An antifouling material and a preparation method and application thereof

Abstract

The application provides an anti-fouling material and a preparation method and application thereof, wherein a linear polymer obtained by sequentially copolymerizing a flexible chain segment with a curing agent and a chain extender is reacted with a cross-linking agent and an anti-fouling additive in sequence, the anti-fouling additive comprises a monofunctionality fluorine-containing compound and a monofunctionality silicon-containing compound; the compounds contain active groups, the active groups comprise at least one of a hydroxyl group, an amino group and an isocyanate group; and the terminal of the linear polymer has a group corresponding to the active group. The anti-fouling material has good anti-calcification, anti-thrombosis and other performances when used as a medical implant material, and can effectively prolong the service life and safety of the material in the in-vivo environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical device materials, in particular to an anti-fouling material and a preparation method and application thereof. BACKGROUND

[0002] Heart valve refers to the valve between atrium and ventricle or between ventricle and artery. The valve plays a key role in the blood circulation activity of the heart that never stops: the valve is equivalent to a gatekeeper, preventing blood from flowing back to the atrium or ventricle just left. Artificial heart valve is one of the most commonly used implanted materials in the field of cardiovascular, and mechanical valve and biological valve have been used for half a century, and have become a very important medical device in the field of cardiovascular treatment. Both mechanical valve and biological valve used in clinical practice have their limitations. For example, patients using mechanical valve are prone to blood clotting and must receive anticoagulant therapy for life; patients using biological valve are prone to calcification of the valve and need to replace the valve frequently.

[0003] In recent years, the application of high polymer materials to artificial interventional heart valve has gradually emerged, and some high polymer materials have good biocompatibility, excellent mechanical properties, and excellent antithrombotic properties, etc., and can be used to prepare artificial heart valve with more ideal performance. Therefore, as a new type of material, the high polymer heart valve does not need anticoagulant and anti-calcification, and has good durability, but long-term use still has the problem of easy adhesion of other substances on the surface, thereby causing thrombosis, calcification and other lesions, thereby limiting its application range.

[0004] Therefore, based on the problems in the prior art, it is necessary to develop a material with improved surface anti-fouling performance for application in artificial heart valve. SUMMARY

[0005] Therefore, based on the problems in the prior art, it is necessary to develop a material with improved surface anti-fouling performance for application in artificial heart valve.

[0006] The flexible chain segment is composed of a macrodiol composed of two mixed macromolecular alcohols and polydimethylsiloxane;

[0007] The curing agent comprises at least one diisocyanate;

[0008] The chain extender comprises at least one dihydric alcohol or at least one diamine;

[0009] The crosslinking agent comprises at least one isocyanate with a functionality not less than 3 or at least one polyol with a functionality not less than 3;

[0010] The anti-fouling aid includes a monofunctional fluorine-containing compound and a monofunctional silicon-containing compound; the compounds contain active groups, the active groups including at least one of a hydroxyl group, an amino group and an isocyanate group; the ends of the linear polymer have groups corresponding to the active groups. After the linear polymer reacts with the crosslinking agent, because the crosslinking agent selected has a functionality of not less than 3, the end groups of the linear polymer are pendant to the linear molecular chain side chain of the crosslinking product, so that when the crosslinking product further reacts with the anti-fouling aid, the anti-fouling aid is introduced into the polymer system through chemical reaction of the active groups with the groups pendant to the linear molecular chain side chain, and is further pendant to the polymer molecular main chain.

[0011] The linear polymer has a repeating unit structure of Formula 1:

[0012]

[0013] wherein A is the dihydric alcohol or diamine, B is the diisocyanate, C is the macromolecular diol, D is the polydimethylsiloxane; n is an integer of 1-100, m is an integer of 1-100, and p is an integer of 1-100.

[0014] Optionally, the macromolecular alcohol is obtained by reacting at least one of poly (hexamethylene oxide), poly (heptamethylene oxide), poly (octamethylene oxide), poly (decamethylene oxide), polydimethylsiloxane diol, poly (butadiene) diol, poly (carbonate) diol, poly (isobutylene) diol, dimethylsiloxane diol, polyhexamethylene oxide (abbreviated as "PHMO"), polyoctanediol, polydecanediol, polycarbonatediol, polytetrahydrofuran diol with a curing agent.

[0015] Optionally, the polydimethylsiloxane includes at least one of α,ω-bis (6-hydroxyethoxypropyl) polydimethylsiloxane, α,ω-bis (3-aminopropyl) polydimethylsiloxane, α,ω-bis (aminomethyl) polydimethylsiloxane, α,ω-bis (2-aminoethyl) polydimethylsiloxane, α,ω-bis (4-aminobutyl) polydimethylsiloxane, α,ω-bis (5-aminopentyl) polydimethylsiloxane.

[0016] Optionally, the molecular weight of the macromolecular alcohol is 500-1500 Da.

[0017] Optionally, the diisocyanate; the diisocyanate includes at least one of an aliphatic isocyanate and an aromatic isocyanate polymer; the aliphatic isocyanate includes at least one of hexamethylene diisocyanate (abbreviated as "HDI") and isophorone diisocyanate (abbreviated as "IPDI"); the aromatic isocyanate polymer includes diphenylmethane diisocyanate (abbreviated as "MDI").

[0018] Optionally, the diol includes at least one silicon-containing diol and at least one silicon-free diol. The silicon-free diol includes at least one of 1,2-ethanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, p-xyleneglycol, 1,4-bis(2-hydroxyethoxy)benzene, 1,12-dodecanediol; and the silicon-containing diol includes at least one of 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane (abbreviated as "BHTD"), 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane.

[0019] Optionally, the diol includes at least one silicon-containing diol and at least one silicon-free diol. The silicon-free diol includes at least one of 1,2-ethanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, p-xyleneglycol, 1,4-bis(2-hydroxyethoxy)benzene, 1,12-dodecanediol; and the silicon-containing diol includes at least one of 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane (abbreviated as "BHTD"), 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane.

[0020] Optionally, the isocyanate with a functionality of not less than 3 includes at least one of MDI polymer, HDI polymer (model number can be selected as HT-100, HK), IPDI polymer (model number can be selected as Z4470BA), TDI polymer (model number can be selected as L75), pentamethylene diisocyanate (abbreviated as "PDI") polymer (model number can be selected as D-3725N).

[0021] Optionally, the polyol with a functionality of not less than 3 includes at least one of glycerol, trimethylolpropane, pentaerythritol, sorbitol, bis-pentaerythritol.

[0022] Optionally, the single-functionality fluorine-containing compound includes at least one of perfluoroalkylpropanol, perfluoroundecanol, heptafluoropentan-2-ol, 4-heptadecafluorodecyl benzyl alcohol, undecafluoro-n-hexan-1-ol, and perfluoropolyether alcohol containing one hydroxyl group.

[0023] Optionally, the single-functionality silicon-containing compound includes at least one of hydroxyl silicone oil, amino silicone oil, and carboxyl silicone oil.

[0024] Optionally, the weight ratio of the macrodiol, the curing agent, the chain extender, the crosslinking agent, and the stain-resistant aid is (40-55):(30-36):(12-15):(0.07-1.12):(1-10).

