A method for synthesizing a high refractive index difference bottlebrush block polymer and a degradable structural color material

Abstract

The application discloses a synthesis method of a high-refractive-index bottle-brush block polymer and 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 cycloalkene derivative capable of undergoing a ring-opening metathesis polymerization (ROMP), and the main chain is a degradable polymer prepared by ring-opening copolymerization of an oxidized styrene (SO) and a comonomer. A series of novel degradable cycloalkene macromonomers are designed and synthesized to replace the non-degradable high-refractive-index polymers such as polystyrene commonly used in the field, and the macromonomers and block copolymer brushes are synthesized through ring-opening polymerization and ring-opening metathesis polymerization, and further, environment-friendly structural color materials capable of covering the whole visible light band are prepared by using a phase separation mechanism.

Description

Technical Field

[0001] This invention relates to the field of organic polymer technology, and in particular to a method for synthesizing a high refractive index difference bottle brush block polymer and a biodegradable structural color material. Background Technology

[0002] Photonic crystals (PCs) are a class of materials with periodic dielectric structures, whose microstructure allows for precise control over light propagation. Utilizing the principle of microphase separation in block copolymers, different types of photonic crystals can be fabricated, providing an effective and cost-efficient method for preparing biomimetic optical materials. Among them, bottlebrush block copolymers (BBCPs) exhibit a unique molecular conformation, consisting of a single polymer backbone densely grafted with a high-density, tightly packed array of polymer side chains. They exhibit less intermolecular chain entanglement and a fast self-assembly rate, demonstrating significant advantages and making them worthy of research.

[0003] Over the past two decades, various brush-like block copolymers with diverse chemical structures have been successfully designed and synthesized, and assembled into photonic crystal materials with structural colors. Taking layered photonic crystals as an example, according to the reflection intensity formula, the generation of structural colors requires a certain refractive index difference between the two phases. Polystyrene (PS), due to its high refractive index, is often chosen as a key block in block copolymer brushes. However, the application of PS components has also brought a series of problems: First, the polymerization process of PS is highly sensitive to reaction conditions, requiring precise control of the free radical polymerization process, 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 fields such as disposable cosmetics, the potential microplastic pollution problem cannot be ignored, thus requiring further improvement. Summary of the Invention

[0004] The purpose of this invention is to provide a method for synthesizing high refractive index difference bottle brush block polymers and biodegradable structural color materials, so as to solve the above-mentioned problems in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] One of the technical solutions of the present invention is to provide a high refractive index degradable macromonomer, wherein the end group of the high refractive index degradable macromonomer is a cyclic olefin derivative capable of undergoing sequential ring-opening metathesis polymerization (ROMP), and the main chain is a degradable polymer obtained by ring-opening copolymerization of styrene oxide (SO) and other monomers.

[0007] Preferably, the types of the cycloolefin derivatives include: cyclopropene end group, cyclobutene end group, norbornene end group, cyclopentene end group, cyclohexene end group, or cyclooctene end group (see...). Figure 1 ).

[0008] Preferably, the types of comonomers include: cyclic sulfide monomers, cyclic anhydride monomers, cyclic thioanhydride monomers, or other compounds; the cyclic sulfide monomers are ethane sulfide, propane sulfide, or thiohexacyclobutane; the anhydride monomers are phthalic anhydride, maleic anhydride, or glutaric anhydride; the thioanhydride monomers are thiohydroxyacetic anhydride, N-carboxylic anhydride, or thiophthalic anhydride; the other compounds are carbon monoxide, carbon dioxide, carbon oxysulfide, and carbon sulfide (…). Figure 2 ).

[0009] Preferably, the high-refractive-index degradable macromonomer has a refractive index n > 1.55 and a molecular weight of 2.5 × 10⁻⁶. 2 -1.0×10 4 Da.

[0010] The second technical solution of the present invention provides a method for synthesizing the above-mentioned high refractive index degradable macromolecular monomer, comprising the following steps:

[0011] 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.

[0012] Preferably, the initiator is exo-norborneol, benzyl alcohol, endo-norborneol, 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 invention provides a method for synthesizing a high refractive index bottle brush polymer, which uses the above-mentioned high refractive index biodegradable macromolecular monomer as raw material to carry out a ring-opening metathesis polymerization (ROMP) reaction to obtain the high refractive index bottle brush polymer.

[0015] Preferably, the degree of polymerization of the high-refractive-index biodegradable macromonomer blocks formed by the polymerization of the high-refractive-index bottle brush polymer is 50-1000, and the molecular weight ranges from 1.25 × 10⁻⁶. 4 -1.0×10 7 Da.

[0016] The fourth technical solution of the present invention provides a high refractive index difference bottle brush block polymer, which uses the above-mentioned high refractive index degradable macromolecular monomer as the high refractive index monomer component in the polymer to form a refractive index difference with the low refractive index component.

[0017] The fifth technical solution of the present invention provides a method for synthesizing a high refractive index difference bottle brush block polymer, which uses the above-mentioned high refractive index degradable macromonomer and low refractive index degradable macromonomer as raw materials to carry out a sequential ring-opening metathesis polymerization (ROMP) reaction to obtain the high refractive index difference bottle brush block polymer.

