Cyclic oligomers, methods for producing the same, compound materials and composite materials containing the same, and medical articles surface-modified or surface-treated therewith.

Abstract

The present invention relates to cyclic oligomers, methods for producing the same, compound materials and composite materials containing the same, and medical articles surface-modified or surface-treated therewith, wherein the cyclic oligomer can be produced by ring-expansion cationic polymerization using cyclic hemiacetal ester initiators and vinyl ether monomers, and is characterized by having surface segregating properties.

Description

[Technical Field]

[0001] This invention relates to cyclic oligomers, methods for producing the same, compound materials and composite materials containing the same, and medical articles surface-modified or surface-treated with the same. [Background technology]

[0002] The biomaterials market is growing every year, and is expected to reach 70 trillion won by 2025, up from 50 trillion won in 2020. Of this, polymer biomaterials account for approximately 30% of the total market and are expected to be used more widely in a variety of application fields in the future. The polymers used may be synthetic or natural polymers, including polyolefins, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polybutadiene (PB), polystyrene (PS), polymethyl acrylate (PMA), polyethyl acrylate (PEA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyhydroxyethyl methacrylate (PHEMA), polyvinylpyrrolidone (PVP), polyethers, polyethylene glycol (PEG), polytetrahydrofuran (PTHF), polyethyleneimine (PEI), and polyester. These include polymers, polycarbonate (PC), polylactide (PLA), polyethylene terephthalate (PET), polyketones, polyether ether ketone (PEEK), polyamides, polyurethane (PU), polyacrylamide (PAAm), polysilanes, polysiloxane, polydimethylsiloxane (PDMS), starch, cellulose, chitosan, hyaluronic acid, alginate, dextran, gelatin, heparin, polypeptides, and polynucleotides. However, polymer biomaterials themselves still have limitations in biocompatibility and biofunctionality, as well as other issues such as the risk of infection and poor tissue bonding.

[0003] When such polymeric biomaterials are applied to invasive medical materials and medical devices within the body, there is a risk of additional problems such as hemolysis, thrombosis, immune rejection, and fibrosis, which makes long-term use of medical materials and medical devices difficult. Furthermore, if blood clots and bacterial biofilms formed by blood coagulation and bacterial infection are left untreated for a long time, these substances can travel through the blood to other organs, potentially causing systemic complications.

[0004] To effectively address these issues, polymer biomaterials employ surface treatment methods that impart functionality to their surfaces. These surface treatment methods can be broadly classified into physical coating, chemical bonding (grafting), and blending. Physical coating involves physically adhering a functional substance to the surface of the polymer biomaterial, and is simple and inexpensive. However, achieving a uniform surface finish is difficult, and the adhesion stability is low, leading to a high probability of peeling in equipment that is bent or moved. Furthermore, this method is prone to damage during long-term use. Chemical bonding is sometimes used as an alternative to coating. Compared to coating, it offers advantages such as higher adhesion stability and easier uniform surface treatment. However, it has the disadvantage of low versatility and a complex surface treatment process, as different bonding methods must be applied depending on the type of polymer biomaterial. Finally, the general blending method has the advantage of high versatility as it eliminates the need for additional surface treatment steps, but it has the limitation of causing changes in the overall properties of the polymer biomaterial, making it difficult to apply locally only to the surface.

[0005] As an alternative to the limitations of conventional surface treatment methods, surface segregating materials are being studied. When a surface segregating material is mixed with a biomaterial and molded, a small amount of the surface segregating material migrates to the surface of the biomaterial, and surface treatment is performed. Therefore, there is an advantage in that the overall physical properties change little and no additional surface treatment steps are required. Currently, the only similar technology that has been put into practical use is endexo®, which is a technology that imparts surface segregation by attaching hydrophobic functional groups to both ends of the polymer chain of the surface segregating material, and is a technology that enables hydrophobic surface treatment. However, this technology has the limitation that hydrophilic surface treatment is not possible, and therefore, the driving force for surface segregation must be provided by a method other than hydrophobic functional groups. Another similar technology is a technology that imparts surface segregation by attaching hydrophilic functional groups to the polymer chain of the surface segregating material. This technology has the advantage of enabling hydrophilic surface treatment, but it has the disadvantage that the surface treatment process must be carried out in water, and there is a limitation that the surface treatment is limited to separation membrane materials.

[0006] On the other hand, among the various surface treatment methods that impart functionality to polymer surfaces, the method of forming polymer brushes is widely applied because it can simultaneously change the physicochemical properties of the polymer surface. There are two main types of brush formation methods: the "grafting onto method" and the "grafting from method." The grafting onto method involves fixing a specific part of a pre-fabricated polymer brush to the surface. In contrast, the grafting from method involves fixing an initiator, rather than a brush, to the polymer surface, and then the polymerization reaction of the brush proceeds from the surface. In the case of the grafting onto method, steric hindrance occurs between the brushes during the reaction to fix the brushes, making it difficult to form a high-density brush on the surface. In contrast, the grafting from method fixes only an initiator with relatively little steric hindrance, resulting in a high density of brushes generated on the surface, which leads to relatively good performance.

[0007] To utilize the graft-from method, several methods for immobilizing an initiator on the surface are used. The most commonly used method is to chemically bond (graft) the functional groups on the polymer surface with the initiator. In this method, since the functional groups possessed vary depending on the type of polymer, there is a drawback that it is necessary to design the reaction through complex modeling. In the case of another method, it is a surface coating method that applies the structure of 3,4-dihydroxyphenyl-L-alanine (DOPA) amino acid, which is the core substance for barnacles to adhere to the rock surface. When using this method, complex modeling is not required depending on the type of polymer, but an additional process for immobilizing the initiator on the surface for surface treatment is still necessary.

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention provides a cyclic oligomer represented by the following formula (1)

Chemical Formula

[0009] (In the formula, R1 is a substituted or unsubstituted C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C3-C15 cycloalkyl group, C6-C15 aryl group or C6-C15 heteroaryl group, R2 is a substituted or unsubstituted C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C3-C15 cycloalkyl group, C6-C15 aryl group or C6-C15 heteroaryl group, or a form in which a functional group having less than 15 carbon atoms is further introduced at the end by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from an initiator, The sum of 2n and m is an integer of 10 to 600.)

[0010] However, the technical problems to be solved by the present invention are not limited to the problems described above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0011] The present invention provides a cyclic oligomer represented by the following formula (1):

Chemical Formula

[0012] (In the formula, R1 is a substituted or unsubstituted C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C3-C15 cycloalkyl group, C6-C15 aryl group or C6-C15 heteroaryl group, R2 is a substituted or unsubstituted C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C3-C15 cycloalkyl group, C6-C15 aryl group or C6-C15 heteroaryl group, or a form in which a functional group having less than 15 carbon atoms is further introduced at the terminal by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from an initiator, The sum of 2n and m is an integer from 10 to 600.)

[0013] R2 may be a C2-C15 alkenyl group or C2-C15 alkynyl group, or a form in which a functional group having less than 15 carbon atoms is further introduced at the terminal by a chemical reaction.

[0014] The chemical reaction may be a click chemical reaction selected from the group consisting of thiol-ene, thiol-yne, azide-ene and azide-yne.

[0015] R2 may be a C2-C15 functional group form containing a functional group derived from an atom transfer radical polymerization (ATRP) initiator.

[0016] The cyclic oligomer may have surface segregating properties.

[0017] The aforementioned cyclic oligomer has a number average molecular weight (M n ) may be between 5,000 and 20,000.

[0018] In one embodiment of the present invention, the following formula (2) [ka]

[0019] (wherein R1 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, The present invention provides a cyclic hemiacetal ester initiator for the production of the cyclic oligomer, comprising a compound represented by (where m is an integer between 2 and 600).

[0020] In another embodiment of the present invention, the following formula (3) [ka]

[0021] The present invention provides a vinyl ether monomer for producing the cyclic oligomer, comprising a compound represented by the formula (wherein R2 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, or a form in which a functional group of less than C15 is introduced at the terminal by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from an initiator).

[0022] In yet another embodiment of the present invention, a method for producing a cyclic oligomer using ring-expansion cationic polymerization is provided for cyclic hemiacetal ester initiators and vinyl ether monomers.

[0023] The ring-expanding cationic polymerization method may be carried out under temperature conditions of -70°C to 0°C.

[0024] In yet another embodiment of the present invention, a compound material comprising the cyclic oligomer and a biocompatible material is provided.

[0025] The aforementioned biocompatible materials include polyolefins, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polybutadiene (PB), polystyrene (PS), polymethyl acrylate (PMA), polyethyl acrylate (PEA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyhydroxyethyl methacrylate (PHEMA), polyvinylpyrrolidone (PVP), polyethers, polyethylene glycol (PEG), polytetrahydrofuran (PTHF), polyethyleneimine (PEI), polyesters, polycarbonate (PC), and poly The material may contain one or more resins selected from the group consisting of relaxide (PLA), polyethylene terephthalate (PET), polyketones, polyether ether ketone (PEEK), polyamides, polyurethane (PU), polyacrylamide (PAAm), polysilanes, polysiloxane, polydimethylsiloxane (PDMS), starch, cellulose, chitosan, hyaluronic acid, alginate, dextran, gelatin, heparin, polypeptides, and polynucleotides.

[0026] In the aforementioned compounding material, the content of the cyclic oligomer may be 0.1% to 5% by weight.

[0027] The aforementioned compounding material may be manufactured by a solvent casting method or a hot-melt extrusion method.

[0028] In yet another embodiment of the present invention, a composite material for surface treatment is provided, comprising the compounding material; and a polymer brush grafted from the compounding material.

[0029] The grafting of the polymer brush may be carried out via atomic transfer radical polymerization (ATRP).

[0030] The polymer brush may also be based on an acrylate series monomer.

[0031] In yet another embodiment of the present invention, a medical article is provided that has been surface-modified or surface-treated using the aforementioned compounding material. [Effects of the Invention]

[0032] The present invention relates to cyclic oligomers, methods for producing the same, compound materials and composite materials containing the same, and medical articles surface-modified or surface-treated therewith, wherein the cyclic oligomers can be produced by ring-expansion cationic polymerization using cyclic hemiacetal ester initiators and vinyl ether monomers, and are characterized by having surface segregating properties.

[0033] When the aforementioned cyclic oligomer is applied as a surface-separating material, it has the advantage of imparting various functionalities (such as antifouling properties) to the surface of biocompatible materials. Therefore, by blending the aforementioned cyclic oligomer with various biocompatible materials, a surface-modifying compound can be manufactured, and this compound can be used to modify the surface of medical articles.

