CN109853233A - A kind of modified poly ethylene nano fibrous membrane and preparation method thereof - Google Patents
A kind of modified poly ethylene nano fibrous membrane and preparation method thereof Download PDFInfo
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- CN109853233A CN109853233A CN201910110989.4A CN201910110989A CN109853233A CN 109853233 A CN109853233 A CN 109853233A CN 201910110989 A CN201910110989 A CN 201910110989A CN 109853233 A CN109853233 A CN 109853233A
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Abstract
The invention belongs to Material Fields more particularly to a kind of modified poly ethylene nano fibrous membrane and preparation method thereof.Modified poly ethylene nano fibrous membrane provided by the invention includes: polyethylene nanofiber basement membrane；With graft polymerization to the function monomer on the polyethylene nanofiber basement membrane；The function monomer contains phosphate ester structure and double bond structure.The present invention is using polyethylene nano fibrous membrane as basement membrane, graft modification is carried out to polyethylene nano fibrous membrane by using the function monomer with nucleic adsorption capacity, film is imparted to the absorption property of specific species, to make its can fast enriching detection environment in target species, effectively prevent in environment as target species content it is too low caused by measure difficult, sensitivity and the analysis efficiency of Radionuclide analysis detection is greatly improved.
Description
Technical field
The invention belongs to Material Fields more particularly to a kind of modified poly ethylene nano fibrous membrane and preparation method thereof.
Background technique
With greatly developing for China's Nuclear Electricity, radionuclide content in the environment and distribution increasingly become public
The environmental security that crowd is concerned about.The distribution of radionuclide in environment monitor in real time or regularly, is effectively to protect
Hinder nuclear facilities operational safety and excludes the effective means of radioactive pollution, it is quickly right in some Nuclear Accident Emergency scenes
The type of contained radionuclide is made with content in the environment at scene timely assesses, and is to make reasonable science to accident in time
Countermeasure and carry out correlative protection work, reduce accident damage important foundation；Meanwhile atmosphere nuclear test is to cause to put
The main reason for penetrating property substance settles in the environment monitors the special radial substance in atmospheric environment in time, is to consider one
Whether country violates the important method that related international regulations carry out atmosphere nuclear test.It can be said that the detection pair to environment Radionuclide
It is played an important role in Environmental security and science decision.
Since the radionuclide content in environment is usually lower, in order to accurately be tested and analyzed to the nucleic in environment,
Develop a kind of adsorbent material that nucleic in environment can be enriched be it is very necessary, this adsorbent material is not only wanted can be right
Nucleic in environment carries out selective absorption, and is limited to the requirement of existing nucleic detecting instrument, it is also necessary to have " nothing
Limit thin ", it is uniform, smooth the features such as.
Polyethylene nano fibrous membrane is a kind of film as made from two-way stretch device with micron order thickness, both
With good profile pattern and uniformity, and specific surface area with higher.If it is possible to make polyethylene Nanowire
Tieing up film has Selective adsorption to the target species in environment, then it will have a good application prospect in nucleic detection field.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of modified poly ethylene nano fibrous membrane and preparation method thereof, this
Inventing the modified poly ethylene nano fibrous membrane provided has Selective adsorption to nucleic, has good answer in nucleic detection field
Use prospect.
The present invention provides a kind of modified poly ethylene nano fibrous membranes, comprising:
Polyethylene nanofiber basement membrane；
With graft polymerization to the function monomer on the polyethylene nanofiber basement membrane；
The function monomer contains phosphate ester structure and double bond structure.
Preferably, the function monomer includes two [2- (methacryloxy) ethyl] phosphates, 2- methyl -2- propylene
Acid -2- (phosphono oxygroup) ethyl ester, phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, methacrylic acid ethylene glycol phosphate, second
One of alkenyl phosphate, vinyl phosphoric acid dimethyl ester and vinyl phosphoric acid diethylester are a variety of.
