CN110467540A - 一种含氟聚乙烯亚胺的合成方法 - Google Patents
一种含氟聚乙烯亚胺的合成方法 Download PDFInfo
- Publication number
- CN110467540A CN110467540A CN201910861974.1A CN201910861974A CN110467540A CN 110467540 A CN110467540 A CN 110467540A CN 201910861974 A CN201910861974 A CN 201910861974A CN 110467540 A CN110467540 A CN 110467540A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- polyethyleneimine
- containing polyethyleneimine
- functional material
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 77
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 42
- -1 perfluoroalkyl carboxylic acid halides Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 238000003682 fluorination reaction Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 239000012296 anti-solvent Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000011243 crosslinked material Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 238000012637 gene transfection Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 12
- 238000013019 agitation Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 7
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000001728 nano-filtration Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- GSJWYIDMIRQHMV-UHFFFAOYSA-N butanoyl fluoride Chemical compound CCCC(F)=O GSJWYIDMIRQHMV-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UFFSXJKVKBQEHC-UHFFFAOYSA-N heptafluorobutyric anhydride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)C(F)(F)F UFFSXJKVKBQEHC-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DXAOXPFFQPRUGW-UHFFFAOYSA-N FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)F.Cl Chemical compound FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)F.Cl DXAOXPFFQPRUGW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001409 amidines Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- HMRWGKIZOBXNRB-UHFFFAOYSA-N octane-1-sulfonyl fluoride Chemical compound CCCCCCCCS(F)(=O)=O HMRWGKIZOBXNRB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C311/05—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms to acyclic carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明涉及一种含氟聚乙烯亚胺的合成方法。所述含氟聚乙烯亚胺由聚乙烯亚胺与全氟烷基酰卤或全氟烷基磺酰卤缩合制备而成。其制备方法为：将聚乙烯亚胺溶解于溶剂中，在加热条件下将全氟烷基酰卤或全氟烷基磺酰卤滴加进反应体系，搅拌反应完毕后去除溶剂，得到所述含氟聚乙烯亚胺交联材料。该材料可应用于分离膜的制备、吸附剂的制备及基因转染材料等领域，具有耐溶剂、耐酸碱、抗污染等性能。
Description
技术领域
本发明属于高分子改性技术领域，具体涉及一种可作分离膜、吸附剂、基因转染材料的含氟聚乙烯亚胺的合成方法。
背景技术
含氟材料具有优良的热稳定性、化学稳定性和低表面能等特性，以聚四氟乙烯、聚偏氟乙烯为代表的含氟聚合物在分离膜制备方面有着成熟的应用。含氟聚合物在诸多溶剂中的溶解性较差，传统的相分离法无法满足更多种类的含氟聚合物分离膜的开发需求。近年来，陆续有采用水溶性较好的含氟交联材料制备含氟功能膜的文献及专利报道。中国发明专利ZL CN 2 201010589192.6“含六氟异丙醇基团的膜功能单体及其纳滤膜制备方法”中发明了一种含六氟异丙醇功能单体的交联材料与酰氯类材料通过界面交联，通过控制反应条件优化出含氟纳滤膜，所制备的含氟纳滤膜对二价阳离子和阴离子截留效果较好，并且具有很强的耐游离氯氧化性能。李亚飞，姜忠义等人通过三乙烯四胺与全氟辛酸的缩合反应制备可溶于水中的含氟多元胺，通过含氟多元胺结构中的胺基与聚酰胺膜表面羧酸的缩合在纳滤膜表面修饰全氟基团，该含氟纳滤膜表现出极好的抗污染性能（Y. Li et al,J. Membr. Sci, 2014, 455,15-23.）。上述发明中用到的含氟聚合物都有着较好的水溶性，适用于更多的制膜方法。
