KR101452820B1 - A preparation method of a hydrophobic polymer membrane - Google Patents
A preparation method of a hydrophobic polymer membrane Download PDFInfo
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- KR101452820B1 KR101452820B1 KR1020120152452A KR20120152452A KR101452820B1 KR 101452820 B1 KR101452820 B1 KR 101452820B1 KR 1020120152452 A KR1020120152452 A KR 1020120152452A KR 20120152452 A KR20120152452 A KR 20120152452A KR 101452820 B1 KR101452820 B1 KR 101452820B1
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- membrane
- hydrophobic polymer
- polymer
- polyvinyl chloride
- perfluoroalkyl acrylate
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- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 229920001600 hydrophobic polymer Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title 1
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 32
- -1 perfluoroalkyl acrylate Chemical compound 0.000 claims abstract description 31
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000004821 distillation Methods 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000009738 saturating Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 16
- 229920005597 polymer membrane Polymers 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- PFYHYHZGDNWFIF-UHFFFAOYSA-N (+)-DMDP Natural products OCC1NC(CO)C(O)C1O PFYHYHZGDNWFIF-UHFFFAOYSA-N 0.000 description 5
- PFYHYHZGDNWFIF-KVTDHHQDSA-N 2,5-bis(hydroxymethyl)-3,4-dihydroxypyrrolidine Chemical compound OC[C@H]1N[C@H](CO)[C@@H](O)[C@@H]1O PFYHYHZGDNWFIF-KVTDHHQDSA-N 0.000 description 5
- PFYHYHZGDNWFIF-OMMKOOBNSA-N 2R,5R-Dihydroxymethyl-3R,4R-dihydroxy-pyrrolidine Natural products OC[C@@H]1N[C@@H](CO)[C@H](O)[C@@H]1O PFYHYHZGDNWFIF-OMMKOOBNSA-N 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01D71/301—Polyvinylchloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- 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
-
- 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
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
- B01D2323/2187—Polyvinylpyrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Abstract
본 발명은 소수성 고분자 분리막의 제조방법에 관한 것으로, 더욱 상세하게는 폴리염화비닐에 일정량의 과불소알킬 아크릴레이트 단량체를 라디칼 공중합시켜 개질시킴으로써 불소기가 포함된 폴리염화비닐 수지를 제조하고 이를 사용하여 투과유량과 제거율이 우수한 소수성 고분자 분리막을 제조하는 방법에 관한 것이다.The present invention relates to a process for producing a hydrophobic polymer membrane, and more particularly, to a process for producing a hydrophobic polymer membrane by preparing a polyvinyl chloride resin containing a fluorine group by modifying a polyvinyl chloride with a certain amount of a perfluoroalkyl acrylate monomer by radical copolymerization, And to a method for producing a hydrophobic polymer membrane excellent in flow rate and removal rate.
Description
본 발명은 소수성 고분자 분리막의 제조방법에 관한 것으로, 더욱 상세하게는 폴리염화비닐에 일정량의 과불소알킬 아크릴레이트 단량체를 라디칼 공중합시켜 개질시킴으로써 불소기가 포함된 폴리염화비닐 수지를 제조하고 이를 사용하여 투과유량과 제거율이 우수한 소수성 고분자 분리막을 제조하는 방법에 관한 것이다.
The present invention relates to a process for producing a hydrophobic polymer membrane, and more particularly, to a process for producing a hydrophobic polymer membrane by preparing a polyvinyl chloride resin containing a fluorine group by modifying a polyvinyl chloride with a certain amount of a perfluoroalkyl acrylate monomer by radical copolymerization, And to a method for producing a hydrophobic polymer membrane excellent in flow rate and removal rate.
막증류법(Membrane Distillation)은 소수성의 고분자 분리막을 통하여 막의 양단에 존재하는 온도 차에 기인한 투과 성분 간의 증기압 차를 구동력으로 하여 혼합물 중의 특정 성분이 선택적으로 분리막을 통과하여 혼합물을 분리 및 정제하는 막 분리공정 중의 하나이다.
Membrane distillation is a process in which a specific component in a mixture passes through a separating membrane selectively and separates and purifies the mixture using a vapor pressure difference between permeation components due to a temperature difference existing at both ends of the membrane through a hydrophobic polymer separating membrane It is one of the separation processes.
이러한 막증류 공정은 비휘발성 물질이나 휘발성이 상대적으로 낮은 물질을 분리 제거하는 탈염 공정에 이용되거나, 수용액 중에 휘발성이 높은 유기물을 분리하는데도 이용할 수 있다. 이에 따라, 막증류 공정은 해수 담수화, 폐수 처리, 식품 산업 등에 다양하게 적용될 수 있다.
Such a membrane distillation process can be used in a desalting process for separating and removing a nonvolatile substance or a substance having a relatively low volatility, or can be used for separating organic substances having high volatility in an aqueous solution. Accordingly, the membrane distillation process can be applied variously to seawater desalination, wastewater treatment, food industry, and the like.
