Polyolefin surface activation modifier, preparation method and application thereof

Abstract

The application provides a polyolefin surface activation modifier, a preparation method and application thereof, and the polyolefin surface activation modifier has the structure shown in the following formula I. The polyolefin surface activation modifier provided in the application has good bacteriostatic effects on staphylococcus aureus and escherichia coli, and the polyolefin surface activation modifier after boiling still has good bacteriostatic effects, has good water resistance, and has relatively low cytotoxicity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis, and particularly relates to a novel polyolefin surface activation modifier, a preparation method and application thereof. BACKGROUND

[0002] Some microorganisms existing in nature not only have great harm to human beings, animals and plants, but also cause decomposition, deterioration and corruption of materials, and bring great economic losses. Therefore, materials with antibacterial and bacteriostatic functions are increasingly concerned by people, and are widely applied in the fields of children's toys, medical health, household supplies and the like.

[0003] Antibacterial agents play a key role in antibacterial materials. However, small-molecule antibacterial agents have limited use due to their non-durability and drug resistance; high-molecular-weight antibacterial agents are widely used due to their durability because they are not easily leached and percolated, but the existing high-molecular-weight antibacterial agents use the antibacterial function of small-molecule antibacterial agents, and the polymer itself only serves as a connection of the antibacterial agent or a carrier, and in principle, the antibacterial agents also inhibit bacteria by combining with specific sites on the bacteria, and thus the bacteria can produce drug resistance, and the more the antibacterial agents are used, the faster the bacteria produce drug resistance, and the antibacterial agents inevitably cause damage to eukaryotic cells.

[0004] In view of the problems of antibacterial agents in the existing antibacterial materials, research on new antibacterial polymers that do not cause drug resistance of bacteria has become a focus of scientific researchers, and in recent years, it has been found that cationic polymers containing halogen amine groups, quaternary ammonium salt groups, quaternary phosphonium salt groups and guanidine groups have good antibacterial performance, and the cationic polymers not only have little toxicity to normal eukaryotic cells, but also do not cause drug resistance of bacteria, and have high-efficiency antibacterial performance and excellent biocompatibility, and the cationic polymers containing guanidine groups have higher-efficiency antibacterial performance, lower toxicity to eukaryotic cells, and better antibacterial performance even after being boiled in water, and are widely applied in the fields of wound dressings, textiles, fiber membranes, drug delivery, insecticides, water treatment and the like.

[0005] Therefore, how to use the cationic polymers containing guanidine groups to prepare a novel polyolefin surface activation modifier with good antibacterial performance and water resistance is a problem to be solved urgently. SUMMARY

[0006] The present application aims to provide a novel polyolefin surface activation modifier, a preparation method and application thereof, so as to solve the problems in the background.

[0007] To achieve the above object, the present application provides the following technical scheme: on one hand, the present application provides a novel polyolefin surface activation modifier, and the novel polyolefin surface activation modifier has the structure shown in the following formula I:

[0008] I;

[0009] wherein, R1 represents formyl, acetyl, substituted or unsubstituted aryl, R2 represents carboxyl containing 1-5 carbon atoms;

[0010] x1, x2, y, z all represent integers, and (x1 + x2):y:z is 30:(10-30):(0-1), a represents 5000-100000, b represents 2-50, * represents a connecting point of a chemical bond;

[0011] when z is 0, x2 is not 0.

[0012] As a further improvement, the ratio of x1 to x2 is (25-30):1.

[0013] As a further improvement, the substituted or unsubstituted aryl in R1 is wherein R3 represents hydrogen, methyl or ethyl.

[0014] On the other hand, the application also provides a preparation method of a new polyolefin surface activation modifier, characterized by comprising the following steps:

[0015] putting the modified polypropylene represented by formula I-A into the organic polymer represented by formula I-B, continuously stirring the reaction at 80-120℃, and after the reaction is completed, post-treatment, to obtain the new polyolefin surface activation modifier;

[0016] I-A;

[0017] I-B.

[0018] As a further improvement, the preparation method of the modified polypropylene comprises the following steps:

[0019] putting polypropylene, glycidyl methacrylate and an initiator into a double-screw extruder, mixing for 2-5min at 100-250℃, to obtain the modified polypropylene.

[0020] As a further improvement, the initiator is at least one of di-t-butyl peroxide, dicumyl peroxide and benzophenone.

