CN1148377A - ω-氢氟烷基醚,前体羧酸及其衍生物,它们的制备和应用 - Google Patents
ω-氢氟烷基醚,前体羧酸及其衍生物,它们的制备和应用 Download PDFInfo
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- CN1148377A CN1148377A CN95193106A CN95193106A CN1148377A CN 1148377 A CN1148377 A CN 1148377A CN 95193106 A CN95193106 A CN 95193106A CN 95193106 A CN95193106 A CN 95193106A CN 1148377 A CN1148377 A CN 1148377A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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Abstract
一类通常是液态的ω-氢氟烷基醚化合物(及其经选择的混合物),该类化合物具有一条饱和的全氟脂肪族碳原子链,所述链中间隔有一个或多个醚氧原子,该类化合物可通过如相应的氟烷基醚羧酸的脱羧制得,并可用于如清洗和干燥。
Description
本发明涉及ω-氢氟烷基醚以及它们的制备和应用。另一方面,本发明涉及全氟(烷氧基链烷)酸及其衍生物和它们的制备。本发明还涉及直接氟化链烷酸或酯类似物制备全氟(烷氧基链烷)酸,并涉及ω-氢氟烷基醚的制备(例如通过所述酸或其烷基酯的脱羧)。另一方面,本发明还涉及全氟(烷氧基链烷)酸及其衍生物的应用。
由于持续地得到关于臭氧层被破坏的坏消息,参加关于“消耗臭氧层物质”的蒙特利尔条约(the Montreal Protocol on Substances That Deplete the OzoneLayer)的国家加快了终止工业化国家生产氯氟化碳(CFCs)和其它消耗臭氧的化学品的步伐(可参见Zurer,P.S.,“Looming Ban on Production of CFCs,HalonsSpurs Switch to Substitute”,Nov 15,1993,Chemical & Engineering News,P.12.)。
以替代化合物和技术代替CFCs和halon类(如CCl2F2、CCl3F、CF3Br和CCl2FCClF2)的工作已在进行。一系列氢氟化碳(HFCs)(如CH2FCF3(HFC-134a))已被用作或建议作为CFC的代用品(HFC-134a被誉为“臭氧的朋友”,可参见Schultz等人的美国专利5,118,494)。如C&EN文章(supra)指出的氢氯氟化碳(HCFCs,如CH3CCl2F(HCFC-141b))是CFC的代用品,但是尽管该产品接近于不损害臭氧层,可是该产品带着消耗臭氧的氯进入同温层。另一种建议的代用品是简单的ω-氢二氟甲基-全氟甲基醚(CF3OCF2H,参见J.L.Adcock等人的“Fluorinated Ethers-A new Family of Halons”,1991 CFCConference Proceedings(1991))。另一种由氟化2-烷氧基丙酸盐脱羧而成的氢-氟烷基醚(或醚氢化物)F[CF(CF3)CF2O]4CFHCF3已作为血液乳剂进行了试验(参见Chem.Pharm.Bull.33,1221(1985))。
Scherer的美国专利4,173,654描述了利用含氟烃的惰性将其用作电子装置的(electronic)冷却剂或泄漏试验的液体,并作为人造血液代用品,并对其它对氧具有良好溶解性的化合物进行了研究。该专利描述了某些含氟烃的“杂”材料,该材料具有代谢活性的烃基,尤其是-CH2-(CH2)m-H。描述某些全氟环醚的Scherer等人的美国专利4,686,024认为在该专利中披露的各种全氟化合物适合于用作氧和二氧化碳的载体。国际公布号为WO93/11868(Kaufman等人)的国际申请描述了某些氯氟化合物及其乳液在各种氧的输送方面的应用,如作为氧的输送剂或“人造血液”。
还有许多其它专利描述了各种氟化碳醚或聚醚。Selman等人的美国专利3,342,875描述了某些由醚的含氢衍生物(如氟化碳醚酸或铵盐)尤其是通过热解而成的“氢改性的氟化碳醚”(或“氢封端的聚醚”),所述醚由氟化碳环氧化物聚合而成。英国专利1,194,431(Montecatini Edison S.P.A.)的说明书描述了某种具有下列通式的全氟化醚和聚醚衍生物:
CF3-O-(C3F6O)M-(CF2O)N-(CF(CF3)-O)L-CF2X
其中,尤其是下标M、N和L是0或1-99的整数,X是氢原子或-COOMe(其中的Me是当量的碱金属或碱土金属),该化合物的例子有五氟二甲醚CF3-OCF2H。
其中,尤其是R是亚烷基、烷氧基亚烷基或全氟亚烷基;R1是氟或三氟甲基,但是是三氟甲基的R1不多于一个;R2是氟或三氟甲基,但是是三氟甲基的R2不多于一个;R3是氟或三氟甲基;R4是氢或卤素,但当R是亚烷基或烷氧基亚烷基时R4是氢;R5是至少具有两个碳原子的全氟亚烷基,R6尤其是氢、三氟甲基或全氟乙基;a是0或1;n和m是0-50的整数,并且n+m为1-50。
国际申请号为WO90/01901(Long)的国际申请描述了某些全氟化碳氢化物,如全氟辛基氢化物,它的乳剂可用于将氧气带至动物体内组织。已公开的欧洲专利申请0 482 938 A1(Chamber等人)描述了具有下列通式的氟化醚:
R″-CF2-CF-O-CF2-R′
R其中,R是氢、氟、烷基或具有1-6个碳原子的氟烷基;R′是氢、烷基或具有1-6个碳原子的氟烷基;R″是氟、烷基或具有1-6个碳原子的氟烷基。
其它描述一种或多种不同的氟烷氧基链烷酸和它们的酯或其它衍生物及其制备的专利有:美国专利2,713,593(Brice等人)、3,214,478(Milian Jr.)、3,393,228(Braun)、4,118,421(Martini)、4,357,282(Anderson等人)、4,729,856(Bernonge)、4,847,427(Nappa)、4,940,814(Schwertfeger)、4,973,716(Calini等人)、5,053,536(Bierschenk等人)、5,093,432(Bierschenk等人)和5,118,494(Schultz等人)以及公布号为WO90/03357(Moore等人)、WO90/06296(Costello等人)的PCT国际申请。上述Brice等人的专利描述了由电化学氟化制得的氟化碳的酸,包括沸点为225℃的酸并且所述酸是n-C8F17OC2F4COOH。上述Nappa、Bierschenk等人、Moore等人和Costello等人的专利描述了直接氟化类似的烃前体制备氟化合物。
本发明的一个方面是提供一种通常是液态(即在环境温度和压力下是液态)的氟烷基醚化合物或通常是液态的组合物,该组合物由或主要由经挑选的化合物的混合物组成,所述化合物具有饱和的全氟脂肪碳链(如4-30个碳原子链),该碳链中间隔有一个或多个(如2-8个)醚(或悬挂在链中的)氧原子。在碳链一端(下面称为近端)的碳原子与一个氢原子(即ω-氢取代基,或伯氢原子)和两个氟原子相键合,所述近端碳原子是二氟甲基或基团(-CF2H)的碳原子,该碳原子直接键合至另一个链碳原子(如全氟亚烷基链段-CNF2N的碳原子)上或键合至所述的醚氧原子上。在该碳链的另一端(远端)的碳原子是该远端基团的一部分,该远端基团选自二氟甲基、二氟氯甲基(-CF2Cl)、用饱和的脂环基(如c-C6F11-)取代的全氟烷基、直链的全氟烷基和支链的全氟烷基。在一个所述化合物中,所述碳链的近端以一个键合至醚氧原子上的二氟甲基结束,此时,所述直链全氟烷基具有至少6个链碳原子(如6-16个链碳原子),所述支链的全氟烷基至少具有4个碳原子(如4-16个碳原子)。这种ω-氢氟烷基醚化合物的例子包括:
CF3(CF2)4-O-CF2CF2H
CF3(CF2)5-O-CF2H
CF3(CF2)7-O-(CF2)5H
CF3(CF2)5-O-(CF2)2-O(CF2)2H
H(CF2)2-O-(CF2)2H
Cl(CF2)4-O-(CF2)4H
如果要求将一种所述的“经挑选的混合物”(即一种预定的经挑选的ω-氢氟烷基醚化合物的混合物)用于具体的用途中,那么可以制得一种所述的本发明组合物,该组合物由或主要由两种或多种所述化合物的混合物组成,每种所述化合物具有所要求的不连续的、非随机的分子量,经挑选的化合物最好具有互补的性能(如在医用中,该化合物作为氧载体包括在乳液中并给予该乳液以经改进的稳定性)。
在“全氟脂族的”、“全氟亚烷基”或“全氟烷基”中的术语“全氟”是指除非另有说明,否则该基团中既无与碳原子键合的、可被氟所取代的氢原子也无任何不饱和键。
本发明的ω-氢氟烷基醚是疏水性的,并且具有比类似的全氟烷基醚更低的疏油性,化学上是惰性的,并且对热稳定,非水溶性,通常(如在20℃)是液态的,按照本发明,它们可以高产率、高纯度地制得并具有很宽的分子量范围。ω-氢和末端的碳之间的共价键(即C-H键)通常可通过大气中的光氧化而降解,从而使得该ω-氢氟烷基醚在环境上可被接受或者相容。该ω-氢氟烷基醚化合物,或由或主要由该化合物组成的液态组合物可用于使用前面提到的CFCs、HCFCs或halon类的场合,例如,作为溶剂,用于电子产品(如唱碟或线路板)的精密或金属清洗;在冰箱、冷库的压缩机或空调机中作为传热剂、致冷剂;在聚氨酯泡沫绝缘体的制备中作为发泡剂或泡孔尺寸的调节剂;或作为化学灭火剂用于流动(streaming)灭火、完全溢流(total flooding)、抑制爆炸及inertion;以及作为高度氟化的聚醚的载体溶剂用作磁记录介质的润滑剂。ω-氢氟烷基醚的另一个应用领域是在各种医用和输氧的乳剂(如人造或合成血液)中。
