A modified resin material, its preparation method and application

Abstract

The present invention provides a modified resin material, comprising a resin carrier and thiol-modified PVP-CTA and ethanolamine grafted onto the surface of the resin carrier via epoxy groups. Due to the grafting of hydrophilic PVP and the presence of hydroxyl groups, the modified carrier provided by the present invention has high biocompatibility, addressing the poor biocompatibility of traditional resins. Furthermore, the modified carrier exhibits mild reaction conditions, a simple processing technique, and low organic solvent usage, resulting in minimal environmental impact. Furthermore, by regulating the ratio of a chain transfer agent to monomers, a series of polymers of varying chain lengths can be synthesized, thereby regulating the balance between hydrophilicity and adsorption properties. Furthermore, ethanolamine end-capping is employed to introduce hydroxyl groups, further enhancing the hydrophilicity of the carrier. This rationally utilizes the remaining epoxy groups, further significantly improving the carrier's hydrophilicity.

Description

Technical Field

[0001] The invention belongs to the technical field of blood purification adsorbents and relates to a modified resin material and a preparation method and application thereof. Background Art

[0002] Currently, the main adsorbents commonly used in hemoperfusion are activated carbon, polysaccharides, and synthetic resins. Activated carbon adsorbents have low mechanical strength, poor blood compatibility, and the small particles are prone to shedding. Polysaccharide adsorbents also have low strength and low adsorption capacity. Therefore, synthetic resin adsorbents, such as polystyrene resins, are the most widely used in hemoperfusion. Currently, the synthetic resin adsorbents used in hemoperfusion devices on the market for removing medium and large molecular toxins are primarily polystyrene-divinylbenzene porous microspheres. Polystyrene-divinylbenzene microspheres offer advantages such as high mechanical strength, good chemical stability, no heat generation, low shedding resistance, affordable price, mature preparation technology, and high adsorption capacity. However, they suffer from inherent limitations such as low elasticity, a lack of polar groups for substrate adhesion, nonspecific adsorption of proteins due to their hydrophobic nature, and poor blood compatibility, limiting their application in hemoperfusion. Therefore, to expand their application, hydrophilic modification of the polystyrene microspheres is necessary to eliminate the hydrophobic regions on their surface.

[0003] Common methods for modifying the surface of polystyrene-divinylbenzene microspheres to make them hydrophilic include physical methods and chemical bonding. The physical method involves "coating" the surface of the PS-DVB microspheres with one or more layers of "amphiphilic" polymers containing both hydrophobic and hydrophilic regions, and then post-crosslinking them to obtain stable hydrophilic microspheres. The currently used coating technology improves the blood compatibility of polystyrene-divinylbenzene microsphere adsorbents, but the technology is still immature and the coating stability is generally poor, and it is easy to fall off. Chemical bonding utilizes the dangling double bonds of polystyrene-divinylbenzene or the para-chloromethylation of the benzene ring. Generally, it is first necessary to convert it into an active group, and then use its group activity to react with the hydrophilic polymer to improve the hydrophilicity of the microspheres.

[0004] Although the chemical bonding grafting method can effectively improve the hydrophilicity of microspheres and thus improve their biocompatibility, the existing technology also has many problems and shortcomings. Common polymers that can be used for bonding and grafting on the surface of microspheres include PVA, PEG and β-cyclodextrin, etc., mainly through the reaction of benzoyl chloride or acetyl chloride (bromide) on the surface of functionalized microspheres with PVA, PEG and β-cyclodextrin. However, benzoyl chloride or acetyl chloride (bromide) has low activity, harsh reaction conditions, and needs to be carried out under strong alkaline conditions. Some researchers have also used thiol groups and the dangling double bonds of polystyrene-divinylbenzene microspheres to directly carry out click chemistry reactions to introduce hydrophilic polymer PVP, but the reaction requires the use of an initiator and must be carried out at a high temperature of 70°C and in an organic solvent. The reaction conditions are harsh and the organic solvent is not easy to remove, which can easily lead to excessive leachable substances, posing a safety risk in clinical applications.

[0005] Therefore, how to find a suitable polystyrene-divinylbenzene resin material to solve the above-mentioned problems in its application, while making the preparation process simpler and the conditions milder, has become one of the focuses of widespread attention of many R&D manufacturers and front-line researchers. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a modified resin material, its preparation method, and its application. The modified resin material provided by the present invention has superior and controllable hydrophilicity and adsorption properties, as well as high biocompatibility. Furthermore, the preparation method has mild reaction conditions, simple processing, low organic solvent usage, minimal environmental impact, and easy control, making it more conducive to industrial-scale production and application.

[0007] The invention provides a modified resin material. The modified resin material comprises a resin carrier and thiol-modified PVP-CTA and ethanolamine grafted onto the surface of the resin carrier via epoxy groups.

[0008] Preferably, the resin carrier comprises one of microspheres, hollow fibers, membranes and non-woven fabrics;

[0009] The resin carrier includes a polymer resin carrier having dangling double bonds on the surface.

[0010] Preferably, the polymer resin carrier having dangling double bonds on the surface includes one or more of a polystyrene-divinylbenzene carrier, a polystyrene carrier with double bonds on the surface, and a polymethyl methacrylate carrier with double bonds on the surface;

[0011] The modified resin material is obtained by grafting thiol-modified PVP-CTA and ethanolamine onto a surface epoxidized resin carrier.

[0012] The PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer and CTA chain transfer agent;

[0013] The CTA chain transfer agent has a structure as shown in formula (I):

[0014]

[0015] wherein Z is selected from N,N-dialkyl, N-alkyl, N-alkyl dithioamino ester groups, and xanthate groups;

[0016] R is a leaving group that can generate highly active free radicals.

[0017] Preferably, the thiolated PVP-CTA forms a thioether bond through a ring-opening reaction between the terminal thiol group and the epoxy group on the surface of the epoxidized resin support, and is grafted onto the surface of the resin support;

[0018] The ethanolamine forms a CN bond through a ring-opening reaction between the terminal amino group and the epoxy group on the surface of the epoxidized resin support, and is grafted onto the surface of the resin support;

[0019] The leaving group capable of generating highly active free radicals includes one or more of tert-butyl, benzyl, ester and carboxyl groups;

[0020] The mass ratio of the thiolated PVP-CTA to the surface epoxidized resin carrier is 1: (1-5);

[0021] The molar ratio of the thiolated PVP-CTA to ethanolamine is 1:(3-8).

[0022] Preferably, the thiolated PVP-CTA includes a thiolated structure in which the terminal group of PVP-CTA is replaced by a thiol-containing functional group, and / or a thiolated structure in which the xanthate bond of PVP-CTA is directly reduced to a thiol group;

[0023] The degree of polymerization of the PVP-CTA is 2 to 100;

[0024] The molecular weight of the PVP-CTA is 300 to 11,000;

[0025] The modified resin material is a modified resin material used for preparing a blood purification adsorbent.

