Polymers and their preparation methods and applications, self-healing antibacterial photocurable coating compositions and their preparation methods and applications and products

Abstract

The present application relates to the field of organic photocuring technology, and particularly relates to a polymer, a preparation method and application thereof, a self-repairing antibacterial photocuring coating composition, a preparation method and application thereof and an article. The polymer comprises a polyurethane segment, a functional structure unit and an acrylate end-capping group; the functional structure unit comprises a structure unit A with a-S-S- group and a structure unit B shown in formula (1); R is a copolymer chain containing a structure unit C shown in formula (2), a structure unit D shown in formula (3) and a structure unit E from a mono-olefin. The polymer provided by the present application comprises reversible covalent bond disulfide bond, quaternary ammonium salt segment and polyurethane segment; the disulfide bond can partially or completely restore the mechanical properties and integrity of the polymer itself under the stimulation of external conditions such as light, heat or acid and alkali, and can realize repair.

Description

Technical Field

[0001] This invention relates to the field of organic photocuring technology, specifically to a polymer and its preparation method and application, a self-healing antibacterial photocurable coating composition and its preparation method and application, and products. Background Technology

[0002] Polyurethane is a general term for a class of polymeric compounds whose main chain contains urethane groups. It is a multi-block polymer formed by the stepwise polymerization of polyols, small-molecule chain extenders, and polyisocyanates. Polyols constitute the soft segments, while small-molecule chain extenders and polyisocyanates constitute the hard segments. The molecular structure and physicochemical properties of polyurethane can be effectively controlled by adjusting the composition and ratio of the soft and hard segments. Ordinary polyurethane coatings lack the ability to resist microbial or bacterial erosion during actual use; coatings contaminated with bacteria can damage human health and the materials themselves. Therefore, polyurethane-based antibacterial coatings have been widely used. Most commercially available polyurethane-based antibacterial coatings are of the exogenous antibacterial agent type, meaning that small-molecule antibacterial agents are incorporated into the coating through physical blending or surface coating, and the antibacterial function is achieved through the release or contact killing of bacteria. However, this type of antibacterial coating has significant limitations; the composite antibacterial agents may migrate, causing a decrease in antibacterial performance or environmental pollution. Therefore, self-antibacterial polyurethane antibacterial coatings, which use chemical modification methods such as graft copolymerization or block copolymerization to polymerize antibacterial groups into the polyurethane host resin through chemical bonds, are receiving increasing attention.

[0003] Meanwhile, UV-curable coatings are widely used in the coating field due to their advantages such as environmental friendliness, energy saving, high efficiency, and fast film formation rate. However, in actual use, coatings often develop microcracks, scratches, or even damage due to friction, collisions, etc. This weakens the dimensional stability and mechanical strength of the coating to varying degrees. Therefore, combining bactericidal and self-healing functions to develop antibacterial coatings with self-healing capabilities is crucial for ensuring antibacterial performance and extending service life. However, there are currently few reports on self-healing antibacterial coatings, and the preparation process is relatively complex with demanding self-healing conditions.

[0004] Therefore, a new type of photocurable coating needs to be invented. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of short service life, poor antibacterial effect, low self-repair rate and long curing time of existing photocurable coatings. It provides a polymer and its preparation method and application, a self-healing antibacterial photocurable coating composition and its preparation method and application and products. The self-healing antibacterial photocurable coating prepared by this polymer has the advantages of long service life, good antibacterial effect, high self-repair rate and short curing time, and can be applied to the surface coating of public goods.

[0006] To achieve the above objectives, the first aspect of the present invention provides a polymer comprising polyurethane segments, functional structural units and acrylate end-capped groups; the functional structural units comprising structural unit A having -SS- groups and structural unit B represented by formula (1);

[0007] R2 is a C1-C6 straight-chain or branched alkyl group, R1 and R3 are each independently of the general formula -O-Z1* or -NH-Z2*, and Z1 and Z2 are each independently of a C1-C6 straight-chain or branched alkylene group.

[0008] R is a copolymer chain containing structural unit C as shown in formula (2), structural unit D as shown in formula (3), and structural unit E from a monoolefin.

[0009]

[0010] R 1 Selected from C1-C6 straight-chain or branched alkylene groups, R 2 Selected from straight-chain or branched alkyl groups of -H or C1-C6, * indicates the position where it is connected to the N element in formula (1); X is selected from F, Cl, Br or I.

[0011] The structure of the polymers described above can be determined by a combination of NMR and IR analytical methods. It can also be determined by the feeding of materials during preparation.

[0012] A second aspect of the present invention provides a method for preparing a polymer, the method comprising the following steps:

[0013] (1) In the presence of a catalyst, polyisocyanate and oligomeric polyol are subjected to polycondensation reaction to generate a solution A containing polyurethane.

[0014] (2) The solution A, the intercalating copolymer, and the disulfide chain extender are copolymerized to obtain a polymer precursor; the intercalating copolymer contains structural unit D as shown in formula (3), structural unit F as shown in formula (5), and structural unit E from a monoolefin.

[0015]

[0016] (3) The polymer precursor and the capping agent are subjected to a capping reaction to obtain a polymer;

[0017] R1, R2, R3, R, R 2 The definition corresponds to the definition in claim 1.

[0018] A third aspect of the present invention provides a polymer prepared by the preparation method described herein.

[0019] A fourth aspect of the present invention provides a self-healing antibacterial photocurable coating composition containing the polymer described in the present invention.

[0020] The fifth aspect of the present invention provides the application of the polymer described herein in a self-healing antibacterial curing coating.

[0021] The sixth aspect of this invention provides a method for preparing a self-healing antibacterial photocurable coating, the method comprising the following steps:

[0022] (1) Mix the polymer, reactive diluent and photoinitiator to obtain mixture A;

[0023] (2) Curing mixture A yields a self-healing antibacterial photocurable coating.

[0024] The seventh aspect of the present invention provides a self-healing antibacterial photocurable coating film prepared by the preparation method described in the present invention.

[0025] The eighth aspect of the present invention provides an application of the self-healing antibacterial photocurable coating of the present invention in the surface coating of public goods.

[0026] The ninth aspect of the present invention provides an article having a self-healing antibacterial photocurable coating as described in the present invention on its surface.

[0027] Compared with the prior art, the advantages of the present invention are as follows:

[0028] The polymer provided by this invention contains reversible covalent disulfide bonds, quaternary ammonium salt segments, and polyurethane segments. Under external stimuli such as light, heat, or acid and alkali, the disulfide bonds can partially or completely restore the mechanical properties and integrity of the polymer itself, thus achieving repair. The quaternary ammonium salt gives the polymer good bactericidal properties, and the polymer of this invention has high quaternization stability. The polyurethane system has strong versatility, excellent and adjustable performance, and has a variety of molecular structures with different structures and properties.