Preferably, the fibre diameter of the polyethylene nanofiber basement membrane is 10~100nm；The polyethylene nanofiber
Basement membrane with a thickness of 2~50 μm；The specific surface area of the polyethylene nanofiber basement membrane is 20~200m2/g；The polyethylene
The porosity of nanofiber basement membrane is 30~80%.
Preferably, grafting rate of the function monomer on the polyethylene nanofiber basement membrane is 10~200%.
The present invention provides a kind of preparation methods of modified poly ethylene nano fibrous membrane, comprising the following steps:
A) it will be grafted containing the function monomer of phosphate ester structure and double bond structure using pre-irradiation method or mutual radiation method poly-
It closes on polyethylene nanofiber basement membrane, obtains modified poly ethylene nano fibrous membrane.
Preferably, the pre-irradiation method specifically includes the following steps:
A1) polyethylene nanofiber basement membrane is irradiated；The polyethylene nanofiber basement membrane after irradiation is dipped in later
It is reacted in solution containing the function monomer, obtains modified poly ethylene nano fibrous membrane；
The mutual radiation method specifically includes the following steps:
A2) polyethylene nanofiber basement membrane is dipped in the solution containing the function monomer, later under radiation parameter
It is reacted, obtains modified poly ethylene nano fibrous membrane.
Preferably, step a1) in, the dosage of the irradiation is 20kGy or more, and the temperature of the reaction is 40~80 DEG C,
The time of the reaction is 2~8h；
Step a2) in, soaking time of the polyethylene nanofiber basement membrane before being irradiated, in the solution
For 1h or more, the dosage of the irradiation is 20kGy or more, and the temperature of the reaction is 15~35 DEG C.
Preferably, step a1) and step a2) in, the reaction carries out in air, nitrogen or rare gas atmosphere.
Preferably, step a1) and step a2) in, the irradiation bomb of the irradiation is cobalt source, electron beam or ultraviolet lamp.
Preferably, step a1) and step a2) in, the function monomer concentration in the solution is 0.1~1mol/L.
Compared with prior art, the present invention provides a kind of modified poly ethylene nano fibrous membranes and preparation method thereof.This hair
The modified poly ethylene nano fibrous membrane of bright offer includes: polyethylene nanofiber basement membrane；It is received with being graft-polymerized to the polyethylene
The rice epilamellar function monomer of fiber；The function monomer contains phosphate ester structure and double bond structure.The present invention is received with polyethylene
Rice tunica fibrosa is grafted polyethylene nano fibrous membrane by using the function monomer with nucleic adsorption capacity as basement membrane
It is modified, impart film to the absorption property of specific species, thus make its can target species in fast enriching detection environment, have
Effect avoid in environment as target species content it is too low caused by measure difficult, the spirit of Radionuclide analysis detection is greatly improved
Sensitivity and analysis efficiency.Preparation method provided by the invention is the following steps are included: a) use pre-irradiation method or mutual radiation method will
It is graft-polymerized containing the function monomer of phosphate ester structure and double bond structure onto polyethylene nanofiber basement membrane, obtains being modified poly- second
Alkene nano fibrous membrane.Preparation method provided by the invention is using the modified method of irradiation grafting on polyethylene nano-fiber film
Be graft-polymerized the function monomer for having adsorption capacity to nucleic, and the preparation method is simple and effective, easy to spread.It is mentioned in the present invention
In the optimal technical scheme of confession, by the optimum choice to preparation condition, it also can further improve function monomer and received in polyethylene
Grafting rate on rice tunica fibrosa, so that the Modified Membrane of preparation be made to show more excellent effect in terms of adsorbing nucleic.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph for the modified poly ethylene nano fibrous membrane that the embodiment of the present invention 1 provides；
Fig. 2 is the scanning electron microscope (SEM) photograph for the polyethylene nano fibrous membrane that the embodiment of the present invention 1 provides；
Fig. 3 be the embodiment of the present invention 1 provide polyethylene nano fibrous membrane before modified after infrared absorption spectrum comparison diagram；
Fig. 4 is the scanning electron microscope (SEM) photograph for the polyethylene nano fibrous membrane that the embodiment of the present invention 2 provides；
Fig. 5 is the scanning electron microscope (SEM) photograph for the modified poly ethylene nano fibrous membrane that the embodiment of the present invention 2 provides；
Fig. 6 be the embodiment of the present invention 2 provide polyethylene nano fibrous membrane before modified after infrared absorption spectrum comparison diagram.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of modified poly ethylene nano fibrous membranes, comprising:
Polyethylene nanofiber basement membrane；
With graft polymerization to the function monomer on the polyethylene nanofiber basement membrane；
The function monomer contains phosphate ester structure and double bond structure.
