A polybutene grafted acyl fluoride copolymer, functionalized copolymer and method of making the same
By introducing acyl fluoride functional groups into the polybutene backbone, the problems of low reactivity and high functionalization cost of polybutene materials are solved, realizing the preparation of efficient and low-cost functionalized copolymers for application in biomedicine, energy and chemical industry and fluorescence.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- EAST CHINA UNIV OF SCI & TECH
- Filing Date
- 2026-04-16
- Publication Date
- 2026-07-03
AI Technical Summary
Existing polybutene materials have low reactivity, and the cost of functionalization reactions is high. Traditional methods are difficult to effectively introduce functional groups and are prone to molecular chain degradation and cross-linking side reactions.
Using carbon monoxide (CO) as the carbon source, acyl fluoride functional groups are introduced into the polybutene backbone under the action of a fluorinating agent. Polybutene grafted with acyl fluoride copolymer is prepared by photo-irradiation reaction, and then reacted with amine-containing functional compounds to prepare functionalized copolymer.
Polybutene materials with excellent reactivity can be prepared, which are easy to functionalize and modify, have low cost and are easy to mass-produce. Functionalized copolymers with different hydrophilicity/phobicity, fluorescence color development properties and thermal stability can be prepared.
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Figure CN122325643A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of functionalized polymer materials technology, and in particular to a polybutene grafted fluoride copolymer, a functionalized copolymer and its preparation method. Background Technology
[0002] Polybutylene (PB) is a high-molecular-weight inert polymer, typically a colorless, odorless, and non-toxic solid. It possesses excellent heat and weather resistance, maintaining structural stability at high temperatures. Furthermore, PB exhibits superior flexibility, tensile strength, and insulation properties. Due to its excellent physicochemical properties, it is widely used in pipes, packaging materials, and cable protection.
[0003] However, because PB's molecular chain is mainly composed of saturated aliphatic hydrocarbon structures, it has high chain segment regularity and strong crystallinity, and lacks active reaction sites on the molecular chain. Furthermore, the PB molecular chain lacks active functional groups such as double bonds, hydroxyl groups, and carboxyl groups, making traditional functionalization pathways such as electrophilic substitution and condensation polymerization difficult to implement directly, thus limiting its subsequent functional modification. If methods such as free radical grafting are used, molecular chain degradation and cross-linking side reactions are likely to occur, leading to a broadening of the material's molecular weight distribution and deterioration of its mechanical properties.
[0004] To enhance the reactivity of polybutene, existing technologies introduce reactive functional groups (such as carbonyl groups) into polybutene, resulting in polybutene materials containing more reactive functional groups. However, existing technologies have the following drawbacks: First, the efficiency of introducing functional groups is low, mostly below 3%; second, the cost of functionalization reactions is high. Although carbon-hydrogen bond (CH) activation strategies can introduce functional groups or structures into the polyolefin backbone, most reactions require noble metal catalysts, significantly increasing the cost of the reaction.
[0005] Based on this, developing novel highly reactive polybutene copolymers and then preparing polybutene materials with richer properties is of great significance for the development of polybutene functional materials. Summary of the Invention
[0006] This application provides a polybutene grafted fluorine copolymer, a functionalized copolymer and a method for preparing the same, aiming to solve the technical problems of low reactivity of existing polybutene and high cost of functionalization reaction.
[0007] To achieve the above objectives, the present application adopts the following technical solution.
[0008] In a first aspect, this application provides a polybutene-grafted fluorine copolymer with the chemical structure shown in formula (1): Equation (1) Where x is an integer from 20 to 100, and y is an integer from 2 to 10.
[0009] Preferably, the number-average molecular weight of the polybutene-grafted fluorine copolymer is 1324 to 6620.
[0010] A second aspect of this application provides a method for preparing the above-mentioned polybutene-grafted fluorine copolymer, comprising: Under an inert atmosphere, polybutene, catalyst, oxidant and fluorinating agent are dissolved in a first organic solvent to obtain a precursor solution; Carbon monoxide is introduced into the precursor solution, and after photoreaction, polybutene grafted fluorine copolymer is obtained.
