CN101210061A - A kind of functionalized olefin copolymer and its preparation method and application - Google Patents

Abstract

The present invention relates to a functionalized olefin copolymer and its preparation method and application. The structural formula of the copolymer is as follows: wherein, X is chlorine, methyl, vinyl or hexyl; Y is methyl, ethyl, propyl, butyl and other alkane groups; R is polyamine and guanidinium oligomer; m, n and p are integers greater than or equal to zero, and q is an integer greater than zero; functionalized olefin copolymer is composed of olefin copolymer resin, polyamine It can be obtained by reaction with guanidinium salt oligomer, olefin monomer, initiator and antioxidant through solution, melting or solid phase reaction; it can be used alone to prepare olefin copolymer products with antibacterial function, and can also be used with some resins Blending to prepare products with antibacterial function. Compared with the prior art, the present invention has the characteristics of safety to human body, excellent antibacterial effect and long-term effect.

Description

A kind of functionalized olefin copolymer and its preparation method and application

technical field

The invention relates to the technical field of polymer reaction and processing, in particular to a functionalized olefin copolymer obtained by reacting an oligomer containing active double bonds, amine groups and guanidine groups with an olefin copolymer.

Background technique

Antibacterial materials are a class of materials with antibacterial or bactericidal functions, which are made by adding one or several specific antibacterial agents. The development and application of antibacterial materials can set up a safety barrier for human health, and it has developed rapidly in recent years. Antibacterial products have huge market demand and bright development prospects.

Due to the wide application of polymer materials in daily life, the requirement of their antibacterial properties is an important aspect in the field of materials. Polymer antibacterial materials can generally be obtained by the following two methods:

(1) Add organic small molecule antibacterial agent or inorganic antibacterial agent directly in the polymer material. For example, inorganic antibacterial agents, such as zeolite materials containing metal ions (silver ions, copper ions, zinc ions, etc.), are directly added to the polymer matrix to prepare corresponding products. In the field of textile industry, fabrics have been treated with organic antibacterial agents of quaternary ammonium salts very early, so that the fabrics have antibacterial properties.

Patent CN 1552767A discloses a method of adding nano- _TiO2 after aluminate coupling agent surface modification to ethylene-vinyl acetate, extruding and granulating to prepare nano-antibacterial and anti-virus plastics; patent CN1115357C discloses a method , adding Ag-based, Cu-based and Zn-based antibacterial agents and benzimidazole antifungal agents to thermoplastic resins such as ethylene-vinyl acetate and polypropylene, and extruding to obtain an antibacterial and antifungal composition; patent CN 1078227C It is disclosed that the inorganic antibacterial agent powder is directly added to ethylene-vinyl acetate and polyethylene, and then extruded and blended to make an antibacterial masterbatch; Korean patent KR 9204827B discloses that quaternary ammonium salt antibacterial agents are added to ethylene-vinyl acetate Antibacterial and deodorant insoles are prepared from ester, polyurethane and polyvinyl chloride; Japanese patent JP9002517 discloses a method in which zeolite powder containing antibacterial metal ions is mixed into ethylene-vinyl acetate, polypropylene and polyethylene to prepare Drug packaging material. In the above patents, no matter adding an inorganic antibacterial agent or an organic small molecule antibacterial agent, their common disadvantage is that the antibacterial agent will be separated from the polymer matrix and lost. On the one hand, the product will lose its antibacterial performance; Harm.

(2) The material has antibacterial properties by chemically modifying the polymer molecular chain. For example, using methods such as grafting reaction, surface chemical modification, polymer block reaction and direct copolymerization of monomers, the functional groups with antibacterial activity are bonded to the molecular chain of the polymer in the form of chemical bonds, so that the material has Antibacterial properties. This is a more advanced method. It solves the problem that the antibacterial polymer material reduces its antibacterial performance due to the prolongation of time and is unsafe to the environment and human body.

Patent CN00125768.4 discloses a preparation method of special polypropylene material. By bonding an oligomer with antibacterial activity to a polypropylene matrix, a special polypropylene material with permanent antibacterial properties is obtained. But this patent is only applicable to the preparation of antibacterial material with polypropylene as base material.

