CN100376584C - 由以钛、铌、钽、锡或锑为主要成分的路易斯酸得到的离子液体及其应用 - Google Patents
由以钛、铌、钽、锡或锑为主要成分的路易斯酸得到的离子液体及其应用 Download PDFInfo
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Abstract
本发明的离子液体是由以钛、铌、钽、锡或锑为主要成分的卤化或氧卤化的路易斯酸与式X+A-有机盐反应生成的,其中A-是卤素阴离子,X+是季铵、季或叔锍阳离子。这些液体特别适用于以HF液相氟化饱和的或不饱和的含有C-C1键的化合物。
Description
本发明涉及离子液体领域,更具体地,本发明的目的是以钛、铌、钽、锡或锑为主要成分的离子液体。
在本申请中认为离子液体是具有离子特性的非水溶性盐,这些盐在适当温度下是液体,并且由有机盐与无机化合物反应而得到。
人们已经知道许多液体离子。如在《美国化学学会杂志》,101∶2,323-327(1979)中,Osteryoung等人公开了在40℃,丁基吡啶氯化物(A)和氯化铝AlCl3(B)混合物在很宽的组成范围(A/B摩尔比1∶0.75至1∶2)内是液体。在《无机化学》,21,1263-1264中,Willkes等人公开了,由AlCl3与例如1-丁基-3-甲基咪唑氯化物的二烷基咪唑氯化物反应得到的这些化合物,在前面描述的同样组成范围内,在室温下也是液体。在这个离子液体实施例中,二烷基咪唑是阳离子,AlCl4是阴离子。其他阴离子,例如硝酸根、醋酸根或四氟硼酸根阴离子也都可以使用的(见公开WO 9618459)。
由于它们广泛的电化学贯通(fenetre),离子液体可以用作电池电解质。因为它们是有机金属化合物的优异溶剂,所以它们还特别可用于催化。因此,例如专利申请FR 2626572和WO 9521806所描述,前面列举的以氯铝酸盐为主要成分的化合物可用于芳族化合物或异链烷烃的烷基化反应的两相催化。
现在,本发明的目的是由以钛、铌、钽、锡或锑为主要成分的路易斯酸得到的离子液体。发现这些离子液体有催化应用,还具有能使两相催化中使用的有机金属化合物溶剂化性质。
本发明的离子液体是非质子性的非水溶性的离子化合物,其在大气压下在适当温度范围内(最好低于100℃)是液体,它是通过以钛、铌、钽、锡或锑为主要成分的卤化或氧卤化的路易斯酸与通式X+A-表示的盐进行反应而获得的,式中A-表示卤素阴离子(溴离子、碘离子,优选地氯离子或氟离子)或六氟锑酸根阴离子(SbF6),X+表示季铵阳离子、季阳离子或叔锍阳离子。
以钛、铌、钽、锡或锑为主要成分的卤化的路易斯酸是氯化、溴化、氟化衍生物或混合衍生物,例如,氯氟化的酸。更特别是具有下列化学式的氯化物、氟化物或氯氟化物:
TiClxFy,x+y=4以及0=x=4
TaClxFy,x+y=5以及0=x=4
NbClxFy,x+y=5以及0=x=5
SnClxFy,x+y=4以及1=x=4
SbClxFy,x+y=5以及0=x=5
作为这些化合物的例子,可以提到下列化合物:TiCl4、TiF4、TaCl5、TaF5、NbCl5、NbF5、SnCl4、SnF4、SbCl5、SbCl4F、SbCl3F2、SbCl2F3、SbClF4、SbF5及其它们的混合物。优选使用下列化合物:TiCl4、SnCl4、TaCl5+TaF5、NbCl5+NbF5、SbCl5、SbFCl4、SbF2Cl3、SbF3Cl2、SbF4Cl、SbF5和SbCl5+SbF5。更特别优选的是锑化合物。
作为本发明使用的氧卤化的路易斯酸的实例,可以举出TiOCl2、TiOF2、SnOCl2、SnOF2以及SbOClxFy(x+y=3)。
在盐X+A-中,阳离子X+是下列通式中之一:
R1R2R3R4N+
R1R2R3R4P+