[0034] On the other hand, the cyclic oligomer is for initiating various polymerization reactions, and is characterized by the ability to bond and graft polymer brushes using an initiator immobilized on its surface. In particular, because the polymer brushes are grafted at high density, various functionalities such as surface roughness, stain resistance, hydrophilicity, and hydrophobicity can be imparted depending on the properties of the polymer brushes, and this can be used to surface treat medical products. [Brief explanation of the drawing]

[0035] [Figure 1] This is a schematic diagram of the synthesis of cyclic hemiacetal ester initiators. [Figure 2] This diagram shows a schematic synthesis of a cyclic oligomer using ethyl vinyl ether, butyl vinyl ether, dodecyl vinyl ether, or allyl vinyl ether according to one embodiment of the present invention; a schematic linearization of a cyclic oligomer using ethyl vinyl ether according to one embodiment of the present invention; and a schematic functionalization of a cyclic oligomer using allyl vinyl ether according to one embodiment of the present invention. [Figure 3A] The synthesis was confirmed by analyzing the cyclic hemiacetal ester initiator using 1H NMR. [Figure 3B] This is the result of analyzing cyclic oligomers (cpEVE-5k, cpEVE-10k, cpEVE-20k, lpEVE-5k, cpBVE-8k, cpDDVE-16k, and cpAVE-5k) according to one embodiment of the present invention using GPC to confirm their synthesis. [Figure 3C] This is the result of analyzing cyclic oligomers (cpEVE-5k, cpEVE-10k, cpEVE-20k, cpBVE-8k, cpDDVE-16k, cpAVE-5k, lpEVE-5k, and cpAVE-F) according to one embodiment of the present invention by proton NMR, and confirming their synthesis. [Figure 3D] This is the result of analyzing cyclic oligomers (cpEVE-5k and IpEVE-5k) according to one embodiment of the present invention using SAXS, DSC, and GPC to confirm their synthesis. [Figure 4] This is a schematic diagram illustrating the manufacturing process of a TPU specimen to which a cyclic oligomer or the like according to one embodiment of the present invention has been added by solvent casting. [Figure 5] This shows the results of analyzing TPU specimens to which cyclic oligomers (cpEVE-5k and lpEVE-5k) according to one embodiment of the present invention were added, using XPS and AR-XPS. [Figure 6] This is the result of XPS analysis to investigate the surface separation characteristics of TPU specimens to which cyclic oligomers (cpEVE-5k, cpEVE-10k, and cpEVE-20k) according to one embodiment of the present invention were added. [Figure 7] The following are the results of analyzing the surface morphology and hydrophilicity of TPU specimens to which cyclic oligomers (cpEVE-5k, cpEVE-10k, cpEVE-20k, cpBVE-8k, cpDDVE-16k, and lpEVE-5k) according to one embodiment of the present invention were added, using AFM and water contact angle analysis. [Figure 8] The following are the results of analyzing TPU specimens to verify the functionality of functionalized cyclic oligomers (cpAVE-5k and cpAVE-F) according to one embodiment of the present invention, using XPS, water contact angle, and protein adsorption. [Figure 9] This shows the results of analyzing PVP specimens to which cyclic oligomers (cpEVE-5k and lpEVE-5k) according to one embodiment of the present invention were added, using XPS and TOF-SIMS. [Figure 10] This is a schematic diagram illustrating the operation (surface separation → polymer brush bonding and grafting) of an ATRP cyclic oligomer according to one embodiment of the present invention. [Figure 11] (a) A schematic diagram of the synthesis of a vinyl ether monomer (BrVE) derived from an ATRP initiator, (b) a schematic diagram of the synthesis of an ATRP cyclic oligomer (cpBrVE), and (c) a schematic diagram of the linearization of an ATRP cyclic oligomer (lpBrVE). [Figure 12] (a) Results of analysis of vinyl ether monomers (BrVE) derived from ATRP initiators by 1H NMR, and (b) to (f) Results of analysis of ATRP cyclic oligomers by GPC, 1H NMR, and DSC. [Figure 13] This is a schematic diagram illustrating the manufacturing process of various biocompatible material specimens to which ATRP cyclic oligomers and other materials according to one embodiment of the present invention have been added by the solvent casting method. [Figure 14] The following are the results of XPS analysis of the surface separation characteristics of TPU specimens to which ATRP cyclic oligomer (cpBrVE) or the like has been added according to one embodiment of the present invention; (a) shows a Br3d peak and (b) shows a C1s peak. [Figure 15] This is the result of analyzing the surface separation characteristics of PS specimens to which ATRP cyclic oligomer (cpBrVE) and the like have been added according to one embodiment of the present invention, using XPS. [Figure 16] This is the result of analyzing the surface separation characteristics of PMMA specimens to which ATRP cyclic oligomer (cpBrVE) or the like has been added according to one embodiment of the present invention, using XPS. [Figure 17] This is the result of analyzing the surface separation characteristics of PVDF specimens to which ATRP cyclic oligomer (cpBrVE) or the like was added according to one embodiment of the present invention, using XPS. [Figure 18] This is the result of a cytotoxicity test performed on TPU specimens to which ATRP cyclic oligomer (cpBrVE) according to one embodiment of the present invention was added. [Figure 19] This is the result of analyzing the water contact angle in a TPU specimen on which an antifouling polymer brush was formed according to one embodiment of the present invention, in order to establish the optimal time for polymer brush formation. [Figure 20] This study verifies the formation of a polymer brush in a TPU specimen on which an antifouling polymer brush has been formed according to one embodiment of the present invention. (a) shows the results of FT-IR analysis, (b) shows the results of XPS (S2p peak), and (c) shows the results of water contact angle analysis. [Figure 21] This is the result of analyzing the surface morphology of a TPU specimen on which an antifouling polymer brush according to one embodiment of the present invention was formed, using AFM. [Figure 22] This is the result of analyzing the surface morphology of a TPU specimen on which an antifouling polymer brush according to one embodiment of the present invention was formed, using SEM. [Figure 23] This is the result of an albumin adhesion test conducted on TPU specimens on which an antifouling polymer brush according to one embodiment of the present invention was formed. [Figure 24] This is the result of a platelet adhesion test conducted on TPU specimens on which an antifouling polymer brush formed according to one embodiment of the present invention was attached. [Figure 25] This shows the results of a bacterial adhesion test conducted on a TPU specimen on which an antifouling polymer brush according to one embodiment of the present invention was formed. [Figure 26] This is the result of analyzing the water contact angle over time in a TPU specimen on which an antifouling polymer brush according to one embodiment of the present invention was formed. [Figure 27] The following are the results of (a) FT-IR and (b) object contact angle analysis of TPU specimens on which various polymer brushes according to one embodiment of the present invention were formed. [Best Mode for Carrying Out the Invention]

[0036] In their research on surface-separable materials that can be incorporated into biocompatible materials, the inventors have produced new cyclic oligomers using ring-expansion cationic polymerization with cyclic hemiacetal ester initiators and vinyl ether monomers. These oligomers possess surface-separable properties and have been confirmed to impart various functionalities (such as antifouling) to the surface of biocompatible materials. On the other hand, they have confirmed that initiators can be immobilized on the surface of biocompatible materials, and subsequently, polymer brushes with various functionalities (surface roughness, antifouling, hydrophilicity, hydrophobicity, etc.) can be grafted onto them using the graft-from method.

[0037] The present invention will be described in detail below.

[0038] <Cyclic oligomer>

[0039] The present invention relates to the following formula (1) [ka]

[0040] (wherein R1 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, R2 is a substituted or unsubstituted C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C3-C15 cycloalkyl group, C6-C15 aryl group, or C6-C15 heteroaryl group, or a form in which a functional group of less than C15 is further introduced at the terminal by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from the initiator. The sum of 2n and m is an integer between 10 and 600. This provides a cyclic oligomer represented by .

[0041] The cyclic oligomer may have surface segregating properties. That is, when the cyclic oligomer is applied as a surface segregating material, it has the advantage of imparting various functionalities (such as antifouling properties) to the surface of biocompatible materials. Therefore, by blending the cyclic oligomer with various biocompatible materials, a surface modification compound can be manufactured, and this compound can be used to modify the surface of medical articles.

[0042] On the other hand, the cyclic oligomer having surface segregation properties can be used to initiate various polymerization reactions. That is, when the cyclic oligomer is applied as a surface segregation material, there is the advantage that the initiator can be fixed to the surface of the compound material described later. Therefore, by compounding the cyclic oligomer with various biocompatible materials, it is possible to manufacture a compound material in which the initiator is fixed to the surface, and polymer brushes can be grafted using the graft-from method with the initiator fixed to the surface. In particular, since the polymer brushes are grafted at high density, various functionalities such as surface roughness, antifouling properties, hydrophilicity, and hydrophobicity can be imparted depending on the properties of the polymer brushes, and medical products can be surface treated using these brushes.

[0043] Specifically, in formula (1) above, the functional group R1 is derived from a cyclic hemiacetal ester initiator as described below, and may be a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group. More specifically, the functional group R1 may be substituted or unsubstituted, and in some cases, the functional group R1 may be diversely substituted with one or more halogen groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, carboxyl groups, etc. The functional group R1 is characterized by having a maximum of 15 total carbon atoms, preferably a maximum of 10, but is not limited thereto.

[0044] Furthermore, in formula (1) above, the functional group R2 is derived from a vinyl ether monomer as described later. First, the functional group R2 may be a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group. More specifically, the functional group R2 may be substituted or unsubstituted, and in some cases, the functional group R2 may be diversely substituted with one or more halogen groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, carboxyl groups, etc. The functional group R2 is a functional group that affects surface separation properties, and is characterized by having a maximum of 15 total carbon atoms, preferably a maximum of 10, but not limited to this. In this case, it can be seen that as the total number of carbon atoms in the functional group R2 increases excessively, the surface separation properties decrease.

[0045] Alternatively, the functional group R2 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, and a functional group R less than C15 is added to the terminal by a chemical reaction. 2’ It may also be in a form in which the functional group R is further introduced. Specifically, the functional group R 2’ The functional group R2 is further introduced by a chemical reaction between the functional group R2 and a compound less than C15, and may contain functional groups such as halogen groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, and carboxyl groups. 2’ These are functional groups that affect surface separation, and the functional groups R2 and R 2’ In this case, the total number of carbon atoms is characterized by being a maximum of 15, preferably a maximum of 10, but not limited to this. In this case, functional group R2 and functional group R 2’ It can be seen that as the total number of carbon atoms increases excessively, the surface separation properties actually decrease. For example, functional group R 2’is a halogen group (F, Cl, Br or I) or a C1-C14 alkyl halide. Particularly, in the case of a fluoro group (F) or a C1-C14 fluoroalkyl, it is preferable from the aspect of ensuring antifouling property to reduce protein adsorption, but is not limited thereto.

[0046] On the other hand, a compound with less than C15 contains a functional group R 2’ and can simultaneously contain a chemical reaction functional group (preferably a click chemical reaction functional group such as a thiol group or an azide group) capable of chemically reacting with the functional group R2. At this time, the compound with less than C15 can have the functional group R 2’ directly linked to the chemical reaction functional group without a hydrocarbon skeleton, or the functional group R 2’ may be linked to the chemical reaction functional group via a C_{1}-C_{14} hydrocarbon skeleton. For example, the C_{1}-C_{14} hydrocarbon skeleton may be a saturated aliphatic compound, an unsaturated aliphatic compound, an aromatic compound, a heteroaromatic compound, an ether compound, an ester compound, a ketone compound, an amide compound, a zwitterion, a peptide, etc.

[0047] Particularly, when the functional group R2 is a C2-C15 alkenyl group or a C2-C15 alkynyl group, it may be in a form in which a functional group R with less than C15 is further introduced at the end by a chemical reaction. The chemical reaction may occur between the functional group R2 and the compound with less than C15. On the other hand, when the compound with less than C15 contains the functional group R 2’ and simultaneously contains a click chemical reaction functional group such as a thiol group or an azide group, the chemical reaction is preferably a click chemical reaction selected from the group consisting of thiol-ene, thiol-yne, azide-ene and azide-yne, but is not limited thereto.

[0048] ​​On the other hand, in formula (1) above, the functional group R2 is derived from a vinyl ether monomer derived from an initiator described below, and the functional group R2 includes functional groups derived from various initiators, but in this specification, "initiator-derived functional group" means a functional group produced using an initiator and containing an initiator. Specifically, the functional group R2 may include a functional group derived from an atom transfer radical polymerization (ATRP) initiator, a functional group derived from a reversible addition-cleavage chain transfer polymerization (RAFT) initiator, a functional group derived from a nitrooxide-mediated living radical polymerization (NMP) initiator, or a functional group derived from a photoinifer-mediated polymerization (PIMP), and may include a functional group derived from an atom transfer radical polymerization (ATRP) initiator, and preferably includes a functional group derived from an atom transfer radical polymerization (ATRP) initiator, but is not limited thereto. On the other hand, functional group R2 can include functional groups such as halogen groups, ester groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, and carboxyl groups, and preferably includes, but is not limited to, halides or alkyl halides (for example, bromide or α-bromoisobutyryl). However, functional group R2 is a functional group that affects surface separation properties, and is characterized by having a maximum of 15 total carbon atoms, preferably a maximum of 10, but is not limited to this. In this case, it can be seen that as the total number of carbon atoms in functional group R2 increases excessively, the surface separation properties actually decrease.

