Polyethylene glycol grafted polypentafluorophenyl ester copolymer, functionalized copolymer and preparation method

Abstract

The present invention provides a polyethylene glycol-grafted polypentafluorophenyl ester copolymer, a functionalized copolymer, and a preparation method. The structure of the polyethylene glycol-grafted polypentafluorophenyl ester copolymer is shown in formula (1): wherein m is an integer from 40 to 200, n is an integer from 1 to 40, and p is an integer from 10 to 80. The polyethylene glycol-grafted polypentafluorophenyl ester copolymer has excellent reactivity and can be easily modified with different functional compounds to obtain functionalized copolymers with different hydrophilicity and color development properties. The functionalized copolymer has broad application prospects in the fields of biomedicine, energy and chemical engineering, fluorescence, and intelligent response.

Description

Technical Field

[0001] The present invention relates to the fields of polymer synthesis and functionalized polymer preparation, and in particular to a polyethylene glycol grafted polypentafluorophenyl ester copolymer, a functionalized copolymer and a preparation method thereof. Background Art

[0002] Since the discovery of polymer materials, the shining jewel of modern science and technology, the question of how to functionalize them to meet the needs of diverse fields has become a crucial and tireless pursuit for scientists worldwide. With the advancement of science and technology, functionalized polymer materials are increasingly appearing in daily life and industrial production. In the electronics field, the introduction of functionalized polymer materials has promoted the miniaturization and efficiency of electronic devices. In the energy and chemical industry, functionalized polymer materials serve as catalysts, separation membranes, or energy storage materials, effectively improving the efficiency of energy conversion and storage. In the biomedicine field, functionalized polymer materials can be used as drug carriers, tissue engineering scaffolds, and other applications, greatly improving drug utilization.

[0003] Polyethylene glycol (PEG), also known as polyethylene oxide, is a widely used chemical in biomedicine, medical devices, cosmetics, food processing, and other fields due to its excellent biocompatibility, low toxicity, and solubility. However, traditional PEG typically contains reactive functional groups at only one or both ends, resulting in only one or two reactive sites capable of reaction / ligation, limiting its application.

[0004] In order to increase the number of reactive functional groups of polyethylene glycol, prior art is by introducing other reactive functional groups (such as ester groups) into polyethylene glycol to obtain polyethylene glycol materials containing more reactive functional groups. For example, Brett P.Fors et al. (Photocontrolled Radical Polymerization from Hydridic CH Bonds, Journal of the American Chemical Society, 2020, 10, 4581-4585) reported that using carbon-hydrogen bonds in polyethylene glycol as initiation sites, using benzophenone derivatives as free radical photoinitiators, using dodecyl disulfide as CTA reagents, introducing polymethyl acrylate chain side chains into polyethylene glycol chains, and obtaining polyethylene glycol materials containing ester groups. However, due to the problem that the reactive functional groups (ester groups) introduced are less reactive, it is impossible to further functionalize the polyethylene glycol materials containing ester groups, it is impossible to meet the diversified and intelligent application requirements of polyethylene glycol.

[0005] Therefore, how to design and synthesize a polyethylene glycol material with high reactivity is a technical problem that needs to be solved urgently in this field. Summary of the Invention

[0006] The invention provides a polyethylene glycol grafted polypentafluorophenyl ester copolymer. The polyethylene glycol grafted polypentafluorophenyl ester copolymer has excellent reactivity and can be easily modified by different functional compounds to obtain functionalized copolymers with different hydrophilicity and different color development properties.

[0007] The present invention also provides a method for preparing a polyethylene glycol grafted polypentafluorophenyl ester copolymer, by which the above-mentioned polyethylene glycol grafted polypentafluorophenyl ester copolymer with excellent reactivity can be prepared. The preparation method is simple and easy to perform, does not require complicated multi-step synthesis and purification processes, and is suitable for wide promotion and application.

[0008] The present invention also provides a method for preparing a functionalized copolymer, by which the above-mentioned polyethylene glycol grafted polypentafluorophenyl ester copolymer can be modified with different functional compounds, thereby preparing functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymers with different hydrophilicity and different color development properties.

[0009] The present invention also provides a functionalized copolymer prepared by the above-mentioned method for preparing the functionalized copolymer. The functionalized copolymer has hydrophilicity and hydrophobicity and color development properties.

