CN108823676A - A method of super hydrophilic PVDF composite nano fiber is prepared based on electrostatic spinning technique - Google Patents
A method of super hydrophilic PVDF composite nano fiber is prepared based on electrostatic spinning technique Download PDFInfo
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- CN108823676A CN108823676A CN201810512136.9A CN201810512136A CN108823676A CN 108823676 A CN108823676 A CN 108823676A CN 201810512136 A CN201810512136 A CN 201810512136A CN 108823676 A CN108823676 A CN 108823676A
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- composite nano
- nano fiber
- electrostatic spinning
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- super hydrophilic
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 53
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 36
- 238000009987 spinning Methods 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000007921 spray Substances 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 11
- 230000033001 locomotion Effects 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000013519 translation Methods 0.000 claims description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 241000208340 Araliaceae Species 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 235000008434 ginseng Nutrition 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- YLBLNTXKGYEVSS-UHFFFAOYSA-N methoxymethane;methyl 2-methylprop-2-enoate Chemical compound COC.COC(=O)C(C)=C YLBLNTXKGYEVSS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000013461 design Methods 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 238000001523 electrospinning Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 description 12
- 238000011161 development Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002059 nanofabric Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carboxyl Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229940085805 fiberall Drugs 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Abstract
The present invention relates to a kind of methods for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique, belong to nanoscale science and technology field.Include the following steps：(1) Kynoar, monomer are dissolved in solvent A, spinning solution I is made；(2) initiator is added in spinning solution I, spinning solution II is made；(3) spinning solution II of a certain amount of complete deaeration is taken to be placed in electrospinning respectivelyR, H and Y location of infusing device (three sets) spray head adjust the location parameter of R, H and Y, carry out electrostatic spinning, and PVDF composite nano fiber is made；(4) PVDF composite nano fiber obtained is placed in water bath with thermostatic control and is heat-treated, super hydrophilic PVDF composite nano fiber is made.This method is easy to operate efficiently, reproducible, can be realized the design of (bear electricity) modified performance super hydrophilic to hydrophobic material PVDF, and hydrophilic (bear electricity) performance of material is made to obtain breakthrough raising.
Description
Technical field
The present invention relates to a kind of methods for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique, belong to and receive
Rice science and technology field.
Background technique
Nano science is one and is related to the forward position cross discipline of the subjects such as physics, chemistry, biology, electronics, including nanometer life
The contents such as object, nanoelectronics, nanochemistry, nano material, nanomechanics, research is size in 0.1~100nm model
Enclose the physical property, chemical property and major function of interior substance.The definition of nano material broad sense is：In three dimensions at least
Have one-dimensional in nanoscale (nano-phase material) or structural material composed of them as basic units (nanostructure material
Material).Nano material basic unit is generally divided into three classes：Zero dimension, peacekeeping two dimension.Zero dimension refers to material ruler in the dimension of three, space
Very little is nanoscale, such as nano particle and elementide；One-dimensional finger material size in the dimension of two, space is nanometer
Scale, such as nanometer rods, nanotube and nanofiber；Two dimension refer to the material only in the dimension of one, space having a size of nanoscale,
Such as nanometer sheet, ultrathin membrane, multilayer film and superlattices.
The depth that the combination of the nanosecond science and technology of 21 century and many industrial fields has caused science and technology is changed, and nanosecond science and technology are
As one of the main drive for pushing countries in the world economic development.By years development, nanosecond science and technology field is largely original
Property achievement continues to bring out out, and the appearance of these original achievements is predictive of the huge market space of nanosecond science and technology and development prospect.
It is in particular in：(1) gradual innovation of the nanosecond science and technology in conjunction with conventional industries, and wear stages then bring a collection of new production
Product and NPD projects；(2) it is achieved in the process in nanoprocessing observation method, nano material, nano-device research with commercialized
Length development.The main reason in following twenty or thirty year, driving national governments are continuously increased investment to nanotechnology, is a nanometer skill
Art is expected to be widely applied to the fields such as information, the energy, environmental protection, biomedicine, manufacture, national defence, generates new technology and changes, forms base
In the new industry of nanotechnology, and promote the transformation and upgrading of conventional industries.
