Synthetic method of bottle brush block polymer with high refractive index difference and degradable structural color material

Abstract

The invention discloses a high-refractive-index-difference bottle brush block polymer and a synthetic method of a degradable structural color material, and belongs to the technical field of organic polymers. The end group of the high-refractive-index degradable macromonomer is a cycloolefin derivative capable of performing sequential ring-opening metathesis polymerization reaction (ROMP), and the main chain is a degradable polymer prepared by performing ring-opening copolymerization reaction on styrene oxide (SO) and a comonomer. A series of novel degradable cycloolefin macromonomers are designed and synthesized to replace polystyrene and other non-degradable high-refractive-index polymers commonly used in the field, and the macromonomers and a block copolymer brush are synthesized through ring-opening polymerization and ring-opening metathesis polymerization. And an environment-friendly structural color material capable of covering a full visible light wave band is further prepared by utilizing a phase separation mechanism.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic polymers, in particular to a synthesis method of bottlebrush block polymers with high refractive index difference and degradable structural color materials. BACKGROUND

[0002] Photonic crystals (PCs) are a class of materials with periodic dielectric structures, whose microstructure can realize precise regulation of light propagation behavior. Using the principle of block copolymer microphase separation, different types of photonic crystals can be prepared, providing an effective way for the simple and low-cost preparation of biomimetic optical materials. Among them, the molecular conformation of bottlebrush block copolymers (BBCPs) is special, which is composed of a single high molecular backbone densely grafted with high density of tightly arranged high molecular side chain array, with less intermolecular chain entanglement, fast self-assembly rate, and good research value.

[0003] In the past two decades, a variety of brush-shaped block copolymers with different chemical structures have been successfully designed and synthesized, and assembled into photonic crystal materials with structural color. Taking layered photonic crystals as an example, according to the reflection intensity formula, the structural color needs to have a certain refractive index difference between the two phases. Polystyrene (PS) is often chosen as the key block in the brush-shaped block copolymer due to its high refractive index. However, the application of PS component also brings a series of problems: first, the polymerization process of PS is highly sensitive to reaction conditions, and precise control of the free radical polymerization process is required, which poses a serious challenge in industrial production; second, its non-degradable nature raises concerns about environmental sustainability. Especially when such materials are widely used in disposable cosmetics and other fields, the potential problem of microplastic pollution cannot be ignored, so further improvement is still needed. SUMMARY

[0004] The present application aims to provide a synthesis method of bottlebrush block polymers with high refractive index difference and degradable structural color materials to solve the above problems in the background art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] One of the technical solutions of the present application: a high refractive index degradable macromonomer is provided, the end group of the high refractive index degradable macromonomer is a cycloalkene derivative capable of undergoing sequential ring-opening metathesis polymerization (ROMP), and the main chain is a degradable polymer prepared by ring-opening copolymerization of styrene oxide (SO) and other monomers.

[0007] Preferably, the species of the cyclic olefin derivative include a cyclopropene end group, a cyclobutene end group, a norbornene end group, a cyclopentene end group, a cyclohexene end group, or a cyclooctene end group (see Figure 1 ).

[0008] Preferably, the species of the comonomer include a cyclic sulfide monomer, a cyclic anhydride monomer, a cyclic thioanhydride monomer, or other compounds; the cyclic sulfide monomer is ethane sulfide, propane sulfide, or a thietane; the anhydride monomer is phthalic anhydride, maleic anhydride, or glutaric anhydride; the thioanhydride monomer is thiohydroxyacetic anhydride, N-carboxyanhydride, or thio-phthalic anhydride; and the other compounds are carbon monoxide, carbon dioxide, oxysulfur carbon, and sulfide carbon Figure 2 ).

[0009] Preferably, the high-refractive-index degradable macromonomer has a refractive index n > 1.55 and a molecular weight of 2.5 x 10 2 - 1.0 x 10 4 Da.

[0010] The second technical solution of the present application provides a synthesis method of the high-refractive-index degradable macromonomer as described above, comprising the following steps:

[0011] The cyclic olefin derivative, the oxidized styrene, the cyclic monomer, the catalyst, and the initiator are mixed to perform ring-opening copolymerization to obtain the high-refractive-index degradable macromonomer capable of undergoing ring-opening metathesis polymerization.

[0012] Preferably, the initiator is exo-norbornene alcohol, benzyl alcohol, endo-norbornene alcohol, or 2-(2-hydroxyethyl)-3A,4,7,7A-tetrahydro-1H-4,7-methoxyisoindole-1,3(2H)-dione.