上述本发明的ω-氢氟烷基醚可通过相应的前体全氟烷基醚羧酸及其盐,最好是其可皂化的烷基酯脱羧制得。或者可通过相应的ω-氯氟烷基醚的还原制得该ω-氢氟烷基醚(可参见WO93/11868)。所述全氟烷基醚羧酸(及其酯)本身(某些这种化合物是新化合物,它们的制备是本发明的另一方面)可通过直接氟化其相应的类似烃化合物制得。ω-氢氟烷基醚基本上是纯氟化物,可以使用该化合物或使用通常是液态的、由或主要由经挑选的这类化合物的混合物组成的组合物形式。如上述本发明的ω-氢氟烷基化合物那样,前体全氟烷基醚羧酸及其酯化合物具有一根饱和的、由许多个碳原子组成的全氟脂肪链,所述链同样间隔有一个或许多个醚氧原子,该链的近端与羧基或烷基酯相连。如上所述,该羧基(或其盐或其可皂化的烷基酯)可被脱羧,从而被前面提到的本发明最终的ω-氢烷基醚中的ω-氢取代基所取代。
前面提到的新型全氟烷基醚酸及其酯同样可被转化成各种其它衍生物(如它们的铵盐),它们作为表面活性剂用于改善液体的表面张力或界面张力。这种化合物在水性介质中和其它有机溶剂中的溶解度大于相应的全氟链烷酸衍生物的溶解度,这将增加其作为表面活性剂的用途。该化合物可方便地通过直接氟化相应的烃醚酸或其衍生物如酯制得,得到的产品具有高的产率和单一的分子种类。
本发明一类通常是液态的ω-氢氟烷基醚化合物可由下列通式表示:
X-Rf-O-(Rf′-O)n-Rf″-H I
其中:
H是伯氢原子;
X是键合在二氟亚甲基(Rf)上的氟原子,伯氢原子,或伯氯原子;
n是0-7的整数,最好为0-3;
Rf、Rf′和Rf″是相同的或不同的全氟亚烷基(直链或支链的),如-CF2-CF2-,该基团可被全氟有机基团所取代或不取代,所述全氟有机基团可含有醚氧原子,例如,Rf可以是-CF2CF(f_)CF2-或-Rf_CF2-,其中,Rf_是具有4-6个环碳原子的饱和全氟脂环基,如全氟环己基、全氟亚环己基;
所附加的条件是:当X是H或Cl时,Rf具有1-18,最好是2-18个链碳原子,Rf′具有1-12,最好是2-12个链碳原子,Rf″具有2-12个链碳原子;
另一个附加条件是:当X是F时,Rf具有至少4个,最好是4-18个链碳原子,Rf′具有1或大于1个,最好是1-12个,优选2-12个链碳原子,Rf″具有2个或大于2个,最好是2-12个链碳原子;
在通式I范围内的一类聚醚化合物可由下面通式表示:
X-Rf-O-(CF2CF2-O)m-Rf″-H II
其中m是0-7的整数,H,X,Rf和Rf″的定义与通式I中的定义相同。
在通式I范围内的另一类化合物可由下面通式表示:
F-Rf-O-(Rf′-O)p-Rf″-H III
其中p是0-2的整数,H,Rf,Rf′和Rf″的定义与通式I中的定义相同,只是Rf具有4-12个链碳原子,Rf′具有1-12个链碳原子,Rf″具有2-12个链碳原子。
其中:
H是伯氢原子;
X是氟原子,伯氢原子,或伯氯原子;
n是0-7的整数;
Rf、Rf′和Rf″各自选自直链或支链的,未取代的全氟亚烷基;直链或支链的全氟烷基或全氟环烷基取代的全氟亚烷基;以及直链或支链的有含醚氧原子的基团取代的全氟亚烷基;
所附加的条件是:当X是H或Cl时,Rf具有1-18个链碳原子,并且每个Rf′和Rf″各自具有1-12个链碳原子;
另一个附加条件是:当X是F时,Rf具有至少4个链碳原子,并且每个Rf′和Rf″各自具有1个或大于1个链碳原子;
再一个附加条件是:当n是0时,Rf是全氟环烷基取代的全氟亚烷基。
本发明ω-氢氟烷基醚化合物的代表性例子列于下:
表A
1.CF3(CF2)5-O-CF2H
2.CF3(CF2)3-O-(CF2)2H
3.c-C6F11CF2-O-(CF2)2H
4.CF3(CF2)3-O-CF2C(CF3)2CF2H
5.(CF3)2CFCF2-O-CF2H
6.CF3(CF2)4-O-(CF2)5H
7.CF3(CF2)6-O-CF2H
8.CF3(CF2)5-O-(CF2)2H
9.CF3(CF2)5-O-(CF2)3H
10.CF3(CF2)6-O-(CF2)2H
11.CF3(CF2)7-O-CF2H
12.CF3(CF2)7-O-(CF2)5H
13.CF3(CF2)7-O-(CF2)6H
14.CF3(CF2)5-O-(CF2)2-O-CF2H
15.CF3(CF2)5-O-(CF2)2-O-(CF2)2H
16.H-(CF2)2-O-(CF2)2H
17.H-(CF2)4-O-(CF2)4H
18.H-(CF2)2-O-(CF2)2-O-(CF2)2H
19.H-CF2-O-CF2C(CF3)2CF2-O-CF2H
20.Cl(CF2)4-O-(CF2)4H
21.H(CF2)2OCF2C(CF3)2CF2O(CF2)2H
22.C8F17OCF2OC3F6H
23.(CF3)3COC2F4OCF2OC2F4OCF2H
其中,Rfp是ROC(O)Rf或F-Rf,Rf如通式I中所定义的,是全氟亚烷基;
Rf′和Rf″如通式I中所定义的,同样是全氟亚烷基;
n同样如通式I中所定义;
Z′是CO2H、CO2R、COF、COCl、CONR1R2或-CF2OC(O)Rf,其中R选自氢、烷基(如具有1-6个碳原子的低级烷基)、环烷基、氟烷基和芳基,R1和R2各自选自氢、烷基、环烷基和含杂原子的环烷基。
通式IV化合物脱羧后,Z′部分被氢原子所取代。
可用下列通式V、VI、VII、VIII和IX表示所述醚酸及其衍生物中的小类,该化合物除了用作本发明ω-氢醚化合物的前体之外,还具有其它用途,例如,如上所述作为表面活性剂,并且相信它们是新的:
Rfo-O-Rfo′-Z V
其中,Rfo是具有,例如1-18个链碳原子,最好是1-12个链碳原子的全氟烷基(直链或支链的);
Rfo′是具有,例如2-11个链碳原子的全氟亚烷基(直链或支链的),其中至少一个Rfo或Rfo′具有至少8个链碳原子;而
Z是-COOH、-COOMI/V、-COONH4、-COOR、-CH2OH、-COF、-COCl、-COR、-CONRR、-CH2NH2、-CH2NCO、-CN、-CH2OSO2R、-CH2OCOR、-CH2OCOCR=CH2、-CONH(CH2)mSi(OR)3或-CH2O(CH2)mSi(OR)3,其中M是铵或化合价“V”是1-4的金属原子,如钠、钾、钛或铝,每个R分别是烷基(如1-14个碳原子的烷基)或环烷基,这些基团可部分或全部氟化,或者芳基(如具有6-10个环碳原子的芳基),任何这种基团都可含有杂原子,m是1-约11的整数。
其中,Rfq是具有约6-18个碳原子,最好是6-12个碳原子的全氟烷基(直链或支链的),
下标a是至少为2的整数,最好3-7,但当a是2时,Rfq至少具有约8个碳原子;
Z如通式V中所定义。
Rfr-O-CF2-O-Rfr′-Z VII
其中,Rfr是具有例如2-18个碳原子,最好是4-12个碳原子的全氟烷基(直链或支链的);
Rfr具有例如1-11个碳原子,最好是1-5个碳原子的全氟亚烷基(直链或支链的);
其中,Rfs是具有例如1-18个碳原子,最好是1-12个碳原子的全氟烷基(直链或支链的);
b是至少为3,最好为3-11的整数;
Z如通式V中所定义。
Rft-(O-Rft′)c-O-(CF2)d-Z IX
其中,Rft是具有例如1-18个碳原子,最好是1-12个碳原子的全氟烷基(直链或支链的);
Rft′是具有例如1-11个碳原子,最好是2-4个碳原子的全氟亚烷基(直链或支链的);
c是至少为1,最好为1-4的整数;
d是3或大于3,最好为3-9的整数;
Z如通式V中所定义。
通式V-IX的羧酸是制备许多通式V-IX的其它衍生物的有用的中间体。这些衍生物包括无官能团的或有官能团的衍生物,如羧酸、盐、酯、酰胺、腈、醇、丙烯酸酯和乙烯基醚。许多专利描述了含氧全氟亚烷基化合物(即全氟聚醚)的许多带官能团的衍生物的制备方法(可参见Mitsch等人的美国专利3,250,808和Moore等人的美国专利4,094,911)。这类衍生物具有许多用途,如作为表面活性剂、弹性体、涂料、润滑剂、制备液晶材料的物质(参见Janulis等人的美国专利5,262,082)以及用于纤维物质的处理,使该纤维物质具有防油性和防水性。羧酸衍生物的铵盐是特别有用的表面活性剂。
通式V的羧酸化合物通常是固体。通式VI、VII、VIII和IX的羧酸化合物通常是液态的,通常是液态的组合物可以由或主要由经挑选的这类化合物的混合物制得。
可用于制备本发明ω-氢氟烷基醚的氟烷基醚酸(或衍生物)的代表性例子如下:
表B
1.CF3(CF2)7-O-CF2CO2H
2.CF3(CF2)11-O-CF2CO2H
3.CF3(CF2)6-O-C2F4CO2H
4.CF3(CF2)4-O-C2F4CO2H
5.CF3(CF2)5-O-C2F4CO2H
6.CF3(CF2)8-O-C2F4CO2H
7.CF3(CF2)7-O-C2F4CO2H
8.CF3(CF2)9-O-C2F4CO2H
9.CF3(CF2)11-O-C2F4CO2H
10.CF3(CF2)5-OC2F4O-C2F4CO2H
11.C8F17-O-(CF2)5CO2H