[0018] Preferably, the end groups of the low-refractive-index degradable macromonomer are cyclic olefin derivatives capable of undergoing sequential ring-opening metathesis polymerization (ROMP), and the main chain is a degradable polymer obtained by ring-opening polymerization of cyclic monomers.

[0019] Preferably, the method for synthesizing the low-refractive-index degradable macromonomer includes the following steps: mixing the cyclic olefin derivative, cyclic monomer, catalyst and initiator, and carrying out a ring-opening copolymerization reaction to obtain the low-refractive-index degradable macromonomer.

[0020] Preferably, 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.

[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, or caprolactone; the cyclic carbonate monomer is trimethyl carbonate, a trimethyl carbonate derivative, or ethylene carbonate (see...). Figure 2 ).

[0022] Preferably, the synthesis method includes method one and method two; method one includes the following steps:

[0023] The high-refractive-index biodegradable macromonomer is mixed with a catalyst and subjected to a ring-opening metathesis polymerization reaction to obtain a high-refractive-index segment.

[0024] The high refractive index segment, the low refractive index biodegradable macromonomer and the catalyst are mixed and subjected to a secondary ring-opening metathesis polymerization reaction to obtain the high refractive index bottle brush block polymer.

[0025] Method 2 includes the following steps:

[0026] The low-refractive-index biodegradable macromonomer is mixed with a catalyst and subjected to a ring-opening metathesis polymerization reaction to obtain a low-refractive-index segment.

[0027] The low-refractive-index segment, the high-refractive-index biodegradable macromonomer, and the catalyst are mixed and subjected to a secondary ring-opening metathesis polymerization reaction to obtain the high-refractive-index bottle brush block polymer.

[0028] Preferably, the ring-opening metathesis polymerization reaction is carried out at room temperature, and the reaction time is 10 min; 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 >0.1, and the molecular weight of the high refractive index difference bottle brush block polymer is 1.0 × 10⁻⁶. 5 -1.2×10 7 Da.

[0030] Preferably, the high refractive index difference bottle brush block polymer is capable of microphase separation to form a highly saturated structural color material.

[0031] The sixth technical solution of the present invention provides an application of the above-mentioned high refractive index difference and biodegradable bottle brush block polymer in the field of structural color materials.

[0032] The seventh technical solution of the present invention provides a method for preparing a structural color material. By utilizing a phase separation mechanism, the above-mentioned high refractive index difference bottle brush block polymer is formulated into an ink, and the ink is self-assembled by means of scraping, spin coating, screen printing or spraying to obtain a high saturation structural color, thereby obtaining the structural color material.

[0033] Preferably, the structural color material is biodegradable and environmentally friendly, and its reflectance spectrum covers the entire visible spectrum.

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

[0035] This invention designs and synthesizes a series of novel biodegradable cyclic olefin macromonomers to replace commonly used non-degradable high-refractive-index polymers such as polystyrene. Macromonomers and bottle-brush block polymers are synthesized through ring-opening copolymerization and ring-opening metathesis polymerization. Furthermore, environmentally friendly structural color materials capable of covering the entire visible light spectrum are prepared using phase separation mechanisms. This invention, on the one hand, gives biodegradable polyester materials higher added value, and on the other hand, provides a perfect alternative to traditional artificial organic pigments, thereby reducing the environmental impact of microplastics and harmful chemicals, and has significant application value.

[0036] This invention designs and synthesizes biodegradable macromonomers with different molecular weights and high refractive indices. Optically, the synthesized high-refractive-index biodegradable macromonomers exhibit high refractive indices (n > 1.55). Synthetically, these monomers are prepared via anionic polymerization, offering advantages such as simplicity, controllability, and ease of scale-up.

[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 monomer 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 this 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 image shows 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 macromolecular monomers 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 this 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 image shows 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 of effect 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 macromolecular monomers 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 degradable polymer obtained by ring-opening copolymerization of styrene oxide and comonomers as its main chain. 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; The comonomer is phthalic anhydride.

2. A method for synthesizing a high refractive index degradable macromonomer as described in claim 1, characterized in that, Includes the following steps: The cyclic olefin derivative, styrene oxide, comonomer, 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 metathesis polymerization.

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

4. A high refractive index difference bottle brush block polymer, characterized in that, Using the high refractive index degradable macromonomer described in claim 1 as a high refractive index monomer component in the polymer to form a refractive index difference with the low refractive index degradable macromonomer; The synthesis method of the high refractive index difference bottle brush block polymer is as follows: using the high refractive index degradable macromonomer and the low refractive index degradable macromonomer as raw materials, a sequential ring-opening metathesis polymerization reaction is carried out to obtain the high refractive index difference bottle brush block polymer. 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. The cyclic monomer is an epoxide monomer, a cyclic ester monomer, or a cyclic carbonate monomer.

5. The application of the high refractive index difference bottle brush block polymer as described in claim 4 in the field of structural color materials.

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