[0025] Optionally, the weight ratio of the macromolecular alcohol and the polydimethylsiloxane is 1:4.

[0026] Based on the same inventive concept, the application also provides a preparation method of the above-mentioned anti-fouling material, comprising the following steps:

[0027] mixing the macrodiol and the curing agent to obtain a prepolymer; mixing the prepolymer with a chain extender to chain extend the prepolymer to obtain a linear polymer; mixing the linear polymer with a crosslinking agent first and then with an anti-fouling aid, and ensuring that the product after the reaction of the linear polymer with the crosslinking agent has a group corresponding to the reactive group of the anti-fouling aid, thereby obtaining an anti-fouling solution; coating the anti-fouling solution into a film to obtain the anti-fouling material.

[0028] Based on the same inventive concept, the application also provides an application of the above-mentioned anti-fouling material or the anti-fouling material prepared by the above-mentioned preparation method as a raw material of a medical implant / intravenous medical device. The medical implant / intravenous medical device can include a heart valve, a biological implant, a drug delivery device, and the like.

[0029] Compared with the prior art, the technical scheme of the embodiment of the application has beneficial effects.

[0030] For example, by adding an aid with an anti-fouling effect, the anti-fouling performance of the final material can be improved. When the material is used as a medical implant material, it has good anti-calcification, anti-thrombus and other performances, which can effectively prolong the service life and safety of the material in the body environment.

[0031] For another example, the linkage mode of the crosslinked polymer and the functional unit of the anti-fouling aid in the application is suspended outside the main chain of the polymer molecule, which has better anti-fouling / anti-thrombus effect than the polymerization of the fluorine / silicon-containing compound in the main chain of the molecule.

[0032] For another example, the preparation process of the application is simple, easy to design and mass production. It has good application prospect in the biomedical field and is expected to become the preferred material of high molecular heart valve. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is a schematic diagram of the crosslinked polymer structure in the anti-fouling solution in the embodiment of the application.

[0034] Figure 2 is a schematic diagram of the anti-fouling material structure in the embodiment of the application.

[0035] Figure 3 is a schematic diagram of the material crosslinked polymer structure in Comparative Example 1 of the application. DETAILED DESCRIPTION

[0036] In order to make the objectives, characteristics and beneficial effects of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below in conjunction with the drawings. It can be understood that the specific embodiments described below are only used to explain the present application, but not to limit the present application. In addition, the same or similar reference signs can be used to refer to the same or similar elements in different embodiments, and the description of the same or similar elements in different embodiments and the description of prior art elements, characteristics, effects, etc. can be omitted.

[0037] As shown in the specification and claims, unless specifically indicated or apparent from the context, all numerical values provided herein are modified by the term "about", and the term "about" should be understood to be within the normal tolerance range in the art. "About" can be understood as allowing a tolerance of 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the numerical value of the numerical value.

[0038] The embodiment of the present application provides an anti-fouling material, which is obtained by cross-linking a linear polymer obtained by block copolymerization of a flexible soft segment and a hard segment, and then reacting the cross-linked polymer with an anti-fouling aid. Specifically, the flexible soft segment is composed of a macromolecular alcohol and a polydimethylsiloxane to form a macroglycol; the hard segment is composed of a curing agent and a chain extender. The linear polymer is obtained by copolymerization of the flexible segment with the curing agent and the chain extender in sequence, and then the linear polymer is cross-linked with a cross-linking agent to obtain a cross-linked polymer. The anti-fouling aid includes a monofunctional fluorine-containing compound and a monofunctional silicon-containing compound; the compound contains at least one of a hydroxyl group, an amino group, and an isocyanate group; the end of the linear polymer has a group corresponding to the active group. The linear polymer is reacted with the cross-linking agent, and the cross-linking agent with a functionality of not less than 3 is selected for cross-linking, so that after the reaction of the linear polymer with the cross-linking agent, the end group of the linear polymer is suspended on the side chain of the linear molecular chain of the cross-linked product. The cross-linked polymer with the suspended active group obtained by cross-linking is reacted with the anti-fouling aid, and the anti-fouling aid is introduced into the polymer system and suspended outside the main chain of the polymer molecule through the chemical reaction of the active group of the cross-linking aid with the group suspended on the side chain of the linear molecular chain.

[0039] The curing agent includes at least one diisocyanate;

[0040] The chain extender includes at least one diol or at least one diamine;

[0041] The cross-linking agent includes at least one isocyanate with a functionality of not less than 3 or at least one polyol with a functionality of not less than 3;

[0042] The linear polymer has a structure of formula 1:

[0043]

[0044] wherein A is a diol or diamine, B is a diisocyanate, C is a macrodiol, D is a polydimethylsiloxane; n is an integer from 1 to 100, m is an integer from 1 to 100, p is an integer from 1 to 100.

[0045] The repeat unit structure of Formula 1 above can be further extended to express as:

[0046]

[0047] wherein A is a diol or diamine, B is a diisocyanate, C is a macrodiol, D is a polydimethylsiloxane; e is an integer from 1 to 100, f is an integer from 1 to 100, j is an integer from 1 to 100.

[0048] In some embodiments, the macrodiol is selected from at least one of poly(hexamethylene oxide), poly(heptamethylene oxide), poly(octamethylene oxide), poly(decamethylene oxide), polydimethylsiloxane diol, poly(butadiene) diol, poly(carbonate) diol, poly(isobutylene) diol, dimethylsiloxane diol, polyhexamethylene oxide (abbreviated as “PHMO”), polyoctanediol, polydecandiol, polycarbonatediol, and polytetrahydrofuran diol, and is obtained by reacting the at least one raw material with a curing agent.

[0049] In some embodiments, the polydimethylsiloxane is selected from at least one of a, w bis(6-hydroxyethoxypropyl)polydimethylsiloxane, a, w bis(3- aminopropyl)polydimethylsiloxane, a, w bis(aminomethyl)polydimethylsiloxane, a, w bis(2-aminoethyl)polydimethylsiloxane, a, w bis(4- aminobutyl)polydimethylsiloxane, a, w bis(5-aminopentyl)polydimethylsiloxane.

[0050] In some embodiments, the macrodiol has a molecular weight of 500-1500 Da.

[0051] In some embodiments, the curing agent comprises at least one diisocyanate. In specific embodiments, the diisocyanate is selected from at least one of an aliphatic isocyanate and an aromatic isocyanate; the aliphatic isocyanate is selected from at least one of HDI and IPDI; the aromatic isocyanate is MDI.

[0052] In some embodiments, the diol is selected from the group consisting of a non-silicon-containing diol and a silicon-containing diol; wherein the non-silicon-containing diol can be selected from at least one of 1,2-ethanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol 1,4-cyclohexanedimethanol, p-xyleneglycol, 1,4-bis(2-hydroxyethoxy)benzene, 1,12-dodecanediol; and the silicon-containing diol can be tetramethyl siloxane, specifically selected from at least one of 1,3 bis(4-hydroxybutyl)-1,1,3,3 tetramethyldisiloxane (abbreviated as “BHTD”), 1,3 bis(3-hydroxypropyl)tetramethyldisiloxane, 1,3 bis(3-hydroxyisobutyl)tetramethyldisiloxane.

