CN104130111A - 全氟叔丁氧基烯丙基和炔丙基醚 - Google Patents
全氟叔丁氧基烯丙基和炔丙基醚 Download PDFInfo
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- 0 C=*CC(C=*)C(OC(C(F)(F)F)(C(F)(F)F)C(F)(F)F)=C Chemical compound C=*CC(C=*)C(OC(C(F)(F)F)(C(F)(F)F)C(F)(F)F)=C 0.000 description 1
- PTRJNETXSUJBTK-UHFFFAOYSA-N C=C=CCOC(C(F)(F)F)(C(F)(F)F)C(F)(F)F Chemical compound C=C=CCOC(C(F)(F)F)(C(F)(F)F)C(F)(F)F PTRJNETXSUJBTK-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and 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
- C08F14/18—Monomers containing fluorine
- C08F14/185—Monomers containing fluorine not covered by the groups C08F14/20 - C08F14/28
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- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C08F14/00—Homopolymers and 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
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- C08F16/00—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1408—Monomers containing halogen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
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Abstract
本发明公开了全氟叔丁氧基烯丙基醚和全氟叔丁氧基炔丙基醚以及用于合成它们的方法。还公开了用于由全氟叔丁氧基烯丙基醚和全氟叔丁氧基炔丙基醚制备聚合物的方法。
Description
发明领域
本发明涉及全氟叔丁氧基烯丙基和炔丙基醚的合成、表征以及用途。
背景技术
全氟叔丁氧基烯丙基醚和全氟叔丁氧基炔丙基醚之前在化学领域中是未知的。然而,已知其他烯丙基醚和炔丙基醚,并已知其作为用于纳入具有优越的电、机械和热特性的均聚物和共聚物中的单体的用途。
发明简述
在第一个方面,本发明涉及式(CF3)3COCH2R的化合物,其中R为-CH=CH2,或-C≡CH。
在第二个方面,本发明涉及包含式III或IV的重复单元的聚合物:
(III)或(IV)。
在第三方面,本发明涉及制备式I化合物的方法,包括将烯丙基卤与(1)九氟叔丁醇盐,或(2)在碱的存在下与九氟叔丁醇进行反应。
在第四方面,本发明涉及制备式II化合物的方法,包括将炔丙基卤与(1)九氟叔丁醇盐,或(2)在碱的存在下与九氟叔丁醇进行反应。
发明详述
取代基通常在引入时被定义并在整个说明书和所有独立权利要求中保持该定义。
在组成方面,本发明涉及式I和II的化合物:
化合物以如下方式合成。
3-[1,1-双(三氟甲基)-2,2,2-三氟乙氧基]丙-1-烯(I)的制备通过在室温下,将12.2mL(141mmol)烯丙基溴加入含有相当于1.1或40.0g(155mmol)九氟叔丁醇钠的40mL N,N-二甲基甲酰胺的搅拌溶液里,并随后在50℃加热。72小时后,向反应混合物中加入20mL水以形成两层液相。分离出下层相,用20mL2M NaOH洗涤4次并用蒸馏水洗涤2次。通过真空转移纯化反应混合物以提供在0℃收集为无色液体的13.9g3-[1,1-双(三氟甲基)-2,2,2-三氟乙氧基]丙-1-烯;分子式为C7H5F9O(MW=276.1);MS(m/e±):276.1;1H NMR(CDCl3中):δ4.51(d,J=5.3Hz,2H),5.29(dtd,J1=10.8Hz,J2=1.3Hz,J3=1.3Hz,1H),5.38(dtd,J1=17.2Hz,J2=1.5Hz,J3=1.5Hz,1H),5.90(ddt,J1=16.0Hz,J2=10.0Hz,J3=6.0Hz,1H);19F NMR(CDCl3中):-73.2ppm;13C NMR(CDCl3中):70.5,80.1,119.0,120.7,和131.6ppm;IR(纯样品):3098(w),3032(vw),2997(w),2970(w),2912(w),1652(vw),1469(w),1430(m),1376(m),1275(vs),1159(s),1089(w),1019(s),973(s),937(m),734(s),727(s)。