막증류법은 소수성 고분자 분리막을 이용하는데, 용매나 용질(친수성 물질)의 표면장력이 분리막 표면보다 커서 액체 상태로는 막 기공(membrane pore)을 통과하지 못하고, 상기 분리막 표면에서 반발되며, 분리막의 표면 기공입구에서 분리대상 물질이 증기상으로 상변환되어 기공 안으로 확산, 투과되어 최종적으로 투과측에서 응축, 분리되는 것이다.
Membrane distillation utilizes a hydrophobic polymer membrane. The membrane or membrane (hydrophilic material) has a surface tension greater than that of the membrane, so that it can not pass through the membrane pore in the liquid state and is repelled on the surface of the membrane. At the pore inlet, the substance to be separated is phase-converted into a vapor phase, diffused and permeated into pores, and finally condensed and separated at the permeation side.
막증류 공정에서 분리효율은 고분자 분리막의 소수성 정도에 따라 큰 영향을 받는다. 효율적인 막증류 공정을 위하여는 소수성이 강한 고분자 분리막의 사용이 필요하다.
In the membrane distillation process, the separation efficiency is greatly influenced by the degree of hydrophobicity of the polymer membrane. For an efficient membrane distillation process, it is necessary to use a polymer membrane with high hydrophobicity.
일반적으로 막증류용 분리막으로는, 평균 기공 크기 0.1 내지 0.5㎛를 가지는 소수성 고분자 분리막으로서, 폴리테트라플루오르에틸렌(PTFE), 폴리비닐리덴플루오르라이드(PVDF) 또는 불소계 합성 고분자로 이루어진 균일막 또는 복합막을 사용한다.
Generally, the membrane separation membrane for membrane distillation is a hydrophobic polymer separation membrane having an average pore size of 0.1 to 0.5 占 퐉, and may be a uniform membrane or a composite membrane made of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) use.
상기 폴리테트라플르오르에틸렌(PTFE)은 물에 대한 접촉각이 폴리비닐리덴플르오르라이드(PVDF)에 비해 커서 소수성이 우수하고, 동일조건에서 물의 투과속도도 우수하다. 다만, PTFE는 우수한 물성에도 불구하고 고분자 성형이 어려운 문제가 있다. 이에 따라, 폴리비닐리덴플르오르라이드(PVDF)가 막증류용 분리막을 위한 범용적인 재질로서 사용되고 있다. 그러나, PVDF도 불소수지 중 하나로서 주로 해외에서 수입되고 있어 다른 종류의 수지에 비해 고가라는 단점이 있다.
The polytetrafluoroethylene (PTFE) has a contact angle to water that is larger than that of polyvinylidene fluoride (PVDF), so that the polytetrafluoroethylene (PTFE) is excellent in hydrophobicity and has excellent water permeation rate under the same conditions. However, PTFE has a problem that it is difficult to form a polymer, despite its excellent physical properties. Accordingly, polyvinylidene fluoride (PVDF) has been used as a general material for a membrane separation membrane. However, PVDF is also one of the fluorine resins, which is mainly imported from abroad, which is disadvantageous in comparison with other resins.
한편, 폴리염화비닐(polyvinyl chloride, PVC)은 염화비닐의 단독중합체 또는 염화비닐을 50% 이상 함유한 혼성중합체를 일컫는다. 결정성이 낮고, 가공 시 접착이 어려운 특징이 있다. PVC는 가격이 저렴하여 연질 제품으로서 포장용·농업용 등의 시트나 필름 등에 사용되고, 경질 제품에서는 압출성형에 의한 수도관의 제조 등에 널리 쓰인다.
On the other hand, polyvinyl chloride (PVC) refers to a homopolymer of vinyl chloride or a copolymer containing 50% or more of vinyl chloride. Low crystallinity, and difficulty in bonding during processing. PVC is a soft product because it is inexpensive and is used in sheets and films for packing and agricultural use. In hard products, it is widely used for extrusion molding of water pipes.
이러한 배경 하에서, 본 발명자들은 폴리염화비닐에 일정량의 과불소알킬 아크릴레이트 단량체를 라디칼 공중합시켜 개질시킴으로써 불소기가 포함된 폴리염화비닐 수지를 제조하고 이를 사용하여 투과유량과 제거율이 우수한 소수성 고분자 분리막을 제조할 수 있음을 확인함으로써 본 발명을 완성하였다.
Under these circumstances, the present inventors prepared a polyvinyl chloride resin containing a fluorine group by modifying a polyvinyl chloride with a certain amount of a perfluoroalkyl acrylate monomer by radical copolymerization, and used it to manufacture a hydrophobic polymer membrane having excellent permeation flow rate and removal rate The present invention has been completed.
본 발명의 목적은 투과유량과 제거율이 우수한 소수성 고분자 분리막을 제조하는 방법을 제공하는 것이다.
It is an object of the present invention to provide a method for producing a hydrophobic polymer membrane excellent in permeation flow rate and removal rate.
상기 과제를 해결하기 위해, 본 발명은 하기 단계를 포함하는 소수성 고분자 분리막의 제조방법을 제공한다.In order to solve the above problems, the present invention provides a method for producing a hydrophobic polymer membrane including the following steps.