[0026] Preferably, the method for preparing the modified resin material comprises the following steps:

[0027] 1) treating the resin carrier surface to obtain a surface epoxidized resin carrier;

[0028] PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer, CTA chain transfer agent, initiator and organic solvent;

[0029] The PVP-CTA obtained in the above step is activated with EDC / NHS, and then β-mercaptoethylamine is added under a protective atmosphere to react in the dark to obtain thiolated PVP-CTA; alternatively, the PVP-CTA obtained in the above step is reduced with a reducing agent to obtain thiolated PVP-CTA;

[0030] 2) The surface epoxidized resin support obtained in the above step, the thiol-modified PVP-CTA and the PBS buffer solution are subjected to a grafting reaction, and the reaction product is washed and then grafted again with ethanolamine to obtain a modified resin material.

[0031] Preferably, the resin carrier comprises a polymer resin carrier having dangling double bonds on the surface;

[0032] The surface treatment method includes treating the surface of the resin carrier with peroxide;

[0033] The peroxide comprises meta-chloroperbenzoic acid and / or hydrogen peroxide;

[0034] The molar ratio of the N-vinyl pyrrolidone monomer to the CTA chain transfer agent is (2-100):1;

[0035] The initiator includes one or more of N,N'-azobisisobutyronitrile, dibenzoyl peroxide and potassium persulfate;

[0036] The organic solvent includes one or more of anhydrous acetonitrile, anhydrous N,N-dimethylformamide and dioxane.

[0037] Preferably, the reaction temperature of the RAFT polymerization is 60-80°C;

[0038] The reaction time of the RAFT polymerization is 8 to 48 hours;

[0039] The pH of the buffer solution is 5.8 to 6.0;

[0040] The activation temperature is 25-40°C;

[0041] The activation time is 0.5 to 2 hours;

[0042] The light-avoidance reaction time is 12 to 24 hours;

[0043] The reducing agent includes NaBH4 and / or Na2S2O4.

[0044] Preferably, the amount of the reducing agent used is 1 to 10 eq relative to the chain end groups of the product body after the second reaction;

[0045] The mass ratio of the thiolated PVP-CTA to the surface epoxidized resin carrier is 1: (1-5);

[0046] The temperature of the grafting reaction is 25 to 40° C.;

[0047] The grafting reaction time is 12 to 48 hours;

[0048] The concentration of the ethanolamine is 0.5 to 2 M;

[0049] The temperature of the secondary grafting reaction is 25 to 40° C.

[0050] The time for the secondary grafting reaction is 8 to 24 hours.

[0051] The present invention also provides the use of the modified resin material described in any one of the above technical solutions in the preparation of biological component adsorption materials, hemodialysis membrane materials, and water treatment materials.

[0052] The present invention provides a modified resin material comprising a resin carrier and thiol-modified PVP-CTA and ethanolamine grafted onto the surface of the resin carrier via epoxy groups. Compared to the prior art, the present invention specifically designs a modified resin material having a specific structure and composition, and also designs a specific preparation route for modifying the resin material by surface grafting of PVP. The present invention synthesizes a series of hydrophilic polymers PVP-CTA via RAFT polymerization, reacts PVP-CTA with β-mercaptoethylamine or directly reduces CTA to obtain terminally thiolated polyvinylpyrrolidone (SH-PVP), then utilizes the reaction of thiol groups with the epoxy groups of the resin material for surface grafting modification, and finally caps the surface by reacting ethanolamine with the remaining epoxy groups, further introducing hydrophilic chains to produce a PVP-grafted hydrophilic resin carrier. The resin carrier is prepared by the above process. On the one hand, the reaction conditions are mild, and the introduction of hydrophilic PVP and ethanolamine hydroxyl groups increases the hydrophilicity of the resin carrier and improves its biocompatibility. The ethanolamine end-capping treatment rationally utilizes the remaining epoxy groups, further enhancing its hydrophilicity, which is better than the effect of simply grafting PVP. On the other hand, by regulating the ratio of chain transfer agent and monomer, a series of polymers with different chain lengths are synthesized, thereby regulating the hydrophilicity and adsorption properties. Furthermore, the long-chain PVP and the short-chain ethanolamine cooperate with each other to better improve the performance of the modified resin material.

[0053] The present invention utilizes RAFT polymerization to synthesize a hydrophilic polymer PVP, which is then grafted onto the surface of an epoxidized polystyrene-divinylbenzene carrier, and finally capped with ethanolamine. Due to the grafting of the hydrophilic PVP and the presence of hydroxyl groups, the PVP has high biocompatibility, thereby solving the problem of poor biocompatibility of traditional resins. In addition, the grafting modification of epoxidized polystyrene-divinylbenzene with terminal thiol polyvinylpyrrolidone (SH-PVP) has mild reaction conditions, a simple processing technology, a small amount of organic solvent, and little impact on the environment. A series of polymers with different chain lengths can also be synthesized by regulating the ratio of a chain transfer agent to a monomer, thereby regulating the balance between hydrophilicity and adsorption performance. At the same time, ethanolamine is used for capping and hydroxyl groups are introduced to further enhance the hydrophilicity of the carrier, rationally utilize the remaining epoxy groups, and further improve the hydrophilicity of the carrier. Modified groups of different chain lengths cooperate with each other, further improving and balancing the comprehensive performance of the modified carrier, as well as providing a wider range and more diverse adjustability, which is more conducive to the practical application of the modified carrier. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 The present invention provides a simplified schematic diagram of the preparation route and microsphere structure of the modified resin microspheres and their preparation method;

[0055] Figure 2 Comparative photos of the hydrophilicity effects of polystyrene-divinylbenzene microspheres before and after modification provided by the present invention. DETAILED DESCRIPTION

[0056] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than for limiting the claims of the invention.

[0057] All raw materials of the present invention are not particularly limited in their sources and can be purchased from the market or prepared according to conventional methods well known to those skilled in the art.

[0058] There is no particular limitation on the purity of all raw materials in the present invention. The present invention preferably adopts analytically pure materials or materials with purity requirements conventional in the field of blood purification adsorbent preparation.

[0059] All raw materials of the present invention, their brands and abbreviations are conventional brands and abbreviations in the field. Each brand and abbreviation is clear and unambiguous in the field of its relevant use. Those skilled in the art can purchase them from the market or prepare them by conventional methods based on the brand, abbreviation and corresponding use.

