Application of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials

Abstract

The present invention provides a functional isocyanate crosslinking agent for surface modification of polyvinyl chloride materials. The functional isocyanate crosslinking agent has a polyether chain in its molecular structure, and the two ends of the polyether chain are respectively connected to sulfobetaine and isocyanate groups. The isocyanate group can chemically crosslink and modify the polyvinyl chloride material whose surface has been activated; at the same time, the isocyanate group is used as a spacer arm to "brush" and comb-bond the sulfobetaine unit on the surface of the polyvinyl chloride material through the polyether chain, thereby giving the polyvinyl chloride surface strong hydrophilicity, wet lubricity after water wetting, conductivity, antibacterial property, antifogging and antifouling, anticoagulation and mechanical property enhancement effects.

Description

Technical Field

[0001] The invention relates to the application of a functional isocyanate crosslinking agent in the surface modification of polyvinyl chloride materials, and particularly to the application of a functional isocyanate crosslinking agent containing bissulfobetaine, gemini quaternary ammonium salt and polyether chain in the molecular structure for crosslinking and modifying the surface of polyvinyl chloride to achieve hydrophilicity, antibacterial, anticoagulant and enhanced biocompatibility, and belongs to the field of functional polymer materials. Technical Background

[0002] Polyvinyl chloride is a thermoplastic synthetic material with excellent mechanical properties and low cytotoxicity. Due to its low price, it is often used as a raw material for the production of medical catheters, hemodialysis tubing, blood storage bags, urine storage bags, etc. However, the hydrophobicity of the surface of polyvinyl chloride materials affects the water-lubricated contact between human tissue or blood and it. In addition, when polyvinyl chloride catheters are placed in the human body for a long time, it is common for bacteria to attach and grow on their surfaces and cause infection. For this reason, people have been tirelessly researching and developing issues such as the hydrophilicity, antibacterial properties, biocompatibility and anticoagulant properties of the surface of polyvinyl chloride materials.

[0003] The main method to improve the hydrophilicity, antibacterial property, anticoagulant property and biocompatibility of the surface of polyvinyl chloride materials is to graft three types of hydrophilic substances such as polyethylene glycol, carboxybetaine / sulfobetaine / phosphorylcholine, or heparin on its surface. Polyethylene glycol is a hydrophilic polymer. Because of its good anti-biological adhesion properties, it is widely used in the anti-bacterial adhesion of polyvinyl chloride materials. The principle is that it can form a hydration layer on the surface of polyvinyl chloride materials by hydrogen bonding with a large number of water molecules. Compared with protein and microbial adhesion, the hydration layer is a physical barrier that can effectively prevent bacteria from adhering, colonizing and growing on the surface of polyvinyl chloride materials. Zwitterions containing units such as carboxybetaine, sulfobetaine or phosphorylcholine have higher hydrophilicity and biocompatibility. They interact strongly with water molecules through ion solvation to produce a hydration layer, rather than the hydrogen bonded water molecules used by polyethylene glycol. At the same time, the exposure of its negative charge also shows the repulsion of negatively charged proteins and bacteria, so these zwitterionic units are grafted on the surface of polyvinyl chloride, making it show significant antifouling function. Heparin is a type of polysaccharide molecule containing a large number of sulfonic acid groups and carboxyl groups and uneven distribution. Its molecular weight is about 20,000, and its sulfur content is about 9-12.9%. It is acidic. At the same time, heparin is easy to absorb moisture and dissolve in water, and it has excellent anticoagulant properties.

[0004] So far, many reports have confirmed that chemical modification after surface activation treatment of polyvinyl chloride materials is the preferred method for the durable and firm surface modification of polyvinyl chloride materials. The so-called surface activation treatment of polyvinyl chloride materials mainly includes ① plasma treatment of polyvinyl chloride materials in a mixed atmosphere of O2, NH3, air, helium / oxygen or argon / oxygen, etc., to obtain the activation effect of surface hydroxylation, amination or carboxylation; ② There is also the use of polyvinyl chloride materials immersed in a dilute alkali solution for alkaline hydrolysis treatment to obtain the activation effect of surface hydroxylation; ③ The surface of the polyvinyl chloride after activation treatment is then treated with a silane coupling agent to introduce functional groups such as OH, NH2, epoxy, NCO, C=C double bonds, etc. on its surface, and then connect the hydrophilic substance by covalent bonding or graft polymerization.