[0010] The first aspect of the present invention provides a polyethylene glycol grafted polypentafluorophenyl ester copolymer, the structure of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is shown in formula (1):

[0011]

[0012] Here, m is an integer from 40 to 200, n is an integer from 1 to 40, and p is an integer from 10 to 80.

[0013] The polyethylene glycol grafted polypentafluorophenyl ester copolymer as described above has a number average molecular weight of 10,000 to 500,000.

[0014] The second aspect of the present invention provides a method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer, comprising the following steps:

[0015] Dissolving a raw material system including polyethylene glycol, a photocatalyst, a CTA reagent, and a monomer pentafluorophenyl acrylate in a first organic solvent to obtain a mixture;

[0016] The mixture is subjected to a freeze-drain treatment and then subjected to a first reaction to obtain a first reaction product;

[0017] The first reaction product is subjected to a first precipitation treatment in methanol and then to a first drying treatment to obtain the polyethylene glycol grafted polypentafluorophenyl ester copolymer.

[0018] In the preparation method of the polyethylene glycol-grafted polypentafluorophenyl ester copolymer as described above, the number average molecular weight of the polyethylene glycol is any one of 2000 and 10000.

[0019] The preparation method of the polyethylene glycol grafted polypentafluorophenyl ester copolymer as described above, the structural formula of the photocatalyst is shown in formula (2):

[0020]

[0021] Wherein, R1 and R2 are each independently any organic substituent group, R1 may be located at the para, meta or ortho position of the benzene ring B, and R2 may be located at the para, meta or ortho position of the benzene ring A;

[0022] And / or, the structural formula of the CTA reagent is as shown in formula (3):

[0023]

[0024] Wherein, R1 and R2 are each independently any organic substituent group.

[0025] In the preparation method of the polyethylene glycol grafted polypentafluorophenyl ester copolymer as described above, in the raw material system, the molar ratio of the polyethylene glycol, the photocatalyst, the CTA reagent, and the monomer pentafluorophenyl acrylate is 3:0.5:1:(20-100).

[0026] The method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer as described above, wherein the first organic solvent comprises 1,2-dichloroethane;

[0027] And / or, the temperature for the first reaction is 40° C. to 60° C., and the time is 10 h to 24 h.

[0028] A third aspect of the present invention provides a method for preparing a functionalized copolymer, comprising dissolving the polyethylene glycol grafted polypentafluorophenyl ester copolymer or the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared by the method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer, a functional compound, and a catalyst in a second organic solvent to obtain a mixed solution, wherein the functional compound has a structural formula of any one of formula (4) and formula (5):

[0029]

[0030] In formula (4) to formula (5), R is independently any organic substituent group;

[0031] The mixed solution is subjected to a second reaction to obtain a second reaction product, and the second reaction product is subsequently subjected to a second precipitation treatment in a third organic solvent and then to a second drying treatment to obtain the functionalized copolymer.

[0032] The method for preparing the functionalized copolymer as described above, wherein the molar ratio of the polyethylene glycol grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst is 1:1.5-5:0.2-1;

[0033] And / or, the temperature for the second reaction is 25°C to 50°C and the time is 24h to 72h;

[0034] And / or, the catalyst is triethylamine or 4-dimethylaminopyridine;

[0035] and / or, the second organic solvent is tetrahydrofuran or N,N-dimethylformamide;

[0036] And / or, the third organic solvent is methanol or diethyl ether.

[0037] The fourth aspect of the present invention provides a functionalized copolymer prepared by the above-mentioned method for preparing the functionalized copolymer.

[0038] The present invention provides a polyethylene glycol-grafted polypentafluorophenyl ester copolymer having a structure represented by formula (1). The present invention obtains a polyethylene glycol-grafted polypentafluorophenyl ester copolymer having excellent reactivity by grafting pentafluorophenyl acrylate monomer onto polyethylene glycol. When reacting with different functional compounds, the polyethylene glycol-grafted polypentafluorophenyl ester copolymer can be easily modified by the different functional compounds to obtain functionalized copolymers having different hydrophilic and chromogenic properties. The functionalized copolymer has broad application prospects in the fields of biomedicine, energy and chemical engineering, fluorescence, and intelligent response. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The H NMR spectrum of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA provided in Example 1 of the present invention;

[0040] Figure 2 The fluorine spectrum NMR image of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA provided in Example 1 of the present invention;