[0060] The invention provides a modified resin material. The modified resin material comprises a resin carrier and thiol-modified PVP-CTA and ethanolamine grafted onto the surface of the resin carrier via epoxy groups.

[0061] In the present invention, the resin carrier preferably comprises one of microspheres, hollow fibers, membranes and non-woven fabrics, more preferably microspheres, hollow fibers, membranes or non-woven fabrics. The resin carrier may be a resin carrier having a porous structure.

[0062] In the present invention, the resin carrier preferably comprises a polymer resin carrier having dangling double bonds on the surface.

[0063] In the present invention, the polymer resin carrier having dangling double bonds on the surface preferably includes one or more of a polystyrene-divinylbenzene carrier, a surface double-bonded polystyrene carrier and a surface double-bonded polymethyl methacrylate carrier, more preferably a polystyrene-divinylbenzene carrier, a surface double-bonded polystyrene carrier or a surface double-bonded polymethyl methacrylate carrier, more preferably a polystyrene-divinylbenzene carrier.

[0064] In the present invention, the modified resin support is preferably obtained by grafting thiolated PVP-CTA and ethanolamine onto a surface-epoxidized resin support. Specifically, the modified resin microspheres are obtained by grafting thiolated PVP-CTA and ethanolamine onto surface-epoxidized polystyrene-divinylbenzene microspheres.

[0065] In the present invention, the PVP-CTA is preferably obtained by RAFT polymerization of N-vinyl pyrrolidone monomer and CTA chain transfer agent.

[0066] In the present invention, the CTA chain transfer agent preferably has a structure as shown in formula (I):

[0067]

[0068] wherein Z is selected from N,N-dialkyl, N-alkyl, N-alkyl dithioamino ester groups, and xanthate groups;

[0069] R is a leaving group that can generate highly active free radicals, wherein the leaving group that can generate highly active free radicals preferably includes one or more of tert-butyl, benzyl, ester and carboxyl groups, and more preferably tert-butyl, benzyl, ester or carboxyl groups.

[0070] In the present invention, the thiolated PVP-CTA is preferably grafted onto the surface of the resin microspheres by forming a thioether bond through a ring-opening reaction between the terminal thiol groups and the epoxy groups on the surface of the epoxidized resin support. Specifically, the thiolated PVP-CTA is preferably grafted onto the surface of the polystyrene-divinylbenzene microspheres by forming a thioether bond through a ring-opening reaction between the terminal thiol groups and the epoxy groups on the surface of the epoxidized polystyrene-divinylbenzene microspheres.

[0071] In the present invention, the ethanolamine is preferably grafted onto the surface of the resin support through a ring-opening reaction between the terminal amino group and the epoxy group on the surface of the epoxidized resin support to form a C-N bond. Specifically, the ethanolamine is preferably grafted onto the surface of the polystyrene-divinylbenzene microspheres through a ring-opening reaction between the terminal amino group and the epoxy group on the surface of the epoxidized polystyrene-divinylbenzene microspheres to form a C-N bond.

[0072] In the present invention, the thiolated PVP-CTA preferably includes a thiolated structure in which the terminal group of PVP-CTA is substituted by a thiol-containing functional group, and / or a thiolated structure in which the xanthate bond of PVP-CTA is directly reduced to a thiol group, more preferably a thiolated structure in which the terminal group of PVP-CTA is substituted by a thiol-containing functional group or a thiol bond of PVP-CTA is directly reduced to a thiol group.

[0073] In the present invention, the mass ratio of the thiolated PVP-CTA to the surface-epoxidized resin carrier is preferably 1:(1-5), more preferably 1:(1.5-4.5), more preferably 1:(2-4), and even more preferably 1:(2.5-3.5). Specifically, it can be the mass ratio of the thiolated PVP-CTA to the surface-epoxidized polystyrene-divinylbenzene microspheres.

[0074] In the present invention, the molar ratio of the thiolated PVP-CTA to ethanolamine is preferably 1:(3-8), more preferably 1:(4-7), and even more preferably 1:(5-6).

[0075] In the present invention, the polymerization degree of the PVP-CTA is preferably 2-100, more preferably 10-80, more preferably 20-60, and more preferably 30-40.

[0076] In the present invention, the molecular weight of the PVP-CTA is preferably 300 to 11,000, more preferably 1,000 to 9,000, more preferably 2,000 to 7,000, and more preferably 3,000 to 5,000.

[0077] In the present invention, the modified resin material is preferably a modified resin material for preparing a blood purification adsorbent.

[0078] The surface of the modified resin microspheres provided by the present invention is simultaneously grafted with long-chain PVP and short-chain ethanolamine (hydroxyl), which jointly provide hydrophilicity. The combination of PVP of different chain lengths and shorter hydroxyl groups increases hydrophilicity while also having good adsorption properties. Because if more PVP is grafted, a relatively compact structure is formed on the surface of the microspheres, and it is difficult for the adsorbed substance to enter the internal pores of the microspheres, and adsorption will be more difficult. Therefore, the present invention adopts the combination of short-chain ethanolamine grafted on the surface of the microspheres and the long chain PVP grafted on the surface of the microspheres to complement the hydrophilicity with the increased hydroxyl groups, and also has good adsorption performance. In addition, the long-short chain binding structure of polyvinyl pyrrolidone and hydroxyl groups further improves the adsorption performance of the microspheres.

[0079] The present invention provides a method for preparing a modified resin material, comprising the following steps:

[0080] 1) treating the resin carrier surface to obtain a surface epoxidized resin carrier;

[0081] PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer, CTA chain transfer agent, initiator and organic solvent;

[0082] The PVP-CTA obtained in the above step is activated with EDC / NHS, and then β-mercaptoethylamine is added under a protective atmosphere to react in the dark to obtain thiolated PVP-CTA; alternatively, the PVP-CTA obtained in the above step is reduced with a reducing agent to obtain thiolated PVP-CTA;

[0083] 2) The surface epoxidized resin support obtained in the above step, the thiol-modified PVP-CTA and the PBS buffer solution are subjected to a grafting reaction, and the reaction product is washed and then grafted again with ethanolamine to obtain a modified resin material.

[0084] The present invention firstly performs surface treatment on a resin carrier to obtain a surface epoxidized resin carrier;

[0085] PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer, CTA chain transfer agent, initiator and organic solvent;

[0086] The PVP-CTA obtained in the above step is activated with EDC / NHS, and then β-mercaptoethylamine is added under a protective atmosphere to react in the dark to obtain thiolated PVP-CTA; alternatively, the PVP-CTA obtained in the above step is reduced with a reducing agent to obtain thiolated PVP-CTA.