Modified poly ethylene nano fibrous membrane provided by the invention includes polyethylene nanofiber basement membrane and is graft-polymerized to institute
State the function monomer on polyethylene nanofiber basement membrane.Wherein, the fibre diameter of the polyethylene nanofiber basement membrane is preferably
10~100nm, more preferably 30~50nm, concretely 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm,
50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm；The polyethylene is nanofiber-based
The thickness of film is preferably 2~50 μm, and more preferably 8~12 μm, concretely 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 17 μ
M, 20 μm, 23 μm, 25 μm, 27 μm, 30 μm, 32 μm, 35 μm, 37 μm, 40 μm, 42 μm, 45 μm, 47 μm or 50 μm；The poly- second
The specific surface area of alkene nanofiber basement membrane is preferably 20~200m2/ g, more preferably 70~90m2/ g, concretely 20m2/g、
25m2/g、30m2/g、35m2/g、40m2/g、45m2/g、50m2/g、55m2/g、60m2/g、65m2/g、70m2/g、75m2/g、
80m2/g、85m2/g、90m2/g、95m2/g、100m2/g、105m2/g、110m2/g、115m2/g、120m2/g、125m2/g、
130m2/g、135m2/g、140m2/g、145m2/g、150m2/g、155m2/g、160m2/g、165m2/g、170m2/g、175m2/g、
180m2/g、185m2/g、190m2/g、195m2/ g or 200m2/g；The porosity of the polyethylene nanofiber basement membrane is preferably 30
~80%, more preferably 55~65%, concretely 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%,
75% or 80%.
In the present invention, the function monomer contains phosphate ester structure and double bond structure, including but not limited to two [2- (first
Base acryloxy) ethyl] phosphate, 2- methyl -2- acrylic acid -2- (phosphono oxygroup) ethyl ester, two (metering system of phosphoric acid hydrogen
Acyloxyethyl) ester, methacrylic acid ethylene glycol phosphate, vinyl phosphate, vinyl phosphoric acid dimethyl ester and vinyl phosphoric acid
One of diethylester is a variety of.In the present invention, grafting of the function monomer on the polyethylene nanofiber basement membrane
Rate is preferably 10~200%, concretely 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%,
60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, 125%,
130%, 135%, 140%, 145%, 150%, 155%, 160%, 165%, 170%, 175%, 180%, 185%,
190%, 195% or 200%.
The present invention is using polyethylene nano fibrous membrane as basement membrane, by using the function monomer pair with nucleic adsorption capacity
Polyethylene nano fibrous membrane carries out graft modification, imparts film to the absorption property of specific species, to keep it quickly rich
Target species in collection detection environment, effectively prevent in environment as target species content it is too low caused by measure it is difficult, greatly
Amplitude improves sensitivity and the analysis efficiency of Radionuclide analysis detection.
The present invention also provides a kind of preparation methods of modified poly ethylene nano fibrous membrane, comprising the following steps:
A) it will be grafted containing the function monomer of phosphate ester structure and double bond structure using pre-irradiation method or mutual radiation method poly-
It closes on polyethylene nanofiber basement membrane, obtains modified poly ethylene nano fibrous membrane.
In preparation method provided by the invention, the function monomer is graft-polymerized first nanofiber-based to polyethylene
On film.Wherein, the polyethylene nanofiber basement membrane is preferably first pre-processed before the function monomer that is graft-polymerized,
The pretreated detailed process includes: that polyethylene nanofiber basement membrane is dipped into solvent, is washed and is dried later；
The solvent includes but is not limited to methanol；The time of the immersion preferably in 1h or more, concretely 1h, 1.5h, 2h, 2.5h,
3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 8h, 9h or 10h；The time of the drying is preferably 5h or more, specifically
It can be 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h.