[0053] In some embodiments, the diol is selected from at least one of 1,2-ethanediol (abbreviated as “EDA”), ethanolamine, 1,4-butanediamine, 1,3-propanediamine, p-phenylenediamine.

[0054] In some embodiments, the isocyanate with functionality not less than 3 includes at least one of MDI polymer, HDI polymer (model number can be selected as HT-100, HK), IPDI polymer (model number can be selected as Z4470BA), TDI polymer (model number can be selected as L75), PDI polymer (model number can be selected as D-3725N). For example, the HDI polymer with functionality of 3 is a HDI trimer, which is obtained by trimerization of HDI under catalysis, and so on.

[0055] In some embodiments, the polyol with functionality not less than 3 is selected from at least one of glycerol, trimethylolpropane, pentaerythritol, sorbitol, bis-pentaerythritol.

[0056] In some embodiments, the monofunctional fluorine-containing compound includes at least one of perfluoroalkylpropanol, perfluoroundecanol, heptafluoropentan-2-ol, 4-heptadecafluorodecylbenzyl alcohol, undecafluoro-n-hexan-1-ol, perfluoropolyether alcohol containing one hydroxyl group.

[0057] In some embodiments, the monofunctional silicon-containing compound includes at least one of hydroxyl silicone oil, amino silicone oil, carboxyl silicone oil.

[0058] In some embodiments, the weight ratio of the large diol, the curing agent, the chain extender, the crosslinking agent, and the anti-fouling aid is (40-55):(30-36):(12-15):(0.07-1.12):(1-10).

[0059] The embodiment of the present application provides a preparation method of the anti-fouling material, comprising the following steps: mixing a macrodiol and a curing agent to obtain a prepolymer; mixing the prepolymer with a chain extender to perform chain extension on the prepolymer, so as to obtain a linear polymer; mixing the linear polymer with a crosslinking agent first, and then mixing the linear polymer with an anti-fouling aid, so as to obtain an anti-fouling solution; and coating the anti-fouling solution into a film, so as to obtain the anti-fouling material. The specific implementation is as follows:

[0060] Embodiment 1

[0061] Preparation of macrodiol

[0062] 700g / mol polyoxymethylene (referred to as "PHMO") is dried under the condition of 0.1 mbar and 105 DEG C for 15h, and the pre-dried PHMO is accurately weighed and placed in a three-necked round-bottom flask provided with a magnetic stirrer and a nitrogen inlet, and the flask is placed in an oil bath at 80 DEG C. The molten MDI is placed in a feeding funnel and added into the flask containing the PHMO in 1 minute under stirring. After the addition of the MDI is completed, the reaction mixture in the flask is further reacted for 2h to obtain the macrodiol PHMO-MDI-PHMO. The completion of the reaction is confirmed by the disappearance of the absorption peak of -NCO at 2270 cm -1 in the Fourier transform infrared (referred to as "FTIR") spectrum.

[0063] The macrodiol has the structure of formula 2:

[0064]

[0065] wherein x is an integer in the range of 1-14, and y is an integer in the range of 1-14.

[0066] The MDI has the structure of formula 3:

[0067]

[0068] Preparation of linear copolymer

[0069] All the glassware is dried at 105 DEG C overnight before use. The molten MDI is weighed into a three-necked round-bottom flask provided with a mechanical stirrer and a nitrogen inlet, and the flask is placed in an oil bath at 70 DEG C. The mixture of the pre-dried macrodiol PHMO-MDI-PHMO and the polydimethylsiloxane (i.e. macrodiol flexible segment) is quickly added into the flask through a feeding funnel under stirring. After the addition is completed, the reaction mixture in the flask is heated to 80 DEG C through the oil bath, and is continuously stirred under nitrogen for 2h to be uniform, so as to obtain the prepolymer.

[0070] The polydimethylsiloxane (referred to as "PDMS") has the structure of formula 4:

[0071]

[0072] wherein z is an integer in the range of 1-19.

[0073] The prepolymer is first chain-extended with BHTD at 80°C, and the reaction is stirred for 2 hours under nitrogen. Solvent, anhydrous dimethylacetamide (abbreviated as "anhydrous DMAc"), is added to obtain a transparent intermediate prepolymer solution. EDA is added dropwise into the cooled reaction solution, and the whole process is slowly stirred, with the reaction temperature controlled within 10°C. After the complete addition of EDA, the solution is stirred for another 30 minutes until all MDI and chain extender EDA are completely reacted. When the solution viscosity increases, the stirring is stopped, and a linear copolymer is obtained.

[0074] Preparation of crosslinked copolymer

[0075] The linear copolymer is heated to 80°C and continues to be stirred. A multifunctional compound, HDI polymer, is added, which can be specifically selected from HT-100, and the reaction is continued for 30 minutes to obtain a clear solution, i.e., a crosslinked copolymer.

[0076] Preparation of stain-resistant crosslinked polymer

[0077] The crosslinked copolymer is added with perfluoroundecanol under nitrogen, and the reaction is continued for 2 hours to obtain a stain-resistant crosslinked polymer.

[0078] wherein the crosslinked polymer structure of the stain-resistant crosslinked polymer is shown in Figure 1 , Figure 1 The middle curve represents the linear polymer, the round ball represents the crosslinking agent, and the arrow represents the stain-resistant functional unit. The linear polymer is mixed and reacted with the crosslinking agent, and the linear polymer is crosslinked through the functional groups of the crosslinking agent. Since the crosslinking agent with a functionality of not less than 3 is used for crosslinking, the terminal groups of the linear polymer are suspended on the side chains of the linear molecular chains of the crosslinked product, i.e., the crosslinked polymer has functional groups suspended on the side chains of the linear molecular chains. The crosslinked polymer with suspended active groups is reacted with the stain-resistant aid perfluoroundecanol, and the stain-resistant aid is introduced into the polymer system and suspended outside the polymer molecular main chain through the chemical reaction between the active groups of the stain-resistant aid and the groups suspended on the side chains of the linear molecular chains.

[0079] The stain-resistant aid is selected as a monofunctional compound, which ensures that each suspended functional group of the crosslinked polymer is reacted with a single functional group of the stain-resistant aid, so that a stain-resistant functional group is linked to each crosslinked functional group of the crosslinked polymer, so that the formed stain-resistant crosslinked polymer has stain-resistant functional groups suspended on the side chains of the linear molecular chains.

[0080] The anti-fouling solution was coated to form a film. The specific steps were as follows: the anti-fouling solution was coated on a coating machine at 50°C, evaporated in a nitrogen oven at 60°C for 24 h, and then further dried in a vacuum environment at 0.1 mbar for 24 h. The anti-fouling film was peeled off from the petri dish after being soaked in water for about 30 min. Finally, it was dried at 50°C in a vacuum environment at 0.1 mbar for 24 h to remove moisture. Then, it was annealed at 125°C for 2 h to obtain an anti-fouling elastomer film with a thickness of 0.2 mm-0.3 mm, as shown in Figure 2 Figure 1. After the anti-fouling film was formed, the anti-fouling functional units existed on the surface of the film to provide anti-fouling properties. The weight ratio of the above raw materials was according to the ratio of Table 1. The anti-fouling material can be subjected to Fourier transform infrared (FTIR) spectroscopy detection to confirm the material structure.

