TWI607023B - 親水性多孔聚四氟乙烯膜(ii) - Google Patents
親水性多孔聚四氟乙烯膜(ii) Download PDFInfo
- Publication number
- TWI607023B TWI607023B TW105120504A TW105120504A TWI607023B TW I607023 B TWI607023 B TW I607023B TW 105120504 A TW105120504 A TW 105120504A TW 105120504 A TW105120504 A TW 105120504A TW I607023 B TWI607023 B TW I607023B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- hydrophilic porous
- porous membrane
- hydrophilic
- ptfe
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims description 59
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims description 38
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims description 38
- -1 polytetrafluoroethylene Polymers 0.000 title claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 30
- 239000012530 fluid Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000004414 alkyl thio group Chemical group 0.000 claims 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical group CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000005336 allyloxy group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000006612 decyloxy group Chemical group 0.000 claims 1
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000034628 Celiac artery compression syndrome Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- LOUICXNAWQPGSU-UHFFFAOYSA-N 2,2,3,3-tetrafluorooxirane Chemical compound FC1(F)OC1(F)F LOUICXNAWQPGSU-UHFFFAOYSA-N 0.000 description 2
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 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 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920006358 Fluon Polymers 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 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
- 150000001768 cations Chemical class 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 239000012531 culture fluid Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- 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
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D71/52—Polyethers
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明係關於親水性多孔聚四氟乙烯膜(II)。
多孔PTFE膜之特性,包括其機械強度、耐化學性或惰性、非黏著性、極佳介電特性、高溫下之熱穩定性及低摩擦係數使其對各種應用非常具有吸引力。然而,對於某些應用而言,其將有益於改善其潤濕特徵而不影響其內部特性。為改變PTFE膜之一或多種特性已作出努力。然而,許多此等努力仍引起PTFE有吸引力之特性中之一或多者(例如機械強度)降低。
前述內容顯示存在對製備具有經改良之潤濕特徵而不會顯著影響其機械強度之多孔PTFE膜的未滿足之需要。
本發明提供一種親水性多孔膜,其包含聚四氟乙烯(PTFE)及下式(I)之兩親媒性共聚物:
其中該兩親媒性共聚物為無規或嵌段共聚物,Rf為經全氟取代之基團,而Rh1及Rh2為親水性基團或氯,m、n及o獨立地為0至1000,其限制條件為m+n+o大於或等於10,且Y為羥基。
本發明進一步提供一種製備親水性多孔PTFE膜之方法,該方法包含:(i)製備摻合物,其包含PTFE及兩親媒性共聚物以及視情況存在之潤滑劑;(ii)將該摻合物擠壓成條帶;(iii)雙軸拉伸該條帶以獲得親水性多孔膜;視情況(iv)使該親水性多孔膜與試劑反應以改變該兩親媒性共聚物之化學結構;且視情況(v)對該親水性多孔膜進行退火;其中該兩親媒性共聚物具有下式(I):
其中該兩親媒性共聚物為均聚物或無規或嵌段共聚物,Rf為經全氟取代之基團,而Rh1及Rh2為親水性基團或氯,m、n及o獨立地為0至1000,其限制條件為m+n+o大於或等於10,且Y為羥基。