R1R2R3S+
式中符号R1至R4可以相同或不同,分别表示饱和的或不饱和的,环状或非环状的,或芳族的有1至10个碳原子的烃基,氯代烃基,氟代烃基,氯氟代烃基,这些基团中的一个或多个还可以含有一个或多个杂原子,例如N、P、S或O。
铵、或锍阳离子X+也可以形成具有1至3个氮、磷或硫原子的饱和的或不饱和的或芳族的杂环的部分,可以下列通式的任何一种表示:
式中,R1及R2的定义同上。
使用在其化学式中含有2个或3个铵、或锍离子位点的盐,并不超出本发明的范围。
作为X+A-盐的实例,可以举出四烷基氯化铵和四烷基氟化铵,四烷基氯化和四烷基氟化以及三烷基氯化锍和三烷基氟化锍,烷基吡啶氯和烷基吡啶氟,二烷基咪唑氯、二烷基咪唑氟、二烷基咪唑溴,三烷基咪唑氯和三烷基咪唑氟。三甲基锍氯或三甲基锍氟、N-乙基-吡啶氯或N-乙基-吡啶氟、N-丁基吡啶氯或N-丁基吡啶氟、1-乙基-3-甲基咪唑氯或1-乙基-3-甲基咪唑氟和1-丁基-3-甲基咪唑氯或1-丁基-3-甲基咪唑氟是更有价值的。
本发明的离子液体可以本身已知的方式,把卤化或氧卤化的路易斯酸与有机盐X+A-适当地混合而制备得到,其混合的摩尔比是0.5/1至3.5/1,优选1/1至2.5/1,更优选1/1至2/1。如果想要得到酸性的离子液体,特别推荐摩尔比要严格超过1/1。
可以在高压釜型反应器内制备所述混合物,选择性地进行冷却,以限制反应放热。通过逐渐地把一种反应剂添加至另一种反应剂中,也可以控制这种放热性。
当路易斯酸/有机盐的摩尔比大于1/1时,已证明加热反应混合物直到固体完全溶解是有利的。
反应物和所得到的离子液体通常是吸湿性的,所以,使用时建议采用本领域技术人员熟知的方法除去水和空气而进行合成。
本发明的离子液体可用于这类化合物巳知的任何用途。当路易斯酸/有机盐摩尔比小于或等于1/1时,可利用这些液体的溶剂化性质(有机合成,有机金属配合物的溶剂)。
当路易斯酸/有机盐摩尔比严格大于1/1时,本发明的离子液体具有酸性,这对于任何催化需要酸性催化剂来说是有意义的,例如,弗瑞德-克来福特催化和氟化催化。
对于在具有C-C1键的饱和或不饱和化合物的液相中采用HF氟化反应,本发明的离子液体具有特别有意义的应用,例如像:CHCl=CH2、CCl2=CCl2、CH2=CCl2、CClH=CCl2、CH2Cl2、CH2ClF、CCl3-CH3、CCl2H-CCl2H、CCl3-CH2Cl、CCl3-CHCl2、CF3-CH2Cl、CCl3-CH2-CHCl2、CF3-CH=CHCl或CCl3-CH2-CCl2-CH3。
可以间断性实施使用本发明离子液体作为催化剂的液相氟化方法。采用的装置是高压釜,在开始反应前,把反应物和催化剂加入高压釜,随着反应进展,可以改变高压釜的压力。HF的摩尔量与起始原料的摩尔量之比是2-50,优选地10-30。反应所需时间取决于起始作用的反应物的量和各种操作参数,这种时间可以通过实验很容易获得。
氟化反应也可以按照半连续方式进行,其使用的装置是由在其上装有单个冷凝器的高压釜,或有回流冷凝器的回流柱,以及压力调节阀构成,调节压力以使反应介质保持在液态。如上所述,反应物和催化剂要事先加入反应器,但是,低沸点的反应产物(氟化产物)和氯化氢(HCl)副产物在反应期间连续抽出,而更高沸点化合物,例如,起始原料、中间产物和HF借助安装在反应器上的冷凝器(或回流柱)大部分以液体形式回流到反应介质中。
按照第3个实施方案,在同样的半连续的装置中可连续进行氟化,但是,至少一种反应物(HF或起始原料)要连续加入。由于工业生产的原因,最好同时供给2种反应物。在反应期间连续抽出反应产物,使未反应的反应物流回到反应器中。供应的HF摩尔量与供应的原料摩尔量之比至少等于2。
催化剂的量取决于操作条件和反应介质(在连续法的情况下),但也取决于催化剂的固有活性。该量为反应介质的0.5-90%(摩尔)。