[0029] The polymer preparation process provided by this invention for obtaining a photocurable coating film is simple, environmentally friendly, highly practical, and has strong antibacterial properties. Detailed Implementation

[0030] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0031] A first aspect of the present invention provides a polymer comprising a polyurethane segment, a functional structural unit and an acrylate end-capped group; the functional structural unit comprises a structural unit A having a -SS- group and a structural unit B shown in formula (1);

[0032] R2 is a C1-C6 straight-chain or branched alkyl group, R1 and R3 are each independently of the general formula -O-Z1* or -NH-Z2*, and Z1 and Z2 are each independently of a C1-C6 straight-chain or branched alkylene group.

[0033] R is a copolymer chain containing structural unit C as shown in formula (2), structural unit D as shown in formula (3), and structural unit E from a monoolefin.

[0034]

[0035] R 1 Selected from C1-C6 straight-chain or branched alkylene groups, R 2 Selected from straight-chain or branched alkyl groups of -H or C1-C6, * indicates the position where it is connected to the N element in formula (1); X is selected from F, Cl, Br or I.

[0036] The polymer provided by this invention contains reversible covalent disulfide bonds, quaternary ammonium salt segments, and polyurethane segments. Under external stimuli such as light, heat, or acid and alkali, the disulfide bonds can partially or completely restore the mechanical properties and integrity of the polymer itself, thus achieving repair. The quaternary ammonium salt gives the polymer good bactericidal properties, and the polymer of this invention has high quaternization stability. The polyurethane system has strong versatility, excellent and adjustable performance, and has a variety of molecular structures with different structures and properties.

[0037] The present invention provides that the polymer has a molecular chain structure in which a structural unit A or a structural unit B is inserted between two adjacent polyurethane segments, and the polymer has acrylate end caps at both ends of the entire molecular chain structure. As the functional structural unit, the structural unit A can provide that the polymer has a -SS- group in its molecular chain structure, and the structural unit B can provide that the polymer has a structure represented by formula (1) in its macromolecular chain.

[0038] In this invention, the N element in structural unit B shown in formula (1) can connect the copolymer chain represented by R, thereby bringing good antibacterial properties and making the polymeric antibacterial units less prone to migration and loss to the macromolecular chain structure of the modified polyurethane.

[0039] In this invention, the two ends of structural unit B shown in formula (1) can be connected to different polyurethane chain segments in the molecular chain structure of the polymer.

[0040] According to a preferred embodiment of the present invention, R2 is selected from -CH3 or -C2H5.

[0041] According to a preferred embodiment of the present invention, Z1 and Z2 are each independently -CH2CH2- or -CH2CH2CH2-.

[0042] According to a preferred embodiment of the present invention, R1 and R3 are each independently the structure shown in the general formula -O-Z1*.

[0043] According to a preferred embodiment of the present invention, R1 and R3 are both -O-CH2CH2*.

[0044] According to a preferred embodiment of the present invention, R 1 Selected from -CH2- or -CH2CH2-.

[0045] According to a preferred embodiment of the present invention, R 2 Selected from -CH3 or -C2H5.

[0046] According to a preferred embodiment of the present invention, X is selected from Cl or Br.

[0047] According to a preferred embodiment of the present invention, the monoolefin is selected from isobutylene, isopentenene, isohexene, isoheptene, and isooctene.

[0048] According to a preferred embodiment of the present invention, the structural unit A has a general formula. or The structures shown indicate that Z3, Z4, Z5, and Z6 are each independently a phenylene or a C1-C6 straight-chain or branched alkylene group. Phenylidene compounds possess... The structure shown has 1 connected to an SS bond and 2 connected to an NH bond. The two ends of the above-described general formula of structural unit A can be respectively connected to different polyurethane chain segments in the molecular chain structure of the modified polyurethane.

[0049] According to a preferred embodiment of the present invention, Z3, Z4, Z5, and Z6 are each independently -CH2CH2- or -C6H4-.

[0050] According to a preferred embodiment of the present invention, the structural unit A has

[0051] The structure shown. -NH- can be substituted at the para and meta positions of the benzene ring, preferably at the para position.

[0052] According to a preferred embodiment of the present invention, the acrylate end-capping group has the structure shown in formula (4).

[0053] R4 is selected from C1-C5 straight-chain or branched alkylene groups.

[0054] According to a preferred embodiment of the present invention, R4 is selected from -CH2-, -CH2CH2- or -CH2CH2CH2-.

[0055] According to a preferred embodiment of the present invention, R5 is selected from straight-chain or branched alkyl groups of -H or C1-C3.

[0056] According to a preferred embodiment of the present invention, R5 is selected from -H or -CH3.

[0057] According to a preferred embodiment of the present invention, the polyurethane segment contains structural units F from polyisocyanates and structural units G from oligomeric polyols.

[0058] In this invention, the polyisocyanate is selected from a wide range, and commonly used types can be used. According to a preferred embodiment of the invention, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. By adopting the aforementioned preferred method, the versatility and excellent adjustability of polyurethane performance can be further improved.

[0059] In this invention, the polyether polyols are selected from a wide range, and commonly used types can be used. According to a preferred embodiment of the invention, the oligomeric polyol is a polyether polyol, preferably selected from at least one of polypropylene glycol-2000, polypropylene glycol-3000, polypropylene glycol-4000, polypropylene glycol-5000, and polypropylene glycol-6000. By adopting the aforementioned preferred selection, the practicality and antibacterial properties of the photocurable coating film prepared by this invention can be further improved.

[0060] According to a preferred embodiment of the present invention, the weight-average molecular weight of the polyurethane segments is 3200-8000 g / mol.

[0061] According to a preferred embodiment of the present invention, in the structural unit B, the molar ratio of structural unit C to structural unit D is 1:(0.5-0.8).

[0062] According to a preferred embodiment of the present invention, in the structural unit B, the molar ratio of structural unit D to structural unit E is 1:(2-10).

[0063] According to a preferred embodiment of the present invention, the copolymer has a weight-average molecular weight of 3000-6000 g / mol.

[0064] According to a preferred embodiment of the present invention, in the functional structural unit, the molar ratio of structural unit A to structural unit B is (2-2.5):1.

[0065] According to a preferred embodiment of the present invention, based on the total amount of the polymer, the molar ratio of the polyurethane segments, functional structural units and acrylate end-cap groups is 1:(1-1.2):(0.8-1).

[0066] According to a preferred embodiment of the present invention, the polymer has a weight-average molecular weight of 8000-15000 g / mol and a viscosity of 100-400 mPa / s at 25°C.

