CN103739786A

CN103739786A - High polymer quaternary phosphonium salt antibacterial material and preparation method thereof

Info

Publication number: CN103739786A
Application number: CN201310753513.5A
Authority: CN
Inventors: 王毛力; 王经武; 李中灵; 夏令红; 位秀莲; 郑世军; 徐慎刚
Original assignee: HENAN JINYU PACKAGING SCIENCE AND TECHNOLOGICAL CO Ltd
Current assignee: HENAN JINYU PACKAGING SCIENCE AND TECHNOLOGICAL CO Ltd
Priority date: 2013-12-31
Filing date: 2013-12-31
Publication date: 2014-04-23
Anticipated expiration: 2033-12-31
Also published as: CN103739786B

Abstract

The invention discloses a high polymer quaternary phosphonium salt antibacterial material and a preparation method thereof. The high polymer quaternary phosphonium salt antibacterial material is prepared by bonding halogenacylhalide type monomers onto macromolecules of an ethylene-vinyl alcohol copolymer (EVOH) through grafting reaction and further performing quaternary phosphonium reaction with trialkylphosphine. The high polymer quaternary phosphonium salt antibacterial material disclosed by the invention has the advantages of broad-spectrum, high-efficient and lasting antibacterial function and good safety, can be shaped and processed into products with the antibacterial function alone, and mixed with polyethylene, polypropylene and other non-polar resin and other types of resin for being shaped and processed into the products with the antibacterial function, and further has broad application prospects. The sterilization efficiency of the high polymer quaternary phosphonium salt antibacterial material prepared by the preparation method disclosed by the invention against escherichia coli, staphylococcus aureus and a variety of bacteria is more than 99%, and the mildew-resistant grade against aspergillus niger, aspergillus terreus and a variety of mildew is 1-0 grade.

Description

Macromolecule quaternary alkylphosphonium salt anti-biotic material and preparation method thereof

One, technical field:

The present invention relates to a kind of high-molecular anti-bacteria material and preparation method thereof, particularly relate to a kind of macromolecule quaternary alkylphosphonium salt anti-biotic material and preparation method thereof.

Two, background technology:

Along with developing rapidly of organic polymer material industry, material and increasingly extensive being employed of goods such as plastics, fiber, rubber, coating and tackiness agent.These materials and goods, as plastic packing product, if do not have antibacterial, products to be packaged are corroded in the meetings such as bacterium, mould makes its rotten or damage.The pollution to product surface such as bacterium, mould and growing, can produce cross infection to using with the people that contact it, and health is formed to certain threat.Anti-biotic material is to extremely sensitive chemical substances of microorganism such as some bacteriums, mould, fungies, not only itself has antibacterial, joined in the materials such as plastics, fiber, rubber, coating and tackiness agent and goods, also can give its antibacterial, not only keep material and goods self not to be subject to the destruction of bacterium, mould etc., as packing articles, can also protect packaged article to never degenerate or sustain damage; Can also avoid or reduce the crossed contaminations such as bacterium between person to person, people and thing, thing and the thing because using these goods to occur, mould, be beneficial to people's health.

Produce now and the high-molecular anti-bacteria material of application, be mostly to be easy to by means of organic polymer material the advantage of forming process, make by simple physical blend or increase-volume physical blending with small molecules inorganic antiseptic, organic antibacterial agent.Be mainly used in the goods such as plastics, fiber, rubber, coating and tackiness agent.Though the anti-biotic material and the goods that make like this have antibacterial, there is an outstanding problem: because the consistency of antiseptic-germicide and matrix is limited, antiseptic-germicide easily moves loss, causes keeping the long-lasting of antibacterial.As wrapping material and goods, also can pollute packaged article, easily human body etc. be damaged again.The organic high molecular compound that is linked with antibacterial functional group both separately forming process become to have the goods of antibacterial, overcome again small molecules antiseptic-germicide physical blending is given antibacterial shortcoming in macromolecular material, also had than the better anti-microbial property of small molecules antiseptic-germicide simultaneously.Therefore, the synthetic and application of high-molecular anti-bacteria material is just becoming a focus of current research and development.