Patent CN02111048.4 further discloses the preparation of other polyolefin antibacterial masterbatches, including polyethylene, polyvinyl chloride, polystyrene and other polyolefin materials, and further expands the use of chemical bonding methods to prepare antibacterial polymer materials, making its application The field is wider. However, the above two patents have not yet involved the copolymer aspect.

Patent US5408022 discloses the method of copolymerization to prepare polymer materials with permanent antibacterial properties. The antibacterial monomers used are quaternary ammonium monomers with double bonds, the number of double bonds can be one or more, and a cross-linked structure can be formed. The other monomers used are mainly acrylates or methacrylates. However, the antimicrobial monomers used have the disadvantage of being expensive.

Patent US6326417B1 discloses a polymerizable antibacterial composition. The antibacterial agents used are salicylic acid, salicylates, sulfonamides, or combinations thereof. Monomers are mainly acrylates and methacrylates. The inventors describe the obtained polymer as having permanent antimicrobial properties.

Although there are already some polymers that can achieve permanent antibacterial modification, limited by the development of technology, there are still many polymer varieties that are difficult to obtain reliable, safe, and long-lasting antibacterial properties.

Contents of the invention

The object of the present invention is to provide a functionalized olefin copolymer with the advantages of safety to the human body, excellent antibacterial effect and long-term effect, and its preparation method and application in order to overcome the defects of the above-mentioned prior art.

The object of the present invention can be achieved through the following technical solutions: a functionalized olefin copolymer, characterized in that the structural formula of the copolymer is as follows:

In the formula, X is chlorine, methyl, vinyl or hexyl; Y is methyl, ethyl, propyl, butyl and other alkane groups; R is polyamine and guanidinium oligomer; m, n and p are An integer greater than or equal to zero, and q is an integer greater than zero.

The molecular weight of the polyamine and guanidinium oligomer is between 300-50000, and its characteristic structure is as follows:

Among them, n is an integer of 2-16, m is an integer of 4-200, Y is an anion, including Cl ^- , NO ₃ ^- , HCO ₃ ^- , H ₂ PO ₄ ^- , X is an ion containing 1-5 active unsaturated Acyl or ester groups with double bonds, such as acryloyl, methacryloyl, maleoyl, fumaryl, itaconyl, undecylenoyl, acrylate, propyl acrylate, or methacrylate hydroxyl groups Propyl ester, etc., Z is hydrogen or X.

A method for preparing a functionalized olefin copolymer, characterized in that the method comprises the following steps: weighing 60wt% to 99.5wt% of olefin copolymer resin and 0.5wt% to 40wt% of polyamine and guanidinium oligomer Prepare a mixture whose total weight is 100%, then add 0-25wt% olefin monomer, 0.02wt%-10.0wt% initiator, 0-10.0wt% antioxidant based on the total weight of the mixture, It is prepared by solution reaction, melting reaction or solid phase reaction.

The olefin monomers include styrene, divinylbenzene, α-methylstyrene, methyl methacrylate, butyl acrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate ester.

Described initiator comprises dicumyl peroxide, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, One or more of 1,4-bis(tert-butylperoxyisopropyl)benzene, azobisisobutyronitrile and azobisisoheptanonitrile are used in combination.

The antioxidants include 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-α-dimethyl Amino-p-cresol, 2,4,6-tri-tert-butylphenol, dilauryl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate , Antioxidant 1010, Antioxidant CA in one or more combination.

The solution reaction method includes the following steps: adding various materials except the initiator into xylene solvent or other olefin copolymer solvents, gradually raising the temperature, and stirring to form a uniform liquid of 5% to 15%, and drumming After the nitrogen removes the oxygen, add the initiator gradually in 3-5 times, maintain the temperature for 2-4 hours, after the reaction, cool down the reaction solution or add a poor solvent to precipitate the solid, filter and dry to obtain the functionalized olefin copolymerization thing.

The melting reaction method includes the following steps: mixing various materials and adding them to a single-screw extruder or twin-screw extruder or internal mixer, and performing a melting reaction at 130°C to 200°C for 1min to 15min, from The functionalized olefin copolymer is collected in the reaction product.

The solid-phase grafting method includes the following steps: under nitrogen atmosphere, mix various materials crushed to more than 80 meshes and add them to the reactor, and carry out solid-phase reaction at 60°C to 120°C, and the reaction time is After 2-6 hours, the functionalized olefin copolymer is collected from the reaction product.