[0081] Example 2

[0082] Preparation of macromolecular alcohol

[0083] 700 g / mol polyoxymethylene hexamethylene (PHMO) was dried at 0.1 mbar and 105°C for 15 h. The pre-dried PHMO was accurately weighed and placed in a three-necked round-bottom flask equipped with a magnetic stirrer and a nitrogen inlet, and the flask was placed in an oil bath at 80°C. The molten MDI was placed in a feeding funnel and added to the flask containing the PHMO within 1 min. After the addition of MDI was completed, the reaction mixture in the flask was further reacted for 2 h to obtain the macromolecular alcohol PHMO-MDI-PHMO. The completion of the reaction was confirmed by the disappearance of the absorption peak of -NCO at 2270 cm -1 in the Fourier transform infrared (FTIR) spectrum.

[0084] The macromolecular alcohol has the structure of Formula 2:

[0085]

[0086] wherein x is an integer in the range of 1-14, and y is an integer in the range of 1-14.

[0087] The MDI has the structure of Formula 3:

[0088]

[0089] Preparation of linear copolymer

[0090] All glassware was dried overnight at 105°C before use. The molten MDI was weighed into a three necked round bottom flask equipped with a mechanical stirrer and nitrogen inlet, and the flask was placed in a 70°C oil bath. The pre-dried mixture of macrodiol PHMO-MDI-PHMO and polydimethylsiloxane (i.e. macrodiol flexible segment) was added rapidly to the flask using an addition funnel while stirring. After the addition was complete, the reaction mixture in the flask was heated to 80°C by the oil bath and stirred continuously under nitrogen for 2h to homogeneity, resulting in a prepolymer.

[0091] Polydimethylsiloxane (abbreviated as "PDMS") has the structure of Formula 4:

[0092]

[0093] wherein z is an integer in the range of 1-19.

[0094] The prepolymer was first chain-extended with BHTD and stirred for 2 hours under nitrogen. Solvent dimethylacetamide (abbreviated as "DMAc") was added to obtain a transparent intermediate prepolymer solution. EDA was added dropwise into the cooled reaction solution and stirred slowly. The whole reaction temperature was controlled within 10°C. After the addition of EDA was complete, the solution was stirred for another 30 minutes until all MDI reacted with the chain extender EDA. When the solution viscosity increased, the stirring was stopped and a linear copolymer was obtained.

[0095] Preparation of crosslinked copolymer

[0096] The linear copolymer was heated to 80°C and continued to be stirred. Multifunctional compound HDI polymer was added, which can be specifically selected from HT-100, and the reaction was continued for 30 minutes to obtain a clear solution, i.e. a crosslinked copolymer.

[0097] The crosslinked copolymer was added with perfluoroalkyl propanol under nitrogen and the reaction was continued for 2 hours to obtain a stain-resistant crosslinked polymer.

[0098] wherein the crosslinked polymer structure of the stain-resistant crosslinked polymer is shown in Figure 1 , Figure 1The middle curve represents the linear polymer, the round ball represents the crosslinking agent, and the arrow represents the anti-fouling functional unit. The linear polymer and the crosslinking agent are mixed and reacted, and the linear polymer is crosslinked through the functional groups of the crosslinking agent. The linear polymer is crosslinked by selecting a crosslinking agent with a functionality of not less than 3, so that after the linear polymer reacts with the crosslinking agent, the end groups of the linear polymer are suspended on the side chain of the linear molecular chain of the crosslinked product, that is, the crosslinked polymer has functional groups suspended on the side chain of the linear molecular chain. The crosslinked polymer with suspended active groups reacts with the anti-fouling agent perfluoroalkyl propanol, and the perfluoroalkyl propanol reacts with the groups suspended on the side chain of the linear molecular chain through its active groups, thereby introducing the anti-fouling agent into the polymer system and suspending it outside the polymer molecular main chain.

[0099] The anti-fouling agent is selected to be a monofunctional compound, ensuring that each suspended functional group of the crosslinked polymer reacts with a single functional group of the anti-fouling agent, thereby linking an anti-fouling functional group to each crosslinked functional group of the crosslinked polymer, so that the formed anti-fouling crosslinked polymer has anti-fouling functional groups suspended on the side chain of the linear molecular chain.

[0100] The anti-fouling solution is coated into a film. The specific steps are as follows: the anti-fouling solution is coated on a coating machine at 50°C, evaporated in a nitrogen oven at 60°C for 24h, and then further dried in a vacuum environment of 0.1 mbar for 24h. The anti-fouling film is peeled off from the culture dish after soaking in water for about 30min. Finally, it is dried at 50°C in a vacuum environment of 0.1 mbar for 24h to remove water. Then, it is annealed at 125°C for 2h to obtain an anti-fouling elastomer film with a thickness of 0.2mm-0.3mm, as shown in Figure 2 The anti-fouling functional unit exists on the surface of the film after the anti-fouling film is formed, providing anti-fouling performance. The weight ratio of the above raw materials is according to Table 1. The anti-fouling material can be detected by Fourier transform infrared (FTIR) spectroscopy to confirm the material structure.

[0101] Example 3

[0102] Preparation of macromolecular alcohol

[0103] 700g / mol polyoxymethylene hexamethylene (PHMO) is dried at 0.1 mbar and 105°C for 15h, and the pre-dried PHMO is accurately weighed and placed in a three-necked round-bottom flask equipped with a magnetic stirrer and a nitrogen inlet, and the flask is placed in an oil bath at 80°C. 4.6g of molten MDI is placed in a feeding funnel and added to the flask containing PHMO within 1 minute. After the addition of MDI is completed, the reaction mixture in the flask is further reacted for 2h to obtain macromolecular alcohol PHMO-MDI-PHMO. The -NCO in the Fourier transform infrared (FTIR) spectrum of the macromolecular alcohol PHMO-MDI-PHMO is at 2270cm -1The completion of the reaction is confirmed by the disappearance of the absorption peak at 1720 cm"1.

[0104] The macromolecular diol A has the structure of Formula 2:

[0105]

[0106] wherein x is an integer in the range of 1-14 and y is an integer in the range of 1-14.

[0107] The MDI has the structure of Formula 3:

[0108]

[0109] Preparation of linear copolymer

[0110] All glassware is dried overnight at 105°C before use. The molten MDI is weighed into a three-necked round bottom flask equipped with a mechanical stirrer and nitrogen inlet, and the flask is placed in an oil bath at 70°C. The pre-dried mixture of macromolecular diol PHMO-MDI-PHMO and polydimethylsiloxane (i.e., macrodiol flexible segment) is added rapidly to the flask using an addition funnel while stirring. After the addition is complete, the reaction mixture in the flask is heated to 80°C by the oil bath and stirred continuously under nitrogen for 2 h to homogeneity, resulting in a prepolymer.

[0111] The polydimethylsiloxane (abbreviated as "PDMS") has the structure of Formula 4:

[0112]

[0113] wherein z is an integer in the range of 1-19.