[0021] As a further improvement, the preparation method of the organic polymer comprises the following steps:

[0022] (1) putting hydroxyethyl acrylate, acrylic acid and a polymerizable guanidino monomer into ethyl acetate and mixing uniformly, adding initiator BPO after mixing uniformly, to obtain a mixed solution;

[0023] (2) adding ethyl acetate into the reaction bottle and heating to 60-80 DEG C, starting to drop the mixed solution of step (1), the dropping time is 2-6 hours, after the dropping is completed, keeping the reaction for 2-4 hours, thus the required organic polymer is obtained;

[0024] wherein the polymerizable guanidyl monomer represents and / or .

[0025] As a further improvement, the preparation method of the polymerizable guanidyl monomer comprises the following steps:

[0026] adding the guanidyl monomer and triethylamine into a low-boiling organic solvent, cooling the system to -10-0 DEG C, dropping acryloyl chloride, after the dropping is completed, keeping the reaction for 2-4 hours, after the reaction is completed, post-treatment, thus the polymerizable guanidyl monomer is prepared;

[0027] wherein the guanidyl monomer represents and / or .

[0028] On the other hand, the application provides a new polyolefin surface activation modifier in the application of antibacterial material.

[0029] As a further improvement, the antibacterial material is a fiber membrane, non-woven fabric, dressing.

[0030] As a further improvement, the guanidyl monomer is acetyl guanidine, phenyl biguanide, guanidyl propionic acid, guanidyl acetic acid, 4-guanidyl butyric acid, etc.

[0031] As a further improvement, the low-boiling organic solvent is toluene, acetone, etc.

[0032] Compared with the prior art, the application has the beneficial effects that the new polyolefin surface activation modifier provided by the application has good bacteriostatic effect on staphylococcus aureus and escherichia coli, and the new polyolefin surface activation modifier after boiling still has good bacteriostatic effect and water resistance, and has lower cytotoxicity;

[0033] and the new polyolefin surface activation modifier provided by the application can combine with all bacteria through electrostatic effect and hydrogen bond coordination mechanism, which makes it have broad-spectrum antibacterial property, and due to the negative charge characteristics of bacterial cell membranes, bacteria are difficult to produce drug resistance. DETAILED DESCRIPTION

[0034] The application will be described below in combination with specific embodiments. It should be noted that the following examples are examples of the application and are only used to illustrate the application, but not to limit the application. Other combinations and various modifications within the concept of the application can be made without departing from the main idea or scope of the application.

[0035] In the following examples, the following compounds are used, except for the compound of formula II-1, the compound of formula I-B-1, the compound of formula I-A-1, the compound of formula I-1, the compound of formula II-2, the compound of formula I-B-2, the compound of formula I-A-2, the compound of formula I-2, the compound of formula II-3, the compound of formula I-B-3, the compound of formula I-3, the compound of formula I-4, the compound of formula I-5, the compound of formula I-A-4, the compound of formula I-6, the compound of formula I-A-5, the compound of formula I-7, the compound of formula I-B-4, the compound of formula I-B-5, the compound of formula I-8, and the related reagents, which are commercially available. The polypropylene (PP1) ), the polypropylene (PP2) ), and the polypropylene (PP3) ) are all purchased from Shanghai Xianghuixin Plastic Co., Ltd.

[0036] The preparation method of the compound of formula I-1 is as follows:

[0037] (1) 35 mol of phenylbiguanide and 4 mol of triethylamine are added to 500 mL of toluene, the system is cooled to -10°C, and 35 mol of acryloyl chloride is added dropwise. After the dropwise addition is completed, the reaction is continued at -10°C for 3 hours. After the reaction is completed, 300 mL of deionized water is added, the organic layer is separated by liquid-liquid extraction, and the toluene is removed by distillation to obtain the compound of formula II-1;

[0038] II-1

[0039] (2) 10 mol of hydroxyethyl acrylate, 1 mol of acrylic acid, and 30 mol of the compound of formula II-1 prepared in step (1) are added to 800 mL of ethyl acetate and mixed uniformly. After mixing, 1 mol of initiator BPO is added to obtain a mixed solution, which is used after standing. After 800 mL of ethyl acetate is added to the reaction bottle, the temperature is raised to 70°C, and the mixed solution is added dropwise. The dropwise addition time is 4 hours. After the dropwise addition is completed, the reaction is maintained for 3 hours. After the ethyl acetate is removed by distillation, the compound of formula I-B-1 is obtained;

[0040] I-B-1

[0041] (3) 1 mol of polypropylene (PP1) ), 50 mol of glycidyl methacrylate, and 1.5 mol of dicumyl peroxide are mixed through a double-screw extruder at 200°C for 3 min to obtain the compound of formula I-A-1;

[0042] I-A-1

[0043] (4) Add 1 mol of compound I-A-1 to 1 mol of compound I-B-1 and stir continuously at 100 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-1.