[0011] Preferably, the catalyst is any one of CuCl2, CuBr2, or Cu(NO3)2; The oxidant is any one of K2S2O8, Na2S2O8 or (NH4)2S2O8; The fluorinating agent is any one of KF, NaF or LiF; The first organic solvent is any one of 1,2-dichloroethane, dichloromethane, or trichloromethane.
[0012] Preferably, the molar ratio of the polybutene, catalyst, oxidant and fluorinating agent is 1~5:0.01~0.5:0.25~1:0.3~30; And / or, The inert atmosphere is nitrogen; And / or, The photoreaction is carried out under blue light with a wavelength of 445 nm, at a temperature of 25℃ to 40℃, and for a time of 24h to 48h.
[0013] A third aspect of this application provides a method for preparing a functionalized copolymer, comprising: The above-mentioned polybutene grafted fluorine copolymer, functional compound and catalyst are added to the first organic solvent for reaction; The functional compound is an organic compound containing an amine group; The reaction product was dissolved in a second solvent and then precipitated in a third organic solvent; the precipitate was dried to obtain the functionalized copolymer.
[0014] Preferably, the functional compound includes any one of benzylamine, methoxy polyethylene glycolamine, or 4-(1,2,2-triphenylvinyl)aniline.
[0015] Preferably, the second organic solvent includes any one of dichloromethane, trichloromethane, or tetrahydrofuran; The third organic solvent is any one of methanol, n-hexane, or diethyl ether.
[0016] Preferably, the molar ratio of the polybutene-grafted fluorine copolymer to the functional compound is 5:0.2~2; The reaction is carried out at a temperature of 25-40°C for 24-48 hours.
[0017] A fourth aspect of this application provides a functionalized copolymer prepared by the above-described preparation method.
[0018] Compared with the prior art, the beneficial effects of this application are as follows: This application utilizes carbon monoxide (CO) as a carbon source to introduce acyl fluoride functional groups into the polybutene backbone under the action of a fluorinating agent, resulting in polybutene materials containing acyl fluoride functional groups with excellent reactivity. The preparation method of this application is simple, requiring no cumbersome multi-step synthesis and purification processes, and is low in cost and easy to prepare on a large scale.
[0019] The polybutene grafted fluoride copolymer of this application has excellent reactivity and readily reacts with different functional compounds containing amine functional groups. By modifying the polybutene grafted fluoride copolymer with different functional compounds, functionalized polybutene copolymers with different hydrophilicity and hydrophobicity, different fluorescence color development properties and different thermal stability can be obtained.
[0020] The functionalized polybutene copolymer prepared in this application has broad application prospects in the fields of biomedicine, energy and chemical industry, fluorescence, and smart response. Attached Figure Description
[0021] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0022] Figure 1 The 1H NMR spectrum of the polybutene-grafted fluorine copolymer PB-F prepared in Example 1; Figure 2 The 1H NMR spectrum of the functionalized polymer PB-BA prepared in Example 2; Figure 3 The 1H NMR spectrum of the functionalized polymer PB-OEG prepared in Example 3; Figure 4 The 1H NMR spectrum of the functionalized polymer PB-AIE prepared in Example 4; Figure 5Infrared spectra of the polybutene material of Example 1 and the functionalized polymers prepared in Examples 2-4; Figure 6 The graph shows the water contact angle test results of the polybutene material in Example 1 and the functionalized polymers prepared in Examples 2-4; Figure 7 The ultraviolet absorption spectra of the polybutene material of Example 1 and the functionalized polymers prepared in Examples 2-4 are shown. Figure 8 The fluorescence spectra of the polybutene material of Example 1 and the functionalized polymers prepared in Examples 2-4 are shown. Figure 9 Thermogravimetric analysis (TGA) diagrams are shown for the polybutene material of Example 1 and the functionalized polymers prepared in Examples 2-4. Detailed Implementation
[0023] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.