[0067] According to a particularly preferred embodiment of the present invention, two adjacent polyurethane segments are connected by the functional structural unit, and the modified polyurethane has macromolecular chains with acrylate end-capping groups at the ends.

[0068] According to a particularly preferred embodiment of the present invention, the modified polyurethane has a macromolecular chain that further comprises a linking group of general formula -NHCO located between the polyurethane chain segment and the functional structural unit.

[0069] In this invention, the linking group can be generated by reacting the -NCO group at the original end of the polyurethane chain segment with the -OH or -NH group at the end of the functional structural unit.

[0070] A second aspect of the present invention provides a method for preparing the polymer of the present invention, the method comprising the following steps:

[0071] (1) In the presence of a catalyst, polyisocyanate and oligomeric polyol are subjected to polycondensation reaction to generate a solution A containing polyurethane.

[0072] (2) The solution A, the intercalating copolymer, and the disulfide chain extender are copolymerized to obtain a polymer precursor; the intercalating copolymer contains structural unit D as shown in formula (3), structural unit F as shown in formula (5), and structural unit E from a monoolefin.

[0073]

[0074] (3) The polymer precursor and the capping agent are subjected to a capping reaction to obtain a polymer;

[0075] R1, R2, R3, R, R 2 The definition corresponds to the definition described in the polymer of this invention.

[0076] In this invention, a disulfide chain extender and hydroxyl groups in the embedded copolymer react with -NCO bonds in the polyurethane to achieve a link with the polyurethane. The resulting polymer precursor is then capped at the ends of the polyurethane chain segments by a capping agent, introducing the capping agent's groups to obtain the polymer.

[0077] The polymer prepared by the method of this invention has good mechanical properties. The quaternized copolymer is an antibacterial component, which is incorporated into the polyurethane resin backbone through polymerization via terminal hydroxyl groups, overcoming the problem of exudation or dissolution that easily occurs when adding blended antibacterial agents. In addition, the high molecular antibacterial units are not easy to migrate and lose, and are safer and less toxic than small molecular organic antibacterial agents. Therefore, the prepared polymer has low toxicity and good antibacterial properties.

[0078] In one embodiment of the present invention, the pretreatment of the isocyanate and the isocyanate group content test are both performed using methods commonly used in the art.

[0079] According to a preferred embodiment of the present invention, step (2) begins when the -NCO content in solution A decreases by 50 wt%.

[0080] According to a preferred embodiment of the present invention, the endpoint of the end-capping reaction in step (3) is: when the -NCO content in the reaction system is less than or equal to 0.3%, the reaction is stopped and the resulting polymer is cooled to room temperature before being discharged.

[0081] According to a preferred embodiment of the present invention, the molar ratio of the polyisocyanate to the oligomeric polyol is (2-2.5):1.

[0082] According to a preferred embodiment of the present invention, the molar ratio of the capping agent to the polyisocyanate is 1:(2-3.5).

[0083] According to a preferred embodiment of the present invention, the amount of catalyst used is 0.05-0.1 wt% relative to the total amount of feed.

[0084] According to a preferred embodiment of the present invention, the amount of the disulfide bond extender is 0.5-2.5 wt% relative to the total amount of feed.

[0085] According to a preferred embodiment of the invention, the amount of the embedded copolymer is 10-22 wt% relative to the total amount of feed.

[0086] According to a preferred embodiment of the present invention, the total amount of the feed is the sum of the feed amounts of the polyisocyanate, oligomeric polyol, intercalating copolymer, catalyst, disulfide chain extender and end capping agent.

[0087] According to a preferred embodiment of the present invention, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.

[0088] According to a preferred embodiment of the present invention, the oligomeric polyol is a polyether polyol, preferably selected from at least one of polypropylene glycol-2000, polypropylene glycol-3000 and polypropylene glycol-6000, with a weight-average molecular weight of 2000-6000 g / mol.

[0089] In this invention, the range of disulfide bond chain extenders is relatively wide. According to a preferred embodiment of this invention, the disulfide bond chain extender is selected from compounds having the general formula HO-Z3-SS-Z4-OH or H2N-Z5-SS-Z6-NH2, wherein Z3, Z4, Z5, and Z6 are each independently phenylene or C1-C6 straight-chain or branched alkylene, preferably Z3 and Z4 are each independently -CH2CH2- or -C6H4-.

[0090] According to a particularly preferred embodiment of the present invention, the disulfide chain extender is selected from at least one of bis(2-hydroxyethyl) disulfide, 4,4'-dithiodiphenylamine, and 2,2-dithiodiphenylamine. By adopting the aforementioned preferred embodiment, the disulfide chain extender contains reversible covalent disulfide bonds, which can partially or completely restore the mechanical properties and integrity of the polymer itself under external stimuli such as light, heat, or acids and alkalis, thereby achieving repair.

[0091] According to a preferred embodiment of the present invention, the type of capping agent can be selected from a wide range, and commonly used capping agents can be used in the present invention, such as hydroxyl-functionalized acrylate capping agents. According to a preferred embodiment of the present invention, the capping agent has the structure shown in formula (A4).

[0092] Wherein, R4 is selected from C1-C5 straight-chain or branched alkylene groups, preferably -CH2-, -CH2CH2-, or -CH2CH2CH2-; R5 is selected from -H or C1-C3 straight-chain or branched alkyl groups, preferably -H or -CH3.

[0093] According to a particularly preferred embodiment of the present invention, the capping agent is selected from at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Through the aforementioned preferred embodiment, the terminal hydroxyl groups are polymerized into the polyurethane resin backbone, overcoming the problem of exudation or dissolution that easily occurs when adding blended antibacterial agents.

[0094] In this invention, the range of catalysts that can be selected is relatively wide, and commonly used catalysts can all be used in this invention. According to a preferred embodiment of this invention, the catalyst is an organotin catalyst, preferably at least one of dibutyltin dilaurate and stannous octoate. By adopting the aforementioned preferred method, the practicality and antibacterial properties of the photocurable coating film prepared by this invention can be further improved.

[0095] In this invention, the embedded copolymer can be a pre-prepared copolymer having the structural units D, F, and E. For example, it can be prepared by the following method:

[0096] (i) In the presence of an initiator system and a solvent, a monoolefin and a monomer d providing structural unit D are subjected to cationic solution polymerization to obtain a binary copolymer solution containing structural unit D and structural unit E.

[0097] (ii) The binary copolymer solution is washed with water and then subjected to a halogenation reaction to obtain a halogenated polymer;

[0098] (iii) The halogenated polymer is subjected to a salting reaction with a polyol amine to obtain the intercalated copolymer.

[0099] In (iii), the polyol amines, through the salting reaction, can bond with some of the halogenated groups in the halogenated polymer using their respective N elements, thereby forming the structural unit F.