[0087] That is, firstly, the resin carrier is subjected to surface treatment to obtain a surface epoxidized resin carrier;

[0088] PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer, CTA chain transfer agent, initiator and organic solvent;

[0089] The PVP-CTA obtained in the above step is activated by EDC / NHS, and then β-mercaptoethylamine is added to react in the dark under a protective atmosphere to obtain thiolated PVP-CTA.

[0090] The thiolated PVP-CTA preferably includes a thiolated structure in which the terminal group of PVP-CTA is substituted by a thiol-containing functional group.

[0091] or,

[0092] Firstly, the resin carrier is subjected to surface treatment to obtain a surface epoxidized resin carrier;

[0093] PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer, CTA chain transfer agent, initiator and organic solvent;

[0094] The PVP-CTA obtained in the above step is subjected to a reduction reaction with a reducing agent to obtain thiolated PVP-CTA.

[0095] The thiolated PVP-CTA preferably includes a thiolated structure in which the xanthate bond of the PVP-CTA is directly reduced to a thiol group.

[0096] In the present invention, the resin carrier preferably comprises a polymer resin carrier having dangling double bonds on the surface.

[0097] In the present invention, the polymer resin carrier having dangling double bonds on the surface preferably includes a polystyrene-divinylbenzene carrier, a polystyrene carrier with double bonds on the surface, and a polymethyl methacrylate carrier with double bonds on the surface.

[0098] In the present invention, the surface treatment method preferably includes treating the surface of the resin carrier with peroxide.

[0099] In the present invention, there is no specific ratio between the polymer resin support having dangling double bonds on the surface and the peroxide. The molar amount of the peroxide preferably needs to be in excess relative to the double bonds on the surface of the resin support.

[0100] In the present invention, the peroxide preferably includes meta-chloroperbenzoic acid and / or hydrogen peroxide, more preferably meta-chloroperbenzoic acid or hydrogen peroxide.

[0101] In the present invention, the CTA chain transfer agent has a structure as shown in formula (I):

[0102]

[0103] wherein Z is selected from N,N-dialkyl, N-alkyl, N-alkyl dithioamino ester groups, and xanthate groups;

[0104] R is a leaving group that can generate highly active free radicals, wherein the leaving group that can generate highly active free radicals preferably includes one or more of tert-butyl, benzyl, ester and carboxyl groups, and more preferably tert-butyl, benzyl, ester or carboxyl groups.

[0105] In the present invention, the molar ratio of the N-vinyl pyrrolidone monomer to the CTA chain transfer agent is preferably (2-100):1, more preferably (10-80):1, and even more preferably (30-60):1.

[0106] In the present invention, the initiator preferably includes one or more of N,N'-azobisisobutyronitrile, dibenzoyl peroxide and potassium persulfate, more preferably N,N'-azobisisobutyronitrile, dibenzoyl peroxide or potassium persulfate.

[0107] In the present invention, the organic solvent preferably includes one or more of anhydrous acetonitrile, anhydrous N,N-dimethylformamide and dioxane, more preferably anhydrous acetonitrile, anhydrous N,N-dimethylformamide or dioxane.

[0108] In the present invention, the reaction temperature of the RAFT polymerization is preferably 60 to 80°C, more preferably 64 to 76°C, and even more preferably 68 to 72°C.

[0109] In the present invention, the reaction time of the RAFT polymerization is preferably 8 to 48 hours, more preferably 16 to 40 hours, and even more preferably 24 to 32 hours.

[0110] In the present invention, the molar ratio of PVP-CTA to EDC is preferably 1:(1-2.5), more preferably 1:(1.3-2.2), and even more preferably 1:(1.6-1.9).

[0111] In the present invention, the molar ratio of PVP-CTA to NHS is preferably 1:(1-3), more preferably 1:(1.4-2.6), and even more preferably 1:(1.8-2.2).

[0112] In the present invention, the pH of the buffer solution is preferably 5.8 to 6.0, more preferably 5.83 to 5.97, and even more preferably 5.85 to 5.95.

[0113] In the present invention, the activation temperature is preferably 25-40°C, more preferably 28-37°C, and even more preferably 31-34°C.

[0114] In the present invention, the activation time is preferably 0.5 to 2 hours, more preferably 0.8 to 1.7 hours, and even more preferably 1.1 to 1.4 hours.

[0115] In the present invention, the light-shielding reaction time is preferably 12 to 24 hours, more preferably 14 to 22 hours, and even more preferably 16 to 20 hours.

[0116] In the present invention, there is no specific ratio for the amount of β-mercaptoethylamine used, and the molar amount needs to be excessive relative to the molar amount of the end groups of PVP-CTA.

[0117] In the present invention, the reducing agent preferably includes NaBH4 and / or Na2S2O4, more preferably NaBH4 or Na2S2O4.

[0118] In the present invention, the amount of the reducing agent used is preferably 1 to 10 eq relative to the chain end groups of the main body of the product after the second reaction, more preferably 3 to 8 eq, and even more preferably 5 to 6 eq.

[0119] The present invention further carries out a grafting reaction on the surface epoxidized polystyrene-divinylbenzene carrier obtained in the above step, thiol-modified PVP-CTA and PBS buffer, washes the reaction product, and then carries out a grafting reaction with ethanolamine again to obtain a modified resin carrier.

[0120] In the present invention, the mass ratio of the thiolated PVP-CTA to the surface-epoxidized polystyrene-divinylbenzene carrier is preferably 1:(1-5), more preferably 1:(1.5-4.5), more preferably 1:(2-4), and more preferably 1:(2.5-3.5).

[0121] In the present invention, the temperature of the grafting reaction is preferably 25 to 40°C, more preferably 28 to 37°C, and even more preferably 31 to 34°C.

[0122] In the present invention, the grafting reaction time is preferably 12 to 48 hours, more preferably 20 to 40 hours, and even more preferably 28 to 32 hours.

[0123] In the present invention, the concentration of ethanolamine is preferably 0.5-2M, more preferably 0.8-1.7M, and even more preferably 1.1-1.4M.

[0124] In the present invention, the temperature of the secondary grafting reaction is preferably 25 to 40°C, more preferably 28 to 37°C, and even more preferably 31 to 34°C.

[0125] In the present invention, the time for the secondary grafting reaction is preferably 8 to 24 hours, more preferably 11 to 21 hours, and even more preferably 14 to 17 hours.

[0126] See also Figure 1 , Figure 1 The present invention provides a simplified schematic diagram of the preparation route and microsphere structure of the modified resin microspheres and their preparation method.