In the present invention, be graft-polymerized the function monomer mode be pre-irradiation method or mutual radiation method.Wherein, described
Pre-irradiation method specifically includes the following steps:
A1) polyethylene nanofiber basement membrane is irradiated；The polyethylene nanofiber basement membrane after irradiation is dipped in later
It is reacted in solution containing the function monomer, obtains modified poly ethylene nano fibrous membrane.
In the specific steps of above-mentioned pre-irradiation method provided by the invention, spoke is carried out to polyethylene nanofiber basement membrane first
According to.Wherein, the irradiation bomb of the irradiation is preferably cobalt source, electron beam or ultraviolet lamp, more preferably cobalt source；The dosage of the irradiation
Preferably 20kGy or more, more preferably 50~100kGy, concretely 20kGy, 25kGy, 30kGy, 35kGy, 40kGy,
45kGy、50kGy、55kGy、60kGy、65kGy、70kGy、75kGy、80kGy、85kGy、90kGy、95kGy、100kGy、
105kGy, 110kGy, 115kGy, 120kGy, 125kGy, 130kGy, 135kGy, 140kGy, 145kGy or 150kGy；The spoke
According to temperature be preferably 15~35 DEG C, concretely 15 DEG C, 20 DEG C, 25 DEG C (room temperature), 30 DEG C or 35 DEG C；The irradiation it is preferred
It carries out in air, nitrogen or rare gas atmosphere, is more preferably carried out in nitrogen or rare gas atmosphere.
In the specific steps of above-mentioned pre-irradiation method provided by the invention, after polyethylene nanofiber basement membrane completes irradiation,
It is dipped in the solution containing the function monomer and is reacted.Wherein, the solvent in the solution includes but is not limited to two
Methylformamide (DMF)；Function monomer concentration in the solution is preferably 0.1~1mol/L, more preferably 0.4~
0.6mol/L, concretely 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L,
0.4mol/L、0.45mol/L、0.5mol/L、0.55mol/L、0.6mol/L、0.65mol/L、0.7mol/L、0.75mol/L、
0.8mol/L, 0.85mol/L, 0.9mol/L, 0.95mol/L or 1mol/L；The solution is preferably first right before impregnating basement membrane
The solution carries out deoxygenation, and the mode of the deoxygenation is preferably bubbled deoxygenation；The reaction is preferably in air, nitrogen or rare gas
It carries out in body atmosphere, is more preferably carried out in nitrogen or rare gas atmosphere；The temperature of the reaction is preferably 40~80 DEG C, more
Preferably 60~70 DEG C, concretely 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C；The reaction
Time be preferably 2~8h, more preferably 6~8h, concretely 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h,
6.5h, 7h, 7.5h or 8h.After reaction, the fiber basement membrane for completing to be graft-polymerized is taken out from solution, is washed and is done
It is dry, obtain modified poly ethylene nano fibrous membrane provided by the invention.
In the present invention, the mutual radiation method specifically includes the following steps:
A2) polyethylene nanofiber basement membrane is dipped in the solution containing the function monomer, later under radiation parameter
It is reacted, obtains modified poly ethylene nano fibrous membrane.