[0049] Furthermore, in equation (1) above, 2n may be an integer between 10 and 600, and m may be an integer between 2 and 600.

[0050] When the cyclic oligomer is applied to the surface modification compound described later, the number average molecular weight (M) of the cyclic oligomer is n The number average molecular weight (M) of the cyclic oligomer may be 5,000 to 20,000, preferably 8,000 to 20,000, and more preferably 15,000 to 20,000, but is not limited thereto. nThe cyclic oligomer can be analyzed by gel permeation chromatography (GPC). At this time, it can be seen that the surface separation ability increases as the molecular weight of the cyclic oligomer increases.Therefore, when the cyclic oligomer is blended with various biocompatible materials to produce a surface modification compound, the surface roughness and hydrophilicity of the specimen decrease as the molecular weight of the cyclic oligomer increases.

[0051] On the other hand, when the cyclic oligomer is applied to the polymer brush bonding compound described later, the number average molecular weight (M) of the cyclic oligomer is n ) may be between 5,000 and 15,000, and preferably between 9,000 and 11,000, but is not limited to this.

[0052] <Cyclic hemiacetal ester initiator for cyclic oligomer production> The present invention relates to the following formula (2) [ka]

[0053] (wherein R1 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, The present invention provides a cyclic hemiacetal ester initiator for the production of the cyclic oligomer, comprising a compound represented by (where m is an integer between 2 and 600).

[0054] In formula (2) above, the functional group R1 may be a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group. More specifically, the functional group R1 may be substituted or unsubstituted, and in some cases, the functional group R1 may be diversely substituted with one or more halogen groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, carboxyl groups, etc. The functional group R1 is characterized by having a maximum of 15 total carbon atoms, preferably a maximum of 10, but is not limited thereto.

[0055] The "cyclic oligomers" produced using the aforementioned cyclic hemiacetal ester initiators have been described above, so a redundant explanation will be omitted.

[0056] <Vinyl ether-based monomers for cyclic oligomer production> The present invention relates to the following formula (3) [ka]

[0057] The present invention provides a vinyl ether monomer for producing the cyclic oligomer, comprising a compound represented by the formula (wherein R2 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, or a form in which a functional group of less than C15 is introduced at the terminal by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from an initiator).

[0058] In formula (3) above, the functional group R2 may be a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group. More specifically, the functional group R2 may be substituted or unsubstituted, and in some cases, the functional group R2 may be diversely substituted with one or more halogen groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, carboxyl groups, etc. The functional group R2 is a functional group that affects surface separation properties, and is characterized by having a maximum of 15 total carbon atoms, preferably a maximum of 10, but not limited to this. In this case, it can be seen that as the total number of carbon atoms in the functional group R2 increases excessively, the surface separation properties decrease.

[0059] Alternatively, the functional group R2 is a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, and a functional group R less than C15 is added to the terminal by a chemical reaction. 2’ It may also be in a form in which the functional group R is further introduced. Specifically, the functional group R 2’ The functional group R2 is further introduced by a chemical reaction between the functional group R2 and a compound less than C15, and may contain functional groups such as halogen groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, and carboxyl groups. 2’ These are functional groups that affect surface separation, and the functional groups R2 and R 2’ In this case, the total number of carbon atoms is characterized by being a maximum of 15, preferably a maximum of 10, but not limited to this. In this case, functional group R2 and functional group R 2’ It can be seen that as the total number of carbon atoms increases excessively, the surface separation properties actually decrease. For example, functional group R 2’The halogen group is a halogen group (F, Cl, Br, or I) or a C1-C14 alkyl halide. In particular, a fluoro group (F) or a C1-C14 fluoroalkyl group is preferred from the standpoint of ensuring antifouling properties because it reduces protein adsorption, but the material is not limited to these.

[0060] On the other hand, compounds with less than C15 have the functional group R 2’ It may also contain a chemically reactive functional group (preferably a click chemically reactive functional group such as a thiol group or an azide group) that can chemically react with functional group R2. In this case, compounds with less than C15 may have a hydrocarbon skeleton without the functional group R 2’ The functional group is either directly linked to the chemical reaction functional group or linked to the functional group R via the C1-C14 hydrocarbon skeleton. 2’ This can be linked to a chemical reaction functional group. For example, the C1-C14 hydrocarbon skeleton may be a saturated aliphatic compound, an unsaturated aliphatic compound, an aromatic compound, a heteroaromatic compound, an ether compound, an ester compound, a ketone compound, an amide compound, a zwitterion, a peptide, or the like.

[0061] In particular, if the functional group R2 is a C2-C15 alkenyl group or a C2-C15 alkynyl group, a functional group with less than C15 may be added to the terminal due to a chemical reaction. R2’ This may be in a further introduced form. The chemical reaction may occur between the functional group R2 and a compound with less than 15 C. On the other hand, if the compound with less than 15 C is the functional group R 2’ Preferably, the chemical reaction is a click reaction selected from the group consisting of thiol-ene, thiol-yne, azide-ene, and azide-yne, by including a click reaction functional group such as a thiol group or an azide group, but is not limited to this.

[0062] In other words, in formula (3), the functional group R2 includes functional groups derived from various initiators, but can include functional groups derived from atom transfer radical polymerization (ATRP) initiators, reversible addition-cleavage chain transfer polymerization (RAFT) initiators, nitrooxide-mediated living radical polymerization (NMP) initiators, or photoinifer-mediated polymerization (PIMP). It is preferable, but not limited, that it may include functional groups derived from atom transfer radical polymerization (ATRP) initiators. On the other hand, the functional group R2 can include functional groups such as halogen groups, ester groups, hydroxyl groups, carbonyl groups, amine groups, aldehyde groups, thiol groups, and carboxyl groups, and is preferable, but not limited, that it may include halides or alkyl halides (e.g., bromide or α-bromoisobutyryl). However, functional group R2 is a functional group that affects surface separation properties, and is characterized by having a maximum of 15 total carbon atoms, preferably 10, but not limited to this. In this case, it can be seen that as the total number of carbon atoms in functional group R2 increases excessively, the surface separation properties actually decrease.

[0063] The vinyl ether monomers can be produced by an SN2 reaction between an alcohol containing vinyl ether and various initiators. In addition, triethylamine can be further added to the SN2 reaction, which can be carried out by stirring at room temperature in the presence of nitrogen gas for about 1 to 5 hours.

[0064] The "cyclic oligomers" produced using the aforementioned vinyl ether monomers have been described above, so a redundant explanation will be omitted.

[0065] The present invention provides a method for producing cyclic oligomers using ring-expansion cationic polymerization, targeting cyclic hemiacetal ester initiators and vinyl ether monomers.

[0066] The "cyclic oligomers" produced using the aforementioned cyclic hemiacetal ester initiators and vinyl ether monomers have been described above, so a redundant explanation will be omitted.

[0067] Specifically, in the ring-expanding cationic polymerization method, 2,6-di-tert-butyl-4-methylpyridine and tin(IV) bromide can be further added, and the ring-expanding cationic polymerization method can be carried out in the presence of nitrogen gas under temperature conditions of -70°C to 0°C by stirring for about 30 minutes to about 5 hours.

[0068] <Composition materials> The present invention provides a compound material comprising the cyclic oligomer and a biocompatible material.

[0069] In this specification, "blended material" means a form (blend or admixture) in which two or more materials are mixed together, or a state in which two or more materials are physically mixed together, and may be for surface modification or polymer brush bonding.

[0070] In this specification, "polymer brush" means an aggregate of polymer chains in which polymers are grafted onto a substrate in a brush form.

[0071] First, the compound material is used for surface modification or surface treatment of various articles, particularly medical articles, and includes the cyclic oligomer, but since the "cyclic oligomer" has been described above, a redundant explanation will be omitted. If a linearized cyclic oligomer is used as a substitute for the cyclic oligomer as a material with surface separability, the surface separability is significantly reduced. On the other hand, due to the surface separability of the cyclic oligomer, an initiator can be fixed to the surface of the compound material. Subsequently, a polymer brush can be joined and grafted using the graft-from method. If a linearized cyclic oligomer is used as a substitute for the cyclic oligomer, the surface separability is significantly reduced.

[0072] Next, the compound material includes biocompatible materials, which include polyolefins, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polybutadiene (PB), polystyrene (PS), polymethyl acrylate (PMA), polyethyl acrylate (PEA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyhydroxyethyl methacrylate (PHEMA), polyvinylpyrrolidone (PVP), polyethers, polyethylene glycol (PEG), polytetrahydrofuran (PTHF), polyethyleneimine (PEI), polyesters, polycarbonate (PC), polylactide (PLA), and poly The material may contain one or more resins selected from the group consisting of ethylene terephthalate (PET), polyketones, polyether ether ketone (PEEK), polyamides, polyurethane (PU), polyacrylamide (PAAm), polysilanes, polysiloxane, polydimethylsiloxane (PDMS), starch, cellulose, chitosan, hyaluronic acid, alginate, dextran, gelatin, heparin, polypeptides, and polynucleotides, and is preferably polyurethane (PU) or polyvinylpyrrolidone (PVP), but is not limited thereto.

[0073] In the aforementioned compounding material, the content of the cyclic oligomer is preferably 0.1% to 5% by weight, but is not limited thereto. The cyclic oligomer is suitable for surface modification because, as described above, surface separation progresses even with only a small amount added, and sufficient functionality can be imparted to the surface. On the other hand, as described above, surface separation progresses even with only a small amount added, and the initiator can be sufficiently fixed to the surface of the compounding material, making it suitable for polymer brush bonding.

[0074] In particular, when the compounding material is for surface modification, i) the volume of the cyclic oligomer relative to the surface is 65% by volume or more (preferably 80% by volume or more, more preferably 90% by volume or more), ii) the weight of the cyclic oligomer relative to a depth of 7 nm from the surface is 10% by weight or more (preferably 50% by weight or more, more preferably 60% by weight or more), and iii) the surface roughness is 2 nm to 15 nm. The compounding material can ensure the above-mentioned surface volume ratio, surface weight ratio, and surface roughness by optimizing the molecular weight and pendant (alkyl group) length of the cyclic oligomer used as the surface separation material. In this case, if a linearized cyclic oligomer is used instead of the cyclic oligomer as the surface separation material, the surface volume ratio will decrease significantly, or the surface roughness (R q ) will increase significantly.

[0075] For example, in the cyclic oligomer, if the functional group with less than C15 contains a fluoro group (F) (preferably a fluoroalkyl functional group), the compound material is characterized by having antifouling properties. Such antifouling properties are due to the functional group containing a fluoro group (F), particularly a fluoroalkyl functional group, present in the cyclic oligomer used as the surface separation material, reducing protein adsorption. The compound material has a water contact angle of 110° or more, or a fibrinogen adsorption amount of 1.5 μg / cm². 2 The following is also acceptable.

[0076] On the other hand, if the compounding material is for polymer brush bonding, the molar ratio of the cyclic oligomer may be 45% by weight or more, preferably 48% by weight or more, based on a depth of 7 nm from the surface.

[0077] Specifically, the compounding material can be manufactured by a solvent casting method or a high-temperature melt extrusion method targeting the cyclic oligomer and the biocompatible material. The compounding material can then be finalized by drying it for 10 to 50 hours under a temperature of 10°C to 50°C.

[0078] <Composite materials for surface treatment> The present invention provides a composite material for surface treatment comprising the aforementioned compounding material and a polymer brush grafted from the aforementioned compounding material.