[0114] The prepolymer is first chain-extended with BHTD and stirred for 2 hours under nitrogen. Solvent anhydrous dimethylacetamide (abbreviated as "anhydrous DMAc") is added to obtain a transparent intermediate prepolymer solution. EDA in 3 mL of DMAc is added dropwise into the cooled reaction solution and stirred slowly, with the whole reaction temperature controlled within 10°C. After the complete addition of EDA, it is stirred for another 30 minutes until all MDI is reacted with the chain extender EDA. When the solution viscosity increases, the stirring is stopped to obtain the linear copolymer.

[0115] Preparation of crosslinked copolymer

[0116] The linear copolymer is heated to 80°C and continues to be stirred. The polyfunctional compound HDI polymer, which can be specifically selected from HT-100, is added and continues to react for 30 minutes to obtain a clear solution, i.e., the crosslinked copolymer.

[0117] Preparation of stain-resistant crosslinked polymer

[0118] The cross-linking copolymer is added with hydroxyl silicone oil (optional brand Shin-etsu X-22-170BX) under nitrogen, and the reaction is continued for 2 hours to obtain the anti-fouling cross-linking polymer.

[0119] The cross-linking polymer structure of the anti-fouling cross-linking polymer is shown in Figure 1 , Figure 1 The middle curve represents a linear polymer, the round ball represents a cross-linking agent, and the arrow represents an anti-fouling functional unit. The linear polymer is mixed and reacted with the cross-linking agent. The linear polymer is cross-linked by the functional groups of the cross-linking agent. The cross-linking agent with a functionality of not less than 3 is selected for cross-linking. After the linear polymer is reacted with the cross-linking agent, the end groups of the linear polymer are suspended on the side chains of the linear molecular chains of the cross-linking product, i.e., the cross-linking polymer has functional groups suspended on the side chains of the linear molecular chains. The cross-linking polymer with suspended active groups is reacted with the anti-fouling auxiliary hydroxyl silicone oil. The hydroxyl silicone oil is chemically reacted with the groups suspended on the side chains of the linear molecular chains through its active groups, so as to introduce the anti-fouling auxiliary into the polymer system and suspend it outside the main chain of the polymer molecule.

[0120] The anti-fouling auxiliary is selected as a monofunctional compound to ensure that each suspended functional group of the cross-linking polymer is reacted with a single functional group of the anti-fouling auxiliary, so that an anti-fouling functional group is correspondingly linked to each cross-linking functional group of the cross-linking polymer, so that the formed anti-fouling cross-linking polymer has anti-fouling functional groups suspended on the side chains of the linear molecular chains.

[0121] The anti-fouling solution is coated into a film. The specific steps are as follows: the anti-fouling solution is coated on a coating machine at 50°C, evaporated in a nitrogen oven at 60°C for 24h, and then further dried in a vacuum environment of 0.1 mbar for 24h. The anti-fouling film is peeled off from the culture dish after being soaked in water for about 30min. Finally, it is dried at 50°C in a vacuum environment of 0.1 mbar for 24h to remove water. Then, it is annealed at 125°C for 2h to obtain an anti-fouling elastomer film with a thickness of 0.2mm-0.3mm, as shown in Figure 2 The weight ratio of the above raw materials is according to Table 1. The anti-fouling material can be subjected to Fourier transform infrared (FTIR) spectrum detection to confirm the material structure.

[0122] Example 4

[0123] Preparation of macromolecular alcohol

[0124] Polyhexamethylene oxide (abbreviated as "PHMO") of 700 g / mol was dried under vacuum at 0.1 mbar and 105 °C for 15 h. The pre-dried PHMO was accurately weighed into a three-necked round bottom flask equipped with a magnetic stirrer and a nitrogen inlet, and the flask was placed in an oil bath at 80 °C. The molten MDI was placed in an addition funnel and added to the flask containing the PHMO over a period of 1 min with stirring. After the addition of MDI was complete, the reaction mixture in the flask was further reacted for 2 h to give the macroalcohol PHMO-MDI-PHMO. The completion of the reaction was confirmed by the disappearance of the absorption peak of -NCO at 2270 cm -1

[0125] The macroalcohol A has the structure of Formula 2:

[0126]

[0127] wherein x is an integer in the range of 1-14 and y is an integer in the range of 1-14.

[0128] The MDI has the structure of Formula 3:

[0129]

[0130] Preparation of the linear copolymer

[0131] All glassware was dried at 105 °C overnight before use. The molten MDI was weighed into a three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet, and the flask was placed in an oil bath at 70 °C. The pre-dried mixture of macroalcohol PHMO-MDI-PHMO and polydimethylsiloxane (i.e., macrodiol flexible segment) was quickly added to the flask using an addition funnel while stirring. After the addition was complete, the reaction mixture in the flask was heated to 80 °C by the oil bath and stirred continuously under nitrogen for 2 h to homogeneity to give the prepolymer.

[0132] The polydimethylsiloxane (abbreviated as "PDMS") has the structure of Formula 4:

[0133] wherein z is an integer in the range of 1-19.

[0134] The prepolymer was first chain-extended with BHTD and stirred for 2 h under nitrogen. Solvent anhydrous dimethylacetamide (abbreviated as "anhydrous DMAc") was added to give a clear intermediate prepolymer solution. EDA in 3 mL of DMAc was added dropwise into the cooled reaction solution with slow stirring, and the whole reaction temperature was controlled within 10 °C. After the addition of EDA was complete, the stirring was continued for another 30 min until all the MDI reacted with the chain extender EDA. The stirring was stopped when the solution viscosity increased to give the linear copolymer.​

[0135] Preparation of cross-linked copolymer

[0136] The linear copolymer was heated to 80°C and stirring was continued. The multifunctional compound glycerol was added and the reaction was continued for 30 minutes to obtain a clear solution, i.e. the cross-linked copolymer.

[0137] Preparation of anti-fouling cross-linked polymer

[0138] The cross-linked copolymer was added with amino silicone oil (optional brand DOWSIL 2-8566) under nitrogen and the reaction was continued for 2 hours to obtain the anti-fouling cross-linked polymer.

[0139] The cross-linked polymer structure of the anti-fouling cross-linked polymer is shown in Figure 1 , Figure 1 The middle curve represents the linear polymer, the round ball represents the cross-linking agent, and the arrow represents the anti-fouling functional unit. The linear polymer is mixed and reacted with the cross-linking agent, and the linear polymer is cross-linked through the functional groups of the cross-linking agent. Since the cross-linking agent with a functional degree not less than 3 is selected for cross-linking, after the linear polymer reacts with the cross-linking agent, the end groups of the linear polymer are suspended on the side chain of the linear molecular chain of the cross-linked product, i.e. the cross-linked polymer has functional groups suspended on the side chain of the linear molecular chain. The cross-linked polymer with suspended active groups reacts with the anti-fouling additive amino silicone oil, and the amino silicone oil reacts with the groups suspended on the side chain of the linear molecular chain through its active groups, thereby introducing the anti-fouling additive into the polymer system and suspending it outside the polymer molecular main chain.

