra-dry anisole solution (solution of cyclic olefin polymerization monomer 1, flow rate set to 3.00 mL / min) through the second T-shaped mixer. The mixture is then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter is 1 mm, reactor is heated in a 70℃ constant temperature oil bath) for polymerization reaction (ring-opening metathesis polymerization). The residence time is 60 s (adjust the length of the stainless steel circular tube so that the residence time of the reactants in the first microreactor is 60 s). After the reaction is completed, the first effluent flows out from the outlet on the other side of the first microreactor.

[0143] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cyclic olefin monomer 2, with a flow rate set at 6.00 mL / min) are mixed evenly through a third T-shaped mixer and then introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 1 mm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time is 90 s (the length of the stainless steel circular tube is adjusted to ensure that the residence time of the reactants in the second microreactor is 90 s). After the reaction is completed, the block copolymer solution flows out from the outlet on the other side of the second microreactor.

[0144] Step (4) specifically involves: introducing the block copolymer solution through a pipe into a fourth T-shaped mixer and mixing it with pure anisole solvent (flow rate set to 79.2 mL / min). The mixed solution then flows 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 decreases from 140 mg / mL to 20 mg / mL, while the temperature of the solution is reduced from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0145] 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.

[0146] Under these conditions, the production of block copolymer-based structural color materials can reach 2.68 kg / day.

[0147] Step (7) specifically involves: under the condition that other conditions remain unchanged, by adjusting the flow rate ratio of catalyst and solvent (1.71 mL / min: 2.49 mL / min, 1.65 mL / min: 2.54 mL / min, 1.60 mL / min: 2.60 mL / min, 1.55 mL / min: 2.65 mL / min, 1.50 mL / min: 2.70 mL / min), polymer porous microspheres with different structural colors are obtained. The polymer molecular weights are 310 kDa, 325 kDa, 341 kDa, 356 kDa and 372 kDa, and the maximum reflection wavelengths are 621 nm, 632 nm, 640 nm, 647 nm and 658 nm, respectively.

[0148] Example 6

[0149] A method for finely adjusting the structural color of block copolymer-based structural color materials:

[0150] (1) Setup of the reaction system: Same as in Example 1.

[0151] (2) Solution preparation: NB-PS (norbornene-terminated polystyrene) macromonomer (molecular weight of 4000 Da, molecular weight distribution index of 1.16), NB-PEG (norbornene-terminated polyethylene glycol) macromonomer (molecular weight of 4000 Da, molecular weight distribution index of 1.13), and Grubbs third-generation catalyst (relative molecular mass of 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.

[0152] The NB-PS ultra-dry ethyl acetate solution, NB-PEG ultra-dry ethyl acetate solution, Grubbs third-generation catalyst ultra-dry ethyl acetate solution (catalyst solution), and pure ethyl acetate solvent were placed in storage tanks equipped with continuous infusion pumps.

[0153] (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) are mixed evenly in the first T-shaped mixer and then mixed evenly with NB-PCL ultra-dry ethyl acetate solution (solution of cyclic olefin polymerization monomer 1, flow rate set to 3.00 mL / min) through the second T-shaped mixer. The mixture is then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter of 2 mm, reactor placed in a 70℃ constant temperature oil bath for heating) to carry out the polymerization reaction (ring-opening metathesis polymerization). The residence time is 100 s (adjust the length of the stainless steel circular tube so that the residence time of the reactants in the first microreactor is 100 s). After the reaction is completed, the first effluent flows out from the outlet on the other side of the first microreactor.

[0154] The first effluent and the NB-PEG ultra-dry ethyl acetate solution (a solution of cyclic olefin monomer 2, with a flow rate set at 3.00 mL / min) were mixed evenly through a third T-shaped mixer and then introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 2 mm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time was 120 s (the length of the stainless steel circular tube was adjusted to ensure that the residence time of the reactants in the second microreactor was 120 s). After the reaction was completed, the block copolymer solution was obtained by flowing out from the outlet on the other side of the second microreactor.

[0155] (4) Dilution and Cooling: The block copolymer solution was piped into the fourth T-shaped mixer and mixed with pure ethyl acetate solvent (flow rate set at 37.7 mL / min). The mixed solution flowed into a stainless steel round 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. At the same time, the temperature of the solution was lowered from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0156] (5) Purification: The cooled block copolymer dilution solution was passed through a column containing Silicycle DMT metal scavenger (the column capacity was 20 mL) to remove residual catalyst online, ensuring that the final product is environmentally friendly and non-toxic, and a purified block copolymer solution with a polymer molecular weight of 2010 kDa was obtained.

[0157] (6) Self-assembly (bulk assembly): The purified block copolymer solution is coated onto a polyethylene terephthalate (PET) film. After the solvent evaporates, a structural color film with a thickness of 5 μm and a wavelength of 521 ± 5 nm is obtained.