The property of nano material and the property of its Component units are closely related, and nano material itself occurs many unique
Property and new rule, such as small-size effect, skin effect, quantum size effect, macro quanta tunnel effect, reason are
Its Component units, these nanometer systems between both macro and micro atom, molecular scale are a new class of substance levels.And
The new function characteristic generated using the unique effect of nano material, designing next-generation nano structure device is that nano-functional material is ground
The important trend studied carefully.
Nano-device is one of the important impetus of function nano Materials, in electronics, military project, information, optics, change
Work, biology and medicine and other fields all have broad application prospects.By the micromanagement constructed and assembled on nanoscale,
The final design that can be achieved to nano material various aspects macro property.The microcosmic regulations of Component units so that nano material magnetic
Property, the physics such as broadcasting and TV, ductility, Selective adsorption, catalytic activity, making a breakthrough property of chemical property improve.Wherein nanometer ruler
It is especially prominent to the research in terms of the micromanagement of nanofiber constructed and assembled on degree.
Emerged a variety of methods for preparing nanofiber in recent years, as phase separation method, template synthesis method, pulling method, from
Construction from part etc., but comprehensively consider equipment complexity, process controllability, spinning suiting range, cost, yield and fibre dimensions controllability
Etc. requirement, these methods still have certain limitation.At the same time, it can directly, continuously be prepared as one kind poly-
The method that nanofiber is made in object nanofiber is closed, electrostatic spinning technique prepares functional nano-fiber and more and more closed
Note.When diameter narrows down to sub-micron or nanometer from micron, polymer nanofiber compared with corresponding conventional polymeric materials,
A variety of excellent physics, chemical property can be showed.Current several main nanofiber preparation techniques are compared as follows shown in table：
The comparison of the current several main nanofiber preparation techniques of table 1
Based on nanofiber and the distinctive performance of functional nano-fiber and function, have in conventional industries and sciemtifec and technical sphere
Application and wide development prospect well.Demand and trade according to fiber industry federation of South Korea to nano-fabric market
The investigation and analysis of situation, between 10 years from now on, it is contemplated that its volume of trade is up to 40,000,000,000 dollars, and international market is to nano-fabric
Demand will expand rapidly.Functional nano-fiber and its textile also will be more wide in the purposes of textile industry and other industrial fields
General, with the further development of nanotechnology, there is a huge market demand potential.In terms of being mainly reflected in following two：(1) function
In terms of the basic research and technology of preparing of nanofiber, in terms of the industrialization development of (2) functional nano-fiber.Wherein high-performance is received
The development of rice fiber and functional nano-fiber all has great meaning for fields such as modern national defense, hard-core technology and energy conservation and environmental protections
Justice.
Summary of the invention
In view of the foregoing defects the prior art has, the invention proposes a kind of new to be surpassed based on electrostatic spinning technique preparation
The method of hydrophilic PVDF composite nano fiber, this method is easy to operate efficiently, reproducible, can be realized to hydrophobic material PVDF
The design of super hydrophilic (bear electricity) modified performance makes hydrophilic (bear electricity) performance of material obtain breakthrough raising, and contact angle is only
It is 0~10 °.
The present invention, which is that the following technical solution is employed, to be realized：
A method of super hydrophilic PVDF composite nano fiber is prepared based on electrostatic spinning technique, is included the following steps：
(1) Kynoar, monomer being dissolved in solvent A, constant temperature, which is continuously stirring to, to be completely dissolved, it is cooled to room temperature,
Spinning solution I is made；
(2) initiator is added in spinning solution I, is continuously stirred after being uniformly dispersed at room temperature, constant temperature causes primary reconstruction &
Raolical polymerizable hydrophilic modifying, is cooled to room temperature, and spinning solution II is made；
(3) spinning solution II of a certain amount of complete deaeration is taken to be placed in respectivelyR, H and Y of infusing device (three sets) spray head
Position adjusts the location parameter of R, H and Y, carries out electrostatic spinning, and PVDF composite nano fiber is made；
(4) PVDF composite nano fiber obtained is placed in water bath with thermostatic control and is heat-treated, be made that super hydrophilic PVDF is compound to be received
Rice fiber.