[0100] According to a preferred embodiment of the present invention, the weight-average molecular weight of the embedded copolymer is 3000-6000 g / mol.

[0101] According to a preferred embodiment of the present invention, the monoolefin is selected from isobutylene, isopentenene, isohexene, isoheptene, and isooctene, preferably isobutylene.

[0102] According to a preferred embodiment of the present invention, the amount of monomer d added satisfies the condition that, based on the total weight of the embedded copolymer, the mass fraction of the structural unit D is 20-40%.

[0103] According to a preferred embodiment of the present invention, the amount of monomer d and polyol amine added satisfies the following condition: in the embedded copolymer, the molar ratio of structural unit F to structural unit D is 1:(0.5-0.8), for example, 1:0.5, 1:0.6, 1:0.7, 1:0.8, or any value within the range of any two of the above values.

[0104] In a preferred embodiment of the present invention, the polyol amine is selected from N-methyldiethanolamine and / or N-methyldipropanolamine.

[0105] The monomer e is selected from one of p-methylstyrene, p-ethylstyrene, and p-isobutylstyrene.

[0106] In a particularly preferred embodiment of the present invention, the polyol amine is N-methyldiethanolamine, the monomer e is p-methylstyrene, the monoolefin is isobutylene, and the halogenation reaction is a bromination reaction.

[0107] A cationic solution polymerization reaction is carried out between a monoolefin and a monomer d that provides structural unit D to obtain a binary copolymer containing structural units D and E.

[0108] The initiator system described in (i) is not particularly limited, as long as it can promote the cationic polymerization reaction of the monoolefin and monomer e. For example, the initiator system contains a proton-donating compound (e.g., HCl), at least one Lewis acid (dichloroethylaluminum, diethylaluminum chloride), and at least one activator (e.g., tetrahydrobenzoquinone, tetrachlorobenzoquinone, tetracyanobenzoquinone, and dichlorodicyanobenzoquinone). In this invention, the advantages of the invention are illustrated by using hydrogen chloride / dichloroethylaluminum / tetrachlorobenzoquinone as the initiator system (molar concentration ratio of 1:10:1). However, this invention is not limited thereto; the solvent can be alkanes and haloalkanes. Hexane / dichloromethane (60 / 40, V / V) is used as an example to illustrate the advantages of this invention, but it is not limited thereto; there are no special restrictions on the amount of solvent and initiator in the initiator system, and those skilled in the art can choose according to their needs, which will not be elaborated here; wherein, the conditions for the solution polymerization reaction include: solution polymerization is carried out in the temperature range of -60℃ to -20℃ to prepare a low-molecular-weight, fully saturated binary copolymer containing structural units D and E. The monomer d and the olefin carbon-carbon double bond in the monoolefin undergo the cationic solution polymerization reaction. Wherein, monomer d provides the structural unit D.

[0109] (ii) The binary copolymer undergoes the halogenation reaction with halogen, wherein the conditions for the halogenation reaction include: washing the binary copolymer solution with water, and then performing a pulsed (10s) photobromination reaction at room temperature using a 595nm light source with slow dropwise addition of liquid bromine for a bromination reaction time of 100-150min. The bromination solution is then washed with water and centrifuged to obtain the halogenated polymer; this can cause some structural units D to contain R... 2 Halogens are substituted to form halogenated side groups in the macromolecular chains of the binary copolymer.

[0110] The conditions for the salting reaction described in (iii) include: a reaction temperature of 50-80℃ and a reaction time of 12-24 h. After the reaction is complete, a certain amount of anhydrous diethyl ether is added to the system, resulting in the precipitation of a large amount of solid. After filtration, washing, and drying, the intercalated copolymer is obtained. The polyol amine reacts with the halogenated side groups through the nitrogen element it contains, thereby forming the structural unit F in the intercalated copolymer.

[0111] In this invention, the structural unit F, through the hydroxyl group introduced by the polyol amine, can react with the isocyanate group contained in the polyurethane contained in the solution A during the copolymerization reaction in step (2) to form a -NHCO- connection.

[0112] In this invention, the disulfide chain extender, through the presence of hydroxyl or amino groups, reacts with the isocyanate groups contained in the polyurethane in solution A during the copolymerization process in step (2) to form a -NHCO- linkage.

[0113] In this invention, through the copolymerization reaction in step (2), the embedded copolymer and the disulfide bond extender are respectively incorporated into the macromolecular chain of polyurethane.

[0114] According to a preferred embodiment of the present invention, the conditions for the polycondensation reaction include: reaction time: 1-2 h, reaction temperature: 60-70 °C.

[0115] According to a preferred embodiment of the present invention, the conditions for the copolymerization reaction include: reaction time: 2-4 h, reaction temperature: 70-80 °C.

[0116] According to a preferred embodiment of the present invention, the conditions for the end-capping reaction include: reaction time: 1-2 h, reaction temperature: 80-85 °C. The terminal hydroxyl groups contained in the end-capping agent react with the isocyanate terminal groups in the polymer precursor to form -NHCO- groups, thereby converting the isocyanate terminal groups into end groups provided by the end-capping agent, overcoming the problem of exudation or dissolution that easily occurs when adding blended antibacterial agents.

[0117] A third aspect of the present invention provides a polymer prepared by the preparation method described herein.

[0118] The polymer provided by this invention has good mechanical properties, antibacterial properties, and stability.

[0119] A fourth aspect of the present invention provides a self-healing antibacterial photocurable coating composition containing the polymer described in the present invention.

[0120] This invention provides a self-healing antibacterial curing coating containing the polymer described in this invention, which can improve the antibacterial properties, mechanical properties, and self-healing properties of the self-healing antibacterial curing coating.

[0121] According to a preferred embodiment of the present invention, the composition further comprises an active diluent and a photoinitiator.

[0122] According to a preferred embodiment of the present invention, based on the total amount of the composition, the polymer comprises 40-55 parts, the reactive diluent comprises 42-55 parts, and the photoinitiator comprises 3-5 parts.

[0123] The fifth aspect of the present invention provides the application of the polymer described herein in a self-healing antibacterial curing coating.

[0124] By applying the polymer prepared in this invention to a self-healing antibacterial curing coating, the antibacterial properties, mechanical properties, and self-healing properties of the coating can be improved.

[0125] The sixth aspect of this invention provides a method for preparing a self-healing antibacterial photocurable coating, the method comprising the following steps:

[0126] (1) Mix the polymer, reactive diluent and photoinitiator to obtain mixture A;

[0127] (2) Curing mixture A yields a self-healing antibacterial photocurable coating.

[0128] According to a preferred embodiment of the present invention, the polymer is the polymer described in the present invention.