In the specific steps of above-mentioned mutual radiation method provided by the invention, polyethylene nanofiber basement membrane is dipped in institute first
It states in solution.Wherein, the solvent in the solution includes but is not limited to dimethylformamide (DMF)；Function in the solution
Monomer concentration is preferably 0.1~1mol/L, more preferably 0.4~0.6mol/L, concretely 0.1mol/L, 0.15mol/L,
0.2mol/L、0.25mol/L、0.3mol/L、0.35mol/L、0.4mol/L、0.45mol/L、0.5mol/L、0.55mol/L、
0.6mol/L, 0.65mol/L, 0.7mol/L, 0.75mol/L, 0.8mol/L, 0.85mol/L, 0.9mol/L, 0.95mol/L or
1mol/L；Soaking time of the polyethylene nanofiber basement membrane in the solution is preferably 1h or more, more preferably 2~
8h, most preferably 6~8h, concretely 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h,
7.5h or 8h.Later, the function monomer solution immersed with polyethylene nanofiber basement membrane is irradiated, it is poly- brings it about grafting
Close reaction.Wherein, the irradiation bomb of the irradiation is preferably cobalt source, electron beam or ultraviolet lamp, more preferably cobalt source；The irradiation
Dosage is preferably 20kGy or more, more preferably 50~100kGy, concretely 20kGy, 25kGy, 30kGy, 35kGy, 40kGy,
45kGy、50kGy、55kGy、60kGy、65kGy、70kGy、75kGy、80kGy、85kGy、90kGy、95kGy、100kGy、
105kGy, 110kGy, 115kGy, 120kGy, 125kGy, 130kGy, 135kGy, 140kGy, 145kGy or 150kGy；It is described anti-
It should preferably carry out in air, nitrogen or rare gas atmosphere, more preferably be carried out in nitrogen or rare gas atmosphere；It is described anti-
The temperature answered is preferably 15~35 DEG C, and concretely 15 DEG C, 20 DEG C, 25 DEG C (room temperature), 30 DEG C or 35 DEG C.Irradiation reaction terminates
Afterwards, the fiber basement membrane for completing to be graft-polymerized is taken out from solution, is washed and is dried, it is poly- to obtain modification provided by the invention
Ethylene nano fibrous membrane.
Preparation method provided by the invention is grafted on polyethylene nano-fiber film using the modified method of irradiation grafting
The function monomer that there is adsorption capacity to nucleic has been polymerize it, the preparation method is simple and effective, easy to spread.Provided by the invention
In optimal technical scheme, by the optimum choice to preparation condition, function monomer also can further improve in polyethylene Nanowire
The grafting rate on film is tieed up, so that the Modified Membrane of preparation be made to show more excellent effect in terms of adsorbing nucleic.
The results showed that selected function monomer successfully can be grafted to polyethylene using preparation method provided by the invention
The surface of nano fibrous membrane, function monomer grafting rate are 10~200%.Also, when selecting following preparation condition, function monomer
Grafting rate be able to maintain that in higher level: selection 30~50nm of fibre diameter, 10 μm of film thickness, specific surface area 80m2/ g, hole
The polyethylene nano fibrous membrane of gap rate 60% is as basement membrane；Irradiance method selects pre-irradiation method；Irradiation bomb selects cobalt source；Irradiatometer
50~100kGy of amount selection；Function monomer concentration in solution selects 0.5mol/L；Solution is first roused before participating in reaction
Steep deoxygenation；Reaction temperature selects 60~70 DEG C；Reaction time selects 6-8h；Irradiation and reaction environment are selected as nitrogen or rare gas
Body atmosphere.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
By the polyethylene nano fibrous membrane of the 3cm square cut, (fibre diameter is 20~50nm, 10 μm of film thickness, compares table
Area is 100m2/ g, porosity 60%) it is placed in methanol solvate and impregnates 3h, it is rinsed for several times, is placed in first alcohol and water after taking-up
12h, weighing are dried in vacuum oven.
Polyethylene nano fibrous membrane is placed in tool plug teat glass and carries out cobalt source irradiation, air atmosphere, room temperature condition, spoke
It is 50kGy according to dosage.
After the completion of irradiation, 10ml (two [2- (methacryloxy) ethyl] phosphoric acid containing function monomer are drawn with syringe
Ester) DMF solution, in injecting tube, the concentration of function monomer is 0.4mol/L in solution, is divided in advance using Bubbling method deoxygenation 10
Clock.
Be passed through nitrogen 20 minutes to test tube at room temperature, be placed in 60 DEG C of baking ovens and reacted, reaction time 6h.