12.C10F21-O-(CF2)5CO2H
13.CF3-O-(CF2)7CO2H
14.C2F5-O-(CF2)7CO2H
15.C3F7-O-(CF2)7CO2H
16.CF3-O-(CF2)9CO2H
17.CF3-O-(CF2)10CO2H
18.CF3(CF2)5-O-C2F4-O-C2F4-O-C2F4-O-
CF2CO2H
19.CF3(CF2)7-O-C2F4-O-C2F4-O-C2F4-O-
CF2CO2H
20.CF3(CF2)9-O-C2F4-O-C2F4-O-C2F4-O-
CF2CO2H
21.CF3(CF2)11-O-C2F4-O-C2F4-O-C2F4-O-
CF2CO2H
22.由BrijTM 30乙酸酯得到的CF3(CF2)11-(OC2F4)1-5-O-
CF2CO2H
23.C6F13OCF2O(CF2)5CO2H
24.CF3(CF2)7-O-CF2-O-CF2CO2H
25.CF3(CF2)7-O-CF2-O-C3F6CO2H
26.(CF3)3COC2F4OCF2OC2F4CO2H
27.C4F9-O-(CF2)3CO2H
28.C5F11-O-(CF2)3CO2H
29.C6F13-O-(CF2)3CO2H
30.C5F11-O-(CF2)4CO2H
31.CF3-O-(CF2)5CO2H
32.C4F9-O-(CF2)5CO2H
33.C5F11-O-(CF2)5CO2H
34.C4F9-O-C4F8-O(CF2)3CO2H
35.C6F13-O-C4F8-O(CF2)3CO2H
36.C4F9-O-C2F4O-C2F4O(CF2)3CO2H
37.CF3-O-(C2F4O)3-(CF2)3CO2H
38.C8F17OCF2OC5F10CO2H
39.(CF3)3COC2F4OCF2OC2F4OCF2CO2H
40.(CF3)2CFCF2CF2O(CF2)5CO2H
41.CF3(CF2)7OC2F4OC2F4OCF2CO2H
42.CF3(CF2)11OC2F4OC2F4OCF2CO2H
下面给出的是可用于制备本发明ω-氢氟烷基醚、使用上面所定义的通式的反应流程图。在这些反应流程图中,所说明的反应产品的通式描述在下一步反应中
Rf-O-(Rf′-O)n-Rf″-H
Rf-O-(Rf′-O)n-Rf″-H
醚的α和ω二氢化物(即在通式I中X是氢)可通过相似的反应流程图制得。例如下列反应流程图IV相似于反应流程图I:
H-Rf-O-(Rf′-O)nRf″-H
先来看上面反应流程图I,在步骤“a”直接氟化中,通过与氟气接触直接氟化一种可氟化的前体醚羧酸酯,如C4H9-O-(CH2)5COOCH3。术语“可氟化的”是指该前体含有与碳原子相键合的氢原子,该氢原子可被氟所取代,以及前体可含有能被氟饱和的不饱和键。描述在步骤b中的产物氟化的醚酸酯化合物可基本上由与其前体相同数量和立体排列的碳和氧原子所构成。如果要求的是一种由或主要由经挑选的氟化醚化合物的混合物组成的氟化醚酸组合物,那么可氟化经挑选的相应的前体化合物的混合物,或者,可分别氟化经挑选的前体化合物,随后掺混之。
可氟化的醚前体的直接氟化可在常用的直接氟化温度下进行,如适度的或接近于环境的温度如-20℃-+50℃,使用化学计量上过量的氟气,氟气最好被惰性气体(如氮)所稀释以减小或避免纯氟气的危害,并控制前体与氟反应时放出的热量。氟化最好在无氧和无水环境中进行,并可在固态颗粒状的净化剂(如氟化钠)的存在下进行以除去产生的氟化氢副产物。可使用惰性液体(如氟化碳或氯氟化碳液体)作为反应介质进行液相直接氟化。如有必要,可同时使用净化剂和惰性液体反应介质。氟化最好是在没有氟化氢净化剂的液相中直接氟化,所述氟化所使用的温度和惰性气体的流动速率应足以使氟化氢副产物挥发,并能够从氟化区域中去除产生的副产物。
另一方面,本发明提供含有上述氟化醚酸或其衍生物作为唯一主要成分的含氟化合物的组合物。
尽管直接氟化是一种包括由氟取代氢原子的取代方法,但是直接氟化与其它取代方法(如电化学氟化和三氟化钴方法,参见,例如Bierschenk等人的美国专利5,093,432)相比具有更高的产率和更纯的产品。通过使用单种前体化合物或其经挑选(而非随机地)的混合物可进一步增加本发明全氟醚酸(或酯)组合物的纯度。
较好的氟化方法是“液相直接氟化技术”,它包括制备很稀的前体在液体反应介质中的分散液,或最好是溶液,反应介质在所使用的氟化温度下对氟是相对惰性的,因此,可氟化的原料的浓度相对较低以便更容易控制反应温度。在反应混合物中还可以含有或分散有氟化氢净化剂(如氟化钠),净化剂与前体的重量比为,例如约0.5∶1-7∶1。可在强力搅拌反应昆合物的同时吹入氟气,最好使用混有浓度为约5-50%(体积),宜为约10-25%(体积)惰性气体(如氮气)的氟气,在整个氟化过程中氟气维持化学计量过量,如过量15-40%或更高,取决于具体的原料和所用设备的效率(如反应器的搅拌)。用这种方法的产率通常为约30-77%(摩尔),根据经验,可得到高达65-约85%(摩尔)的全氟化产品。
在液相直接氟化技术中作为反应介质使用的合适的液体是氯氟化碳,如FreonTM11氟三氯甲烷;氯氟醚;FluorinertTM电子液体(electronic liquids)FC-75,FC-72和FC-40;全氟链烷如全氟戊烷和全氟萘烷;全氟聚醚;和全氟乙缩醛。可以使用这些液体的混合物,以便前体和中间反应产物能很好地分散。反应介质可方便地在大气压力下使用,也可使用上述反应介质的较低分子量的同系物,但此时需要提升压力以形成液相。
如果使用氟化氢净化剂,那么液相直接氟化反应常在约-10~+50℃,最好在约-10-0℃的温度下进行,如果不使用这种净化剂,反应温度常为约0-150℃,最好为0-50℃,优选约10-30℃,所用温度应足以挥发氟化氢副产物,并且在以足够的速率流动的惰性气体的帮助下,从氟化反应器中吹除产生的这种副产物。在该温度下,用作反应介质的液体与稀氟气不发生明显的反应,基本上是惰性的。反应介质和其它有机物会在某种程度上存在于气态的反应废气中,可使用冷凝器冷凝气态的反应介质和在废气中的这些物质,并使得冷凝液回流至反应器中。可操纵冷凝器以减少或防止氟化氢副产物回流至反应器中,如果在氟化过程中允许该副产物滞留在反应器中,它会影响产品的产率。可通过选择性地冷凝有机物,而使得氟化氢通过冷凝器以减少或防止氟化氢的回流,或者通过同时将氟化氢和有机物冷凝至一个单独的容器中,如有必要,随后再分离作为上层液相的氟化氢并回流下层液相。
液相氟化反应可使用分批的方式进行,即在氟化前将全部前体加入液体中,形成前体浓度高达约10%(重量)的溶液,然后将含氟气体吹入含前体的液体中。反应还可以以半连续的方式进行,即在吹入氟气(如氟流速为约40-120ml/min、惰性气体的流速为约150-600ml/min)的同时,向反应器中连续泵入或以其它形式投入纯前体,或它在用作反应介质的合适类型的液体中的稀溶液或分散液(如以约1-3g/h的速率投入至400ml液态反应混合物中)。还可以用连续的方式进行氟化,即将前体(纯的或溶解、分散在用作反应介质的合适类型的液体中的前体)连续地泵入或以其它方式投入含有反应介质的的反应器中,同时如上所述引入含氟气体,并且未反应的氟气、氟化氢气体和惰性载气被连续地从反应器中移走,同样移走含有全氟化产物、未完全氟化的前体和惰性的液态反应介质,随后进行必要的分离以回收氟烷基醚组合物。如有必要,可循环使用未反应的氟和未完全氟化的前体。可通过加入循环使用的或新鲜的液体将反应器中的惰性液态介质的量保持在恒定的水平上。
由于氟化反应相对高的放热量,通常使用冷却液或冰浴以达到可接受的反应速率。反应完成后,用氟气吹洗反应器并移走反应器中的物料。当在氟化氢净化剂的存在下使用液相氟化技术进行氟化时,用过的净化剂可通过过滤或倾析从液态反应器物料中分离,随后蒸馏该物料以便将反应介质从粗产品中除去。当无氟化氢净化剂存在时使用液相氟化技术进行氟化时,可通过蒸馏反应产物混合物回收产品。
可用于制备本发明的ω-氢氟烷基醚的有用的代表性前体可氟化的醚酸酯是列于上面表A中的结构的烃对应物,只是端接的氢原子被酯结构中端接的-Z′(同通式IV中所定义)或-CH2OC(O)R(如反应流程图II所示)所代替且前体可含有不饱和键。
本发明的(或用于本发明的)氟醚酸的代表性例子包括上述前体即可氟化的酸酯的全氟化(即基本上所有的氢都被氟所取代)的对应物。当前体含不饱和键时,相应的氟化醚酸是饱和的。
如上所述,氟醚酸及其衍生物可用作制备ω-氢氟烷基醚的前体,并且,它们可用作例如表面活性剂。
可使用脱羧方法将上述氟醚酸或其酯(如烷基酯,如甲酯)转化成本发明的ω-氢氟烷基醚。在一种该方法中,制得一种KOH在乙二醇中的溶液,并向该溶液中加入氟醚酸或酯前体(纯的或在惰性溶剂如全氟化的液体中的溶液),所述加料最好在环境温度或室温下边搅拌边滴入。随后可缓慢地将形成的混合物加热至,例如190℃,在此期间蒸馏甲醇(来自甲酯的皂化)、水(来自酸的中和)以及脱羧产物。在这种苛刻的碱性条件下,本发明的ω-氢氟烷基醚令人惊讶地稳定。可在中和后,在例如真空中低温除去惰性溶剂(如果使用的话)。最终含有ω-氢氟烷基醚产品的馏出物可用水洗涤,用硅胶或硫酸镁干燥,随后蒸馏纯化。如有必要,ω-氢氟烷基醚产品可与高锰酸钾在丙酮中的溶液一起回流以除去容易氧化的杂质。通常,醚产品的产率较高,产品相当纯净,由或主要由要求的ω-氢氟烷基醚组成。