Application number is the patent application of 200710027027.X, disclose a kind of by dimethylaminoethyl methacrylate alkyl halide and two kinds of monomer copolymerizations of maleic anhydride, or a kind of reactable polymer antibacterial agent being formed by any one material in acrylamide, butyl acrylate or vinylbenzene and dimethylaminoethyl methacrylate alkyl halide and three kinds of monomer copolymerizations of maleic anhydride, this polymer antibacterial agent provides a kind of wide spectrum, efficient, safe durable antibiotic material.Application number is 200910144560.3 patent application, discloses a kind of method of being prepared guanidine family macromolecule antiseptic-germicide by functionalization guanidinesalt and vinylbenzene or acrylamide copolymerization, and this antibacterial antiplaque agent effect is remarkable, and thermotolerance is better, and antibacterial functional group is difficult for migration.But, the now high-molecular anti-bacteria material of research and development, or because of the thermo-sensitivity of antibacterial functional group, make the thermotolerance of antimicrobial macromolecule material not good enough, directly affect its application; Or because of bad with the consistency of large kind organic polymer material (as resins such as polyethylene, polypropylene), also make its Application Areas be very restricted.

Three, summary of the invention:

The technical problem to be solved in the present invention is: a kind of macromolecule quaternary alkylphosphonium salt anti-biotic material and preparation method thereof is provided.The present invention is keyed to halogen acyl halide class monomer on ethylene-vinyl alcohol copolymer EVOH macromole by graft reaction, further carries out quaternary phosphine with trialkyl phosphine and reacts, and prepares product macromolecule quaternary alkylphosphonium salt anti-biotic material of the present invention.Macromolecule quaternary alkylphosphonium salt anti-biotic material prepared by the present invention both separately forming process become to have the goods of long-acting, clean antibacterial, be easy to again and the resin alloy such as polyethylene, polypropylene the goods such as that forming process becomes to have is long-acting, the antibacterial polyethylene of sanitary characteristics, polypropylene.

In order to address the above problem, the technical solution used in the present invention is:

The invention provides a kind of macromolecule quaternary alkylphosphonium salt anti-biotic material, the general structure of described macromolecule quaternary alkylphosphonium salt anti-biotic material is:

Wherein R ₁that halogen acyl halide class monomer reacts the group forming with hydroxyl-OH on ethylene-vinyl alcohol copolymer EVOH molecular chain; R ₂r ₁group carries out quaternary phosphine with trialkyl phosphine and reacts formation quaternary alkylphosphonium salt group.

According to above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, described halogen acyl halide class monomer is that chloroacetyl chloride, 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride, 4-chloromethyl benzoic acid chlorides, 3-are chloro-2,2-dimethyl propylene acyl chlorides, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride, 5-bromine valeryl chloride, 6-bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and to any in brooethyl benzoyl bromide.

According to above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, described trialkyl phosphine is any in tripropyl phosphine, tributylphosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopentyl phosphines, tricyclohexyl phosphine, triphenylphosphine and three p-methylphenyl phosphines.

According to above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, structural unit-CH in described a Wei quaternary alkylphosphonium salt anti-biotic material general structure ₂-CH ₂-number; Structural unit in b Wei quaternary alkylphosphonium salt anti-biotic material general structure

number; Structural unit in c Wei quaternary alkylphosphonium salt anti-biotic material general structure

number; Structural unit in d Wei quaternary alkylphosphonium salt anti-biotic material general structure number.