The application of a functionalized olefin copolymer is characterized in that the copolymer can be used alone to prepare olefin copolymer products with antibacterial function; it can also be used as a modifier for resins, and can be added to ethylene-octene in a certain proportion Copolymer (POE), ethylene-propylene rubber (EPR), ethylene-propylene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene Copolymer (ABS) and other resins are used to prepare plastic products with antibacterial functions.

Compared with the prior art, the functionalized olefin copolymer of the present invention is composed of olefin copolymer resin, polyamine and guanidinium oligomer, olefin monomer, initiator and antioxidant, through the method of solution, melting or solid phase reaction And get. It can be used alone to prepare olefin copolymer products with antibacterial function, and can also be combined with ethylene-octene copolymer (POE), ethylene-propylene rubber (EPR), ethylene-propylene terpolymer (EPDM), ethylene-vinyl acetate Copolymer (EVA), polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS) and other resins are blended to prepare corresponding products with antibacterial functions, and oligomers of polyamines and guanidine salts It is bonded to the molecular chain of olefin copolymer in the form of chemical bonds, which has the advantages of safety to the human body, excellent antibacterial effect and long-term effect, and avoids the traditional addition of inorganic or organic antibacterial agents that will gradually seep out or degrade in the product Phenomenon.

Detailed ways

The methods and processes involved in the present invention will be described below in conjunction with specific examples.

In the following specific examples, the bonding efficiency of the functionalized olefin copolymer is tested using infrared spectroscopy to measure the relative intensity of the characteristic peaks before and after purification, and the bonding efficiency can be obtained according to Lambert-Beer's law. The calculation formula is:

Bonding efficiency = C ₂ /C ₁ *100%

Wherein, C ₂ is the content of polyamine and guanidinium oligomer after purification; C ₁ is the content of polyamine and guanidine oligomer before purification.

The obtained functionalized olefin copolymer and its products blended with other resins have the bacteria performance test standard QB/T2591-2003.

Example 1

Get 100 grams of ethylene-vinyl acetate (EVA) resins, 15 grams of methacryloyl polyhexamethylenediamine guanidine nitrate, molecular weight 1000, styrene 4 grams, 1010 antioxidant 0.1 grams, join in the flask of 2000ml, then Add 1300 g of xylene, and gradually raise the temperature to 100°C. After all the solids were dissolved and nitrogen was blown to exclude oxygen, 1.3 grams of benzoyl peroxide was taken and added to the flask in 5 times within 4 hours, and the reaction was maintained at 100°C. After the reaction, the flask was cooled to room temperature, 100 g of acetone was added, and after stirring, the solid was completely precipitated, and then dried to obtain functionalized EVA. (No.: 1#)

The bonding efficiency measured by infrared spectroscopy was 75.3%.

Example 2

Get 10 kilograms of ethylene-octene copolymer resin (POE), 3 kilograms of acryloyl of polyethylenediamine guanidine hydrochloride, molecular weight is 3000, 200 grams of styrene, 1.5 grams of 1010 antioxidants, 3 grams of benzoyl peroxide, 16 grams of lauryl peroxide were all put into a high-speed mixer and mixed for 2 minutes before discharging. The compound was put into a single-screw extruder, and was extruded at a speed of 60 rpm. The extruded product was collected to obtain the functionalized POE. (No.: 2#)

The bonding efficiency measured by infrared spectroscopy was 85%.

Example 3

Get 5 kilograms of ethylene-propylene rubber (EPR), 100 grams of maleyl of polyethylenediamine carbonate guanidine carbonate, molecular weight is 5000, 10 grams of α-methylstyrene, 2 grams of dicumyl peroxide, all put into high-speed mixing Mix in the machine for 2 minutes and discharge. The compound was added into a twin-screw extruder, and was extruded at a speed of 50 rpm. The extruded product was collected to obtain the functionalized EPR.

The bonding efficiency measured by infrared spectroscopy was 90%. The functionalized EPR was molded to obtain a test sample, numbered as: A.

Example 4

Get 1.0 kilograms of ethylene-vinyl chloride copolymer resin after pulverizing, 30 grams of fumaryl powder material of polyhexamethylenediamine phosphate guanidine, molecular weight is 6000, 5 grams of hydroxyethyl methacrylate, mix and add to 2000ml belt In a reaction kettle with a ribbon-type stirring paddle, the temperature was raised to 100° C., and 3 grams of dicumyl peroxide was added three times within two hours to initiate the reaction. After the reaction, the functionalized ethylene-vinyl chloride copolymer was collected.