[0140] The anti-fouling additive is selected as a monofunctional compound to ensure that each suspended functional group of the cross-linked polymer reacts with a single functional group of the anti-fouling additive, thereby linking an anti-fouling functional group to each cross-linked functional group of the cross-linked polymer, so that the formed anti-fouling cross-linked polymer has anti-fouling functional groups suspended on the side chain of the linear molecular chain.

[0141] The anti-fouling solution was coated into a film. The specific steps are as follows: the anti-fouling solution was coated on a coating machine at 50°C, evaporated in a nitrogen oven at 60°C for 24h, and then further dried in a vacuum environment of 0.1 mbar for 24h. The anti-fouling film was peeled off from the culture dish after soaking in water for about 30min. Finally, it was dried at 50°C in a vacuum environment of 0.1 mbar for 24h to remove water. Then, it was annealed at 125°C for 2h to obtain an anti-fouling elastomer film with a thickness of 0.2mm-0.3mm, as shown in Figure 2 The weight ratio of the above raw materials is according to Table 1. Fourier transform infrared (FTIR) spectroscopy can be used to detect the structure of the anti-fouling material.

[0142] Example 5

[0143] Preparation of macrodiols

[0144] A macrodiol, polyoxohexamethylene (abbreviated as "PHMO") of 700 g / mol, was dried under vacuum at 0.1 mbar and 105 °C for 15 h. The pre-dried PHMO was accurately weighed into a three-necked round bottom flask equipped with a magnetic stirrer and a nitrogen inlet, and the flask was placed in an oil bath at 80 °C. The molten MDI was placed in an addition funnel and added to the flask containing the PHMO over a period of 1 min with stirring. After the addition of MDI was complete, the reaction mixture in the flask was further reacted for 2 h to obtain the macrodiol PHMO-MDI-PHMO. The completion of the reaction was confirmed by the disappearance of the absorption peak of -NCO at 2270 cm"1 in the Fourier transform infrared (abbreviated as "FTIR") spectrum. -1

[0145] The macrodiol A has the structure of Formula 2:

[0146]

[0147] wherein x is an integer in the range of 1-14 and y is an integer in the range of 1-14.

[0148] The MDI has the structure of Formula 3:

[0149]

[0150] Preparation of linear copolymer

[0151] All glassware was dried at 105 °C overnight before use. The molten MDI was weighed into a three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet, and the flask was placed in an oil bath at 70 °C. The pre-dried mixture of macrodiol PHMO-MDI-PHMO and polydimethylsiloxane (i.e., macrodiol flexible segment) was quickly added to the flask using an addition funnel while stirring. After the addition was complete, the reaction mixture in the flask was heated to 80 °C by the oil bath and continuously stirred under nitrogen for 2 h to homogeneity to produce the prepolymer.

[0152] The polydimethylsiloxane (abbreviated as "PDMS") has the structure of Formula 4:

[0153]

[0154] wherein z is an integer in the range of 1-19.

[0155] ​The prepolymer is first chain-extended with BHTD, stirring the reaction under nitrogen for 2 hours, adding solvent anhydrous dimethylacetamide (abbreviated as "anhydrous DMAc") to obtain a transparent intermediate prepolymer solution. EDA in 3 mL of DMAc is dropped into the cooled reaction solution, slowly stirring, and the whole reaction temperature needs to be controlled within 10°C. After the complete addition of EDA, stirring for another 30 minutes until all MDI is reacted with the chain extender EDA. When the solution viscosity increases, stop stirring to obtain a linear polymer.

[0156] Preparation of crosslinked copolymer

[0157] The linear copolymer is heated to 80°C and continues to stir. A multifunctional compound HDI polymer is added, which can be specifically selected from HT-100, and continues to react for 30 minutes to obtain a clear solution, i.e. a crosslinked copolymer.

[0158] Preparation of anti-fouling crosslinked polymer

[0159] The crosslinked copolymer is added with carboxyl silicone oil (optionally with the brand of Shin-etsu X-22-3710) under nitrogen, and continues to react for 2 hours to obtain an anti-fouling crosslinked polymer.

[0160] The crosslinked polymer structure of the anti-fouling crosslinked polymer is shown in Figure 1 , Figure 1 The middle curve represents a linear polymer, the round ball represents a crosslinking agent, and the arrow represents an anti-fouling functional unit. The linear polymer is mixed and reacted with the crosslinking agent, and the linear polymer is crosslinked through the functional groups of the crosslinking agent. Since the crosslinking agent with a functionality of not less than 3 is used for crosslinking, after the linear polymer is reacted with the crosslinking agent, the terminal groups of the linear polymer are suspended on the side chain of the linear molecular chain of the crosslinked product, i.e. the crosslinked polymer has functional groups suspended on the side chain of the linear molecular chain. The crosslinked polymer with suspended active groups is reacted with the anti-fouling aid carboxyl silicone oil, and the carboxyl silicone oil is chemically reacted with the groups suspended on the side chain of the linear molecular chain through its active groups, so as to introduce the anti-fouling aid into the polymer system and suspend it outside the main chain of the polymer molecule.

[0161] The anti-fouling aid is selected to be a monofunctional compound, which ensures that each suspended functional group of the crosslinked polymer is reacted with a single functional group of an anti-fouling aid, so that an anti-fouling functional group is linked to each crosslinked functional group of the crosslinked polymer, so that the anti-fouling crosslinked polymer formed has anti-fouling functional groups suspended on the side chain of the linear molecular chain.

[0162] The anti-fouling solution was coated to form a film. The specific steps were as follows: the anti-fouling solution was coated on a coater at 50°C, evaporated in a nitrogen oven at 60°C for 24 h, and then further dried in a vacuum environment at 0.1 mbar for 24 h. The anti-fouling film was peeled off from the petri dish after being soaked in water for about 30 min. Finally, it was dried at 50°C in a vacuum environment at 0.1 mbar for 24 h to remove moisture. Then, it was annealed at 125°C for 2 h to obtain an anti-fouling elastomer film with a thickness of 0.2 mm-0.3 mm, as shown in Figure 2 Figure 1. After the anti-fouling film was formed, the anti-fouling functional units existed on the surface of the film to provide anti-fouling properties. The weight ratio of the above raw materials was according to the ratio of Table 1. The anti-fouling material can be subjected to Fourier transform infrared (FTIR) spectroscopy detection to confirm the material structure.

[0163] Example 6

[0164] Preparation of macromolecular alcohol

[0165] The polyoxymethylene hexamethylene (PHMO) with a molecular weight of 700 g / mol was dried at 0.1 mbar and 105°C for 15 h. The pre-dried 32.25 g of PHMO was accurately weighed and placed in a three-necked round-bottom flask equipped with a magnetic stirrer and a nitrogen inlet, and the flask was placed in an oil bath at 80°C. 4.6 g of molten MDI was placed in a feeding funnel and added into the flask containing PHMO within 1 min. After the addition of MDI was completed, the reaction mixture in the flask was further reacted for 2 h to obtain the macromolecular alcohol PHMO-MDI-PHMO. The completion of the reaction was confirmed by the disappearance of the absorption peak of -NCO at 2270 cm -1 in the Fourier transform infrared (FTIR) spectrum.