聚乙烯亚胺是一种聚阳离子型水溶性高分子聚合物，具有直线状和支链状两种结构，其骨架中存在大量胺基，其中支化聚乙烯亚胺结构中伯胺、仲胺、叔胺比例1:2:1，具有极好的反应活性。聚乙烯亚胺可通过交联其他小分子制备微球如中国专利ZL201110140086.4、美国专利US2010/0267108A1等等或薄膜材料，在基因转染材料、吸附材料、分离膜材料中有着较多的应用，其结构中活性胺基可进行多种化学改性。中国发明专利ZL CN 201610584829.X“一种修饰的聚乙烯亚胺化合物及其制备方法和应用”中发明了一种修饰的聚乙烯亚胺化合物，由七氟丁酸酐对分子量为1.8k的聚乙烯亚胺中的伯胺氢取代得到，可作为优良的基因递送系统。然而七氟丁酸酐成本较高，如何通过对含氟试剂和反应条件的筛选，制备具有水溶性、低成本的含氟聚乙烯亚胺使其在分离膜、吸附剂甚至基因转染材料等领域具体更好的应用前景是本发明需要解决的问题。
发明内容
本发明的目的在于解决水溶性低成本的含氟交联材料的匮乏，提供一种可用于分离膜制备、基因转染材料和吸附材料的新型低成本含氟功能材料的制备方法。
本发明是通过如下技术方案实现的：
一种含氟聚乙烯亚胺功能材料的结构片段通式如下：
其中虚线代表N原子连接支链或氢，Z为磺酰基（）或酰基（）；R为全氟烷基，
通式CnF2n+1, n为1-18。
一种含氟聚乙烯亚胺功能材料的制备方法，包括以下步骤，将聚乙烯亚胺溶解于溶剂中，将全氟烷基酰卤或全氟烷基磺酰卤滴加进该溶液，在加热条件下，搅拌反应完毕后去除溶剂，得到所述含氟聚乙烯亚胺材料。
根据本发明所述的含氟聚乙烯亚胺材料的制备方法，聚乙烯亚胺为底物，其分子量为600 Da，1800 Da，10000 Da和70000 Da的一种或几种；
根据本发明所述的含氟聚乙烯亚胺材料的制备方法，所涉及的氟化试剂 全氟烷基酰
卤结构通式为， 全氟烷基磺酰卤结构通式为，其中，R为全氟烷基，通式
CnF2n+1，n为1-18，X为卤素原子，包括氟，氯，溴，碘中的一种。
根据本发明所述的含氟聚乙烯亚胺材料的制备方法，其特征在于，步骤中所涉及的氟化试剂与聚乙烯亚胺底物的质量比包括范围从1：1 ~ 1：100。
根据本发明所述的含氟聚乙烯亚胺材料的制备方法，反应溶剂包括甲醇，乙醇，异丙醇，乙腈，甲苯，吡啶，四氢呋喃，N, N-二甲基甲酰胺（DMF），N, N-二甲基乙酰胺（DMAc），N-甲基吡咯烷酮（NMP），二甲亚砜中的一种或几种。
根据本发明所述的含氟聚乙烯亚胺材料的制备方法，加热温度为25 ℃ ~ 120℃。
有益效果：
本发明的优点在于选用多种溶剂保证反应物的溶解以促进反应的发生，进而提高聚乙烯亚胺的氟化接枝率，通过反应条件的控制可调节全氟基团的接枝率。所得氟化聚乙烯亚胺同时含有低表面能的全氟基团链段和高反应活性的胺基官能团，便于应用于交联、表面涂覆等过程制备微球及薄膜，是一种低成本高效的功能化交联材料。
附图说明
图1 实施例1所述含氟聚乙烯亚胺红外图谱。
图2 实施例1所述含氟聚乙烯亚胺核磁图谱。
具体实施方式
以下结合具体实施例对本发明进行进一步描述，但所给的实施例不构成对权利要求饱和范围的限制。
实施例 1
含氟聚乙烯亚胺功能材料的合成，底物为1800分子量聚乙烯亚胺，氟化试剂全氟丁基磺酰氟，含氟量为40 wt%，（1 : 2.5）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5 g，加入DMF 50 mL，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟丁基磺酰氟2 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到40 wt%接枝量的氟化聚乙烯亚胺产物。
产物红外图谱如图1所示，对比原PEI红外图谱，N-H伸缩震动吸收（3354 cm-1，3328-1）明显减弱，CF3、CF2基团特征吸收出现（1204 cm-1、1130 cm-1）。产物核磁图谱如图2所示，化学位移-82.3 ppm，-114.4 ppm，-122.2 ppm和-127.1 ppm分别对应全氟丁基上的CF3和三组CF2基团。氟信号变宽证明其接枝在聚合物PEI上。杂质主要为全氟丁基磺酸，含量<5%。证明产品接枝率>95%。
实施例 2
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂全氟丁酰氯，含氟量为100 wt% （1 : 1）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5 g，加入50 mL 甲苯，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟丁酰氯5 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到100 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 3
含氟聚乙烯亚胺功能材料的合成，底物为70000分子量聚乙烯亚胺，氟化试剂全氟丁基磺酰氟，含氟量为1 wt%（1 : 100）
向茄形瓶中加入70000 Da分子量的聚乙烯亚胺5 g，加入50 mL DMF和10 mL异丙醇，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟丁基磺酰氟50 mg，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到1 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 4
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂全氟辛基磺酰氟，含氟量为20 wt%（1 : 5）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5g，加入50 mL乙腈和10 mL异丙醇，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟丁基磺酰氟1 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到20 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 5
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂全氟辛基磺酰氟，含氟量为20 wt%（1 : 5）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5g，加入50 mL甲苯和10 mL异丙醇，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟辛基磺酰氟1 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到20 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 6