[0044] Formula I-1

[0045] The preparation method of compound I-2 is as follows:

[0046] (1) Add 35 mol of phenyl biguanide and 4 mol of triethylamine to 500 mL of toluene, cool the system to -10 °C, add 35 mol of acryloyl chloride dropwise, and continue the reaction at -10 °C for 3 hours after the addition is complete. After the reaction is complete, add 300 mL of deionized water, extract the organic layer by separation, and remove the toluene by distillation to obtain the compound of formula II-1.

[0047] II-1

[0048] (2) Add 40 mol of guanidinoacetic acid and 4.5 mol of triethylamine to 550 mL of toluene, cool the system to -8 °C, add 40 mol of acryloyl chloride dropwise, and continue the reaction at -8 °C for 4 hours after the addition is complete. After the reaction is complete, add 400 mL of deionized water, extract the organic layer by separation, and remove the toluene by distillation to obtain the compound of formula II-2.

[0049] II-2

[0050] (3) Add 20 mol of hydroxyethyl acrylate, 1 mol of acrylic acid, 29 mol of compound II-1 obtained in step (1), and 1 mol of compound II-2 obtained in step (2) to 1000 mL of ethyl acetate and mix well. After mixing well, add 1.1 mol of initiator BPO to obtain a mixed solution and set aside. Add 1000 mL of ethyl acetate to the reaction flask and heat to 80 °C. Start adding the mixed solution dropwise over 5 hours. After the addition is complete, keep the reaction at the temperature for 2 hours. After distilling off the ethyl acetate, compound I-B-2 is obtained.

[0051] I-B-2

[0052] (3) Add 1 mol of polypropylene ( 40 mol of glycidyl methacrylate and dicumyl peroxide were mixed in a twin-screw extruder at 220°C for 3 min to obtain a compound of formula I-A-2;

[0053] Ⅰ-A-2

[0054] (4) Add 1 mol of compound I-A-2 to 1 mol of compound I-B-2 and stir continuously at 80 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-2.

[0055] Ⅰ-2

[0056] The preparation method of compound I-3 is as follows:

[0057] (1) 62 mol of guanidinopropionic acid and 7 mol of triethylamine were added to 800 mL of toluene. The system was cooled to -10 °C and 62 mol of acryloyl chloride was added dropwise. After the addition was complete, the reaction was continued at -10 °C for 3 hours. After the reaction was completed, 700 mL of deionized water was added, the organic layer was extracted by separation, and the toluene was removed by distillation to obtain the compound of formula II-1.

[0058] II-3

[0059] (2) Add 40 mol of hydroxyethyl acrylate, 2 mol of acrylic acid, and 60 mol of the polymerizable guanidine monomer obtained in step (1) to 1500 mL of ethyl acetate and mix well. After mixing well, add 1 mol of initiator BPO to obtain a mixed solution and set it aside. Add 1500 mL of ethyl acetate to the reaction flask and heat to 70 °C. Start adding the mixed solution dropwise over 4 hours. After the addition is complete, keep the reaction at the temperature for 3 hours. After distilling off the ethyl acetate, the compound of formula I-B-3 is obtained.

[0060] I-B-3

[0061] (3) Add 1 mol of polypropylene ( 50 mol of glycidyl methacrylate and 1.4 mol of dicumyl peroxide were mixed in a twin-screw extruder at 200°C for 3 min to obtain the compound of formula I-A-1.

[0062] Ⅰ-A-1

[0063] (4) Add 2 mol of compound I-A-1 to 1 mol of compound I-B-3 and stir continuously at 100 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-3.

[0064] Ⅰ-3

[0065] The preparation method of compound I-4 uses the same components and contents as the preparation method of compound I-1, except that steps (3) and (4) are not used.

[0066] The preparation method of compound I-5 uses the same components and contents as the preparation method of compound I-1, except that steps (3) and (4) of the following steps are replaced with steps (3) and (4) of the preparation method of compound I-1, as follows:

[0067] (3) Add 1 mol of polypropylene ( 50 mol of glycidyl methacrylate and dicumyl peroxide were mixed in a twin-screw extruder at 200°C for 3 min to obtain a compound of formula I-A-4;

[0068] I-A-4

[0069] (4) Add 1 mol of compound I-A-4 to 1 mol of compound I-B-1 and stir continuously at 100 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-5.

