CN103739786B - Macromolecule quaternary salt anti-biotic material and preparation method thereof - Google Patents
Macromolecule quaternary salt anti-biotic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of macromolecule quaternary salt anti-biotic material and preparation method thereof.This macromolecule quaternary salt anti-biotic material is to be keyed on ethylene-vinyl alcohol copolymer EVOH macromole by halogen acyl halide class monomer by graft reaction, and the method carrying out quaternary reaction further with trialkyl phosphine prepares.The macromolecule quaternary salt anti-biotic material of the present invention has wide spectrum, efficient, lasting antibacterial functions and good safety, both the goods with antibacterial functions can separately formed be processed into, can become there are the goods of antibacterial functions with the non-polar resin such as polyethylene, polypropylene and other resin alloy processing and forming again, have broad application prospects.The macromolecule quaternary salt anti-biotic material that the present invention prepares reaches more than 99% to the various bacteria germicidal efficiency such as escherichia coli, staphylococcus aureus, and the mildew-resistant grade of mycete multiple to aspergillus niger, aspergillus terreus etc. is 1~0 grade.
Description
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 salt anti-biotic material
And preparation method thereof.
Two, background technology:
Along with material and goods such as developing rapidly of high-molecular organic material industry, plastics, fiber, rubber, coating and adhesive
Increasingly extensive is employed.These materials and goods, such as plastic packing product, if not having antibacterial functions, antibacterial, mycete etc.
Can corrode products to be packaged makes it rotten or damage.Antibacterial, mycete etc. are to the pollution of product surface and grow, and to using and can connect
The people touching it produce cross infection, and health is constituted certain threat.Anti-biotic material is to some antibacterials, mycete, fungus etc.
The extremely sensitive chemical substance of microorganism, not only itself has antibacterial functions, adds it to plastics, fiber, rubber, coating
With the material such as adhesive with in goods, it is possible to give its antibacterial functions, not only keep material and goods self not by antibacterial, mycete
Deng destruction, packaged article can also be protected to never degenerate or sustain damage as packing articles;Can also avoid or reduce because of
The cross-contaminations such as antibacterial between person to person, people and the thing, thing and the thing that use these goods and occur, mycete, are beneficial to people
Health.
Produce now and the high-molecular anti-bacteria material of application, be by mean of high-molecular organic material more and be prone to the advantage of processing and forming,
With little molecule inorganic antiseptic, organic antibacterial agent are blended by simple physical or increase-volume physical blending prepares.Be mainly used in plastics,
The goods such as fiber, rubber, coating and adhesive.Though the anti-biotic material so prepared and goods have antibacterial functions, but have one
Outstanding problem: due to the limited compatibility of antibacterial Yu matrix, antibacterial easily migrates loss, causes keeping antibacterial functions
Long-lasting.Also can pollute packaged article as packaging material and goods, easily human body etc. be damaged again.It is linked with anti-
The organic high molecular compound of bacterium functional group both separately formed can be processed into the goods with antibacterial functions, overcomes again little molecule
Antibacterial physical blending gives the shortcoming of antibacterial functions in macromolecular material, the most also has more antibacterial than little molecule antibacterial
Performance.Therefore, synthesis and the application of high-molecular anti-bacteria material is just becoming the current focus researched and developed.
The patent application of Application No. 200710027027.X, discloses a kind of by dimethylaminoethyl methacrylate alkyl halide
Thing and two kinds of monomer copolymerizations of maleic anhydride, or by any one material in acrylamide, butyl acrylate or styrene and first
Base dimethylaminoethyl acrylate alkyl halide and a kind of reactable high-molecular anti-bacteria of three kinds of monomer copolymerizations of maleic anhydride
Agent, this polymer antibacterial agent provides a kind of wide spectrum, efficient, safe durable antibiotic material.Application No. 200910144560.3
Patent application, disclose and a kind of prepared guanidine polymer antibacterial agent by functionalization guanidinesalt with styrene or acrylamide copolymerization
Method, this antibacterial antiplaque agent effect is notable, and thermostability is preferable, and antibacterial functional group is difficult to migrate.But, the high score of research and development now
Sub-anti-biotic material, or because of the thermal sensitivity of antibacterial functional group, the thermostability making antimicrobial macromolecule material is not good enough, directly affects its application;
Or because of bad with the compatibility of big kind high-molecular organic material (such as the resin such as polyethylene, polypropylene), also make its application
It is very restricted.
Three, summary of the invention:
The technical problem to be solved in the present invention is: provide a kind of macromolecule quaternary salt anti-biotic material and preparation method thereof.The present invention is led to
Cross graft reaction to be keyed on ethylene-vinyl alcohol copolymer EVOH macromole by halogen acyl halide class monomer, further with trialkyl phosphine
Carry out quaternary reaction, prepare product macromolecule quaternary salt anti-biotic material of the present invention.Macromolecule quaternary salt prepared by the present invention resists
Bacterium material both can separately formed be processed into has long-acting, the goods of cleaning antibacterial functions, is prone to again and polyethylene, polypropylene etc.