1) 폴리염화비닐과, 하기 화학식 1로 표시되는 과불소알킬 아크릴레이트를 라디칼 공중합하여, 폴리염화비닐 주쇄에 상기 과불소알킬 아크릴레이트가 측쇄부로 도입된 불소계 소수성 고분자를 제조하는 단계(단계 1); 1) a step (step 1) of radical-copolymerizing polyvinyl chloride and a perfluoroalkyl acrylate represented by the following general formula (1) to prepare a fluorinated hydrophobic polymer having the perfluoroalkyl acrylate introduced into a polyvinyl chloride main chain in a side chain portion, ;
2) 상기 불소계 소수성 고분자를 유기 용매 중에 용해시켜 고분자 용액을 제조하는 단계(단계 2); 및 2) dissolving the fluorine-based hydrophobic polymer in an organic solvent to prepare a polymer solution (step 2); And
3) 상기 고분자 용액을 물에 침지하는 단계(단계 3):3) immersing the polymer solution in water (step 3):
[화학식 1][Chemical Formula 1]
CF3(CF2)n(CH2)mCOOCH=CH2 CF 3 (CF 2 ) n (CH 2 ) m COOCH = CH 2
상기 식에서,In this formula,
n은 1 내지 20의 정수이고,n is an integer of 1 to 20,
m은 1 내지 10의 정수이다.
m is an integer of 1 to 10;
바람직하기로, 상기 단계 2)와 단계 3) 사이에 상기 고분자 용액을 수증기로 포화시키는 단계(단계 2-1)를 추가로 포함할 수 있다.
Preferably, the step (2-1) of saturating the polymer solution with water vapor between the step 2) and the step 3) may be further included.
이하, 본 발명의 구성을 상세히 설명한다.
Hereinafter, the configuration of the present invention will be described in detail.
상기 단계 1은, 폴리염화비닐과, 화학식 1로 표시되는 과불소알킬 아크릴레이트를 라디칼 공중합하여, 폴리염화비닐 주쇄에 상기 과불소알킬 아크릴레이트가 측쇄부로 도입된 불소계 소수성 고분자를 제조하는 단계로서, 폴리염화비닐을 개질하여 불소기가 포함된 소수성 고분자를 제조하는 단계이다.
The step 1 is a step of radical-copolymerizing polyvinyl chloride and a perfluoroalkyl acrylate represented by the general formula (1) to produce a fluorinated hydrophobic polymer having the perfluoroalkyl acrylate introduced into the side chain of the polyvinyl chloride main chain, Polyvinyl chloride is modified to prepare a hydrophobic polymer containing a fluorine group.
본 발명은 폴리염화비닐 주쇄에 과불소알킬 아크릴레이트가 측쇄부로 도입된 불소계 소수성 고분자를 제조하고 이를 사용하여 소수성 고분자 분리막을 제조하는 것을 특징으로 한다.
The present invention is characterized in that a fluorinated hydrophobic polymer having a perfluoroalkyl acrylate introduced into a side chain portion of a polyvinyl chloride main chain is prepared and the hydrophobic polymer separation membrane is produced.
본 발명에서 사용하는 용어 "폴리염화비닐(poly(vinyl chloride), PVC)"은 염화비닐(vinyl chloride)의 단일중합체 또는 염화비닐을 50% 이상 함유한 혼성중합체를 의미한다. 바람직하기로, 본 발명에서는 폴리염화비닐로서 염화비닐의 단일중합체를 사용한다.
The term "poly (vinyl chloride), PVC" used in the present invention means a homopolymer of vinyl chloride or a copolymer containing 50% or more of vinyl chloride. Preferably, a homopolymer of vinyl chloride is used as the polyvinyl chloride in the present invention.
본 발명에서, 폴리염화비닐의 수평균분자량은 10,000 내지 1,000,000인 것이 바람직하다. 만일 상기 폴리염화비닐의 수평균분자량이 상기 하한보다 작으면 필름 형성이 어려운 단점이 있고 상기 상한보다 크면 점도가 너무 높아 성형이 어려운 단점이 있다.
In the present invention, the polyvinyl chloride preferably has a number average molecular weight of 10,000 to 1,000,000. If the number average molecular weight of the polyvinyl chloride is less than the above lower limit, there is a disadvantage that film formation is difficult. If the number average molecular weight is larger than the upper limit, the viscosity is too high and molding is difficult.
본 발명에서, 폴리염화비닐은 시판되는 것을 구입하여 사용할 수도 있고 공지의 방법으로 합성하여 사용할 수도 있다.
In the present invention, commercially available polyvinyl chloride may be purchased and used, or synthesized by a known method.
본 발명에서 사용하는 용어 "과불소알킬 아크릴레이트"는 하기 화학식 1로 표시되는 화합물을 의미한다.The term "perfluoroalkyl acrylate" used in the present invention means a compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
CF3(CF2)n(CH2)mCOOCH=CH2 CF 3 (CF 2 ) n (CH 2 ) m COOCH = CH 2
상기 식에서,In this formula,
n은 1 내지 20의 정수이고,n is an integer of 1 to 20,
m은 1 내지 10의 정수이다.
m is an integer of 1 to 10;
본 발명에서, 상기 단계 1)의 폴리염화비닐과 과불소알킬 아크릴레이트의 중량비는 바람직하기로 1 내지 10:0.5 내지 1.5, 더욱 바람직하기로 2 내지 4:1, 가장 바람직하기로 2:1이다. 만일 상기 과불소알킬 아크릴레이트의 중량비가 상기 범위보다 작으면 소수성이 크지 않은 문제가 있고 상기 범위보다 크면 용해도가 떨어져서 분리막 성형이 어려운 단점이 있다.