該親水性多孔膜享有PTFE膜之諸多優點,例如機械強度,且同時展現高水準之水可濕性。
本發明進一步提供經由此等親水性多孔PTFE膜來過濾流體
之方法。
圖1描繪在150℃下經退火之親水性PTFE膜的表面之光學顯微圖。
圖2描繪在250℃下經退火之親水性PTFE膜的表面之光學顯微圖。
圖3描繪在350℃下經退火之親水性PTFE膜的表面之光學顯微圖。
根據一具體實例,本發明提供一種親水性多孔膜,其包含聚四氟乙烯(PTFE)及下式(I)之兩親媒性共聚物:
其中兩親媒性共聚物為無規或嵌段共聚物,Rf為經全氟取代之基團,而Rh1及Rh2為親水性基團或氯,m及n獨立地為0至1000,其限制條件為m+n+o大於或等於10,且Y為羥基。
在具體實例中,m、n及o表示各別單體之聚合度,且各自獨立地為約10至約1000或1000以上,較佳為約100至約200。
在其他具體實例中,m、n及o表示共聚物中所存在之單體的莫耳分率且各單體可獨立地在0至99莫耳%,較佳10至40莫耳%之間的範圍內。
各別單體嵌段可以任何適合之質量%存在於嵌段共聚物中,例如在一具體實例中,約99%:約1%至約50%:約50%,較佳約90%:約10%至約70%:約30%,且更佳約75%:約25%。
共聚物可具有任何適合之分子量,例如,在一具體實例中,數量或重量(Mn或Mw)平均分子量為約10kDa至約1000kDa,較佳約75kDa至約500kDa,且更佳約250kDa至約500kDa。
可藉由任何適合之方法來製備本發明之兩親媒性共聚物,例如藉由經氟化之環氧化合物之開環聚合反應。參見例如US 2009/0030175 A1。在三烷基鋁及具有有機相對陽離子之鹽的存在下進行開環聚合反應,如下文針對以下兩種單體之混合物所說明:全氟烷基環氧化物及第三丁基縮水甘油醚(TGBE)。所得二嵌段共聚物與諸如三氟乙酸之酸反應以移除第三丁基且提供全氟環氧乙烷與羥甲基環氧乙烷之共聚物:
在一具體實例中,為製備三嵌段共聚物,首先製備由全氟環氧乙烷及TGBE所獲得之二嵌段共聚物,諸如二嵌段嵌段共聚物,且可添加第三單體且繼續進行聚合反應。
在適合溶劑,例如經氟化之溶劑中進行單體之聚合反應。可基於待形成的經氟化之聚合物的適當可溶性來選擇溶劑。適合溶劑之實例為六氟苯。適合溶劑之實例包括芳族烴,諸如苯、甲苯及二甲苯;脂族烴,諸如正戊烷、己烷及庚烷;脂環烴,諸如環己烷;及鹵化烴,諸如二氯甲
烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯及三氯苯;以及其混合物。
單體濃度可在1至50wt%,較佳2至45wt%,且更佳3至40wt%之範圍內。
聚合反應可在任何適合之溫度,例如0至150℃,較佳0℃至80℃下進行。
為製備嵌段共聚物,舉例而言,聚合反應可進行適合於獲得各嵌段之適當鏈長之任何時間,其可為約1分鐘至100小時。
可在任何適合之量內選擇催化劑之量。舉例而言,催化劑與單體之莫耳比可為約1:10至約1:1000,較佳約1:50至1:500,且更佳約1:100至約1:200。舉例而言,催化劑與單體之莫耳比可為1:n、1:m或1:o,其中n、m及o為平均聚合度。
聚合物可藉由適合技術,例如用非溶劑沈澱來分離。
可藉由任何已知技術使共聚物之分子量及分子量分佈特性化。舉例而言,可採用MALS-GPC技術。該技術經由高壓泵使用移動相通過一組充填固定相之管柱來洗提聚合物溶液。固定相根據鏈大小分離聚合物樣本,隨後藉由三種不同偵測器偵測聚合物。可採用一系列偵測器,例如成一列之紫外線偵測器(UV-偵測器(Ultraviolet detector)),之後為多角度雷射光散射偵測器(MALS-偵測器(multi-angle laser light scattering detector)),按順序,其後為折射率偵測器(RI-偵測器(refractive index detector)。UV-偵測器量測254nm波長之聚合物光吸收;MALS-偵測器量測相對於移動相來自聚合物鏈之散射光。
共聚物之多分散性視反應條件而定。舉例而言,共聚物之Mw/Mn為1.05至2.5,較佳1.1至1.2。
兩親媒性共聚物、其結構及用於形成經親水性改質之PTFE膜的代表性配方之實例在下表1中給出。
本發明進一步提供一種製備親水性多孔PTFE膜之方法,該方法包含:(i)製備摻合物,其包含PTFE及兩親媒性共聚物以及視情況存在之
潤滑劑;(ii)將摻合物擠壓成條帶;(iii)雙軸拉伸條帶以獲得親水性多孔膜;視情況(iv)使親水性多孔膜與試劑反應以改變兩親媒性共聚物之化學結構;且視情況(v)對親水性多孔膜進行退火;其中兩親媒性共聚物具有下式(I):
其中兩親媒性共聚物為無規或嵌段共聚物,Rf為經全氟取代之基團,而Rh1及Rh2為親水性基團或氯,m、n及o獨立地為0至1000,其限制條件為m+n+o大於或等於10,且Y為羥基。
使所需量之PTFE粉末與共聚物於適合溶劑,例如酮類溶劑(諸如丙酮或甲基乙基酮)中之溶液混合以獲得摻合物,其隨後與潤滑劑,諸如無氣味之礦油精(例如Isopar G)混合,且將所得糊狀物例如在雙輥機中進行剪切,且在約300psi或300psi以上之壓力下,至少施加兩次,各持續約55秒之時段,形成為坯料。所得坯料在室溫下平衡約12小時或12小時以上。隨後將坯料擠成所需形狀。舉例而言,以26mm模隙尺寸、最大壓力及55℃恆定溫度進行擠壓,產生管狀PTFE條帶。接著,將管狀條帶沿中心軸切開且環繞吸管再輥壓,產生新坯料(非壓縮)。在與第一擠壓製程期間所用條件相同的條件下對新坯料進行再擠壓。添加此步驟以向PTFE條
帶提供有利的橫向機械特性。在30℃下進行壓延,目標為達成9-10密耳之條帶厚度,且切成4×4"。隨後在125℃下乾燥所得條帶1小時,藉此自經擠壓之條帶移除潤滑劑。
隨後在以下條件下拉伸條帶:在300%/sec拉伸速率下,縱向(machine direction;MD)及橫向(transverse direction;TD)拉伸比為3。拉伸烘箱中之溫度設定為150℃。
隨後將經拉伸之條帶退火。在350℃下在退火烘箱中進行退火5秒,接著冷卻條帶。上述拉伸步驟所產生之孔隙在冷卻後得以保持。
視情況,使以上所獲得之多孔膜與酸反應。