Resin alloy, processing and forming becomes to have the goods such as long-acting, the antibacterial polyethylene of sanitary characteristics, polypropylene.
In order to solve the problems referred to above, the technical solution used in the present invention is:
The present invention provides a kind of macromolecule quaternary salt anti-biotic material, and the general structure of described macromolecule quaternary salt anti-biotic material is:
Wherein R1It is halogen acyl halide class monomer and the base of hydroxyl-OH reaction formation on ethylene-vinyl alcohol copolymer EVOH strand
Group;R2It is R1Group and trialkyl phosphine carry out the quaternary groups that quaternary reaction is formed.
According to above-mentioned macromolecule quaternary salt anti-biotic material, described halogen acyl halide class monomer is chloracetyl 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 propionyl
Chlorine, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride, 5-bromine valeric chloride, 6-bromine caproyl chloride, bromoacetyl bromide,
2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and to any one in bromomethyl benzoyl bromide.
According to above-mentioned macromolecule quaternary salt anti-biotic material, described trialkyl phosphine be tripropyl phosphine, tributylphosphine, three hexyl phosphines,
Any one in tri octyl phosphine, tri-butyl phosphine, three cyclopenta phosphines, tricyclohexyl phosphine, triphenylphosphine and three p-methylphenyl phosphines.
According to above-mentioned macromolecule quaternary salt anti-biotic material, described a is construction unit in quaternary salt anti-biotic material general structure
—CH2—CH2Number;B is construction unit in quaternary salt anti-biotic material general structureNumber;C is
Construction unit in quaternary salt anti-biotic material general structureNumber;D is in quaternary salt anti-biotic material general structure
Construction unitNumber.
Additionally, it is provided that the preparation method of a kind of macromolecule quaternary salt anti-biotic material, described preparation method comprises the following steps:
A, with ethylene-vinyl alcohol copolymer EVOH and halogen acyl halide class monomer as base stock, described ethylene-vinyl alcohol copolymer
On the mol ratio of-OH and halogen acyl halide class monomer be 1:1~1.4;First with solvent dissolve EVOH, EVOH and solvent it
Between the ratio of addition be 1g EVOH:4~8mL solvent, drip halogen acyl halide class monomer after dissolving, will reaction after dripping
System temperature rises to 70~120 DEG C, with this understanding, and the response time 8~16h;After reaction terminates, reactant liquor is poured slowly into
Precipitating in precipitating agent, precipitating agent volumetric usage is 2~8 times of reactant liquor volume, gained precipitating liquid place under the conditions of 25 DEG C 4~
Carry out sucking filtration after 8h, obtain filter cake;The precipitating agent of gained filter cake reactant liquor volume 1~2 times is soaked, and soaks 4~8h
After again carry out sucking filtration, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains connecing of EVOH and halogen acyl halide
Branch thing;
B, EVOH step a obtained dissolve with the graft solvent of halogen acyl halide, and the quality of described solvent is EVOH
With 1.5~4.5 times of halogen acyl halide graft quality, add-Cl in trialkyl phosphine, trialkyl phosphine and EVOH graft after dissolving
Between mol ratio be 1:1~2.0;Controlling temperature of reaction system is 100~135 DEG C, and the response time is 20~80h;Reaction knot
Being poured slowly in precipitating agent by gained reactant liquor after bundle and carry out precipitating, precipitating agent volumetric usage is 2~8 times of reactant liquor volume, institute
Obtain sucking filtration after precipitating liquid places 4~8h under the conditions of 25 DEG C, obtain filter cake;Gained filter cake is heavy with reactant liquor volume 1~2 times
Analysis agent is soaked, and again carries out sucking filtration, obtain filter cake after soaking 4~8h;Filter cake is vacuum dried 12h under the conditions of 80 DEG C,
Obtain product macromolecule quaternary salt anti-biotic material after drying.
According to the preparation method of above-mentioned macromolecule quaternary salt anti-biotic material, ethylene-vinyl alcohol copolymer EVOH described in step a
Vinyl alcohol units mass content be 7~55%, ethylene-vinyl alcohol copolymer EVOH temperature be 190 DEG C, load be 21.168N
Under the conditions of quality melt flow rate (MFR) be 2.0~300.0g/10min.
According to the preparation method of above-mentioned macromolecule quaternary salt anti-biotic material, the monomer of halogen acyl halide class described in step a is chloracetyl
Chlorine, 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride, 4-chloromethyl benzoic acid chlorides,
3-chloro-2,2-dimethylpropionic acid chloride, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride, 5-bromine valeric chloride, 6-
Bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and in bromomethyl benzoyl bromide
Any one.
According to the preparation method of above-mentioned macromolecule quaternary salt anti-biotic material, solvent described in step a be toluene, dimethylbenzene, two
Any one in oxygen six ring and oxolane;Described precipitating agent is methanol, ethanol or acetone.