In addition, provide a kind of preparation method of macromolecule quaternary alkylphosphonium salt anti-biotic material, described preparation method comprises the following steps:

A, take ethylene-vinyl alcohol copolymer EVOH and halogen acyl halide class monomer as basic raw material, on described ethylene-vinyl alcohol copolymer-mol ratio of OH and halogen acyl halide class monomer is 1:1～1.4; First use dissolution with solvents EVOH, between EVOH and solvent, the ratio of add-on is 1g EVOH:4～8mL solvent, drips halogen acyl halide class monomer after dissolving, and after dripping, temperature of reaction system is risen to 70～120 ℃, with this understanding, and reaction times 8～16h; After reaction finishes, slowly pour reaction solution in precipitating agent precipitating, precipitating agent volumetric usage is 2～8 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 4～8h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the precipitating agent of 1～2 times of reaction solution volume, after immersion 4～8h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts of EVOH and halogen acyl halide;

The grafts dissolution with solvents of b, the EVOH that step a is obtained and halogen acyl halide, the quality of described solvent is EVOH and halogen acyl halide grafts quality 1.5～4.5 times, after dissolving, add trialkyl phosphine, in trialkyl phosphine and EVOH grafts-mol ratio between Cl is 1:1～2.0; Controlling temperature of reaction system is 100～135 ℃, and the reaction times is 20～80h; After reaction finishes, gained reaction solution is slowly poured in precipitating agent and carried out precipitating, precipitating agent volumetric usage is 2～8 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4～8h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the precipitating agent of 1～2 times of reaction solution volume, after immersion 4～8h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains product macromolecule quaternary alkylphosphonium salt anti-biotic material.

According to the preparation method of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, the vinyl alcohol units mass content of the EVOH of ethylene-vinyl alcohol copolymer described in step a is 7～55%, and ethylene-vinyl alcohol copolymer EVOH is that 190 ℃, load are that quality melt flow rate (MFR) under 21.168N condition is 2.0～300.0g/10min in temperature.

According to the preparation method of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, the class of halogen acyl halide described in step a monomer is that chloroacetyl chloride, 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride, 4-chloromethyl benzoic acid chlorides, 3-are chloro-2,2-dimethyl propylene acyl chlorides, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride, 5-bromine valeryl chloride, 6-bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and to any in brooethyl benzoyl bromide.

According to the preparation method of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, solvent described in step a is any in toluene, dimethylbenzene, dioxane and tetrahydrofuran (THF); Described precipitating agent is methyl alcohol, ethanol or acetone.

According to the preparation method of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, trialkyl phosphine described in step b is any in tripropyl phosphine, tributylphosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopentyl phosphines, tricyclohexyl phosphine, triphenylphosphine and three p-methylphenyl phosphines.

According to the preparation method of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material, solvent described in step b is toluene, dimethylbenzene or dioxane; Described precipitating agent is sherwood oil, acetone or ether.

Positive beneficial effect of the present invention:

1, the antibacterial functional group of macromolecule quaternary alkylphosphonium salt anti-biotic material that prepared by the present invention is connected on macromole, and or not containing free small-molecule substance, not only antibacterial is not lasting, and the goods of material and forming process have good spatter property.

2, the matrix resin ethylene-vinyl alcohol copolymer EVOH Polymer chain flexibility that the present invention adopts is good, be conducive to strengthen antibacterial, the macromolecule quaternary alkylphosphonium salt anti-biotic material of preparing reaches more than 99% various bacteria germ-killing efficiencies such as intestinal bacteria, streptococcus aureuses, to the mildew-resistant grade of the multiple moulds such as aspergillus niger, terreus, is 1～0 grade.

3, the macromolecule quaternary alkylphosphonium salt anti-biotic material that prepared by the present invention both separately forming process become to have the goods of long-acting, clean antibacterial, consistency because having had with the large kind organic polymer material such as polyethylene, polypropylene again, be easy to and its blend, give the antibacterial of polyethylene, polypropylene etc., forming process becomes to have the goods such as the antibacterial polyethylene, polypropylene of long-acting, sanitary characteristics, and Application Areas is wide.