ω-氢氟烷基醚组合物是无毒的,能够溶解和输送氧,因此可用作血液代用品,用于治疗外伤、血管梗阻、作为辅助药物用于癌症的放疗和化疗以及作为成像造影剂。用于这种用途的组合物乳剂可通过例如下列专利描述的方法制得:Clark的美国专利3,911,138和Long的美国专利5,077,036以及公开的PCT国际申请WO93/11868(Kaufman等人)。ω-氢氟烷基醚也可作为溶剂用于清洁和干燥,可参见Flynn等人的美国专利5,125,089,Brandreth的3,903,013和Zuber的4,169,807。可向氟醚组合物中加入小量任选的组分(如表面活性剂)以赋予特别要求的性能以用于特别的场合。醚组合物还可用作冰箱或冷库的压缩机或空调中的传热剂和致冷剂,在聚氨酯泡沫绝缘体的制备中作为发泡剂或泡沫尺寸的调节剂;或作为化学灭火剂用于流动(streaming)灭火、完全溢流(totalflooding)、抑制爆炸以及inertion;以及作为高度氟化的聚醚的载体溶剂用作磁记录介质的润滑剂。
在用本发明的ω-氢氟烷基醚组合物干燥或从制品表面(如印刷线路板)上置换水分时,可使用描述在Flynn等人的美国专利5,125,978中的干燥或置换水份方法。概括地说,该方法包括使制品的表面与含有本发明的醚组合物的液体组合物(最好混有非离子型氟脂族表面活性剂)相接触。将湿的制品浸入液体组合物中并在其中搅动,置换出来的水份从液体组合物中分离出来,并将形成的无水制品从液体组合物中取出。该方法的进一步说明以及可处理的制品可参见所述美国专利5,125,978。
在将本发明的醚组合物作为传热液用于气相焊接时,可使用Hansen的美国专利5,104,034中描述的方法,简单地说,该方法包括将欲焊接的部件浸入含有本发明的醚组合物的蒸气中以熔化该焊接料。为实施这种方法,可在一个容器中使本发明的醚组合物的液体加热沸腾,使之在沸腾的液体和冷凝体(means)之间的空间中形成饱和的蒸气,将欲焊接的工件浸入该蒸气中,蒸气冷凝在工件的表面以便熔融和软熔(reflow)该焊接件,然后将该焊接了的工件从含有蒸气的空间中取出。
在将本发明的醚组合物作为发泡剂用于制造泡沫塑料(如发泡聚氨酯)时,可使用描述在Dams等人的美国专利5,210,106中的方法试剂和反应条件。为实施这种方法,在包括本发明的醚组合物、催化剂和表面活性剂的发泡剂混合物的存在下,混合有机聚异氰酸酯和具有至少两个活性氢原子的高分子化合物(如多元醇)。
将通过下列实施例进一步说明本发明,但在这些实施例中例举的具体的材料、用量以及其它条件和细节不应看作是对本发明的限制。
实施例1对从C8F17-O-C2F4CO2CH3制备C8F17-O-C2F4H
由正辛醇对丙烯腈的碱催化迈克尔加成反应,随后进行酸催化甲醇分解制得有机原料C8H17-O-C2H4CO2CH3。用氟气直接氟化甲酯生成氟化酯C8F17-O-C2F4CO2CF3。所述氟化在一个2升的、装有磁力搅拌器、进气管、有机试剂进料管以及回流冷凝器夹套的MonelTM金属反应器中进行。进气管是直径为0.3cm的管道,通至搅拌器叶片底部的下面。进料管的直径为0.15cm,与一个注射泵(syringe)相联。回流冷凝器由约6米长的两根盘绕的同轴管组成,内管直径为1.27cm,外管直径为2.54cm。来自反应器的气体在内管中被流动于两根管子的环形缝中的冷冻剂乙二醇-水所冷却。反应器加有约1.8升FreonTM 113氯氟化碳并用650ml/min流量的氮吹洗20分钟。随后改用310ml/min氟和1100ml/min氮的混合气流。约12分钟后,以13ml/h(5g/h进料速率)的速率向反应器中加入用260ml FreonTM113氯氟化碳稀释的100g C8H17-O-C2H4CO2CH3。在氟化过程中反应料液的温度保持在约16-18℃。冷凝器温度约为-22℃。有机物进料完成后,继续通入氟气流10分钟。然后用氮气吹洗反应器1小时。粗全氟化酯的FreonTM113溶液用150ml 14%BF3在甲醇中的溶液处理并强力搅拌24小时。用水洗涤混合物,用硫酸镁干燥之,蒸馏(b.p.40℃/0.2torr)后得到C8F17-O-C2F4CO2CH3(产率47%)。为进行脱羧,将39g85%KOH溶解于约300ml乙二醇中,然后在室温下边搅拌边向该KOH溶液中滴加上述氟化的甲酯。加料完成后,反应混合物的pH值为8-9。边搅拌边缓慢加热该混合物,并蒸馏脱羧产物C8F17-O-C2F4H以及甲酯皂化形成的甲醇、来自KOH的水和少量的乙二醇。当反应混合物的温度达到170℃时,停止加热。分离馏出物下层的含氟化合物相,用水洗涤并干燥之,用三块塔板的斯奈德蒸馏塔(three-plate Snyder column)进行蒸馏,主要馏份的沸点为146-150℃,得122g产品。产品试样的气相色谱和质谱(GC/MS)显示样品的纯度为94%,并确认它的结构为C8F17-O-C2F4H。
实施例2:由C8F17-O-C2F4CO2H制备C8F17-O-C2F4H
由正辛醇对丙烯腈的碱催化迈克尔加成反应,随后进行酸催化的甲醇分解制得C8H17-O-C2H4CO2CH3。用基本上相同于实施例1中所描述的氟化方法直接氟化该羧酸酯,水解后生成相应的醚酸C8F17-O-C2F4COOH。差示扫描量热法(Differential scanning calorimetry)显示多次转变,这是同质多晶现象的特点。
在3升圆底烧瓶中制备116g 85%KOH在800ml乙二醇中的溶液。将1000gC8F17-O-C2F4COOH滴入搅拌的KOH溶液中。加料完成后,另外加入10g KOH并加热混合物。脱羧后的含氟化合物产品与少量的来自酸中和的水一起蒸馏。分离馏出物的下层含氟化合物相,用盐水洗涤并用硫酸钠干燥之,并如实施例1那样蒸馏,得到817g C8F17-O-C2F4H。
实施例3:由C7F15-O-C2F4COOCH3制备C7F15-O-C2F4H
由正庚醇对丙烯腈的碱催化迈克尔加成反应,随后进行酸催化的甲醇分解制得C7H15-O-C2H4CO2CH3。将550g相应的甲酯C7F15-O-C2F4CO2CH3(以基本相同于实施例1的氟化和甲醇分解方法制得)滴入166.6g KOH在约880ml乙二醇中的溶液中。用基本相同于实施例1的方法回收含氟化合物产品(440g)。该产品通过六块塔板的斯奈德蒸馏塔蒸馏并收集沸点为130-31℃的馏份(340g)。将该馏份与8.5g高锰酸钾和约350g丙酮相混合并加热回流。4小时后,另外加入5g高锰酸钾并将形成的混合物再加热3小时。过滤该化合物,滤饼用丙酮洗涤,向滤液中加入水使之形成下层含氟化合物相,该层依次用水、浓硫酸、水洗涤,然后经二氧化硅过滤。1H NMR和19F NMR确认反应产品具有要求的C7F15-O-C2F4H结构。试样的气-液色谱表明它的纯度为98.7%。
实施例4:由C6F13-O-C2F4OCF2COOCH3制备C6F13-O-C2F4-O-CF2H
可用乙酰氯将己氧基乙氧基乙醇乙酰化,制得原料C6H13-O-C2H4-O-C2H4-O-COCH 3 。随后用基本相同于实施例1中的氟化和甲醇分解方法将该乙酸酯转化成C6F13-O-C2F4-O-CF2CO2CH3。将548g这种含氟化合物与144.2g KOH在600g乙二醇中的溶液相混合。将所形成的混合物加热,蒸馏,并如同实施例1回收产品C6F13-O-C2F4-O-CF2H。总产量为433g。在大气压力下通过12英寸(30.5cm)多孔板蒸馏塔再次蒸馏该产品(b.p.131℃)。由1H NMR和19F NMR确认反应产品的结构如同C6F13-O-C2F4-OCF2H的结构。GC/MS表明其纯度为99.6%。
实施例5:从C8F17-O-CF2CO2CH3制备C8F17-O-CF2H
使用三氟乙酸酐酰化辛氧基乙醇制得C8H17-O-C2H4-O-(CO)CF3。用基本相同于实施例1中的氟化方法直接氟化100g该三氟乙酸酯,用三氟化硼在甲醇中的溶液骤冷(quench)氟化产物,生成C8F17-O-CF2CO2CH3粗产品,并进一步蒸馏纯化之(b.p.92-97℃/20torr)。
使用10.8g KOH在乙二醇中的溶液对58g后面形成的甲酯进行脱羧,用如实施例1的方法回收产物C8F17-O-CF2H。产物的结构通过19F NMR确认。GLC显示产物的纯度为99.6%,b.p.134-136℃。
实施例6:由C4F9-O-C2F4CO2CH3制备C4F9-O-C2F4H
由正丁醇对丙烯腈的碱催化的迈克尔加成反应,随后进行酸催化的甲醇分解制得C4H9-O-C2H4CO2CH3甲酯。随后使用基本相同于实施例1中的氟化和甲醇分解方法将该甲酯转化成相应的氟化甲酯C4F9-O-C2F4CO2CH3。
边搅拌边将1160g后面形成的甲酯滴入3103g乙二醇和129.5g NaOH中。蒸馏该产物(b.p.83℃),用高锰酸钾/丙酮处理之,并如实施例3中的步骤操作。纯化合物C4F9-O-C2F4H的结构通过1H和19F NMR和GC/MS确认。
通过测量经挑选的烃溶剂在试样中的溶解度评价这种化合物的试样在精密清洗方面的应用。高的溶解度意味着作为清洗剂相对于全氟化碳溶剂的性能有所改进。发现下列烃溶剂可溶解高达50%(重量)的醚氢化物:己烷、庚烷、甲苯、丙酮、2-丁酮、4-甲基-2-戊酮、乙酸乙酯、甲醇、乙醇、异丙醇、二甲基甲酰胺、反-1,2-二氯乙烯和异丙醚。发现邻二甲苯可溶解19重量%。氯仿可溶解45重量%。乙二醇可溶解小于15重量%并且轻质烃油可溶解小于0.05重量%。
