CN106883447B - A kind of application of high-strength polymer film, preparation method and diluent - Google Patents
A kind of application of high-strength polymer film, preparation method and diluent Download PDFInfo
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- 239000003085 diluting agent Substances 0.000 title claims abstract description 43
- 229920006254 polymer film Polymers 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000002145 thermally induced phase separation Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 30
- 238000005266 casting Methods 0.000 claims description 24
- 239000002033 PVDF binder Substances 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 2
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 claims description 2
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 2
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical group COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 27
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract 1
- 238000010094 polymer processing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 6
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 6
- -1 2- ethyl hexyl Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of high-strength polymer film, preparation method and a kind of new opplications of diluent, using thermally induced phase separation, the diluent lower and containing carbon-carbon double bond using toxicity simultaneously, plasticizer is used as in Polymer Processing forming process, and melting graft reaction occurs with polymer, a small amount of diluent is grafted in polymer chain, makes to be made polymer porous film with very high intensity and flexibility.Therefore obtained plate membrane or hollow-fibre membrane mechanical performance with higher, tensile strength can reach 10MPa, pure water flux 1000L/ (m2× h) more than.
Description
Technical field
The invention mainly relates to the technologies of preparing of polyvinylidene fluoride porous film, prepare especially with thermally induced phase separation poly-
The method of the high intensity, porous film of vinylidene.
Background technique
With the rapid development of world economy, shortage of water resources and water environment pollution have become and restrict China its people warp
An important factor for Ji sustainable development and living standards of the people improve.It is that alleviation is watery that sewage collecting processing renewable resources, which are utilized,
The most effective most economical approach of condition.Isolation technics using film as core component is in sea water desalination, Industrial Wastewater Treatment, life
The water treatment fields such as sewage treatment have a wide range of applications, including micro-filtration, ultrafiltration, nanofiltration, reverse osmosis, electrodialysis etc..
Kynoar (PVDF) is a kind of white powder semicrystalline polymeric, and fusing point is 172 DEG C, heat distortion temperature
112 DEG C ~ 145 DEG C, long-term use temperature be -40 DEG C ~ 150 DEG C, Kynoar have excellent mechanical strength, strong-hydrophobicity,
The features such as chemical stability, radiation resistance, heat resistance, still has very high fade resistance and uvioresistant in extreme environment
Performance can have good resistance in the case where facing severe water environment conditions, therefore gradually be widely used in water treatment field.
The preparation method of seperation film is usually to be codetermined by the property and required membrane structure performance of membrane material.Such as
When organic material and inorganic material are as membrane material, since their performance differs greatly, the prepared film come out in structure and
There are huge differences in performance, therefore are very different using film-forming method, and used film-forming method also has difference, mesh
The preparation method of preceding polyvinylidene fluoride film is mainly the following.
Immersion precipitation is also known as phase separation method (NIPS), is in current film-forming method using more, NIPS
Method can simply be summarized as following steps: a certain amount of polymer and stirring solvent are weighed first into uniform casting solution,
Casting solution blade coating is sprayed on the supporting plate or by spinning head again, then casting solution is immersed in non-solvent, makes casting solution
In solvent and non-solvent in coagulating bath phase counterdiffusion occurs, system occurs mutually separation and forms porous flat plate film or hollow fibre
Tie up film.There are many influence factor of NIPS method, are mainly made of casting solution, coagulation bath composition, air residence time etc., and obtain
Membrane structure type is also very much, as bicontinuous structure, spongelike structure, dendritic structure, finger-like pore etc., especially finger-like pore, meeting
Substantially reduce the mechanical performance and separating property of film.
Thermally induced phase separation (TIPS) be by temperature-induced casting film liquid system generation mutually separate, the method be by polymer with
The compound mixing of certain higher boilings, low molecular weight, stirs at high temperature, makes the mutual phased soln of mixture to form homogeneous casting film
Then casting solution is formed different shapes by mold, and immersed in cooling bath by liquid, then reduce temperature, makes casting solution
Solid-liquid or liquid-liquid phase separation form perforated membrane after then being removed diluent with the methods of solvent extraction, wherein fenestra is dilute
It releases and is formed by the position that it originally occupied after agent is removed.The factor for influencing the polymer film performance of TIPS method preparation mainly has
Polymer concentration, interaction force between cooling velocity and polymer and diluent, and TIPS method are by controlling casting film
The heat exchange of liquid system occurs mutually to separate, and controls mass exchange generation between solvent and non-solvent with NIPS method and mutually separates phase
Than heat exchange is rapider, so as to accurately control the morphosis of film.