Preferably, the mass fraction of Kynoar is：0~30wt.%；Solvent A is ethyl alcohol, polyethylene glycol, phosphoric acid
Triethyl, trimethyl phosphate, tricresyl phosphate propyl ester, dimethyl sulfoxide, acetone, dimethylformamide, N-Methyl pyrrolidone, diformazan
One of yl acetamide, dioctyl phthalate and dibutyl phthalate are a variety of, and monomer is mixing free radical list
Body, preferably 2- M Cr, poly- diethanol monomethyl ether methyl methacrylate, acrylic acid, 2- butenoic acid ethyl, 2- methyl
Acrylic acid, ethyl acrylate, 2- butenoic acid, 1- M Cr, ethyl 2-methacrylate, methyl acrylate, 2- methyl-prop
At least two in e pioic acid methyl ester, 1- butenoic acid and 1- butenoic acid ethyl.
Preferably, initiator is water-soluble or oil-soluble with hydrophilic radicals such as carboxyl, sulfonic groups in step (2)
Azo-compound, the preferably different cyanogen in heptan of azo two, azo-bis-isobutyl cyanide, azo diisobutyl amidine hydrochloride, isopropylbenzene peroxidating
The mass fraction of one or more of hydrogen and benzoyl peroxide, initiator is：0.01~10.0%, cause in situ from group
The thermostat temperature for filling & Raolical polymerizable hydrophilic modifying is 25~200 DEG C, causes primary reconstruction & Raolical polymerizable
The time of hydrophilic modifying is 1~24 hour.
Preferably, the amount that the complete deaeration spinning solution II of spray head R, H and Y location is placed in step (3) be respectively 1~
100 milliliters.
Preferably, the translation parameters of the position electrostatic spinning process nozzle adjustable R, H and Y is in step (3)：It moves
Dynamic 0~600mm of stroke, translates number 1~9999 time, alternating translational 0~300mm of distance, 1~500mm/min of movement speed.
Preferably, the reception parameter of the position electrostatic spinning process nozzle adjustable R, H and Y is in step (3)：It is flat
10~800cm of plate receiver area2, 0~140rpm of spinneret receiver revolving speed.
Preferably, the parameter of injecting of the position electrostatic spinning process nozzle adjustable R, H and Y is in step (3)：Spray
50~300mm of spacing is penetrated, carries out 0~100mm of outbound, injects 0.001~90mm/min of speed.
Preferably, in step (3) position spray head R, H and Y electrostatic spinning process angle adjustable parameter be -45 °~
45°。
Preferably, the adjustable positive high voltage of the position spray head R, H and Y spinning process and negative high voltage parameter point in step (3)
It is not：0~50V and -50~0V；The position spray head R, H and Y tunable electrostatic spinning temperature and humidity ginseng in the step (3)
Number is respectively：10~45 DEG C and 25~70%.
Preferably, the water bath with thermostatic control temperature that PVDF composite nano fiber is heat-treated in step (4) is 0~100 DEG C；Constant temperature
It is 1~72 hour that the time is handled in water-bath.
The beneficial effects of the invention are as follows：Compared with prior art, the present invention is support with hydrophobic polymeric polymer P VDF
Structure, hydrophilic (bear electricity) the modified method of design primary reconstruction & Raolical polymerizable, using electrostatic spinning technique, preparation is super
Hydrophilic (bear electricity) PVDF composite nano fiber；The present invention is based on electrostatic spinning techniques, primary reconstruction & Raolical polymerizable
Hydrophilic (bear electricity) modified method, primary reconstruction & Raolical polymerizable hydrophilic (bear electricity) modified method reaction efficiency are high, hydrophilic
Modified sites are more, and electrospinning conditions are flexibly controllable, and preparation process is simple, spinning efficiency is high；UsingInfusing device (three
Set) electrostatic spinning apparatus by the synchronous electrostatic of primary reconstruction & Raolical polymerizable hydrophilic (bear electricity) modified spinning solution
Spinning prepares super hydrophilic (bear electricity) PVDF composite nano fiber；Super hydrophilic (bear electricity) PVDF composite nano fiber obtained is fine
Tie up even thickness and surface super hydrophilic (0~10 ° of contact angle).
Detailed description of the invention
Fig. 1 is flow chart of the method for the present invention.
Fig. 2 is the electron microscope of super hydrophilic PVDF composite nano fiber made from embodiment one.
Fig. 3 is the electron microscope of super hydrophilic PVDF composite nano fiber made from embodiment two.
Fig. 4 is the electron microscope of super hydrophilic PVDF composite nano fiber made from embodiment three.
Specific embodiment
In order to fully understand the purpose of the present invention, feature and effect, by following specific embodiments, the present invention is made detailed
It describes in detail bright.For process of the invention in addition to following the description, remaining is all made of the conventional method or device of this field.Following names
Word term is unless otherwise stated, all have the normally understood meaning of those skilled in the art.