[0005] Accordingly, according to the principle of molecular design, the present inventors have designed a functional isocyanate crosslinking agent for the modification of the surface of polyvinyl chloride materials by integrating the surface structural characteristics of surface activated polyvinyl chloride, the structural characteristics and functional applications of polyethylene glycol and sulfobetaine. The functional isocyanate crosslinking agent refers to a functional isocyanate crosslinking agent containing disulfobetaine, gemini quaternary ammonium salt and polyether chain, and the two ends of the polyether chain in its molecular structure are respectively connected to sulfobetaine and quaternary ammonium salt and isocyanate group. Among them, the isocyanate group can covalently bond the polyvinyl chloride material with the surface activated; at the same time, the isocyanate group is used as a spacer arm to bond the sulfobetaine and gemini quaternary ammonium salt to the surface of the polyvinyl chloride material in a "brush-like" manner through the polyether chain, thereby giving the polyvinyl chloride surface strong hydrophilicity, wet lubrication, conductivity, antibacterial property, antifogging and antifouling, anticoagulation and mechanical property enhancement effects. The functional isocyanate crosslinking agent of the present invention is used for the surface modification of polyvinyl chloride materials, which is simple, convenient and easy to implement, and has a significant modification effect. Summary of the invention

[0006] The invention provides a functional isocyanate crosslinking agent containing bissulfobetaine, gemini quaternary ammonium salt and polyether chain in the molecular structure, which is applied to the modification of the surface of polyvinyl chloride material. The modification is achieved by adopting the following steps: at room temperature, immersing a surface activated polyvinyl chloride material in a functional isocyanate crosslinking agent solution containing bissulfobetaine, gemini quaternary ammonium salt and polyether chain in the molecular structure, and evenly immersing the surface activated polyvinyl chloride material; or spraying, rolling or brushing the functional isocyanate crosslinking agent solution on the surface activated polyvinyl chloride material, and then sending the surface activated polyvinyl chloride material into a reactor at 60-130 DEG C for heat treatment for 0.2-20 hours, and then taking the material out for cooling, so as to obtain a polyvinyl chloride material with bissulfobetaine, gemini quaternary ammonium salt and polyether chain bonded on the surface, which is called surface modified polyvinyl chloride material.

[0007] The surface activated polyvinyl chloride material refers to a surface clean polyvinyl chloride material which is subjected to plasma treatment in a plasma chamber with an oxygen, ammonia or air atmosphere, with a gas pressure of 30 to 50 Pa in the chamber, a temperature of 10 to 40° C. in the chamber, a radio frequency power of 50 to 500 watts, and an irradiation time of 50 to 500 seconds. After the plasma treatment, -OH (hydroxyl) groups or -NH2 (amino) groups are generated on the surface of the clean polyvinyl chloride material, which is called a surface activated polyvinyl chloride material; or the surface clean polyvinyl chloride material is immersed in an alkali solution with a mass percentage concentration of 0.01 to 10%, ultrasonically hydrolyzed at room temperature for 2 to 200 minutes, taken out and washed with deionizer until neutral, and vacuum dried at 60° C., -OH (hydroxyl) groups are generated on the surface of the clean polyvinyl chloride material, which is called a surface activated polyvinyl chloride material.

[0008] The clean polyvinyl chloride material refers to the polyvinyl chloride raw material that is washed with ethanol and deionized water in sequence, and then dried under vacuum at 60°C to obtain the surface clean polyvinyl chloride material;

[0009] The polyvinyl chloride raw material specifically includes one of polyvinyl chloride artificial organs, polyvinyl chloride catheters, polyvinyl chloride blood storage bags, polyvinyl chloride containers, polyvinyl chloride foams, polyvinyl chloride films, polyvinyl chloride filter membranes, polyvinyl chloride filter screens, polyvinyl chloride nonwoven fabrics or polyvinyl chloride fibers.

[0010] The alkaline solution refers to an aqueous solution of potassium hydroxide, sodium hydroxide, N,N,N-trimethyl-N-benzylammonium hydroxide, N,N,N-triethyl-N-benzylammonium hydroxide or N,N,N,N-tetrabutylammonium hydroxide.