[0070] Ⅰ-5

[0071] The preparation method of compound I-6 uses the same components and contents as the preparation method of compound I-1, the difference being that steps (3) and (4) of the following steps are replaced with steps (3) and (4) of the preparation method of compound I-1, as follows:

[0072] (3) Add 1 mol of polypropylene ( 50 mol of glycidyl methacrylate and 1.3 mol of dicumyl peroxide were mixed in a twin-screw extruder at 200°C for 3 min to obtain a compound of formula I-A-5;

[0073] Ⅰ-A-5

[0074] (4) Add 1 mol of compound I-A-5 to 1 mol of compound I-B-1 and stir continuously at 100 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-6.

[0075] Ⅰ-6

[0076] The preparation method of compounds of formula I-7 is as follows:

[0077] (1) Add 35 mol of phenyl biguanide and 4 mol of triethylamine to 500 mL of toluene, cool the system to -10 °C, add 35 mol of acryloyl chloride dropwise, and continue the reaction at -10 °C for 3 hours after the addition is complete. After the reaction is complete, add 300 mL of deionized water, extract the organic layer by separation, and remove the toluene by distillation to obtain the compound of formula II-1.

[0078] II-1

[0079] (2) Add 5 mol of hydroxyethyl acrylate, 1 mol of acrylic acid, and 30 mol of the compound of formula II-1 obtained in step (1) to 800 mL of ethyl acetate and mix well. After mixing well, add 1 mol of initiator BPO to obtain a mixed solution and set aside. Add 800 mL of ethyl acetate to the reaction flask and heat to 70 °C. Start adding the mixed solution dropwise over 4 hours. After the addition is complete, keep the reaction at the temperature for 3 hours. After distilling off the ethyl acetate, the compound of formula I-B-4 is obtained.

[0080] I-B-4

[0081] (3) Add 1 mol of polypropylene ( 50 mol of glycidyl methacrylate and 1.5 mol of dicumyl peroxide were mixed in a twin-screw extruder at 200°C for 3 min to obtain the compound of formula I-A-1.

[0082] Ⅰ-A-1

[0083] (4) Add 1 mol of compound I-A-1 to 1 mol of compound I-B-4 and stir continuously at 100 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-7.

[0084] Ⅰ-7

[0085] The preparation method of compounds of formula I-8 is as follows:

[0086] (1) Add 35 mol of phenyl biguanide and 4 mol of triethylamine to 500 mL of toluene, cool the system to -10 °C, add 35 mol of acryloyl chloride dropwise, and continue the reaction at -10 °C for 3 hours after the addition is complete. After the reaction is complete, add 300 mL of deionized water, extract the organic layer by separation, and remove the toluene by distillation to obtain the compound of formula II-1.

[0087] II-1

[0088] (2) Add 40 mol of guanidinoacetic acid and 4.5 mol of triethylamine to 550 mL of toluene, cool the system to -8 °C, add 40 mol of acryloyl chloride dropwise, and continue the reaction at -8 °C for 4 hours after the addition is complete. After the reaction is complete, add 400 mL of deionized water, extract the organic layer by separation, and remove the toluene by distillation to obtain the compound of formula II-2.

[0089] II-2

[0090] (3) Add 10 mol of hydroxyethyl acrylate, 1 mol of acrylic acid, 29 mol of compound II-1 obtained in step (1), and 1 mol of compound II-2 obtained in step (2) to 1000 mL of ethyl acetate and mix well. After mixing well, add 1 mol of initiator BPO to obtain a mixed solution and set aside. Add 1000 mL of ethyl acetate to the reaction flask and heat to 70 °C. Start adding the mixed solution dropwise over 4 hours. After the addition is complete, keep the reaction at the temperature for 3 hours. After distilling off the ethyl acetate, the compound I-B-5 is obtained.

[0091] I-B-5

[0092] (3) Add 1 mol of polypropylene ( 50 mol of glycidyl methacrylate and 1.5 mol of dicumyl peroxide were mixed in a twin-screw extruder at 200°C for 3 min to obtain the compound of formula I-A-1.

[0093] Ⅰ-A-1

[0094] (4) Add 1 mol of compound I-A-1 to 1 mol of compound I-B-5 and stir continuously at 100 °C. After the reaction is complete, filter to collect solid particles, wash the surface with ethyl acetate, and finally dry to obtain compound I-8.