[0129] The photocuring technology provided by the method of this invention has outstanding advantages in the preparation of antibacterial polymer film coatings. The method has mild reaction conditions, fast reaction speed and high efficiency, which helps to maintain the activity of antibacterial groups and avoids the disadvantages of loss of antibacterial activity caused by traditional thermal polymerization and its processing. It is green and environmentally friendly and highly practical.

[0130] In this invention, the range of types of reactive diluents is relatively wide, and commonly used types can be used. According to a preferred embodiment of this invention, the reactive diluent is selected from at least one of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, and isobornyl acrylate. By adopting the aforementioned preferred method, the reactive diluent is used as a reactive diluent for photocurable coatings. The multiple active functional groups of the reactive diluent can participate in the reaction, thereby not only improving the curing rate of the photocurable coating but also enhancing the overall performance of the material.

[0131] According to a preferred embodiment of the present invention, the reactive diluent is selected from at least one of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, and isobornyl acrylate. By employing the aforementioned preferred method, the reactive diluent is used as a reactive diluent for photocurable coatings. The multiple active functional groups of the reactive diluent can participate in the reaction, thereby not only improving the curing rate of the photocurable coating but also enhancing the overall performance of the material.

[0132] According to a preferred embodiment of the present invention, the mass ratio of the tripropylene glycol diacrylate, 1,6-hexanediol diacrylate and isobornyl acrylate is (12-20):(10-15):(15-25).

[0133] According to a preferred embodiment of the present invention, the photoinitiator is selected from at least one of 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide. By adopting the aforementioned preferred embodiment, the absorption spectrum of the photoinitiator matches the emission spectrum of the radiation source, which can efficiently induce chemical reactions between unsaturated double bonds in the system and improve the photoinitiation efficiency.

[0134] According to a preferred embodiment of the present invention, the photoinitiator is selected from 2-hydroxy-2-methyl-1-phenylpropanone. By adopting the aforementioned preferred embodiment, the absorption spectrum of the photoinitiator matches the emission spectrum of the radiation source, which can efficiently induce chemical reactions between unsaturated double bonds in the system and improve the photoinitiation efficiency.

[0135] According to a particularly preferred embodiment of the present invention, the curing machine has a power of 1000-1500W, a main emission wavelength of 365nm and 385nm, and an irradiation distance of 20-25cm.

[0136] According to a preferred embodiment of the present invention, the mixing conditions include a reaction temperature of 30-60°C.

[0137] According to a preferred embodiment of the present invention, the mixing conditions include a reaction time of 2-5 hours.

[0138] According to a preferred embodiment of the present invention, the curing conditions include: a temperature of 20-30°C and a time of 1-10 min.

[0139] According to a preferred embodiment of the present invention, the polymer comprises 40-55 parts, the reactive diluent comprises 42-55 parts, and the photoinitiator comprises 3-5 parts by weight.

[0140] The seventh aspect of the present invention provides a self-healing antibacterial photocurable coating film prepared by the preparation method described in the present invention.

[0141] The self-healing antibacterial photocurable coating prepared by this invention has excellent antibacterial and self-healing properties.

[0142] The eighth aspect of the present invention provides an application of the self-healing antibacterial photocurable coating of the present invention in the surface coating of public goods.

[0143] The self-healing antibacterial photocurable coating prepared according to this invention is applied to the surface of public goods, giving them excellent antibacterial properties.

[0144] The ninth aspect of the present invention provides an article having a self-healing antibacterial photocurable coating as described in the present invention on its surface.

[0145] To make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments. These embodiments are for illustrative purposes only and should not be considered as limiting the scope of the present invention. Unless otherwise specified, specific conditions in the embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Unless otherwise stated, all raw materials involved in the embodiments are commercially available products. The composition and structure of the obtained polymer are determined by the amount of raw materials fed.

[0146] Self-healing efficiency: The sample was divided into two parts. One part was cut in half with scissors, and the two pieces were tightly bonded together and placed in a 50℃ oven for 2 hours. The other part was the original sample without any treatment. The tensile strength of the repaired sample and the original sample were tested after 2 hours, and their self-healing efficiency was calculated. The self-healing efficiency H is the ratio of the tensile strength of the repaired sample to the tensile strength of the original sample.

[0147] Antibacterial performance test: The antibacterial effect of the antibacterial coating was tested according to ISO 22196 standard. The experimental subject was Gram-negative bacteria Escherichia coli. The plate count method was used to characterize the antibacterial rate of the coating against Escherichia coli at different times. The entire process was carried out under aseptic conditions.

[0148] Water absorption rate: Cut the membrane into 25mm×25mm thin sheets, dry them in an oven at 60℃ for 24 hours, and weigh them as W1. Then place the dried sheets in 50mL of deionized water for 24 hours, absorb the unabsorbed water on the surface, and weigh them as W2. The water absorption rate is then calculated as (W2-W1 / W1)×100%.

[0149] Method for determining polymer molecular weight: The molecular weight was determined using an LC-20A gel permeation chromatograph with tetrahydrofuran as solvent, sample concentration of 20 mg / 10 mL, injection volume of 100 μL, and flow rate of 1.0 mL / min. The calibration curve was determined using PS as a standard.

[0150] Viscosity: A digital rotational viscometer was used, and a suitable rotor was selected to measure the viscosity of the sample at various temperatures. The resin must be able to completely cover the rotor.

[0151] Preparation Example

[0152] Used to illustrate the preparation of embedded copolymers:

[0153] Using hydrogen chloride / dichloroethylaluminum / tetrachlorobenzoquinone (molar concentration ratio of 1:10:1) as the initiating system and hexane / dichloromethane (60 / 40, V / V) as the solvent, isobutylene and p-methylstyrene were subjected to cationic solution polymerization in the range of -60℃ to -20℃ to obtain isobutylene-p-methylstyrene copolymer solution.

[0154] After washing the isobutylene-p-methylstyrene copolymer solution with water, the isobutylene-p-methylstyrene copolymer solution was subjected to photobromination reaction by slowly adding liquid bromine at room temperature and under irradiation conditions of 595nm light source pulse (10s). The bromination reaction time was 60-150min. The product was washed with water and centrifuged to obtain the brominated polymer.