[0166] The macromolecular alcohol A has the structure of Formula 2:

[0167]

[0168] wherein x is an integer in the range of 1-14, and y is an integer in the range of 1-14.

[0169] The MDI has the structure of Formula 3:

[0170]

[0171] Preparation of linear copolymer

[0172] All glassware was dried overnight at 105°C before use. The molten MDI was weighed into a three necked round bottom flask equipped with a mechanical stirrer and nitrogen inlet, and the flask was placed in a 70°C oil bath. The pre-dried mixture of macrodiol PHMO-MDI-PHMO and polydimethylsiloxane (i.e. macrodiol flexible segment) was added rapidly to the flask using an addition funnel while stirring. After the addition was complete, the reaction mixture in the flask was heated to 80°C by the oil bath and stirred continuously under nitrogen for 2h to homogeneity, resulting in a prepolymer.

[0173] Polydimethylsiloxane (abbreviated as "PDMS") has the structure of Formula 4:

[0174]

[0175] wherein z is an integer in the range of 1-19.

[0176] The prepolymer was first chain extended with BHTD and stirred for 2 hours under nitrogen. Solvent dimethylacetamide (abbreviated as "DMAc") was added to obtain a transparent intermediate prepolymer solution. EDA in 3 mL of DMAc was added dropwise into the cooled reaction solution and stirred slowly. The whole reaction temperature was controlled within 10°C. After the addition of EDA was complete, the solution was stirred for another 30 minutes until all MDI reacted with the chain extender EDA. When the solution viscosity increased, the stirring was stopped and a linear copolymer was obtained.

[0177] Preparation of crosslinked copolymer

[0178] The linear copolymer was heated to 80°C and continued to stir. Multifunctional compound HDI polymer was added, which can be selected from HT-100, and the reaction was continued for 30 minutes to obtain a clear solution, i.e. crosslinked copolymer.

[0179] Preparation of stain resistant crosslinked polymer

[0180] The crosslinked copolymer was added with hydroxyl silicone oil (optionally Shin-etsu X-22-170BX) under nitrogen and the reaction was continued for 2 hours to obtain a stain resistant crosslinked polymer.

[0181] wherein the crosslinked polymeric structure of the crosslinked polymer is shown in Figure 1 , Figure 1The middle curve represents the linear polymer, the round ball represents the crosslinking agent, and the arrow represents the anti-fouling functional unit. The linear polymer and the crosslinking agent are mixed and reacted, and the linear polymer is crosslinked through the functional groups of the crosslinking agent. The linear polymer is crosslinked by selecting a crosslinking agent with a functionality of not less than 3, so that after the linear polymer reacts with the crosslinking agent, the end groups of the linear polymer are suspended on the side chain of the linear molecular chain of the crosslinked product, that is, the crosslinked polymer has functional groups suspended on the side chain of the linear molecular chain. The crosslinked polymer with suspended active groups reacts with the anti-fouling aid hydroxyl silicone oil, and the hydroxyl silicone oil chemically reacts with the groups suspended on the side chain of the linear molecular chain through its active groups, thereby introducing the anti-fouling aid into the polymer system and suspending it outside the polymer molecular main chain.

[0182] The anti-fouling aid is selected to be a monofunctional compound, which ensures that each suspended functional group of the crosslinked polymer reacts with a single functional group of an anti-fouling aid, thereby linking an anti-fouling functional group to each crosslinked functional group of the crosslinked polymer, so that the formed anti-fouling crosslinked polymer has anti-fouling functional groups suspended on the side chain of the linear molecular chain.

[0183] The anti-fouling solution is coated into a film. The specific steps are as follows: the anti-fouling solution is coated on a coating machine at 50°C, evaporated in a nitrogen oven at 60°C for 24h, and then further dried in a vacuum environment of 0.1 mbar for 24h. The anti-fouling film is peeled off from the petri dish after being soaked in water for about 30min. Finally, it is dried at 50°C in a vacuum environment of 0.1 mbar for 24h to remove water. Then, it is annealed at 125°C for 2h to obtain an anti-fouling elastomer film with a thickness of 0.2mm-0.3mm, as shown in Figure 2 The anti-fouling functional units exist on the surface of the film after the anti-fouling film is formed, to provide anti-fouling performance. The weight ratio of the above raw materials is according to Table 1. The anti-fouling material can be detected by Fourier transform infrared (FTIR) spectroscopy to confirm the material structure.

[0184] Comparative Example 1

[0185] Preparation of macromolecular alcohol

[0186] 700g / mol polyoxymethylene hexamethylene (PHMO) is dried at 0.1 mbar and 105°C for 15h, and the pre-dried PHMO is accurately weighed and placed in a three-necked round-bottom flask equipped with a magnetic stirrer and a nitrogen inlet, and the flask is placed in an oil bath at 80°C. The molten MDI is placed in a feeding funnel and added into the flask containing PHMO within 1 minute. After the addition of MDI is completed, the reaction mixture in the flask is further reacted for 2h to obtain macromolecular alcohol PHMO-MDI-PHMO. The -NCO in the Fourier transform infrared (FTIR) spectrum of the macromolecular alcohol PHMO-MDI-PHMO is at 2270cm -1The completion of the reaction is confirmed by the disappearance of the absorption peak at 1720 cm"1.

[0187] The macrodiol has the structure of Formula 2:

[0188]

[0189] wherein x is an integer in the range of 1-14 and y is an integer in the range of 1-14.

[0190] The MDI has the structure of Formula 3:

[0191]

[0192] Preparation of Linear Copolymer

[0193] All glassware was dried overnight at 105°C before use. The molten MDI was weighed into a three-necked round bottom flask equipped with a mechanical stirrer and nitrogen inlet, and the flask was placed in an oil bath at 70°C. The mixture of pre-dried macrodiol PHMO-MDI-PHMO and polydimethylsiloxane (i.e., macrodiol flexible segment) was added rapidly to the flask using an addition funnel while stirring. After the addition was complete, the reaction mixture in the flask was heated to 80°C by the oil bath and stirred continuously under nitrogen for 2 h to homogeneity, resulting in a prepolymer.

[0194] The polydimethylsiloxane (abbreviated as "PDMS") has the structure of Formula 4:

[0195]

[0196] wherein z is an integer in the range of 1-19.

[0197] The prepolymer was first chain-extended with BHTD. Solvent dimethylacetamide (abbreviated as "DMAc") was added to obtain a transparent intermediate prepolymer solution. EDA in 3 mL DMAc was added dropwise into the cooled reaction solution, and the whole reaction temperature was controlled within 10°C. After the complete addition of EDA, the solution was stirred for another 30 minutes until all MDI reacted with the chain extender EDA. When the solution viscosity increased, the stirring was stopped, and a linear copolymer was obtained.

[0198] Preparation of Crosslinked Copolymer

[0199] The linear copolymer was heated to 80°C and continued to be stirred. The polyfunctional compound HDI polymer, specifically HT-100, was added, and the reaction was continued for 30 minutes to obtain a clear solution, i.e., a crosslinked copolymer.