Embodiment one：
As depicted in figs. 1 and 2, step (1)：Kynoar (PVDF), quality point by mass fraction for 10.0wt.%
Number is the 2- M Cr and poly glycol monomethyl ether methyl methacrylate (MW of 6.0wt.%：Monomer 800g/mol) is mixed
It closes object to be dissolved in dimethylformamide (DMF), the matter of 2- M Cr and poly glycol monomethyl ether methyl methacrylate
Amount is than being 1:2,60 DEG C of constant temperature continuously stir 12 hours to being completely dissolved, and are cooled to room temperature, and spinning solution I is made；
Step (2)：The initiator isopropyl benzene hydroperoxide (CHPO) that mass fraction is 0.02wt.% is added into spinning solution
It in I, is continuously stirred after being uniformly dispersed at room temperature, 60 DEG C of constant temperature cause the hydrophilic (bear of primary reconstruction & Raolical polymerizable
Electricity) modified-reaction 12 hours, it is cooled to room temperature, spinning solution II is made；
Step (3)：The spinning solution II of 10 milliliters of complete deaerations is taken to be placed in respectivelyThe spray head R of infusing device (three sets),
H and Y location adjust 25 DEG C of spinning temperature, spinning humidity 45%, positive high voltage 8.96V, negative high voltage -3.66V, R, H and Y location three
The angle of spray head is respectively 30 °, 60 ° and 0 °, carries out electrostatic spinning；In spinning process, spray head R, H and Y location placeIt pushes away
The translation parameters of dispensing device (three sets) is：Spacing 35mm is sprayed, carries out outbound 60mm, injects speed 0.32mm/min；Spray head R, H
With Y location placeThe reception device parameter of infusing device (three sets) is：Shift motion 180mm is translated number 3879 times,
Alternating translational distance 160mm, movement speed 240mm/min；The place of spray head R, H and Y location Infusing device (three sets)
Receiving parameter is：Spray head R, H and the corresponding flat receiver area 360cm of Y location2, spinneret receiver revolving speed 76rpm.
Step (4)：PVDF composite nano fiber obtained is placed in 80 DEG C of waters bath with thermostatic control and is heat-treated 24 hours, it is final to make
Obtain super hydrophilic (bear electricity) PVDF composite nano fiber.
Each parameter of super hydrophilic (bear electricity) PVDF composite nano fiber is as follows：
Fibre diameter/nm：425±65
Nanofiber surface constituent content/wt.%：C 40.24±1.17O 22.81±3.11F 36.95±2.16
Contact angle：3.1±1.1°
From above-mentioned parameter it can be seen that：PVDF composite nano fiber surface oxygen element content is up to 22.81%, and contact angle
Only 3.1 ± 1.1 °, this illustrates the Superhydrophilic of PVDF composite nano fiber.
Embodiment two：
As shown in figures 1 and 3, step (1)：Kynoar (PVDF), quality point by mass fraction for 7.0wt.%
Number is the acrylic acid and poly glycol monomethyl ether methyl methacrylate (MW of 6.0wt.%：Monomer mixture 800g/mol) is molten
For solution in dimethylformamide (DMF), the mass ratio of acrylic acid and poly glycol monomethyl ether methyl methacrylate is 1:1,60
DEG C constant temperature continuously stirs 12 hours to being completely dissolved, and is cooled to room temperature, and spinning solution I is made；
Step (2)：The initiator azo-bis-isobutyl cyanide (AIBN) that mass fraction is 0.02wt.% is added into spinning solution I
In, it is continuously stirred after being uniformly dispersed at room temperature, it is hydrophilic (bear electricity) that 60 DEG C of constant temperature cause primary reconstruction & Raolical polymerizable
It modified-reaction 12 hours, is cooled to room temperature, spinning solution II is made；
Step (3)：The spinning solution II of 10 milliliters of complete deaerations is taken to be placed in respectivelyThe spray head R of infusing device (three sets),
H and Y location adjust 25 DEG C of spinning temperature, spinning humidity 45%, positive high voltage 6.12V, negative high voltage -2.78V, R, H and Y location three
The angle of spray head is respectively 30 °, 60 ° and 0 °, carries out electrostatic spinning；In spinning process, spray head R, H and Y location placeIt pushes away
The translation parameters of dispensing device (three sets) is：Spacing 35mm is sprayed, carries out outbound 60mm, injects speed 0.06mm/min；Spray head R, H
With Y location placeThe reception device parameter of infusing device (three sets) is：Shift motion 180mm is translated number 8731 times,
Alternating translational distance 160mm, movement speed 240mm/min；The place of spray head R, H and Y location Infusing device (three sets)
Receiving parameter is：Spray head R, H and the corresponding flat receiver area 360cm of Y location2, spinneret receiver revolving speed 76rpm.