The polymer porous film major advantage prepared by TIPS method is: first, expand the range of choice of diluent.
Some diluents are smaller due to acting on high molecular polymer, so that dissolubility is poor, room temperature or compared with low temperature when cannot be molten
Solution can not be prepared using NIPS method.But when being heated to certain temperature, polymer/diluent system just will form homogeneous molten
Liquid occurs mutually to separate after cooling, can be prepared by perforated membrane after extracting diluent.Second, the controllability of membrane structure improves.TIPS
Legal system film influence factor is fewer, by control polymer content, diluent, coagulating bath type or rate of temperature fall, can produce
Different types of film (microfiltration membranes, ultrafiltration membrane), diversity also may be implemented in membrane structure pattern, and (co-continuous is netted, spheroidal cementite, sea
Continuous shape etc.).Third, membrane structure is than more complete.The porous membrane structure prepared by TIPS method does not refer in membrane structure than more complete
Shape hole is less, even aperture distribution and satisfactory mechanical property.
Currently, TIPS method prepares polymer porous film, usually used diluent has phthalate, such as adjacent benzene two
Formic acid dimethyl ester, dibutyl phthalate, phthalic acid two (2- ethyl hexyl) ester ... cyclohexanone, 1,4- butyrolactone etc..
But it is all to have certain toxicity that usually used diluent is most of.Phthalic acid ester is a kind of current industrially quilt
Widely used diluent, but it has very big harm to environment, is confirmed to be the 4th class poisonous chemical substance in Taiwan, it is American-European
Country, which is making laws, to be forbidden using this phenyl ring class diluent.Therefore the film diluent in the development of the following green chemistry chemical technology
Selection be particularly important.
In practical engineering applications, porous diffusion barrier will be applied in water treatment procedure in the form of component, and transported
The operation that will be faced high pressure water flow during row and wash away and backwash, the case where film fracture can be often found in membrane module.Cause
This, preparing high-intensitive porous diffusion barrier is particularly important.In plastics industry field, thanks and continue bright wait the study found that poly- third
Grafted maleic anhydride-styrene on alkene, certain raising can be obtained to the mechanical performance of polypropylene plastics, and (Xie Xuming, Li Ying open
The polyacrylic influence factor of Jing Chun, Yang Xun maleic anhydride-styrene fusion-grafting and its performance study [J] polymer science
Report, 2002, (01): 7-12.).Patent CN105418851A causes grafting maleic anhydride on molten polypropylene by ultraviolet light irradiation,
And the steam that maleic anhydride generates at high temperature has certain toxicity, damages the organs such as the eyes of people.In the present invention, it selects
Higher boiling, hypotoxicity and the dibutyl maleate with polarized and reactive functionality are applied to seperation film field, using melting
The method of grafting is prepared with high-intensitive polymer porous film.
Summary of the invention
Usually during TIPS method prepares polymer porous film, diluent is blended simultaneously with polymer at high temperature first
Stirring, forms homogeneous casting solution, by quenching split-phase, finally again extracts remaining diluent by the solvent that can be dissolved each other with it
It takes and removes, so there is no remnants in perforated membrane for diluent, present invention discover that the esters containing carbon-carbon double bond used are dilute
It releases agent and prepares perforated membrane, porous film strength can be greatly improved.The reason is that: carbon-carbon double bond have stronger reactivity and
Copolymerized ability, when being used to prepare PVDF polymer film, in casting solution heating process, portion of diluent and polymer occur instead
It answers, increases the mechanical property of perforated membrane.Compared with perforated membrane prepared by traditional TIPS method, mechanical property obtains biggish mention
It is high；Furthermore selected diluent itself is basic functionality monomer, have toxicity lower compared to adjacent benzene class diluent, to human body
Stimulate the advantages that small.