According to the preparation method of above-mentioned macromolecule quaternary salt anti-biotic material, trialkyl phosphine described in step b be tripropyl phosphine, three
Butyl phosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopenta phosphines, tricyclohexyl phosphine, triphenylphosphine and three pairs of first
Any one in Phenylphosphine.
According to the preparation method of above-mentioned macromolecule quaternary salt anti-biotic material, solvent described in step b is toluene, dimethylbenzene or two
Oxygen six ring;Described precipitating agent is petroleum ether, acetone or ether.
The positive beneficial effect of the present invention:
1, the antibacterial functional group of macromolecule quaternary salt anti-biotic material that prepared by the present invention is all to be connected on macromole, without dissociate
Small-molecule substance, not only antibacterial functions is lasting, and the goods of material and processing and forming have preferable spatter property.
2, the matrix resin ethylene-vinyl alcohol copolymer EVOH Polymer chain flexibility that the present invention uses is good, is conducive to strengthening anti-
Bacterium function, the macromolecule quaternary salt anti-biotic material prepared is to the various bacteria germicidal efficiency such as escherichia coli, staphylococcus aureus
Reaching more than 99%, the mildew-resistant grade of mycete multiple to aspergillus niger, aspergillus terreus etc. is 1~0 grade.
3, the macromolecule quaternary salt anti-biotic material that prepared by the present invention both can separately formed be processed into have long-acting, clean antibacterial merit
The goods of energy, the compatibility having had because of kind high-molecular organic material big with polyethylene, polypropylene etc. again, it is easy to blended,
Giving the antibacterial functions of polyethylene, polypropylene etc., processing and forming becomes to have long-acting, the antibacterial polyethylene of sanitary characteristics, polypropylene
In goods, application 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 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 ultrared spectrum of the product of Fig. 4 ethylene-vinyl alcohol copolymer EVOH grafting 4-chloromethyl benzoic acid chlorides and tributylphosphine
Figure.
Five, detailed description of the invention:
The present invention is expanded on further below in conjunction with embodiment, but is not limiting as present disclosure.
Embodiment 1:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 4-chlorobutanoylchloride as base stock,
First 53.0g EVOH is joined in 500mL four-hole boiling flask, add 320mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 28.2g4-chlorobutanoylchloride, after dripping, isothermal reaction under the conditions of 85 DEG C
9h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 5 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 6h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 6h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 68.8g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 75.6%;The concrete structure formula of gained semi-finished product is:
The product i.e. infrared spectrum of semi-finished product of EVOH grafting 4-chlorobutanoylchloride refers to accompanying drawing 1;
B, 68.8g EVOH graft product semi-finished product step a obtained join in 500mL four-hole boiling flask, add 175mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 61.1g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 5 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 6h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 94.5g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 84.3%;The concrete structure formula of product is above-mentioned macromolecule quaternary salt
The structural formula of anti-biotic material.
The present embodiment EVOH grafting 4-chlorobutanoylchloride refers to accompanying drawing with the product i.e. infrared spectrum of final products of tributylphosphine
2。
Embodiment 2:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is with embodiment 1.
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 4-chlorobutanoylchloride as base stock,
First 53.0g EVOH is joined in 500mL four-hole boiling flask, add 320mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 36.7g4-chlorobutanoylchloride, after dripping, isothermal reaction under the conditions of 85 DEG C
9h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 3 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 7h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 6h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 70.8g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 85.0%;The concrete structure formula of gained semi-finished product is same
Embodiment 1;
B, 35.4g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 90mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 34.3g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 4 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 7h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks,
Again carry out sucking filtration after soaking 6h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 50.0g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 85.1%;The concrete structure formula of its product is with embodiment 1.
Embodiment 3:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is with embodiment 1.
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 4-chlorobutanoylchloride as base stock,
First 53.0g EVOH is joined in 500mL four-hole boiling flask, add 320mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 36.7g4-chlorobutanoylchloride, after dripping, isothermal reaction under the conditions of 85 DEG C
9h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 8 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.8 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 70.8g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 85.0%;The concrete structure formula of gained semi-finished product is same
Embodiment 1;
B, 35.4g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 90mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 20.6g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 8 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.8 times soaks,
Again carry out sucking filtration after soaking 4h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 47.3g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 69.4%;The concrete structure formula of final products is with embodiment 1.