[0095] Formula I-8

[0096] The testing method is as follows:

[0097] 1. Antibacterial test standard: QB / T 2591-2003A "Test method and antibacterial effect of antibacterial plastics", bacteria used for testing: Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538.

[0098] The antibacterial test procedure is performed according to the antibacterial plastic detection standard QB / T 2591-2003. The specific steps are as follows: the sample to be tested is sterilized with 75% ethanol and dried, and the bacteria are diluted with sterile water to form a bacterial suspension of appropriate concentration for standby use. 0.2 ml of the bacterial suspension is dropped on the surface of the sample, and a 0.1 mm thick polyethylene film (4.0 cm x 4.0 cm) is covered on it to form a uniform liquid film between the sample and the film. Incubate at 37°C with a relative humidity of 90% for 20 hours. Wash the bacterial solution with sterile water, dilute it to an appropriate concentration gradient, and evenly coat 0.1 ml on the prepared sterile agar medium. Incubate at 37°C for 20 hours, and observe the results. The negative control uses a sterile plate instead, and the other operations are the same.

[0099] Sample preparation of Example 1 to Example 3, Example 5, Comparative Example 1 to Comparative Example 4:

[0100] Put 3000 g of polypropylene (purchased from Shanghai Hongwei Plastic Co., Ltd., brand M800E), 3.5 g of antioxidant 1010 (purchased from BASF official flagship store, item number 50375087 BCH), and 15 g of compound of formula I into a low-speed mixer and stir evenly, then melt blend the mixture through a twin-screw extruder with a temperature of 200°C and a rotation speed of 300 rpm to form granules. Dry the extruded granules in a constant-temperature oven at 90°C for 9 hours, then inject the sample into a 50 mm x 50 mm sample at an injection temperature of 200°C for antibacterial testing. At the same time, the samples of Example 1 to Example 4 and Comparative Example 1 to Comparative Example 4 are boiled in water at 60°C for 48 hours, and then subjected to antibacterial testing.

[0101] Sample preparation of Example 4:

[0102] Put 3000 g of polypropylene (purchased from Shanghai Hongwei Plastic Co., Ltd., brand M800E), 3.5 g of antioxidant 1010 (purchased from BASF official flagship store, item number 50375087 BCH), and 15 g of compound of formula I into a low-speed mixer and stir evenly, then melt blend the mixture through a twin-screw extruder with a temperature of 200°C and a rotation speed of 300 rpm to form granules. Dry the extruded granules in a constant-temperature oven at 90°C for 9 hours, then inject the sample into a 50 mm x 50 mm sample at an injection temperature of 200°C for antibacterial testing. At the same time, the samples of Example 1 to Example 4 and Comparative Example 1 to Comparative Example 4 are boiled in water at 60°C for 48 hours, and then subjected to antibacterial testing.

[0103] In the above, Example 1 uses the compound of Formula I-1, Example 2 uses the compound of Formula I-2, Example 3 uses the compound of Formula I-3, Example 4 uses the compound of Formula I-1, Example 5 uses the compound of Formula I-8, Comparative Example 1 uses the compound of Formula I-4, Comparative Example 2 uses the compound of Formula I-5, Comparative Example 3 uses the compound of Formula I-6, and Comparative Example 4 uses the compound of Formula I-7.

[0104] Preparation of Comparative Example 5 sample:

[0105] The polypropylene 3000 g, antioxidant 1010 3.5 g, and silicone quaternary ammonium salt 15 g were put into a low-speed mixer and stirred evenly, and then the mixture was melt blended by a twin-screw extruder at a temperature of 200°C and a rotation speed of 300 rpm to form an extruded pellet. The extruded pellet was dried in a constant-temperature oven at 90°C for 9 h, and then injected into a sample of 50 mm x 50 mm at an injection temperature of 200°C for antibacterial testing. Meanwhile, the sample of Comparative Example 5 was boiled in water at 60°C for 48 h, and then subjected to antibacterial testing.

[0106] The test results are shown in Table 1, and are as follows:

[0107]

[0108] As can be seen from the comparison of Example 1, Comparative Examples 1 to 5, the new polyolefin surface activation modifier provided in the present application has good bacteriostatic effect on Staphylococcus aureus and Escherichia coli, and the new polyolefin surface activation modifier after boiling still has good bacteriostatic effect.

[0109] As can be seen from the comparison of Example 1 and Example 4, when the new polyolefin surface activation modifier provided in the present application is used to inhibit Staphylococcus aureus and Escherichia coli, even if the amount of the new polyolefin surface activation modifier is reduced, the new polyolefin surface activation modifier still has good bacteriostatic effect.