[0013] Preferably, the catalyst is stannous octoate or 1,8-diazabicycloundec-7-ene.

[0014] The third technical solution of the present application provides a synthesis method of a high-refractive-index bottlebrush polymer, which uses the high-refractive-index degradable macromonomer as described above as a raw material to perform ring-opening metathesis polymerization (ROMP) to obtain the high-refractive-index bottlebrush polymer.

[0015] Preferably, the high-refractive-index degradable macromonomer in the high-refractive-index bottlebrush polymer has a polymerization degree of 50-1000 and a molecular weight in a range of 1.25 x 10 4 - 1.0 x 10 7 Da.

[0016] The fourth technical scheme of the present application provides a bottle brush block polymer with high refractive index difference, wherein the high refractive index degradable macromonomer with high refractive index is used as a high refractive index monomer component in the polymer to form a refractive index difference with a low refractive index component.

[0017] The fifth technical scheme of the present application provides a synthesis method of a bottle brush block polymer with high refractive index difference, wherein the high refractive index degradable macromonomer and a low refractive index degradable macromonomer are used as raw materials to perform a sequential ring-opening metathesis polymerization (ROMP) to obtain the bottle brush block polymer with high refractive index difference.

[0018] Preferably, the end group of the low refractive index degradable macromonomer is a cycloalkene derivative capable of undergoing a sequential ring-opening metathesis polymerization (ROMP), and the main chain is a degradable polymer prepared by ring-opening polymerization of a cyclic monomer.

[0019] Preferably, the synthesis method of the low refractive index degradable macromonomer comprises the following steps: mixing the cycloalkene derivative, the cyclic monomer, the catalyst and the initiator to perform a ring-opening copolymerization to obtain the low refractive index degradable macromonomer.

[0020] Preferably, the types of the cycloalkene derivative include a cyclopropene end group, a cyclobutene end group, a norbornene end group, a cyclopentene end group, a cyclohexene end group or a cyclooctene end group.

[0021] Preferably, the cyclic monomer is an epoxide monomer, a cyclic ester monomer or a cyclic carbonate monomer; the epoxide monomer is propylene oxide, ethylene oxide or cyclohexene oxide; the cyclic ester monomer is lactide, glycolide and caprolactone; and the cyclic carbonate monomer is trimethyl carbonate, a trimethyl carbonate derivative or ethylene carbonate (see Figure 2 ).

[0022] Preferably, the synthesis method comprises Method I and Method II; the Method I comprises the following steps:

[0023] The high refractive index degradable macromonomer is mixed with a catalyst to perform a ring-opening metathesis polymerization to obtain a high refractive index segment;

[0024] The high refractive index segment, the low refractive index degradable macromonomer and a catalyst are mixed to perform a second ring-opening metathesis polymerization to obtain the bottle brush block polymer with high refractive index difference;

[0025] The Method II comprises the following steps:

[0026] The low refractive index degradable macromonomer is mixed with a catalyst to perform a ring-opening metathesis polymerization to obtain a low refractive index segment;

[0027] Mixing the low refractive index segment, the high refractive index degradable macromonomer and the catalyst, a secondary ring-opening metathesis polymerization reaction is performed to obtain the high refractive index difference bottle brush block polymer.

[0028] Preferably, the temperature of the ring-opening metathesis polymerization reaction is room temperature, and the reaction time of the ring-opening metathesis polymerization reaction is 10 min; and the reaction time of the secondary ring-opening metathesis polymerization reaction is 1 h.

[0029] Preferably, the refractive index difference between the high refractive index segment and the low refractive index segment is greater than 0.1, and the molecular weight of the high refractive index difference bottle brush block polymer is 1.0*10 5 -1.2*10 7 Da.

[0030] Preferably, the high refractive index difference bottle brush block polymer can undergo microphase separation to form a high-saturation structural color material.

[0031] The sixth technical scheme of the present application provides an application of the high refractive index difference and degradable bottle brush block polymer in the field of structural color materials.

[0032] The seventh technical scheme of the present application provides a preparation method of a structural color material, which utilizes a phase separation mechanism, and a high-saturation structural color is obtained by preparing the high refractive index difference bottle brush block polymer into ink and self-assembling in a manner of doctor blading, spin coating, screen printing or spraying to obtain the structural color material.

[0033] Preferably, the structural color material is degradable and environmentally friendly, and the reflection spectrum covers the entire visible spectrum.