[0079] First, the composite material for surface treatment includes the compounding material, which is for joining polymer brushes. Since the "compounding material" has been described above, a redundant explanation will be omitted.

[0080] Next, the surface treatment composite material includes polymer brushes grafted from the compounding material, the polymer brushes being biocompatible and possessing various functionalities, and depending on the properties of the polymer brushes, various functionalities such as surface roughness, antifouling properties, hydrophilicity, and hydrophobicity can be imparted. The polymer brushes can be joined and grafted using an initiator fixed to the surface of the compounding material. In particular, by using the cyclic oligomer in the compounding material, the polymer brushes can be grafted at a higher density compared to when a linearized cyclic oligomer is used.

[0081] Specifically, the polymer brush may be based on various materials, but may also be based on acrylate series monomers. More specifically, the polymer brush is preferably based on acrylate series zwitterion monomers, or on poly(ethylene glycol) methacrylate (PEGMA) or methyl methacrylate (MMA) monomers, but is not limited thereto. On the other hand, when the polymer brush is based on acrylate series zwitterion monomers (for example, 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonate (SBMA)), the zwitterions form a hydration layer, which provides antifouling properties. As a result, 1) the surface roughness is 60 nm to 180 nm, or 2) the albumin adsorption amount is 1 μg / cm². 2 3) Platelet attachment rate is 200 platelets / mm³ 2 4) E. coli bacterial adhesion capacity is 2 × 10 3 CFU / cm 2 Less than or S. aureus bacterial adhesion capacity of 3 × 10 4 CFU / cm 2 It may be less than 5) the water contact angle from the initial stage to 28 days later may be 15° or less.

[0082] The grafting of the polymer brush can be carried out via various known polymerization methods, including atom transfer radical polymerization (ATRP), reversible addition-cleavage chain transfer polymerization (RAFT), nitrooxide-mediated living radical polymerization (NMP), or photoinifer-mediated polymerization (PIMP), with atom transfer radical polymerization (ATRP) being preferred, but not limited thereto. Specifically, the grafting of the polymer brush can be carried out at a temperature of 30°C to 80°C for 1 to 20 hours, and is preferably carried out at a temperature of 40°C to 60°C for 10 to 20 hours, but is not limited thereto.

[0083] <Surface-modified or surface-treated medical articles> The present invention provides a medical article that has been surface-modified or surface-treated using the aforementioned compounding material.

[0084] The aforementioned medical article is surface-modified or surface-treated using the aforementioned compounding material, and since the "compounding material" has been described above, a redundant explanation will be omitted.

[0085] When the medical article is a bio-contact type and / or implantable type, it is preferable in that the compounding material can impart biocompatibility and biofunctionality, but it is not limited to this.

[0086] The medical articles (molded articles) may be surgical articles, filters, medical devices, etc. Specifically, the surgical articles may be one or more selected from the group consisting of surgical caps, surgical sheets, surgical cover garments, surgical gowns, surgical masks, surgical gloves, and surgical drapes; the filters may be one or more selected from the group consisting of respiratory protective equipment filters, water filters, air filters, and face mask filters; and the medical devices may be one or more selected from the group consisting of artificial heart valves, cardiac assist devices, dialysis circuits, extracorporeal membrane oxygenation devices, catheters, stents, prosthetic implants, artificial sphincters, and drug delivery devices.

[0087] As discussed above, the present invention relates to a cyclic oligomer, a method for producing the same, compounding materials and composite materials containing the same, and medical articles surface-modified or surface-treated therewith, wherein the cyclic oligomer can be produced by ring-expansion cationic polymerization using a cyclic hemiacetal ester initiator and a vinyl ether monomer, and is characterized by having surface segregating properties.

[0088] When the aforementioned cyclic oligomer is applied as a surface-separating material, it has the advantage of imparting various functionalities (such as antifouling properties) to the surface of biocompatible materials. Therefore, by blending the aforementioned cyclic oligomer with various biocompatible materials, a surface-modifying compound can be manufactured, and this compound can be used to modify the surface of medical articles.

[0089] On the other hand, the cyclic oligomer is for initiating various polymerization reactions, and is characterized by the ability to bond and graft polymer brushes using an initiator fixed to its surface. In particular, since the polymer brushes are grafted at high density, various functionalities such as surface roughness, stain resistance, hydrophilicity, and hydrophobicity can be imparted depending on the properties of the polymer brushes, and medical products can be surface treated using this method.

[0090] The following are preferred embodiments to aid in understanding the present invention. However, these embodiments are provided to facilitate understanding of the present invention and do not limit the scope of the present invention.

[0091] Examples Example 1-1: Synthesis of cyclic hemiacetal ester initiators The cyclic hemiacetal ester initiator was prepared from cyclohexanone having a methoxy functional group by the Bayer-Villiger oxidation reaction. A schematic diagram of the synthesis of the cyclic hemiacetal ester initiator is shown in Figure 1.

[0092] 1.09 g of sodium bicarbonate (TCI), 2.935 g of 3-chloroperbenzoic acid (Sigma-Aldrich), 1.28 mL of 2-methoxycyclohexanone (TCI), chloroform (Sigma-Aldrich), saturated aqueous solution of sodium sulfite (Sigma-Aldrich), saturated aqueous solution of sodium bicarbonate (TCI), saturated aqueous solution of sodium chloride (Samchun Chemical), and sodium sulfate (Sigma-Aldrich) were prepared.

[0093] After removing water from a three-necked round-bottom flask, sodium bicarbonate, 50 mL of chloroform, and 3-chloroperbenzoic acid were added sequentially. Then, 2-methoxycyclohexanone was added gradually over 30 minutes at 0°C, and the mixture was stirred for another 30 minutes in the presence of nitrogen gas. The synthesized substance was then washed with a saturated sodium sulfite solution to terminate the reaction. The completed solution was washed again sequentially with saturated sodium bicarbonate solution and saturated sodium chloride solution to remove acid and water. After further removal of any remaining water in the solution with sodium sulfate, the mixture was filtered, and finally, the solvent of the product was removed using a rotary evaporator. The obtained product was stored at -20°C in a highly viscous liquid form.

[0094] Examples 1-2: Synthesis of cyclic oligomers using ethyl vinyl ether The cyclic oligomers (cpEVE-5k, cpEVE-10k, cpEVE-20k) were synthesized by ring-expansion cationic polymerization of ethyl vinyl ether to the cyclic hemiacetal ester initiator prepared in Example 1-1. A schematic diagram of the synthesis of the cyclic oligomers using ethyl vinyl ether is shown in Figure 2(a).

[0095] Ethyl vinyl ether (TCI) and toluene (Sigma-Aldrich) were prepared by removing water using potassium hydroxide pellets (Sigma-Aldrich), and 1.54 mg of 2,6-di-tert-butyl-4-methylpyridine (Sigma-Aldrich), 109.6 mg of tin(IV) bromide (Sigma-Aldrich), 36 mg of the cyclic hemiacetal ester initiator prepared in Example 1-1, and methanol (Sigma-Aldrich) were prepared.

[0096] After removing water from the three-necked round-bottom flask, 50 mL of toluene was added, followed by the addition of 0.73, 2.18, and 3.64 mL of ethyl vinyl ether, respectively, at -40°C according to the experimental procedure. Subsequently, 2,6-di-tert-butyl-4-methylpyridine, tin(IV) bromide, and the cyclic hemiacetal initiator prepared in Example 1-1 were added sequentially, and the mixture was stirred in the presence of nitrogen gas for 1 hour. Immediately after the reaction time was completed, the product was mixed with methanol at 4°C to terminate the reaction. The product was then washed in a funnel containing deionized water, and finally, the solvent of the product was removed using a rotary evaporator.

[0097] Examples 1-3: Synthesis of cyclic oligomers using butyl vinyl ether The cyclic oligomer (cpBVE-8k) was synthesized by ring-expanding cationic polymerization of butyl vinyl ether to the cyclic hemiacetal ester initiator prepared in Example 1-1. A schematic diagram of the synthesis of the cyclic oligomer using butyl vinyl ether is shown in Figure 2(a).

[0098] Butyl vinyl ether (manufactured by Sigma-Aldrich) and toluene (manufactured by Sigma-Aldrich) were prepared by removing water using potassium hydroxide pellets (manufactured by Sigma-Aldrich), and 1.54 mg of 2,6-di-tert-butyl-4-methylpyridine (manufactured by Sigma-Aldrich), 109.6 mg of tin(IV) bromide (manufactured by Sigma-Aldrich), 36 mg of the cyclic hemiacetal ester initiator prepared in Example 1-1, and methanol (manufactured by Sigma-Aldrich) were prepared.

[0099] After removing water from a three-necked round-bottom flask, 50 mL of toluene was added, followed by 1.85 mL of butyl vinyl ether at -40°C. Then, 2,6-di-tert-butyl-4-methylpyridine, tin(IV) bromide, and the cyclic hemiacetal ester initiator prepared in Example 1-1 were added sequentially, and the mixture was stirred in the presence of nitrogen gas for 1 hour. Immediately after the reaction time was completed, the product was mixed with methanol at 4°C to terminate the reaction. The product was then washed in a funnel containing deionized water, and finally, the solvent of the product was removed using a rotary evaporator.

[0100] Examples 1-4: Synthesis of cyclic oligomers using dodecyl vinyl ether The cyclic oligomer (cpDDVE-16k) was synthesized by ring-expanding cationic polymerization of dodecyl vinyl ether to the cyclic hemiacetal ester initiator prepared in Example 1-1. A schematic diagram of the synthesis of the cyclic oligomer using dodecyl vinyl ether is shown in Figure 2(a).

[0101] Dodecyl vinyl ether (manufactured by Sigma-Aldrich) and toluene (manufactured by Sigma-Aldrich) were prepared by removing water using potassium hydroxide pellets (manufactured by Sigma-Aldrich), and 1.54 mg of 2,6-di-tert-butyl-4-methylpyridine (manufactured by Sigma-Aldrich), 109.6 mg of tin(IV) bromide (manufactured by Sigma-Aldrich), 36 mg of the cyclic hemiacetal ester initiator prepared in Example 1-1, and methanol (manufactured by Sigma-Aldrich) were prepared.

[0102] After removing water from the three-necked round-bottom flask, 50 mL of toluene was added, followed by 10.5 mL of dodecyl vinyl ether at -40°C. Then, 2,6-di-tert-butyl-4-methylpyridine, tin(IV) bromide, and the cyclic hemiacetal ester initiator prepared in Example 1-1 were added sequentially, and the mixture was stirred in the presence of nitrogen gas for 1 hour. Immediately after the reaction time was completed, the product was mixed with methanol at 4°C to terminate the reaction. The product was then washed in a funnel containing deionized water, and finally, the solvent of the product was removed using a rotary evaporator.

[0103] Examples 1-5: Synthesis of cyclic oligomers using allyl vinyl ether The cyclic oligomer (cpAVE-5k) was synthesized by ring-expanding cationic polymerization of allyl vinyl ether to the cyclic hemiacetal ester initiator prepared in Example 1-1. A schematic diagram of the synthesis of the cyclic oligomer using allyl vinyl ether is shown in Figure 2(a).

[0104] Allyl vinyl ether (manufactured by Thermo Fisher Scientific) and toluene (manufactured by Sigma-Aldrich) were prepared by removing water using potassium hydroxide pellets (manufactured by Sigma-Aldrich), and 1.54 mg of 2,6-di-tert-butyl-4-methylpyridine (manufactured by Sigma-Aldrich), 109.6 mg of tin(IV) bromide (manufactured by Sigma-Aldrich), 36 mg of the cyclic hemiacetal ester initiator prepared in Example 1-1, and methanol (manufactured by Sigma-Aldrich) were prepared.