In the present invention, the weight ratio of the polyvinyl chloride to the perfluoroalkyl acrylate in step 1) is preferably 1 to 10: 0.5 to 1.5, more preferably 2 to 4: 1, most preferably 2: 1 . If the weight ratio of the perfluoroalkyl acrylate is less than the above range, there is a problem in that the hydrophobicity is not large. If the weight ratio is larger than the above range, the solubility decreases and molding of the membrane is difficult.
본 발명에서, 상기 단계 1)의 라디칼 공중합은 개시제로서 4,4'-디메틸-2,2'-디피리딜(4,4'-dimethyl-2,2'-dipyridyl, DMDP) 및 CuCl을 사용할 수 있다.
In the present invention, the radical copolymerization in the above step 1) is carried out by using 4,4'-dimethyl-2,2'-dipyridyl (DMDP) and CuCl as an initiator .
본 발명에서, 상기 4,4'-디메틸-2,2'-디피리딜의 사용량은 과불소알킬 아크릴레이트 100 중량부에 대하여 바람직하기로 0.1 내지 2 중량부, 더욱 바람직하기로 0.5 내지 1 중량부, 가장 바람직하기로 1 중량부이다. 만일 상기 4,4'-디메틸-2,2'-디피리딜의 사용량이 0.1 중량부보다 적으면 과불소알킬 아크릴레이트 치환도가 떨어지는 단점이 있고 2 중량부보다 많으면 고분자 주사슬이 분해되어 분자량이 떨어지는 단점이 있다.
In the present invention, the amount of 4,4'-dimethyl-2,2'-dipyridyl to be used is preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1 part by weight per 100 parts by weight of perfluoroalkyl acrylate Most preferably 1 part by weight. If the amount of 4,4'-dimethyl-2,2'-dipyridyl is less than 0.1 parts by weight, the degree of substitution of perfluoroalkyl acrylate decreases. If more than 2 parts by weight, the polymer main chain is decomposed, There is a downside to this.
본 발명에서, 상기 CuCl의 사용량은 과불소알킬 아크릴레이트 100 중량부에 대하여 바람직하기로 0.1 내지 2 중량부, 더욱 바람직하기로 0.25 내지 1 중량부, 가장 바람직하기로 1 중량부이다. 만일 상기 CuCl의 사용량이 0.1 중량부보다 적으면 반응성이 떨어지는 단점이 있고 2 중량부보다 많으면 고분자 주사슬이 분해되어 분자량이 떨어지는 단점이 있다.
In the present invention, the amount of CuCl to be used is preferably 0.1 to 2 parts by weight, more preferably 0.25 to 1 part by weight, and most preferably 1 part by weight based on 100 parts by weight of perfluoroalkyl acrylate. If the amount of CuCl is less than 0.1 parts by weight, the reactivity is poor. If more than 2 parts by weight, the main chain of the polymer is decomposed and the molecular weight is lowered.
본 발명에서, 상기 단계 1)의 라디칼 공중합은 유기 용매로서 디메틸아세트아미이드, N-메틸-2-피롤리돈, 디메틸포름아마이드 및 디메틸술폭시드 등 고분자와 과불소알킬 아크릴레이트가 용해되는 용매로 이루어진 군으로부터 선택된 1종 이상을 사용하여 수행할 수 있다.
In the present invention, the radical copolymerization in the step 1) is carried out by using a solvent in which a polymer such as dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide and dimethylsulfoxide and a perfluoroalkyl acrylate are dissolved And at least one selected from the group consisting of
본 발명에서, 상기 단계 1)의 라디칼 공중합은 80 내지 100℃의 반응온도에서 수행할 수 있다. 만일 상기 반응온도가 상기 하한보다 낮으면 반응성이 떨어지는 단점이 있고 상기 상한보다 높으면 반응이 급격하게 일어나서 고분자 주사슬이 분해되는 단점이 있다.
In the present invention, the radical copolymerization of step 1) may be carried out at a reaction temperature of 80 to 100 ° C. If the reaction temperature is lower than the lower limit, the reactivity is lowered. If the reaction temperature is higher than the upper limit, the reaction occurs rapidly and the polymer main chain is decomposed.
본 발명에서, 상기 단계 1)의 라디칼 공중합은 12 내지 48 시간의 반응시간 동안 수행할 수 있다. 만일 상기 반응시간이 상기 하한보다 짧으면 반응성이 떨어지는 단점이 있고 상기 상한보다 길어도 더 이상 반응이 일어나지 않아 불필요하다.