Step (4)：PVDF composite nano fiber obtained is placed in 80 DEG C of waters bath with thermostatic control and is heat-treated 24 hours, it is final to make
Obtain super hydrophilic (bear electricity) PVDF composite nano fiber.
Each parameter of super hydrophilic (bear electricity) PVDF composite nano fiber is as follows：
Fibre diameter/nm：330±31
Nanofiber surface constituent content/wt.%：C 42.23±2.17O 24.22±2.98F 33.56±1.63
Contact angle：1.9±1.2°
From above-mentioned parameter it can be seen that PVDF composite nano fiber surface oxygen element content is up to 24.22%, and contact angle
Only 1.9 ± 1.2 °, this illustrates the Superhydrophilic of PVDF composite nano fiber.
Embodiment three：
As shown in Figure 1 and Figure 4, step (1)：Kynoar (PVDF), quality point by mass fraction for 11.0wt.%
The monomer dissolved mixture of acrylic acid and methacrylic acid that number is 8.0wt.% is in dimethylformamide (DMF), acrylic acid
Mass ratio with methacrylic acid is 1:1.5,60 DEG C of constant temperature continuously stir 12 hours to being completely dissolved, and are cooled to room temperature, and are made
Spinning solution I；
Step (2)：The initiator azo-bis-isobutyl cyanide (AIBN) that mass fraction is 0.03wt.% is added into spinning solution I
In, it is continuously stirred after being uniformly dispersed at room temperature, it is hydrophilic (bear electricity) that 60 DEG C of constant temperature cause primary reconstruction & Raolical polymerizable
It modified-reaction 12 hours, is cooled to room temperature, spinning solution II is made；
Step (3)：The spinning solution II of 10 milliliters of complete deaerations is taken to be placed in respectivelyThe spray head R of infusing device (three sets),
H and Y location adjust 25 DEG C of spinning temperature, spinning humidity 45%, positive high voltage 9.41V, negative high voltage -3.26V, R, H and Y location three
The angle of spray head is respectively 30 °, 60 ° and 0 °, carries out electrostatic spinning；In spinning process, spray head R, H and Y location placeIt pushes away
The translation parameters of dispensing device (three sets) is：Spacing 35mm is sprayed, carries out outbound 60mm, injects speed 0.28mm/min；Spray head R, H
With Y location placeThe reception device parameter of infusing device (three sets) is：Shift motion 180mm is translated number 4120 times,
Alternating translational distance 160mm, movement speed 240mm/min；The place of spray head R, H and Y location Infusing device (three sets)
Receiving parameter is：Spray head R, H and the corresponding flat receiver area 360cm of Y location2, spinneret receiver revolving speed 76rpm.
Step (4)：PVDF composite nano fiber obtained is placed in 80 DEG C of waters bath with thermostatic control and is heat-treated 24 hours, it is final to make
Obtain super hydrophilic (bear electricity) PVDF composite nano fiber.
Each parameter of super hydrophilic (bear electricity) PVDF composite nano fiber is as follows：
Fibre diameter/nm：512±61
Nanofiber surface constituent content/wt.%：C 41.26±1.3O 23.58±1.19F 35.14±2.08
Contact angle：0.9±1.5°
From above-mentioned parameter it can be seen that：PVDF composite nano fiber surface oxygen element content is up to 23.58%, and contact angle
Only 0.9 ± 1.5 °, this illustrates the Superhydrophilic of PVDF composite nano fiber.
The foregoing is merely presently preferred embodiments of the present invention and oneself, not with the present invention for limitation, it is all in essence of the invention
Made impartial modifications, equivalent substitutions and improvements etc., should be included in patent covering scope of the invention within mind and principle.