[0105] After removing water from the three-necked round-bottom flask, 50 mL of toluene was added, followed by 5.13 mL of allyl vinyl ether at -40°C. Then, 2,6-di-tert-butyl-4-methylpyridine, tin(IV) bromide, and the cyclic hemiacetal ester initiator prepared in Example 1-1 were added sequentially, and the mixture was stirred for 1 hour in the presence of nitrogen gas. Immediately after the reaction time was complete, the product was mixed with methanol at 4°C to terminate the reaction. The product was then washed in a funnel containing deionized water, and finally, the solvent was removed from the product using a rotary evaporator.

[0106] Comparative Example 1-1: Linearization of cyclic oligomers using ethyl vinyl ether The cyclic oligomer (cpEVE-5k) prepared in Examples 1-2 was linearized by cleaving the hemiacetal ester by acid hydrolysis (IpEVE-5k). A schematic diagram of the linearization of the cyclic oligomer using ethyl vinyl ether is shown in Figure 2(b).

[0107] A 1 wt% ethyl vinyl ether solution in 20 mL of THF was added to a vial, followed by 1 mL of H2O / TFA (1 / 2 v / v) solution. The mixture was stirred at room temperature for 1 hour. The solution was then added to 2 g of Amberlyst® A21 freebase, the residual acid was removed, the mixture was filtered, and finally the solvent of the product was removed using a vacuum oven.

[0108] Examples 1-6: Functionalization of cyclic oligomers using allyl vinyl ether The cyclic oligomers (cpAVE-5k) produced in Examples 1-5 were functionalized via a thiol-ene click chemistry reaction, and functionality was imparted by the attachment of a C10 fluoroalkyl functional group (cpAVE-F). A schematic diagram of the functionalization of the cyclic oligomer using allyl vinyl ether is shown in Figure 2(c).

[0109] Dichloromethane (manufactured by Sigma-Aldrich) was prepared by removing water using potassium hydroxide pellets (manufactured by Sigma-Aldrich), and the cyclic oligomer (cpAVE-5k), 2,2-azobisisobutyronitrile (manufactured by Junsei Chemicals), and methanol (manufactured by Sigma-Aldrich) produced in Examples 1-5 were prepared.

[0110] After removing water from the three-necked round-bottom flask, 10 mL of dichloromethane was added, followed by the sequential addition of the cyclic oligomer (cpAVE-5k) prepared in Examples 1-5 and 2,2-azobisisobutyronitrile. The mixture was then stirred at room temperature in the presence of nitrogen gas for 24 hours. Immediately after the reaction time was complete, the solvent was removed using a rotary evaporator. The resulting slurry was washed by mixing it with methanol using a centrifuge, and any remaining solvent was removed using a vacuum hood.

[0111] Examples 1-7: Analysis of cyclic hemiacetal ester initiators and cyclic oligomers (NMR, GPC, DSC) (1) Analysis of cyclic hemiacetal ester initiators The cyclic hemiacetal ester initiator prepared in Example 1-1 is used in proton nuclear magnetic resonance ( 1 The synthesis was confirmed by analysis using 1H NMR, and the results are shown in Figure 3A.

[0112] (2) Analysis of cyclic oligomers The cyclic oligomers (cpEVE-5k, cpEVE-10k, cpEVE-20k, cpBVE-8k, cpDDVE-16k, and cpAVE-5k) prepared in Examples 1-2 to 1-5 were analyzed by gel permeation chromatography and proton NMR to confirm their synthesis, and the results are shown in Figures 3B and 3C.

[0113] According to the GPC analysis results, cpEVE-5k, cpEVE-10k, and cpEVE-20k are ethyl vinyl ether-based cyclic oligomers, and the GPC analysis confirmed that they have number-average molecular weights (Mn) of approximately 5,800, 12,200, and 18,900, respectively. The molecular weights for the remaining vinyl ether-based cyclic oligomers are also presented (Figure 3B).

[0114] Furthermore, proton NMR analysis revealed that peaks a, b, and c were located at 3.46 ppm, 1.59 ppm, and 3.97 ppm in cpEVE-5k, cpEVE-10k, cpEVE-20k, cpBVE-8k, cpDDVE-16k, and cpAVE-5k, respectively. These correspond to protons present in the vinyl ether main chain structure. Protons present in the pendants were also confirmed by proton NMR. Specifically, protons located on the methyl group of the ethyl vinyl ether-based cyclic oligomer were identified as a peak at 1.16 ppm, protons located on the vinyl group of the allyl vinyl ether-based cyclic oligomer were identified as peaks at 1.85 ppm, 2.81 ppm, 2.79 ppm, and 2.73 ppm, and corresponding peaks were also shown for the remaining vinyl ether-based cyclic oligomers (Figure 3C(a)-(f)).

[0115] (3) Analysis of linearized cyclic oligomers The linearized cyclic oligomer (IpEVE-5k) produced in Comparative Example 1 was analyzed by gel permeation chromatography (GPC) and proton NMR to confirm its synthesis, and the results of these analyses are shown in Figures 3B and 3C. Furthermore, the linearized cyclic oligomer (IpEVE-5k) produced in Comparative Example 1 was analyzed by small-angle X-ray scattering (SAXS), time-difference injection calorimeter (DSC), and gel permeation chromatography (GPC), and the results of these analyses are shown in Figure 3D.

[0116] Proton NMR results showed that when comparing cpEVE-5k and lpEVE-5k, a small peak appeared around 9.5 ppm after linearization. This is because an aldehyde group was generated at the end of the main chain during linearization (Figure 3C(a) and (g)).

[0117] As another analysis, SAXS was performed, and the results were converted into a Guinier plot. Subsequently, the radius of gyration was calculated according to Guinier's law, and it was confirmed that cpEVE-5k and lpEVE-5k have radii of gyration of approximately 6.68 nm and approximately 7.14 nm, respectively. Thus, the smaller radius of gyration of cyclic oligomers compared to linear oligomers can be interpreted as being due to the constraints on the chain structure (conformation) (Figure 3D(a)).

[0118] In another analysis, DSC was performed to measure the glass transition temperature, confirming that cpEVE-5k and lpEVE-5k have glass transition temperatures of approximately -33°C and -44°C, respectively. The slightly higher glass transition temperature of cpEVE-5k can be interpreted as being due to reduced fluidity resulting from the restricted morphology of the cyclic oligomer, its small size, and the lack of chain ends (Figure 3D(b)).

[0119] As a final analysis, GPC analysis of the size confirmed that cpEVE-5k has a smaller size than lpEVE-5k, similar to the results for the radius of rotation (Figure 3D(c)).

[0120] (4) Analysis of functionalized cyclic oligomers The functionalized cyclic oligomers (cpAVE-F) produced in Examples 1-6 were analyzed by proton NMR to confirm their synthesis, and the results of this analysis are shown in Figure 3C.

[0121] According to the proton NMR results, in cpAVE-F, protons located at the pendant were identified as peaks at 1.85 ppm, 2.81 ppm, 2.79 ppm, and 2.73 ppm (Figure 3C(h)).

[0122] Examples 1-8: Production of TPU specimens with added cyclic oligomers, etc. As a compound material with added cyclic oligomers, TPU specimens were manufactured by solvent casting. A schematic diagram of the manufacturing process of TPU specimens with added cyclic oligomers, etc., by solvent casting is shown in Figure 4.

[0123] For the thermoplastic polyurethane (TPU), we used K-480A product from Kolon Industries, and for the cyclic oligomers, we used the oligomers produced in Examples 1-2 to 1-6 and Comparative Example 1-1 (cpEVE-5k, cpEVE-10k, cpEVE-20k, cpBVE-8k, cpDDVE-16k, cpAVE-5k, cpAVE-F, and IpEVE-5k).

[0124] To prepare the TPU specimens, 1 mg of oligomer, 99 mg of TPU, and 10 mL of dichloromethane were dissolved in a 30 mL vial, and after sonication, the vial was stored for 5 hours to remove air bubbles. Subsequently, 60 μL of the prepared solution was placed in a 1 × 1 cm² area. 2 After casting the solution onto a silicone wafer, the TPU specimen was fabricated by removing it after 24 hours of evaporation at room temperature.

[0125] Examples 1-9: Production of PVP specimens with added cyclic oligomers, etc. As a compound material to which cyclic oligomers and other elements were added, the PVP specimens were manufactured using the same solvent casting method as the TPU specimens.

[0126] For polyvinylpyrrolidone, we used the 40,000 Mw product from Sigma-Aldrich, and for cyclic oligomers, we used the oligomers (cpEVE-5k and lpEVE-5k) produced in Example 1-2 and Comparative Example 1-1.

[0127] Examples 1-10: Analysis of TPU specimens with added cyclic oligomers, etc. (1) Comparative analysis of surface separation properties between cyclic oligomers and linearized cyclic oligomers To investigate the surface separation characteristics of TPU specimens to which cyclic oligomers (cpEVE-5k and lpEVE-5k) prepared in Examples 1-8 were added, analysis was performed using X-ray photoelectron spectroscopy (XPS) and angle-resolved X-ray photoelectron spectroscopy (AR-XPS). The results of this analysis were replaced with C=O bond ratios by peak deconvolution, and the replaced C=O bond ratios were converted to the weight ratio of oligomers located on the surface of the TPU specimens. The results of this analysis are shown in Figure 5. At this time, the oligomers added to the TPU specimens were set as the specimen names.

[0128] TPU exhibits a high concentration of C=O bonds, while cyclic oligomers have very few C=O bonds. Based on these characteristics, XPS analysis revealed that cpEVE-5k had a higher weight ratio than lpEVE-5k in the 7nm range from the surface of the TPU specimen (Figure 5(a)).

[0129] Furthermore, AR-XPS analysis revealed that cpEVE-5k was located approximately 1.5 times more frequently on the surface of the TPU specimen compared to lpEVE-5k (Figures 5(b) and (c)).

[0130] (2) Comparative analysis of surface separation characteristics of cyclic oligomers based on molecular weight / pendant (alkyl group) length To investigate the surface separation characteristics of TPU specimens to which the cyclic oligomers (cpEVE-5k, cpEVE-10k, and cpEVE-20k) prepared in Examples 1-8 were added, i.e., ethyl vinyl ether-based cyclic oligomers with different molecular weights added, X-ray photoelectron spectroscopy (XPS) was used for analysis. The results of this analysis are shown in Figure 6.

[0131] XPS analysis revealed that for cyclic oligomers with a number-average molecular weight of approximately 20,000 or less, the weight ratio of cyclic oligomers located on the surface of the TPU specimen increased as the molecular weight increased, while conversely, the molar ratio of cyclic oligomers located on the surface of the TPU specimen decreased (Figure 6). On the other hand, as the length of the pendant (alkyl group) of the cyclic oligomer increased, the weight ratio of cyclic oligomers located on the surface of the TPU specimen temporarily increased before decreasing again. This confirmed that there is an optimal pendant (alkyl group) length that optimizes the surface separation characteristics.

[0132] (3) Comparative analysis of surface morphology and hydrophilicity based on surface separation characteristics of cyclic oligomers To verify the surface morphology and hydrophilicity of TPU specimens to which the functionalized cyclic oligomers (cpEVE-5k, cpEVE-10k, cpEVE-20k, cpBVE-8k, cpDDVE-16k, and lpEVE-5k) produced in Examples 1-8 were added, analysis was performed using an atomic force microscope (AFM) and water contact angle. The results of the analysis are shown in Figure 7.

[0133] According to the AFM analysis results, no surface separation development was observed in either the cpEVE-5k-TPU or lpEVE-5k-TPU specimens, and the surface roughness tended to increase in the order of TPU, cpEVE-5k-TPU, and lpEVE-5k-TPU specimens. On the other hand, the water contact angle tended to decrease, indicating that surface roughness affected hydrophilicity according to the Wenzel model (Figure 7(a)).