[0024] In the following description of this embodiment, the terms "including", "comprising", "having", and "containing" are all open-ended terms, meaning that they include but are not limited to.
[0025] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.
[0026] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.
[0027] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.
[0028] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.
[0029] Those skilled in the art will understand that the numerical ranges in the embodiments of this application should be understood as each intermediate value between the upper and lower limits of the specifically disclosed range. Each 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 application. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0030] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. 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.
[0031] This application provides a polybutene-grafted fluorine copolymer, the chemical structure of which is shown in formula (1): Equation (1) Where x is an integer from 20 to 100, and y is an integer from 2 to 10.
[0032] In this application, the number-average molecular weight of the polybutene grafted with fluorine copolymer is 1324–6620, preferably 1500–4000. When the number-average molecular weight of the polybutene material containing fluorine functional groups is within the above range, the polybutene material containing fluorine functional groups has excellent reactivity.
[0033] The polybutene-grafted acyl fluoride copolymer of this application possesses acyl fluoride functional groups, giving it excellent reactivity. It can react with different functional organic compounds to prepare polybutene copolymers with different functions, such as functionalized polybutene copolymers with different hydrophilicity / phobicity, different fluorescence color development properties, and different thermal stability.
[0034] This application utilizes carbon monoxide (CO) as a carbon source to introduce acyl fluoride functional groups into the polybutene backbone under the action of a fluorinating agent, thereby obtaining a polybutene material containing acyl fluoride functional groups with excellent reactivity. The preparation method specifically includes: Under an inert atmosphere, polybutene, catalyst, oxidant and fluorinating agent are dissolved in a first organic solvent to obtain a precursor solution; Carbon monoxide is introduced into the precursor solution, and a photochemical reaction is carried out to obtain a polybutene-grafted fluorine copolymer. The inert atmosphere is preferably nitrogen.
[0035] Specifically, in this application, polybutene, a catalyst, an oxidant, and a fluorinating agent are placed in an egg-shaped flask. The flask is then evacuated and purged with nitrogen gas three times. After this process, a first organic solvent is injected while maintaining the nitrogen purging. Following the injection of the first organic solvent, carbon monoxide (CO) is bubbled to replace the gas in the flask for ten minutes. Finally, the reaction is carried out under light while maintaining the continuous CO purging, resulting in a polybutene material containing acyl fluoride functional groups, i.e., a polybutene-grafted acyl fluoride copolymer.
[0036] In this application, the average molecular weight of the polybutene is preferably 1324-6620.
[0037] The catalyst is a soluble divalent copper salt, such as any one of CuCl2, CuBr2, or Cu(NO3)2, preferably CuCl2. When CuCl2 is used as a catalyst, it can effectively promote the smooth progress of the first reaction, which is beneficial to the HAT process, thereby introducing more acyl fluoride functional groups into the polybutene backbone. This is beneficial to preparing polybutene materials with excellent reactivity containing acyl fluoride functional groups, and other metal chlorine catalysts do not provide better reaction efficiency.
[0038] The oxidant can be any one of K2S2O8, Na2S2O8, or (NH4)2S2O8, with K2S2O8 being preferred. When K2S2O8 is used as the oxidant, it is beneficial to improve the conversion rate of the thioesterification intermediate generated during the reaction, thereby facilitating the preparation of polybutene materials containing acyl fluorine functional groups with high yield and excellent reactivity.
[0039] The fluorinating agent can be any one of KF, NaF, or LiF, preferably KF. Because KF has a high fluorine content, it exhibits high selectivity for the target product and fewer side reactions during the reaction. Furthermore, the reaction conditions are mild, which is more conducive to converting the thioesterification intermediate into acyl fluoride, thus facilitating the preparation of polybutene materials containing acyl fluoride functional groups with high yield and excellent reactivity.
[0040] The first organic solvent is any one of 1,2-dichloroethane, dichloromethane, or trichloromethane, preferably 1,2-dichloroethane.