The bonding efficiency measured by infrared spectroscopy was 88%. The functionalized ethylene-vinyl chloride was molded to obtain a sample, numbered as: B.

Example 5

Get 10 kilograms of vinyl chloride-vinyl acetate copolymer resins, 100 grams of undecylenyl polybutylene diamine guanidine carbonate, molecular weight is 2000, 20 grams of ethyl methacrylate, 1,4-bis(tert-butyl peroxide) 2 grams of cumene oxide, all put into the high-speed mixer and mix for 2 minutes, discharging. The compound was added into a single-screw extruder and extruded at a speed of 50 rpm. The extruded product was collected to obtain a functionalized vinyl chloride-vinyl acetate copolymer.

The bonding efficiency measured by infrared spectroscopy was 92%. The sample is obtained by molding the functionalized material, and the number is: C.

Example 6

Get 5 kilograms of vinyl chloride-ethylene-vinyl acetate terpolymer resins, 200 grams of acryl of polyethylenediamine guanidine carbonate, molecular weight is 7000, 30 grams of methyl methacrylate, 2 grams of azobisisoheptanonitrile, Put all in a high-speed mixer and mix for 2 minutes, then discharge. The compound was added into a single-screw extruder and extruded at a speed of 50 rpm. The extruded product was collected to obtain functionalized vinyl chloride-ethylene-vinyl acetate.

The bonding efficiency measured by infrared spectroscopy was 87%. The functionalized vinyl chloride-ethylene-vinyl acetate is molded to obtain a sample, and the code is: D.

Example 7

Get 5 kilograms of ethylene-butadiene copolymer resins, 250 grams of polypropylene diamine guanidine carbonate methacryloyl, molecular weight is 3500, 50 grams of butyl acrylate, 3 grams of azobisisobutyronitrile, 0.3 grams of 1010 antioxidant , all put into a high-speed mixer and mix for 2 minutes, then discharge. The compound was added into a single-screw extruder, and extruded at a speed of 80 rpm. The extruded product was collected to obtain functionalized ethylene-butadiene.

The bonding efficiency measured by infrared spectroscopy was 82%. Functionalized ethylene-butadiene was molded to obtain a test sample, numbered as: E.

Application examples of functionalized olefin copolymers:

Example 8

Get 2 kilograms of ethylene-vinyl acetate (EVA), 200 grams of 1# functionalized EVA, 8 grams of 1010 antioxidants, in a twin-screw extruder, mix and granulate at 160 ° C to obtain EVA with antibacterial properties, No. For: F.

Example 9

Take 2 kg of PE, 200 grams of 2# functionalized POE, and 10 grams of 1010 antioxidant, mix and granulate in a twin-screw extruder at 160 ° C to obtain PE with antibacterial properties, code: G.

Example 10

Take 2 kg of PVC, 160 grams of 1# functionalized EVA, 50 grams of di-n-octyltin bis (isooctylthioglycolate), 6 grams of di-n-octyltin laurate, 4 grams of paraffin, 8 grams of stearic acid, stearyl alcohol 8 grams, granulate by twin-screw extruder, obtain the PVC with antibacterial property, numbering is: H.

Comparative example

Comparative example 1: the pure EVA material is molded into a sheet, and the sample number is: I.

Comparative example 2: get 2 kilograms of PVC, two (isooctyl thioglycolate) di-n-octyl tin 50 grams, 6 grams of di-n-octyl tin laurate, 4 grams of paraffin, 8 grams of stearic acid, 8 grams of stearyl alcohol, Pelletized by twin-screw extruder, molded to obtain a PVC sample, number: J.

Comparative example 3: Soak samples A, B, C, D, E, F, G, and H in water for 30 days, take them out, rinse with water, and number the samples as A', B', C', D', E', F', G' and H'.