3-[1,1-双(三氟甲基)-2,2,2-三氟乙氧基]丙-1-烯为无色液体,在25℃下nD=1.3055;在25℃下ρ=1.5992;在大气压下沸点为82℃。
3-[1,1-双(三氟甲基)-2,2,2-三氟乙氧基]丙-1-炔(II)的制备通过在室温下,将1.3mL(17.8mmol)炔丙基氯加入含有相当于1.1或5.1g(19.6mmol)九氟叔丁醇钠的5mL N,N-二甲基甲酰胺的搅拌溶液里,并随后在90℃加热。16小时后,向反应混合物中加入2mL水以形成两层液相,其中分离出下层氟相。氟相被10mL蒸馏水洗涤3次。通过在大气压下蒸馏来纯化反应混合物。所需产物,2.74g3-[1,1-双(三氟甲基)-2,2,2-三氟乙氧基]丙-1-炔在63℃被收集为无色液体:(56%收率);MS(m/e+):274;1H NMR(d6-DMSO中):54.69(d,J=2.4Hz,2H),3.36(t,J=2.4Hz,1H);19F NMR(d6-DMSO中):-75.4ppm;13C NMR(d6-DMSO中):58.2,76.0,78.9,79.5(2JC-F=30Hz),120.2ppm(1JC-F=291Hz)IR(纯样品):3317(s),2965(m),2140(m),1463(m),1276(vs),1153(s),1026(s),972(s),727(s)。3-[1,1-双(三氟甲基)-2,2,2-三氟乙氧基]丙-1-炔为在22℃下具有密度1.4452g/mL的无色液体,其在大气压下沸点为82℃。
概括的说,可以通过将烯丙基卤与九氟叔丁醇金属盐进行反应,或在碱的存在下将烯丙基卤与九氟叔丁醇进行反应来制备化合物I。可以通过将炔丙基卤与九氟叔丁醇金属盐进行反应,或在碱的存在下将炔丙基卤与九氟叔丁醇进行反应来制备化合物II。优选的金属盐包括银盐、钙盐、镁盐和碱金属盐。优选的碱金属盐包括锂、钾、钠和铷盐。碱包括在相转移催化剂存在下的固体碱金属氢氧化物。反应可以在惰性溶剂中进行。优选的溶剂将是水溶性的,这是由于其便于分离产物。反应可以在20°到100℃之间的温度方便地进行。
化合物I和II可用于制备具有优越特性的聚合物。例如,全氟叔丁氧基烯丙基醚均聚物可以显示高的氟溶解度和分配性(partition),并同时显示降低的毒性和生物累积。全氟叔丁氧基烯丙基醚共聚物可以显示类似的优点。适合与化合物I和II制备共聚物的单体包括乙烯、丙烯、苯乙烯和氯乙烯。类似地,全氟叔丁氧基炔丙基醚均聚物和共聚物预期为电导体,但具有抗油和水的表面。
可以通过本领域公知的聚合烯丙基醚,特别是聚合吸电子单体的方法,来从对应单体制备全氟叔丁氧基烯丙基醚的均聚物和共聚物。例如,KyokoNozaki实验室已经为极性单体提供了同质的有机金属催化剂[“Synthesis ofFunctional Polyolefins Using Cationic Bisphosphine Monoxide-PalladiumComplexes”,Carrow和Nozaki,J.Am.Chem.Soc.,2012,134(21),第8802-8805页]。此外,美国专利5,886,115描述了烯丙基醚的直接阳离子聚合,然而Venkatesh等[J Poly Sci Part A:Ploym Chem42:3271-3284,2004]描述了以丙烯酸盐的共聚合。类似地,可以通过本领域公知的聚合炔丙基醚的方法,来从对应单体制备全氟叔丁氧基炔丙基醚的均聚物和共聚物。例如,Balcar等人[Polymer39,4443-4447(1998)]描述了在具有钼基和钨基的催化剂下的炔丙基醚的均聚合,而Tomita等人[J Polym Sci Part A:Ploym Chem34:1853-1856,1996]描述了在叔丁醇钾的存在下,由自由基引发的炔丙基醚的均聚合。炔丙基醚特别适合基于“点击”化学的聚合物构建。Golas等人[Austral.J.Chem.60,400-404(2007)]描述了在CuBr/PMDETA催化剂存在下,从与炔丙基醚偶联的二叠氮基封端的聚苯乙烯-b-聚(环氧乙烷)-b-聚苯乙烯ABA嵌段共聚物制备的嵌段共聚物。也以另外的二叠氮基封端的三嵌段共聚物,聚(丙烯酸丁酯)-b-聚(甲基丙烯酸甲酯)-b-聚(丙烯酸丁酯)和二叠氮基封端的五嵌段共聚物:聚苯乙烯-b-聚(丙烯酸丁酯)-b-聚(甲基丙烯酸甲酯)-b-聚(丙烯酸丁酯)-b-聚苯乙烯来演示炔丙基醚的点击偶联。