使用的催化剂是以锑为主要成分的时,为保持锑的氧化态为5,这时加氯是有利的。
进行氟化反应的温度(间歇或连续条件下)通常在30-180℃之间,优选80-130℃。
以半连续或连续方式进行反应的压力,应选择能使反应介质保持在液相的压力。该压力通常是5-50巴,优选地是10-40巴;在连续反应的条件下,如果HF是反应介质,则选择的操作压力一般选择是在所要求的反应温度下HF的饱和蒸气压。按照反应期间能抽出产物的量和性质来决定冷凝器的温度。该温度通常是-50至150℃,优选0至100℃。
氟化反应器的材料应该是能在上述压力和温度条件下进行操作的材料。还必需经得住氟化氢产生的腐蚀。因此,不锈钢或蒙乃尔合金、因科镍合金或耐盐酸镍基合金是特别优选的。
下面实施例说明本发明,但不限制其发明。
实施例1
在氩气吹扫下,把7.3克1-乙基-3-甲基咪唑氯(emim-Cl)装入Schlenk管中,然后,把该管浸入冰中。接着,在搅拌下逐惭加入氯氟化锑SbF3Cl2。该反应是放热的,但冰可以使管中温度保持在大约10℃。在加入12.6克SbF3Cl2后,此时相当于SbF3Cl2/emim-Cl的摩尔比为1,把Schlenk管加热至约40℃,以使生成的离子液体完全液化。然后,在室温下继续添加SbF3Cl2直至其总量达到25.3克,这相当于SbF3Cl2/emim-Cl的摩尔比为2。
在室温下搅拌18小时后,得到32.6充离子液体。该化合物用红外和拉曼光谱分析,具有下列主要特征:
IR:
1.在1600cm-1的带(属于C=N键)
2.在550-600cm-1的带
拉曼
3.在370cm-1的带
4.在174cm-1的带。
实施例2
与实施例1同样操作,但用31.7克五氯化钽和五氟化钽的等摩尔混合物代替氯氟化锑,用8.7充1-丁基-3-甲基-咪唑氯(bmim-Cl)代替emim-Cl。
实施例3-14
采用与实施例1和2同样的方式得到的本发明离子化合物的另一些实施例汇总于下表中。不能快速得到液体时,可把Schlenk管插入120℃油浴中,在120℃加热路易斯酸和emim-Cl的混合物。所有得到的产物在120℃以下都是液体。
表
实施例 | 路易斯酸 | 路易斯酸/emim-Cl摩尔比 | 特性,分析的金属质量% |
3 | TiCl<sub>4</sub> | 1∶1 | 14 |
4 | TiCl<sub>4</sub> | 2∶1 | 18 |
5 | SnCl<sub>4</sub> | 1∶1 | 29 |
6 | SbF<sub>4</sub>Cl | 1∶1 | 31 |
7 | SbF<sub>4</sub>Cl | 2∶1 | 39 |
8 | NbCl<sub>5</sub> | 1∶1 | 22 |
9 | NbCl<sub>5</sub> | 1∶1 | 29 |
10 | NbCl<sub>5</sub>+NbF<sub>5</sub><sup>*</sup> | 2∶1 | 31 |
11 | SbF<sub>5</sub> | 1∶1 | 33 |
12 | SbF<sub>5</sub> | 2∶1 | 43 |
13 | SbCl<sub>5</sub> | 1∶1 | 27 |
14 | SbCl<sub>5</sub> | 2∶1 | 33 |
*是NbCl5和NbF5的等摩尔混合物
实施例15-24
采用与实施例1和2同样的方式得到的本发明离子化合物的另一些实施例汇总于下表中,但使用1-丁基-3-甲基-咪唑氯(bmim-Cl)作为季铵盐。不能快速得到液体时,可把Schlenk管插入l20℃油浴中,在120℃加热路易斯酸和bmim-Cl的混合物。所有得到的产物在120℃以下都是液体。
表
实施例 | 路易斯酸 | 路易斯酸/bmim-Cl摩尔比 | 特性,分析的金属质量% |