还对该样品进行无渍(spot-free)干燥应用方面的评价(参见Flynn等人的美国专利5,125,978)。将0.2重量%C4F9-O-C2F4OCF2CONHC2H4OH溶解在C4F9-O-C2F4H中制得水置换组合物。在一个超声波浴中将该溶液加热至45℃。使用美国专利5,125,978中描述的方法,将玻璃和不锈钢的取样管用水湿润,随后将其浸入超声波搅拌的该溶液中。所有的水分在60秒内被置换。
还对该化合物的试样作为洗涤剂在助溶剂洗涤方面的应用(可参见例如国际专利申请WO92/22678(PetrofermInc.))。发现在两相清洗应用中使用有机酯如癸酸甲酯作为溶剂,全氟己烷作为载液和漂洗剂是有用的。将癸酸甲酯和C4F9-O-C2F4H各自放置在不同的容器中并在超声波浴中加热至50℃。用0.0831g轻质烃油污染50×25×1.5mm的铝取样管。先将污染的取样管浸入癸酸甲酯中60秒,随后浸入C4F9-O-C2F4H中约60秒。C4F9-O-C2F4H将取样管中的油和癸酸甲酯100%(由重量差测得)地清洗掉。在相同条件下,全氟己烷仅除掉98.5%的油和癸酸甲酯。表明C4F9-O-C2F4H是比全氟己烷更有效的载液和漂洗剂。
实施例7:由CH3OC(O)C2F4-O-C2F4-O-C2F4C(O)OCH3制备HCF2CF2-O-CF2CF2-O-CF2CF2H
由乙二醇对丙烯腈的碱催化迈克尔加成反应,随后进行酸催化的甲醇分解制得原料CH3OC(O)C2H4-O-C2H4-O-C2H4C(O)OCH3。随后使用基本相同于实施例1中的方法使该原料氟化和甲醇分解,生成CH3OC(O)C2F4-O-C2F4-O-C2F4C(O)OCH3。
将1136g该氟化的酯加入至305.6g KOH在2665g乙二醇中的混合物中。使用基本相同于实施例1中的方法脱羧,但在相分离后不用水洗涤蒸馏粗产物。馏出物中残存的甲醇可依次用浓硫酸和两次水洗涤除去。得到要求的氢化醚产物695g,沸点为93-94℃。
实施例8:由C4F9-O-(CF2)5-COOH制备C4F9-O-(CF2)5H
将118.2g(1.0mol)1,6-己二醇,4.4g AdogenTM 464季铵盐,80.0g(2.0mol)NaOH和250ml四氢呋喃搅拌回流。加入80ml水使之较好地混合。20分钟以后,在0.5小时内加入137g(1.0mol)溴丁烷,并搅拌回流过夜。反应混合物用1升水骤冷,将上层与下层的醚萃取液合并,用硫酸镁干燥,并在旋转蒸发器中分离(stripped)之。向得到的分离层(151g)在100ml CHCl3中的溶液中滴入150ml乙酰氯,随后加热回流4小时,除去溶剂后得到225.4g液体。蒸馏该液体得到176.0g(b.100-104℃/0.9torr)馏出液。GLC表明其中56%是要求的乙酸6-丁氧基己酯,其余是二乙酸己二醇酯和二丁氧基己烷。基本按照实施例1的方法氟化100g这种混合物。用30ml 10重量%的硫酸水溶液处理生成的氟化产物并在室温下振摇2小时,滤出固态氟化己二酸,分离F-113层,用硫酸镁干燥之,蒸馏,生成的主要馏份是73.4g,b.116℃/20乇,96%纯度的C4F9-O-(CF2)5-COOH。将该产物加至10.0g(0.25mol)NaOH和100ml乙二醇的溶液中,并将混合物加热至120℃,将氟化的杂质C4F9-O-(CF2)6-O-C4F9收集在Dean-Stark阱中。继续加热,开始放出气体,将液体C4F9-O-(CF2)5-H(44.6g)收集在阱中,并在170℃结束。收集到的液体用硅胶干燥并在4英寸(10.2cm)Uigreux蒸馏塔中蒸馏,生成38.8g,b.p.131℃。F-NMR确认其是高纯度的C4F9-O-(CF2)5-H。
实施例9:由C5F11-O-(CF2)5-COOH制备C5F11-O-(CF2)5-H
使用相同于实施例8的方法,用溴正戊烷烷基化己二醇,将产物乙酰化,并蒸馏粗乙酸酯C5F11-O-(CF2)6-OCOCH3(b.125℃/3torr),基本按实施例1中的氟化方法氟化馏出物。将氟化的酯水解成相应的酸。将该氟化的酸(C5F11-O-(CF2)5-COOH)用NaOH脱羧,生成829g产物。用水洗涤该产物,用硫酸镁干燥之,并蒸馏,生成555g C5F11-O-(CF2)5-H,b.p.145-149℃。
实施例10:由C8F17-O-(CF2)5-COOH制备C8F17-O-(CF2)5-H
使用相同于实施例8的方法,用溴正辛烷烷基化己二醇,将产物乙酰化,生成的C8H17-O-(CH2)6-OCOCH3如实施例8所述直接氟化和水解成C8F17-O-(CF2)5-COOH,并在全氟己烷中重结晶之。重结晶后的酸(37.5g)与4.0g NaOH和100ml乙二醇相混合并加热至185℃。产物用水洗涤,蒸馏27.9g残余物,生成纯C8H17-O-(CF2)5H,微量测定沸点为195℃。
实施例11:由C4F9-O-CF2C(CF3)2-CF2Cl制备C4F9-O-CF2C(CF3)2-CF2H
基本按实施例8的方法使用溴正丁烷烷基化2,2-二甲基-1,3-丙二醇,生成单烷基化粗产物,用SOCl2处理该粗产物,生成C4H9-O-CH2C(CH3)2-CH2Cl,b.80-90℃/20-30torr。随后如实施例1氟化该产物,生成C4F9-O-CF2C(CF3)2-CF2Cl。将20.0g这种氯化物与5.3g以水湿润的阮内镍和50ml以氨饱和的甲醇相混合。将该混合物在Parr氢化装置上,在约25℃振摇3天,21kPa(3psig)的氢压降大部分在第一天发生,通过过滤回收产物并在水中骤冷,去掉机械损耗后得到7.9g产物。19F-NMR确认产物是C4F9-O-CF2C(CF3)2-CF2H。按比例放大即100g生成47g产物,蒸馏的沸点为135℃。
实施例12:由Cl(CF2)4-O-(CF2)4Cl制备H(CF2)4-O-(CF2)4H
如实施例1氟化Cl(CH2)4-O-(CH2)4Cl生成Cl(CF2)4-O-(CF2)4Cl。将30.3gCl(CF2)4-O-(CF2)4Cl,11.3g新鲜的以水湿润的阮内镍以及200ml甲醇的混合物用氨吹洗数分钟,并在约25℃,在Parr氢化装置中压入310kPa(45psig)氢。17小时后,压力降至255kPa(37psig)并且混合物变成酸性,观看到玻璃腐蚀现象。加入更多的氨并继续进行还原,压力再次下降62kPa (9psig)。过滤反应产物并在水中骤冷之,生成15.4g下相,GLC确认68%纯度的产品是H(CF2)4-O-(CF2)4H,蒸馏后得到27.0g产物,b.121-124℃,87%纯度。
实施例13:由Cl(CF2)4-O-(CF2)4Cl制备H(CF2)4-O-(CF2)4H和Cl(CF2)4-O-(CF2)4H
将50.0g Cl(CF2)4-O-(CF2)4Cl和30g锌在丁醇中的混合物在110℃搅拌2天。生成的反应产物的试样的GLC表明部分发生了转化。再加入21g锌并再将混合物加热1天。过滤并将生成的物料在水中骤冷,得到27.0g无色液体。该产物是35%H(CF2)4-O-(CF2)4H,42%一氢化物以及16%未还原的二氯化物。
实施例14:由C6F13-O-C2F4CO2H制备C6F13-O-CF2CF2H
由己醇对丙烯腈的迈克尔加成反应,随后用甲醇进行酸催化酯化制得原料C6H13-O-C2H4CO2CH3。随后氟化和水解得到的酯,生成C6F13-O-C2F4CO2H。
将500g酸C6F13-O-C2F4CO2H缓慢地加至68.7g KOH在700g乙二醇中的溶液中。在加料结束时,向均匀的溶液中加入另外5g KOH使之pH达到9。如实施例1进行脱羧并随后进行蒸馏,生成327g产物,b.104-107℃。使用基本相同于实施例3中的方法用高锰酸钾处理该产物。GC/MS,19F-NMR,1H-NMR和IR确认产物的结构是C6F13-O-CF2CF2H。
实施例15:由C6F13-O-CF2CO2CH3制备C6F13-O-CF2H
使用基本相同于实施例1中的方法将乙二醇单己基醚乙酰化制得的原料C6H13-O-C2H4OCOCH3氟化和脱羧,生成146g C6F13-O-CF2H(b.92-96℃)。
实施例16:由CF3CF(CF3)CF2-O-CF2CO2CH3制备CF3CF(CF3)CF2-O-CF2H
将乙二醇单异丁基醚乙酰化制得原料CH3CH(CH3)CH2-O-CH2CH2OC(O)CH3,随后基本按实施例1的氟化和甲醇分解方法转化,生成甲酯CF3CF(CF3)CF2-O-CF2CO2CH3 b.118-120℃。
将149g甲酯快速滴至28.6g KOH在700g乙二醇中的溶液中,脱羧后,经蒸馏,得到70g产物,b.45-47℃,GLC测得纯度为99%。通过GC/MS,1H-NMR和19F-NMR分析确定其结构是CF3CF(CF3)CF2-O-CF2H。
实施例17:由C4F9-O-(CF2)4-O-(CF2)3CO2CH3制备C4F9-O-(CF2)4-O-(CF2)3H
基本按照实施例1的方法将原料C4H9-O-(CH2)4-O-(CH2)3CH2OCOCH3直接氟化和甲醇分解成C4F9-O-(CF2)4-O-(CF2)3CO2CH3。将56g该产物快速加至5.6g KOH在250ml乙二醇中的溶液中。进行脱羧并分离产物相,用盐水洗涤一次,蒸馏后得到36.6g GLC纯度为100%的产物(b.p.155-158℃)。GC/MS,1H-NMR和19F-NMR分析确定该产物是C4F9-O-(CF2)4-O-(CF2)3H。
实施例18:由(C2F5)2CFCF2-O-(CF2)2-COOCH3制备(C2F5)2CFCF2-O-(CF2)2H