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂全氟辛酰氯，含氟量为20 wt%（1 : 5）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5 g，加入50 mL NMP和10 mL异丙醇，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟辛酰氯1 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到20 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 7
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂全氟丁酰氟，含氟量为20wt%（1 : 5）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5g，加入50 mL吡啶，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟丁酰氟1 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到20 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 8
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂三氟甲烷磺酰氯，含氟量为20 wt%（1 : 5）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5 g，加入50 mL DMF，加热到25摄氏度将其溶解。在此温度下缓慢滴加三氟甲烷磺酰氯1 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到20 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 9
含氟聚乙烯亚胺功能材料的合成，底物为600分子量聚乙烯亚胺，氟化试剂全氟十六酰氯，含氟量为10 wt%（1 : 10）
向茄形瓶中加入600 Da分子量的聚乙烯亚胺5g，加入DMAc，加热到60摄氏度将其溶解。在此温度下缓慢滴加全氟十六酰氯1 g，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到10 wt%接枝量的氟化聚乙烯亚胺产物。
实施例 10
含氟聚乙烯亚胺功能材料的合成，底物为70000分子量聚乙烯亚胺，氟化试剂全氟丁基磺酰氟，含氟量为5 wt%（1 : 20）
向茄形瓶中加入70000 Da分子量的聚乙烯亚胺5 g，加入50 mL DMF，加热到120摄氏度将其溶解。在此温度下缓慢滴加全氟丁基磺酰氟250 mg，磁力搅拌反应12小时。用旋转蒸发仪除去溶剂，然后真空干燥得到5 wt%接枝量的氟化聚乙烯亚胺产物。
Claims (7)
1.一种含氟聚乙烯亚胺功能材料，该氟化材料的结构片段通式如下：
其中虚线代表N原子连接支链或氢，Z为磺酰基或酰基；R为全氟烷基，通式CnF2n+1，n为1-18。
2.一种含氟聚乙烯亚胺功能材料的合成方法，其特征在于，包括以下步骤，将聚乙烯亚胺溶解于溶剂中，将全氟烷基酰卤或全氟烷基磺酰卤滴加进该溶液，在加热条件下，搅拌反应完毕后去除溶剂，得到含氟聚乙烯亚胺材料。
3. 如权利要求 2 所述的含氟聚乙烯亚胺功能材料的合成方法，其特征在于，聚乙烯亚胺其分子量为600 Da，1800 Da，10000 Da和70000 Da的一种或几种。
4.如权利要求 2 所述的含氟聚乙烯亚胺功能材料的合成方法，其特征在于，所涉及的氟化试剂为全氟烷基酰卤或全氟烷基磺酰卤。
5. 如权利要求 2 所述的含氟聚乙烯亚胺功能材料的合成方法，其特征在于，步骤中所涉及的氟化试剂与聚乙烯亚胺的质量比为1：1 ~ 1：100。
6. 如权利要求2 所述的含氟聚乙烯亚胺功能材料的合成方法，其特征在于，反应溶剂为甲醇，乙醇，异丙醇，乙腈，甲苯，吡啶，四氢呋喃，N, N-二甲基甲酰胺，N, N-二甲基乙酰胺，N-甲基吡咯烷酮，二甲亚砜中的一种或几种。
7.如权利要求2 所述的含氟聚乙烯亚胺功能材料的合成方法，其特征在于，加热温度为25 ℃ ~ 120 ℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910861974.1A CN110467540A (zh) | 2019-09-12 | 2019-09-12 | 一种含氟聚乙烯亚胺的合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910861974.1A CN110467540A (zh) | 2019-09-12 | 2019-09-12 | 一种含氟聚乙烯亚胺的合成方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110467540A true CN110467540A (zh) | 2019-11-19 |
Family
ID=68515560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910861974.1A Pending CN110467540A (zh) | 2019-09-12 | 2019-09-12 | 一种含氟聚乙烯亚胺的合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110467540A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114848830A (zh) * | 2022-04-26 | 2022-08-05 | 复旦大学附属眼耳鼻喉科医院 | 一种用于提高角膜交联效果的制剂及角膜交联组合制剂 |
| CN116731557A (zh) * | 2023-07-26 | 2023-09-12 | 江苏唐彩新材料科技股份有限公司 | 高耐水聚酰胺印刷油墨及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769307A (en) * | 1968-04-18 | 1973-10-30 | Us Agriculture | Fluoroamide-amino polymers and process for imparting oleophobic yet hydrophilic properties to fibrous materials |
| CN1531522A (zh) * | 2000-10-16 | 2004-09-22 | 西巴特殊化学品控股有限公司 | 全氟烷基取代的不饱和酸的单酰胺和多酰胺 |
-
2019