[0041] Figure 3 This is the H NMR spectrum of the functionalized copolymer 3a provided in Example 2 of the present invention;

[0042] Figure 4 This is the H NMR spectrum of the functionalized copolymer 3b provided in Example 3 of the present invention;

[0043] Figure 5 This is the H NMR spectrum of the functionalized copolymer 3c provided in Example 4 of the present invention;

[0044] Figure 6 This is a gel chromatogram of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA and the raw material PEG2000 in Example 1 of the present invention;

[0045] Figure 7 The water contact angle graphs of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA in Example 1 of the present invention and the functionalized copolymers in Examples 2-4;

[0046] Figure 8 The UV / visible absorption spectra of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA in Example 1 of the present invention and the functionalized copolymers in Examples 2-4;

[0047] Figure 9 These are fluorescence spectra of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA in Example 1 of the present invention and the functionalized copolymers in Examples 2-4. DETAILED DESCRIPTION

[0048] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0049] Unless otherwise specified, the raw materials and reagents used in the following examples can be obtained from commercial sources; the processes used, unless otherwise specified, are conventional processes in the art.

[0050] It should be noted that, if there are descriptions of “first”, “second”, “third”, etc. in the present invention, the descriptions of “first”, “second”, “third”, etc. are only used for descriptive purposes and therefore cannot be understood as limitations on the present invention.

[0051] The first aspect of the present invention provides a polyethylene glycol grafted polypentafluorophenyl ester copolymer, the structure of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is shown in formula (1):

[0052]

[0053] Here, m is an integer from 40 to 200, n is an integer from 1 to 40, and p is an integer from 10 to 80.

[0054] The polyethylene glycol-grafted polypentafluorophenyl ester copolymer provided by the present invention is prepared from a raw material system including polyethylene glycol, a photocatalyst, a CTA reagent, and the monomer pentafluorophenyl acrylate. This polyethylene glycol-grafted polypentafluorophenyl ester copolymer has excellent reactivity and can be easily modified with different functional compounds to obtain functionalized polyethylene glycol-grafted polypentafluorophenyl ester copolymers with varying hydrophilicity and color development properties.

[0055] In the present invention, CTA (chain transfer agent, CTA) reagent refers to a chain transfer agent, which is a type of chemical reagent that controls free radical polymerization reactions. It can control the chain growth of polymers through reversible addition-fragmentation reactions, thereby regulating the molecular weight and structure of the final polymer.

[0056] In a specific embodiment, the number average molecular weight of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is 10,000 to 500,000, and preferably 11,600 to 14,600.

[0057] When the number average molecular weight of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is within the above range, the polyethylene glycol grafted polypentafluorophenyl ester copolymer has excellent reactivity.

[0058] The second aspect of the present invention provides a method for preparing a polyethylene glycol grafted polypentafluorophenyl ester copolymer, comprising the following steps:

[0059] Dissolving a raw material system including polyethylene glycol, a photocatalyst, a CTA reagent, and a monomer pentafluorophenyl acrylate in a first organic solvent to obtain a mixture;

[0060] The mixture is subjected to freeze-drying treatment and then subjected to a first reaction to obtain a first reaction product;

[0061] The first reaction product is subjected to a first precipitation treatment in methanol and then to a first drying treatment to obtain a polyethylene glycol grafted polypentafluorophenyl ester copolymer.

[0062] In the present invention, the photocatalyst absorbs energy under light and becomes excited. The excited photocatalyst then converts polyethylene glycol into polyethylene glycol free radicals through a hydrogen atom transfer process. The polyethylene glycol free radicals continuously add to the monomer pentafluorophenyl acrylate to form propagating chain free radicals. The CTA reagent absorbs light energy and undergoes homolysis and chain termination with the propagating chain free radicals, resulting in a polyethylene glycol-grafted polypentafluorophenyl ester copolymer containing a CTA motif at the end of the polypentafluorophenyl ester. Under further control of the CTA reagent, the side chain polypentafluorophenyl ester in the polyethylene glycol-grafted polypentafluorophenyl ester copolymer containing a CTA motif at the end of the polypentafluorophenyl ester further undergoes chain growth, ultimately preparing the polyethylene glycol-grafted polypentafluorophenyl ester copolymer. In the present invention, because the CTA reagent has the properties of reversible chain scission and addition, the growth process of the side chain polypentafluorophenyl ester in the polyethylene glycol-grafted polypentafluorophenyl ester copolymer exhibits active and controllable free radical polymerization characteristics.