In the present invention, the radical copolymerization of step 1) may be carried out for a reaction time of 12 to 48 hours. If the reaction time is shorter than the lower limit, there is a disadvantage that the reactivity is lowered, and even if the reaction time is longer than the upper limit, the reaction does not occur and is unnecessary.
본 발명에서, 상기 단계 1)의 라디칼 공중합은 질소 기류 하에서 수행할 수 있다.
In the present invention, the radical copolymerization in the step 1) can be carried out in a nitrogen stream.
본 발명에서, 상기 단계 1)에서 라디칼 공중합이 완료된 후 고분자 생성물을 물에 침지하여 고분자 이외의 물질을 제거하고, 90 내지 110℃의 온도에서 건조시켜 이후 단계에서 사용할 수 있다.
In the present invention, after completion of the radical copolymerization in the step 1), the polymer product may be immersed in water to remove materials other than the polymer, and dried at a temperature of 90 to 110 ° C to be used in a subsequent step.
상기 단계 2는, 상기 불소계 소수성 고분자를 유기 용매 중에 용해시켜 고분자 용액을 제조하는 단계로서, 분리막 제조를 위한 불소계 소수성 고분자 용액을 제조하는 단계이다.
The step 2 is a step of preparing a fluorine-based hydrophobic polymer solution for preparing a separation membrane by dissolving the fluorine-based hydrophobic polymer in an organic solvent to prepare a polymer solution.
본 발명에서, 상기 단계 2)의 유기 용매는 디메틸아세트아미이드, N-메틸-2-피롤리돈, 디메틸포름아마이드 및 디메틸술폭시드 등 고분자와 과불소알킬 아크릴레이트가 용해되는 용매로 이루어진 군으로부터 선택된 1종 이상일 수 있다.
In the present invention, the organic solvent in step 2) may be selected from the group consisting of dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide and dimethylsulfoxide, and a solvent in which perfluoroalkyl acrylate is dissolved It may be at least one selected.
본 발명에서, 상기 단계 2)의 고분자 용액에 첨가제로서 폴리비닐피롤리돈(polyvinylpyrrolidone)을 추가로 첨가할 수 있다.
In the present invention, polyvinylpyrrolidone may be further added as an additive to the polymer solution of step 2).
본 발명에서, 상기 폴리비닐피롤리돈의 첨가량은 불소계 소수성 고분자 100 중량부에 대하여 바람직하기로 50 내지 200 중량부, 더욱 바람직하기로 80 내지 120 중량부, 가장 바람직하기로 100 중량부이다. 만일 상기 폴리비닐피롤리돈의 첨가량이 50 중량부보다 적으면 기공이 잘 형성되지 않는 단점이 있고 200 중량부보다 많으면 점도가 너무 높아 성형이 어려운 단점이 있다.
In the present invention, the amount of the polyvinylpyrrolidone to be added is preferably 50 to 200 parts by weight, more preferably 80 to 120 parts by weight, and most preferably 100 parts by weight, based on 100 parts by weight of the fluorine-based hydrophobic polymer. If the amount of the polyvinylpyrrolidone is less than 50 parts by weight, pores are not formed well. If the amount is more than 200 parts by weight, the viscosity is too high and molding is difficult.
또한, 본 발명에서, 상기 단계 2)의 고분자 용액에 물을 추가로 첨가할 수 있다. 상기 물의 첨가량은 불소계 소수성 고분자 100 중량부에 대하여 바람직하기로 10 내지 20 중량부일 수 있다.
Further, in the present invention, water may be further added to the polymer solution of the step 2). The amount of the water added may be 10 to 20 parts by weight based on 100 parts by weight of the fluorine-based hydrophobic polymer.
상기 단계 2-1은, 상기 고분자 용액을 수증기로 포화시키는 단계로서, 고분자 용액을 수증기로 포화시킨 상태에서 일정 시간 동안 유지시키는 단계이다.
Step 2-1 is a step of saturating the polymer solution with water vapor, and maintaining the polymer solution in a saturated state with water vapor for a predetermined time.
본 발명에서, 상기 단계 2-1)은 10초 내지 1 분 동안 수행할 수 있다. 만일 상기 단계 2-1)의 수행 시간이 상기 하한보다 짧으면 기공이 잘 형성되지 않는 단점이 있고 상기 상한보다 길어도 더 이상 기공 형성에 큰 효과가 없어 불필요하다.
In the present invention, the step 2-1) may be performed for 10 seconds to 1 minute. If the execution time of the step 2-1) is shorter than the lower limit, there is a disadvantage that the pores are not formed well, and even if the execution time is longer than the upper limit, there is no effect for forming pores.
상기 단계 3은, 상기 고분자 용액을 물에 침지하는 단계로서, 고분자 용액을 물에 침지하여 분리막을 성형하는 단계이다.
Step 3 is a step of immersing the polymer solution in water, wherein the polymer solution is immersed in water to form a separation membrane.
본 발명에서, 상기 단계 3)의 물은 80 내지 95℃의 온도일 수 있다. 만일 상기 물 온도가 상기 하한보다 낮으면 기공이 잘 형성되지 않는 단점이 있고 상기 상한보다 높으면 분리막 형성시 제어가 어려운 단점이 있다.