[0034] The beneficial technical effects of the present application are as follows:

[0035] The present application designs and synthesizes a series of novel degradable cycloolefin macromonomers to replace the commonly used non-degradable high refractive index polymers such as polystyrene, and synthesizes macromonomers and bottle brush block polymers through ring-opening copolymerization and ring-opening metathesis polymerization, and further utilizes a phase separation mechanism to prepare an environmentally friendly structural color material capable of covering the entire visible light band. The present application gives a higher added value to degradable polyester materials, and provides a perfect substitute for traditional artificial organic pigments, thereby reducing the influence of microplastics and harmful chemicals on the environment, and has good application value.

[0036] The present application designs and synthesizes degradable and high refractive index macromonomers with different molecular weights. In terms of optical properties, the prepared high refractive index degradable macromonomer has a high refractive index (n>1.55); in terms of synthesis, the monomer is prepared through anionic polymerization, and has the advantages of simplicity, controllability and easy amplification.

[0037] Gel permeation chromatography (GPC) analysis showed that the present invention can obtain a high refractive index bottle brush polymer with controllable molecular weight and narrow distribution, with a degree of polymerization of 50-1000 and a polymer molecular weight distribution (PDI) of 1.0-1.3.

[0038] This invention synthesizes a biodegradable high-refractive-index bottle brush block polymer by introducing high-refractive-index and low-refractive-index biodegradable macromonomers for ROMP. The polymer exhibits a single-peak GPC peak distribution and a molecular weight (Mw) of 1.0 × 10⁻⁶. 5 -1.2×10 7 Da, PDI≤1.30. Attached Figure Description

[0039] 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.

[0040] Figure 1 This is a schematic diagram of the ring-opening metasomatic polymerization process of the biodegradable macromolecular monomers of the present invention and its end-group structure.

[0041] Figure 2 This is a schematic diagram of the structure of the high refractive index degradable macromonomer and the low refractive index degradable macromonomer of the present invention.

[0042] Figure 3 This is a schematic diagram of the structure of PSOPE with different end bases according to the present invention.

[0043] Figure 4 This diagram illustrates the synthesis process of PSOPE with different end groups according to the present invention. Wherein, a. is Example 1, b. is Example 2, c. is Example 3, and d. is Example 4.

[0044] Figure 5 The above is the 1H NMR spectrum of NB-PSOPE synthesized in one step according to Example 1 of the present invention.

[0045] Figure 6 These are physical images of the equipment and products used in the kilogram-scale scale-up experiment of Embodiment 1 of the present invention. The first and second images from the left are physical images of the equipment, and the third image from the left is a physical image of the product.

[0046] Figure 7 The above is the hydrogen NMR spectrum of NB-PSOPE synthesized by a two-step method in Example 2 of this invention.

[0047] Figure 8The above is the 1H NMR spectrum of the endo-NB-PSOPE synthesized in Example 3 of this invention.

[0048] Figure 9 The above is the 1H NMR spectrum of the NA-PSOPE synthesized in Example 4 of this invention.

[0049] Figure 10 This is a schematic diagram illustrating the synthesis process of different low-refractive-index macromonomers according to the present invention. Wherein, a. represents NB-PLA, b. represents NB-PCL, and c. represents NB-PEO.

[0050] Figure 11 The image shows the hydrogen NMR spectrum of the NB-PLA synthesized in Example 5 of this invention.

[0051] Figure 12 The image shows the hydrogen NMR spectrum of the NB-PCL synthesized in Example 5 of this invention.

[0052] Figure 13 The image shows the 1H NMR spectrum of NB-PEO synthesized in Example 5 of this invention.

[0053] Figure 14 The refractive index test results are for the high refractive index biodegradable macromonomers synthesized in Examples 1-4 of this invention.

[0054] Figure 15 The refractive index test results are for the low refractive index degradable macromolecular monomers NB-PLA, NB-PCL, and NB-PEO used in this invention.

[0055] Figure 16 The GPC is a high refractive index bottle brush polymer prepared in Example 6 of the present invention.

[0056] Figure 17 This is a schematic diagram of the structure of the block copolymer brushes PNPSOPE-b-PNPLA, PNPSOPE-b-PNPCL, and PNPSOPE-b-PNPEO of the present invention.

[0057] Figure 18 The image shows the 1H NMR spectrum of the PNPSOPE-b-PNPLA synthesized in this invention.

[0058] Figure 19 The GPC for PNPSOPE-b-PNPLA synthesized in this invention.

[0059] Figure 20 The image shows the 1H NMR spectrum of the PNPSOPE-b-PNPCL synthesized in this invention.

[0060] Figure 21 The image shows the 1H NMR spectrum of the PNPSOPE-b-PNPEO synthesized in this invention.