Embodiment 4:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 4-chlorobutanoylchloride as base stock,
First 26.5g EVOH is joined in 250mL four-hole boiling flask, add 160mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 18.3g4-chlorobutanoylchloride, after dripping, isothermal reaction under the conditions of 85 DEG C
9h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 3 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 8h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 8h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 35.4g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 85.0%;The concrete structure formula of gained semi-finished product is:
B, 35.4g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 90mL
Dimethylbenzene, stirs and is warming up to 125 DEG C, after being completely dissolved, drips 27.2g tripropyl phosphine, after dripping under the conditions of 125 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 3 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 8h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1 times soaks,
Again carry out sucking filtration after soaking 8h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 46.0g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 78.3%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 5:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 7.7%) and 3-bromo propionyl chloro as base stock,
First 27.9g EVOH is joined in 250mL four-hole boiling flask, add 140mL dimethylbenzene and dissolve, stir and heat up
To 95 DEG C, after EVOH is completely dissolved, drip 14.8g3-bromo propionyl chloro, after dripping, isothermal reaction under the conditions of 95 DEG C
12h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 33.2g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 80.2%;The concrete structure formula of gained semi-finished product is:
B, 33.2g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 110mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 15.8g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 5 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 39.9g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 84.5%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 6:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 2-chlorpromazine chloride as base stock,
First 28.3g EVOH is joined in 250mL four-hole boiling flask, add 150mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 16.3g2-chlorpromazine chloride, after dripping, isothermal reaction under the conditions of 85 DEG C
10h;After reaction terminates, reactant liquor being poured slowly into precipitating in methanol, methanol volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The methanol of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 36.2g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 81.3%;The concrete structure formula of gained semi-finished product is:
B, 36.2g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 110mL
Dimethylbenzene, stirs and is warming up to 135 DEG C, after being completely dissolved, drips 26.3g tributylphosphine, after dripping under the conditions of 135 DEG C
Isothermal reaction 50h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 5 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 49.4g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 75.6%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 7:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 36.3%) and 4-bromobutanoylchloride as base stock,
First 20.1g EVOH is joined in 250mL four-hole boiling flask, add 150mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 40.0g4-bromobutanoylchloride, after dripping, isothermal reaction under the conditions of 85 DEG C
10h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 41.3g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 85.6%;The concrete structure formula of gained semi-finished product is:
B, 41.3g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 56.1g tri-p-methylphenyl phosphine, at 130 DEG C of bars after dripping
Isothermal reaction 80h under part;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 5 times of reactant liquor volume,
Gained precipitating liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The gained filter cake petroleum ether of reactant liquor volume 1.5 times
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, dried
To 68.6g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 63.2%.The concrete structure formula of final products is above-mentioned
The structural formula of macromolecule quaternary salt anti-biotic material.
Embodiment 8:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 5-Chlorovaleryl Chloride as base stock,
First 30.2g EVOH is joined in 250mL four-hole boiling flask, add 160mL dioxane and dissolve, stir and rise
Temperature is to 90 DEG C, after EVOH is completely dissolved, drips 22.9g5-chlorine valeric chloride, and after dripping, under the conditions of 90 DEG C, constant temperature is anti-
Answer 12h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume,
Gained precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;Gained filter cake is with the third of reactant liquor volume 1.5 times
Ketone soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains
42.0g semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 87.3%;The concrete structure of gained semi-finished product
Formula is:
B, 42.0g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 26.1g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 50h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 5 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 56.6g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 72.5%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 9:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 36.3%) and 2-bromo propionyl chloro as base stock,
First 21.3g EVOH is joined in 250mL four-hole boiling flask, add 160mL dimethylbenzene and dissolve, stir and heat up
To 80 DEG C, after EVOH is completely dissolved, drip 42.2g2-bromo propionyl chloro, after dripping, isothermal reaction under the conditions of 80 DEG C
8h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 39.2g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 75.8%;The concrete structure formula of gained semi-finished product is:
B, 39.2g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 135 DEG C, after being completely dissolved, drips 64.1g tri octyl phosphine, after dripping under the conditions of 135 DEG C
Isothermal reaction 40h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 5 times of reactant liquor volume, gained
Precipitating liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The petroleum ether of gained filter cake reactant liquor volume 1.5 times is carried out
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
59.6g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 41.2%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 10:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 4-chloromethyl benzoic acid chlorides as base
This raw material, first joins 26.5g EVOH in 250mL four-hole boiling flask, adds 160mL dimethylbenzene and dissolves, stirs
Mix and be warming up to 100 DEG C, after EVOH is completely dissolved, dripping 24.6g4-chloromethyl benzoic acid chlorides, after dripping, at 100 DEG C
Under the conditions of isothermal reaction 9h;After reaction terminates, reactant liquor being poured slowly into precipitating in ethanol, ethanol volumetric usage is reaction liquid
Long-pending 6 times, gained precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;Gained filter cake reaction liquid
The ethanol of long-pending 1.5 times soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried under the conditions of 60 DEG C
12h, obtains the graft of 36.8g semi-finished product i.e. EVOH and halogen acyl halide, and its-OH conversion ratio is 67.5%;Gained semi-finished product
Concrete structure formula be:
The infrared spectrum such as accompanying drawing 3 of EVOH grafting 4-chloromethyl benzoic acid chlorides;
B, 36.8g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 140mL
Toluene, stirs and is warming up to 110 DEG C, after being completely dissolved, drips 17.7g tributylphosphine, permanent under the conditions of 110 DEG C after dripping
Temperature reaction 40h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 5 times of reactant liquor volume, gained precipitating liquid
Under the conditions of 25 DEG C, place sucking filtration after 6h, obtain filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks, leaching
Again carry out sucking filtration after bubble 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 48.5g product after drying
Macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 85.6%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
EVOH grafting 4-chloromethyl benzoic acid chlorides and the product i.e. infrared spectrum of the final products such as accompanying drawing 4 of tributylphosphine.