In the present invention, the water of step 3) may be a temperature of 80 to 95 캜. If the water temperature is lower than the lower limit, pores are not formed well. If the water temperature is higher than the upper limit, control is difficult when forming the separation membrane.
또한, 본 발명은 상기 방법으로 제조된 소수성 고분자 분리막을 제공한다.
The present invention also provides a hydrophobic polymer membrane prepared by the above method.
본 발명에서, 상기 소수성 고분자 분리막은 10 ㎚ 내지 0.5 ㎛의 기공 크기를 갖는다. 일반적인 막증류용 분리막이 0.1 내지 0.5㎛의 기공 크기를 갖는 것에 비하여 본 발명의 소수성 고분자 분리막은 10 ㎚ 내지 0.5 ㎛로 보다 작은 기공 크기를 갖는다. 이로써, 본 발명의 소수성 고분자 분리막은 물에 젖지 않고 수증기만 선택적으로 통과시키는 장점이 있다.
In the present invention, the hydrophobic polymer membrane has a pore size of 10 nm to 0.5 m. In general, the membrane separation membrane for membrane distillation has a pore size of 0.1 to 0.5 mu m, whereas the hydrophobic polymer membrane of the present invention has a smaller pore size of 10 nm to 0.5 mu m. Thus, the hydrophobic polymer separation membrane of the present invention has an advantage of selectively passing only water vapor without getting wet.
본 발명의 소수성 고분자 분리막은, 불소기를 포함하는 화합물을 라디칼 중합시켜 개질시킨 폴리염화비닐을 사용하여 제조됨으로써 소수성이 향상된다. 본 발명의 소수성 고분자 분리막은 향상된 소수성으로 인하여 막증류용으로 사용할 수 있다.
The hydrophobic polymer membrane of the present invention is produced by using polyvinyl chloride modified by radical polymerization of a compound containing a fluorine group, thereby improving hydrophobicity. The hydrophobic polymer membrane of the present invention can be used for membrane distillation due to its improved hydrophobicity.
또한, 본 발명의 소수성 고분자 분리막은 막증류용 이외에 정밀여과, 한외여과, 또는 나노여과 등에 사용될 수 있다.
Further, the hydrophobic polymer membrane of the present invention can be used for microfiltration, ultrafiltration, nanofiltration and the like in addition to membrane distillation.
본 발명의 소수성 고분자 분리막은 우수한 소수성으로 인하여 막증류시 투과유량 및 제거율이 뛰어난 특징을 갖는다.
The hydrophobic polymer membrane of the present invention is characterized by excellent permeation flow rate and removal rate during membrane distillation due to its excellent hydrophobicity.
구체적으로, 본 발명의 일 실시예 및 실험예에서는 폴리염화비닐에 퍼플루오로알킬 아크릴레이트를 라디칼 중합시켜 개질시킨 후 상기 개질된 폴리염화비닐을 사용하여 소수성 고분자 분리막을 제조한 다음, 상기 소수성 고분자 분리막의 투과유량 및 제거율을 측정한 결과, 4.1 내지 12.1 L/m2hr의 우수한 투과유량을 나타내고 99.8% 이상의 뛰어난 제거율을 나타냄을 확인하였다.
Specifically, in one embodiment and experimental examples of the present invention, a perfluoroalkyl acrylate is modified by radical polymerization to polyvinyl chloride, and the modified polyvinyl chloride is used to prepare a hydrophobic polymer membrane. Then, the hydrophobic polymer The permeate flow rate and the removal rate of the separator were measured. As a result, it was confirmed that the permeate flow was excellent in the range of 4.1 to 12.1 L / m 2 hr and the excellent removal rate was 99.8% or more.
본 발명은 폴리염화비닐에 일정량의 과불소알킬 아크릴레이트 단량체를 라디칼 공중합시켜 개질시킴으로써 불소기가 포함된 폴리염화비닐 수지를 제조한 다음 이를 사용함으로써 소수성을 갖는 고분자 분리막을 제조할 수 있는 효과가 있다. 또한, 상기 고분자 분리막이 갖는 소수성으로 인하여 상기 고분자 분리막을 막증류용으로 사용할 경우 투과유량과 제거율이 우수한 효과가 있다.
The present invention has the effect of producing a polymeric membrane having hydrophobicity by preparing a polyvinyl chloride resin containing a fluorine group by modifying a polyvinyl chloride with a certain amount of a perfluoroalkyl acrylate monomer by radical copolymerization and then using it. Also, when the polymer separator is used for membrane distillation due to the hydrophobicity of the polymer separator, there is an effect of excellent permeation flow rate and removal rate.
이하, 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나 이들 실시예는 본 발명을 예시적으로 설명하기 위한 것으로 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.
실시예Example 1 One
폴리염화비닐(LG화학, 대한민국) 20g을 디메틸아세트아마이드 160g에 90℃ 하에서 녹인 다음, 상기 폴리염화비닐 용액에 4,4'-디메틸-2,2'-디피리딜(DMDP) 0.1g, 퍼플루오로알킬 아크릴레이트(perfluoroalkyl acrylate)(CF3(CF2)7CH2CH2COOCH=CH2) 10g, CuCl 0.1g, 및 HCl 0.1g을 첨가하여 90℃, 질소기류 하에서 24시간 동안 반응시켰다. 반응이 종료된 후, 물에 침지하여 고분자 이외의 물질을 제거한 후, 100℃에서 건조하여 고분자(polyperfluoroalkylacrlyate, PPFAA)를 얻었다.