[0061] Figure 22 The results are the alcoholysis kinetics test results of the PNPSOPE-b-PNPLA synthesized in this invention.

[0062] Figure 23 GPCs of bottle brush polymers with different degrees of polymerization prepared in Example 10 of the present invention.

[0063] Figure 24 This is a macroscopic photograph of the biodegradable structural color material prepared in Example 10 of the present invention.

[0064] Figure 25 The reflectance spectrum is shown for the biodegradable structural color material prepared in Example 10 of this invention. Detailed Implementation

[0065] 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. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0066] Furthermore, regarding the 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. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0067] 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. It should be noted that any aspects of this invention not described in detail are conventional practices in the art and are not the focus of this invention.

[0068] The terms “comprising,” “including,” “having,” “containing,” etc., used in this invention are all open-ended terms, meaning that they include but are not limited to.

[0069] Unless otherwise specified, "room temperature" in this invention refers to 10-30°C.

[0070] All raw materials used in the following embodiments and comparative examples of the present invention are commercially available products.

[0071] Figure 1 This is a schematic diagram of the ring-opening metasomatic polymerization process of the biodegradable macromolecular monomers of the present invention and its end-group structure.

[0072] Figure 2 This is a schematic diagram of the structure of the high refractive index degradable macromonomer and the low refractive index degradable macromonomer of the present invention.

[0073] Figure 3 This is a schematic diagram of the structure of PSOPE with different end bases according to the present invention.

[0074] Figure 4 This diagram illustrates the synthesis process of PSOPE with different end groups according to the present invention. Wherein, a. is Example 1, b. is Example 2, c. is Example 3, and d. is Example 4.

[0075] Figure 10 This is a schematic diagram illustrating the synthesis process of different low-refractive-index macromonomers according to the present invention. Wherein, a. represents NB-PLA, b. represents NB-PCL, and c. represents NB-PEO.

[0076] Example 1

[0077] The synthesis method of high refractive index degradable macromonomers is as follows: Figure 4 a):

[0078] One-step synthesis: exo-norborneol was used as the initiator, stannous octoate as the catalyst, and styrene oxide (SO₄) and phthalic anhydride (PA) were used as monomers for ring-opening copolymerization. In a glove box, the initiator (0.17 g), catalyst (0.05 g), styrene oxide (10 g), and phthalic anhydride (10 g) were added sequentially to a polymerization flask. After sealing, the mixture was heated and stirred in an oil bath at 120 °C for 12 h. After the reaction was complete, the monomer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, yielding a white macromonomer (yield 88%, denoted as NB-PSOPE). The results of the 1H NMR spectroscopy analysis were as follows (…). Figure 5 This confirms that the target structure has been successfully synthesized.

[0079] Kilogram-scale scale-up experiment: A stainless steel reactor, model AHZN-2LFJ-QZD, with a volume of 2L, was used for the kilogram-scale synthesis of macromonomers. exo-norbornenol (3.4g), stannous octoate (1g), SO (200g), and PA (200g) were added sequentially to the reactor. The reactor was evacuated three times with nitrogen to achieve an anhydrous and oxygen-free nitrogen reaction atmosphere. After sealing, the reactor was heated and stirred in a 120℃ oil bath for 12 hours. After the reaction was complete, the macromonomer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, yielding a white macromonomer (NB-PSOPE). The theoretical yield was 400g, while the actual yield was 360.10g, resulting in a yield of 90%.

[0080] Figure 5The above is the 1H NMR spectrum of NB-PSOPE synthesized in one step according to Example 1 of the present invention.

[0081] Figure 6 These are physical images of the equipment and products used in the kilogram-scale scale-up experiment of Embodiment 1 of the present invention. The first and second images from the left are physical images of the equipment, and the third image from the left is a physical image of the product.

[0082] Example 2

[0083] The synthesis method of high refractive index degradable macromonomers is as follows: Figure 4 b):

[0084] Two-step synthesis: Benzoyl alcohol was used as the initiator, stannous octoate as the catalyst, and SO and PA as monomers for the ring-opening copolymerization reaction. In a glove box, the initiator (0.15 g), catalyst (0.05 g), styrene oxide (10 g), and phthalic anhydride (10 g) were added sequentially to a polymerization flask. After sealing, the mixture was heated and stirred in an oil bath at 120 °C for 12 h. After the reaction was completed, the polymer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, thus obtaining a white polymer with benzyl alcohol at one end and a hydroxyl group at the other end.