[0063] The object of preparation of the present invention is a polyethylene glycol grafted polypentafluorophenyl ester copolymer. Specifically, the polyethylene glycol grafted polypentafluorophenyl ester copolymer is prepared from a raw material system including polyethylene glycol, a photocatalyst, a CTA reagent, and a monomer pentafluorophenyl acrylate. The polyethylene glycol grafted polypentafluorophenyl ester copolymer has excellent reactivity and is easily modified by different functional compounds containing hydroxyl (-OH) or amino (-NH2) groups to obtain polyethylene glycol grafted polypentafluorophenyl ester copolymers with different structures and properties. For example, by introducing different reactive functional groups, functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymers with different hydrophilicity and different color development properties can be prepared.

[0064] The present invention does not particularly limit the sources of the various substances in the above raw material system, and they can be obtained through commercial channels or prepared by methods known to those skilled in the art.

[0065] The present invention has no particular limitation on the amount of the first organic solvent, as long as it can fully dissolve the raw material system including polyethylene glycol, photocatalyst, CTA reagent, and monomer pentafluorophenyl acrylate.

[0066] The present invention has no particular limitation on the freeze-pumping method, and a freeze-pumping technical solution well known to those skilled in the art may be used, such as placing the mixture under liquid nitrogen for freeze-pumping.

[0067] The present invention does not particularly limit the method for performing the first drying treatment, and any drying treatment technical solution well known to those skilled in the art may be used.

[0068] In a specific embodiment, the number average molecular weight of the polyethylene glycol is any one of 2000 and 10000. Furthermore, the number average molecular weight of the polyethylene glycol may preferably be 2000.

[0069] When the polyethylene glycol has the above-mentioned number average molecular weight, it is beneficial to improve the conversion rate of the monomer pentafluorophenyl acrylate and reduce the residual unreacted monomer pentafluorophenyl acrylate, thereby preparing a polyethylene glycol-grafted polypentafluorophenyl ester copolymer with high yield and excellent reactivity.

[0070] In a specific embodiment, the structural formula of the above-mentioned photocatalyst is shown in formula (2):

[0071]

[0072] Wherein, R1 and R2 are each independently any organic substituent group, R1 can be located at the para position, meta position or ortho position of the benzene ring B, and R2 can be located at the para position, meta position or ortho position of the benzene ring A; further, the above-mentioned photocatalyst can be preferably

[0073] The present invention does not particularly limit the source or specific preparation method of the photocatalyst, which can be purchased from commercial channels or prepared according to methods well known in the art or according to preparation methods in the literature.

[0074] When the above substances are selected as photocatalysts, the first reaction can be effectively carried out, which is beneficial to improving the conversion rate of the monomer pentafluorophenyl acrylate, reducing the residual unreacted monomer pentafluorophenyl acrylate, and is beneficial to preparing a polyethylene glycol-grafted polypentafluorophenyl ester copolymer with high yield and excellent reaction activity.

[0075] In one embodiment, the structural formula of the above-mentioned CTA reagent is shown in formula (3):

[0076]

[0077] Wherein, R1 and R2 are each independently any organic substituent group; further, the above CTA reagent can be preferably

[0078] The present invention does not particularly limit the source or specific preparation method of the CTA reagent, which can be purchased from commercial channels or prepared according to methods well known in the art or according to preparation methods in the literature.

[0079] When the above substances are selected as CTA reagents, it is beneficial to improve the conversion rate of monomer pentafluorophenyl acrylate and reduce the residual unreacted monomer pentafluorophenyl acrylate, thereby preparing a polyethylene glycol-grafted polypentafluorophenyl ester copolymer with high yield and excellent reactivity.

[0080] In a specific embodiment, in the above raw material system, the molar ratio of polyethylene glycol, photocatalyst, CTA reagent, and monomer pentafluorophenyl acrylate is 3:0.5:1:(20-100).

[0081] When the molar ratio of polyethylene glycol, photocatalyst, CTA reagent, and monomer pentafluorophenyl acrylate in the above raw material system is within the above range, the components can be better matched, and the first reaction can be fully and effectively carried out, thereby preparing a polyethylene glycol-grafted polypentafluorophenyl ester copolymer with high yield and excellent reactivity.