通过这些方法制备的聚合物含有式III或IV的重复单元:
(III)或(IV)。
Claims (11)
1.式(CF3)3COCH2R的化合物,其中R为-CH=CH2,或-C≡CH。
2.根据权利要求1的化合物,其具有式I:
3.根据权利要求1的化合物,其具有式II:
4.包含式III或IV的重复单元的聚合物:
(III)或(IV)。
5.根据权利要求4的聚合物,包含式III的重复单元。
6.根据权利要求4的聚合物,包含式IV的重复单元。
7.根据权利要求4的均聚物。
8.根据权利要求4的共聚物。
9.制备式I化合物的方法,包括将烯丙基卤与(1)九氟叔丁醇盐,或(2)在碱的存在下与九氟叔丁醇进行反应。
10.制备式II化合物的方法,包括将炔丙基卤与(1)九氟叔丁醇盐,或(2)在碱的存在下与九氟叔丁醇进行反应。
11.根据权利要求9或10的方法,包括将烯丙基卤或炔丙基卤与九氟叔丁醇的碱金属盐进行反应。
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Citations (1)
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US5886115A (en) * | 1997-02-18 | 1999-03-23 | Rensselaer Polytechnic Institute | Process for the direct polymerization of allyl ethers, crotyl ethers and allyl alcohols |
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Publication number | Priority date | Publication date | Assignee | Title |
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US3541159A (en) * | 1965-02-18 | 1970-11-17 | Us Agriculture | Fluorinated allyl ethers and use thereof |
GB1153187A (en) * | 1966-07-18 | 1969-05-29 | Ici Ltd | Derivatives of Perfluorotertiary Alcohols |
US4029867A (en) * | 1971-02-22 | 1977-06-14 | The United States Of America As Represented By The Secretary Of Agriculture | Terpolymers of fluoroalkyl ethers and maleic anhydride |
FR2566401B1 (fr) * | 1984-06-20 | 1986-09-12 | Atochem | Procede de preparation d'olefines fluorees et nouvelles olefines en resultant |
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US5886115A (en) * | 1997-02-18 | 1999-03-23 | Rensselaer Polytechnic Institute | Process for the direct polymerization of allyl ethers, crotyl ethers and allyl alcohols |
Non-Patent Citations (2)
Title |
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RYAN GUTERMAN: "Fluorinated polymerizable phosphonium salts from PH3:surface properties of photopolymerized films", 《JOURNAL OF POLYMER SCIENCE, PART A:POLYMER CHEMISTRY》 * |
刘金刚: "新型含氟端炔丙基醚单体的合成及其固化研究", 《第十届绝缘材料与绝缘技术学术交流会论文集》 * |
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