[0085] Esterification of the white polymer: 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) was used as the coupling agent (1.5 g), 4-dimethylaminopyridine (DMAP) as the catalyst (0.07 g), and exo-norbornene carboxylic acid and the aforementioned white polymer were used as reactants (10 g). The reagents were added to a flask, and dichloromethane (50 mL) was added as the solvent. The flask was sealed and reacted at room temperature for 48 h. After precipitation, methanol was added dropwise to obtain the white macromonomer (NA-PSOPE) with a yield of 90%. (1H NMR spectroscopy) Figure 7 The analysis results confirm that the target structure has been successfully synthesized.

[0086] Figure 7 The above is the hydrogen NMR spectrum of NB-PSOPE synthesized by a two-step method in Example 2 of this invention.

[0087] Example 3

[0088] The synthesis method of high refractive index degradable macromonomers is as follows: Figure 4 c):

[0089] endo-norborneol was selected as the initiator, 1,8-diazabicycloundec-7-ene as the catalyst, and SO and phthalic anhydride (PA) as monomers for the ring-opening copolymerization reaction. In a glove box, the initiator (0.15 g), catalyst (0.05 g), styrene oxide (10 g), and phthalic anhydride (10 g) were added sequentially to a polymerization flask. After sealing, the mixture was heated and stirred in an oil bath at 120 °C for 12 h. After the reaction was complete, the monomer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, yielding a white macromonomer (yield 88%, denoted as endo-NB-PSOPE). The results of the proton nuclear magnetic resonance (NMR) spectroscopy analysis were obtained (…). Figure 8 This confirms that the target structure has been successfully synthesized.

[0090] Figure 8 The above is the 1H NMR spectrum of the endo-NB-PSOPE synthesized in Example 3 of this invention.

[0091] Example 4

[0092] The synthesis method of high refractive index degradable macromonomers is as follows: Figure 4 d):

[0093] 2-(2-hydroxyethyl)-3A,4,7,7A-tetrahydro-1H-4,7-methoxyisoindole-1,3(2H)-dione was selected as the initiator, 1,8-diazabicycloundec-7-ene as the catalyst, and SO and phthalic anhydride (PA) as monomers for the ring-opening copolymerization reaction. In a glove box, the initiator (0.1 g), catalyst (0.05 g), styrene oxide (10 g), and phthalic anhydride (10 g) were added sequentially to a polymerization flask. After sealing, the mixture was heated and stirred in an oil bath at 120 °C for 12 h. After the reaction was completed, the monomer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, yielding a white macromonomer (NA-PSOPE) with a yield of 87%. The results of the 1H NMR spectroscopy analysis were as follows (…). Figure 9 This confirms that the target structure has been successfully synthesized.

[0094] Figure 9 The above is the 1H NMR spectrum of the NA-PSOPE synthesized in Example 4 of this invention.

[0095] Example 5

[0096] The synthesis method of low refractive index degradable macromonomers includes the following steps:

[0097] The steps for synthesizing NB-PLA are as follows: Figure 10a): Exo-norborneol was selected as the initiator, stannous octoate as the catalyst, and lactide (LA) as the monomer for the ring-opening polymerization reaction. In a glove box, the initiator (0.1 g), catalyst (0.05 g), and LA (10 g) were added sequentially to the polymerization flask. After sealing, the mixture was heated and stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the monomer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, thus obtaining a white macromolecular monomer (yield 80%, denoted as NB-PLA). The results of the 1H NMR spectroscopy analysis (…) Figure 11 This confirms that the target structure has been successfully synthesized.

[0098] Figure 11 The image shows the hydrogen NMR spectrum of the NB-PLA synthesized in Example 5 of this invention.

[0099] The synthesis of NB-PCL follows these steps ( Figure 10 b): Exo-norborneol was selected as the initiator, stannous octoate as the catalyst, and caprolactone (CL) as the monomer for the ring-opening polymerization reaction. In a glove box, the initiator (0.12 g), catalyst (0.05 g), and CL (10 g) were added sequentially to the polymerization flask. After sealing, the mixture was heated and stirred in an oil bath at 120°C for 1 hour. After the reaction was complete, the monomer was dissolved in dichloromethane and then added dropwise to methanol for precipitation, thus obtaining a white macromolecular monomer (yield 90%, denoted as NB-PCL). The results of the 1H NMR spectroscopy analysis (…) Figure 12 This confirms that the target structure has been successfully synthesized.

[0100] Figure 12 The image shows the hydrogen NMR spectrum of the NB-PCL synthesized in Example 5 of this invention.