基本按照实施例1中的方法将由2-乙基丁醇对丙烯腈进行迈克尔加成反应,随后用甲醇进行酸催化的酯化制得的原料(C2H5)2CHCH2-O-(CH2)2-COOCH3氟化和甲醇分解,生成(C2F5)2CFCF2-O-(CF2)2-COOCH3,b.p.159℃,按甲酯原料计算直接氟化的产率为88%。
基本按实施例1的方法进行脱羧,得到的产物在108-110℃蒸馏,生成145g产物。经IR分析证实其具有(C2F5)2CFCF2-O-(CF2)2H的结构。
实施例19:由c-C6F11CF2-O-(CF2)2-COOCH3制备c-C6F11CF2-O-(CF2)2H
通过环己基甲醇与丙烯腈反应,随后用甲醇进行酸催化的酯化制得的原料c-C6H11CH2-O-(CH2)2-COOCH3,然后基本按照实施例1的方法氟化该产物并用BF3在甲醇中进行甲醇分解,生成65%(按氟化物计)的c-C6F11CF2-O-(CF2)2-COOCH3。
将224g得到的氟化酯加入至28.2g 85%KOH和466g乙二醇保持60℃的溶液中。然后将形成的混合物加热至100℃并加入5g 45重量%的KOH水溶液将其pH值调节至大于7。通过蒸馏生成的混合物进行脱羧。分离出馏出物的下层含氟化合物相,用等体积的水洗涤之,并在123-126℃蒸馏,得到155g产物(99.7%纯度)。产物用高锰酸钾在丙酮中进行处理,得到c-C6F11CF2-O-(CF2)2-H。
实施例20:由C4F9-O-(CF2)2-O-C3F6COOCH3制备C4F9-O-(CF2)2-O-C3F6H
基本按照实施例1的方法氟化并甲醇分解C4H9-O-(CH2)2-O-C4H8OCOCH3。将419g产物C4F9-O-(CF2)2-O-C3F6COOCH3快速滴入49.4g KOH在800g乙二醇中的混合物中。随后将形成的混合物缓慢地加热至最终的烧瓶温度190℃。在加热过程中,酯皂化形成的甲醇、水和C4F9-O-(CF2)2-O-C3F6H从反应混合物中蒸馏出来,向馏出物中加入水并分离下层含氟化合物相(355g),蒸馏(b.120-122℃)后得到308g C4F9-O-(CF2)2-O-C3F6H(82%产率)。
实施例21:由C6F13-O-(CF2)4-COOCH3制备C6F13-O-(CF2)4-H
用溴己烷单烷基化1,5-戊二醇,随后用乙酰氯进行乙酰化制得原料C6H13-O-(CH2)5-OCOCH3。基本按照实施例1的方法氟化并甲醇分解该化合物,生成C6F13-O-(CF2)4-COOCH3,b.p.100℃/13torr。通过加热200g该酯在250ml乙二醇中的溶液与30g KOH对该酯进行脱羧,直至蒸馏出氢化物产物。得到的液体用水洗涤,以硫酸镁干燥,得到128g 82%纯度的C6F13-O-(CF2)4-H。使用12块塔板的玻璃填料塔进一步蒸馏纯化该产物(b.p.146℃),用19F确认其结构。
实施例22:由C6F13-O-(CF2)3-COO-K+制备C6F13-O-(CF2)3H
用溴己烷单烷基化1,4-丁二醇,随后用乙酸酐进行乙酰化制得原料C6H13-O-(CH2)4-OCOCH3。基本按照实施例1的方法氟化并甲醇分解该化合物,生成C6F13-O-(CF2)3-COOCH3.使用过量的KOH皂化该甲酯,随后在真空烘箱中干燥之,生成钾盐。将575g钾盐在250ml乙二醇中边搅拌边加热,蒸馏回收氢化物产物(b.p.129℃)。用19F NMR确认其结构。
实施例23:由C5F11-O-(CF2)4-COO-Na+制备C5F11-O-(CF2)4-H
用溴戊烷单烷基化1,5-戊二醇,随后用乙酰氯进行乙酰化制得原料C5H11-O-(CH2)5-OCOCH3。基本按照实施例1的方法氟化并甲醇分解该化合物,生成C5F11-O-(CF2)4-COOCH3。使用过量的NaOH皂化甲酯,并基本按照实施例22进行脱羧和蒸馏,蒸馏是通过12块塔板的玻璃填料塔进行的,生成C5H11-O-(CF2)4-H。b.p.125℃。其结构通过19F NMR确认。
实施例24:由C4F9-O-(CF2)3-COO-Na+制备C4F9-O-(CF2)3-H
用溴丁烷单烷基化1,4-丁二醇,随后用乙酰氯进行乙酰化制得原料C4H9-O-(CH2)4-OCOCH3。基本按照实施例1的方法氟化并甲醇分解该化合物,生成C4F9-O-(CF2)3-COOCH3。使用如实施例23中的方法对该甲酯进行皂化、脱羧并回收粗的氢化物产物。然后进一步蒸馏得到纯C4F9-O-(CF2)3-H,b.p.90℃,其结构通过19F NMR确认。
实施例25:评价全氟醚羧酸的表面活性
将酸转化成相应的铵盐后,使用DeNuoy张力计测定本发明的新型全氟醚羧酸的表面活性。酸通过直接氟化其烃前体,随后水解制得。用过量的氨水处理所述的酸,然后冷冻干燥制得铵盐。结果以达因/厘米为单位列于表C中, 所列的是铵盐的母体酸(来自表B):
表C
来自表B的母体酸 | 酸的熔点(℃) | 表面张力(达因/厘米) | |||
铵盐的浓度 | |||||
50ppm | 100ppm | 500ppm | 1000ppm | ||
18 | -1 | 24 | 21 | 18 | |
2 | 21 | 24 | |||
4 | 63 | 59 | 39 | 29 | |
5 | 33 | 33 | 26 | 22 | |
7 | 19 | 37 | 26 | 19 | 17 |
6 | 31 | 23 | 18 | 17 | |
8 | 33 | 31 | 26 | 24 | |
9 | 38 | 24 | 20 | 18 |
来自表B的母体酸 | 酸的熔点(℃) | 表面张力(达因/厘米) | |||
铵盐的浓度 | |||||
50ppm | 100ppm | 500ppm | 1000ppm | ||
10 | 38 | 35 | 24 | 19 | |
27 | -39 | 67 | 63 | 50 | 43 |
29 | -9 | 49 | 43 | 29 | 23 |
35 | 18 | 18 | 16 | 16 | |
25 | -9 | 19 | 15 | 15 | 14 |
30 | 46 | 43 | 32 | 24 | |
31 | 69 | 68 | 48 | 52 | |
32 | 63 | 54 | 31 | 21 | |
33 | 28 | 21 | 15 | ||
40 | 48 | 41 | 23 | 19 | |
11 | 49,59 | 18 | 15 | 15 | |
14 | 39 | 31 | 18 | ||
15 | 16,-27 | 30 | 17 | 17 | |
16 | 24 | 19 | 18 | 17 | |
17 | 90 | 14 | 15 | 15 |
实施例26:对醚作为灭火剂的评价
根据美国国家防火协会2001防火标准(National Fire Protection Association2001 Fire Protection Standard),使用经改进的燃烧杯(cup burner)处理液态的化合物,对本发明的ω-氢氟烷基醚化合物作为灭火剂进行评价。结果(列于表D中)表明该类化合物可能是一类有效的灭火剂、防爆剂,以及易燃气体的钝化剂。
表D
试剂 | 防火浓度(体积%) |
C4F9OC2F4H | 5.6 |
HC3F6OC3F6H | 5.7 |
实施例27:制备发泡聚氨酯
根据Dams等人的美国专利5,210,106披露的方法,对本发明ω-氢氟烷基醚作为泡沫的发泡剂进行评价。组分A含有15.0重量份PAPITM 27,即一种购自DowChemical的异氰酸酯当量为134.0的二苯基二异氰酸亚甲基酯。泡沫组分B含有10.5重量份(pbw)VoranolTM 360,即一种购自Dow Chemical、羟基数为360的聚醚聚醇;0.26pbw水;0.26pbw低聚的含氟化合物表面活性剂(如美国专利3,787,351的实施例1所述);0.13pbw PolycatTM8,即一种购自Air Products的N,N-二甲基环己胺催化剂;1.87pbw C4F9OCF2CF2H作为发泡剂。
混合B组分的成分,形成乳液,随后将其与组分A相混合并在2500rpm下搅拌10秒钟。泡沫的膏化期约10秒钟。上升时间和消粘时间分别为约2和3分钟。形成的聚氨酯泡沫具刚性,具有均匀分布的很细的闭孔。
实施例28:制备(CF3)3COC2F4OCF2OCF2CO2CH3
用叔丁氧基乙醇烷基化二氯甲烷制得前体(t-C4H9OC2H4O)2CH2。基本按照实施例1的方法氟化和甲醇分解该前体,生成(CF3)3COC2F4OCF2OCF2CO2CH3。在18torr沸点为80-82℃,其结构通过19F-NMR确认。
实施例29:由C8F17OCF2OC3F6CO2CH3制备C8F17OCF2OC3F6H
用辛基氯甲基醚单烷基化丁二醇制得前体C8H17OCH2OC4H8OH。该前体首先使用乙酰氯在含有三乙胺的二氯甲烷中进行乙酰化,然后氟化,通过硫酸水溶液的处理使部分全氟化粗产品水解,接着蒸馏,得到羧酸C8F17OCF2OC3F6CO2H,在1.1torr沸点为100-106℃。差示扫描量热法显示酸的Tg为-97.0℃,几个晶体放热峰(several crystalline exotherms)为-77.4、-61.5、-37.7℃并有熔距宽的(broad)熔点-9.0℃。
基本按照实施例1中的方法甲醇分解另一部分全氟化粗产品,生成C8F17OCF2OC3F6CO2CH3,在25torr的沸点为124-130℃。然后使用实施例1的方法使得到的甲酯脱羧,得到C8F17OCF2OC3F6H,沸点为178-183℃。使用19F-NMR确认该氢化物和前体氟化酯的结构。