Four, accompanying drawing explanation:

The infrared spectrum of Fig. 1 ethylene-vinyl alcohol copolymer EVOH grafting 4-chlorobutanoylchloride;

The infrared spectrum of the reaction product of Fig. 2 ethylene-vinyl alcohol copolymer EVOH grafting 4-chlorobutanoylchloride and tributylphosphine;

The infrared spectrum of Fig. 3 ethylene-vinyl alcohol copolymer EVOH grafting 4-chloromethyl benzoic acid chlorides;

The infrared spectrum of the reaction product of Fig. 4 ethylene-vinyl alcohol copolymer EVOH grafting 4-chloromethyl benzoic acid chlorides and tributylphosphine.

Five, embodiment:

Below in conjunction with embodiment, further set forth the present invention, but do not limit content of the present invention.

Embodiment 1:

Macromolecule quaternary alkylphosphonium salt anti-biotic material of the present invention, its concrete structure formula is:

The preparation method of the above-mentioned macromolecule quaternary alkylphosphonium salt of the present invention anti-biotic material, its detailed step is as follows:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 4-chlorobutanoylchloride as basic raw material, first 53.0g EVOH is joined in 500mL four-hole boiling flask, add again 320mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 28.2g4-chlorobutanoylchloride, after dripping, isothermal reaction 9h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 5 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 6h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 6h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 68.8g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 75.6%; The half-finished concrete structure formula of gained is:

The reaction product of EVOH grafting 4-chlorobutanoylchloride is that half-finished infrared spectrum refers to accompanying drawing 1;

B, the 68.8g EVOH graft product work in-process that step a is obtained join in 500mL four-hole boiling flask, add again 175mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 61.1g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 6h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 94.5g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 84.3%; The concrete structure formula of product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

The reaction product of the present embodiment EVOH grafting 4-chlorobutanoylchloride and tributylphosphine is that the infrared spectrum of the finished product refers to accompanying drawing 2.

Embodiment 2:

Macromolecule quaternary alkylphosphonium salt anti-biotic material of the present invention, its concrete structure formula is with embodiment 1.

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 4-chlorobutanoylchloride as basic raw material, first 53.0g EVOH is joined in 500mL four-hole boiling flask, add again 320mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 36.7g4-chlorobutanoylchloride, after dripping, isothermal reaction 9h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 3 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 7h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 6h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 70.8g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 85.0%; The half-finished concrete structure formula of gained is with embodiment 1;

B, the 35.4g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 90mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 34.3g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 4 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 7h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 6h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 50.0g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 85.1%; The concrete structure formula of its product is with embodiment 1.

Embodiment 3:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 4-chlorobutanoylchloride as basic raw material, first 53.0g EVOH is joined in 500mL four-hole boiling flask, add again 320mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 36.7g4-chlorobutanoylchloride, after dripping, isothermal reaction 9h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 8 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.8 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 70.8g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 85.0%; The half-finished concrete structure formula of gained is with embodiment 1;

B, the 35.4g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 90mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 20.6g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 8 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 5h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1.8 times of reaction solution volumes, after immersion 4h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 47.3g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 69.4%; The concrete structure formula of the finished product is with embodiment 1.

Embodiment 4:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 4-chlorobutanoylchloride as basic raw material, first 26.5g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 18.3g4-chlorobutanoylchloride, after dripping, isothermal reaction 9h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 3 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 8h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1 times of reaction solution volume, after immersion 8h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 35.4g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 85.0%; The half-finished concrete structure formula of gained is:

B, the 35.4g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 90mL dimethylbenzene, stir and be warming up to 125 ℃, after dissolving completely, drip 27.2g tripropyl phosphine, after dripping under 125 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 3 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 8h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1 times of reaction solution volume, after immersion 8h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 46.0g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 78.3%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 5:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 7.7%) and 3-bromo propionyl chloro as basic raw material, first 27.9g EVOH is joined in 250mL four-hole boiling flask, add again 140mL dimethylbenzene to dissolve, stir and be warming up to 95 ℃, after EVOH dissolves completely, drip 14.8g3-bromo propionyl chloro, after dripping, isothermal reaction 12h under 95 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 33.2g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 80.2%; The half-finished concrete structure formula of gained is:

B, the 33.2g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 110mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 15.8g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 39.9g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 84.5%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 6:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 2-chlorpromazine chloride as basic raw material, first 28.3g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 16.3g2-chlorpromazine chloride, after dripping, isothermal reaction 10h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in methyl alcohol precipitating, methyl alcohol volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the methyl alcohol of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 36.2g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 81.3%; The half-finished concrete structure formula of gained is:

B, the 36.2g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 110mL dimethylbenzene, stir and be warming up to 135 ℃, after dissolving completely, drip 26.3g tributylphosphine, after dripping under 135 ℃ of conditions isothermal reaction 50h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 49.4g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 75.6%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 7:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 36.3%) and 4-bromobutanoylchloride as basic raw material, first 20.1g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 40.0g4-bromobutanoylchloride, after dripping, isothermal reaction 10h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 41.3g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 85.6%; The half-finished concrete structure formula of gained is:

B, the 41.3g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 56.1g tri-p-methylphenyl phosphines, after dripping under 130 ℃ of conditions isothermal reaction 80h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 68.6g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 63.2%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 8:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 5-Chlorovaleryl Chloride as basic raw material, first 30.2g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dioxane to dissolve, stir and be warming up to 90 ℃, after EVOH dissolves completely, drip 22.9g5-chlorine valeryl chloride, after dripping, isothermal reaction 12h under 90 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 42.0g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 87.3%; The half-finished concrete structure formula of gained is:

B, the 42.0g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 26.1g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 50h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 56.6g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 72.5%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 9:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 36.3%) and 2-bromo propionyl chloro as basic raw material, first 21.3g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 80 ℃, after EVOH dissolves completely, drip 42.2g2-bromo propionyl chloro, after dripping, isothermal reaction 8h under 80 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 39.2g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 75.8%; The half-finished concrete structure formula of gained is:

B, the 39.2g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 135 ℃, after dissolving completely, drip 64.1g tri octyl phosphine, after dripping under 135 ℃ of conditions isothermal reaction 40h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 59.6g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 41.2%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 10:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 4-chloromethyl benzoic acid chlorides as basic raw material, first 26.5g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 100 ℃, after EVOH dissolves completely, drip 24.6g4-chloromethyl benzoic acid chlorides, after dripping, isothermal reaction 9h under 100 ℃ of conditions; After reaction finishes, slowly pour reaction solution in ethanol precipitating, ethanol volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the ethanol of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 36.8g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 67.5%; The half-finished concrete structure formula of gained is:

The infrared spectrum of EVOH grafting 4-chloromethyl benzoic acid chlorides is as accompanying drawing 3;

B, the 36.8g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, then add 140mL toluene, stir and be warming up to 110 ℃, after dissolving completely, drip 17.7g tributylphosphine, after dripping under 110 ℃ of conditions isothermal reaction 40h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 48.5g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 85.6%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

The reaction product of EVOH grafting 4-chloromethyl benzoic acid chlorides and tributylphosphine is that the infrared spectrum of the finished product is as accompanying drawing 4.