[0101] The synthesis of NB-PEO follows these steps ( Figure 10 c): 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) was used as the coupling agent (1.5 g), 4-dimethylaminopyridine (DMAP) as the catalyst (0.07 g), exo-norbornene carboxylic acid and the above-mentioned monohydroxy PEO (10 g, purchased from Aladdin) were added to a flask. Dichloromethane (50 mL) was added as a solvent, and the mixture was sealed and reacted at room temperature for 48 h. Afterward, methanol was added dropwise for precipitation to obtain a white macromonomer (NA-Peo) with a yield of 90%. (1H NMR spectroscopy) Figure 13 The analysis results confirm that the target structure has been successfully synthesized.

[0102] Figure 13 The image shows the 1H NMR spectrum of NA-PEO synthesized in Example 5 of this invention.

[0103] Example 1

[0104] The refractive index of the high-refractive-index macromonomers and low-refractive-index macromonomers prepared in Examples 2-4 was tested: After spin-coating the above monomers into films, their refractive indices were measured using an ellipsometer (UVISELPLUS, dispersion model: new amorphous, incident angle 70°). The test results are as follows. Figure 14 and 15 As shown.

[0105] Figure 14 The refractive index test results are for the high refractive index biodegradable macromonomers synthesized in Examples 1-4 of this invention.

[0106] Figure 15 The refractive index test results are for the low refractive index degradable macromolecular monomers NB-PLA, NB-PCL, and NB-PEO used in this invention.

[0107] Depend on Figure 14 It can be seen that the refractive index of the coatings made from the products of Examples 1-4 is higher than 1.55.

[0108] Calculation of refractive index difference: The refractive index of NB-PSOPE is 1.59, while the refractive indices of NB-PLA, NB-PCL, and NB-PEO are 1.45, 1.46, and 1.46, respectively. Figure 15 The refractive index difference = high refractive index - low refractive index, meaning that the refractive index difference of the above bottle brush block polymers is greater than 0.1.

[0109] Example 6

[0110] The method for synthesizing high-refractive-index bottle brush polymers uses NB-PSOPE synthesized in one step in Example 1 as a raw material to synthesize bottle brush polymers of different molecular weights. The polymer brushes are synthesized via ring-opening metathesis polymerization (ROMP). The specific steps are as follows:

[0111] The NB-PSOPE(M) synthesized in the one-step method in Example 1 n =2.3kDa, M w / M n =1.15, 1g added) was added to a Schlenk polymerization flask, and ultra-dry dichloromethane was added to completely dissolve it (initial concentration [M]0 = 0.05M). Under N2 atmosphere, third-generation Grubbs catalyst (0.01mg) was added via syringe to initiate the polymerization of NB-PSOPE. After reacting at room temperature for 10 min, the reaction was terminated with ethyl vinyl ether (0.5mL), and then simply dried in a vacuum oven to remove the solvent and ethyl vinyl ether to obtain a high refractive index bottle brush polymer.

[0112] By changing the feed ratio of catalyst and monomer, i.e., keeping the catalyst constant while changing the molar amount of monomer, brush-like polymers with a main chain of 50-1000 DP can be obtained (e.g., catalyst:monomer = 1:100, resulting in a degree of polymerization of 100 DP; catalyst:monomer = 1:1000, resulting in a degree of polymerization of 1000 DP). The molecular weight (M) of the high refractive index bottle brush polymers was determined by gel permeation chromatography (with a DAWNHELEOS multi-angle light scattering (MALS) detector). w And PDI.

[0113] Figure 16 The GPC is a high refractive index bottle brush polymer prepared in Example 6 of the present invention.

[0114] It was measured that its M w =1.25×10 4 -1.0×10 7 Da, PDI < 1.3.

[0115] Example 7

[0116] The synthesis method of high refractive index difference bottle brush block polymer (PNPSOPE-b-PNPLA) is as follows:

[0117] The NB-PSOPE(M) synthesized in the one-step method in Example 1 n =2.3kDa, M w / M n =1.15, addition amount 1g) was added to a Schlenk polymerization flask, and ultra-dry dichloromethane was added to completely dissolve it (initial concentration of NB-PSOPE in dichloromethane [M]0 = 0.05M). Under N2 atmosphere, third-generation Grubbs catalyst (0.01mg) was added via syringe to initiate the polymerization of NB-PSOPE. After reacting at room temperature for 10 min, a dichloromethane solution of NB-PLA (M) was added. n =2.5kDa, M w / M n =1.15, addition amount 1g, [M]0 = 0.05M), to carry out the second stage of polymerization, and continue the reaction at room temperature for 1h. Then, the reaction was terminated with ethyl vinyl ether (0.5mL), and then simply dried in a vacuum oven to remove the solvent and ethyl vinyl ether to obtain the block copolymer brush (denoted as PNPSOPE-b-PNPLA). (NMR 1H spectrum analysis results) Figure 18 The target structure has been successfully synthesized. (Note: NB-PLA and NB-PSOPE were fed in a 1:1 ratio. DP = 50 + 50 means that NB-PLA:G3:NB-PSOPE = 50:1:50, that is, NB-PLA and NB-PSOPE each have 50 DPs.)