Embodiment 11:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 2-bromo-2-methyl-prop acylbromide as base
This raw material, first joins 26.5g EVOH in 250mL four-hole boiling flask, adds 150mL dimethylbenzene and dissolves, stirs
Mix and be warming up to 90 DEG C, after EVOH is completely dissolved, dripping 29.9g2-bromo-2-methyl-prop acylbromide, after dripping, at 90 DEG C
Under the conditions of isothermal reaction 12h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is reactant liquor
6 times of volume, gained precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;Gained filter cake reactant liquor
The acetone that volume is 1.5 times soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake vacuum under the conditions of 60 DEG C is done
Dry 12h, obtains the graft of 36.5g semi-finished product i.e. EVOH and halogen acyl halide, and its-OH conversion ratio is 67.3%;Gained half becomes
The concrete structure formula of product is:
B, 36.5g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 100mL
Dimethylbenzene, stirs and is warming up to 135 DEG C, after being completely dissolved, drips 27.2g tributylphosphine, after dripping under the conditions of 135 DEG C
Isothermal reaction 70h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 5 times of reactant liquor volume, gained
Precipitating liquid places sucking filtration after 6h under the conditions of 25 DEG C, obtains filter cake;The petroleum ether of gained filter cake reactant liquor volume 1.5 times is carried out
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
44.9g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 61.6%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 12:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 7.7%) and bromoacetyl bromide as base stock, first
First 29.3g EVOH is joined in 250mL four-hole boiling flask, add 150mL toluene and dissolve, stir and be warming up to
90 DEG C, after EVOH is completely dissolved, drip 13.5g bromoacetyl bromide, after dripping, isothermal reaction 10h under the conditions of 90 DEG C;
After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained precipitating
Liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks
Bubble, again carries out sucking filtration after soaking 5h, obtains filter cake;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 33.7g half and becomes
Product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 71.2%;The concrete structure formula of gained semi-finished product is:
B, 33.7g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 100mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 14.7g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 7 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 39.6g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 80.5%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 13:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 6-bromine caproyl chloride as base stock,
First 25.1g EVOH is joined in 250mL four-hole boiling flask, add 150mL dimethylbenzene and dissolve, stir and heat up
To 90 DEG C, after EVOH is completely dissolved, drip 26.3g6-bromine caproyl chloride, after dripping, isothermal reaction under the conditions of 90 DEG C
12h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 39.3g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 84.7%;The concrete structure formula of gained semi-finished product is:
B, 39.3g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 100mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 32.4g tricyclohexyl phosphine, 130 DEG C of conditions after dripping
Lower isothermal reaction 80h;Gained reactant liquor pours precipitating in ether into, and ether volumetric usage is 8 times of reactant liquor volume, and gained sinks
Analysis liquid places sucking filtration after 5h under the conditions of 25 DEG C, obtains filter cake;The ether of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 49.5g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 63.1%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 14:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 4-chlorobutanoylchloride as base stock,
First 26.5g EVOH is joined in 250mL four-hole boiling flask, add 160mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 18.3g4-chlorobutanoylchloride, after dripping, isothermal reaction under the conditions of 85 DEG C
9h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 35.4g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 85.0%;The concrete structure formula of gained semi-finished product is:
B, 35.4g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 90mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 40.5g tri-cyclopenta phosphine, 130 DEG C of conditions after dripping
Lower isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 8 times of reactant liquor volume, and gained sinks
Analysis liquid places sucking filtration after 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 51.0g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 77.1%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 15:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 7.7%) and 2-bromo propionyl chloro as base stock,
First 28.7g EVOH is joined in 250mL four-hole boiling flask, add 160mL dimethylbenzene and dissolve, stir and heat up
To 90 DEG C, after EVOH is completely dissolved, drip 14.1g2-bromo propionyl chloro, after dripping, isothermal reaction under the conditions of 90 DEG C
12h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 33.8g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 75.3%;The concrete structure formula of gained semi-finished product is:
B, 33.8g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 105mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 14.7g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 8 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 39.8g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 78.5%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 16:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 7.7%) and be basic to bromomethyl benzoyl bromide
Raw material, first joins 28.6g EVOH in 250mL four-hole boiling flask, adds 160mL dimethylbenzene and dissolves, stirring
And it is warming up to 110 DEG C, after EVOH is completely dissolved, 18.1g is to bromomethyl benzoyl bromide, after dripping, at 110 DEG C in dropping
Under the conditions of isothermal reaction 12h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is reactant liquor
6 times of volume, gained precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;Gained filter cake reactant liquor
The acetone that volume is 1.5 times soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake vacuum under the conditions of 60 DEG C is done
Dry 12h, obtains the graft of 34.7g semi-finished product i.e. EVOH and halogen acyl halide, and its-OH conversion ratio is 62.4%;Gained half becomes
The concrete structure formula of product is:
B, 34.7g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 105mL
Dimethylbenzene, stirs and is warming up to 110 DEG C, after being completely dissolved, drips 8.2g tributylphosphine, after dripping under the conditions of 110 DEG C
Isothermal reaction 40h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The petroleum ether of gained filter cake reactant liquor volume 2 times is carried out