Embodiment 11:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and the bromo-2-methyl-prop of 2-acylbromide as basic raw material, first 26.5g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 90 ℃, after EVOH dissolves completely, drip the bromo-2-methyl-prop of 29.9g2-acylbromide, after dripping, isothermal reaction 12h under 90 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 36.5g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 67.3%; The half-finished concrete structure formula of gained is:

B, the 36.5g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 100mL dimethylbenzene, stir and be warming up to 135 ℃, after dissolving completely, drip 27.2g tributylphosphine, after dripping under 135 ℃ of conditions isothermal reaction 70h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 5 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 6h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 44.9g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 61.6%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 12:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 7.7%) and bromoacetyl bromide as basic raw material, first 29.3g EVOH is joined in 250mL four-hole boiling flask, add again 150mL toluene to dissolve, stir and be warming up to 90 ℃, after EVOH dissolves completely, drip 13.5g bromoacetyl bromide, after dripping, isothermal reaction 10h under 90 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 33.7g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 71.2%; The half-finished concrete structure formula of gained is:

B, the 33.7g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 100mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 14.7g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 7 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 39.6g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 80.5%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 13:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 6-bromine caproyl chloride as basic raw material, first 25.1g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 90 ℃, after EVOH dissolves completely, drip 26.3g6-bromine caproyl chloride, after dripping, isothermal reaction 12h under 90 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 39.3g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 84.7%; The half-finished concrete structure formula of gained is:

B, the 39.3g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 100mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 32.4g tricyclohexyl phosphine, after dripping under 130 ℃ of conditions isothermal reaction 80h; Gained reaction solution is poured precipitating in ether into, and ether volumetric usage is 8 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 5h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the ether of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 49.5g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 63.1%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 14:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 4-chlorobutanoylchloride as basic raw material, first 26.5g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 18.3g4-chlorobutanoylchloride, after dripping, isothermal reaction 9h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 35.4g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 85.0%; The half-finished concrete structure formula of gained is:

B, the 35.4g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 90mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 40.5g tri-cyclopentyl phosphines, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 8 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 5h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 51.0g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 77.1%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 15:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 7.7%) and 2-bromo propionyl chloro as basic raw material, first 28.7g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 90 ℃, after EVOH dissolves completely, drip 14.1g2-bromo propionyl chloro, after dripping, isothermal reaction 12h under 90 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 33.8g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 75.3%; The half-finished concrete structure formula of gained is:

B, the 33.8g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 105mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 14.7g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 8 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 5h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 39.8g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 78.5%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 16:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 7.7%) and to brooethyl benzoyl bromide as basic raw material, first 28.6g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 110 ℃, after EVOH dissolves completely, drip 18.1g to brooethyl benzoyl bromide, after dripping, isothermal reaction 12h under 110 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 34.7g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 62.4%; The half-finished concrete structure formula of gained is:

B, the 34.7g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 105mL dimethylbenzene, stir and be warming up to 110 ℃, after dissolving completely, drip 8.2g tributylphosphine, after dripping under 110 ℃ of conditions isothermal reaction 40h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 40.0g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 84.6%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 17:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 7.7%) and 3-chloro-2,2-dimethyl propylene acyl chlorides is basic raw material, first 28.6g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 100 ℃, after EVOH dissolves completely, drip 10.9g3-chloro-2,2-dimethyl propylene acyl chlorides, after dripping, isothermal reaction 10h under 100 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 32.6g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 68.3%; The half-finished concrete structure formula of gained is:

B, the 32.6g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 100mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 13.8g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 37.2g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 66.5%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 18:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 36.3%) and bromoacetyl chloride as basic raw material, first 22.5g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 80 ℃, after EVOH dissolves completely, drip 35.1g bromoacetyl chloride, after dripping, isothermal reaction 8h under 80 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 42.0g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 86.3%; The half-finished concrete structure formula of gained is:

B, the 42.0g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 135 ℃, after dissolving completely, drip 68.7g tri-hexyl phosphines, after dripping under 135 ℃ of conditions isothermal reaction 50h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 75.7g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 73.6%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 19:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 6-chlorine caproyl chloride as basic raw material, first 27.1g EVOH is joined in 250mL four-hole boiling flask, add again 130mL dimethylbenzene to dissolve, stir and be warming up to 90 ℃, after EVOH dissolves completely, drip 24.2g6-chlorine caproyl chloride, after dripping, isothermal reaction 14h under 90 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 38.4g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 83.7%; The half-finished concrete structure formula of gained is:

B, the 38.4g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 125 ℃, after dissolving completely, drip 22.5g tributylphosphine, after dripping under 125 ℃ of conditions isothermal reaction 70h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 50.4g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 69.5%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 20:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 36.3%) and 3-bromo propionyl chloro as basic raw material, first 20.6g EVOH is joined in 250mL four-hole boiling flask, add again 160mL dimethylbenzene to dissolve, stir and be warming up to 80 ℃, after EVOH dissolves completely, drip 37.9g3-bromo propionyl chloro, after dripping, isothermal reaction 8h under 80 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 40.1g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 84.8%; The half-finished concrete structure formula of gained is:

B, the 40.1g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 75.5g triphenylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 50h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 59.5g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 50.2%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 21:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and 3-chlorpromazine chloride as basic raw material, first 27.5g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 17.1g3-chlorpromazine chloride, after dripping, isothermal reaction 10h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 35.5g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 85.7%; The half-finished concrete structure formula of gained is:

B, the 35.5g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 105mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 26.9g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 50.4g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 83.2%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 22:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 36.3%) and 5-bromine valeryl chloride as basic raw material, first 22.9g EVOH is joined in 250mL four-hole boiling flask, add again 150mL dimethylbenzene to dissolve, stir and be warming up to 85 ℃, after EVOH dissolves completely, drip 49.0g5-bromine valeryl chloride, after dripping, isothermal reaction 10h under 85 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 48.6g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 83.3%; The half-finished concrete structure formula of gained is:

B, the 48.6g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 120mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 57.3g tricyclohexyl phosphine, after dripping under 130 ℃ of conditions isothermal reaction 80h; Gained reaction solution is poured precipitating in sherwood oil into, and sherwood oil volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the sherwood oil of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 75.7g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 61.4%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 23:

A, take ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol massfraction as 16.6%) and chloroacetyl chloride as basic raw material, first 26.5g EVOH is joined in 250mL four-hole boiling flask, add again 150mL tetrahydrofuran (THF) to dissolve, stir and be warming up to 70 ℃, after EVOH dissolves completely, drip 14.7g chloroacetyl chloride, after dripping, isothermal reaction 16h under 70 ℃ of conditions; After reaction finishes, slowly pour reaction solution in acetone precipitating, acetone volumetric usage is 6 times of reaction solution volume, and gained precipitating liquid carries out suction filtration place 5h under 25 ℃ of conditions after, obtains filter cake; Gained filter cake soaks with the acetone of 1.5 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 60 ℃ of conditions, obtains the grafts that 33.2g work in-process are EVOH and halogen acyl halide, its-OH transformation efficiency is 87.5%; The half-finished concrete structure formula of gained is:

B, the 33.2g EVOH graft product work in-process that step a is obtained join in 250mL four-hole boiling flask, add again 100mL dimethylbenzene, stir and be warming up to 130 ℃, after dissolving completely, drip 26.5g tributylphosphine, after dripping under 130 ℃ of conditions isothermal reaction 60h; Gained reaction solution is poured precipitating in acetone into, and acetone volumetric usage is 6 times of reaction solution volume, and suction filtration after gained precipitating liquid is placed 4h under 25 ℃ of conditions, obtains filter cake; Gained filter cake soaks with the acetone of 2 times of reaction solution volumes, after immersion 5h, again carries out suction filtration, obtains filter cake; Filter cake is vacuum-drying 12h under 80 ℃ of conditions, after being dried, obtains 47.9g product macromolecule quaternary alkylphosphonium salt anti-biotic material, and Qi quaternary phosphine efficiency is 83.1%.The concrete structure formula of the finished product is the structural formula of above-mentioned macromolecule quaternary alkylphosphonium salt anti-biotic material.