[0118] Figure 17 This is a schematic diagram of the structure of the block copolymer brushes PNPSOPE-b-PNPLA, PNPSOPE-b-PNPCL, and PNPSOPE-b-PNPEO of the present invention.

[0119] Figure 18 The image shows the 1H NMR spectrum of the PNPSOPE-b-PNPLA synthesized in this invention.

[0120] Figure 19 The GPC for PNPSOPE-b-PNPLA synthesized in this invention.

[0121] The M value of the polymer PNPSOPE-b-PNPLA was determined by GPC characterization. w =1.0×10 5 -1.2×10 7 Da, PDI < 1.3.

[0122] Regarding low refractive index macromonomers, in addition to NB-PLA, this invention also selected two other macromonomers, NB-PCL and NB-PEO, for verification. The difference from PNPSOPE-b-PNPLA in Example 6 is only that NB-PLA was replaced with equal masses of NB-PCL and NB-PEO, respectively, yielding high refractive index difference bottle brush block polymers PNPSOPE-b-PNPCL and PNPSOPE-b-PNPEO. The results of the proton nuclear magnetic resonance (NMR) spectroscopy analysis (…) Figure 20 , 21 It was confirmed that the target structure was successfully synthesized, and the specific operations were as described in Examples 8 and 9.

[0123] Example 8

[0124] The synthesis method of high refractive index difference bottle brush block polymer (PNPSOPE-b-PNPCL) is as follows:

[0125] The NB-PSOPE(M) synthesized in the one-step method in Example 1 n =2.3kDa, M w / M n =1.15, addition amount 1g) was added to a Schlenk polymerization flask, and ultra-dry dichloromethane was added to completely dissolve it ([M]0 = 0.05M). Under N2 atmosphere, third-generation Grubbs catalyst (0.01mg) was added via syringe to initiate the polymerization of NB-PSOPE. After reacting at room temperature for 10 min, a dichloromethane solution of NB-PCL (M) was added. n =2.3kDa, M w / M n=1.12, addition amount 1g, [M]0 = 0.05M), to carry out the second stage of polymerization, and after continuing the reaction at room temperature for 1h, the reaction was terminated with ethyl vinyl ether (0.5mL), and then simply dried in a vacuum oven to remove the solvent and ethyl vinyl ether to obtain the block copolymer brush. The results of the 1H NMR spectroscopy analysis ( Figure 20 This confirms that the target structure has been successfully synthesized.

[0126] Example 9

[0127] The synthesis method of high refractive index difference bottle brush block polymer (PNPSOPE-b-PNPEO) is as follows:

[0128] The NB-PSOPE(M) synthesized in the one-step method in Example 1 n =2.3kDa, M w / M n =1.15, addition amount 1g) was added to a Schlenk polymerization flask, and ultra-dry dichloromethane was added to completely dissolve it ([M]0 = 0.05M). Under N2 atmosphere, third-generation Grubbs catalyst (0.01mg) was added via syringe to initiate the polymerization of NB-PSOPE. After reacting for 10 min at room temperature, a dichloromethane solution of NB-PEO (M) was added. n =2.5kDa, M w / M n =1.15, added amount 1g, [M]0 = 0.05M), to carry out the second stage of polymerization. After continuing the reaction at room temperature for 1h, the reaction was terminated with ethyl vinyl ether (0.5mL). Then, the solvent and ethyl vinyl ether were removed by simple drying in a vacuum oven to obtain the block copolymer brush. The results of the 1H NMR spectroscopy analysis ( Figure 21 This confirms that the target structure has been successfully synthesized.

[0129] Figure 20 The image shows the 1H NMR spectrum of the PNPSOPE-b-PNPCL synthesized in this invention.

[0130] Figure 21 The image shows the 1H NMR spectrum of the PNPSOPE-b-PNPEO synthesized in this invention.