根據本發明之一具體實例,親水性多孔PTFE膜為多孔膜,例如奈米多孔膜,例如孔直徑在1nm與100nm之間的膜,或孔直徑在1μm與10μm之間的微孔膜。
所得多孔膜之表面張力可如下測定。舉例而言,在室溫下藉由用IPA溶劑預濕潤膜薄片且將膜浸泡於濃度範圍介於0.1質量%與10質量%之間之塗佈聚合物溶液中來塗佈PTFE多孔載體之薄片。塗佈時間在(1分鐘至12小時)之間的範圍內。在浸泡載體之後,在100℃至160℃下在對流烘箱中將其乾燥。乾燥時間在(10分鐘至12小時)之間的範圍內。藉由量測臨界潤濕表面張力來量測所得多孔PTFE膜之潤濕特徵。
藉由量測臨界潤濕表面張力(critical wetting surface tension;CWST)來量測關於表面張力之表面改質之變化。該方法依賴於一組某些組成物之溶液。各溶液具有特定表面張力。溶液之表面張力以小非等效增量處於25至92達因/公分之範圍內。為量測膜表面張力,將膜定位於白光台
頂部之上,將一滴具有一定表面張力之溶液施加至膜表面上,且記錄下液滴滲透通過膜且變為亮白色(作為光穿過膜之指示)所耗費之時間。當液滴滲透膜所耗費之時間10秒時,視為即刻潤濕。若時間>10秒,則溶液被視為將膜部分潤濕。
根據本發明之具體實例之親水性多孔PTFE膜可用於多種應用中,包括例如診斷應用(包括例如樣品製備及/或診斷性側流裝置)、噴墨應用、微影術(例如替代基於HD/UHMW PE之介質)、過濾用於醫藥行業之流體、金屬移除、製備超純水、處理工業及表面水、過濾用於醫學應用之流體(包括用於家庭及/或患者使用,例如靜脈內應用,亦包括例如,過濾生物流體,諸如血液(例如病毒移除))、過濾用於電子行業之流體(例如過濾微電子行業中之光阻流體及熱SPM)、過濾用於食品及飲料行業之流體、啤酒過濾、澄清、過濾含抗體及/或蛋白質之流體、過濾含核酸之流體、細胞偵測(包括原位)、細胞捕獲及/或過濾細胞培養物流體。或者,或另外,根據本發明之具體實例之多孔膜可用於過濾空氣及/或氣體,及/或可用於排氣應用(例如允許空氣及/或氣體穿過但不允許液體穿過其間)。根據本發明之具體實例之多孔膜可用於多種裝置中,包括手術裝置及產品,諸如眼科手術產品。
根據本發明之具體實例,親水性多孔PTFE膜可具有多種組態,包括平坦狀、扁平片狀、褶狀、管狀、螺旋狀及中空纖維狀。
根據本發明之具體實例之親水性多孔PTFE膜典型地安置於包含至少一個入口及至少一個出口且界定入口與出口之間的至少一個流體流動路徑之殼體中,其中至少一個本發明膜或包括至少一個本發明膜之過
濾器跨越流體流動路徑,以提供過濾裝置或過濾模組。在一具體實例中,提供包含以下之過濾裝置:包含入口及第一出口且界定入口與第一出口之間的第一流體流動路徑的殼體;及至少一個本發明膜或包含至少一個本發明膜之過濾器,本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑安置於殼體中。
較佳地,對於交叉流應用,至少一個本發明多孔膜或包含至少一個本發明膜之過濾器安置於包含至少一個入口及至少兩個出口且界定入口與第一出口之間的至少一個第一流體流動路徑及入口與第二出口之間的第二流體流動路徑之殼體中,其中本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑以提供過濾裝置或過濾模組。在例示性具體實例中,過濾裝置包含交叉流過濾模組、殼體,該殼體包含入口、含濃縮物出口之第一出口及含滲透物出口之第二出口且界定入口與第一出口之間的第一流體流動路徑及入口與第二出口之間的第二流體流動路徑,其中至少一個本發明膜或包含至少一個本發明膜之過濾器跨越第一流體流動路徑安置。
過濾裝置或模組可為可滅菌的。可採用具有適合形狀且提供一個入口及一或多個出口之任何殼體。
殼體可由任何適合的剛性不可滲透性材料製造,該材料包括任何不可滲透性熱塑性材料,其與處理中之流體相容。舉例而言,殼體可由金屬,諸如不鏽鋼或由聚合物,例如透明或半透明聚合物,諸如丙烯酸、聚丙烯、聚苯乙烯或聚碳酸酯樹脂製造。
本發明進一步提供一種藉由上述方法製備之經親水性改質
之多孔PTFE膜。
本發明進一步提供一種過濾流體之方法,該方法包含使該流體穿過上文所述之親水性多孔PTFE膜。
以下實施例進一步說明本發明,但當然不應解釋為以任何方式限制其範圍。
此實施例展示一種製備根據本發明之一具體實例之親水性多孔PTFE膜的方法。
使200g PTFE樹脂粉末(FLUON CD123)與所需量之共聚物(PF8PO)100-r-(TBGE)200於丙酮溶劑(25%)中及Isopar G潤滑劑(50%)混合以獲得含有5%或10%共聚物之摻合物。將摻合物於雙輥機中混合。藉由施加300psi之壓力至少兩次,各持續約55秒之時段而使摻合物形成為坯料。所得坯料在室溫下平衡約12小時。隨後在最大壓力及55℃恆定溫度下經由26mm模具擠壓坯料,產生管狀PTFE條帶。將管狀條帶沿中心軸(沿其長度)切開且環繞吸管輥壓,產生新坯料(非壓縮)。在與第一擠壓製程期間所用條件相同的條件下對新坯料進行擠壓。在30℃下進行壓延,目標為達成9-10密耳之條帶厚度,且切成4×4"。在125℃下乾燥所得條帶1小時,藉此自條帶移除潤滑劑。在300%/sec之拉伸速率下,沿縱向及橫向以3之MD/TD比率拉伸條帶。拉伸烘箱之溫度設定為150℃。如以下表2中所列舉,在150℃或350℃下在退火烘箱中對所得膜進行多次退火。膜效能特徵在以下表2中列舉,且曝露於甲酸(formic acid;FA)、硫酸(sulfuric acid;SA)及三氟乙酸(trifluoroacetic acid;TFA)之結果在下表3中列舉。
本文中所引用之所有參考文獻(包括公開案、專利申請案及專利)均以引用之方式併入本文中,該引用程度如同個別及特定地指示各參考文獻以引用之方式併入且全文闡述於本文中一般。