[0200] wherein the crosslinked polymeric structure of the crosslinked copolymer is shown in Figure 3 , Figure 3The middle curve represents a linear polymer, and the round ball represents a crosslinking agent. The linear polymer is mixed with the crosslinking agent and reacts to crosslink the linear polymer through the functional groups of the crosslinking agent.

[0201] The solution was coated into a film. The specific steps were as follows: the solution was coated on a coating machine at 50 DEG C, evaporated in a nitrogen oven at 60 DEG C for 24 h, and then further dried in a vacuum environment of 0.1 mbar for 24 h. The film was peeled off from the petri dish after being soaked in water for about 30 min. Finally, it was dried at 50 DEG C in a vacuum environment of 0.1 mbar for 24 h to remove moisture. Then, it was annealed at 125 DEG C for 2 h to obtain an elastomer film with a thickness of 0.2 mm-0.3 mm. The weight ratio of the above raw materials was according to the ratio of Table 1.

[0202] Table 1

[0203]

[0204] Test experiment:

[0205] The film material prepared according to the method shown in Examples 1-6 and Comparative Example 1 above was subjected to tensile property determination according to GBT 1040.3-2006. In vitro cytotoxicity test was performed according to the method shown in GB / T 16886.5-2017. In vitro hemolysis performance test was performed according to the method shown in GB / T 16886.4-2022. The test results are shown in Table 2.

[0206] Table 2

[0207] Performance parameters Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Tensile strength MPa 18.5 18.9 21.0 20.1 23.5 24.1 27.6 Elastic modulus MPa 21.2 22.4 24.3 23.8 27.2 26.5 31.2 Elongation at break % 725 705 640 708 624 688 541 Cytotoxicity ○ ○ ○ ○ ○ ○ ○ Hemolysis ○ ○ ○ ○ ○ ○ ○ Calcification (the bigger the number the better) 1 2 3 3 4 4 5 Thrombosis (the bigger the number the better) 1 1 3 2 4 4 5

[0208] Note: o represents test qualified, non-toxic or no hemolysis. It can be found from the above experimental data that:

[0209] On the one hand, the anti-fouling material prepared by the preparation method provided in the examples of the present application can significantly improve the anti-calcification and anti-thrombosis ability of the material compared with the preparation method of functional expansion without adding anti-fouling aids (Comparative Example 1), and the anti-fouling performance of Example 6 is optimal.

[0210] On the other hand, the anti-fouling material provided in the examples of the present application has no potential toxic effect on L929 cells.

[0211] On the other hand, direct contact with the anti-fouling material provided in the examples of the present application has no effect on hemolysis performance.

[0212] In addition, the anti-fouling material provided in the examples of the present application has excellent biocompatibility and can be used as a raw material for implantation / intervention medical devices. The implantation / intervention medical devices can include heart valves, biological implants, and drug delivery devices, etc. The preparation method provided in the examples of the present application is also more simple and easy to control.

[0213] Although specific embodiments have been described above, these embodiments are not intended to limit the scope of the present disclosure, even if only a single embodiment is described with respect to a particular feature. The examples of features provided in the present disclosure are intended to be illustrative rather than restrictive. In practice, one or more features of a dependent claim can be combined with features of the independent claim to which the dependent claim relates, and the features from the respective independent claims can be combined in any appropriate manner rather than only the specific combinations enumerated in the claims.

[0214] Although the present disclosure has been described with reference to the above embodiments, the present disclosure is not limited to the above embodiments. Any person skilled in the art, without departing from the spirit and scope of the present disclosure, can make various modifications and changes, and the scope of protection of the present disclosure should be limited by the scope defined in the claims.

Claims

1. An anti-fouling material, characterized by, A linear polymer obtained by sequentially copolymerizing a flexible segment with a curing agent and a chain extender, and then sequentially reacting with a crosslinking agent and an anti-fouling aid; The flexible segment is composed of a macrodiol composed of a mixture of a macromolecular alcohol and a polydimethylsiloxane; wherein the weight ratio of the macromolecular alcohol to the polydimethylsiloxane is 1:4; the weight ratio of the macrodiol, the curing agent, the chain extender, the crosslinking agent, the anti-fouling aid is (40-55):(30-36):(12-15):(0.07-1.12):(1-10); The raw material of the macromolecular alcohol is selected from at least one of poly( hexylene oxide), poly( heptylene oxide), poly( octylene oxide), poly( decamethylene oxide), polydimethylsiloxane diol, poly( butadiene) diol, poly( carbonate) diol, poly( isobutylene) diol, dimethylsiloxane diol, polyhexamethylene oxide, polyoctanediol, polydecadiol, and polytetrahydrofuran diol, obtained by reacting at least one of the above raw materials with a curing agent; The curing agent includes at least one diisocyanate; The chain extender includes at least one diol and at least one diamine; the diol is 1,3 bis(4-hydroxybutyl)-1,1,3,3 tetramethyldisiloxane; the diamine is 1,2 ethylenediamine; The crosslinking agent includes at least one isocyanate with a functionality not less than 3; The anti-fouling aid includes a monofunctional fluorine-containing compound and / or a monofunctional silicon-containing compound; the compound contains active groups, the active groups include at least one of hydroxyl and amino; the terminal of the linear polymer has a group corresponding to the active group; after the linear polymer sequentially reacts with the crosslinking agent and the anti-fouling aid, the anti-fouling functional groups of the anti-fouling aid are suspended outside the polymer molecular main chain; The linear polymer has a repeating unit structure of formula 1: ， Wherein, A is the at least one diol and at least one diamine, B is the diisocyanate, C is the macromolecular alcohol, D is the polydimethylsiloxane; n is an integer of 1-100, m is an integer of 1-100, p is an integer of 1-100.

2. The stain resistant material of claim 1, wherein, The diisocyanate includes at least one of aliphatic isocyanate and aromatic isocyanate; the aliphatic isocyanate includes at least one of hexamethylene diisocyanate and isophorone diisocyanate; the aromatic isocyanate includes diphenylmethane diisocyanate.

3. The stain resistant material of claim 1, wherein, The isocyanate with a functionality not less than 3 includes at least one of MDI polymer, HDI polymer, IPDI polymer, TDI polymer, and PDI polymer.

4. The stain resistant material of claim 1, wherein, The monofunctional fluorine-containing compound includes at least one of perfluoroalkyl propanol, perfluoroundecanol, heptafluoropentan-2-ol, 4-heptadecafluorodecyl benzyl alcohol, undecafluoro-n-hexan-1-ol, and perfluoropolyether alcohol; the monofunctional silicon-containing compound includes at least one of hydroxyl silicone oil and amino silicone oil.

5. The method of making a stain resistant material according to any one of claims 1-4, wherein, The method includes the following steps: mixing a macrodiol and a curing agent to obtain a prepolymer; mixing the prepolymer with a chain extender to chain extend the prepolymer to obtain a linear polymer; mixing and reacting the linear polymer with a crosslinking agent and an antifouling aid in sequence to obtain an antifouling solution; coating the antifouling solution into a film to obtain the antifouling material.

6. The antifouling material according to any one of claims 1-4, or prepared by the method of claim 5, for use as a raw material for a medical implant / interventional device.

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