After reaction, thin-film material is taken out from test tube, and is successively rinsed for several times with DMF and water, and homopolymer is got rid of
With remaining reaction monomers, it is placed in drying in vacuum oven, obtains modified poly ethylene nano fibrous membrane, is weighed.
The sight of surface sweeping Electronic Speculum is carried out to the modified poly ethylene nano fibrous membrane of polyethylene nano fibrous membrane and preparation before modified
It examines, as a result as shown in Fig. 1~2, Fig. 1 is the scanning electron microscope (SEM) photograph for the modified poly ethylene nano fibrous membrane that the embodiment of the present invention 1 provides；
Fig. 2 is the scanning electron microscope (SEM) photograph for the polyethylene nano fibrous membrane that the embodiment of the present invention 1 provides.By Fig. 1~2 as can be seen that being modified
Obvious variation has occurred in front and back, the surface topography of polyethylene nanofiber, and grafting occurs mainly in the surface of fiber, function
Energy monomer wraps fiber, forms " core-sheath " structure.
Infrared spectroscopy inspection is carried out to the modified poly ethylene nano fibrous membrane of polyethylene nano fibrous membrane and preparation before modified
Survey, as a result as shown in figure 3, Fig. 3 embodiment of the present invention 1 provide polyethylene nano fibrous membrane before modified after infrared absorption spectrum
Comparison diagram, in Fig. 3, top curve is that before modified, it is modified for issuing curve.As seen in Figure 3, modified polyethylene
There is apparent functional group's absorption peak in nano-fiber film, this function monomer also in side light embodiment is grafted to
On polyethylene nano-fiber film.
Embodiment 2
By the polyethylene nano fibrous membrane of the 3cm square cut, (fibre diameter is 20~50nm, 10 μm of film thickness, compares table
Area is 100m2/ g, porosity 60%) it is placed in methanol solvate and impregnates 3h, after taking-up for several times with first alcohol and water repeated flushing,
It is placed in vacuum oven and dries 12h, weighing.
Polyethylene nano fibrous membrane is soaked in the pre-configured (two [2- (methacryloxy) containing function monomer
Ethyl] phosphate) DMF solution in, function monomer concentration be 0.4mol/L, soaking time 6h；N is filled later215 minutes.
Test tube equipped with polyethylene nano-fiber film and polymeric solution is placed under room temperature cobalt source environment and is irradiated, agent is irradiated
Amount control is in 50kGy.
After irradiation, polyethylene nano-fiber film is taken out, it is for several times with DMF and deionized water repeated flushing, dry, it obtains
To modified poly ethylene nano fibrous membrane, weighing.
The sight of surface sweeping Electronic Speculum is carried out to the modified poly ethylene nano fibrous membrane of polyethylene nano fibrous membrane and preparation before modified
It examines, as a result as shown in Figures 4 and 5, Fig. 4 is the scanning electron microscope (SEM) photograph for the polyethylene nano fibrous membrane that the embodiment of the present invention 2 provides；Fig. 5
It is the scanning electron microscope (SEM) photograph for the modified poly ethylene nano fibrous membrane that the embodiment of the present invention 2 provides.By Fig. 4~5 as can be seen that being modified
Obvious variation has occurred in front and back, the surface topography of polyethylene nanofiber, and grafting occurs mainly in the surface of fiber, function
Energy monomer wraps fiber, forms " core-sheath " structure.
Infrared spectroscopy inspection is carried out to the modified poly ethylene nano fibrous membrane of polyethylene nano fibrous membrane and preparation before modified
Survey, as a result as shown in fig. 6, Fig. 6 embodiment of the present invention 2 provide polyethylene nano fibrous membrane before modified after infrared absorption spectrum
Comparison diagram, in Fig. 6, top curve be it is modified, issuing curve is before modified.As seen in Figure 6, modified polyethylene
There is new functional group's absorption peak in nano-fiber film, this function monomer also in side light embodiment has been grafted to poly-
On ethylene nano-fiber film.