[0041] In this application, the photoreaction is carried out under blue light with a wavelength of 445 nm, at a temperature of 25°C to 40°C, and for a time of 24 to 48 hours. When the temperature and time are within this range, the reaction can proceed fully and effectively, improving the efficiency of the HAT (Hydrogen Atom Transfer) process initiated by a single catalyst in polybutene. Furthermore, it is beneficial to improve the CO capture efficiency, thereby increasing the amount of thioesterification intermediates produced, thus obtaining polybutene materials containing fluorine-containing functional groups with high yield and excellent reactivity.
[0042] In this application, the reaction formula for preparing polybutene-grafted fluorine copolymer is shown below:
[0043] In this application, the catalyst forms an excited-state complex under light irradiation, initiating a ligand-metal charge transfer process to generate highly active chlorine radicals. These chlorine radicals undergo a HAT (Hydrogen Atom Transfer) process with the Csp3-H bonds on the polybutene backbone, forming a carbon-centered radical intermediate. This intermediate captures CO to form an acyl radical intermediate. The acyl radical then reacts with a key thiosulfonate intermediate to generate a thioesterification product. Finally, the thioesterification product is fluorinated with a fluorinating agent to form an acyl fluoride functional group, ultimately yielding a polybutene material containing an acyl fluoride functional group.
[0044] In this application, the preferred molar ratio of polybutene, catalyst, oxidant, and fluorinating agent is 1~5:0.01~0.5:0.25~1:0.3~30, more preferably 5:0.1:1:1.5. Exemplarily, in the above raw material system, the molar ratio of polybutene, catalyst, oxidant, and fluorinating agent can be any one of 5:0.1:1:1.5, 3:0.5:1:30, 5:0.075:0.75:1.125, 5:0.05:0.5:0.75, 5:0.025:0.25:0.375, 1:0.01:1:1.5, or any ratio within this range.
[0045] When the molar ratio of polybutene, catalyst, oxidant, and fluorinating agent in the above raw material system is within the above range, the components can be better matched, and the first reaction can be carried out fully and effectively, thereby preparing a polybutene material containing acyl fluorine functional groups with excellent reactivity.
[0046] This application does not impose any special restrictions on the amount of the first organic solvent used, as long as it is sufficient to fully dissolve the polybutene.
[0047] The preparation method of this application is simple, does not require complicated multi-step synthesis and purification processes, is low in cost and easy to prepare on a large scale.
[0048] The polybutene grafted fluoride copolymer of this application exhibits excellent reactivity, readily reacting with various functional compounds containing amine functional groups. By modifying the polybutene grafted fluoride copolymer with different functional compounds, functionalized polybutene copolymers with different hydrophilicity / phobicity, different fluorescence color development properties, and different thermal stability are obtained. The preparation method of the functionalized copolymer of this application includes: The above-mentioned polybutene grafted fluorine copolymer, functional compound and catalyst are added to a first organic solvent for reaction; wherein the reaction temperature is 25~40℃ and the time is 24h~48h.
[0049] The reaction product was dissolved in a second solvent and then precipitated in a third organic solvent; the precipitate was dried to obtain the functionalized copolymer.
[0050] In this application, the functional compound is an organic compound containing an amine group, which is modified by a ring reaction between the amine group and a polybutene grafted fluoride copolymer. For example, the functional compound may be any one of benzylamine, methoxy polyethylene glycolamine, or 4-(1,2,2-triphenylvinyl)aniline.
[0051] The catalyst is a soluble divalent copper salt, such as any one of CuCl2, CuBr2 or Cu(NO3)2, preferably CuCl2.
[0052] The second organic solvent includes any one of dichloromethane, trichloromethane, or tetrahydrofuran, preferably dichloromethane, which can fully dissolve polybutene materials and functional compounds containing acyl fluoride functional groups, providing a good solvent environment for the preparation of functionalized copolymers with hydrophilic and fluorescent properties.
[0053] The third organic solvent is any one of methanol, n-hexane, or diethyl ether, preferably methanol. It is used to remove impurities and improve the purity of the functionalized copolymer.