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
40.0g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 84.6%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 17:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 7.7%) and 3-chloro-2,2-dimethylpropionic acid chloride be
Base stock, first joins 28.6g EVOH in 250mL four-hole boiling flask, adds 150mL dimethylbenzene and dissolves,
Stir and be warming up to 100 DEG C, after EVOH is completely dissolved, dropping 10.9g3-chloro-2,2-dimethylpropionic acid chloride, after dripping,
Isothermal reaction 10h under the conditions of 100 DEG C;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is
6 times of reactant liquor volume, gained precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;Gained filter cake is used
The acetone that reactant liquor volume is 1.5 times soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is under the conditions of 60 DEG C
Vacuum drying 12h, obtains the graft of 32.6g semi-finished product i.e. EVOH and halogen acyl halide, and its-OH conversion ratio is 68.3%;Institute
The concrete structure formula obtaining semi-finished product is:
B, 32.6g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 100mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 13.8g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 6 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 37.2g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 66.5%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 18:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 36.3%) and bromoacetyl chloride as base stock, first
First 22.5g EVOH is joined in 250mL four-hole boiling flask, add 160mL dimethylbenzene and dissolve, stir and be warming up to
80 DEG C, after EVOH is completely dissolved, drip 35.1g bromoacetyl chloride, after dripping, isothermal reaction 8h under the conditions of 80 DEG C;
After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained precipitating
Liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times soaks
Bubble, again carries out sucking filtration after soaking 5h, obtains filter cake;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 42.0g half and becomes
Product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 86.3%;The concrete structure formula of gained semi-finished product is:
B, 42.0g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 135 DEG C, after being completely dissolved, drips 68.7g tri-hexyl phosphine, after dripping under the conditions of 135 DEG C
Isothermal reaction 50h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The petroleum ether of gained filter cake reactant liquor volume 2 times is carried out
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
75.7g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 73.6%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 19:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 6-chlorine caproyl chloride as base stock,
First 27.1g EVOH is joined in 250mL four-hole boiling flask, add 130mL dimethylbenzene and dissolve, stir and heat up
To 90 DEG C, after EVOH is completely dissolved, drip 24.2g6-chlorine caproyl chloride, after dripping, isothermal reaction under the conditions of 90 DEG C
14h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 38.4g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 83.7%;The concrete structure formula of gained semi-finished product is:
B, 38.4g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 125 DEG C, after being completely dissolved, drips 22.5g tributylphosphine, after dripping under the conditions of 125 DEG C
Isothermal reaction 70h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 6 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 50.4g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 69.5%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 20:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 36.3%) and 3-bromo propionyl chloro as base stock,
First 20.6g EVOH is joined in 250mL four-hole boiling flask, add 160mL dimethylbenzene and dissolve, stir and heat up
To 80 DEG C, after EVOH is completely dissolved, drip 37.9g3-bromo propionyl chloro, after dripping, isothermal reaction under the conditions of 80 DEG C
8h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 40.1g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 84.8%;The concrete structure formula of gained semi-finished product is:
B, 40.1g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 75.5g triphenylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 50h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The petroleum ether of gained filter cake reactant liquor volume 2 times is carried out
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
59.5g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 50.2%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 21:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and 3-chlorpromazine chloride as base stock,
First 27.5g EVOH is joined in 250mL four-hole boiling flask, add 150mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 17.1g3-chlorpromazine chloride, after dripping, isothermal reaction under the conditions of 85 DEG C
10h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 35.5g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 85.7%;The concrete structure formula of gained semi-finished product is:
B, 35.5g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 105mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 26.9g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The petroleum ether of gained filter cake reactant liquor volume 2 times is carried out
Soak, again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
50.4g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 83.2%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 22:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 36.3%) and 5-bromine valeric chloride as base stock,
First 22.9g EVOH is joined in 250mL four-hole boiling flask, add 150mL dimethylbenzene and dissolve, stir and heat up
To 85 DEG C, after EVOH is completely dissolved, drip 49.0g5-bromine valeric chloride, after dripping, isothermal reaction under the conditions of 85 DEG C
10h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 48.6g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 83.3%;The concrete structure formula of gained semi-finished product is:
B, 48.6g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 120mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 57.3g tricyclohexyl phosphine, 130 DEG C of conditions after dripping
Lower isothermal reaction 80h;Gained reactant liquor pours precipitating in petroleum ether into, and petroleum ether volumetric usage is 6 times of reactant liquor volume, institute
Obtain precipitating liquid under the conditions of 25 DEG C, place sucking filtration after 4h, obtain filter cake;The petroleum ether of gained filter cake reactant liquor volume 2 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains after drying
75.7g product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 61.4%.The concrete structure formula of final products is above-mentioned height
The structural formula of molecule quaternary salt anti-biotic material.
