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

Abstract

The 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 as a formula (1): # imgabs0 #, 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 reaction activity, can be easily modified by different functional compounds to obtain functional copolymers with different hydrophilic and hydrophobic properties and different color development properties, and has wide application prospects in the fields of biological medicine, energy and chemical industry, fluorescence, intelligent response and the like.

Description

Technical Field

[0001] The invention relates to the field 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 pearl in the field of modern science and technology, how to functionalize them according to the needs of different fields has become an important topic that scientists around the world have been exploring tirelessly. With the advancement of science and technology, functional polymer materials continue to emerge in daily life and industrial production. In the field of electronics, the introduction of functional polymer materials has promoted the miniaturization and efficiency of electronic devices; in the field of energy and chemical industry, functional polymer materials are used as catalysts, separation membranes or energy storage materials, effectively improving the efficiency of energy conversion and storage; in the field of biomedicine, functional polymer materials can be used as drug carriers, tissue engineering scaffolds, etc., greatly improving the utilization rate of drugs.

[0003] Among them, polyethylene glycol (also known as polyethylene oxide, polyethylene glycol, PEG) has the advantages of good biocompatibility, low toxicity and good solubility, and is widely used in the fields of biomedicine, equipment, cosmetics, food processing, etc. However, traditional polyethylene glycol usually has only one end or both ends containing reactive functional groups, so there are only one or two reactive active sites that can participate in the reaction / connection, which limits its application.

[0004] In order to increase the number of reactive functional groups of polyethylene glycol, the prior art is to introduce 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 the carbon-hydrogen bond in polyethylene glycol was used as the initiation site, benzophenone derivatives were used as free radical photoinitiators, and dodecyl disulfide was used as CTA reagents. The side chain of polymethyl acrylate chain was introduced into the polyethylene glycol chain to obtain a polyethylene glycol material containing an ester group. However, due to the problem of low reactivity of the introduced reactive functional group (ester group), it is impossible to further functionalize the polyethylene glycol material containing an ester group, and 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 a functionalized copolymer 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 polyethylene glycol grafted polypentafluorophenyl ester copolymer with excellent reaction activity 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 by using different functional compounds, thereby preparing a functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer with different hydrophilicity and different color development properties.

[0009] The present invention also provides a functionalized copolymer, which is prepared by the preparation method of the functionalized copolymer, and has hydrophilicity and color development performance.

[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 of 40 to 200, n is an integer of 1 to 40, and p is an integer of 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-drainage 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] The third aspect of the present invention provides a method for preparing a functionalized copolymer, wherein 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 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):

[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 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 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 functionalized copolymer preparation method.

[0038] The present invention provides a polyethylene glycol grafted polypentafluorophenyl ester copolymer, wherein the polyethylene glycol grafted polypentafluorophenyl ester copolymer has a structure shown in formula (1). The present invention obtains a polyethylene glycol grafted polypentafluorophenyl ester copolymer having excellent reactivity by grafting monomer pentafluorophenyl acrylate onto polyethylene glycol. When the polyethylene glycol grafted polypentafluorophenyl ester copolymer reacts with different functional compounds, it is easily modified by different functional compounds to obtain functionalized copolymers having different hydrophilicity and different color development properties, and the functionalized copolymer has broad application prospects in the fields of biomedicine, energy and chemical industry, fluorescence, intelligent response, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The hydrogen nuclear magnetic 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 hydrogen NMR spectrum of the functionalized copolymer 3a provided in Example 2 of the present invention;

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

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

[0044] Figure 6 The 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 diagrams 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] Fig. 9 It is the 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] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are 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 creative work are 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, in the present invention, there are descriptions involving "first", "second", "third", etc., and the descriptions of "first", "second", "third", etc. are only 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 of 40 to 200, n is an integer of 1 to 40, and p is an integer of 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 a monomer pentafluorophenyl acrylate. The polyethylene glycol grafted polypentafluorophenyl ester copolymer has excellent reactivity and is easily modified by different functional compounds to obtain a functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer with different hydrophilicity and different 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 a freeze-drainage 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 an excited state, and then the excited photocatalyst converts polyethylene glycol into polyethylene glycol free radicals through a hydrogen atom transfer process, and the polyethylene glycol free radicals continuously add to the monomer pentafluorophenyl acrylate to become a growth chain free radical, and the CTA reagent absorbs light energy and undergoes homolysis and chain termination with the growth chain free radical, and after termination, a polyethylene glycol grafted polypentafluorophenyl ester copolymer containing a CTA unit at the end of the polypentafluorophenyl ester is obtained; under further regulation of the CTA reagent, the side chain polypentafluorophenyl ester in the polyethylene glycol grafted polypentafluorophenyl ester copolymer containing a CTA unit at the end of the polypentafluorophenyl ester further undergoes chain growth, and finally a polyethylene glycol grafted polypentafluorophenyl ester copolymer is prepared. In the present invention, since the CTA reagent has the properties of reversible chain cleavage and addition, the growth process of the side chain polypentafluorophenyl ester in the polyethylene glycol grafted polypentafluorophenyl ester copolymer has 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) 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 used, 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. Further, the number average molecular weight of the polyethylene glycol may preferably be 2000.