[0082] Illustratively, in the above raw material system, the molar ratio of polyethylene glycol, photocatalyst, CTA reagent, and monomer pentafluorophenyl acrylate can be any one of 3:0.5:1:20, 3:0.5:1:30, 3:0.5:1:40, 3:0.5:1:50, 3:0.5:1:60, 3:0.5:1:70, 3:0.5:1:80, 3:0.5:1:90, and 3:0.5:1:100, and a range consisting of any four of them.

[0083] In one specific embodiment, the first organic solvent includes 1,2-dichloroethane.

[0084] When the above substance is selected as the first organic solvent, it can fully dissolve the raw material system including polyethylene glycol, photocatalyst, CTA reagent, and monomer pentafluorophenyl acrylate, providing a good solvent environment for preparing polyethylene glycol-grafted polypentafluorophenyl ester copolymer with excellent reaction activity.

[0085] In a specific embodiment, the temperature for the first reaction is 40° C. to 60° C., and the time is 10 h to 24 h.

[0086] When the temperature and time parameters for the first reaction are each within the above ranges, the first reaction can be fully and effectively carried out, the conversion rate of the monomer pentafluorophenyl acrylate is improved, and the residual unreacted monomer pentafluorophenyl acrylate is reduced, thereby preparing a polyethylene glycol-grafted polypentafluorophenyl ester copolymer with high yield and excellent reactivity.

[0087] The third aspect of the present invention provides a method for preparing a functionalized copolymer, wherein a polyethylene glycol grafted polypentafluorophenyl ester copolymer or a polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared by the method for preparing a polyethylene glycol grafted polypentafluorophenyl ester copolymer, a functional compound, and a catalyst are dissolved in a second organic solvent to obtain a mixed solution, wherein the structural formula of the functional compound is any one of formula (4) and formula (5):

[0088]

[0089] In formula (4) to formula (5), R is independently any organic substituent group;

[0090] The mixed solution is subjected to a second reaction to obtain a second reaction product, and then the second reaction product is subjected to a second precipitation treatment in a third organic solvent and then to a second drying treatment to obtain a functionalized copolymer.

[0091] Furthermore, the functional compound may preferably be any one of 2,5,8,11,14-pentaoxahexadecan-16-amine, 9-carbazoleethanol, and 6-bromo-2-(2-hydroxyethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione.

[0092] The present invention does not particularly limit the source or specific preparation method of the functional compound, which can be purchased through commercial channels or prepared according to methods well known in the art or according to preparation methods in the literature.

[0093] The present invention uses the above-mentioned method for preparing a functionalized copolymer to prepare a functionalized copolymer (functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer) having hydrophilicity and color development properties. This preparation method can modify the above-mentioned polyethylene glycol grafted polypentafluorophenyl ester copolymer with different functional compounds to prepare functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymers having different hydrophilicity and color development properties.

[0094] The present invention has no particular limitation on the amount of the second organic solvent, as long as it can fully dissolve the polyethylene glycol-grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst.

[0095] In a specific embodiment, the molar ratio of the polyethylene glycol grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst is 1:1.5-5:0.2-1.

[0096] When the molar ratio of the polyethylene glycol grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst is within the above range, the components can interact better and the second reaction can be carried out fully and effectively, thereby preparing a functionalized copolymer with hydrophilic and color-developing properties.

[0097] In a specific embodiment, the temperature for the second reaction is 25° C. to 50° C., and the time is 24 h to 72 h.

[0098] When the temperature and time parameters for the second reaction are respectively within the above ranges, the second reaction can be fully and effectively carried out, thereby preparing a functionalized copolymer having hydrophilic and color-developing properties.

[0099] In one specific embodiment, the catalyst is triethylamine or 4-dimethylaminopyridine.

[0100] When the above substances are selected as catalysts, the second reaction can be effectively carried out, thereby preparing a functionalized copolymer with hydrophilic and hydrophobic properties and color development properties.

[0101] In one specific embodiment, the second organic solvent is tetrahydrofuran or N,N-dimethylformamide.

[0102] When the above substance is selected as the second organic solvent, it can fully dissolve the polyethylene glycol grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst, and provide a good solvent environment for preparing the functionalized copolymer with hydrophilic and hydrophobic properties and color development properties.

[0103] In a specific embodiment, the third organic solvent is methanol or diethyl ether.

[0104] When the above substances are selected as the third organic solvent, impurities can be removed, thereby preparing a functional copolymer with higher purity.