[0011] The functional isocyanate cross-linking agent has a structure shown in general formula (A):

[0012]

[0013] Wherein R in the general formula (A) is selected from H or methyl, R1 and R2 are selected from C1 to C 18 A hydrocarbon group, wherein n is a natural number selected from 1 to 2000, and Y are selected from C1 to C 18 Hydrocarbylene, Selected from C1~C 18 Alkylene or One of the following, Q is selected from C1~C 18 Hydrocarbon or One of the following, where p is a natural number between 0 and 2000, and X - Refers to Cl - Br - ,I - or p-CH3C6H4SO3- One of them.

[0014] The mass percentage concentration of the functional isocyanate crosslinking agent in the functional isocyanate crosslinking agent solution is 0.5-50%, and the usage of the functional isocyanate crosslinking agent solution is 5-500% of the mass of the surface activated polyvinyl chloride material.

[0015] The preparation of the functional isocyanate crosslinking agent comprises the following steps: dissolving a dihydroxy diamine of the general formula (B) in an organic solvent at room temperature, stirring, slowly adding acryloyloxy polyether sulfobetaine, wherein the amount of acryloyloxy polyether sulfobetaine is 2.0 to 2.2 times the molar amount of the general formula (B), raising the reaction temperature to 50 to 90° C. after the addition of acryloyloxy polyether sulfobetaine is completed, and reacting for 2 to 20 hours; maintaining the reaction temperature, adding an alkylating agent to the reaction system, wherein the amount of the alkylating agent is 1.8 to 2.2 times the molar amount of the general formula (B), and reacting for 2 to 20 hours; sequentially adding a catalyst, a diluent and a polyisocyanate into the reaction system, continuing the reaction by heat preservation and stirring, detecting whether the NCO content in the material in the reactor is consistent with the predetermined value, and lowering the temperature of the reaction product system to room temperature to obtain a solution of a functional isocyanate crosslinking agent containing bissulfobetaine, gemini quaternary ammonium salt and a polyether chain in the molecular structure.

[0016] Wherein the general formula (B) refers to dihydroxydiamine, which has the structure shown in the general formula (B):

[0017]

[0018] Wherein the general formula (B) Selected from C1~C 18 Alkylene or One of the following, wherein p is selected from a natural number between 0 and 2000, and Y is selected from C1 to C 18 Alkylene.

[0019] The acryloxypolyether sulfobetaine has a structure shown in the general formula (C):

[0020]

[0021] Wherein R in the general formula (C) is selected from H or methyl, R1 and R2 are selected from C1 to C 18 The hydrocarbon group, wherein n is a natural number selected from 1 to 2000.

[0022] The organic solvent refers to one or more of tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide; the amount of the organic solvent used is 1 to 10 times the mass of the dihydroxydiamine of general formula (B).

[0023] The catalyst refers to a composite of organic tin and organic amine; wherein the organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, di(dodecylsulfide) dibutyltin or dibutyltin diacetate; the organic amine refers to one of triethylamine, p-dimethylaminopyridine, N,N-dimethylformamide, triethylenediamine, dialkylpiperazine, alkylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine carboxylate, dialkylpiperazine carboxylate or alkylimidazole carboxylate; the mass ratio of the organic tin to the organic amine is 1:0-1.5; the amount of the catalyst is 0.05-5% of the mass of the polyisocyanate of general formula (D).

[0024] The polyisocyanate has a structure shown in general formula (D):

[0025]

[0026] Wherein q in the general formula (D) is selected from a positive integer of 1 to 5, Selected from C1~C 18 alkylene;

[0027] The amount of the polyisocyanate used is 2.02 to 2.25 times the molar amount of the dihydroxydiamine of the general formula (B).

[0028] The diluent refers to one or more of acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide; the amount of the diluent is 1 to 10 times the mass of the dihydroxydiamine of general formula (B).