20 g of polyvinyl chloride (LG Chem, Korea) was dissolved in 160 g of dimethylacetamide at 90 DEG C, and then 0.1 g of 4,4'-dimethyl-2,2'-dipyridyl (DMDP) 10 g of perfluoroalkyl acrylate (CF 3 (CF 2 ) 7 CH 2 CH 2 COOCH═CH 2 ), 0.1 g of CuCl and 0.1 g of HCl were added and reacted at 90 ° C. under a stream of nitrogen for 24 hours . After completion of the reaction, the polymer was immersed in water to remove materials other than the polymer, and dried at 100 ° C to obtain a polymer (polyperfluoroalkylacrylate, PPFAA).
상기 고분자 15g을 디메틸아세트아마이드 68g에 녹인 다음, 상기 고분자 용액에 폴리비닐피롤리돈(polyvinylpyrrolidone) 15g 및 물 2g을 첨가하고 60℃로 승온시킨 후, 상기 고분자 용액을 수증기로 포화시킨 상태에서 20초간 유지시키고, 90℃의 물에 침지하여 고분자 분리막을 제조하였다.
15 g of the polymer was dissolved in 68 g of dimethylacetamide. To the polymer solution, 15 g of polyvinylpyrrolidone and 2 g of water were added and the temperature of the polymer solution was raised to 60 ° C. The polymer solution was saturated with water vapor for 20 seconds And immersed in water at 90 DEG C to prepare a polymer membrane.
실시예Example 2 2
퍼플루오로알킬 아크릴레이트를 5g의 양으로 사용한 것을 제외하고는 실시예 1과 동일하게 고분자 분리막을 제조하였다.
A polymer membrane was prepared in the same manner as in Example 1, except that perfluoroalkyl acrylate was used in an amount of 5 g.
실시예Example 3 3
퍼플루오로알킬 아크릴레이트를 2.5g의 양으로 사용한 것을 제외하고는 실시예 1과 동일하게 고분자 분리막을 제조하였다.
A polymer membrane was prepared in the same manner as in Example 1, except that perfluoroalkyl acrylate was used in an amount of 2.5 g.
실시예Example 4 4
DMDP를 0.05g의 양으로 사용한 것을 제외하고는 실시예 1과 동일하게 고분자 분리막을 제조하였다.
A polymer membrane was prepared in the same manner as in Example 1 except that DMDP was used in an amount of 0.05 g.
실시예Example 5 5
DMDP를 0.025g의 양으로 사용한 것을 제외하고는 실시예 1과 동일하게 고분자 분리막을 제조하였다.
A polymer membrane was prepared in the same manner as in Example 1, except that DMDP was used in an amount of 0.025 g.
실시예Example 6 6
고분자 용액을 수증기로 포화시키지 않고 상온에서 20초간 방치한 후, 물에 침지한 것을 제외하고는 실시예 1과 동일하게 고분자 분리막을 제조하였다.
A polymer membrane was prepared in the same manner as in Example 1, except that the polymer solution was allowed to stand at room temperature for 20 seconds without being saturated with water vapor, and then immersed in water.
실험예Experimental Example 1: 본 발명 고분자 분리막을 이용한 1: Using the polymer separator of the present invention 막증류시At membrane distillation 투과유량 및 제거율 조사 Investigation of permeate flow rate and removal rate
상기 실시예 1 내지 6에서 제조한 본 발명의 고분자 분리막을 이용하여 막증류를 수행한 후 투과유량 및 제거율 조사하였다.Membrane distillation was performed using the polymer membranes of the present invention prepared in Examples 1 to 6, and permeate flow rate and removal rate were examined.
구체적으로, 3.5 중량% NaCl 수용액을 60℃의 온도로 승온시키고 순환시키면서 막 표면에 접촉시키고 반대편은 15℃의 초순수를 순환시키면서 증가된 무게를 계산하여 투과유량을 측정하고 변화된 전도도를 측정하여 제거율을 계산하였다. 6시간 동안 순환시킨 후 측정하였다. 그 결과는 표 1에 나타내었다.Specifically, an aqueous solution of 3.5 wt% NaCl was heated to a temperature of 60 ° C. and brought into contact with the surface of the membrane while being circulated. On the other side, the permeated flow rate was measured by circulating the ultrapure water at 15 ° C., Respectively. After circulating for 6 hours, it was measured. The results are shown in Table 1.
상기 표 1을 통해, 본 발명의 고분자 분리막을 이용하여 막증류를 수행할 경우 4.1 내지 12.1 L/m2hr의 우수한 투과유량을 나타내고 99.8% 이상의 뛰어난 제거율을 나타냄을 확인하였다. From Table 1, it was confirmed that membrane distillation using the polymer membrane of the present invention exhibited an excellent permeation flow rate of 4.1 to 12.1 L / m 2 hr and an excellent removal rate of 99.8% or more.