Embodiment 3
Select basement membrane parameter for avarage fiber diameter 100nm, 50 μm of film thickness, specific surface area 30m2/ g, porosity 30%
Polyethylene nano fibrous membrane cuts to be placed in methanol solution and impregnates a few hours, rinsed well, set with deionized water after taking-up
In drying in oven, weighing.
Polyethylene nano fibrous membrane is placed in tool plug teat glass and is irradiated, irradiation bomb is cobalt source, and irradiation dose is
50kGy, radiation parameter are room temperature, air atmosphere.
After the completion of irradiation, 10ml (two [2- (methacryloxy) ethyl] phosphoric acid containing function monomer are drawn with syringe
Ester) DMF solution, in injecting tube, the concentration of function monomer is 0.4mol/L in solution, is divided in advance using Bubbling method deoxygenation 10
Clock.
Be passed through nitrogen 20 minutes to test tube at room temperature, be placed in 60 DEG C of baking ovens and reacted, reaction time 6h.
After reaction, thin-film material is taken out from test tube, and is successively rinsed for several times with DMF and water, and homopolymer is got rid of
With remaining reaction monomers, it is placed in drying in vacuum oven, obtains modified poly ethylene nano fibrous membrane, is weighed.
Embodiment 4
Selection basement membrane parameter be 20~50nm of avarage fiber diameter, 10 μm of film thickness, specific surface area 100m2/ g, porosity
For 60% polyethylene nano fibrous membrane, cutting, which is placed in methanol solution, impregnates 3 hours, and taking-up is rinsed dry with deionized water
Only, dry, weighing is placed in vacuum oven.
Polyethylene nano fibrous membrane after drying and weighing is placed in tool plug teat glass and is irradiated, irradiation dose is
10kGy, radiation parameter are air atmosphere, room temperature.
After the completion of irradiation, 10ml (two [2- (methacryloxy) ethyls] containing function monomer are injected into teat glass
Phosphate) DMF solution, monomer concentration 0.4mol/L, solution in advance with Bubbling method remove oxygen.
Be passed through nitrogen 20 minutes to test tube at room temperature, be placed in 60 DEG C of baking ovens and reacted, reaction time 6h.
After reaction, thin-film material is taken out from test tube, and is successively rinsed for several times with DMF and water, and homopolymer is got rid of
With remaining reaction monomers, it is placed in drying in vacuum oven, obtains modified poly ethylene nano fibrous membrane, is weighed.
Embodiment 5
Selection basement membrane parameter be 20~50nm of avarage fiber diameter, 10 μm of film thickness, specific surface area 100m2/ g, porosity
For 60% polyethylene nano fibrous membrane, cutting, which is placed in methanol solution, impregnates 3 hours, and taking-up is rinsed dry with deionized water
Only, dry, weighing is placed in vacuum oven.
Polyethylene nano fibrous membrane after drying and weighing is placed in tool plug teat glass and is irradiated, irradiation dose is
50kGy, radiation parameter are air atmosphere, room temperature.
After the completion of irradiation, 10ml (two [2- (methacryloxy) ethyls] containing function monomer are injected into teat glass
Phosphate) DMF solution, monomer concentration 0.4mol/L, solution in advance with Bubbling method remove oxygen.
Be passed through nitrogen 20 minutes to test tube at room temperature, be placed in 40 DEG C of baking ovens and reacted, reaction time 4h.
After reaction, thin-film material is taken out from test tube, and is successively rinsed for several times with DMF and water, and homopolymer is got rid of
With remaining reaction monomers, it is placed in drying in vacuum oven, obtains modified poly ethylene nano fibrous membrane, is weighed.
Embodiment 6
Selection basement membrane parameter be 20~50nm of avarage fiber diameter, 10 μm of film thickness, specific surface area 100m2/ g, porosity
For 60% polyethylene nano fibrous membrane, cutting, which is placed in methanol solution, impregnates 3 hours, and taking-up is rinsed dry with deionized water
Only, dry, weighing is placed in vacuum oven.
Polyethylene nano fibrous membrane after drying and weighing is placed in tool plug teat glass and is irradiated, irradiation dose is
50kGy, radiation parameter are air atmosphere, room temperature.