[0127] The present invention is a complete and detailed overall technical solution, which better ensures the specific composition and structure of the modified resin carrier, better improves the hydrophilicity and adsorption performance of the modified resin carrier, and further improves the controllability of the balance between hydrophilicity and adsorption performance. The modified resin carrier and its preparation method may specifically include the following contents:

[0128] A modified resin carrier has polyvinyl pyrrolidone grafted onto its surface. The modified resin carrier is obtained by grafting an epoxy-activated resin carrier with terminal mercapto-polyvinyl pyrrolidone (SH-PVP) and capping with ethanolamine.

[0129] Specifically, the reaction temperature is 25-40°C.

[0130] Specifically, the stirring rate of the reaction is 150-200 rpm, and the reaction time is 12-48 h.

[0131] Specifically, the mass ratio of the SH-PVP to the epoxidation carrier is 1:(1-5)

[0132] Specifically, the concentration of ethanolamine used in the capping reaction is 0.5-2 M, and the reaction time is 8-24 h.

[0133] Specifically, the SH-PVP is obtained by reacting polyvinyl pyrrolidone (PVP-CTA), wherein the PVP-CTA uses N-vinyl pyrrolidone (NVP) as a monomer and CTA as a chain transfer agent, and is obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization.

[0134] Specifically, the CTA has the following structure:

[0135]

[0136] The Z end is N, N dialkyl, N-alkyl, N-alkyl dithioamino esters and xanthates;

[0137] R should be a good leaving group, and the generated free radical R· should have a long life span and high activity, for example, it can efficiently reinitiate the polymerization reaction, such as tertiary carbon free radicals, benzyl free radicals, etc.

[0138] Specifically, the molar ratio of the monomer NVP to the chain transfer agent CTA is (2-100):1.

[0139] Specifically, the degree of polymerization of the polyvinyl pyrrolidone (PVP-CTA) is 2-100.

[0140] Specifically, the molecular weight of the polyvinyl pyrrolidone (PVP-CTA) ranges from 300 to 11,000.

[0141] The present invention adopts specific requirements for degree of polymerization and molecular weight, further taking into account the requirements for hydrophilicity and adsorption.

[0142] Specifically, the initiator of the reaction is N,N'-azobisisobutyronitrile (AIBN), the reaction temperature is 60-80°C, and the reaction time is 8-48 hours.

[0143] Specifically, the SH-PVP is obtained by reacting PVP-CTA with mercaptoethylamine.

[0144] Specifically, the SH-PVP is obtained by direct reduction of PVP-CTA.

[0145] Specifically, the reducing agent is NaBH4 or Na2S2O4.

[0146] Specifically, the amount of the reducing agent is 1 to 10 eq relative to the chain end group.

[0147] Specifically, the resin carrier is polystyrene-divinylbenzene or polystyrene resin.

[0148] The functional resin carrier provided by the present invention comprises the resin carrier as described above, and active groups grafted onto the surface of the resin carrier.

[0149] Specifically, the functional resin carrier further includes a ligand grafted to the active group.

[0150] The present invention provides the use of the resin carrier or functional resin carrier described above in the adsorption of biological components.

[0151] The present invention provides the use of the modified resin carrier described in any one of the above technical solutions or the modified resin carrier prepared by the preparation method described in any one of the above technical solutions in the preparation of biological component adsorption materials, hemodialysis membrane materials, and water treatment materials.

[0152] In the present invention, the biocomponent adsorption material preferably includes a blood purification adsorbent, more preferably an adsorbent for blood perfusion, and even more preferably an adsorbent for a blood perfusion device for removing medium and large molecular toxins.

[0153] The above content of the present invention provides a modified resin carrier, a preparation method, and an application thereof. The present invention specifically designs modified resin microspheres with a specific structure and composition, as well as a specific preparation route for modifying the resin microspheres by grafting the surface of PVP. The present invention synthesizes a series of hydrophilic polymers PVP-CTA through RAFT polymerization, reacts PVP-CTA with β-mercaptoethylamine or directly reduces CTA to obtain terminal thiolated polyvinylpyrrolidone (SH-PVP), then utilizes the thiol group to react with the epoxy group of polystyrene-divinylbenzene microspheres for surface grafting modification, and finally uses ethanolamine to react with the remaining epoxy groups to cap the ends, and further introduces hydrophilic chains to obtain PVP-grafted hydrophilic resin microspheres. The resin microsphere carrier is prepared by the above process. On the one hand, the reaction conditions are mild, and the introduction of hydrophilic PVP and ethanolamine hydroxyl groups increases the hydrophilicity of the polystyrene-divinylbenzene microspheres and improves their biocompatibility. The ethanolamine end-capping treatment method rationally utilizes the remaining epoxy groups, so that the hydrophilicity is further enhanced, which is better than the effect of simple grafting of PVP, and it is also a dihydroxy structure. On the other hand, by regulating the ratio of chain transfer agent and monomer, a series of polymers with different chain lengths are synthesized, thereby regulating the hydrophilicity and adsorption properties. Furthermore, the long-chain PVP and the short-chain ethanolamine cooperate with each other to better improve the performance of the modified resin microspheres.

[0154] The present invention utilizes RAFT polymerization to synthesize a hydrophilic polymer PVP, which is then grafted onto the surface of epoxidized polystyrene-divinylbenzene microspheres, and finally capped with ethanolamine. Due to the grafting of the hydrophilic PVP and the presence of hydroxyl groups, the microspheres have high biocompatibility, thereby solving the problem of poor biocompatibility of traditional resins. In addition, the grafting modification of epoxidized polystyrene-divinylbenzene with terminal thiol polyvinylpyrrolidone (SH-PVP) has mild reaction conditions, a simple processing technology, a small amount of organic solvent, and little impact on the environment. A series of polymers with different chain lengths can also be synthesized by regulating the ratio of a chain transfer agent to a monomer, thereby regulating the balance between hydrophilicity and adsorption performance. At the same time, ethanolamine is used for capping and hydroxyl groups are introduced to further enhance the hydrophilicity of the microspheres, and the remaining epoxy groups are reasonably utilized, so that the hydrophilicity of the microspheres is further improved. The modification groups of different chain lengths cooperate with each other, further improving and balancing the comprehensive performance of the modified microspheres, and providing a wider range and more diverse adjustability, which is more conducive to the practical application of the modified microspheres.

[0155] In order to further illustrate the present invention, a modified resin material provided by the present invention, a preparation method thereof, and an application thereof are described in detail below in conjunction with examples. However, it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating processes are provided only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention. The scope of protection of the present invention is not limited to the following examples.