The antibacterial test results of various samples are shown in Table 1:

The antibacterial test result of table 1 sample

sample Antibacterial rate against Escherichia coli (within 24 hours) Antibacterial rate against Staphylococcus aureus (within 24 hours) A ＞99% ＞99% B ＞99% ＞99% C ＞99% ＞99% D ＞99% ＞99% E ＞99% ＞99% F ＞99% ＞99% G ＞99% ＞99% h ＞99% ＞99%

I ＜10% ＜10% J ＜15% ＜15% A' ＞99% ＞99% B' ＞99% ＞99% C' ＞99% ＞99% D' ＞99% ＞99% E' ＞99% ＞99% F' ＞99% ＞99% G' ＞99% ＞99% H' ＞99% ＞99%

It can be seen from the above test results that the obtained functionalized olefin copolymer can be made into antibacterial products alone, or can be blended with other resins to make corresponding antibacterial products. The obtained antibacterial product has excellent antibacterial performance, and meanwhile, the antibacterial performance will not decrease with soaking in water. Products without functionalized antibacterial materials basically do not have antibacterial properties.

The above-mentioned examples and comparative examples are some specific illustrations of the present invention, rather than limiting the present invention.

The raw materials and consumption that prepare said functionalized olefin copolymer masterbatch adopt are as follows:

The olefin copolymer resin of 60%-99.5% (parts by weight) of the component (1) includes ethylene-octene copolymer (POE), ethylene-propylene rubber (EPR), ethylene-propylene terpolymer (EPDM), Ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl chloride copolymer, vinyl chloride-ethylene-vinyl acetate terpolymer, ethylene-butylene copolymer, vinyl chloride-vinyl acetate, etc.

The component (2) is 0.5% to 40% (by weight) polyamine and guanidinium oligomer, and its molecular weight ranges from 300 to 50,000. If the molecular weight is less than 300, it is difficult to increase the amount of reaction in the olefin copolymer, so that the number of antibacterial functional groups decreases; however, if the molecular weight is greater than 50,000, the melt viscosity of the polyamine and the guanidinium salt oligomer will increase, and the reaction Cross-linking reaction is prone to occur when the functionalized olefin copolymer is used, resulting in a decrease in the performance of the functionalized olefin copolymer. Therefore, the suitable molecular weight range of polyamine and guanidinium salt oligomer is 300-50000; the usage amount thereof is 0.5%-40% by weight. If the amount of polyamine and guanidinium oligomer used is less than 0.5%, the antibacterial performance of the obtained functionalized olefin copolymer is not strong. However, if the amount is greater than 40% (weight), on the one hand, it will cause crosslinking of the olefin copolymer, reducing the fluidity, usability or economical applicability of the functionalized resin.

The sum of the weight of components (1) and (2) is 100%. The added amounts of the following components are based on the weight sum of (1) and (2).

(3) 0-25% (weight) of olefin monomers, such as styrene, divinylbenzene, α-methylstyrene, methyl methacrylate, butyl acrylate, ethyl methacrylate, methacrylic acid Hydroxyethyl ester, hydroxypropyl methacrylate, etc. Said olefin monomer is used in an amount of 0-25.0% by weight. Adding olefin monomers can improve the bonding efficiency, but if the amount is greater than 25.0% (weight), homopolymerization of olefins and residual monomers may occur, deteriorating the performance of functionalized olefin copolymers.

(4) 0.02% to 10.0% initiators, such as dicumyl peroxide, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl Benzoate peroxide, 1,4-bis(t-butylperoxyisopropyl)benzene, etc., or azobisisobutyronitrile, azobisisoheptylonitrile, etc. If the consumption of initiator is lower than 0.02% (weight), the concentration of free radicals produced is too low, and the bonding rate of polyamine and guanidinium oligomer will be greatly reduced, which will affect the antibacterial performance of functionalized olefin copolymer, and also cause Free residues of polyamines and guanidinium oligomers. If the amount of the initiator is more than 10.0% by weight, it will cause cross-linking reaction and reduce the processability and other properties of the functionalized olefin copolymer. One of the initiators can be used alone or several initiators can be used in combination.

(5) 0-10% (weight) of antioxidants, such as 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6- Di-tert-butyl-α-dimethylamino-p-cresol, 2,4,6-tri-tert-butylphenol, dilauryl thiodipropionate, dioctadecyl thiodipropionate, thiodipropionate Dipropionate di(tetradecyl), antioxidant 1010 or antioxidant CA, etc. The amount of said antioxidant is 0-10% (weight). The addition of antioxidant can adjust the reaction and melt fluidity of the functionalized olefin copolymer, but if the addition is greater than 10%, the concentration of free radicals in the grafting reaction will be reduced, and effective bonding reactions cannot be produced. One or several antioxidants can be used alone or in combination.