实施例30:制备C8F17O(C2F4O)2CF2CO2H
使用溴辛烷单烷基化三甘醇,随后乙酰化制得前体。如实施例1氟化该前体,用硫酸水溶液处理使之水解并蒸馏,产物C8F17O(C2F4O)2CF2CO2H在1.4torr的沸点为105-110℃,熔点为24℃。
实施例31:由CH3O(CO)C3F6OC3F6CO2CH3制备HC3F6OC3F6H
用乙酰氯乙酰化聚1,4-丁二醇(平均分子量250)得到原料二乙酸酯CH3C(O)OC4H8O(C4H8O)nC4H8OCOCH3。随后按照基本相同于实施例1中描述的氟化和甲醇分解方法将该二乙酸酯转化成CH3OC(O)C3F6O(C4F8O)nC3F6COOCH3。将1400g该二酯的混合物在10块塔板的玻璃填料塔中蒸馏以分离CH3OC(O)C3F6OC3F6CO2CH3。
将278g分离得到的含氟化合物与72gKOH在250ml乙二醇中的混合物相混合。将得到的混合物加热,蒸馏,基本按照实施例1中的方法回收产物HC3F6OC3F6H(b.p.84℃)。用19F NMR确认其结构。
实施例32:制备n-C12F25OC2F4OC2F4OCF2COOH
使用溴正十二烷单烷基化三甘醇制得前体n-C12H25O(C2H4O)3H。乙酰化后,基本按照实施例1中的方法将产物氟化,并浓缩氟化的产物,然后用55.0g NaOH在300ml水中的溶液处理之。在蒸汽浴中加热5小时后,用过量的50重量%的硫酸水溶液酸化该产物,随后用在蒸汽浴中加热至约60℃的FluorinertTM FC-75全氟化的液体(一种C8全氟化化合物的混合物,b.p.103℃)萃取。蒸馏后得到纯的n-C12F25OC2F4OC2F4OCF2COOH(DSC测得的Tg=-62.7℃,Tm=69.2℃)
基本按照实施例1中的方法将原料2-(3,4-二甲氧基苯基)乙酸甲酯氟化,水解后得到全氟化2-(3,4-二甲氧基环己基)乙酸。基本按实施例1的方法脱羧后得到全氟化醚氢化物。
用丙二酸缩合4-乙氧基苯甲醛,随后进行酯化制得原料3-(4-乙氧基苯基)-反-2-丙烯酸甲酯。基本按照实施例1中的方法对该甲酯进行氟化、甲醇分解和脱羧,生成全氟化醚氢化物。
用3-氧代戊二酸二甲酯缩合2,2-二乙基丙二醇制得原料。基本如实施例1对该二甲酯进行氟化、甲醇分解成二酯,随后脱羧生成全氟化醚二氢化物。
用碳酸亚乙酯与2,6-二甲基酚反应随后用乙酰氯乙酰化制备原料。基本如实施例1对该乙酸酯进行氟化、甲醇分解并脱羧,生成全氟化醚氢化物(b.p.132℃)。
用亚硫酰二氯处理实施例36中的2-(2,6-二甲基苯氧基)乙醇制得原料。基本按实施例1的方法氟化该原料,随后基本按实施例12中的方法用阮内镍还原该氯化物。制得全氟化的醚氢化物。
由β-萘酚对碳酸亚乙酯的加成反应,随后用乙酰氯进行乙酰化制得原料。基本按照实施例1中的方法对该乙酸酯进行氟化、甲醇分解以及脱羧,生成全氟化的醚氢化物(b.p.171℃)。
实施例39:由C5H11OCH2C(CH3)2CH2Cl制备C5F11OCF2C(CF3)2CF2H
基本按照实施例11中的方法制得原料。基本按实施例1中的方法氟化该氯化醚,随后基本按实施例11中的方法用阮内镍还原该氯化物,生成全氟化的醚氢化物(b.p.148℃)。
实施例40:由(C4H9O)2CHCH2Cl制备(C4F9O)2CFCF2H
用正丁醇对2-氯乙醛的加成反应制得原料,基本按实施例1中的方法氟化之,随后基本按实施例11中的方法用阮内镍还原该氯化物,生成全氟化醚氢化物。
实施例41:由CH3O(CH2)10OAc制备CF3O(CF2)9H
用硫酸二甲酯单烷基化1,1O-癸二醇、随后用乙酰氯进行乙酰化制得原料。基本按实施例1中的方法对该乙酸酯进行氟化、水解和脱羧,生成全氟化醚氢化物。
实施例42:由C9H19OC2H4OAc制备C9F19OCF2H
用溴正壬烷单烷基化乙二醇,然后用乙酰氯乙酰化制备原料。基本按实施例1中的方法对该乙酸酯进行氟化、水解和脱羧,生成全氟化醚氢化物(b.p.155℃)。
实施例43:由(iso-C3H7)2CHOC2H4CO2CH3制备(iso-C3F7)2CFOC2F4H
由2,4-二甲基-3-戊醇对丙烯腈的迈克尔加成反应,随后甲醇分解成甲酯制得原料。基本按实施例1中的方法对该酯进行氟化、水解和脱羧,生成全氟化醚氢化物。
实施例44:由
制备
用氯乙酸甲酯烷基化4-乙基酚制得原料。基本按实施例1中的方法对该酯进行氟化、水解和脱羧,生成全氟化醚氢化物(b.p.131℃)。
实施例45:比较大气寿命(atmospheric lifetime)和沸点
根据Y.Tang,Atmospheric Fate of Various Fluorocarbons,M.S.Thesis,Massachusetts Institute of Technology(1993)中描述的方法计算各种试样化合物的大气寿命。如下表所示,在醚氧原子和端氢原子之间具有两个或更多的碳原子的醚氢化物的大气寿命明显地低于在醚氧原子和端氢原子之间仅具有一个碳原子的醚氢化物的大气寿命。由于本发明化合物具有较短的大气寿命,使得该类化合物更为环境所接受。
化合物 大气寿命(年)
C6F13OC2F4OCF2H >170
C4F9OC2F4OCF2H >170
C8F17OCF2CF2H 80
另外,如下表所示,在醚氧原子和端氢原子之间具有两个或更多的碳原子的醚氢化物的沸点比类似的非醚化合物低,并且沸点明显地低于在醚氧原子和端氢原子之间仅具有一个碳原子的类似的醚氢化物。本发明化合物的这种意外的低沸点使得该类化合物能用于处理涉及温度敏感的作用物如塑料的工艺。(例如,在蒸气清洗中,作用物在沸腾液体的冷凝的蒸气中进行清洗;在冷凝加热(condensation heating)中,通过将作用物浸入沸腾的液体中进行加热)。在这类应用中,最好使用低沸点的液体以避免损伤作用物。同时,还了解可通过选择有较少碳原子的化合物来降低沸点,从而可在出现对其它性能(如溶解度)的负面影响的同时将沸点降低25℃或更多。
在不偏离本发明的范围和精神的情况下,对本领域中的一般技术人员来说,本发明的各种改进和变化是显而易见的。
Claims (12)
2.一类通常是液态的ω-氢氟烷基醚化合物,由下列通式表示:
其中:
H是伯氢原子;
n是0-7的整数;
Rf、Rf′和Rf_分别选自直链或支链的,未取代的全氟亚烷基;直链或支链的全氟烷基或全氟环烷基取代的全氟亚烷基;以及直链或支链的、被含醚氧原子的基团取代的全氟亚烷基;
Rf具有至少4个链碳原子,Rf′和Rf_别具有1个或大于1个链碳原子;
附加条件是:当n是0时,Rf是全氟环烷基取代的全氟亚烷基。
3.一种制备如权利要求1所述的ω-氢氟烷基醚化合物的方法,包括将相应的前体氟烷基醚羧酸,所述羧酸的可水解的衍生物或可水解的前体脱羧成所述羧酸或所述衍生物,所述脱羧是将所述前体羧酸或酯与无机碱在质子性溶剂中的溶液接触,并加热反应混合物而完成的。
4.一种从表面置换水的方法,包括使该表面与含有通常是液态的ω-氢氟烷基醚化合物的液体组合物相接触,所述化合物具有饱和的全氟脂肪碳链,该碳链间隔有一个或多个醚氧原子,在链的一端(近端)的碳原子是二氟甲基的碳原子,该碳原子与另一个链碳原子或所述醚氧原子相键合,在该链的另一端(远端)的碳原子是该远端基团的一部分,该远端基团选自二氟甲基,二氟氯甲基,直链全氟触,并加热反应混合物而完成的。
4.一种从表面上置换水的方法,包括将该表面与含有如权利要求1中所述的ω-氢氟烷基醚化合物的液态组合物相接触。
5.一种蒸气相焊接的方法,包括将欲焊接的部件浸入或封入氟化液体蒸气内以熔化该焊接体。随后将该部件从蒸气内取出,其特征在于作为氟化液体使用的组合物至少包括一种如权利要求1中所述的ω-氢氟烷基醚化合物。
6.一种制造发泡塑料的方法,包括:
在1)至少包括一种如权利要求1中所述的ω-氢氟烷基醚化合物的发泡剂混合物;
2)一种催化剂;
3)一种表面活性剂;
的存在下,混合有机聚异氰酸酯和具有至少两个活性氢原子的高分子化合物。
7.一种制品去污的方法,包括将该制品与由至少一种如权利要求1中所述的ω-氢氟烷基醚化合物组成的组合物相接触。
8.一种灭火的方法,包括将至少含有一种如权利要求1中所述的ω-氢氟烷基醚化合物的组合物施加至火焰上。
9.一种将-CF2Cl基团转化成-CF2H基团的方法,包括将至少一种含有至少一个-CF2Cl基团的化合物与氢气相接触,所述接触是在低于约200℃的温度下,在碱溶液和至少一种催化量的金属或载体上的金属的存在下进行的,所述金属选自镍、钯和铂。
10.一种由下式表示的化合物:
Rfs-O-(CF2)b-Z
其中,Rfs是直链的或支链的、具有1-18个碳原子的全氟烷基;
b是至少为3的整数;
Z选自-COOH、-COOMI/V、-COONH4、-COOR、-CH2OH、-COF、-COCl、-COR、-CONRR、-CH2NH2、-CH2NCO、-CN、-CH2OSO2R、-CH2OCOR、-CH2OCOCR=CH2、-CONH(CH2)mSi(OR)3和-CH2O(CH2)mSi(OR)3,其中M是铵基或化合价“V”是1-4的金属原子,每个R分别选自具有1-14个碳原子的烷基、具有1-14个碳原子的氟烷基、具有6-10个环碳原子的芳基和含有杂原子的具有1-14个碳原子的烷基、含杂原子的具有1-14个碳原子的氟烷基、含杂原子的具有6-10个环碳原子的芳基,m是1-11的整数。