[0054] In this application, the preferred molar ratio of the polybutene grafted with fluorine copolymer to the functional compound is 5:0.2~2. When the molar ratio of the polybutene material containing fluorine functional groups to the functional compound is within the above range, the components can interact better, allowing the second reaction to proceed fully and effectively, thereby preparing a functionalized copolymer with hydrophilic and hydrophobic properties and fluorescence.
[0055] This invention, through the above-described method for preparing functionalized copolymers, enables the preparation of functionalized copolymers (functionalized carbonyl-modified polybutene materials) with different hydrophilicity / phobicity, fluorescence properties, and thermal stability. The functionalized copolymers of this application possess hydrophilicity / phobicity, fluorescence properties, and thermal stability, and have broad application prospects in fields such as biomedicine, energy and chemical engineering, fluorescence, and smart response.
[0056] The present application will be further described below through specific embodiments.
[0057] Example 1 This embodiment provides a method for preparing a polybutene-grafted fluorine copolymer, comprising: 560 mg (0.01 mol) of polybutene, 116 mg (0.002 mol) of KF, 27 mg (0.002 mol) of CuCl2, and 810 mg (0.003) of K2S2O8 were added to a 100 ml egg-shaped flask. After evacuation, nitrogen gas was introduced and the mixture was circulated three times. While maintaining a continuous nitrogen gas supply, 20 mL of ultra-dry 1,2-dichloroethane (DCE) was added to obtain the precursor solution. The precursor solution was bubbled with CO through a long needle for 10 minutes, and then CO was continuously bubbled through a short needle to obtain a reaction mixture. The reaction mixture was then irradiated with a blue LED lamp with a power of 20W and a wavelength of 445nm at 25°C for 48 hours to obtain a polybutene-grafted fluorine copolymer, denoted as PB-F.
[0058] The reaction formula is shown below:
[0059] Example 2 This embodiment provides a method for preparing a functionalized polymer, including: After the reaction in Example 1 was completed, the blue LED lamp was removed, and 428 mg (0.004 mol) of benzylamine was added to the reaction flask. The reaction was carried out at 25 °C for 24 h to obtain the reaction product. The reaction product was dissolved in dichloromethane, followed by precipitation in ice-cold methanol. The precipitate was collected, dissolved in a small amount of dichloromethane, and then precipitated again in ice-cold methanol. This cycle was repeated three times to obtain the final precipitate, which was then dried to obtain the functionalized polymer, denoted as PB-BA. The reaction formula is shown below:
[0060] Example 3 This embodiment provides a method for preparing a functionalized polymer, including: After the reaction in Example 1 was completed, the blue LED lamp was removed, and 176 mg (0.004 mol) of methoxy oligoethylene glycolamine (OEG-NH2) was added to the reaction flask. The reaction was carried out at 25 °C for 24 h to obtain the reaction product. The reaction product was dissolved in dichloromethane, followed by precipitation in ice-cold methanol. The precipitate was collected, dissolved in a small amount of dichloromethane, and then precipitated again in ice-cold methanol. This cycle was repeated three times to obtain the final precipitate, which was then dried to obtain the functionalized polymer, denoted as PB-OEG. The reaction formula is shown below:
[0061] Example 4 This embodiment provides a method for preparing a functionalized polymer, including: After the reaction in Example 1 was completed, the blue LED lamp was removed, and 1390 mg (0.004 mol) of 4-(1,2,2-triphenylvinyl)aniline (AIE-NH2) was added to the reaction flask. The reaction was carried out at 25 °C for 24 h to obtain the reaction product. The reaction product was dissolved in dichloromethane, followed by precipitation in ice-cold methanol. The precipitate was collected, dissolved in a small amount of dichloromethane, and then precipitated again in ice-cold methanol. This cycle was repeated three times to obtain the final precipitate, which was then dried to obtain the functionalized polymer, denoted as PB-AIE. The reaction formula is shown below:
[0062] The polybutene-grafted fluorine copolymer and functionalized polymer prepared in this application were characterized as follows: I. Structural Characterization 1. The chemical structures of the polybutene grafted fluoride copolymer prepared in Example 1 and the functionalized polymers prepared in Examples 2-4 were evaluated by proton NMR spectroscopy.