특히, 모든 실시예에서 제거율은 99.9% 수준으로 매우 뛰어났으나, 투과유량면에서는 실시예들 사이에 다소 차이가 있는 것으로 나타났다. 구체적으로, 다른 실시예들에 비하여 실시예 1 및 2에서 투과유량이 더욱 우수하였다. 이를 통해, 폴리염화비닐과 퍼플루오로알킬 아크릴레이트의 중량비는 2 내지 4:1인 것이 더욱 바람직함을 알 수 있었다. 또한, DMDP의 사용량은 퍼플루오로알킬 아크릴레이트 100 중량부에 대하여 0.5 내지 1 중량부인 것이 더욱 바람직함을 알 수 있었다. 더 나아가, 고분자 용액을 수증기로 포화시킨 다음 물에 침지시키는 방식이 더욱 우수한 투과유량을 갖는 고분자 분리막을 제공할 수 있는 것으로 나타났다.In particular, the removal rate was very good at 99.9% in all the examples, but there was a slight difference between the embodiments in terms of permeate flux. Specifically, the permeate flow rates in Examples 1 and 2 were superior to those in the other Examples. As a result, it was found that the weight ratio of polyvinyl chloride and perfluoroalkyl acrylate was more preferably 2 to 4: 1. It is further found that the amount of DMDP to be used is more preferably 0.5 to 1 part by weight per 100 parts by weight of the perfluoroalkyl acrylate. Further, it has been found that the method of saturating the polymer solution with water vapor and immersing it in water can provide a polymer membrane having a higher permeation flow rate.
Claims (10)
폴리염화비닐과, 하기 화학식 1로 표시되는 과불소알킬 아크릴레이트를 라디칼 공중합하여, 폴리염화비닐 주쇄에 상기 과불소알킬 아크릴레이트가 측쇄부로 도입된 불소계 소수성 고분자를 제조하는 단계(단계 1);
상기 불소계 소수성 고분자를 유기 용매 중에 용해시켜 고분자 용액을 제조하는 단계(단계 2);
상기 고분자 용액을 수증기로 포화시키는 단계(단계 2-1); 및
상기 고분자 용액을 물에 침지하는 단계(단계 3):
[화학식 1]
CF3(CF2)n(CH2)mCOOCH=CH2
상기 식에서,
n은 1 내지 20의 정수이고,
m은 1 내지 10의 정수이다.
A process for producing a hydrophobic polymer membrane for membrane distillation comprising the steps of:
(Step 1) of radical-copolymerizing polyvinyl chloride and a perfluoroalkyl acrylate represented by the following formula (1) to prepare a fluorinated hydrophobic polymer having the perfluoroalkyl acrylate introduced into the side chain of the polyvinyl chloride main chain;
Dissolving the fluorine-based hydrophobic polymer in an organic solvent to prepare a polymer solution (step 2);
Saturating the polymer solution with water vapor (step 2-1); And
Immersing the polymer solution in water (step 3):
[Chemical Formula 1]
CF 3 (CF 2 ) n (CH 2 ) m COOCH = CH 2
In this formula,
n is an integer of 1 to 20,
m is an integer of 1 to 10;
The method of claim 1, wherein the weight ratio of polyvinyl chloride to perfluoroalkyl acrylate in step 1) is 1 to 10: 0.5 to 1.5.
4. The method of claim 3, wherein the weight ratio of polyvinyl chloride to perfluoroalkyl acrylate in step 1) is from 2 to 8: 1.
The method according to claim 1, wherein the radical copolymerization of step 1) comprises using 4,4'-dimethyl-2,2'-dipyridyl and CuCl as an initiator.
6. The method according to claim 5, wherein the amount of 4,4'-dimethyl-2,2'-dipyridyl is 0.1 to 2 parts by weight based on 100 parts by weight of perfluoroalkyl acrylate.
The method according to claim 1, wherein the organic solvent in step 2) is at least one selected from the group consisting of dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide and dimethylsulfoxide.
The method according to claim 1, wherein polyvinylpyrrolidone is further added as an additive to the polymer solution of step 2).
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| US5403483A (en) | 1992-07-22 | 1995-04-04 | Mitsubishi Rayon Co., Ltd. | Hydrophobic porous membranes and process for the manufacture thereof |
| KR19990061662A (en) * | 1997-12-31 | 1999-07-26 | 이정국 | Separation membrane containing perfluorinated alkyl group |
| KR19990086230A (en) * | 1998-05-26 | 1999-12-15 | 김충섭 | Perfluoroalkyl-containing copolymers and membranes using them |
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| US5403483A (en) | 1992-07-22 | 1995-04-04 | Mitsubishi Rayon Co., Ltd. | Hydrophobic porous membranes and process for the manufacture thereof |
| KR19990061662A (en) * | 1997-12-31 | 1999-07-26 | 이정국 | Separation membrane containing perfluorinated alkyl group |
| KR19990086230A (en) * | 1998-05-26 | 1999-12-15 | 김충섭 | Perfluoroalkyl-containing copolymers and membranes using them |
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