[0134] Furthermore, it was confirmed that phase separation phenomena were observed in the cpEVE-5k-TPU, cpEVE-10k-TPU, and cpEVE-20k-TPU specimens, in that order, as the molecular weight of the cyclic oligomer increased. Surface roughness was highest in the cpEVE-5k-TPU specimen, and then decreased as the molecular weight increased. In contrast, the water contact angle increased as the molecular weight of the cyclic oligomer increased, but similarly, according to the Wenzel model, it was found that the surface roughness of the TPU specimen affected the hydrophilicity (Figure 7(b)).

[0135] Furthermore, as the length of the cyclic oligomer pendant (alkyl group) increased, a protruding structure was observed on the surface of the TPU specimen. Additionally, as the length of the cyclic oligomer pendant (alkyl group) increased, the surface roughness of the TPU specimen decreased before increasing. In contrast, despite the hydrophobic properties of the alkyl group, the water contact angle decreased as the length of the cyclic oligomer pendant (alkyl group) increased, followed by an increase in the hydrophilicity of the TPU specimen surface. This is thought to be due to the low surface separability of cpDDVE-16k, as seen in Figure 6, which affected the surface morphology (Figure 7(c)).

[0136] (4) Functionality verification using functionalized cyclic oligomers To verify the functionality of TPU specimens containing the functionalized cyclic oligomers (cpAVE-5k and cpAVE-F) prepared in Examples 1-8, analysis was performed using X-ray photoelectron spectroscopy (XPS), water contact angle, and protein adsorption. The results of these analyses are shown in Figure 8.

[0137] According to the XPS analysis results, unlike the TPU specimen or the TPU specimen to which cpAVE-5k was added, a large amount of fluorine was observed in the TPU specimen to which cpAVE-F was added due to the fluoroalkyl functional group present in cpAVE-F (Figure 8(a)).

[0138] Furthermore, analysis of the water contact revealed a significant increase in hydrophobicity in the TPU specimens to which cpAVE-F was added. This is because the fluoroalkyl functional groups present in cpAVE-F are hydrophobic, and it is thought that the surface properties changed significantly and surface separation progressed with only a 1 wt% addition (Figure 8(b)).

[0139] Finally, according to the results of the protein adsorption analysis, the fluoroalkyl functional group present in cpAVE-F has the effect of preventing protein adsorption, and therefore, protein adsorption was significantly reduced in the TPU specimen to which cpAVE-F was added, confirming that it has an antifouling effect (Figures 8(c) and (d)).

[0140] Examples 1-11: Analysis of PVP specimens with added cyclic oligomers, etc. To investigate the surface separation characteristics of PVP specimens to which cyclic oligomers (cpEVE-5k and lpEVE-5k) prepared in Examples 1-9 were added, analysis was performed using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ionization (TOF-SIMS). The results of the analysis are shown in Figure 9.

[0141] Firstly, polyvinylpyrrolidone has a high concentration of C=O bonds, while the cyclic oligomer has very few. Secondly, polyvinylpyrrolidone has nitrogen elements, while the cyclic oligomer does not. Based on these characteristics, XPS analysis revealed a low ratio of C=O bonds to total carbon bonds on the PVP specimen surface, confirming that cpEVE-5k migrated relatively more to the surface (Figure 9(a)).

[0142] Furthermore, after confirming the mass ratio of nitrogen elements on the PVP specimen surface and converting it to mole fractions, it was similarly confirmed that cpEVE-5k had migrated to the surface in relatively large quantities (Figure 9(b)).

[0143] TOF-SIMS analysis results confirmed that, similar to XPS analysis results, cpEVE-5k was relatively abundant on the outermost surface of the PVP specimen (Figure 9(c)).

[0144] Therefore, cyclic oligomers are considered to be more versatile as additives to a wider range of materials compared to linearized cyclic oligomers.

[0145] Example 2-1: Synthesis of vinyl ether monomers derived from ATRP initiator (BrVE) The vinyl ether monomers derived from the ATRP initiator were produced by a Williamson ether synthesis reaction from an alcohol containing vinyl ether and an ATRP initiator containing a bromide functional group. The reaction is an SN2 reaction in which the alcohol acts as a nucleophile, and a schematic diagram of the synthesis of the vinyl ether monomers (BrVE) derived from the ATRP initiator is shown in Figure 11(a).

[0146] Specifically, 50 mL of dichloromethane was added to a 250 mL round-bottom flask that had been heated and dried, and then the temperature was lowered to 0°C. Then, 6.38 g of 1,4-butanediol vinyl ether and 11.5 g of triethylamine were uniformly dissolved in the solvent while stirring, and 11.5 g of α-bromoisobutyryl was slowly added to the solution. The temperature of the prepared solution was raised from 0°C to room temperature and stirred for 3 hours. Afterward, the reaction was stopped by washing with 50 mL of distilled water, and then the solution was washed three more times with 50 mL of saturated aqueous ammonium chloride solution. Anhydrous magnesium sulfate was then added to remove water from the organic solution, and the organic solution was concentrated under low pressure and purified using silica gel column chromatography. The eluent used for the column was a mixture of n-hexane and ethyl acetate in a ratio of 39:1. After final purification, a clear organic compound, 4-vinyloxybutyl 2-bromomethylpropanoate, was obtained.

[0147] Example 2-2: Synthesis of cyclic oligomers using vinyl ether monomers derived from ATRP initiators (cpBrVE) The ATRP cyclic oligomer (cpBrVE) was synthesized by ring-expanding cationic polymerization of a vinyl ether monomer (BrVE) derived from the ATRP initiator prepared in Example 2-1 to a cyclic hemiacetal ester. A schematic diagram of the synthesis of the ATRP cyclic oligomer (cpBrVE) is shown in Figure 11(b).

[0148] Specifically, toluene (manufactured by Sigma-Aldrich) was prepared by removing water using potassium hydroxide pellets (manufactured by Sigma-Aldrich), and then 1.54 mg of 2,6-di-tert-butyl-4-methylpyridine (manufactured by Sigma-Aldrich), 109.6 mg of tin(IV) bromide (manufactured by Sigma-Aldrich), 36 mg of cyclic hemiacetal ester, and methanol (manufactured by Sigma-Aldrich) were prepared.

[0149] After removing water from a three-necked round-bottom flask, 50 mL of toluene was added, followed by the addition of 5.3 g of vinyl ether (BrVE) derived from the ATRP initiator at -40°C. Subsequently, 2,6-di-tert-butyl-4-methylpyridine, tin(IV) bromide, and a cyclic hemiacetal substance were added sequentially, and the mixture was stirred in the presence of nitrogen gas for 5 hours. Immediately after the reaction time was completed, the product was mixed with methanol at 4°C to terminate the reaction. The product was then washed in a funnel containing deionized water, and finally, the solvent of the product was removed using a rotary evaporator.

[0150] Comparative Example 2-1: Linearization of cyclic oligomers using vinyl ether monomers derived from ATRP initiators (lpBrVE) The ATRP cyclic oligomer (cpBrVE) prepared in Example 2-2 was linearized by cleaving the hemiacetal ester bond through acid hydrolysis. A schematic diagram of the linearization of the ATRP cyclic oligomer (lpBrVE) is shown in Figure 11(c).

[0151] Specifically, a 1 wt% ethyl vinyl ether solution in 20 mL of THF was added to a vial, followed by the addition of 1 mL of H2O / TFA (1 / 2 v / v) solution, and the mixture was stirred at room temperature for 1 hour. The solution was then placed on 2 g of Amberlyst® A21 free base, and after removing any residual acid, it was washed and filtered, and finally the solvent of the product was removed using a vacuum oven.

[0152] Examples 2-3: Analysis of vinyl ether monomers (BrVE) and ATRP cyclic oligomers (cpBrVE) derived from ATRP initiators (NMR, GPC, DSC) (1) Analysis of vinyl ether monomers (BrVE) derived from ATRP initiators The vinyl ether monomer (BrVE) derived from the ATRP initiator prepared in Example 2-1 exhibits proton nuclear magnetic resonance ( 1 The synthesis was confirmed by analysis using 1H NMR, and the results of that analysis are shown in Figure 12(a).

[0153] (2) Comparative analysis of ATRP cyclic oligomer (cpBrVE) and linearized ATRP cyclic oligomer (lpBrVE) The ATRP cyclic oligomer (cpBrVE) produced in Example 2-2 and the linearized ATRP cyclic oligomer (lpBrVE) produced in Comparative Example 1 were analyzed by gel permeation chromatography (GPC), proton NMR, and differential scanning calorimetry (DSC) to confirm their synthesis. The results are shown in Figures 12(b) to (f).

[0154] According to the GPC analysis results, cpBrVE had a number-average molecular weight (Mn) of approximately 9,400, while lpBrVE had a number-average molecular weight (Mn) of approximately 10,400 (Figure 12(b)).

[0155] Furthermore, proton NMR analysis revealed that cpBrVE has the f peak at 4.20 ppm, the a and c peaks at 3.45 ppm, and the b, d, e, and g peaks at 1.78 ppm. When comparing cpBrVE and lpBrVE, it was observed that lpBrVE produced a small peak around 9.5 ppm after linearization, which is due to the generation of an aldehyde group at the end of the main chain during linearization (Figures 12(c) and (d)).

[0156] Furthermore, DSC analysis revealed that cpBrVE and lpBrVE have glass transition temperatures of approximately -19.4°C and -20.1°C, respectively. The slightly higher glass transition temperature of cpBrVE is thought to be due to its limited fluidity resulting from the restricted morphology of the cyclic oligomer, its small size, and the lack of chain ends (Figures 12(e) and (f)).

[0157] Examples 2-4: Preparation of TPU specimens with added ATRP cyclic oligomer (cpBrVE), etc. As a compound material with added cyclic oligomers, TPU specimens were manufactured by solvent casting. A schematic diagram of the manufacturing process of TPU specimens with added ATRP cyclic oligomers, etc., by solvent casting is shown in Figure 13.

[0158] For the thermoplastic polyurethane (TPU), we used Elastollan® S85A10 product manufactured by BASF, and for the cyclic oligomer, we used the ATRP cyclic oligomer (cpBrVE) manufactured in Example 2-2. On the other hand, for the linearized cyclic oligomer, we used the ATRP cyclic oligomer linearized (lpBrVE) manufactured in Comparative Example 1.

[0159] Specifically, 6 mg of cpBrVE, 594 mg of TPU, and 10 mL of tetrahydrofuran were added to a 30 mL vial, dissolved at 50°C, and then sonicated and stored for 5 hours to remove air bubbles. Subsequently, the TPU solution was poured into a glass petri dish, cast, evaporated at room temperature for 24 hours, and then removed to prepare TPU specimens with added cpBrVE.

[0160] Examples 2-5: Preparation of PS specimens with added ATRP cyclic oligomer (cpBrVE), etc. As a compound material to which cyclic oligomers were added, PS specimens were manufactured by the solvent casting method. A schematic diagram of the manufacturing process of PS specimens to which ATRP cyclic oligomers and other materials were added by the solvent casting method is shown in Figure 13.

[0161] For the polystyrene (PS), we used a product from Sigma-Aldrich with an average molecular weight of 35,000, and for the cyclic oligomer, we used the ATRP cyclic oligomer (cpBrVE) produced in Example 2-2. On the other hand, for the linearized cyclic oligomer, we used the ATRP cyclic oligomer linearized (lpBrVE) produced in Comparative Example 1.

[0162] Specifically, 6 mg of cpBrVE, 94 mg of PS, and 10 mL of tetrahydrofuran were added to a 30 mL vial, dissolved at 50°C, and then sonicated and stored for 5 hours to remove air bubbles. Subsequently, the PS solution was poured onto a silicone wafer, and after solution casting, it was evaporated at room temperature for 24 hours before being extracted to produce PS specimens with added cpBrVE.