[0029] The functional isocyanate crosslinking agent molecular structure containing bissulfobetaine, gemini quaternary ammonium salt and polyether chain provided by the present invention has N + R1 and R2 can be selected from C1 to C2 according to the actual needs of functional modification of polyvinyl chloride materials and their performance changes. 18 Hydrocarbon; Secondly, if the main purpose is to enhance the tensile strength of polyvinyl chloride materials through cross-linking, The polyether chain of the acryloyloxy polyether betaine of general formula (C) can be selected to be shorter; if the modification is mainly for hydrophilicity, antifouling, biocompatibility, etc., the The polyether chain in the acryloxy polyether betaine of general formula (C) can be selected to be longer. The concentration of the functional isocyanate crosslinking agent solution used to modify the polyvinyl chloride material can be adjusted, and the number of modification treatments can be increased or decreased. In summary, the present invention provides a flexible and effective preferred method for surface modification of polyvinyl chloride materials using the functional isocyanate crosslinking agent. DETAILED DESCRIPTION

[0030] In order to further understand the present invention, it is specifically described by way of examples, the purpose of which is to better understand the content of the present invention. Therefore, the use of functional isocyanate crosslinking agents not listed in the examples for surface modification of polyvinyl chloride materials should not be regarded as limiting the scope of protection of the present invention.

[0031] Example 1 Modified polyvinyl chloride film (I-1)

[0032] Preparation and activation of polyvinyl chloride diaphragm: Dissolve 5 grams of SH-200 polyvinyl chloride powder produced by Shanghai Chlor-Alkali Chemical Co., Ltd. in 55 grams of tetrahydrofuran to prepare a solution, pour the polyvinyl chloride solution into a flat plate mold, and after the solvent evaporates naturally, make a film with a thickness of 0.2 mm, cut into 80*80 mm diaphragms, use ethanol and deionized water for ultrasonic washing in turn, and vacuum dry at 60°C for 10 hours to obtain a polyvinyl chloride diaphragm with a clean surface.

[0033] The surface-cleaned polyvinyl chloride film is placed in a plasma chamber, the O2 pressure in the chamber is 30 Pa, the temperature in the chamber is 35° C., the radio frequency power is 100 W, and the irradiation time is 100 seconds to obtain a surface-activated polyvinyl chloride film.

[0034] Preparation of functional isocyanate crosslinking agent solution of formula (A-1): dissolve 20 grams of N,N'-dihydroxyethylethylenediamine in 180 grams of tetrahydrofuran and put it into a reactor, start stirring, slowly add 90 grams of formula (c-1) at room temperature, raise the temperature to 45-50°C, react for 4 hours, then add 28 grams of benzyl chloride into the reactor, raise the temperature to 70°C and react for 12 hours, then add 0.22 grams of dibutyltin dilaurate, 0.15 grams of triethylenediamine, 120 grams of toluene and 45 grams of toluene diisocyanate into the reactor, continue stirring and heat preservation to react, detect the NCO value in the reaction product system and it is in the range of 4.55-4.88%, cool down and stop the reaction, and obtain a solution of isocyanate crosslinking agent with a structure shown in formula (A-1) containing bissulfobetaine, gemini quaternary ammonium salt and polyether chain.

[0035]

[0036] The product of formula (A-1) was tested by infrared spectroscopy. A strong peak of NCO appeared near 2270nm in its IR spectrum, a characteristic absorption peak belonging to carbamate NH appeared at 3482nm, and a characteristic peak of carbamate C=O appeared at 1726nm, which was consistent with the structural characteristics of formula (A-1). It was confirmed that the chemical structure of the product was consistent with the theoretical design of formula (A-1). The isocyanate group percentage in the isocyanate crosslinker solution containing bissulfobetaine in the structure shown in formula (1) was detected by the method specified in GB / T 29493.6-2013, and was 4.78%.

[0037] Surface modification of polyvinyl chloride membrane: At room temperature, the surface activated polyvinyl chloride membrane is immersed in the functional isocyanate crosslinking agent solution of formula (A-1). After being evenly dipped, it is sent into a reactor at 80-90°C for 6 hours. After that, it is taken out and cooled to obtain surface modified polyvinyl chloride membrane Ⅰ-1.

[0038] After the functional isocyanate crosslinking agent solution of formula (A-1) was diluted by 1 times with ethylene glycol dimethyl ether, the polyvinyl chloride film to be modified was treated in the same manner to obtain surface modified polyvinyl chloride film I-2.

[0039] After the functional isocyanate crosslinking agent solution of formula (1) was diluted by 1 time with ethylene glycol dimethyl ether, the modified polyvinyl chloride film I-2 was repeatedly treated with the same method to obtain the surface secondary modified polyvinyl chloride film I-3.