[0155] N-methyldiethanolamine was reacted with a brominated polymer at 50-80°C for 10-24 hours. After the reaction was complete, a certain amount of anhydrous diethyl ether was added to the system, resulting in the precipitation of a large amount of solid. After filtration, washing, and drying, the intercalated copolymer was obtained, and its schematic structure is shown below:

[0156] By adjusting the conditions and the amount of raw materials added, we obtained the following results:

[0157] Intercalated copolymer I: weight average molecular weight 3200 g / mol, mass fraction of structural unit D is 25%, molar ratio of structural unit F to structural unit D is 1:0.5;

[0158] Embedded copolymer II: weight average molecular weight 3000 g / mol, the mass fraction of structural unit D is 25%, and the molar ratio of structural unit F to structural unit D is 1:0.7;

[0159] Embedded copolymer III: weight average molecular weight 5100 g / mol, the mass fraction of structural unit D is 40%, and the molar ratio of structural unit F to structural unit D is 1:0.6;

[0160] Embedded copolymer IV: weight average molecular weight 6000 g / mol, the mass fraction of structural unit D is 20%, and the molar ratio of structural unit F to structural unit D is 1:0.8.

[0161] Example 1

[0162] A thermometer and a constant-pressure dropping funnel were set up in a three-necked flask, and 4.44 g of pretreated isophorone diisocyanate was added. Then, 0.02 g of dibutyltin dilaurate catalyst was added and stirred evenly. Next, 30.07 g of oligomeric propylene glycol PPG3000 was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the reaction was carried out for 1 h to generate a polyurethane-containing solution A with a weight-average molecular weight of 4000 g / mol. During the reaction, samples were continuously taken and the content of isocyanate groups in the system was measured.

[0163] When the isocyanate group content decreased to half of its original value, 6.31 g of intercalation copolymer I and 0.62 g of disulfide bond extender bis(2-hydroxyethyl) disulfide were added to solution A containing polyurethane. The temperature was raised to 80 °C and the reaction was continued for 1 h. Finally, 1.04 g of hydroxyethyl methacrylate was added dropwise for end-capping, and the reaction was carried out at 80 °C for 1 h. During the reaction, samples were continuously taken and the isocyanate group content in the system was measured. The reaction was terminated when the content was lower than 0.3%. The solution was cooled to room temperature and discharged. The resulting viscous liquid was polymer A1, with a weight-average molecular weight of 8500 g / mol and a viscosity of 130 mPa·s at 25 °C.

[0164] Example 2

[0165] A thermometer and a constant-pressure dropping funnel were set up in a three-necked flask, and 4.44 g of pretreated isophorone diisocyanate was added. Then, 0.02 g of dibutyltin dilaurate catalyst was added and stirred evenly. Next, 30.07 g of oligomeric propylene glycol PPG3000 was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the reaction was carried out for 1 h to generate a polyurethane-containing solution A with a weight-average molecular weight of 4000 g / mol. During the reaction, samples were continuously taken and the content of isocyanate groups in the system was measured.

[0166] When the isocyanate group content decreased to half of its original value, 6.31 g of intercalation copolymer II and 0.62 g of disulfide bond extender bis(2-hydroxyethyl) disulfide were added to solution A containing polyurethane. The temperature was raised to 80 °C and the reaction was continued for 1 hour. Finally, 1.04 g of hydroxyethyl methacrylate was added dropwise for end-capping, and the reaction was carried out at 80 °C for 1 hour. During the reaction, samples were continuously taken and the isocyanate group content in the system was measured. The reaction was terminated when the content was lower than 0.3%. The solution was cooled to room temperature and discharged. The resulting viscous liquid was polymer A2, with a weight-average molecular weight of 8700 g / mol and a viscosity of 140 mPa·s at 25 °C.

[0167] Example 3

[0168] A thermometer and a constant-pressure dropping funnel were set up in a three-necked flask, and 3.48 g of pretreated toluene diisocyanate was added. Then, 0.02 g of dibutyltin dilaurate catalyst was added and stirred evenly. Next, 20.01 g of oligomeric propylene glycol PPG2000 was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the reaction was carried out for 2 h to generate a polyurethane-containing solution A with a weight-average molecular weight of 3200 g / mol. During the reaction, samples were continuously taken and the content of isocyanate groups in the system was measured.

[0169] When the isocyanate group content decreased to half of its original value, 7.02 g of intercalation copolymer III and 0.54 g of disulfide bond extender bis(2-hydroxyethyl) disulfide were added to solution A containing polyurethane. The temperature was raised to 80 °C and the reaction continued for 2 hours. Finally, 1.20 g of hydroxyethyl acrylate was added dropwise for end-capping, and the reaction was carried out at 80 °C for 2 hours. During the reaction, samples were continuously taken and the isocyanate group content in the system was measured. The reaction ended when the content was below 0.3%. The solution was cooled to room temperature and discharged. The resulting viscous liquid was polymer A3, with a weight-average molecular weight of 9000 g / mol and a viscosity of 200 mPa·s at 25 °C.

[0170] Example 4

[0171] A thermometer and a constant-pressure dropping funnel were set up in a three-necked flask, and 3.48 g of pretreated toluene diisocyanate was added. Then, 0.02 g of dibutyltin dilaurate catalyst was added and stirred evenly. Next, 20.01 g of oligomeric propylene glycol PPG2000 was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the reaction was carried out for 2 h to generate a polyurethane-containing solution A with a weight-average molecular weight of 3200 g / mol. During the reaction, samples were continuously taken and the content of isocyanate groups in the system was measured.

[0172] When the isocyanate group content decreased to half of its original value, 7.02 g of intercalation copolymer IV and 0.54 g of disulfide bond extender bis(2-hydroxyethyl) disulfide were added to solution A containing polyurethane. The temperature was raised to 80 °C and the reaction was continued for 2 hours. Finally, 1.20 g of hydroxyethyl acrylate was added dropwise for end-capping, and the reaction was carried out at 80 °C for 2 hours. During the reaction, samples were continuously taken and the isocyanate group content in the system was measured. The reaction was terminated when the content was lower than 0.3%. The solution was cooled to room temperature and discharged. The resulting viscous liquid was polymer A4, with a weight-average molecular weight of 9500 g / mol and a viscosity of 220 mPa·s at 25 °C.

[0173] Example 5

[0174] A thermometer and a constant-pressure dropping funnel were set up in a three-necked flask, and 4.01 g of pretreated toluene diisocyanate was added. Then, 0.06 g of dibutyltin dilaurate catalyst was added and stirred evenly. Next, 60.02 g of oligomeric propylene glycol PPG6000 was slowly added dropwise. After the addition was completed, the temperature was raised to 60 °C and the reaction was carried out for 2 h to generate a polyurethane-containing solution A with a weight-average molecular weight of 7100 g / mol. During the reaction, samples were continuously taken and the content of isocyanate groups in the system was measured.

[0175] When the isocyanate group content decreased to half of its original value, 12.66 g of intercalation copolymer IV and 0.65 g of disulfide bond extender bis(2-hydroxyethyl) disulfide were added to solution A containing polyurethane. The temperature was raised to 80 °C and the reaction was continued for 2 hours. Finally, 0.95 g of hydroxyethyl acrylate was added dropwise for end-capping, and the reaction was carried out at 80 °C for 2 hours. During the reaction, samples were continuously taken and the isocyanate group content in the system was measured. The reaction was terminated when the content was lower than 0.3%. The solution was cooled to room temperature and discharged. The resulting viscous liquid was polymer A5, with a weight-average molecular weight of 15000 g / mol and a viscosity of 380 mPa·s at 25 °C.