[0163] Examples 2-6: Preparation of PMMA specimens with added ATRP cyclic oligomer (cpBrVE), etc. PMMA specimens containing cyclic oligomers were manufactured using the solvent casting method. A schematic diagram of the manufacturing process of PMMA specimens containing ATRP cyclic oligomers, etc., by the solvent casting method is shown in Figure 13.

[0164] For the polymethyl methacrylate (PMMA), we used a product manufactured by Sigma-Aldrich with an average molecular weight of 120,000, and for the cyclic oligomer, we used the ATRP cyclic oligomer (cpBrVE) prepared in Example 2-2. On the other hand, for the linearized cyclic oligomer, we used the ATRP cyclic oligomer linearized (lpBrVE) prepared in Comparative Example 1.

[0165] Specifically, 6 mg of cpBrVE, 594 mg of PMMA, and 10 mL of tetrahydrofuran were added to a 30 mL vial, dissolved at 50°C, and then sonicated and stored for 5 hours to remove air bubbles. Subsequently, the PMMA solution was poured onto a silicone wafer, and after solution casting, it was evaporated at room temperature for 24 hours before being extracted to produce PMMA specimens with added cpBrVE.

[0166] Example 2-7: Preparation of PVDF specimens with ATRP cyclic oligomer (cpBrVE) added. As a compound material with added cyclic oligomers, PVDF specimens were prepared by solvent casting. A schematic diagram of the preparation of PVDF specimens with added ATRP cyclic oligomers by solvent casting is shown in Figure 13.

[0167] For the polyvinylidene fluoride (PVDF), we used a product from Sigma-Aldrich with an average molecular weight of 180,000, and for the cyclic oligomer, we used the ATRP cyclic oligomer (cpBrVE) prepared in Example 2-2. On the other hand, for the linearized cyclic oligomer, we used the ATRP cyclic oligomer linearized (lpBrVE) prepared in Comparative Example 1.

[0168] Specifically, 6 mg of cpBrVE, 594 mg of PVDF, and 10 mL of dimethylformamide were added to a 30 mL vial, dissolved at 50°C, and then sonicated and stored for 5 hours to remove air bubbles. Subsequently, the PVDF solution was poured onto a silicone wafer, and after solution casting, it was evaporated at room temperature for 24 hours before being extracted to produce PVDF specimens with added cpBrVE.

[0169] Example 2-8: Analysis of surface separation properties of TPU specimens to which ATRP cyclic oligomer (cpBrVE) and other substances have been added. The surface separation characteristics of TPU specimens to which ATRP cyclic oligomers (cpBrVE) and other materials prepared in Examples 2-4 were added were analyzed by X-ray photoelectron spectroscopy (XPS).

[0170] The Br peaks analyzed by XPS are shown in Figure 14(a). At this time, the specimen names were set as cpBrVE and lpBrVE, respectively, based on the oligomer added to the TPU specimen. TPU has the characteristic that Br ions are absent, while they are present only in the oligomer. Based on these characteristics, XPS analysis results confirmed that, using a 7nm range from the surface of the TPU specimen as a reference, the proportion of surface-immobilized cpBrVE was higher than that of surface-immobilized lpBrVE (Figure 14(a)).

[0171] Furthermore, the graph of C1s analyzed by XPS is shown in Figure 14(b). Similarly, based on the oligomers added to the TPU specimens, the specimen names were set as cpBrVE and lpBrVE, respectively. The ratio of C=O bonds analyzed by XPS could be converted to the weight ratio of the oligomers through theoretical calculations. As a result, it was confirmed that the weight ratio of cpBrVE fixed to the surface was approximately 48 wt%, and the weight ratio of lpBrVE fixed to the surface was approximately 27 wt%, based on a 7 nm range from the surface of the TPU specimen (Figure 14(b)).

[0172] Example 2-9: Analysis of surface separation properties of PS specimens to which ATRP initiator-derived cyclic oligomers (cpBrVE) and other substances have been added. The surface separation characteristics of PS specimens to which ATRP initiator-derived cyclic oligomers (cpBrVE) and other materials prepared in Examples 2-5 were added were analyzed by X-ray photoelectron spectroscopy (XPS).

[0173] The elemental ratios analyzed by XPS are shown in Figure 15. At this time, Br ions were absent in PS, while they were present only in the oligomer. Based on these characteristics, the XPS analysis results showed no significant difference in the Br ratio compared to the theoretical value, but the high O ratio confirmed that surface separation occurred, indicating that the surface separation properties also apply to PS specimens (Figure 15).

[0174] Example 2-10: Analysis of surface separation properties of PMMA specimens to which ATRP initiator-derived cyclic oligomers (cpBrVE) and other substances have been added. The surface separation characteristics of PMMA specimens to which ATRP cyclic oligomers (cpBrVE) and other materials prepared in Example 2-6 were added were analyzed by X-ray photoelectron spectroscopy (XPS).

[0175] The elemental ratios analyzed by XPS are shown in Figure 16. At this time, PMMA exhibits the characteristic of not containing Br ions, while the ions are present only in the oligomer. Based on these characteristics, the XPS analysis results show that the Br ratio is higher than the theoretical value, confirming that surface separation occurs. This indicates that the surface separation properties also apply to PMMA specimens (Figure 16).

[0176] Example 2-11: Analysis of surface separation properties of PVDF specimens to which ATRP initiator-derived cyclic oligomers (cpBrVE) and other substances have been added. The surface separation characteristics of PVDF specimens to which ATRP cyclic oligomers (cpBrVE) and other materials prepared in Example 2-7 were added were analyzed by X-ray photoelectron spectroscopy (XPS).

[0177] The elemental ratios analyzed by XPS are shown in Figure 17. At this time, PVDF does not contain Br ions, while the oligomers possess this characteristic. Based on these characteristics, the XPS analysis results show that although the Br ratio is slightly lower than the theoretical value, the O ratio is significantly higher and the F ratio is significantly lower, confirming that surface separation occurs. This indicates that the surface separation properties also apply to PVDF specimens (Figure 17).

[0178] Example 2-12: Biocompatibility verification using TPU specimens with added ATRP cyclic oligomer (cpBrVE), etc. To verify the biocompatibility of TPU specimens to which ATRP cyclic oligomers (cpBrVE) and other materials prepared in Example 2-7 were added, a cytotoxicity test was performed according to the ISO 10993-5:2009 method, and the results are shown in Figure 18.

[0179] Specifically, the cells used to assess cytotoxicity were NIH / 3T3. In the cytotoxicity test, 6 cm³ was observed per 1 mL of culture. 2 The TPU specimens were eluted for 24 hours, and then the eluted culture was treated with cells for 24 hours. Cell survival rates were confirmed by CCK-8 analysis. As a result, it was confirmed that there was no significant difference in cell survival rates between the TPU specimen (TPU) and the TPU specimen with added oligomer (cpBrVE). It was also revealed that the 100% extracted culture medium of the TPU specimen with added oligomer (cpBrVE) showed a cell survival rate of over 79%. This was judged to be non-cytotoxic according to the cytotoxicity assessment criteria of ISO 10993-5.

[0180] Example 2-13: Surface-initiated atom transfer radical polymerization (SI-ATRP) using zwitterionic monomers and formation of antifouling polymer brushes on TPU specimens with added ATRP cyclic oligomers (cpBrVE), etc. The formation of antifouling polymer brushes (surface-graft) was carried out by surface-initiated atom transfer radical polymerization (SI-ATRP).

[0181] Specifically, the catalyst aqueous solution for surface-initiated atom transfer radical polymerization (SI-ATRP) was prepared by dissolving 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonate (SBMA) at a concentration of 20 mg / mL, L-ascorbic acid at a concentration of 2 mg / mL, 2,2'-bipyridyl at a concentration of 0.152 mg / mL, and copper(II) bromide at a concentration of 0.08 mg / mL in distilled water from which oxygen had been completely removed with nitrogen gas. Subsequently, a TPU specimen containing the ATRP cyclic oligomer (cpBrVE) prepared in Example 2-4 was added to a 70 mL vial, and the 70 mL vial was filled with the prepared catalyst aqueous solution. The vial was then sealed with a lid to minimize oxygen exchange. Surface-initiated atom transfer radical polymerization (SI-ATRP) was carried out for 3 hours, 6 hours, and 15 hours, respectively, under reaction temperature conditions of 50°C. After the formation of the antifouling polymer brush (surface graft) was completed, the specimens were washed five times with ethanol and then dried overnight.

[0182] To establish the optimal time for polymer brush formation, the water contact angle was measured, and the results are shown in Figure 19. As the reaction time increased, the water contact angle gradually decreased, and 15 hours, which showed a value of less than 10°, was fixed as the optimal time for polymer brush formation in future experiments (Figure 19).

[0183] Example 2-14: Confirmation of polymer brush formation in TPU specimens with antifouling polymer brushes formed on them. In the TPU specimens on which the antifouling polymer brushes were formed, manufactured in Example 2-13, analysis was performed using Fourier transform infrared spectrometer (FT-IR), X-ray photoelectron spectroscopy (XPS), and water contact angle to verify the formation of polymer brushes. The analysis results are shown in Figures 20(a) to (c). At this time, based on the oligomer added to the TPU specimen, the specimens without polymer brush formation were named cpBrVE and lpBrVE, and the specimens with polymer brush formation were named cpBrVE-g-pSB and lpBrVE-g-pSB, respectively.

[0184] TPU does not have S=O bonds, but polymer brushes manufactured using SBMA do. As a result, Fourier transform infrared spectroscopy (FT-IR) results show that the polymer brush-formed specimen has a higher S=O peak (1037 cm⁻¹) compared to the specimen without a polymer brush. -1 This was further confirmed (Figure 20(a)).

[0185] Furthermore, while TPU does not contain sulfur (S), polymer brushes manufactured using SBMA do contain sulfur (S), and are chemically bonded to it. As a result, X-ray photoelectron spectroscopy (XPS) confirmed that no S2p peak was observed in specimens without polymer brushes, while an S2p peak was generated in specimens with polymer brushes. In addition, it was confirmed that cpBrVE-g-pSB showed a higher S2p peak compared to lpBrVE-g-pSB, which confirmed that the polymer brush density was higher in cpBrVE-g-pSB at a depth of 7 nm from the surface (Figure 20(b)).

[0186] Compared to TPU, polymer brushes manufactured using SBMA have very high hydrophilicity due to the presence of zwitterions. As a result, analysis using water contact angle revealed that the water contact angle was measured to be significantly lower in the polymer brush-less specimen compared to the specimen without a polymer brush (Figure 20(c)).

[0187] Example 2-15: Analysis of the surface morphology of TPU specimens on which antifouling polymer brushes have been formed. The surface morphology of the TPU specimens on which the antifouling polymer brushes were formed, manufactured in Example 2-13, was analyzed using an atomic force microscope (AFM) and a field emission scanning electron microscope. The analysis results are shown in Figures 21 and 22, respectively. At this time, based on the oligomer added to the TPU specimen, the specimens without polymer brush formation were named cpBrVE and lpBrVE, and the specimens with polymer brush formation were named cpBrVE-g-pSB and lpBrVE-g-pSB, respectively.

[0188] According to the AFM analysis results, the surface roughness of the polymer brush-formed specimens (cpBrVE-g-pSB and lpBrVE-g-pSB) tended to increase compared to the specimens without polymer brushes (cpBrVE and lpBrVE), which is thought to be due to the morphology resulting from the formation of polymer brushes. Furthermore, the surface roughness of cpBrVE-g-pSB tended to be lower than that of lpBrVE-g-pSB, which is because the voids disappeared due to the increased brush density on the surface, and the difference in height decreased (Figure 21).