Embodiment 23:
Macromolecule quaternary salt anti-biotic material of the present invention, its concrete structure formula is:
The preparation method of the present invention above-mentioned macromolecule quaternary salt anti-biotic material, its detailed step is as follows:
A, with ethylene-vinyl alcohol copolymer EVOH(vinyl alcohol mass fraction for 16.6%) and chloracetyl chloride as base stock, first
First 26.5g EVOH is joined in 250mL four-hole boiling flask, add 150mL oxolane and dissolve, stir and heat up
To 70 DEG C, after EVOH is completely dissolved, drip 14.7g chloracetyl chloride, after dripping, isothermal reaction under the conditions of 70 DEG C
16h;After reaction terminates, reactant liquor being poured slowly into precipitating in acetone, acetone volumetric usage is 6 times of reactant liquor volume, gained
Precipitating liquid carries out sucking filtration after placing 5h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 1.5 times enters
Row soaks, and again carries out sucking filtration, obtain filter cake after soaking 5h;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains 33.2g
Semi-finished product i.e. EVOH and the graft of halogen acyl halide, its-OH conversion ratio is 87.5%;The concrete structure formula of gained semi-finished product is:
B, 33.2g EVOH graft product semi-finished product step a obtained join in 250mL four-hole boiling flask, add 100mL
Dimethylbenzene, stirs and is warming up to 130 DEG C, after being completely dissolved, drips 26.5g tributylphosphine, after dripping under the conditions of 130 DEG C
Isothermal reaction 60h;Gained reactant liquor pours precipitating in acetone into, and acetone volumetric usage is 6 times of reactant liquor volume, gained precipitating
Liquid places sucking filtration after 4h under the conditions of 25 DEG C, obtains filter cake;The acetone of gained filter cake reactant liquor volume 2 times soaks,
Again carry out sucking filtration after soaking 5h, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 80 DEG C, obtains 47.9g after drying and produces
Product macromolecule quaternary salt anti-biotic material, its quaternary efficiency is 83.1%.The concrete structure formula of final products is above-mentioned macromolecule season
The structural formula of salt anti-biotic material.
Embodiment 24:
Anti-biotic material 5 weight portion embodiment 2 prepared and the low density polyethylene mixing of 95 weight portions, through twin screw
Extruder extruding pelletization.Double screw extruder driving screw rotating speed is 90r/min, and extruder is set to from the temperature being fed to head
130℃、150℃、180℃、180℃、170℃。
Embodiment 25:
Anti-biotic material 5 weight portion prepared by embodiment 2 and the ethylene-vinyl acetate copolymer EVA mixing of 95 weight portions, warp
Double screw extruder extrusion mixing pelletize.Double screw extruder driving screw rotating speed is 80r/min, and extruder is from the temperature being fed to head
Degree is set to 130 DEG C, 150 DEG C, 175 DEG C, 175 DEG C, 165 DEG C.
Anti-microbial property: carry out antibiotic property according to QB/T2591-2003 " antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect "
Can test.
Table 1 product of the present invention and utilize the anti-microbial property of macromolecule quaternary salt anti-biotic material prepared by product of the present invention
Note: testing in table 1 with mycete is aspergillus niger, aspergillus terreus, paecilomyces varioti, penicillium funiculosum, Aureobasidium pullulans, ball hair
The mixing spore suspension of mycete in shell six.
Claims (6)
1. a macromolecule quaternary salt anti-biotic material, it is characterised in that the general structure of described macromolecule quaternary salt anti-biotic material
For:
Wherein R1It is halogen acyl halide class monomer and the base of hydroxyl-OH reaction formation on ethylene-vinyl alcohol copolymer EVOH strand
Group;R2It is R1Group and trialkyl phosphine carry out the quaternary groups that quaternary reaction is formed;
The vinyl alcohol units mass content of described ethylene-vinyl alcohol copolymer EVOH is 7~55%, ethylene-vinyl alcohol copolymer
EVOH temperature be 190 DEG C, load be the quality melt flow rate (MFR) under the conditions of 21.168N be 2.0~300.0g/10min;
Described halogen acyl halide class monomer be 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride,
4-chloromethyl benzoic acid chlorides, 3-chloro-2,2-dimethylpropionic acid chloride, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromine butyryl
Chlorine, 5-bromine valeric chloride, 6-bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and right
Any one in bromomethyl benzoyl bromide;
Described trialkyl phosphine is tripropyl phosphine, tributylphosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopenta phosphines
With any one in tricyclohexyl phosphine.