- 2019-09-12 CN CN201910861974.1A patent/CN110467540A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769307A (en) * | 1968-04-18 | 1973-10-30 | Us Agriculture | Fluoroamide-amino polymers and process for imparting oleophobic yet hydrophilic properties to fibrous materials |
| CN1531522A (zh) * | 2000-10-16 | 2004-09-22 | 西巴特殊化学品控股有限公司 | 全氟烷基取代的不饱和酸的单酰胺和多酰胺 |
Non-Patent Citations (2)
| Title |
|---|
| 王又蓉等: "《膜技术问答》", 31 January 2007, 国防工业出版社 * |
| 赵正保等: "《有机化学（供药学类专业用）》", 31 January 2016, 中国医药科技出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114848830A (zh) * | 2022-04-26 | 2022-08-05 | 复旦大学附属眼耳鼻喉科医院 | 一种用于提高角膜交联效果的制剂及角膜交联组合制剂 |
| CN116731557A (zh) * | 2023-07-26 | 2023-09-12 | 江苏唐彩新材料科技股份有限公司 | 高耐水聚酰胺印刷油墨及其制备方法 |
| CN116731557B (zh) * | 2023-07-26 | 2024-03-05 | 江苏唐彩新材料科技股份有限公司 | 高耐水聚酰胺印刷油墨及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112717712B (zh) | 一种耐酸型纳滤膜及其制备方法和应用 | |
| Xu et al. | Preparation and performance of a charge-mosaic nanofiltration membrane with novel salt concentration sensitivity for the separation of salts and dyes | |
| WO2016095580A1 (zh) | 一种大通量聚酰胺复合膜 | |
| CN110467540A (zh) | 一种含氟聚乙烯亚胺的合成方法 | |
| CN107344074B (zh) | 一种掺杂氨基化石墨烯量子点的高通量耐溶剂有机/无机杂化复合膜的制备方法 | |
| CN111514768B (zh) | 耐溶剂聚合物纳滤膜及其制备方法和应用 | |
| CN104844764B (zh) | 一种碱性阴离子交换膜及其制备方法 | |
| CN104031260B (zh) | 一种侧基含羧基的高分子量聚芳醚砜聚合物的制备方法及其应用 | |
| CN108993180B (zh) | 一种接枝型聚离子液体聚酰亚胺膜及其制备方法 | |
| CN109499395A (zh) | 一种高通量反渗透海水膜的制备方法 | |
| US4659744A (en) | Fluorocarbon anion exchangers and processes for their preparation | |
| Briones et al. | Synthesis and characterization of poly (ionic liquid) derivatives of N-alkyl quaternized poly (4-vinylpyridine) | |
| Sun et al. | Poly (aryl ether ketone) membrane with controllable degree of sulfonation for organic solvent nanofiltration | |
| Yan et al. | Preparation and characterization of chloromethylated/quaternized poly (phthalazinone ether sulfone ketone) for positively charged nanofiltration membranes | |
| CN104959047B (zh) | 一种单胺接枝改性交联聚酰亚胺耐溶剂纳滤膜的制备方法 | |
| CN112675716A (zh) | 一种uio-66-nh2基衍生物制备高通量、无缺陷聚酰胺膜的方法 | |
| EP0166015B1 (en) | Fluorcarbon anion exchangers and processes for their preparation | |
| CN115554849A (zh) | 一种聚乙烯亚胺基荷正电纳滤膜的制备方法 | |
| CN111151137A (zh) | 一种高通量高截盐反渗透复合膜及其制备方法 | |
| CN102190810B (zh) | 基于溴化聚苯醚胍基化的均相阴离子交换膜的制备方法 | |
| CN109121441A (zh) | 离子传导性高分子电解质膜铸造过程中根据提高极性溶剂的相分离的效果使离子通道的大小得到调节的离子传导性高分子电解质膜及其制备方法 | |
| Mehrabi et al. | Polyimide-based separation membranes for liquid separation: A review on fabrication techniques, applications, and future perspectives | |
| CN109692579A (zh) | 反渗透膜及其制备方法和应用 | |
| Lakshmi et al. | Synthesis, characterisation and membrane properties of sulphonated poly (aryl ether sulphone) copolymers | |
| Sakaguchi et al. | Synthesis of poly (diphenylacetylene) s bearing various polar groups and their gas permeability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191119 |
|
| RJ01 | Rejection of invention patent application after publication |