[0110] As can be seen from the comparison of Example 1 to Example 3 and Example 5, when the new polyolefin surface activation modifier provided in the present application is used to inhibit Staphylococcus aureus and Escherichia coli, and the x:y:z in the new polyolefin surface activation modifier is 30:(10-30):(0-1), a represents 5000-100000, and b represents 2-50, the new polyolefin surface activation modifier has good bacteriostatic effect on Staphylococcus aureus and Escherichia coli, and the new polyolefin surface activation modifier after boiling still has good bacteriostatic effect, and the 3T3 fibroblasts and primary mesenchymal stem cells show low cytotoxicity.

[0111] In summary, the new polyolefin surface activation modifier provided in the present application has good bacteriostatic effect on Staphylococcus aureus and Escherichia coli, and the new polyolefin surface activation modifier after boiling still has good bacteriostatic effect and water resistance, and has low cytotoxicity.

[0112] The above embodiments are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the present application and implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.

Claims

1. A polyolefin surface activation modifier characterized by: The preparation method of the polyolefin surface activation modifier comprises the following steps: The modified polypropylene is put into the organic polymer, and the reaction is continuously stirred at 80-120 DEG C, after the reaction is completed, the post-treatment is carried out, and the polyolefin surface activation modifier is obtained; The preparation method of the modified polypropylene comprises the following steps: The polypropylene, glycidyl methacrylate and initiator are sent into a double screw extruder, and the mixing time is 2-5 min at 100-250 DEG C, so that the modified polypropylene is prepared; The preparation method of the organic polymer comprises the following steps: (1) the hydroxyethyl acrylate, acrylic acid and polymerizable guanidine monomer are added into ethyl acetate and uniformly mixed, and the initiator BPO is added after uniform mixing, so that a mixed solution is obtained; (2) ethyl acetate is added into a reaction bottle, and the temperature is raised to 60-80 DEG C, the mixed solution of step (1) is started to be added dropwise, the dropwise adding time is 2-6 hours, and after the dropwise adding is completed, the reaction is preserved for 2-4 hours, so that the required organic polymer is obtained; wherein the polymerizable guanidinium monomer is represented by and / or ; R1 represents formyl, acetyl, substituted or unsubstituted aryl, and R2 represents carboxyl containing 1-5 carbon atoms.

2. The method for preparing a polyolefin surface-activating modifier according to claim 1, characterized in that: The preparation method of the modified polypropylene comprises the following steps: The modified polypropylene is put into the organic polymer, and the reaction is continuously stirred at 80-120 DEG C, after the reaction is completed, the post-treatment is carried out, and the polyolefin surface activation modifier is obtained; The preparation method of the modified polypropylene comprises the following steps: The polypropylene, glycidyl methacrylate and initiator are sent into a double screw extruder, and the mixing time is 2-5 min at 100-250 DEG C, so that the modified polypropylene is prepared; The preparation method of the organic polymer comprises the following steps: (1) the hydroxyethyl acrylate, acrylic acid and polymerizable guanidine monomer are added into ethyl acetate and uniformly mixed, and the initiator BPO is added after uniform mixing, so that a mixed solution is obtained; (2) ethyl acetate is added into a reaction bottle, and the temperature is raised to 60-80 DEG C, the mixed solution of step (1) is started to be added dropwise, the dropwise adding time is 2-6 hours, and after the dropwise adding is completed, the reaction is preserved for 2-4 hours, so that the required organic polymer is obtained; wherein the polymerizable guanidinium monomer is represented by and / or .

3. A method for preparing a polyolefin surface-activating modifier according to claim 2, characterized in that: The initiator is at least one of di-t-butyl peroxide, dicumyl peroxide and benzophenone.

4. The method for preparing a polyolefin surface-activating modifier according to claim 3, characterized in that: The preparation method of the polymerizable guanidine monomer comprises the following steps: The guanidine monomer and triethylamine are added into a low-boiling organic solvent, the system is cooled to-10-0 DEG C, acryloyl chloride is added dropwise, after the dropwise adding is completed, the reaction is carried out for 2-4 hours, after the reaction is completed, the post-treatment is carried out, and the polymerizable guanidine monomer is prepared; wherein the guanidinium monomer is represented by and / or .

5. The polyolefin surface activation modifier in claim 1 is applied to the preparation of antibacterial materials.

6. Use according to claim 5, characterized in that: The antibacterial materials are fiber membranes, non-woven fabrics and dressings.

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