Claims (10)

1. a functional olefin copolymers is characterized in that, the structural formula of this multipolymer is as follows:

In the formula, X is chlorine, methyl, vinyl or hexyl; Y is alkane groups such as methyl, ethyl, propyl group, butyl; R is polyamine and guanidinesalt oligopolymer; M, n and p are the integer more than or equal to zero, and q is the integer greater than zero.

2. a kind of functional olefin copolymers according to claim 1 is characterized in that, described polyamine and guanidinesalt oligopolymer, and its molecular weight is between 300-50000, and feature structure is as follows:

Wherein, n is the integer of 2-16, and m is the integer of 4-200, and Y is a negatively charged ion, comprises Cl ^-, NO ₃ ^-, HCO ₃ ^-, H ₂PO ₄ ^-, X is acyl class or the ester class group that contains 1-5 active unsaturated double-bond, as acryloyl, methacryloyl, maleoyl, fumaryl, clothing health acyl, undecylene acyl, acrylate, propyl acrylate or methacrylic acid hydroxyl propyl ester etc., Z is hydrogen or X.

3. the preparation method of a functional olefin copolymers, it is characterized in that, this method may further comprise the steps: taking by weighing the polyamine of the olefin copolymer resin of 60wt%～99.5wt% and 0.5wt%～40wt% and guanidinesalt oligopolymer, to be made into the weight summation be 100% mixture, gross weight with this mixture is the olefinic monomer that benchmark adds 0～25wt% again, the initiator of 0.02wt%～10.0wt%, the oxidation inhibitor of 0-10.0wt% adopts the method for solution reaction, frit reaction or solid state reaction to be prepared.

4. the preparation method of a kind of functional olefin copolymers according to claim 3, it is characterized in that described olefinic monomer comprises vinylbenzene, Vinylstyrene, alpha-methyl styrene, methyl methacrylate, butyl acrylate, Jia Jibingxisuanyizhi, hydroxyethyl methylacrylate, Rocryl 410.

5. the preparation method of a kind of functional olefin copolymers according to claim 3, it is characterized in that, described initiator comprises dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate, 1, and one or several in two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-, azobisisobutyronitrile, azo two eyeball in different heptan are united use.

6. the preparation method of a kind of functional olefin copolymers according to claim 3, it is characterized in that, described oxidation inhibitor comprises 2,6-di-t-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4, one or more in 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, the antioxidant CA are united use.

7. the preparation method of a kind of functional olefin copolymers according to claim 3, it is characterized in that, described solution reaction method comprises the steps: the various materials except that initiator are joined in xylene solvent or other the olefin copolymer solvent, progressively heat up, and stir, form 5%～15% uniform liquid, after drum nitrogen is got rid of oxygen, divide and progressively add initiator 3-5 time, holding temperature reaction 2～4 hours is after reaction finishes, with reaction solution cooling or adding poor solvent, solid is separated out, after filtration, obtain functional olefin copolymers after the drying.

8. the preparation method of a kind of functional olefin copolymers according to claim 3, it is characterized in that, described frit reaction method comprises the steps: and will join after the various mixing of materials in single screw extrusion machine or twin screw extruder or the Banbury mixer, under 130 ℃～200 ℃, carry out frit reaction 1min～15min, collecting function olefin copolymer from reaction product.

9. the preparation method of a kind of functional olefin copolymers according to claim 3, it is characterized in that, described solid phase grafting method comprises the steps: under nitrogen atmosphere, to join in the reactor after the various mixing of materials that are crushed to more than 80 orders, under 60 ℃～120 ℃, carry out solid state reaction, reacted collecting function olefin copolymer from reaction product 2～6 hours.

10. the application of a functional olefin copolymers is characterized in that, this multipolymer may be used solely to prepare the olefin-copolymerization Tetramune with antibacterial; Also can be used as the properties-correcting agent of resin, join in certain proportion in ethylene-octene copolymer (POE), ethylene-propylene rubber(EPR) (EPR), ethylene-propylene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride (PVC), the acrylonitrile-butadiene-styrene copolymer resins such as (ABS), preparation has the plastics of antibacterial.