除非本文中另外指示或與上下文明顯矛盾,否則在描述本發明之上下文中(尤其在以下申請專利範圍之上下文中)使用術語「一(a/an)」及「該(the)」及「至少一者(at least one)」及類似指示物應理解為涵蓋單數及複數兩者。除非本文中另外指示或與上下文明顯矛盾,否則使用後接一或多個項目之清單(例如「A及B中之至少一者(at least one of A and B)」)之術語「至少一者(at least one)」應理解為意謂選自所列舉項目之一個項目(A或B)或所列舉項目中之兩者或兩者以上之任何組合(A及B)。除非另外指出,否則術語「包含(comprising)」、「具有(having)」、「包括(including)」及「含有(containing)」應理解為開放式術語(亦即,意謂「包括(但不限於)(including,but not limited to)」。除非本文另外指示,否則本文中數值範圍之列舉僅意欲充當個別提及屬於該範圍內之各獨立值之簡寫方法,且各獨立值併入本說明書中,如同在本文中個別敍述一般。除非本文中另外指示或另外與上下文明顯矛盾,否則本文中所描述之所有方法可以任何適合
之次序進行。除非另外主張,否則本文所提供之任何及所有實例或例示性語言(例如,「諸如(such as)」)之使用僅意欲更好地闡明本發明且並不對本發明之範圍造成限制。本說明書中之語言不應理解為指示任何未主張之要素對於實踐本發明而言必不可少。
本發明之較佳具體實例描述於本文中,包括本發明人已知用於實施本發明之最佳模式。在閱讀以上描述之後,彼等較佳具體實例之變化形式對於一般熟習此項技術者可變得顯而易見。本發明人期望熟習此項技術者按需要採用該等變化形式,且本發明人意欲以不同於本文中所特定描述之方式來實踐本發明。相應地,若適用法律允許,則本發明包括在此隨附之申請專利範圍中所陳述之標的物的所有修改及等效物。此外,除非本文另外指示或另外與上下文明顯矛盾,否則本發明涵蓋上文所描述之要素在其所有可能變化形式中之任何組合。
Claims (11)
- 一種親水性多孔膜,其包含聚四氟乙烯(PTFE)及下式(I)之兩親媒性共聚物:
- 如申請專利範圍第1項之親水性多孔膜,其中Rf為經全氟取代之烷基,其中烷基鏈在該鏈中可視情況含有一或多個氧原子。
- 如申請專利範圍第1項或第2項之親水性多孔膜,其中Rf為CpF2p+1-(CH2)q(OCH2)r,其中p為1至12,q為0至3且r為0至2。
- 如申請專利範圍第3項之親水性多孔膜,其中Rf係獨立地選自C8F17CH2、C6F13(CH2)2OCH2、C4F9CH2及CF3。
- 如申請專利範圍第4項之親水性多孔膜,其中Rf係選自C8F17CH2及C6F13(CH2)2OCH2。
- 如申請專利範圍第1項或第2項之親水性多孔膜,其中Rh1及Rh2獨立地選自羥基、醯氧基、三氟乙醯基、烷基氧基、氯、烯丙氧基、烷硫基及烷硫基丙氧基,其中該烷硫基及烷硫基丙氧基之烷基部分視情況經羥基、羧基、磺基、膦酸基、四級銨陽離子、烷磺醯基或雜環基取代。
- 如申請專利範圍第6項之親水性多孔膜,其中Rh1及Rh2係選自羥基及三氟乙醯基。
- 如申請專利範圍第1項之親水性多孔膜,其中該兩親媒性共聚物係選自:
- 一種製備親水性多孔PTFE膜之方法,該方法包含:(i)製備摻合物,其包含PTFE及兩親媒性共聚物以及視情況存在之潤滑劑;(ii)將該摻合物擠壓成條帶;(iii)雙軸拉伸該條帶以獲得親水性多孔膜;視情況(iv)使該親水性多孔膜與試劑反應以改變該兩親媒性共聚物之化學結構;且視情況(v)對該親水性多孔膜進行退火;其中該兩親媒性共聚物具有下式(I):
- 一種親水性多孔膜,其藉由如申請專利範圍第9項之方法製備。
- 一種過濾流體之方法,該方法包含使該流體穿過如申請專利範圍第1項至第8項或第10項中任一項之親水性多孔膜。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/815,578 US10315168B2 (en) | 2015-07-31 | 2015-07-31 | Hydrophilic porous polytetrafluoroethylene membrane (II) |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201710302A TW201710302A (zh) | 2017-03-16 |
TWI607023B true TWI607023B (zh) | 2017-12-01 |
Family
ID=56235611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW105120504A TWI607023B (zh) | 2015-07-31 | 2016-06-29 | 親水性多孔聚四氟乙烯膜(ii) |
Country Status (7)
Country | Link |
---|---|
US (1) | US10315168B2 (zh) |
EP (1) | EP3124102B9 (zh) |
JP (1) | JP6372520B2 (zh) |
KR (1) | KR101921701B1 (zh) |
CN (1) | CN106390782B (zh) |
SG (1) | SG10201604946UA (zh) |
TW (1) | TWI607023B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10787231B2 (en) * | 2016-07-29 | 2020-09-29 | California Institute Of Technology | Systems, methods, and apparatuses for reducing hydrodynamic frictional drag |
JP6858540B2 (ja) * | 2016-12-08 | 2021-04-14 | 株式会社ミズホメディー | 核酸増幅反応用デバイス |
WO2019107746A1 (ko) * | 2017-11-28 | 2019-06-06 | 주식회사 엘지화학 | 불소계 수지 다공성 막의 제조방법 |
KR20190062168A (ko) | 2017-11-28 | 2019-06-05 | 주식회사 엘지화학 | 불소계 수지 다공성 막의 제조방법 |
CN108636139B (zh) * | 2018-05-07 | 2020-11-24 | 杭州骥海过滤科技有限公司 | 一种亲水型聚四氟乙烯平板膜的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201041955A (en) * | 2009-04-06 | 2010-12-01 | Entegris Inc | Non-dewetting porous membranes |