[0040] Example 2 Modified polyvinyl chloride film (II-1)

[0041] Preparation of functional isocyanate crosslinking agent of formula (2): According to the method and operation steps of Example 1, N,N'-dihydroxyethylethylenediamine in Example 1 is replaced by N,N-bis(6-hydroxyhexyl)-p-phenylenediamine, formula (c-1) is replaced by formula (c-2), benzyl chloride is replaced by methoxy polyethylene glycol-2000 p-toluenesulfonate, and toluene diisocyanate is replaced by diphenylmethane diisocyanate to obtain a solution of functional isocyanate crosslinking agent of formula (2).

[0042]

[0043] After infrared spectroscopy testing, a strong peak of NCO appeared near 2271nm in the IR spectrum of formula (A-2), a characteristic absorption peak belonging to carbamate NH appeared at 3487nm, and a characteristic peak of carbamate C=O appeared at 1728nm, which was consistent with the structural characteristics of formula (A-2), confirming that the chemical structure of the product was consistent with the theoretical design of formula (A-2). The percentage of isocyanate groups in the functional isocyanate crosslinker solution of formula (A-2) was detected by the method specified in GB / T 29493.6-2013, and was 1.32%.

[0044] Surface modification of polyvinyl chloride membrane: At room temperature, the surface activated polyvinyl chloride membrane is immersed in a functional isocyanate crosslinking agent solution of formula (A-2), evenly soaked and allowed to stand for 3 minutes, and then sent to a reactor at 80-90°C for a residence time of 10 hours. Thereafter, it is taken out and cooled to obtain a modified polyvinyl chloride membrane II-1.

[0045] Example 3 Modified polyvinyl chloride urinary catheter (I-1)

[0046] According to the method and steps of Example 1, the polyvinyl chloride catheter produced by Jiangsu Jiadingcheng Medical Instrument Co., Ltd. was ultrasonically cleaned with ethanol and deionized water in sequence, and vacuum dried at 60° C. for 10 hours to obtain a surface-cleaned polyvinyl chloride catheter.

[0047] The surface-cleaned polyvinyl chloride catheter is placed in a plasma chamber, the O2 pressure in the chamber is 40 Pa, the temperature in the chamber is 25° C., the radio frequency power is 100 W, and the irradiation time is 100 seconds, so as to obtain a surface-activated polyvinyl chloride catheter.

[0048] At room temperature, the surface activated polyvinyl chloride catheter is immersed in the functional isocyanate crosslinking agent solution (A-1), evenly dipped into a reactor at 80-90°C and kept for 10 hours, then taken out and cooled to obtain a modified polyvinyl chloride catheter Ⅰ-1.

[0049] Example 4 Modified polyvinyl chloride urinary catheter (II-1)

[0050] According to the method and steps of Example 1, the polyvinyl chloride catheter produced by Jiangsu Jiadingcheng Medical Instrument Co., Ltd. was ultrasonically cleaned with ethanol and deionized water in sequence, and vacuum dried at 60° C. for 10 hours to obtain a surface-cleaned polyvinyl chloride catheter.

[0051] The surface-cleaned polyvinyl chloride catheter is placed in a plasma chamber, the O2 pressure in the chamber is 40 Pa, the temperature in the chamber is 25° C., the radio frequency power is 100 W, and the irradiation time is 150 seconds to obtain a surface-activated polyvinyl chloride catheter.

[0052] At room temperature, the surface activated polyvinyl chloride catheter is immersed in the functional isocyanate crosslinking agent solution (A-2), evenly dipped into the solution and sent into a reactor at 80-90°C for 10 hours, after which it is taken out and cooled to obtain a modified polyvinyl chloride catheter II-1.

[0053] Example 5 Modified polyvinyl chloride fishing net (Ⅰ-1)

[0054] According to the method and steps of Example 1, the polyvinyl chloride fishing net produced by Lianyungang Xingqiu Plastic Co., Ltd. was ultrasonically washed with ethanol and deionized water in sequence, and vacuum dried at 60° C. for 10 hours to obtain a surface-cleaned polyvinyl chloride fishing net.

[0055] The surface-cleaned polyvinyl chloride fishing net is placed in a plasma chamber, the O2 pressure in the chamber is 30 Pa, the temperature in the chamber is 25° C., the radio frequency power is 100 W, and the irradiation time is 80 seconds to obtain a surface-activated polyvinyl chloride fishing net.