[0156] Example 1

[0157] This embodiment provides a method for synthesizing PVP-CTA with different polymerization degrees using RAFT polymerization, as follows:

[0158]

[0159] Accurately weigh the initiator N, N'-azobisisobutyronitrile (AIBN), use the reaction solvent anhydrous acetonitrile to prepare a 100 mg / mL AIBN solution for standby use; take a round-bottom flask, add a magnetic rod and mark it, add the monomer N-vinyl pyrrolidone (NVP), the chain transfer agent 2-ethylxanthogenylisobutyric acid (a type of CTA) and anhydrous acetonitrile, and mix evenly; according to the feed ratio, draw an appropriate volume of 100 mg / mL AIBN solution and add it to the above reaction solution, plug the rubber stopper after mixing, pass nitrogen for 30 minutes, then put it into an oil bath to maintain constant temperature, and stir the reaction for 24 hours; after the reaction is completed, stop heating, take out the round-bottom flask, open the bottle stopper, immerse the bottle in liquid nitrogen to quench the reaction, use an appropriate amount of dichloromethane to dissolve the generated product, and then precipitate it in ether to obtain the pure product PVP-CTA. The ratios of monomers, chain transfer agents and initiators are shown in Table 1. Table 1 is the ratio of monomers, chain transfer agents and initiators in Example 1 of the present invention.

[0160] Table 1

[0161]

[0162] Five polymers with different degrees of polymerization, namely PVP-CTA 0, PVP-CTA1, PVP-CTA2, PVP-CTA3 and PVP-CTA4, were obtained.

[0163] Example 2

[0164] This embodiment provides a method for introducing a functional group thiol (-SH) using β-mercaptoethylamine and then performing surface grafting modification on polystyrene-divinylbenzene microspheres, as follows:

[0165]

[0166] Weigh 2g of polymer PVP-CTA (using different polymerization degrees), a certain amount of EDC and NHS ((PVP:EDC:NHS)=1:(1~2.5):(1~3)) and place them in a flask, add 12ml of 0.2M phosphate buffer (pH 5.8~6.0), and react at 37℃ for 1h; add a certain equivalent of mercaptoethylamine (molar ratio (PVP:NH2CH2CH2SH=1:(1~3)), pass nitrogen protection, and react at room temperature in the dark for 12h. Dialyze with deoxygenated water in the dark for 48h, and freeze-dry to obtain the final sample HS-PVP.

[0167] The certain amount of EDC and NHS is in a molar ratio of (PVP:EDC:NHS)=1:(1-2.5):(1-3); the certain equivalent amount of mercaptoethylamine is in a molar ratio of PVP:NH2CH2CH2SH=1:(1-3).

[0168] Weigh 2g of HS-PVP, dissolve it in PBS, and then add a certain amount of activated polystyrene-divinylbenzene microspheres (the mass ratio of SH-PVP to microspheres is 1: (1-5)), place it in a flask, and react at 25-40°C for 24-48h. After the reaction is completed, pour out the microspheres and wash them with pure water to wash out the polymer that is not grafted on the surface of the microspheres. Use 0.5-2M ethanolamine at 25-40°C, stir the reaction and cap the ends, and wash with pure water to obtain modified microspheres PS-DVB-PVP1(a), PS-DVB-PVP2(a), PS-DVB-PVP3(a), and PS-DVB-PVP4(a). The reaction conditions of each microsphere product are shown in Table 2, which shows the reaction conditions of each microsphere product in Example 2 of the present invention.

[0169] Table 2

[0170]

[0171] Example 3

[0172] This embodiment provides a method for directly reducing the xanthate bond in CTA to a thiol (-SH) group, and then performing surface grafting modification on polystyrene-divinylbenzene microspheres, as follows:

[0173]

[0174] Weigh 2g of PVP-CTA (using different degrees of polymerization) into a flask and add PBS to dissolve. Add a suitable amount of reducing agent (NaBH₄ or Na₂S₂O₄) and stir for a while. Adjust the pH of the reaction mixture to neutral.

[0175] Take 2g of the prepared SH-PVP, add a certain amount of activated polystyrene-divinylbenzene microspheres (mass ratio (SH-PVP: microspheres) = 1:5), place it in a flask, and react at 25-40℃ for 24-48h. After the reaction is completed, pour out the microspheres and wash them with pure water to wash out the polymer that is not grafted on the surface of the microspheres. Use 0.5-2M ethanolamine at 25-40℃, stir the reaction and cap, and wash with pure water to obtain modified microspheres PS-DVB-PVP1(b), PS-DVB-PVP2(b), PS-DVB-PVP3(b), and PS-DVB-PVP4(b). The reaction conditions of each microsphere product are shown in Table 3, which shows the reaction conditions of each microsphere product in Example 3 of the present invention.

[0176] Table 3

[0177]

[0178] Comparative Example 1

[0179] 2 g of polymer PVP-CTA2, a certain amount of EDC and NHS ((PVP:EDC:NHS)=1:2:2.4) were weighed and placed in a flask, 12 ml of 0.2 M phosphate buffer (pH 6.0) was added, and the reaction was carried out at 37 ° C for 1 h; a certain equivalent of mercaptoethylamine (molar ratio (PVP:NH2CH2CH2SH=1:2) was added, nitrogen was passed through, and the reaction was carried out at room temperature in the dark for 12 h. The final sample HS-PVP was dialyzed with deoxygenated water for 48 h in the dark and freeze-dried to obtain the final sample HS-PVP.

[0180] Take 1g of polystyrene-divinylbenzene microspheres and place them in a single-necked flask. Add 15ml of acetonitrile solvent and pass nitrogen for 30min to eliminate oxygen in the solution. Then, add 0.5g of the prepared HS-PVP and AIBN (molar ratio (HS-PVP / AIBN) = 1:10) under light-proof conditions, stir and mix evenly, place the single-necked flask in an oil bath at 70°C under nitrogen protection and stir to react for 48h. After the reaction, pour out the microspheres and wash them with a large amount of ethanol to obtain modified microspheres DB-PS-DVB-PVP2(a).

[0181] Comparative Example 2

[0182] Weigh 2g of polymer PVP-CTA2 into a flask and add PBS to dissolve. Add a certain amount of reducing agent NaBH4 (reducing agent: chain end group (eq) = 6) and stir for a while. Adjust the pH of the reaction solution to neutral to obtain HS-PVP.

[0183] Take 1g of polystyrene-divinylbenzene microspheres and place them in a single-necked flask, add 15ml of acetonitrile solvent, and pass nitrogen for 30min to eliminate oxygen in the solution. Then, add 0.5g of the prepared HS-PVP and AIBN (molar ratio (HS-PVP / AIBN) = 1:10) under light-proof conditions, stir and mix evenly, place the single-necked flask in a 70℃ oil bath under nitrogen protection and stir to react for 48h. After the reaction, pour out the microspheres and wash them with a large amount of ethanol to obtain modified microspheres DB-PS-DVB-PVP2(b).