Claims (10)
1. a kind of method for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique, which is characterized in that including with
Lower step：
(1) Kynoar, monomer are dissolved in solvent A, constant temperature, which is continuously stirring to, to be completely dissolved, and is cooled to room temperature, and is made
Spinning solution I；
(2) initiator is added in spinning solution I, is continuously stirred after being uniformly dispersed at room temperature, it is free that constant temperature causes primary reconstruction &
Base polymerization reaction hydrophilic modifying, is cooled to room temperature, and spinning solution II is made；
(3) spinning solution II of a certain amount of complete deaeration is taken to be placed in respectivelyR, H and Y location of infusing device (three sets) spray head,
The location parameter of R, H and Y are adjusted, electrostatic spinning is carried out, PVDF composite nano fiber is made；
(4) PVDF composite nano fiber obtained is placed in water bath with thermostatic control and is heat-treated, it is fine that super hydrophilic PVDF composite Nano is made
Dimension.
2. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that the mass fraction of the Kynoar is：0~30wt.%；The solvent A be ethyl alcohol, polyethylene glycol,
Triethyl phosphate, trimethyl phosphate, tricresyl phosphate propyl ester, dimethyl sulfoxide, acetone, dimethylformamide, N-Methyl pyrrolidone,
One of dimethyl acetamide, dioctyl phthalate and dibutyl phthalate are a variety of, and the monomer is mixing
Free radical monomer, preferably 2- M Cr, poly- diethanol monomethyl ether methyl methacrylate, acrylic acid, 2- butenoic acid second
Ester, 2- methacrylic acid, ethyl acrylate, 2- butenoic acid, 1- M Cr, ethyl 2-methacrylate, methyl acrylate,
At least two in 2- methyl methacrylate, 1- butenoic acid and 1- butenoic acid ethyl.
3. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that initiator is the hydrophilic radicals such as water-soluble or oil-soluble band carboxyl, sulfonic group in the step (2)
Azo-compound, the preferably different cyanogen in heptan of azo two, azo-bis-isobutyl cyanide, azo diisobutyl amidine hydrochloride, isopropylbenzene peroxide
Change one or more of hydrogen and benzoyl peroxide, the mass fraction of initiator is：0.01~10.0%, cause in situ from group
The thermostat temperature for filling & Raolical polymerizable hydrophilic modifying is 25~200 DEG C, causes primary reconstruction & Raolical polymerizable
The time of hydrophilic modifying is 1~24 hour.
4. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that the amount that the complete deaeration spinning solution II of spray head R, H and Y location is placed in the step (3) is respectively 1~
100 milliliters.
5. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that the translation parameters of the position electrostatic spinning process nozzle adjustable R, H and Y is in the step (3)：
0~600mm of shift motion is translated number 1~9999 time, alternating translational 0~300mm of distance, 1~500mm/min of movement speed.
6. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that the reception parameter of the position electrostatic spinning process nozzle adjustable R, H and Y is in the step (3)：
10~800cm of flat receiver area2, 0~140rpm of spinneret receiver revolving speed.
7. the method according to claim 1 that super hydrophilic PVDF composite nano fiber is prepared based on electrostatic spinning technique,
It is characterized in that, the parameter of injecting of the position electrostatic spinning process nozzle adjustable R, H and Y is in the step (3)：Between injection
Away from 50~300mm, carries out 0~100mm of outbound, inject 0.001~90mm/min of speed.
8. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that in the step (3) position spray head R, H and Y electrostatic spinning process angle adjustable parameter be -45 °~
45°。
9. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that the adjustable positive high voltage of the position spray head R, H and Y spinning process and negative high voltage parameter point in the step (3)
It is not：0~50V and -50~0V；The position spray head R, H and Y tunable electrostatic spinning temperature and humidity ginseng in the step (3)
Number is respectively：10~45 DEG C and 25~70%.
10. a kind of side for preparing super hydrophilic PVDF composite nano fiber based on electrostatic spinning technique according to claim 1
Method, which is characterized in that the water bath with thermostatic control temperature that PVDF composite nano fiber is heat-treated in the step (4) is 0~100 DEG C；It is permanent
It is 1~72 hour that the time is handled in tepidarium.
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| CN103282393A (en) * | 2010-12-22 | 2013-09-04 | 索尔维特殊聚合物意大利有限公司 | Hydrophilic vinylidene fluoride polymers |
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| CN110158177A (en) * | 2019-05-27 | 2019-08-23 | 长江师范学院 | A kind of polymerization based on electrostatic spinning technique |
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