[0176] Comparative Example 1

[0177] Similar to Example 1, except that no intercalating copolymer was added, and other reaction conditions remained unchanged. The resulting viscous liquid was polyurethane oligomer D1, with a weight-average molecular weight of 4200 g / mol and a viscosity of 94 mPa s at 25°C.

[0178] Comparative Example 2

[0179] Similar to Example 1, except that the disulfide chain extender bis(2-hydroxyethyl) disulfide is not added, and other reaction conditions remain unchanged. The resulting viscous liquid is polyurethane oligomer D2, with a weight-average molecular weight of 8000 g / mol and a viscosity of 110 mPas at 25°C.

[0180] Comparative Example 3

[0181] Similar to Example 1, except that hydroxyethyl methacrylate was not added, and other reaction conditions remained unchanged. A disulfide chain extender was added, and the reaction was continued at 80°C for 1 hour before the reaction was terminated. Since hydroxyethyl methacrylate was not added, the -NCO content in the polymer was always higher than 0.3%. The final viscous liquid was polyurethane oligomer D3, with a weight-average molecular weight of 7600 g / mol and a viscosity of 100 mPas at 25°C.

[0182] Preparation Examples 1-10

[0183] Weigh all raw materials according to the proportions in Table 1 by weight. Add the synthesized polyurethane oligomer, reactive diluent, and photoinitiator to separate containers and stir magnetically under light-protected conditions until uniformly mixed to obtain mixture A. Then, use a wire rod coater to evenly coat the mixture onto a tin-plated tinplate sheet, controlling the cured layer thickness to 0.4 mm. Place the sheet in a UV curing machine for UV curing to obtain a UV-cured coating. The stirring conditions include: stirring temperature of 40℃, stirring time of 3 hours, UV curing machine power of 1300W, main emission wavelengths of 365nm and 385nm, irradiation distance of 25cm, temperature of 25℃, and time of 4-5 minutes. Prepare the UV-cured coating according to the formula shown in Table 1.

[0184] Table 1

[0185]

[0186] Test case

[0187] The properties of the photocurable coatings prepared in Examples 1-10 above were tested, and the results are shown in Table 2.

[0188] Table 2

[0189]

[0190]

[0191] As shown in Table 2, the photocurable coatings obtained in Preparation Examples 1-6, 9, and 10 of this invention contain reversible covalent disulfide bonds, exhibiting repairability under external stimuli such as heating, with a self-repair rate of over 95% after 2 hours. In contrast, the photocurable film obtained in Preparation Example 7 does not contain reversible covalent disulfide bonds, and its self-repair rate after 2 hours is only 31.8%. Preparation Example 8 did not include an acrylate-based end-capping agent, and the polymer molecular chain ends lack active sites for photoreaction with the reactive diluent; therefore, the photocurable coating has poor film-forming properties and a low self-repair rate. Furthermore, using quaternized isobutylene / p-methylstyrene copolymer as the antibacterial component, which is polymerized into the polyurethane resin backbone via terminal hydroxyl groups, overcomes the problem of exudation or dissolution that easily occurs with blended antibacterial agents, effectively protecting the bactericidal unit and exhibiting good bactericidal performance. The photocurable films obtained from Preparation Examples 1-5 and 7-9 showed an anti-E. coli rate of over 45% after 1 hour of contact and an anti-E. coli rate of over 98% after 3 hours. In contrast, the photocurable film obtained from Preparation Example 6 showed an anti-E. coli rate of only 20.6% after 1 hour of contact and an anti-E. coli rate of 15.4% after 3 hours. This indicates that the quaternary ammonium salt enables the photocurable film prepared by the present invention to have an antibacterial effect.

[0192] The water absorption rate of the coating was measured to determine its water absorption and hydrolytic stability. As shown in Preparation Example 6, the coating without the quaternary ammonium salt antibacterial unit possesses a certain degree of hydrophobicity and is not easily dissolved by water absorption. Data from Preparation Examples 2 and 9, and Preparation Examples 5 and 10 in Table 2 show that the water absorption rate increases with the increase of the quaternary ammonium salt component, which is a result of the quaternary ammonium salt cations readily binding water.

[0193] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polymer, characterized in that, The polymer comprises a polyurethane segment, a functional structure unit and an acrylate end-capping group; wherein the functional structure unit comprises a structure unit A with a -S-S- group and a structure unit B shown in formula (1); Formula (1), wherein R2 is a C1-C6 linear or branched alkyl group, R1, R3 are each independently a structure represented by general formula -O-Z1* or -NH-Z2*, wherein Z1, Z2 are each independently a C1-C6 linear or branched alkylene group, R is a copolymer chain containing a structure unit C shown in formula (2), a structure unit D shown in formula (3) and a structure unit E from a mono-olefin, Formula (2), Formula (3), wherein R 1 selected from C1-C6 linear or branched alkylene, R 2 selected from -H or C1-C6 linear or branched alkyl, * is the position of attachment to the N element in formula (1); X is selected from F, Cl, Br or I; The weight average molecular weight of the polyurethane segment is 3200-8000 g / mol; In the structure unit B, the molar ratio of structure unit C to structure unit D is 1:(0.5-0.8); The molar ratio of structure unit D to structure unit E is 1:(2-10); The weight average molecular weight of the copolymer is 3000-6000 g / mol; The molar ratio of the polyurethane segment, the functional structure unit and the acrylate end-capping group is 1:(1-1.2):(0.8-1) based on the total amount of the polymer; The weight average molecular weight of the polymer is 8000-15000 g / mol.

2. The polymer of claim 1, wherein, R2 is selected from -CH3 or -C2H5; And / or, Z1, Z2 are each independently -CH2CH2- or -CH2CH2CH2-; and / or, R 1 is selected from -CH2- or -CH2CH2-; and / or, R 2 is selected from -CH3or -C2H5; And / or, X is Cl or Br; And / or, the mono-olefin is selected from one of isobutene, isopentene, isohexene, isoheptene and isooctene.

3. The polymer of claim 1, wherein, R1 and R3 are each independently a structure shown in general formula -O-Z1*.

4. The polymer of claim 1, wherein, R1 and R3 are both -O-CH2CH2*.

5. The polymer of any one of claims 1-4, wherein, The structural unit A has the general formula or as shown, wherein Z3, Z4, Z5, Z6 are each independently phenylene or a C1-C6 straight-chain or branched alkylene group.