[0184] Through the above cases, it was found that the reaction of the epoxy-activated microspheres and HS-PVP provided by the present invention is more mild in reaction conditions and simpler in reaction process than the direct grafting method of dangling double bonds in the comparative case. On the other hand, the direct grafting method of dangling double bonds requires an anhydrous and oxygen-free environment, so the preparation process of HS-PVP in the previous step is more stringent and must be completely dried, which is a cumbersome process and leads to a reduced yield.

[0185] Performance test data:

[0186] (1) Hydrophilicity test:

[0187] Unmodified PS-DVB microspheres, PS-DVB-PVP2 microspheres (a), and PS-DVB-PVP2 microspheres (b) were taken and dried at 105°C for 4 hours to remove moisture from the polystyrene-divinylbenzene microspheres. They were then added into purified water to observe the hydrophilic effect of the polystyrene-divinylbenzene microspheres before and after modification.

[0188] See also Figure 2 , Figure 2 The following is a comparison of the hydrophilicity of polystyrene-divinylbenzene microspheres before and after modification provided by the present invention. Figure 2 As shown, it can be seen that most of the microspheres before modification float on the water surface, while the hydrophilicity of the microspheres in Examples 2 and 3 is significantly increased after modification, and most of them sink to the bottom of the water.

[0189] In addition, the resin microspheres before and after modification in Examples 2 and 3 and Comparative Examples 1 and 2 were ground and prepared into sheet samples with a diameter of 13 mm and a thickness of 1 mm using an oil pressure tablet press. The contact angle test results are shown in Table 4. Table 4 shows the contact angle test results of the modified microspheres prepared in Examples 2 and 3 of the present invention, the modified microspheres prepared in Comparative Examples 1 and 2, and the unmodified microspheres.

[0190] Table 4

[0191] sample Contact angle (°) PS-DVB microspheres (unmodified) 90.2 PS-DVB-PVP1 microspheres (a) 81.3 PS-DVB-PVP2 microspheres (a) 79.5 PS-DVB-PVP3 microspheres (a) 76.6 PS-DVB-PVP4 microspheres (a) 72.8 PS-DVB-PVP1 microspheres (b) 70.5 PS-DVB-PVP2 microspheres (b) 65.8 PS-DVB-PVP3 microspheres (b) 60.3 PS-DVB-PVP4 microspheres (b) 56.2 DB-PS-DVB-PVP2(a) 84.5 DB-PS-DVB-PVP2(b) 79.3

[0192] Hydrophilicity tests were conducted on modified microspheres grafted with polyvinyl pyrrolidone of varying degrees of polymerization (PS-DVB-PVP1, PS-DVB-PVP2, PS-DVB-PVP3, and PS-DVB-PVP4). The results showed that hydrophilicity increased with increasing polymer degree of polymerization. This is attributed to the increasing chain length of the grafted hydrophilic polymer, which further enhances the hydrophilicity of the microspheres. The microspheres produced using method b showed a more pronounced improvement in hydrophilicity.

[0193] By comparing the test results of the comparative examples DB-PS-DVB-PVP2 (a) and PS-DVB-PVP2 microspheres (a), and DB-PS-DVB-PVP2 (b) and PS-DVB-PVP2 microspheres (b), it was found that the modified microspheres prepared by first epoxy-activating the polystyrene-divinylbenzene microspheres and then grafting PVP using the methods of Examples 2 and 3, and finally using ethanolamine end-capping, were more significantly improved in hydrophilicity due to the increase in surface hydroxyl groups compared to the modified microspheres prepared by direct thiol and double bond click reaction.

[0194] Comparing the test results of DB-PS-DVB-PVP2(a) with those of Example 2, it can be found that the increase in surface hydroxyl groups can reduce the amount of HS-PVP used, while still achieving a better hydrophilic effect.

[0195] (2) Adsorption performance test of β2-microglobulin

[0196] Prepare fresh phosphate buffered saline (PBS, pH = 7.4) containing 0.1% bovine serum albumin (BSA). Add an appropriate amount of β2-microglobulin to the PBS to prepare a 10 mg / L β2-microglobulin solution. Take 10 mL and place it in a conical flask. Weigh 0.2 g of wet adsorbent and place it in the flask. Place it in a constant temperature oscillator at (37 ± 1) °C and a rate of (180 ± 10) times / min for 2 h. Measure the concentration of the β2-microglobulin solution using a biochemical analyzer and calculate the adsorption rate according to formula (A.6):

[0197]

[0198] Where:

[0199] c r4 -β2-microglobulin adsorption rate, %;

[0200] C o ─Concentration of β2-microglobulin solution before adsorption, in mg / L;

[0201] c t ─ Concentration of β2-microglobulin solution after 2 hours of adsorption, in mg / L;

[0202] The measurement results are shown in Table 5. Table 5 shows the test results of the adsorption performance of the β2-microglobulin provided by the present invention.

[0203] Table 5

[0204]

[0205] It can be seen that with the increase of the molecular weight of the grafted PVP, that is, the gradual growth of the molecular chain, the adsorption efficiency of the modified microspheres on β-microglobulin gradually decreases. The molecular weight of the grafted PVP actually used needs to comprehensively consider the hydrophilicity and adsorption efficiency. It is preferred to use PVP-CTA2 for grafting modification, that is, the prepared PS-DVB-PVP2 microspheres, which have good hydrophilicity and the adsorption performance is less affected by the PVP grafted chain.

[0206] Comparison of the adsorption effects of DB-PS-DVB-PVP2 (b) and PS-DVB-PVP2 microspheres (b) prepared in Comparative Example 2 shows that the microspheres without ethanolamine end-capping have a relatively lower adsorption efficiency for β-microglobulin at a comparable amount of PVP grafting, and the structure in which the surface hydroxyl groups are combined with the long and short chains of PVP is more conducive to the adsorption of β-microglobulin.

[0207] (3) Hemolysis rate test

[0208] Weigh 2g of the modified PS-DVB-PVP2 microspheres prepared in Example 2 and Example 3 and the modified DB-PS-DVB-PVP2 prepared in Comparative Examples 1 and 2 respectively in a test tube and inject 10mL of normal saline as a test sample. Place the test tube, negative tube (only 10mL of normal saline is injected), and positive tube (only 10mL of distilled water is injected) in a 37°C water bath and keep warm for 30min. Add 0.2mL of diluted anticoagulated rabbit blood to the test tube, negative tube, and positive tube respectively and mix gently. Continue to keep warm in a 37°C constant temperature water bath for 60min. After the water bath ends, pour out the liquid in the tube, centrifuge at 800g for 5min, take the supernatant and place it in an ultraviolet spectrophotometer, measure the absorbance at 545nm, calculate the hemolysis rate (the hemolysis rate should be ≤5%), and the hemolysis rate calculation formula is as follows:

[0209]

[0210] Where: A─absorbance of the test solution;

[0211] B─ absorbance of negative control solution;

[0212] C─ Absorbance of positive control solution.