US20110073541A1 (en) * | 2009-09-30 | 2011-03-31 | Fujifilm Corporation | Crystalline polymer microporous membrane, method for producing the same, and filtration filter |
CN103772692A (zh) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | 一种全氟烷基缩水甘油醚与环醚的共聚二醇及其制备方法 |
Family Cites Families (60)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2697256A (en) * | 1951-11-14 | 1954-12-21 | Journal Box Servicing Corp | Waste separating shaker |
JPS5833886B2 (ja) | 1976-09-14 | 1983-07-22 | 東ソー株式会社 | 陽イオン交換膜並びにその製法 |
US4975507A (en) | 1987-05-27 | 1990-12-04 | Monsanto Company | Cyclopentanedioxocarbonyl vinylene polymers |
DE3724198A1 (de) | 1987-07-22 | 1989-02-02 | Hoechst Ag | Verfahren zur herstellung von perfluoralkyl enthaltenden epoxiden und neue perfluoralkyl enthaltende epoxide |
US5294493A (en) | 1990-12-07 | 1994-03-15 | E. I. Du Pont De Nemours And Company | Polymeric films for second order nonlinear optics |
US5200470A (en) | 1990-12-19 | 1993-04-06 | Monsanto Company | Norbornene dicarboxy phenylimide polymers |
US5117327A (en) | 1990-12-19 | 1992-05-26 | Monsanto Company | Norbornene dicarboximide polymer dielectric devices |
US5219662A (en) | 1991-05-23 | 1993-06-15 | E. I. Du Pont De Nemours And Company | Biocompatible polyurethanes by treatment with polyoxazoline block copolymers |
US5266076A (en) | 1992-01-24 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Fluorinated finishes for aramids |
US5807977A (en) | 1992-07-10 | 1998-09-15 | Aerojet General Corporation | Polymers and prepolymers from mono-substituted fluorinated oxetane monomers |
FR2697256B1 (fr) * | 1992-10-23 | 1994-12-09 | Centre Nat Rech Scient | Polyéthers perfluoroalkylés hydroxylés, procédé de préparation et application à la synthèse de matériaux polyuréthanes. |
US5418277A (en) | 1994-04-26 | 1995-05-23 | E. I. Du Pont De Nemours And Company | Aqueous ink jet inks containing fluorinated polymers |
IT1269816B (it) | 1994-05-23 | 1997-04-15 | Ausimont Spa | Composizioni solide espandibili a base di perfluoropolimeri e processoper la loro preparazione |
WO1998015595A1 (fr) | 1996-10-09 | 1998-04-16 | Nippon Zeon Co., Ltd. | Composition a base d'un polymere de norbornene |
US6080826A (en) | 1997-01-06 | 2000-06-27 | California Institute Of Technology | Template-directed ring-closing metathesis and ring-opening metathesis polymerization of functionalized dienes |
US6354443B1 (en) * | 1997-05-01 | 2002-03-12 | Millipore Corporation | Surface modified porous membrane and process |