Embodiment 24:

Anti-biotic material 5 weight parts prepared by embodiment 2 mix with the low density polyethylene of 95 weight parts, through twin screw extruder extruding pelletization.Twin screw extruder driving screw rotating speed is 90r/min, and forcing machine is set to 130 ℃, 150 ℃, 180 ℃, 180 ℃, 170 ℃ from being fed to the temperature setting of head.

Embodiment 25:

Anti-biotic material 5 weight parts prepared by embodiment 2 mix with the ethylene-vinyl acetate copolymer EVA of 95 weight parts, through twin screw extruder, extrude mixing granulation.Twin screw extruder driving screw rotating speed is 80r/min, and forcing machine is set to 130 ℃, 150 ℃, 175 ℃, 175 ℃, 165 ℃ from being fed to the temperature setting of head.

Anti-microbial property: carry out anti-microbial property test according to QB/T2591-2003 < < antibiotic plastic-anti-microbial property test method and antibacterial effect > >.

Table 1 product of the present invention and utilize the anti-microbial property of macromolecule quaternary alkylphosphonium salt anti-biotic material prepared by product of the present invention

Note: in table 1, test is the mixing spore suspension of mould in aspergillus niger, terreus, paecilomyces varioti, penicillium funiculosum, Aureobasidium pullulans, ball hair shell six with mould.

Claims

1. a polymer quaternary alkylphosphonium salt anti-biotic material, is characterized in that, the general structure of described polymer quaternary alkylphosphonium salt anti-biotic material is:

2. macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 1, it is characterized in that: described halogen acyl halide class monomer is that chloroacetyl chloride, 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride, 4-chloromethyl benzoic acid chlorides, 3-are chloro-2 2-dimethyl propylene acyl chlorides, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride, 5-bromine valeryl chloride, 6-bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and to any in brooethyl benzoyl bromide.

3. macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 1, is characterized in that: described trialkyl phosphine is any in tripropyl phosphine, tributylphosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopentyl phosphines, tricyclohexyl phosphine, triphenylphosphine and three p-methylphenyl phosphines.

4. macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 1, is characterized in that: structural unit-CH in described a Wei quaternary alkylphosphonium salt anti-biotic material general structure ₂-CH ₂-number; Structural unit in b Wei quaternary alkylphosphonium salt anti-biotic material general structure

number; Structural unit in d Wei quaternary alkylphosphonium salt anti-biotic material general structure

number.

5. a preparation method for polymer quaternary alkylphosphonium salt anti-biotic material claimed in claim 1, is characterized in that, described preparation method comprises the following steps:

6. the preparation method of macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 5, it is characterized in that: the vinyl alcohol units mass content of the EVOH of ethylene-vinyl alcohol copolymer described in step a is 7～55%, ethylene-vinyl alcohol copolymer EVOH is that 190 ℃, load are that quality melt flow rate (MFR) under 21.168N condition is 2.0～300.0g/10min in temperature.

7. the preparation method of macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 5, it is characterized in that: the class of halogen acyl halide described in step a monomer is chloroacetyl chloride, 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride, 4-chloromethyl benzoic acid chlorides, 3-chloro-2, 2-dimethyl propylene acyl chlorides, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride, 5-bromine valeryl chloride, 6-bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and to any in brooethyl benzoyl bromide.

8. the preparation method of macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 5, is characterized in that: solvent described in step a is any in toluene, dimethylbenzene, dioxane and tetrahydrofuran (THF); Described precipitating agent is methyl alcohol, ethanol or acetone.

9. the preparation method of macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 5, is characterized in that: trialkyl phosphine described in step b is any in tripropyl phosphine, tributylphosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopentyl phosphines, tricyclohexyl phosphine, triphenylphosphine and three p-methylphenyl phosphines.

10. the preparation method of macromolecule quaternary alkylphosphonium salt anti-biotic material according to claim 5, is characterized in that: solvent described in step b is toluene, dimethylbenzene or dioxane; Described precipitating agent is sherwood oil, acetone or ether.