[0056] At room temperature, the surface activated polyvinyl chloride fishing net is immersed in the functional isocyanate crosslinking agent solution of formula (1), evenly dipped into the solution and sent into a reactor at 80-90°C for a residence time of 10 hours, then taken out and cooled to obtain modified polyvinyl chloride fishing net I-1.

[0057] Example 6 Modified polyvinyl chloride fishing net (II-1)

[0058] According to the method and steps of Example 1, the polyvinyl chloride fishing net produced by Lianyungang Xingqiu Plastic Co., Ltd. was ultrasonically washed with ethanol and deionized water in sequence, and vacuum dried at 60° C. for 10 hours to obtain a surface-cleaned polyvinyl chloride fishing net.

[0059] The surface-cleaned polyvinyl chloride fishing net is placed in a plasma chamber, the O2 pressure in the chamber is 30 Pa, the temperature in the chamber is 25° C., the radio frequency power is 100 W, and the irradiation time is 100 seconds to obtain a surface-activated polyvinyl chloride fishing net.

[0060] At room temperature, the surface activated polyvinyl chloride fishing net is immersed in the functional isocyanate crosslinking agent solution (A-2), evenly dipped into a reactor at 80-90°C and kept for 10 hours, then taken out and cooled to obtain modified polyvinyl chloride fishing net II-1.

[0061] Example 7 Changes in properties of polyvinyl chloride materials before and after modification of Examples 1 to 6

[0062] The polyvinyl chloride materials before and after modification of Examples 1 to 6 were respectively taken, placed in anhydrous ethanol for ultrasonic washing, and then vacuum dried at 60° C. to constant weight, and the weight gain and water contact angle were measured. The results are shown in Table 1.

[0063] Table 1 Properties of polyvinyl chloride materials before and after modification

[0064]

[0065] From the data in Table 1, it can be seen that after the polyvinyl chloride film is modified by the functional isocyanate crosslinker, its weight increases and the water contact angle of the material surface decreases. Repeated treatment of the polyvinyl chloride film with the functional isocyanate crosslinker can also achieve similar modification effects. Under the same conditions, the weight gain rate of the polyvinyl chloride fishing net after treatment with the functional isocyanate crosslinker is significantly higher than that of the polyvinyl chloride catheter and the polyvinyl chloride film, indicating that the larger the specific surface area of ​​the material to be modified, the better the surface modification effect, indicating that the grafting efficiency is higher.

Claims

1. Application of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials, characterized in that The method is achieved by the following steps: at room temperature, immersing the surface activated polyvinyl chloride material in a functional isocyanate crosslinking agent solution, evenly immersing the surface activated polyvinyl chloride material, or spraying, rolling or brushing the functional isocyanate crosslinking agent solution on the surface activated polyvinyl chloride material, and then putting the surface activated polyvinyl chloride material into a reactor at 60 to 130° C. for heat treatment for 0.2 to 20 hours, and then taking the surface activated polyvinyl chloride material out for cooling to obtain a surface modified polyvinyl chloride material; The surface activated polyvinyl chloride material refers to a surface clean polyvinyl chloride material which is subjected to plasma treatment in a plasma chamber with an oxygen, ammonia or air atmosphere, with a gas pressure of 30 to 50 Pa in the chamber, a temperature of 10 to 40° C. in the chamber, a radio frequency power of 50 to 500 W, and an irradiation time of 50 to 500 seconds, and -OH groups or -NH2 groups are generated on the surface of the clean polyvinyl chloride material, which is called a surface activated polyvinyl chloride material; or the surface clean polyvinyl chloride material is immersed in an alkali solution with a mass percentage concentration of 0.01 to 10%, ultrasonically hydrolyzed at room temperature for 2 to 200 minutes, taken out and washed with deionizer until neutral, and vacuum dried at 60° C., and -OH groups are generated on the surface of the clean polyvinyl chloride material, which is called a surface activated polyvinyl chloride material; The functional isocyanate cross-linking agent has a structure shown in general formula (A): Wherein R in the general formula (A) is selected from H or methyl, R1 and R2 are selected from C1 to C 18 A hydrocarbon group, wherein n is a natural number selected from 1 to 2000, and Y are selected from C1 to C 18 Hydrocarbylene, Selected from C1~C 18 Alkylene or One of the following, Q is selected from C1~C 18 Hydrocarbon or One of the following, where p is a natural number between 0 and 2000, and X - Refers to Cl - Br - ,I - or p-CH3C6H4SO3 - One of; The mass percentage concentration of the functional isocyanate crosslinking agent in the functional isocyanate crosslinking agent solution is 0.5-50%, and the usage of the functional isocyanate crosslinking agent solution is 5-500% of the mass of the surface activated polyvinyl chloride material.