US5976380A (en) | 1997-05-01 | 1999-11-02 | Millipore Corporation | Article of manufacture including a surface modified membrane and process |
DE69806631T2 (de) | 1997-11-19 | 2003-01-02 | Minnesota Mining & Mfg | Fluoroverbindung enthaltende thermoplastische polymerfolie |
EP0947556B1 (en) | 1998-04-01 | 2004-11-10 | Solvay Solexis, Inc. | Compatible blends of polyvinylidene fluoride and aromatic polyimide |
TW558559B (en) | 1998-06-30 | 2003-10-21 | Ind Tech Res Inst | An oxygen atom-containing heterocyclic dione polymer and photosensitive composition comprising the same |
GB9916235D0 (en) | 1999-07-09 | 1999-09-15 | Univ Durham | Process for polymerisation of olefins and novel polymerisable olefins |
EP1238996B1 (en) | 1999-08-25 | 2004-11-03 | Zeon Corporation | Norbornene open-ring polymers, products of hydrogenation thereof and processes for the production of both |
US6436476B1 (en) | 2000-02-14 | 2002-08-20 | Owens Corning Fiberglas Technology, Inc. | Polyolefin fiber-reinforced composites using a fiber coating composition compatible with romp catalysts |
AUPR143400A0 (en) * | 2000-11-13 | 2000-12-07 | Usf Filtration And Separations Group Inc. | Modified membranes |
WO2002092660A2 (en) | 2001-05-14 | 2002-11-21 | Omnova Soltions Inc | Polymeric surfactants derived from cyclic monomers having pendant fluorinated carbon groups |
EP1483300A4 (en) | 2002-02-19 | 2009-04-08 | California Inst Of Techn | RINGER EXPLOITATION OF CYCLIC OLEFINES BY OLEFINMETATHESE ACTIONS WITH ACYCLIC SERVICE |
JP2003246906A (ja) | 2002-02-25 | 2003-09-05 | Asahi Kasei Corp | フッ素系共重合体含有組成物 |
JP2005029527A (ja) | 2003-07-09 | 2005-02-03 | Central Glass Co Ltd | フッ素系環状化合物、フッ素系重合性単量体、フッ素系高分子化合物、並びにそれを用いたレジスト材料及びパターン形成方法 |
US7514499B2 (en) | 2004-11-09 | 2009-04-07 | E. I. Du Pont De Nemours And Company | Ring opening polymerization of cyclic amides using N-heterocyclic carbene catalysts |
WO2006064814A1 (ja) | 2004-12-15 | 2006-06-22 | Nihon University | ノルボルネン系付加(共)重合体の製造方法 |
GB0428172D0 (en) | 2004-12-23 | 2005-01-26 | Ici Plc | Olefin metathesis polymerisation |
KR20080059243A (ko) | 2005-09-22 | 2008-06-26 | 니폰 제온 가부시키가이샤 | 노보넨 화합물 부가 중합체, 그 제조 방법, 상기 중합체로이루어지는 성형품 및 그 용도 |
TW200736311A (en) | 2006-01-30 | 2007-10-01 | Zeon Corp | Film comprising norbornene compound addition polymer |
WO2007105653A1 (ja) | 2006-03-10 | 2007-09-20 | Asahi Glass Co., Ltd. | 含フッ素エポキシ化合物の開環重合による含フッ素重合体の製造方法 |
TW200804479A (en) | 2006-05-23 | 2008-01-16 | Zeon Corp | Oriented film of addition polymer of norbornene compound alone, process for producing the same and use thereof |
ATE509676T1 (de) | 2006-10-17 | 2011-06-15 | Firestone Polymers Llc | Golfballkern |
WO2008068897A1 (ja) | 2006-12-05 | 2008-06-12 | Mitsui Chemicals, Inc. | 環状オレフィン系重合体組成物、その用途、環状オレフィン系重合体 |