11.一种由下式表示的化合物:
Rft-(O-Rft′)c-O-(CF2)d-Z
其中,Rft是直链或支链的具有1-18个碳原子的全氟烷基;
Rft′是直链或支链的具有1-11个碳原子的全氟亚烷基;
c是至少为1的整数;
d是至少为3的整数;
Z选自-COOH、-COOMI/V、-COONH4、-COOR、-CH2OH、-COF、-COCl、-COR、-CONRR、-CH2NH2、-CH2NCO、-CN、-CH2OSO2R、-CH2OCOR、-CH2OCOCR=CH2、-CONH(CH2)mSi(OR)3和-CH2O(CH2)mSi(OR)3,其中M是铵基或化合价“V”是1-4的金属原子,每个R分别选自具有1-14个碳原子的烷基、具有1-14个碳原子的氟烷基、具有6-10个环碳原子的芳基和含有杂原子的具有1-14个碳原子的烷基、含杂原子的具有1-14个碳原子的氟烷基、含杂原子的具有6-10个环碳原子的芳基,m是1-11的整数。
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US08/246,962 US5476974A (en) | 1994-05-20 | 1994-05-20 | Omega-hydrofluoroalkyl ethers, precursor carboxylic acids and derivatives thereof, and their preparation and application |
US08/246,962 | 1994-05-20 | ||
US08/440,450 US5658962A (en) | 1994-05-20 | 1995-05-12 | Omega-hydrofluoroalkyl ethers, precursor carboxylic acids and derivatives thereof, and their preparation and application |
US08/440,450 | 1995-05-12 |
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JP (3) | JP3590067B2 (zh) |
CN (1) | CN1110473C (zh) |
CA (1) | CA2190116A1 (zh) |
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-
1995
- 1995-05-12 US US08/440,450 patent/US5658962A/en not_active Expired - Lifetime
- 1995-05-15 EP EP95919208A patent/EP0760809B1/en not_active Revoked
- 1995-05-15 CA CA002190116A patent/CA2190116A1/en not_active Abandoned
- 1995-05-15 DE DE69527527T patent/DE69527527T2/de not_active Revoked
- 1995-05-15 EP EP01120757A patent/EP1170275A3/en not_active Ceased
- 1995-05-15 CN CN95193106A patent/CN1110473C/zh not_active Expired - Fee Related
- 1995-05-15 JP JP53036995A patent/JP3590067B2/ja not_active Expired - Fee Related
- 1995-05-15 RU RU96124387/04A patent/RU2177934C2/ru not_active IP Right Cessation
- 1995-05-15 WO PCT/US1995/006110 patent/WO1995032174A1/en active IP Right Grant
-
1997
- 1997-06-24 US US08/881,347 patent/US6204299B1/en not_active Expired - Fee Related
-
1998
- 1998-09-11 US US09/151,857 patent/US6024176A/en not_active Expired - Fee Related
-
1999
- 1999-12-02 US US09/452,711 patent/US6214253B1/en not_active Expired - Lifetime
-
2000
- 2000-08-17 US US09/641,192 patent/US6361713B1/en not_active Expired - Fee Related
-
2001
- 2001-02-20 US US09/789,788 patent/US6491983B2/en not_active Expired - Fee Related
-
2002
- 2002-09-12 US US10/241,901 patent/US6863211B2/en not_active Expired - Fee Related
-
2004
- 2004-01-06 JP JP2004000846A patent/JP3971389B2/ja not_active Expired - Fee Related
-
2006
- 2006-11-29 JP JP2006321806A patent/JP2007186679A/ja active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102264682A (zh) * | 2008-11-03 | 2011-11-30 | 3M创新有限公司 | 制备氟化醚的方法、氟化醚、以及它们的用途 |
CN103068805A (zh) * | 2010-07-23 | 2013-04-24 | 索尔维公司 | 1-取代-3-氟烷基-吡唑-4-羧酸酯的制备方法 |
CN103079533A (zh) * | 2010-09-03 | 2013-05-01 | 花王株式会社 | 清洁剂组合物 |
US8703108B2 (en) | 2010-09-03 | 2014-04-22 | Kao Corporation | Cleansing composition |
CN103079533B (zh) * | 2010-09-03 | 2014-05-07 | 花王株式会社 | 清洁剂组合物 |
CN105934430A (zh) * | 2014-01-24 | 2016-09-07 | 拜耳作物科学股份公司 | 制备1-烷基-3-二氟甲基-5-氟-1h-吡唑-4-甲醛和1-烷基-3-二氟甲基-5-氟-1h-吡唑-4-甲酸酯的方法 |
CN105934430B (zh) * | 2014-01-24 | 2018-03-16 | 拜耳作物科学股份公司 | 制备1‑烷基‑3‑二氟甲基‑5‑氟‑1h‑吡唑‑4‑甲醛和1‑烷基‑3‑二氟甲基‑5‑氟‑1h‑吡唑‑4‑甲酸酯的方法 |
Also Published As
Publication number | Publication date |
---|---|
US5658962A (en) | 1997-08-19 |
US6491983B2 (en) | 2002-12-10 |
RU2177934C2 (ru) | 2002-01-10 |
US6361713B1 (en) | 2002-03-26 |
JP3590067B2 (ja) | 2004-11-17 |
EP0760809B1 (en) | 2002-07-24 |
EP1170275A3 (en) | 2004-04-14 |
DE69527527T2 (de) | 2003-05-08 |
US20030166487A1 (en) | 2003-09-04 |
US6024176A (en) | 2000-02-15 |
US6214253B1 (en) | 2001-04-10 |
JP3971389B2 (ja) | 2007-09-05 |
CN1110473C (zh) | 2003-06-04 |
WO1995032174A1 (en) | 1995-11-30 |
EP1170275A2 (en) | 2002-01-09 |
US20010027172A1 (en) | 2001-10-04 |
US6863211B2 (en) | 2005-03-08 |
CA2190116A1 (en) | 1995-11-30 |
JPH10500950A (ja) | 1998-01-27 |
JP2007186679A (ja) | 2007-07-26 |
US6204299B1 (en) | 2001-03-20 |
EP0760809A1 (en) | 1997-03-12 |
JP2004203889A (ja) | 2004-07-22 |
DE69527527D1 (de) | 2002-08-29 |
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