15 | TiCl<sub>4</sub> | 1∶1 | 13 |
16 | TiCl<sub>4</sub> | 2∶1 | 17 |
17 | TiF<sub>4</sub> | 1∶1 | 16 |
18 | SnCl<sub>4</sub> | 1∶1 | 27 |
19 | NbCl<sub>5</sub> | 1∶1 | 21 |
20 | TaCl<sub>5</sub> | 1∶1 | 34 |
21 | SbCl<sub>5</sub> | 1∶1 | 26 |
22 | SbCl<sub>5</sub> | 2∶1 | 31 |
23 | SbF<sub>5</sub> | 1∶1 | 31 |
24 | SbF<sub>5</sub> | 2∶1 | 40 |
实施例25
往装有7.3克在30毫升丙酮中保持悬浮状的emim-Cl的Schlenk管里,在强烈搅拌下加入12.9克六氟锑酸钠。即刻生成了胶乳状沉淀,在搅拌18小时后,用Celite过滤该沉淀。在真空下蒸去丙酮后,得到半透明的液体,将该管插入冰中,以便冷却,往该液体添加10.8克五氟化锑,然后让该混合物回升到室温。
实施例26
在0.15升的316L不锈钢的高压釜中,相继加入30.6g实施例7的离子液体、21.5g二氯甲烷(F30)和20.8gHF。将高压釜插入130℃的油浴、冷凝器温度保持在15-20℃,调节压力保持在10绝对巴。在该压力下,反应介质的温度为约100℃。
在反应期间,挥发的反应产物连续排出,通过水的起泡器,然后,在收集入经液氮冷却的不锈钢阱之前先进入干燥器。在反应290分钟以后,用循环水冷却高压釜。在降到室温后,将高压釜脱气,洗涤反应产物,干燥,与上述同样进行收集。
收集的不同气相和液相样品进行分析表明84%的原料F30被转化,其中69%转化为二氟甲烷,31%转化为氯氟甲烷(摩尔%)。
实施例27
在1升316L不锈钢高压釜中,该高压釜配有磁搅拌器,其上装有单冷凝器,以及在冷凝器顶部有调节压力的阀,并用该阀排出反应产物,相继装入740克三氯乙烯和102克实施例12的离子液体。通过油浴供给高压釜夹套,以使在高压釜中达到125℃的温度,并通过加入水使冷凝器的温度保持在55℃。达到所要求的温度时,连续供给42克/小时三氯乙烯,27克/小时HF和3克/升氯。在这个试验期间,进行持久地使压力调节阀开启,以表示在反应器出口的气体流量。
在相当于达到在高压釜中反应介质平衡组成的14小时稳定期后,调节阀的开口变得稳定。在反应器出口的气体组成这时确定为95%Fl33a(CF3-CH2Cl)和5%Fl32b(CF2Cl-CH2Cl)。
在稳定进行25小时后,停止加入Cl2。下表列出了从停止加入Cl2起阀的开口值。很清楚地看到,从20小时开始调节阀的开口值没有变化,这相当于运行非常平稳。
对比例28
重复前面的实施例,装入749克三氯乙烯和53.2克SbCl5代替前面使用的离子液体。在达到稳定运行后,高压釜的温度稳定在125℃。
在稳定运行25小时后,停止加入氯气。停止加入Cl2后压力调节阀的开口值列于下面表中。可看到,在反应约4小时后,关闭阀,这相当于停止反应。
在停止加入Cl<sub>2</sub>后压力调节阀开口值,% | ||
时间,小时 | 实施例27 | 对比例28 |
1 | 10 | 13 |
2 | 11 | 13 |
3 | 10 | 11 |
4 | 10 | 3 |
5 | 10 | 0 |
7 | 10 | 0 |
10 | 12 | 0 |
15 | 12 | 0 |
20 | 10 | 0 |
Claims (11)
1.一种离子液体,它由至少一种以钛、铌、钽、锡或锑为主要成分的卤化或氧卤化的路易斯酸与通式X+A-有机盐的反应产物构成;