EP1942125A1 (en) | 2006-12-20 | 2008-07-09 | 3M Innovative Properties Company | Compositions curable by ring opening metathesis polymerarization at low temperatures and their application in the dental field |
CN100496683C (zh) * | 2007-04-28 | 2009-06-10 | 浙江大学 | 两亲性含氟共聚物对聚四氟乙烯多孔膜的表面改性方法 |
TWI347955B (en) | 2007-07-19 | 2011-09-01 | Univ Nat Taiwan Science Tech | Norbornene monomers with fluorene group and polymer material thereof |
TWI357416B (en) | 2007-08-08 | 2012-02-01 | Univ Nat Taiwan Science Tech | Norbornene monomers with epoxy group and polymer m |
JP2009120775A (ja) | 2007-11-19 | 2009-06-04 | Sumitomo Electric Fine Polymer Inc | フッ素樹脂多孔質体の表面改質方法 |
US8215496B2 (en) | 2008-01-28 | 2012-07-10 | Promerus Llc | Polynorbornene pervaporation membrane films, preparation and use thereof |
US8223472B1 (en) | 2008-11-14 | 2012-07-17 | Sandia Corporation | Norbornylene-based polymer systems for dielectric applications |
US20110266220A1 (en) | 2009-01-07 | 2011-11-03 | Cms Technologies Holdings, Inc. | Separations with highly selective fluoropolymer membranes |
US9688631B2 (en) | 2009-03-02 | 2017-06-27 | Isp Investments Llc | Thermosetting ring-opening metathesis polymerization materials with thermally degradable linkages |
US8283410B2 (en) | 2009-03-30 | 2012-10-09 | Isp Investments Inc. | Ring-opening metathesis polymerization of norbornene and oxanorbornene moieties and uses thereof |
US8143369B2 (en) | 2009-06-02 | 2012-03-27 | International Business Machines Corporation | Polymers bearing pendant pentafluorophenyl ester groups, and methods of synthesis and functionalization thereof |
US8207351B2 (en) | 2010-04-30 | 2012-06-26 | International Business Machines Corporation | Cyclic carbonyl compounds with pendant carbonate groups, preparations thereof, and polymers therefrom |
JP2012000571A (ja) | 2010-06-17 | 2012-01-05 | Nitto Denko Corp | 脱気用多孔体およびそれを備えた脱気装置 |
US8906999B2 (en) | 2011-02-17 | 2014-12-09 | Ccp Composites Us Llc | Styrene-free unsaturated polyester |
KR101305942B1 (ko) | 2011-05-04 | 2013-09-12 | 웅진케미칼 주식회사 | 친수성으로 개질된 ptfe 공중합체를 함유한 ptfe계 다공질 막, 그의 제조방법 및 그 막의 용도 |
CN102432782B (zh) * | 2011-09-01 | 2013-03-27 | 四川大学 | 两亲性三嵌段共聚物及其制备方法和由其共混改性的聚醚砜中空纤维膜 |
US9206271B2 (en) | 2012-03-25 | 2015-12-08 | Wisconsin Alumni Research Foundation | Fully backbone degradable and functionalizable polymers derived from the ring-opening metathesis polymerization (ROMP) |
CN103007787A (zh) * | 2012-12-19 | 2013-04-03 | 绍兴锐意环保科技有限公司 | 两亲性共聚物改性pvdf中空纤维超微过滤膜的新方法 |
US20140231340A1 (en) | 2013-02-15 | 2014-08-21 | Pall Corporation | Composite including ptfe membrane |