[0189] The results of the SEM analysis were similar to those of the AFM analysis, confirming that the polymer brush density increased in cpBrVE-g-pSB compared to lpBrVE-g-pSB (Figure 22).

[0190] Example 2-16: Verification of antifouling properties in TPU specimens with antifouling polymer brushes formed on them. To verify the antifouling properties of the TPU specimens on which the antifouling polymer brushes produced in Example 2-13 were formed, adhesion tests for albumin, platelets, and bacteria were conducted, and the results are shown in Figures 23 to 25, respectively. At this time, based on the oligomer added to the TPU specimen, the specimens without polymer brush formation were named cpBrVE and lpBrVE, and the specimens with polymer brush formation were named cpBrVE-g-pSB and lpBrVE-g-pSB, respectively.

[0191] To perform the albumin adhesion test, 1 cm 2 After contacting the specimens with a 1 mg / mL albumin PBS solution for 1 hour, the number of attached albumins was analyzed by BCA assay. The analysis confirmed a decrease in albumin adhesion in the polymer brush-forming specimens (cpBrVE-g-pSB and lpBrVE-g-pSB). In particular, a greater effect was observed in cpBrVE-g-pSB compared to lpBrVE-g-pSB, and in the case of the cpBrVE-g-pSB specimen, the albumin adhesion was 1 μg / cm³. 2 A certain level of albumin was attached (Figure 23).

[0192] Also, 1cm 2 I spent an hour on the sample and 10 6 After attaching individual platelets, the number and activity level of the platelets were examined. To analyze the number of platelets, staining was performed using CD41a with FITC attached, and the activity level was analyzed by SEM imaging. The results of the analysis confirmed that the number and activity level of platelets were lower with cpBrVE than with lpBrVE. Furthermore, a decrease in the number and activity level of platelets was confirmed in polymer brush-forming specimens (cpBrVE-g-pSB and lpBrVE-g-pSB), but this effect was confirmed to be greater with cpBrVE-g-pSB than with lpBrVE-g-pSB (Figure 24).

[0193] To perform a bacterial adhesion test, 1 cm 2 The sample was prepared over 4 hours, taking 10 minutes. 4After contact with 50 μL of a bacterial solution at a TPU / mL concentration, the attached bacteria were transferred to a solid culture medium and the number of bacteria was analyzed. The analysis confirmed a reduction in bacterial adhesion on polymer brush-forming specimens (cpBrVE-g-pSB and lpBrVE-g-pSB). In particular, when E. coli bacteria were attached, a greater effect was observed with cpBrVE-g-pSB compared to lpBrVE-g-pSB, with cpBrVE-g-pSB specimens showing a reduction of 2 × 10⁻⁶ bacteria. 3 CFU / cm 2 Bacteria below a certain level were attached. When S. aureus bacteria were attached, the cpBrVE-g-pSB sample did not show a significant difference compared to the lpBrVE-g-pSB sample, but a significant difference was observed compared to the TPU sample. In the case of the cpBrVE-g-pSB sample, 3 × 10⁶ 4 CFU / cm 2 Bacteria were found at sub-zero levels (Figure 25).

[0194] Example 2-17: Analysis of polymer brush leaching amount in TPU specimens with antifouling polymer brushes formed on them. To compare and analyze the amount of polymer brush leaching in the TPU specimens on which the antifouling polymer brushes produced in Example 2-13 were formed, the water contact angle over 28 days was analyzed, and the results are shown in Figure 26. At this time, the polymer brush-forming specimens were named cpBrVE-g-pSB and lpBrVE-g-pSB, respectively, based on the oligomer added to the TPU specimens.

[0195] As a result, the initial water contact angles of cpBrVE-g-pSB and lpBrVE-g-pSB were at the 10° level, but it was confirmed that the water contact angle increased over time as the polymer brushes leached out. In the case of cpBrVE-g-pSB, it was confirmed that the tendency for the water contact angle to increase was less compared to the lpBrVE-g-pSB specimen due to the strengthening of the polymer entanglement phenomenon and the decrease in the contact area (Figure 26).

[0196] Example 2-18: Surface-initiated atom transfer radical polymerization (SI-ATRP) and formation of PEG polymer brushes using PEGMA monomers on TPU specimens to which ATRP cyclic oligomers (cpBrVE) and other substances have been added. The formation of PEG polymer brushes (surface grafts) was carried out by surface-initiated atom transfer radical polymerization (SI-ATRP).

[0197] Specifically, the catalyst aqueous solution for surface-initiated atom transfer radical polymerization (SI-ATRP) was prepared by dissolving poly(ethylene glycol) methacrylate (PEGMA) at a concentration of 31 μL / mL, L-ascorbic acid at a concentration of 2 mg / mL, 2,2'-bipyridyl at a concentration of 0.152 mg / mL, and copper(II) bromide at a concentration of 0.08 mg / mL in distilled water from which oxygen had been completely removed with nitrogen gas. Subsequently, a TPU specimen to which the ATRP cyclic oligomer (cpBrVE) prepared in Example 2-4 had been added was placed in a 70 mL vial, and the 70 mL vial was filled with the prepared catalyst aqueous solution, sealed with the lid, and oxygen exchange was minimized. Surface-initiated atom transfer radical polymerization (SI-ATRP) was carried out under reaction temperature conditions of 50°C for 15 hours. After the formation of the PEG polymer brush (surface graft) was complete, the specimen was washed five times with ethanol and dried overnight.

[0198] To confirm the formation of PEG polymer brushes, measurements were taken using a Fourier transform infrared spectrometer and water contact angle, and the results are shown in Figure 27. According to these measurements, the water contact angle of the PEG polymer brushes was approximately 10°, confirming their hydrophilicity.

[0199] Example 2-19: Surface-initiated atom transfer radical polymerization (SI-ATRP) and PMMA brush formation using MMA monomers on TPU specimens with added ATRP cyclic oligomers (cpBrVE), etc. PMMA brushes (surface grafts) were formed by surface-initiated atom transfer radical polymerization (SI-ATRP).

[0200] Specifically, the catalyst aqueous solution for surface-initiated atom transfer radical polymerization (SI-ATRP) was prepared by dissolving methyl methacrylate (MMA) at a concentration of 7.6 μL / mL, L-ascorbic acid at a concentration of 2 mg / mL, 2,2'-bipyridyl at a concentration of 0.152 mg / mL, and copper(II) bromide at a concentration of 0.08 mg / mL in distilled water from which oxygen had been completely removed with nitrogen gas. Subsequently, a TPU specimen to which the ATRP cyclic oligomer (cpBrVE) prepared in Example 2-4 had been added was placed in a 70 mL vial, and the vial was filled to capacity with the prepared catalyst aqueous solution. The vial was then sealed with the lid to minimize oxygen exchange. Surface-initiated atom transfer radical polymerization (SI-ATRP) was carried out under reaction temperature conditions of 50°C for 15 hours. After the PMMA brush formation (surface graft) was complete, the specimen was washed five times with ethanol and dried overnight.

[0201] To confirm PMMA brush formation, the water contact angle was measured using a Fourier transform infrared spectrometer, and the results are shown in Figure 27. This confirmed that the water contact angle of the PMMA polymer brush was approximately 120°, indicating hydrophobicity.

[0202] The above description of the present invention is illustrative, and a person with ordinary skill in the art will understand that it can be easily modified into other specific forms without altering the technical idea or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R 1 However, these are substituted or unsubstituted C1-C15 alkyl groups, C2-C15 alkenyl groups, C2-C15 alkynyl groups, C3-C15 cycloalkyl groups, C6-C15 aryl groups, or C6-C15 heteroaryl groups. R 2 However, it is a substituted or unsubstituted C1-C15 alkyl group, C2-C15 alkenyl group, C2-C15 alkynyl group, C3-C15 cycloalkyl group, C6-C15 aryl group, or C6-C15 heteroaryl group, or a form in which a functional group of less than C15 is further introduced at the terminal by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from an initiator. A cyclic oligomer represented by ) where the sum of 2n and m is an integer between 10 and 600.

2. The aforementioned R 2 The cyclic oligomer according to claim 1, characterized in that it is a C2-C15 alkenyl group or a C2-C15 alkynyl group, or a form in which a functional group of less than C15 is further introduced at the terminal by a chemical reaction.

3. The cyclic oligomer according to claim 2, characterized in that the chemical reaction is a click reaction selected from the group consisting of thiol-ene, thiol-yne, azide-ene, and azide-yne.

4. The aforementioned R 2 The cyclic oligomer according to claim 1, characterized in that it has a C2-C15 functional group form containing a functional group derived from an atom transfer radical polymerization (ATRP) initiator.

5. The cyclic oligomer according to claim 1, characterized in that the cyclic oligomer has surface segregating properties.

6. The cyclic oligomer has a number average molecular weight (M n The cyclic oligomer according to claim 1, characterized in that the number of ) is 5,000 to 20,000.

7. The following formula (2) 【Chemistry 2】 (In the formula, R 1 However, these are substituted or unsubstituted C1-C15 alkyl groups, C2-C15 alkenyl groups, C2-C15 alkynyl groups, C3-C15 cycloalkyl groups, C6-C15 aryl groups, or C6-C15 heteroaryl groups. A cyclic hemiacetal ester initiator for producing cyclic oligomers according to claim 1, comprising a compound represented by (where m is an integer from 2 to 600).

8. The following formula (3) 【Transformation 3】 (In the formula, R 2 The vinyl ether monomer for producing cyclic oligomers according to claim 1, comprising a compound represented by: a substituted or unsubstituted C1-C15 alkyl group, a C2-C15 alkenyl group, a C2-C15 alkynyl group, a C3-C15 cycloalkyl group, a C6-C15 aryl group, or a C6-C15 heteroaryl group, or a form in which a functional group of less than C15 is introduced at the terminal by a chemical reaction; or a C2-C15 functional group form containing a functional group derived from an initiator.

9. A method for producing a cyclic oligomer according to claim 1, using ring-expansion cationic polymerization, with respect to a cyclic hemiacetal ester initiator and a vinyl ether monomer.

10. The method for producing a cyclic oligomer according to claim 9, characterized in that the ring-expanding cationic polymerization method is carried out under temperature conditions of -70°C to 0°C.

11. A compound material comprising the cyclic oligomer and biocompatible material described in claim 1.

12. The biocompatible materials include polyolefins, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polybutadiene (PB), polystyrene (PS), polymethyl acrylate (PMA), polyethyl acrylate (PEA), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyhydroxyethyl methacrylate (PHEMA), polyvinylpyrrolidone (PVP), polyethers, polyethylene glycol (PEG), polytetrahydrofuran (PTHF), polyethyleneimine (PEI), polyesters, polycarbonate (PC), and polylactide (PL). A) The compound material according to claim 11, characterized by comprising one or more resins selected from the group consisting of polyethylene terephthalate (PET), polyketones, polyether ether ketone (PEEK), polyamides, polyurethane (PU), polyacrylamide (PAAm), polysilanes, polysiloxane, polydimethylsiloxane (PDMS), starch, cellulose, chitosan, hyaluronic acid, alginate, dextran, gelatin, heparin, polypeptides, and polynucleotides.

13. The compounding material according to claim 11, characterized in that the content of the cyclic oligomer in the compounding material is 0.1% by weight to 5% by weight.

14. The compounding material according to claim 11, characterized in that the compounding material is manufactured by a solvent casting method or a hot-melt extrusion method.

15. The compounding material according to claim 11; and A polymer brush grafted from the aforementioned compounding material; A composite material for surface treatment that includes [specific material].

16. The composite material for surface treatment according to claim 15, characterized in that the grafting of the polymer brush is carried out via atomic transfer radical polymerization (ATRP).

17. The composite material for surface treatment according to claim 15, characterized in that the polymer brush is based on an acrylate monomer.

18. A medical article whose surface has been modified or surface-treated using the compounding material described in claim 11.

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