[0213] The results are shown in Table 6, which is the hemolysis rate test results of the modified resin microspheres provided by the present invention.

[0214] Table 6

[0215] Sample name Sample 1 Sample 2 Sample 3 average value Hemolysis rate (%) Positive control 0.715 0.732 0.718 0.7217 / Negative control 0.016 0.007 0.015 0.0127 / PS-DVB microspheres (unmodified) 0.031 0.044 0.062 0.0457 4.65 PS-DVB-PVP2 microspheres (a) 0.012 0.015 0.019 0.0153 0.37 PS-DVB-PVP2 microspheres (b) 0.012 0.013 0.015 0.0133 0.08 DB-PS-DVB-PVP2(a) 0.023 0.026 0.021 0.0233 1.49 DB-PS-DVB-PVP2(b) 0.024 0.023 0.017 0.0213 1.22

[0216] From the results in Table 6, it can be seen that the hemolysis rate of the modified polystyrene-divinylbenzene microspheres meets the standard requirement of <5%, and has good biocompatibility. In addition, the improvement effect of Examples 2 and 3 on the hemolysis rate is better than that of Comparative Examples 1 and 2.

[0217] The modified resin microspheres provided by the present invention, as well as their preparation methods and applications, are described in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only intended to help understand the methods and core concepts of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including the manufacture and use of any device or system, and the implementation of any combined method. It should be noted that, for a person skilled in the art, without departing from the principles of the present invention, several improvements and modifications may be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be conceived by a person skilled in the art. If these other embodiments have structural elements that are not different from the literal wording of the claims, or if they include equivalent structural elements that are not substantially different from the literal wording of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A modified resin material, characterized in that: The modified resin material includes a resin carrier and thiol-modified PVP-CTA and ethanolamine grafted onto the surface of the resin carrier via epoxy groups; The modified resin material is obtained by grafting thiol-modified PVP-CTA and ethanolamine onto a surface epoxidized resin carrier. The PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer and CTA chain transfer agent; The thiolated PVP-CTA forms a thioether bond through a ring-opening reaction between the terminal thiol group and the epoxy group on the surface of the epoxidized resin support, and is grafted onto the surface of the resin support; The mass ratio of the thiolated PVP-CTA to the surface epoxidized resin carrier is 1: (1-5); The molar ratio of the thiolated PVP-CTA to ethanolamine is 1:(3-8).

2. The modified resin material according to claim 1, characterized in that The resin carrier includes one of microspheres, hollow fibers, membranes and non-woven fabrics; The resin carrier includes a polymer resin carrier having dangling double bonds on the surface.

3. The modified resin material according to claim 2, characterized in that The polymer resin carrier having dangling double bonds on the surface includes one or more of a polystyrene-divinylbenzene carrier, a polystyrene carrier with double bonds on the surface, and a polymethyl methacrylate carrier with double bonds on the surface; The CTA chain transfer agent has a structure as shown in formula (I): （I）； wherein Z is selected from N,N-dialkyl, N-alkyl, N-alkyl dithioamino ester groups, and xanthate groups; R is a leaving group that can generate highly active free radicals.

4. The modified resin material according to claim 3, characterized in that The ethanolamine forms a CN bond through a ring-opening reaction between the terminal amino group and the epoxy group on the surface of the epoxidized resin support, and is grafted onto the surface of the resin support; The leaving group capable of generating highly active free radicals includes one or more of tert-butyl, benzyl, ester and carboxyl groups.

5. The modified resin material according to claim 1, characterized in that The thiolated PVP-CTA includes a thiolated structure in which the terminal group of the PVP-CTA is replaced by a thiol-containing functional group, and / or a thiolated structure in which the xanthate bond of the PVP-CTA is directly reduced to a thiol group; The degree of polymerization of the PVP-CTA is 2 to 100; The molecular weight of the PVP-CTA is 300-11000; The modified resin material is a modified resin material used for preparing a blood purification adsorbent.

6. The modified resin material according to claim 1, characterized in that The preparation method of the modified resin material comprises the following steps: 1) The resin carrier is subjected to surface treatment to obtain a surface epoxidized resin carrier; PVP-CTA is obtained by RAFT polymerization of N-vinyl pyrrolidone monomer, CTA chain transfer agent, initiator and organic solvent; The PVP-CTA obtained in the above step is activated with EDC / NHS, and then β-mercaptoethylamine is added under a protective atmosphere to react in the dark to obtain thiolated PVP-CTA; alternatively, the PVP-CTA obtained in the above step is reduced with a reducing agent to obtain thiolated PVP-CTA; 2) The surface epoxidized resin support obtained in the above step, the thiol-modified PVP-CTA and the PBS buffer solution are subjected to a grafting reaction. After the reaction product is washed, it is grafted again with ethanolamine to obtain a modified resin material.

7. The modified resin material according to claim 6, characterized in that The resin carrier includes a polymer resin carrier having dangling double bonds on the surface; The surface treatment method includes treating the surface of the resin carrier with peroxide; The peroxide comprises meta-chloroperbenzoic acid and / or hydrogen peroxide; The molar ratio of the N-vinyl pyrrolidone monomer to the CTA chain transfer agent is (2-100):1; The initiator includes one or more of N, N'-azobisisobutyronitrile, dibenzoyl peroxide and potassium persulfate; The organic solvent includes one or more of anhydrous acetonitrile, anhydrous N,N-dimethylformamide and dioxane.

8. The modified resin material according to claim 6, characterized in that The reaction temperature of the RAFT polymerization is 60-80°C; The reaction time of the RAFT polymerization is 8 to 48 hours; The pH of the buffer solution is 5.8-6.0; The activation temperature is 25-40°C; The activation time is 0.5~2h; The light-avoidance reaction time is 12 to 24 hours; The reducing agent includes NaBH4 and / or Na2S2O4.

9. The modified resin material according to claim 6, characterized in that The amount of the reducing agent used is 1 to 10 eq relative to the chain end group of the product body after the second reaction; The mass ratio of the thiolated PVP-CTA to the surface epoxidized resin carrier is 1: (1-5); The temperature of the grafting reaction is 25-40°C; The grafting reaction time is 12 to 48 hours; The concentration of the ethanolamine is 0.5~2M; The temperature of the secondary grafting reaction is 25-40°C; The time for the secondary grafting reaction is 8 to 24 hours.

10. Use of the modified resin material according to any one of claims 1 to 9 in the preparation of biocomponent adsorption materials, hemodialysis membrane materials, and water treatment materials.

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