[0105] The fourth aspect of the present invention provides a functionalized copolymer prepared by the above-mentioned method for preparing a functionalized copolymer, so that the functionalized copolymer has hydrophilicity and color development properties.

[0106] The present invention is further described below through specific examples.

[0107] The 4-methoxy-4'-trifluoromethoxybenzophenone used in the following examples was synthesized according to the method in the reference (Photocontrolled radical polymerization from hydridic C–H bonds, Journal of the American Chemical Society, 2020, 10, 4581-4585); the structural formula used in the following examples is The CTA reagent was prepared according to the reference (Photocontrolled radical polymerization from hydridic C–H bonds, Journal of the American Chemical Society, 2020, 10, 4581-4585). method is used.

[0108] Example 1

[0109] In this embodiment, a polyethylene glycol-grafted polypentafluorophenyl ester copolymer was prepared by the following process:

[0110] 60 mg (0.03 mmol) of polyethylene glycol (PEG2000) with a number average molecular weight of 2000, 1.4 mg (0.005 mmol) of 4-methoxy-4'-trifluoromethoxybenzophenone (prepared in the laboratory), 5.5 mg (0.01 mmol) of CTA reagent (Product No. B463501, commercially available), and 238 mg (1 mmol) of pentafluorophenyl acrylate (PFMA) were dissolved in 1 mL of ultra-dry 1,2-dichloroethane (DCE) to obtain a mixture;

[0111] The mixture was placed under liquid nitrogen and subjected to freeze extraction treatment three times to obtain a reaction mixture;

[0112] The reaction mixture was reacted at 40°C for 24 hours under 40W energy-saving light to obtain a reaction product;

[0113] The reaction product was precipitated three times in frozen methanol to obtain a precipitate, which was then dried to obtain a polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA (142 mg, yield 59.7%) as shown in formula (6). Its H NMR spectrum is as follows: Figure 1 As shown, its NMR fluorine spectrum is as follows Figure 2 As shown;

[0114] The structure of the above-mentioned 4-methoxy-4'-trifluoromethoxybenzophenone is:

[0115]

[0116] The structure of the above CTA reagent is:

[0117]

[0118] The reaction formula is as follows:

[0119]

[0120] Wherein, x=m+n.

[0121] Example 2

[0122] This embodiment provides a method for preparing a functionalized copolymer, comprising the following steps:

[0123] 119 mg (0.5 mmol) of the polyethylene glycol-grafted polypentafluorophenyl ester copolymer prepared in Example 1, 158 mg (0.75 mmol) of 9-carbazoleethanol, and 12 mg (0.1 mmol) of 4-dimethylaminopyridine (DMAP) were dissolved in 4 mL of N,N-dimethylformamide (DMF) to obtain a mixed solution;

[0124] The mixed solution was reacted at 50°C for 48 hours to obtain a reaction product, which was then precipitated three times in methanol to obtain a precipitate. The precipitate was dried to obtain a functionalized copolymer 3a (functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer). Its H NMR spectrum is as follows: Figure 3 The reaction formula is shown below:

[0125]

[0126] Example 3

[0127] This embodiment provides a method for preparing a functionalized copolymer, comprising the following steps:

[0128] 119 mg (0.5 mmol) of the polyethylene glycol-grafted polypentafluorophenyl ester copolymer prepared in Example 1, 126 mg (0.75 mmol) of 2,5,8,11,14-pentaoxahexadecan-16-amine, and 5 mg (0.1 mmol) of triethylamine (TEA) were dissolved in 4 mL of tetrahydrofuran (THF) to obtain a mixed solution;

[0129] The mixed solution was reacted at 50° C. for 48 h to obtain a reaction product, which was then precipitated three times in ether to obtain a precipitate. The precipitate was dried to obtain a functionalized copolymer 3b (functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer). The H NMR spectrum thereof is as follows: Figure 4 The reaction formula is shown below:

[0130]

[0131] Example 4

[0132] This embodiment provides a method for preparing a functionalized copolymer, comprising the following steps:

[0133] 119 mg (0.5 mmol) of the polyethylene glycol-grafted polypentafluorophenyl ester copolymer prepared in Example 1, 250.5 mg (0.75 mmol) of 6-bromo-2-(2-hydroxyethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione, and 12 mg (0.1 mmol) of 4-dimethylaminopyridine (DMAP) were dissolved in 4 mL of tetrahydrofuran (THF) to obtain a mixed solution;