After the completion of irradiation, 10ml (two [2- (methacryloxy) ethyls] containing function monomer are injected into teat glass
Phosphate) DMF solution, monomer concentration 0.1mol/L, solution in advance with Bubbling method remove oxygen.
Be passed through nitrogen 20 minutes to test tube at room temperature, be placed in 60 DEG C of baking ovens and reacted, reaction time 6h.
After reaction, thin-film material is taken out from test tube, and is successively rinsed for several times with DMF and water, and homopolymer is got rid of
With remaining reaction monomers, it is placed in drying in vacuum oven, obtains modified poly ethylene nano fibrous membrane, is weighed.
Grafting rate calculates
According to the grafting rate of the weight change computing function monomer of rear tunica fibrosa before modified, the results are shown in Table 1:
1 fiber membrane of table before modification after weight change and grafting rate
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of modified poly ethylene nano fibrous membrane, comprising:
Polyethylene nanofiber basement membrane；
With graft polymerization to the function monomer on the polyethylene nanofiber basement membrane；
The function monomer contains phosphate ester structure and double bond structure.
2. modified poly ethylene nano fibrous membrane according to claim 1, which is characterized in that the function monomer includes two
[2- (methacryloxy) ethyl] phosphate, 2- methyl -2- acrylic acid -2- (phosphono oxygroup) ethyl ester, two (first of phosphoric acid hydrogen
Base acrylyl oxy-ethyl) ester, methacrylic acid ethylene glycol phosphate, vinyl phosphate, vinyl phosphoric acid dimethyl ester and ethylene
One of base diethyl phosphate is a variety of.
3. modified poly ethylene nano fibrous membrane according to claim 1, which is characterized in that the polyethylene is nanofiber-based
The fibre diameter of film is 10~100nm；The polyethylene nanofiber basement membrane with a thickness of 2~50 μm；The polyethylene nanometer
The specific surface area of fiber basement membrane is 20~200m2/g；The porosity of the polyethylene nanofiber basement membrane is 30~80%.
4. modified poly ethylene nano fibrous membrane according to claim 1, which is characterized in that the function monomer is described poly-
Grafting rate on ethylene nanofiber basement membrane is 10~200%.
5. a kind of preparation method of modified poly ethylene nano fibrous membrane, comprising the following steps:
A) it will be arrived containing the graft polymerization of the function monomer of phosphate ester structure and double bond structure using pre-irradiation method or mutual radiation method
On polyethylene nanofiber basement membrane, modified poly ethylene nano fibrous membrane is obtained.
6. preparation method according to claim 5, which is characterized in that the pre-irradiation method specifically includes the following steps:
A1) polyethylene nanofiber basement membrane is irradiated；Later by the polyethylene nanofiber basement membrane after irradiation be dipped in containing
It is reacted in the solution of the function monomer, obtains modified poly ethylene nano fibrous membrane；
The mutual radiation method specifically includes the following steps:
A2) polyethylene nanofiber basement membrane is dipped in the solution containing the function monomer, is carried out under radiation parameter later
Reaction, obtains modified poly ethylene nano fibrous membrane.
7. in preparation method according to claim 6, which is characterized in that step a1) in, the dosage of the irradiation is
20kGy or more, the temperature of the reaction are 40~80 DEG C, and the time of the reaction is 2~8h；
Step a2) in, for the polyethylene nanofiber basement membrane before being irradiated, the soaking time in the solution is 1h
More than, the dosage of the irradiation is 20kGy or more, and the temperature of the reaction is 15~35 DEG C.
8. in preparation method according to claim 6, which is characterized in that step a1) and step a2) in, the reaction exists
It is carried out in air, nitrogen or rare gas atmosphere.
9. in preparation method according to claim 6, which is characterized in that step a1) and step a2) in, the irradiation
Irradiation bomb is cobalt source, electron beam or ultraviolet lamp.
10. in preparation method according to claim 6, which is characterized in that step a1) and step a2) in, in the solution
Function monomer concentration be 0.1~1mol/L.
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