[0063] The 1H NMR spectrum of the polybutene-grafted fluorine copolymer prepared in Example 1 is shown below. Figure 1 As shown. From Figure 1 A chemical shift at 2.02 ppm can be observed corresponding to -C. H The signal peak (d) of H in the methylene group of 2COF indicates that the acyl fluoride group was successfully introduced into PB by grafting.
[0064] The 1H NMR spectra of the functionalized polymers prepared in Examples 2-4 are shown in the following figures. Figure 2-4 As shown. From Figure 2 It can be observed that the corresponding benzylamine moiety -CONHC HThe NMR results show that the 2-methylene hydrogen signal peak at 3.65 ppm (e) and the corresponding phenyl hydrogen signal peak at 7.36 ppm (f, g, h) indicate that a benzylamine group was successfully introduced into PB containing an acyl fluoride unit.
[0065] from Figure 3 It can be observed that -OC corresponds to oligoethylene oxide. H 2C H The 2-methylene hydrogen signal peak at 3.65 ppm (f, g, h) indicates that the oligomeric epoxy group was successfully introduced into PB containing acyl fluoride moieties.
[0066] from Figure 4 Signal peaks (e, f, g, h, i) corresponding to the phenyl hydrogen in tetravinylbenzene can be observed at 6.62 ppm, 6.85 ppm, and 7.16 ppm. These NMR results indicate that tetraphenylethylene groups have been successfully introduced into PB containing acyl fluoride units.
[0067] The above results demonstrate that functional units with different structures and properties can be introduced by the amidation reaction of the acyl fluoride unit introduced into PB with the amino group, thus achieving further functionalization of PB.
[0068] 3. Fourier transform infrared spectroscopy analysis was performed on the polybutene material of Example 1 and the functionalized polymers prepared in Examples 2-4. The results are as follows: Figure 5 As shown.
[0069] Depend on Figure 5 It can be seen that the functionalized copolymers PB-BA, PB-OEG, and PB-AIE prepared in Examples 2-4 have a growth rate of 1615 cm⁻¹. -1 Vibrational characteristic peaks of carbonyl groups (C=O) appeared in the vicinity, and were observed at 1125 cm⁻¹. -1 The vibrational characteristic peaks of amino groups (NH) were observed in the vicinity. This indicates that the polybutene grafted fluoride copolymer prepared in Example 1 reacted with the functional compound containing amino groups to form amide bonds.
[0070] II. Performance Testing 1. Hydrophilicity test The water contact angle of the polybutene material used in Example 1 and the functionalized copolymers prepared in Examples 2-4 were tested, and the results are as follows: Figure 6 As shown.
[0071] Depend on Figure 6 It can be seen that the water contact angle of the polybutene material used in Example 1 is 80.1°. o The functionalized copolymer PB-BA prepared in Example 2 has a water contact angle of 77.7°. oThe functionalized copolymer PB-OEG prepared in Example 3 had a water contact angle of 14.6°. o The functionalized copolymer PB-AIE prepared in Example 4 has a water contact angle of 84.1°. o This demonstrates that by introducing acyl fluoride functional groups into the polybutene used in Example 1, and then introducing different groups, functionalized copolymers with different hydrophilicity and hydrophobicity can be prepared. This is based on the fact that the reactive functional group (acyl fluoride) of the polybutene material containing acyl fluoride functional groups in Example 1 has high reactivity. Therefore, different functional compounds can be used to modify the polybutene material containing acyl fluoride functional groups prepared in the examples of this invention, introducing different groups into the polybutene material containing acyl fluoride functional groups, thereby obtaining functionalized copolymers with different hydrophilicity and hydrophobicity.