6. The polymer of claim 5, wherein, Z3, Z4, Z5, Z6 are each independently -CH2CH2- or -C6H4-.

7. The polymer of claim 6, wherein, The structural unit A has or the structure shown.

8. The polymer of any one of claims 1-4, wherein, The acrylate end-capping group has a structure shown in formula (4), Formula (4), wherein R4 is selected from C1-C5 straight or branched alkylene, preferably -CH2-, -CH2CH2- or -CH2CH2CH2-; R5 is selected from -H or a linear or branched C1-C3 alkyl.

9. The polymer of claim 8, wherein, R4 is -CH2-, -CH2CH2- or -CH2CH2CH2-; And / or, R5 is -H or -CH3.

10. The polymer of any one of claims 1-4, wherein, The polyurethane segment contains a structure unit F from a polyisocyanate and a structure unit G from an oligomeric polyol.

11. The polymer of claim 10, wherein, The polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate; Alternatively, the oligomeric polyol is a polyether polyol.

12. The polymer of claim 11, wherein, The oligomeric polyol is at least one of polypropylene glycol-2000, polypropylene glycol-3000, polypropylene glycol-4000, polypropylene glycol-5000 and polypropylene glycol-6000.

13. The polymer of any one of claims 1-4, wherein, In the functional structure unit, the molar ratio of the structure unit A to the structure unit B is (2-2.5):

1.

14. The polymer of any one of claims 1-4, wherein, The viscosity of the polymer at 25°C is 100-400 mPa·s.

15. A process for the preparation of a polymer according to any one of claims 1 to 14, characterized in that, The method comprises the following steps: (1) In the presence of a catalyst, polycondensation reaction is carried out on a polyisocyanate and an oligomeric polyol to generate a solution A containing a polyurethane; (2) Solution A, an embedded copolymer and a disulfide chain extender are subjected to copolymerization to obtain a polymer precursor; wherein the embedded copolymer contains a structure unit D shown in formula (3), a structure unit F shown in formula (5) and a structure unit E from a mono-olefin, Formula (3), Formula (5); (3) End-capping reaction is carried out on the polymer precursor and an end-capping agent to obtain a polymer; The weight average molecular weight of the oligomer polyol is 2000-6000 g / mol. The weight average molecular weight of the intercalated copolymer is 3000-6000 g / mol. The molar ratio of the structural unit F: structural unit D is 1:(0.5-0.8).

16. The preparation method according to claim 15, wherein, The molar ratio of the polyisocyanate to the oligomer polyol is (2-2.5):1; and / or The molar ratio of the end-capping agent to the polyisocyanate is 1:(2-3.5); and / or The amount of the catalyst is 0.05-0.1 wt% relative to the total amount of the feedstock; and / or The amount of the disulfide chain extender is 0.5-2.5 wt%; and / or The amount of the intercalated copolymer is 10-22 wt%. The total amount of the feedstock is the total amount of the polyisocyanate, the oligomer polyol, the intercalated copolymer, the catalyst, the disulfide chain extender and the end-capping agent. Z3, Z4 are each independently -CH2CH2- or -C6H4-.

17. The method of making according to claim 15, wherein, The disulfide chain extender is selected from the group consisting of compounds having the general formula or wherein Z3, Z4, Z5, Z6are each independently phenylene or a C1-C6straight chain or branched alkylene.

18. The method of making according to claim 17, wherein, The disulfide chain extender is selected from at least one of bis(2-hydroxyethyl) disulfide, 4,4'-dithiodianiline, 2,2-dithiodianiline.

19. The method of making according to claim 18, wherein, The end-capping agent has a structure shown in formula (A4), 20. The method of making according to claim 15, wherein, The end-capping agent is selected from at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate. Formula (A4).

21. The method of making according to claim 20, wherein, The catalyst is an organotin catalyst.

22. The method of making according to claim 15, wherein, 23. The preparation method according to claim 22, wherein the catalyst is at least one of dibutyltin dilaurate, stannous octoate. The mono-olefin is selected from isobutylene.

24. The method of making according to any one of claims 15-23, wherein, The mass fraction of the structural unit D is 20-40% based on the total weight of the intercalated copolymer.

25. The method of making according to any one of claims 15-23, wherein, 26. The preparation method according to any one of claims 15-23, wherein, The conditions of the polycondensation reaction include: reaction time: 1-2 h, reaction temperature: 60-70℃; Alternatively, the conditions of the copolymerization reaction include: reaction time: 2-4 h, reaction temperature: 70-80℃; Alternatively, the conditions of the end-capping reaction include: reaction time: 1-2 h, reaction temperature: 80-85℃.

27. A self-repairing antibacterial photocured coating film composition, which comprises the polymer according to any one of claims 1-14. The composition further comprises an active diluent, a photoinitiator.

28. The self-repairing antibacterial photocured coating film composition according to claim 27, wherein, The polymer is 40-55 parts, the active diluent is 42-55 parts, and the photoinitiator is 3-5 parts based on the total amount of the composition.

29. The self-repairing antibacterial photocured coating film composition according to claim 28, wherein, 30. Use of the polymer according to any one of claims 1-14 in a self-repairing antibacterial photocured coating film. The preparation method comprises the following steps:

31. A method for preparing a self-repairing antibacterial photocured coating film, characterized by, (1) mixing the polymer, the active diluent and the photoinitiator to obtain a mixture A; (2) curing the mixture A to obtain a self-repairing antibacterial photocured coating film; The polymer is the polymer according to any one of claims 1-14.

32. The preparation method according to claim 31, wherein, ​ The active diluent is at least one of tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate and isobornyl acrylate.

33. The method of manufacturing according to claim 32, wherein, The active diluent is tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate and isobornyl acrylate.

34. The method of manufacturing according to claim 33, wherein, The mass ratio of tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate and isobornyl acrylate is (12-20):(10-15):(15-25).

35. The method of manufacturing according to claim 32, wherein, The photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone and (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide.

36. The method of manufacturing according to claim 32, wherein, The photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.

37. The preparation method of any one of claims 31-36, wherein, The mixing condition comprises: reaction temperature is 30-60℃, reaction time is 2-5h; and / or The curing condition comprises: temperature is 20-30℃, time is 1-10min.

38. The method of making according to any one of claims 31-36, wherein, The polymer is 40-55 parts, the active diluent is 42-55 parts, and the photoinitiator is 3-5 parts by weight.

39. A self-repairing antibacterial photocured coating film prepared by the preparation method of any one of claims 31-38.

40. Use of the self-repairing antibacterial photocured coating film of claim 39 in surface decoration of public articles.

41. An article having the self-repairing antibacterial photocured coating film of claim 40 on the surface thereof.

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