JP6271595B2 (ja) | 2013-02-27 | 2018-01-31 | マテリア, インコーポレイテッド | 金属カルベンオレフィンメタセシス2種の触媒組成物 |
CN103214678A (zh) * | 2013-05-06 | 2013-07-24 | 曹曙光 | 一种具有两亲性的多嵌段共聚物聚电解质及其合成方法 |
CN103709388B (zh) * | 2013-12-27 | 2015-09-23 | 南京信息工程大学 | 一种全氟取代环氧乙烷与环醚的共聚二醇及其制备方法 |
US9849428B2 (en) | 2015-04-30 | 2017-12-26 | Pall Corporation | Hydrophilically modified fluorinated membrane (VI) |
-
2015
- 2015-07-31 US US14/815,578 patent/US10315168B2/en active Active
-
2016
- 2016-06-16 SG SG10201604946UA patent/SG10201604946UA/en unknown
- 2016-06-16 JP JP2016119785A patent/JP6372520B2/ja active Active
- 2016-06-20 EP EP16175311.6A patent/EP3124102B9/en active Active
- 2016-06-28 KR KR1020160081137A patent/KR101921701B1/ko active IP Right Grant
- 2016-06-29 TW TW105120504A patent/TWI607023B/zh active
- 2016-06-29 CN CN201610496695.6A patent/CN106390782B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201041955A (en) * | 2009-04-06 | 2010-12-01 | Entegris Inc | Non-dewetting porous membranes |
US20110073541A1 (en) * | 2009-09-30 | 2011-03-31 | Fujifilm Corporation | Crystalline polymer microporous membrane, method for producing the same, and filtration filter |
CN103772692A (zh) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | 一种全氟烷基缩水甘油醚与环醚的共聚二醇及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106390782B (zh) | 2019-03-22 |
JP2017071755A (ja) | 2017-04-13 |
SG10201604946UA (en) | 2017-02-27 |
US10315168B2 (en) | 2019-06-11 |
EP3124102B1 (en) | 2020-06-03 |
EP3124102B9 (en) | 2020-10-07 |
US20170028362A1 (en) | 2017-02-02 |
KR101921701B1 (ko) | 2018-11-26 |
TW201710302A (zh) | 2017-03-16 |
CN106390782A (zh) | 2017-02-15 |
KR20170015138A (ko) | 2017-02-08 |
EP3124102A1 (en) | 2017-02-01 |
JP6372520B2 (ja) | 2018-08-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI607023B (zh) | 親水性多孔聚四氟乙烯膜(ii) | |
Sharma et al. | Impact of synthesized amino alcohol plasticizer on the morphology and hydrophilicity of polysulfone ultrafiltration membrane | |
EP2963076B1 (en) | Hydrophilic block copolymers and membranes prepared therefrom | |
CA2976508C (en) | Fluoropolymers and membranes comprising fluoropolymers (ii) | |
JP6377633B2 (ja) | 親水性フルオロポリマー | |
TW201622805A (zh) | 微孔性聚偏二氟乙烯平面膜 | |
JP6217992B2 (ja) | 親水性改質フッ素化膜(vi) | |
EP2962746B1 (en) | Hydrophilic membranes and method of preparation thereof | |
KR101831267B1 (ko) | 친수성 다공성 폴리테트라플루오로에틸렌 막(ⅰ) | |
EP1057521B1 (en) | Membranes of (per)fluorinated amorphous polymers | |
JP6060448B2 (ja) | 親水性改質フッ素化膜(ii) | |
EP3296011B1 (en) | Membranes comprising fluoropolymers | |
EP2992948A1 (en) | Robust polymeric membrane | |
US20170165613A1 (en) | Hollow fiber membranes formed from trans-1,3,3,3-tetrafluoropropene and vinylidene difluoride fluoropolymers |