[0131] Example 2

[0132] Degradability test: 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was used as the organic base catalyst. PNPSOPE-b-PNPLA (DP=300+300) was subjected to alcoholysis at 60℃ by mixing DBU:ester bond:methanol at a molar ratio of 0.1:1:20. Figure 17GPC analysis of alcoholysis kinetics revealed that the molecular weight of the bottle brush block polymer gradually decreased over time, eventually yielding M... w =7.12×10 4 Da, and the theoretical only contain norbornene segments (i.e., only the non-degradable cyclic olefin backbone remains, without side chains), M w =7.44×10 4 This is consistent with the results of the test, which proves that the side-chain polyester of the bottle brush block polymer can be completely degraded with a degradation efficiency of over 95%.

[0133] Figure 22 The results are the alcoholysis kinetics test results of the PNPSOPE-b-PNPLA synthesized in this invention.

[0134] Example 10

[0135] Preparation of highly saturated structural color materials using bottle-brush block polymers:

[0136] Using a drop-coating process, PNPSOPE-b-PNPLA bottle brush block polymers with different degrees of polymerization (DP = 240+240, 280+280, 320+320, 360+360, 400+400, 440+440) were dissolved in tetrahydrofuran and then drop-coated onto a clean glass substrate. After the solvent completely evaporated, a structural color film covering the entire visible spectrum was obtained. Figure 24 ).

[0137] Figure 23 GPCs of bottle brush polymers with different degrees of polymerization prepared in Example 10 of the present invention.

[0138] Figure 24 This is a macroscopic photograph of the biodegradable structural color material prepared in Example 10 of the present invention.

[0139] Reflectance spectroscopy test: UV-Vis absorption and reflectance spectroscopy tests were performed on a Shimadzu UV-3600Plus spectrophotometer equipped with an ISR-603 integrating sphere, using a solid sample holder.

[0140] Figure 25 The reflectance spectrum is shown for the biodegradable structural color material prepared in Example 10 of this invention.

[0141] Depend on Figure 25 As can be seen, with the increase of polymerization degree, the reflection peak redshifts successively, and the wavelength increases from 420nm to 720nm, achieving complete coverage of the entire visible light spectrum.

[0142] Since there are many types of synthesized monomers and block copolymers, the above-described embodiments are only 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, all modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A high-refractive-index biodegradable macromolecular monomer, characterized in that, The high-refractive-index degradable macromonomer has cyclic olefin derivatives as its end groups and a main chain that is a degradable polymer obtained by ring-opening copolymerization of styrene oxide and a comonomer.

2. The high refractive index biodegradable macromolecular monomer according to claim 1, characterized in that, The types of cyclic olefin derivatives include: cyclopropene end group, cyclobutene end group, norbornene end group, cyclopentene end group, cyclohexene end group, or cyclooctene end group.

3. The high refractive index biodegradable macromolecular monomer according to claim 1, characterized in that, The types of comonomers include: cyclic sulfide monomers, cyclic anhydride monomers, cyclic thioanhydride monomers, or other compounds; the other compounds are carbon monoxide, carbon dioxide, carbon oxysulfide, and carbon sulfide.

4. A method for synthesizing a high refractive index degradable macromonomer according to any one of claims 1-3, characterized in that, Includes the following steps: The cyclic olefin derivative, styrene oxide, cyclic monomer, catalyst and initiator are mixed and subjected to a ring-opening copolymerization reaction to obtain a high-refractive-index degradable macromonomer capable of undergoing ring-opening metasomatic polymerization.

5. A method for synthesizing a high refractive index bottle brush polymer, characterized in that, Using the high refractive index biodegradable macromolecular monomer described in any one of claims 1-3 as raw material, a ring-opening metathesis polymerization reaction is carried out to obtain the high refractive index bottle brush polymer.

6. A high refractive index difference bottle brush block polymer, characterized in that, The high refractive index degradable macromonomer described in any one of claims 1-3 is used as the high refractive index monomer component in the polymer to form a refractive index difference with the low refractive index component.

7. A method for synthesizing a high refractive index difference bottle brush block polymer, characterized in that, Using the high refractive index biodegradable macromonomer and the low refractive index biodegradable macromonomer as raw materials, a sequential ring-opening metathesis polymerization reaction is carried out to obtain the high refractive index bottle brush block polymer.

8. The synthesis method according to claim 7, characterized in that, The low-refractive-index degradable macromonomer has cyclic olefin derivatives as its end groups and a cyclic monomer as its main chain, which is a degradable polymer obtained by ring-opening polymerization.

9. The synthesis method according to claim 8, characterized in that, The cyclic monomer is an epoxide monomer, a cyclic ester monomer, or a cyclic carbonate monomer.

10. The application of the high refractive index difference bottle brush block polymer of claim 6 in the field of structural color materials.

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