[0069] When the polyethylene glycol is the polyethylene glycol with the above 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 reaction activity.

[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 through 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 monomer pentafluorophenyl acrylate, reducing the residual unreacted monomer pentafluorophenyl acrylate, and is beneficial to preparing polyethylene glycol grafted polypentafluorophenyl ester copolymers with high yield and excellent reaction activity.

[0075] In a specific embodiment, the structural formula of the above 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 may be preferably

[0078] The present invention does not particularly limit the source or specific preparation method of the CTA reagent, 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.

[0079] When the above substances are selected as CTA reagents, 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 reaction activity.

[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 reaction activity.

[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 of any four thereof.

[0083] In a 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 10h to 24h.

[0086] When the temperature and time parameters of the first reaction are respectively 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 reaction activity.

[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 can prepare a functional copolymer (functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer) having hydrophilicity and color development properties through the preparation method of the functionalized copolymer. The preparation method can modify the polyethylene glycol grafted polypentafluorophenyl ester copolymer using 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 fully and effectively carried out, thereby preparing a functional copolymer with hydrophilicity and color development properties.

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

[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 hydrophilicity and color development properties.

[0099] In a 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 functional copolymer having hydrophilicity and hydrophobicity and color development properties.

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

[0102] When the above substances are selected as the second organic solvent, the polyethylene glycol grafted polypentafluorophenyl ester copolymer, the functional compound and the catalyst can be fully dissolved, providing a good solvent environment for preparing a functional copolymer with hydrophilicity and hydrophobicity 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 embodiments.

[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 preparation of CTA reagent was synthesized 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, the polyethylene glycol grafted polypentafluorophenyl ester copolymer is 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 number B463501, commercially available) and 238 mg (1 mmol) of monomer 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 for freeze extraction three times to obtain a reaction mixture;

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

[0113] The reaction product was precipitated in frozen methanol for three times 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 Its NMR fluorine spectrum is as shown Figure 2 As shown;

[0114] The structure of the above 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 h to obtain a reaction product, which was then precipitated in methanol three times 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 As shown; the reaction formula is as follows:

[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 in ether three times to obtain a precipitate. The precipitate was dried to obtain a functionalized copolymer 3b (functionalized polyethylene glycol grafted polypentafluorophenyl ester copolymer). Its H NMR spectrum is as follows: Figure 4 As shown; the reaction formula is as follows:

[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 in ether three times 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 As shown; the reaction formula is as follows:

[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] It can be seen from Table 1 that the conversion rate of pentafluorophenyl acrylate monomer in Example 1 of the present invention is 90.9%, which indicates that 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 tested by nuclear magnetic resonance hydrogen spectrum and fluorine spectrum. 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 a characteristic signal peak corresponding to the main chain polyethylene glycol and a 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, which shows that the target product, namely the polyethylene glycol grafted polypentafluorophenyl ester copolymer, is prepared in the 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, the number average molecular weight of the polyethylene glycol grafted polypentafluorophenyl ester copolymer is 14500 Dalton (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), which indicates that PEG2000 in Example 1 of the present invention triggers the polymerization of monomer 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 are 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 copolymer 3a, functionalized copolymer 3b and functionalized copolymer 3c respectively showed characteristic signal peaks corresponding to the target group and characteristic signal peaks corresponding to the polyethylene glycol main chain and the polyacrylate side chain, indicating that the embodiment of the present invention prepared functionalized copolymers containing different groups.

[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 different 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 the present invention can be modified by different functional compounds, and different groups are introduced into the polyethylene glycol grafted polypentafluorophenyl ester copolymer PEG2000-g-PPFMA, thereby obtaining functionalized copolymers with different hydrophilicity and hydrophobicity. Therefore, the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared by the present invention has excellent reactivity, and the functionalized copolymer prepared by the present invention has adjustable 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 8As shown; the polyethylene glycol grafted polypentafluorophenyl ester copolymer prepared in Example 1 and the functionalized copolymers prepared in Examples 2-4 were tested for fluorescence spectroscopy, and the results were as follows Fig. 9 shown.

[0150] Depend on Figure 8 and Fig. 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, which shows that the functionalized copolymer prepared in the 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 by different functional compounds to obtain functionalized copolymers with different hydrophilicity and different color development properties, indicating that the functionalized copolymer can be applied to 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned 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 of 40 to 200, n is an integer of 1 to 40, and p is an integer of 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 10,000-500,000.

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-drainage 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, characterized in that: 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, characterized in that: 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, characterized in that: 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, characterized in that: 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 method for preparing 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 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 the functionalized copolymer.

9. The method for preparing a functionalized copolymer according to claim 8, characterized in that: 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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