[0134] The mixed solution was reacted at 50° C. for 48 h to obtain a reaction product, which was then precipitated three times in ether to obtain a precipitate. The precipitate was dried to obtain a functionalized copolymer 3c (functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer). Its H NMR spectrum is as follows: Figure 5 The reaction formula is shown below:

[0135]

[0136] Results

[0137] 1. The PEG2000 used in Example 1 was evaluated. The conversion rate of the monomer pentafluorophenyl acrylate and the number average molecular weight and polydispersity index of the prepared polyethylene glycol-grafted polypentafluorophenyl ester copolymer were shown in Table 1.

[0138] Table 1 Conversion rate of pentafluorophenyl acrylate monomer, number average molecular weight and polydispersity index of polyethylene glycol grafted polypentafluorophenyl ester copolymer

[0139]

[0140] As shown in Table 1, the conversion rate of pentafluorophenyl acrylate monomer in Example 1 of the present invention is 90.9%, indicating that the pentafluorophenyl acrylate monomer in Example 1 of the present invention is polymerized.

[0141] 2. The polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in Example 1 was subjected to nuclear magnetic resonance hydrogen spectrum and fluorine spectrum tests. The results are as follows: Figure 1 and Figure 2 shown.

[0142] Depend on Figure 1 It can be seen that the prepared polyethylene glycol grafted polypentafluorophenyl ester copolymer simultaneously shows the characteristic signal peak corresponding to the main chain polyethylene glycol and the signal peak of the side chain polypentafluorophenyl ester; Figure 2 It can be seen that the prepared polyethylene glycol grafted polypentafluorophenyl ester copolymer shows a characteristic signal peak corresponding to the pentafluorophenyl group, indicating that the target product, namely the polyethylene glycol grafted polypentafluorophenyl ester copolymer, is prepared in this embodiment of the present invention.

[0143] 3. The polyethylene glycol grafted polypentafluorophenyl ester copolymer (PEG2000-g-PPFMA) prepared in Example 1 and the raw material PEG2000 were subjected to gel chromatography tests respectively. The results are as follows: Figure 6 shown.

[0144] Depend on Figure 6 It can be seen that the retention time of the polyethylene glycol grafted polypentafluorophenyl ester copolymer in Example 1 of the present invention is shorter than the retention time of the raw material PEG2000, and the number average molecular weight of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is 14500 Daltons (Da), which is higher than the number average molecular weight of the raw material PEG2000 (the number average molecular weight measured by gel permeation chromatography is 2600 Da), and the peak of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is a relatively symmetrical single peak, and its polydispersity index is 1.18 (Table 1), indicating that PEG2000 in Example 1 of the present invention triggers the polymerization of monomeric pentafluorophenyl acrylate to obtain the polyethylene glycol grafted polypentafluorophenyl ester copolymer.

[0145] 4. The functionalized copolymers prepared in Examples 2-4 were tested by nuclear magnetic resonance hydrogen spectrum. The results were as follows: Figure 3 、 Figure 4 and Figure 5 shown.

[0146] Depend on Figure 3 、 Figure 4 and Figure 5 It can be seen that after introducing different groups into the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA prepared in Example 1, the obtained functionalized copolymers 3a, functionalized copolymers 3b and functionalized copolymers 3c respectively showed characteristic signal peaks corresponding to the target groups and characteristic signal peaks corresponding to the polyethylene glycol main chain and the polyacrylate side chain, indicating that functionalized copolymers containing different groups were prepared in the examples of the present invention.

[0147] 5. The polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in Example 1 and the functionalized copolymers prepared in Examples 2-4 were tested for water contact angle. The results are as follows: Figure 7 shown.

[0148] Depend on Figure 7 It can be seen that the water contact angle of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA prepared in Example 1 is 89.1°, the water contact angle of the functionalized copolymer 3a prepared in Example 2 is 45.5°, the water contact angle of the functionalized copolymer 3b prepared in Example 3 is 6.0°, and the water contact angle of the functionalized copolymer 3c prepared in Example 4 is 64.8°, which shows that different groups are introduced into the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA prepared in Example 1. Functionalized copolymers with varying hydrophilicity and hydrophobicity can be prepared. This is because the reactive functional group (pentafluorophenyl ester) of the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA in Example 1 of the present invention has high reactivity. Therefore, the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in this example of the present invention can be modified with different functional compounds, introducing different groups into the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA, thereby obtaining functionalized copolymers with varying hydrophilicity and hydrophobicity. Therefore, the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in the present invention has excellent reactivity and tunable hydrophilicity and hydrophobicity.