[0158] Under these conditions, the production of block copolymer-based structural color materials can reach 1.38 kg / day.

[0159] (7) Fine adjustment of structural color: Under the condition that other conditions remain unchanged, polymer structural color films with different structural colors were obtained by adjusting the flow rate ratio of catalyst and solvent (2.34 mL / min:1.86 mL / min, 2.32 mL / min:1.88 mL / min, 2.30 mL / min:1.90 mL / min, 2.28 mL / min:1.92 mL / min, 2.26 mL / min:1.94 mL / min). The polymer molecular weights were 2026 kDa, 2042 kDa, 2058 kDa, 2074 kDa and 2089 kDa, and the maximum reflection wavelengths were 526 nm, 532 nm, 540 nm, 547 nm and 558 nm, respectively.

[0160] Example 7

[0161] A method for finely adjusting the structural color of block copolymer-based structural color materials:

[0162] (1) Setup of the reaction system: Same as in Example 1.

[0163] (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 mass 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.

[0164] NB-PMMA ultra-dry ethyl acetate solution, NB-PS ultra-dry ethyl acetate solution, Grubbs third-generation catalyst ultra-dry ethyl acetate solution (catalyst solution), and pure ethyl acetate solvent were placed in storage tanks equipped with continuous infusion pumps.

[0165] (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) are mixed evenly in the first T-shaped mixer and then mixed evenly with NB-PCL ultra-dry ethyl acetate solution (solution of cyclic olefin polymerization monomer 1, flow rate set to 3.00 mL / min) through the second T-shaped mixer. The mixture is then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter of 2 mm, reactor placed in a 70℃ constant temperature oil bath for heating) to carry out the polymerization reaction (ring-opening metathesis polymerization). The residence time is 120 s (adjust the length of the stainless steel circular tube so that the residence time of the reactants in the first microreactor is 120 s). After the reaction is completed, the first effluent flows out from the outlet on the other side of the first microreactor.

[0166] The first effluent and the NB-PS ultra-dry ethyl acetate solution (a solution of cyclic olefin monomer 2, with a flow rate set at 3.00 mL / min) were mixed evenly through a third T-shaped mixer and then introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 2 mm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time was 120 s (the length of the stainless steel circular tube was adjusted to ensure that the residence time of the reactants in the second microreactor was 120 s). After the reaction was completed, the block copolymer solution was obtained by flowing out from the outlet on the other side of the second microreactor.

[0167] (4) Dilution and Cooling: The block copolymer solution was piped into the fourth T-shaped mixer and mixed with pure ethyl acetate solvent (flow rate set at 37.7 mL / min). The mixed solution flowed into a stainless steel round 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. At the same time, the temperature of the solution was lowered from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0168] (5) Purification: The cooled block copolymer dilution solution was passed through a column containing Silicycle DMT metal scavenger (the column capacity was 20 mL) to remove residual catalyst online, ensuring that the final product is environmentally friendly and non-toxic, and a purified block copolymer solution with a polymer molecular weight of 1632 kDa was obtained.

[0169] (6) Self-assembly (bulk assembly): The purified block copolymer solution is coated onto a polyethylene terephthalate (PET) film. After the solvent evaporates, a structural color film with a thickness of 5 μm and a wavelength of 425 ± 5 nm is obtained.

[0170] Under these conditions, the production of block copolymer-based structural color materials can reach 1.38 kg / day.

[0171] (7) Fine adjustment of structural color: Under the condition that other conditions remain unchanged, polymer structural color films with different structural colors were obtained by adjusting the flow rate ratio of catalyst and solvent (2.91 mL / min: 1.29 mL / min, 2.88 mL / min: 1.32 mL / min, 2.85 mL / min: 1.35 mL / min, 2.82 mL / min: 1.38 mL / min, 2.79 mL / min: 1.41 mL / min). The polymer molecular weights were 1648 kDa, 1664 kDa, 1680 kDa, 1696 kDa and 1712 kDa, and the maximum reflection wavelengths were 432 nm, 439 nm, 446 nm, 452 nm and 461 nm, respectively.

[0172] Comparative Example 1

[0173] Same as Example 1, except that step (2) is specifically as follows: 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) are respectively prepared 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;

[0174] NB-PCL ultra-dry anisole solution, NB-PEG ultra-dry anisole solution, Grubbs third-generation catalyst ultra-dry anisole solution (catalyst solution), and pure anisole solvent were placed in storage tanks equipped with continuous infusion pumps.