2. the preparation method of the macromolecule quaternary salt anti-biotic material described in a claim 1, it is characterised in that described preparation side
Method comprises the following steps:
A, with ethylene-vinyl alcohol copolymer EVOH and halogen acyl halide class monomer as base stock, described ethylene-vinyl alcohol copolymer
On the mol ratio of-OH and halogen acyl halide class monomer be 1:1~1.4;First with solvent dissolve EVOH, EVOH and solvent it
Between the ratio of addition be 1g EVOH:4~8mL solvent, drip halogen acyl halide class monomer after dissolving, will reaction after dripping
System temperature rises to 70~120 DEG C, with this understanding, and the response time 8~16h;After reaction terminates, reactant liquor is poured slowly into
Precipitating in precipitating agent, precipitating agent volumetric usage is 2~8 times of reactant liquor volume, gained precipitating liquid place under the conditions of 25 DEG C 4~
Carry out sucking filtration after 8h, obtain filter cake;The precipitating agent of gained filter cake reactant liquor volume 1~2 times is soaked, and soaks 4~8h
After again carry out sucking filtration, obtain filter cake;Filter cake is vacuum dried 12h under the conditions of 60 DEG C, obtains connecing of EVOH and halogen acyl halide
Branch thing;
The vinyl alcohol units mass content of described ethylene-vinyl alcohol copolymer EVOH is 7~55%, ethylene-vinyl alcohol copolymer
EVOH temperature be 190 DEG C, load be the quality melt flow rate (MFR) under the conditions of 21.168N be 2.0~300.0g/10min;
B, EVOH step a obtained dissolve with the graft solvent of halogen acyl halide, and the quality of described solvent is EVOH
With 1.5~4.5 times of halogen acyl halide graft quality, add-Cl in trialkyl phosphine, trialkyl phosphine and EVOH graft after dissolving
Between mol ratio be 1:1~2.0;Controlling temperature of reaction system is 100~135 DEG C, and the response time is 20~80h;Reaction knot
Being poured slowly in precipitating agent by gained reactant liquor after bundle and carry out precipitating, precipitating agent volumetric usage is 2~8 times of reactant liquor volume, institute
Obtain sucking filtration after precipitating liquid places 4~8h under the conditions of 25 DEG C, obtain filter cake;Gained filter cake is heavy with reactant liquor volume 1~2 times
Analysis agent is soaked, and again carries out sucking filtration, obtain filter cake after soaking 4~8h;Filter cake is vacuum dried 12h under the conditions of 80 DEG C,
Obtain product macromolecule quaternary salt anti-biotic material after drying.
The preparation method of macromolecule quaternary salt anti-biotic material the most according to claim 2, it is characterised in that: institute in step a
Stating halogen acyl halide class monomer is 2-chlorpromazine chloride, 3-chlorpromazine chloride, 4-chlorobutanoylchloride, 5-Chlorovaleryl Chloride, 6-chlorine caproyl chloride, 4-chlorine
Methyl benzoyl chloride, 3-chloro-2,2-dimethylpropionic acid chloride, bromoacetyl chloride, 2-bromo propionyl chloro, 3-bromo propionyl chloro, 4-bromobutanoylchloride,
5-bromine valeric chloride, 6-bromine caproyl chloride, bromoacetyl bromide, 2 bromo propionyl bromide, 3-bromopropionyl bromide, 2-bromo-2-methyl-prop acylbromide and to bromine first
Any one in base benzoyl bromide.
The preparation method of macromolecule quaternary salt anti-biotic material the most according to claim 2, it is characterised in that: institute in step a
Stating solvent is any one in toluene, dimethylbenzene, dioxane and oxolane;Described precipitating agent is methanol, ethanol or acetone.
The preparation method of macromolecule quaternary salt anti-biotic material the most according to claim 2, it is characterised in that: institute in step b
Stating trialkyl phosphine is tripropyl phosphine, tributylphosphine, three hexyl phosphines, tri octyl phosphine, tri-butyl phosphine, three cyclopenta phosphines and three rings
Any one in hexyl phosphine.
The preparation method of macromolecule quaternary salt anti-biotic material the most according to claim 2, it is characterised in that: institute in step b
Stating solvent is toluene, dimethylbenzene or dioxane;Described precipitating agent is petroleum ether, acetone or ether.
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CN105906664A (en) * | 2016-02-02 | 2016-08-31 | 北京大学口腔医院 | Quaternary phosphonium salt-type antibacterial monomer and preparation method thereof |
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CN107347909B (en) * | 2017-05-15 | 2020-09-22 | 北京化工大学 | Four-season phosphonium cation antibacterial agent containing dihydroxyl and preparation method thereof |
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CN109824805B (en) * | 2019-01-08 | 2021-06-11 | 暨南大学 | Polyvinyl alcohol grafted quaternary phosphonium salt material and preparation method and application thereof |
CN111205454B (en) * | 2020-01-17 | 2022-09-02 | 广东省微生物研究所(广东省微生物分析检测中心) | Triphenylphosphine modified polyethyleneimine antibacterial material and preparation method thereof |
CN112225984B (en) * | 2020-10-26 | 2022-12-13 | 晋江泉得利体育用品有限公司 | Antibacterial EVA sole and preparation method thereof |
CN117447942B (en) * | 2023-12-22 | 2024-03-26 | 汕头市炜星工艺实业有限公司 | Modified polyvinyl alcohol mildew-proof adhesive, preparation method thereof and application thereof in paper product processing |
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