[0149] 6. The polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in Example 1 and the functionalized copolymers prepared in Examples 2-4 were tested by UV / visible absorption spectroscopy. The results are as follows: Figure 8Fluorescence spectrum test was performed on the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in Example 1 and the functionalized copolymer prepared in Examples 2-4. The results were as shown. Figure 9 shown.

[0150] Depend on Figure 8 and Figure 9 It can be seen that by introducing different groups into the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA prepared in Example 1, functionalized copolymers with different colors can be prepared, indicating that the functionalized copolymer prepared in this embodiment of the present invention has adjustable color rendering properties.

[0151] In summary, the polyethylene glycol-grafted polypentafluorophenyl ester copolymer provided by the present invention has excellent reactivity and can be easily modified with different functional compounds to obtain functionalized copolymers with different hydrophilicity and different color development properties, indicating that the functionalized copolymer can be applied in biomedicine, energy and chemical industry, fluorescence, intelligent response and other fields.

[0152] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyethylene glycol grafted polypentafluorophenyl ester copolymer, characterized in that: The structure of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is shown in formula (1): Here, m is an integer from 40 to 200, n is an integer from 1 to 40, and p is an integer from 10 to 80.

2. The polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 1, characterized in that: The number average molecular weight of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is 10,000 to 500,000.

3. A method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 1 or 2, characterized in that: The steps include: Dissolving a raw material system including polyethylene glycol, a photocatalyst, a CTA reagent, and a monomer pentafluorophenyl acrylate in a first organic solvent to obtain a mixture; The mixture is subjected to a freeze-drain treatment and then subjected to a first reaction to obtain a first reaction product; The first reaction product is subjected to a first precipitation treatment in methanol and then to a first drying treatment to obtain the polyethylene glycol grafted polypentafluorophenyl ester copolymer.

4. The method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 3, wherein: The number average molecular weight of the polyethylene glycol is any one of 2000 and 10000.

5. The method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 3, wherein: The structural formula of the photocatalyst is shown in formula (2): Wherein, R1 and R2 are each independently any organic substituent group, R1 may be located at the para, meta or ortho position of the benzene ring B, and R2 may be located at the para, meta or ortho position of the benzene ring A; And / or, the structural formula of the CTA reagent is as shown in formula (3): Wherein, R1 and R2 are each independently any organic substituent group.

6. The method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 3, wherein: In the raw material system, the molar ratio of the polyethylene glycol, the photocatalyst, the CTA reagent, and the monomer pentafluorophenyl acrylate is 3:0.5:1:(20-100).

7. The method for preparing the polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 3, wherein: The first organic solvent includes 1,2-dichloroethane; And / or, the temperature for the first reaction is 40° C. to 60° C., and the time is 10 h to 24 h.

8. A method for preparing a functionalized copolymer, characterized in that: The polyethylene glycol grafted polypentafluorophenyl ester copolymer according to claim 1 or 2 or the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared by the preparation method of the polyethylene glycol grafted polypentafluorophenyl ester copolymer according to any one of claims 3 to 7, a functional compound and a catalyst are dissolved in a second organic solvent to obtain a mixed solution, wherein the structural formula of the functional compound is any one of formula (4) and formula (5): In formula (4) to formula (5), R is independently any organic substituent group; The mixed solution is subjected to a second reaction to obtain a second reaction product, and the second reaction product is subsequently subjected to a second precipitation treatment in a third organic solvent and then to a second drying treatment to obtain the functionalized copolymer.

9. The method for preparing a functionalized copolymer according to claim 8, wherein: The molar ratio of the polyethylene glycol grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst is 1:1.5-5:0.2-1; And / or, the temperature for the second reaction is 25°C to 50°C and the time is 24h to 72h; And / or, the catalyst is triethylamine or 4-dimethylaminopyridine; and / or, the second organic solvent is tetrahydrofuran or N,N-dimethylformamide; And / or, the third organic solvent is methanol or diethyl ether.

10. A functionalized copolymer, characterized in that The functionalized copolymer is prepared by the preparation method of claim 8 or 9.

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