The first aspect of the invention:
A kind of high intensity pvdf membrane, the repetitive unit with structure shown in formula (III) in film layer:
1(III).
Wherein, R1And R2Independently selected from the substituted or unsubstituted alkyl containing 1~10 carbon atom.
The alkyl is selected from straight chain, band branch or with cricoid alkyl.
The R1And R2Independently selected from methyl, ethyl, n-propyl, isobutyl group, normal-butyl or cyclopropyl.
The second aspect of the invention:
A kind of preparation method of high-strength polymer film, includes the following steps:
I) a kind of esters diluent containing C=C key is provided；
Ii) a kind of PVDF polymer is provided；
Iii it) will be dissolved by heating after diluent and PVDF mixed with polymers, obtain casting solution；
Iv) casting solution to be prepared into the film of setting shape after, the quenching in quenching liquid makes casting solution split-phase；
V) after being diluted the extraction of agent to the film after split-phase, polymer film is formed.
The structure of the esters diluent containing C=C key such as formula (I) or (shown in II):
(I)；(II)；
Wherein, R1And R2Independently selected from the substituted or unsubstituted alkyl containing 1~10 carbon atom.
The alkyl is selected from straight chain, band branch or with cricoid alkyl.
The R1And R2Independently selected from methyl, ethyl, n-propyl, isobutyl group, normal-butyl or cyclopropyl.
The esters diluent containing C=C key is more preferably dimethyl maleate, maleic acid diethyl
Ester, dibutyl maleate, dioctyl maleate, dimethyl fumarate, diethyl fumarate, anti-butylene
The mixing of one or more of two acid butyl esters or dioctyl fumarate.
It is that one or more of PVDF between 3~900,000 is mixed that PVDF polymer, which is by weight average molecular weight,.
Step iii) in dissolve by heating temperature be 100~300 DEG C.
Step iii) in diluent and PVDF polymer mass percent shared in casting solution be respectively 90~20% Hes
10~80%.
The step iii) in, after mixing casting solution prepares, it is also necessary to be handled by deaeration；When preparing polymer
When plate membrane, using mechanical stirring, the time of standing and defoaming is 1~10 hour, and hollow-fibre membrane then passes through double screw extruder
Extrusion molding.
The step iv) in, casting solution is prepared as tabular or hollow fiber.
The step iv) in, the temperature range of quenching bath is 0~100 DEG C, and quenching bath is the poor solvent of polymer,
The mixture of water or water and other solvents, non-solvent be can choose as quenching media.
In the step v), select alcohol or ether solvent as extractant.
The third aspect of the invention:
Contain the Ester of C=C key as thermally induced phase separation diluent improve PVDF polymer film strength,
Application in water flux or porosity.
Beneficial effect
The present invention has following substantial effect and conspicuousness progress compared with the immediate prior art:
It is more to prepare polymer by TIPS method using a kind of new Ester of the diluent-containing carbon-carbon double bond for invention
Pore membrane, and TIPS process is combined with polypropylene fusion graft process, make diluent and polymer that melting graft reaction occur, makes institute
The polymer film of system has very strong mechanical property, and institute is high using diluent boiling point, flash-point is high, diluent is easy to extract,
The advantages that volatility is small in film-forming process, and film produced by the present invention has flux big, and intensity is high, and porosity is high.
Detailed description of the invention
Fig. 1 is PVDF plate membrane section electromicroscopic photograph prepared by the embodiment of the present invention 1.
Fig. 2 is plate membrane and PVDF(6010 prepared by the embodiment of the present invention 1) infrared spectrogram.
Specific embodiment
Embodiment 1
Precise different types of 160 g of diluent, PVDF(6010) 40 g, PVDF mass fraction is 20%, maleic
Adipate 80% pours into pre-prepd glassware, then glassware is put into oil bath pan after mixing evenly, if
Stand oil bath temperature is 180 DEG C, is passed through nitrogen as protective gas, then later in oil bath with electric mixer agitating solution 2h
4 h of standing and defoaming；Gained casting solution is poured into and suppresses film forming in homemade mold, then is put into 15 DEG C of water and quenches while hot together with mold
Film after solidification is put in ethanol repeatedly extraction, extracts remaining diluent and obtain PVDF plate membrane by cold curing.