2. The use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 1, characterized in that The surface clean polyvinyl chloride material refers to the polyvinyl chloride raw material that is washed with ethanol and deionized water in sequence, and then dried under vacuum at 60°C to obtain the surface clean polyvinyl chloride material; The polyvinyl chloride raw material refers to one of polyvinyl chloride artificial organs, polyvinyl chloride catheters, polyvinyl chloride blood storage bags, polyvinyl chloride containers, polyvinyl chloride foams, polyvinyl chloride films, polyvinyl chloride filter membranes, polyvinyl chloride filter screens, polyvinyl chloride nonwoven fabrics or polyvinyl chloride fibers.

3. Use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 1, characterized in that The alkaline solution refers to one or more of an aqueous solution of potassium hydroxide, sodium hydroxide, N,N,N-trimethyl-N-benzylammonium hydroxide, N,N,N-triethyl-N-benzylammonium hydroxide or N,N,N,N-tetrabutylammonium hydroxide.

4. The use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 1, characterized in that The preparation method of the functional isocyanate crosslinking agent is as follows: at room temperature, dissolving the dihydroxy diamine of the general formula (B) in an organic solvent, stirring is started, and acryloyloxy polyether sulfobetaine is slowly added, wherein the amount of acryloyloxy polyether sulfobetaine is 2.0 to 2.2 times the molar amount of the general formula (B); after the addition of acryloyloxy polyether sulfobetaine is completed, the reaction temperature is increased to 50 to 90° C., and the reaction is carried out for 2 to 20 hours; maintaining the reaction temperature, adding an alkylating agent to the reaction system, wherein the amount of the alkylating agent is 1.8 to 2.2 times the molar amount of the general formula (B), and the stirring reaction is continued for 2 to 20 hours. After the quaternization reaction is completed, the catalyst, the diluent and the polyisocyanate are sequentially added to the reaction system, and the reaction is continued by keeping the temperature and stirring. The NCO content in the material in the reactor is detected to be consistent with the predetermined value, and the temperature of the reaction product system is reduced to room temperature to obtain the solution of the functional isocyanate crosslinking agent; The dihydroxy diamine has a structure shown in the general formula (B): Wherein the general formula (B) Selected from C1~C 18 Alkylene or One of the following, wherein p is selected from a natural number between 0 and 2000, and Y is selected from C1 to C 18 Alkylene.

5. Use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 4, characterized in that The organic solvent refers to one or more of tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide; the amount of the organic solvent used is 1 to 10 times the mass of the dihydroxydiamine of general formula (B).

6. Use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 4, characterized in that The acryloxypolyether sulfobetaine has a structure shown in the general formula (C): Wherein R in the general formula (C) is selected from H or methyl, R1 and R2 are selected from C1 to C 18 The hydrocarbon group, wherein n is a natural number selected from 1 to 2000.

7. Use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 4, characterized in that The catalyst refers to a compound of organotin and organoamine; The organic tin is one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, di(dodecylsulfide) dibutyltin or dibutyltin diacetate; the organic amine is one of triethylamine, p-dimethylaminopyridine, N,N-dimethylformamide, triethylenediamine, dialkylpiperazine, alkylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine carboxylate, dialkylpiperazine carboxylate or alkylimidazole carboxylate; the mass ratio of the organic tin to the organic amine is 1:0 to 1.5; the amount of the catalyst is 0.05 to 5% of the mass of the polyisocyanate of the general formula (D).

8. Use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 4, characterized in that The polyisocyanate has a structure shown in general formula (D): Wherein q in the general formula (D) is selected from a positive integer of 1 to 5, Selected from C1~C 18 alkylene; The amount of the polyisocyanate used is 2.02 to 2.25 times the molar amount of the general formula (B).

9. Use of a functional isocyanate crosslinking agent in surface modification of polyvinyl chloride materials according to claim 4, characterized in that The diluent refers to one or more of acetone, butanone, cyclohexanone, methyl acetate, ethyl acetate, ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide; the amount of the diluent is 1 to 10 times the mass of the general formula (B).

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