[0175] Step (3) is as follows: The catalyst solution (flow rate set to 8.10 mL / min) and pure anisole solvent (flow rate set to 8.71 mL / min) are mixed evenly in the first T-shaped mixer and then mixed evenly with NB-PCL ultra-dry anisole solution (solution of cyclic olefin polymerization monomer 1, flow rate set to 12.00 mL / min) through the second T-shaped mixer. The mixture is then introduced into the first microreactor (stainless steel circular tube reactor, pipe inner diameter is 4 mm, reactor is heated in a 70℃ constant temperature oil bath) for polymerization reaction (ring-opening metathesis polymerization). The residence time is 10 s (adjust the length of the stainless steel circular tube so that the residence time of the reactants in the first microreactor is 10 s). After the reaction is completed, the first effluent flows out from the outlet on the other side of the first microreactor.

[0176] The first effluent and the NB-PEG ultra-dry anisole solution (a solution of cyclic olefin monomer 2, with a flow rate set at 28.80 mL / min) are mixed evenly through a third T-shaped mixer and then introduced into a second microreactor (a stainless steel circular tube reactor with an inner diameter of 4 mm, heated in a 70°C constant temperature oil bath) for polymerization (ring-opening metathesis polymerization). The residence time is 10 s (the length of the stainless steel circular tube is adjusted to ensure that the residence time of the reactants in the second microreactor is 10 s). After the reaction is completed, the block copolymer solution flows out from the outlet on the other side of the second microreactor.

[0177] Step (4) specifically involves: introducing the block copolymer solution through a pipe into a fourth T-shaped mixer and mixing it with pure anisole solvent (flow rate set to 253.1 mL / min). The mixed solution then flows into a stainless steel circular tube with an inner diameter of 5 mm for further dilution and cooling. During this process, the concentration of the block copolymer solution decreases from 131 mg / mL to 20 mg / mL, while the temperature of the solution is reduced from 70°C during the polymerization reaction to room temperature through air cooling in the pipe, resulting in a cooled diluted block copolymer solution.

[0178] After emulsion assembly, the product is colorless. This is because the residence time of the reactants in the microreactor is too short, and the monomers are not completely converted. This causes the first monomer to be incorporated into the second block of the block copolymer, resulting in an unclear chain structure and the inability to separate the phases to produce a structurally colored material with a good phase separation structure.

[0179] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for preparing a block copolymer-based structural color material, characterized in that, Includes the following steps: Monomer 1 and catalyst solution are mixed and subjected to a first polymerization reaction. The product is then mixed with monomer 2 and subjected to a second polymerization reaction to obtain a block copolymer. The block copolymer is then self-assembled to obtain the block copolymer-based structural color material.

2. The method for preparing the block copolymer-based structural color material according to claim 1, characterized in that, The block copolymer preparation process is carried out in a series of microreactors, which include the following devices connected in series: a first T-shaped mixer for mixing the catalyst and solvent to prepare a catalyst solution, a second T-shaped mixer for mixing the catalyst solution and monomer 1, a first microreactor for carrying out a first polymerization reaction, a third T-shaped mixer for mixing the product and monomer 2, a second microreactor for carrying out a second polymerization reaction, a fourth T-shaped mixer for mixing the block copolymer and solvent, a diluent for diluting the block copolymer, and an adsorption column for removing the catalyst.

3. The method for preparing block copolymer-based structural color materials according to claim 2, characterized in that, Monomer 1 and monomer 2 are different cyclic olefin polymerization monomers; Or, the molecular weight of the cyclic olefin polymer monomer is 500 to 10000 Da; Or, the block copolymer has a bottle brush-like topology; And / or, the temperatures of the first polymerization reaction and the second polymerization reaction are 15–100°C; And / or, the pore inner diameter of the series-connected microreactors is 0.5–5 mm.

4. The method for preparing the block copolymer-based structural color material according to claim 1, characterized in that, The self-assembly is either emulsion assembly or bulk assembly.

5. The method for preparing the block copolymer-based structural color material according to claim 4, characterized in that, The emulsion assembly includes: The block copolymer solution and PVA aqueous solution were mixed and emulsified. After the solvent evaporated, the block copolymer-based structural color material was obtained.

6. The method for preparing the block copolymer-based structural color material according to claim 4, characterized in that, The body assembly includes: A solution of the block copolymer is coated onto the surface of a substrate, and the block copolymer-based structural color material is obtained after the solvent evaporates.

7. A block copolymer-based structural color material prepared by the preparation method according to any one of claims 1 to 6.

8. The application of the block copolymer-based structural color material of claim 7 in pigment preparation.

9. A method for finely adjusting the structural color of a block copolymer-based structural color material, characterized in that, Includes the following steps: Monomer 1 and catalyst solution are mixed and subjected to a first polymerization reaction. The product is then mixed with monomer 2 and subjected to a second polymerization reaction to obtain a block copolymer. The block copolymer self-assembles to obtain a block copolymer-based structural color material.

10. The method according to claim 9, characterized in that, The reflection wavelength of the block copolymer-based structural color material is 400–700 nm.

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