其中有机盐X+A-是氯化物或氟化物,阳离子X+是相当于下列通式中的一种:
R1R2R3R4N+
R1R2R3R4P+
R1R2R3S+
式中符号R1至R4相同或不同,各表示饱和的或不饱和的,环状的或非环状的,或芳族的、有1至10个碳原子的烃基,氯代烃基,氟代烃基,氯氟代烃基,氟碳化物基团;这些基团中的一个或多个基团还含有一个或多个杂原子
或
其中有机盐X+A-是氯化物或氟化物,阳离子X+是含有1至3个氮、磷或硫原子的饱和的或不饱和的或芳族杂环的一部分,并且是相当于下列通式的任何一种:
其中R1和R2的限定同上。
2.根据权利要求1所述的离子液体,其中路易斯酸/有机盐的摩尔比是0.5/1至3.5/1。
3.根据权利要求2所述的离子液体,其中路易斯酸/有机盐的摩尔比是1/1至2.5/1。
4.根据权利要求3所述的离子液体,其中路易斯酸/有机盐的摩尔比是1/1至2/1。
5.根据权利要求1所述的离子液体,其中路易斯酸是钛、铌、钽、锡或锑的氯化物、氟化物或氯氟化物。
6.根据权利要求2所述的离子液体,其中路易斯酸是钛、铌、钽、锡或锑的氯化物、氟化物或氯氟化物。
7.根据权利要求5中所述的离子液体,其中路易斯酸是锑化合物。
8.根据权利要求6中所述的离子液体,其中路易斯酸是锑化合物。
9.根据权利要求1-8中任一项所述的离子液体,其中阳离子X+是四烷基铵、四烷基鏻、三烷基锍、烷基吡啶鎓、二烷基咪唑鎓或三烷基咪唑鎓的阳离子。
10.根据权利要求9所述的离子液体,其中阳离子X+是三甲基锍、N-乙基吡啶鎓、N-丁基吡啶鎓、1-乙基-3-甲基咪唑鎓或1-丁基-3-甲基咪唑鎓阳离子。
11.一种用HF使具有C-C1键的饱和或不饱和的化合物进行液相氟化的方法,其特征在于,使用权利要求1-10中任一项所述的离子液体作为催化剂;其中路易斯酸/有机盐的摩尔比大于1。
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CN114262255B (zh) * | 2021-12-01 | 2023-10-20 | 西安近代化学研究所 | 一种合成反式-1,1,1,4,4,4-六氟-2-丁烯的方法 |
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- 2001-04-24 JP JP2001578441A patent/JP5072162B2/ja not_active Expired - Fee Related
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EP1276743A1 (fr) | 2003-01-22 |
ATE335749T1 (de) | 2006-09-15 |
EP1276743B1 (fr) | 2006-08-09 |
CN1433420A (zh) | 2003-07-30 |
JP5072162B2 (ja) | 2012-11-14 |
US20040033892A1 (en) | 2004-02-19 |
DE60122127T2 (de) | 2007-03-08 |
WO2001081353A1 (fr) | 2001-11-01 |
JP2003535054A (ja) | 2003-11-25 |
US6881698B2 (en) | 2005-04-19 |
FR2808268A1 (fr) | 2001-11-02 |
DE60122127D1 (de) | 2006-09-21 |
FR2808268B1 (fr) | 2002-08-30 |
ES2269387T3 (es) | 2007-04-01 |
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