It is as shown in the table using the pvdf membrane characterization result being prepared under the conditions of different diluents:
* the esters diluent of C=C key is free of；# common diluent.
Can be seen that by the above characterization result can be effective using the esters diluent with carbon-carbon double bond of the invention
Ground improves the intensity of pvdf membrane, and film stretching intensity is far better than the esters diluent for not containing double bond, also superior to conventional dilution
The preparation effect of agent.
The pvdf membrane being prepared using dibutyl maleate as diluent (section electromicroscopic photograph is as shown in Figure 1)
Infrared tabletting machine is used on a small quantity, carries out examination of infrared spectrum with identical method.By infrared spectroscopy comparison it can be found that
High temperature makes polymer and diluent that melting graft reaction occur can see in Fig. 2 in the infrared spectrogram of pvdf membrane
Out, in 1724cm-1The stretching vibration absworption peak of place's discovery ester group (C=O), shows there is dibutyl maleate on pvdf membrane
Presence, further demonstrate dibutyl maleate and be grafted successfully, and dibutyl maleate strand is grafted to
In PVDF strand, after graft reaction, the C-F key on PVDF is grafted with C=C key, is formd shown in formula (III)
Structure so that the mechanical property of polymer is largely improved, while the pvdf membrane also has more conventional dilution
The film that agent is prepared has higher water flux and porosity.
Claims (6)
1. containing the Ester of C=C key as the diluent of thermally induced phase separation in improving PVDF polymer film strength
Using, which is characterized in that include the following steps: in the application
I) a kind of Ester containing C=C key is provided；
Ii) a kind of PVDF polymer is provided；
Iii the Ester containing C=C key and PVDF mixed with polymers are uniformly dissolved by heating afterwards), obtain casting solution；
Iv) casting solution to be prepared into the film of setting shape after, the quenching in quenching liquid makes casting solution split-phase；
V) after the extraction for carrying out the Ester containing C=C key to the film after split-phase, polymer film is formed；
The Ester containing C=C key is dimethyl maleate, diethyl maleate, maleic acid two
In butyl ester, dioctyl maleate, dimethyl fumarate, diethyl fumarate or dioctyl fumarate
One or more of mixing；
The step iv) in, the temperature range of quenching bath is -10~100 DEG C, and quenching bath is water；
In the step v), select alcohol or ether solvent as extractant.
2. application according to claim 1, which is characterized in that PVDF polymer be by weight average molecular weight be 3~900,000 it
Between one or more of PVDF mix.
3. application according to claim 1, which is characterized in that step iii) in dissolve by heating temperature be 100~300
℃。
4. application according to claim 1, which is characterized in that step iii) in Ester and PVDF containing C=C key
Polymer mass percent shared in casting solution is respectively 20~90% and 10~80%.
5. application according to claim 1, which is characterized in that the step iii) in, it is uniformly mixed and refers to and pass through machine
Tool stirring and standing and defoaming are mixed using double screw extruder.
6. application according to claim 1, which is characterized in that the step iv) in, casting solution be prepared as tabular or
Hollow fiber.
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| CN114504955B (en) * | 2022-03-10 | 2023-02-28 | 北京师范大学 | Method for preparing polymer porous membrane by low-temperature thermally induced phase separation and product thereof |
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|---|---|---|---|---|
| CN101790413A (en) * | 2007-10-19 | 2010-07-28 | 川崎重工业株式会社 | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| CN104772049A (en) * | 2014-01-15 | 2015-07-15 | 天津海之凰科技有限公司 | Method for preparing polyvinylidene fluoride hydrophobic microporous membrane by thermally-induced phase separation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101790413A (en) * | 2007-10-19 | 2010-07-28 | 川崎重工业株式会社 | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| CN104772049A (en) * | 2014-01-15 | 2015-07-15 | 天津海之凰科技有限公司 | Method for preparing polyvinylidene fluoride hydrophobic microporous membrane by thermally-induced phase separation method |
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| Novel porous poly(propylene fumarate-co-caprolactone) scaffolds fabricated by thermally induced phase separation;Ji Guo, et al.;《JOURNAL OF BIOMEDICAL MATERIALS RESEARCH A》;20161014;第105卷(第1期);第226-235页 |
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