[0072] 2. Ultraviolet absorption and fluorescence color development properties The polybutene used in Example 1 and the functionalized copolymers prepared in Examples 2-4 were subjected to ultraviolet absorption spectroscopy and fluorescence spectroscopy tests, and the test results are as follows: Figure 7 and Figure 8 As shown. Among them, Figure 7 This is a UV absorption spectrum. Figure 8 This is a fluorescence spectrum.
[0073] Depend on Figure 7 and Figure 8 It is known that introducing different functional groups into the polybutene grafted fluoride copolymer of Example 1 can prepare functional copolymers with different ultraviolet absorption peaks at 275nm and 345nm respectively and fluorescence emission peaks at 395nm (fluorescence emission range from 300nm to >480nm), indicating that the functional copolymers obtained in this application have ultraviolet absorption and fluorescence color development properties.
[0074] 3. Thermal stability Thermogravimetric analysis was performed on the polybutene used in Example 1 and the functionalized copolymers prepared in Examples 2-4, and the results are as follows: Figure 9 As shown.
[0075] Depend on Figure 9 It is evident that introducing different functional groups into the polybutene-grafted fluorinated copolymer of Example 1 can prepare functional copolymers with different thermal stability, demonstrating that the functional copolymers obtained in this application have different thermal stability properties.
[0076] Although this application has been described in detail in this specification with general descriptions and specific embodiments, some modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, such modifications or improvements made without departing from the spirit of this application are all within the scope of protection claimed in this application.
Claims
1. A polybutene-grafted fluorine copolymer, characterized in that, Its chemical structure is shown in formula (1): Equation (1) Where x is an integer from 20 to 100, and y is an integer from 2 to 10.
2. The polybutene-grafted fluorine copolymer according to claim 1, characterized in that, The number-average molecular weight of the polybutene-grafted fluorine copolymer is 1324–6620.
3. The method for preparing the polybutene-grafted fluorine copolymer according to claim 1, characterized in that, include: Under an inert atmosphere, polybutene, catalyst, oxidant and fluorinating agent are dissolved in a first organic solvent to obtain a precursor solution; Carbon monoxide is introduced into the precursor solution, and after photoreaction, polybutene grafted fluorine copolymer is obtained.
4. The preparation method according to claim 3, characterized in that, The catalyst is any one of CuCl2, CuBr2 or Cu(NO3)2; The oxidant is any one of K2S2O8, Na2S2O8 or (NH4)2S2O8; The fluorinating agent is any one of KF, NaF or LiF; The first organic solvent is any one of 1,2-dichloroethane, dichloromethane, or trichloromethane.
5. The preparation method according to claim 3, characterized in that, The molar ratio of the polybutene, catalyst, oxidant, and fluorinating agent is 1~5:0.01~0.5:0.25~1:0.3~30; And / or, The inert atmosphere is nitrogen; And / or, The photoreaction is carried out under blue light with a wavelength of 445 nm, at a temperature of 25℃ to 40℃, and for a time of 24h to 48h.
6. A method for preparing a functionalized copolymer, characterized in that, include: The polybutene grafted fluoride copolymer, functional compound, and catalyst described in claim 1 or 2 are added to a first organic solvent for reaction. The functional compound is an organic compound containing an amine group; The reaction product was dissolved in a second solvent and then precipitated in a third organic solvent; the precipitate was dried to obtain the functionalized copolymer.
7. The preparation method according to claim 6, characterized in that, The functional compound includes any one of benzimidamine, methoxy polyethylene glycolamine, or 4-(1,2,2-triphenylvinyl)aniline.
8. The preparation method according to claim 6, characterized in that, The second organic solvent is any one of dichloromethane, trichloromethane, or tetrahydrofuran; The third organic solvent is any one of methanol, n-hexane, or diethyl ether.
9. The preparation method according to claim 6, characterized in that, The molar ratio of the polybutene-grafted fluorine copolymer to the functional compound is 5:0.2~2; The reaction is carried out at a temperature of 25-40°C for 24-48 hours.
10. The functionalized copolymer prepared by the preparation method according to any one of claims 6-9.