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CN1171098A - 乙烯羰基化作用的方法和该方法所使用的催化剂体系 - Google Patents

乙烯羰基化作用的方法和该方法所使用的催化剂体系 Download PDF

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CN1171098A
CN1171098A CN95197050A CN95197050A CN1171098A CN 1171098 A CN1171098 A CN 1171098A CN 95197050 A CN95197050 A CN 95197050A CN 95197050 A CN95197050 A CN 95197050A CN 1171098 A CN1171098 A CN 1171098A
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王晓兰
R·P·图泽
G·R·伊斯特哈姆
K·维斯顿
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Abstract

一种能够催化乙烯羰基化反应的催化剂体系和使用这种催化剂体系的方法,其中催化剂体系是通过将Ⅷ族金属如Pd或Ⅷ族化合物和二齿如双(二叔丁基膦基)－邻—二甲苯结合制得。

Description

乙烯羰基化作用的方法和该方法 所使用的催化剂体系
本发明涉及在一催化剂体系存在下，使用CO进行乙烯羰基化作用的方法和这种方法所使用的催化剂体系。
在许多欧洲专利和专利申请中，例如EP-A-04489472号、EP-A-0055875号、EP-A-0106379号、EP-A-0235864号、EP-A-0274795号、EP-A-0499329号、EP-A-0386833号、EP-A-0441447号、EP-A-0489472号、EP-A-0282142号、EP-A-0227160号、EP-A-0495547号和EP-A 0495548号，已经公开了在醇或水和包括VIII族金属例如Pd的催化剂体系及膦配位体例如烷基膦配位体、环烷基膦配位体、芳基膦配位体、吡啶基膦配位体或二齿膦配位体存在下，使用CO进行乙烯羰基化作用的方法。特别是，EP-A-0227160号、EP-A-0495547号和EP-A-0495548号公开了一些二齿膦配位体所提供的催化剂体系能够达到更高的反应速率。
现有技术中所公开的催化剂体系的主要问题是，虽然可以得到较高的反应速率，但是Pd催化剂很快地减活，这使得必须频繁的补充催化剂，其结果形成了在工业上没有吸引力的方法。
现在人们已经发现，二齿膦化合物的特殊的一组可以提供显著稳定的催化剂，这些催化剂需要很少或不补充；使用这些二齿膦化合物催化剂，使反应速率明显高于现有技术公开的反应速率；在高转化率下产生很少杂质或不产生杂质。
因此，本发明提供了一种用于乙烯羰基化作用的方法，该方法包括在羟基源和催化剂体系存在下，进行乙烯与CO的羰基化反应，其中催化剂体系是通过将(a)和(b)结合而制得，所述的(a)和(b)是：(a)VIII族金属或VIII族金属的化合物；和(b)通式(1)的二齿膦化合物
其中R0是一叔碳原子；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12的每一个是独立地可以取代的侧有机基，它带一个与相应的R0连接的碳原子：
L1和L2的每一个是选自可以取代的连接相应磷原子与基X的低碳亚烷基链的独立地连接基；和
X是一包括可以取代的在可利用的相邻碳原子上连接磷原子的芳基的桥连基。
再者，本发明提供了能够催化乙烯的羰基化反应的一种催化剂体系，该催化剂体系是从(a)和(b)生成，
(a)VIII族金属或VIII族金属化合物；和
(b)通式(1)的二齿膦化合物
其中R0是一叔碳原子；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12的每一个是独立地可以取代的侧有机基，它带有一个连接相应R0的碳原子：
L1和L2的每一个是选自可以取代的连接相应磷原子与基X的低碳亚烷基链的独立地连接基；和
X是一个包括可以取代在可利用的相邻碳原子上连接磷原子的芳基的桥连基。
可以取代的有机基R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12可以是独立的，选自成分广泛的范围。优选，侧基是可取代的低碳烷基，例如C1-8烷基，而且，侧基可以是支链或直链的烷基。
当有机基R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12与它们相应的R0碳原子生成至少像叔丁基那样的空间位阻的复合基时，是特别优选的。在这方面，空间位阻如“HomogeneousTransition Metal Catalysis-A Gentle Art”在14页等所述，由C Masters著，1981年由Chapman and Hall出版。
连接基L1和L2独立的，选自可以取代的，特别是低碳烷基如C1-4烷基，可以取代的低碳亚烷基，例如C1-4链。当L1和L2都是亚甲基时是特别优选的。
桥连基X是一芳基，例如苯基，它可以被取代，只要两个磷原子与相邻的碳原子，例如在苯基1和2位上的碳原子连接就行。芳基可以被其它的有机基，例如烷基，特别是C1-8烷基、芳基、烷氧基、烷氧羰基、卤素、硝基、三卤代甲基和氰基取代。而且，芳基可以稠合成多环基，例如萘、亚联苯基或茚基。
适宜的二齿配体的实例是双(二叔丁基膦基)-邻-二甲苯(也称为1，2双(二叔丁基膦基甲基)苯)、双(二叔新戊基膦基)-邻-二甲苯和双(二叔丁基膦基)萘。此外，二齿膦经过至少一个桥连基X、连接基L1或L2可以键合成一适宜的聚合作用物，例如双(二叔丁基膦基)-邻-二甲苯经二甲苯与聚苯乙烯键合就得到了固定的多相催化剂。
所使用的二齿配位体的量可以在一宽的范围内变化。优选地，二齿配位体以使存在的二齿配位体的摩尔数与存在的VIII族金属的摩尔数的比为1-50，例如1-10和特别是1-5mol/mol这样的量存在。
在反应中，CO是以存在于惰性的其它气体中使用。这些其它气体的实例包括H2、N2、CO2和稀有气体如Ar气。
本发明的方法优选在20-250℃，特别是40-150℃和更优选70-120℃的温度下进行。
本发明的方法可以在总压为1×105-100×105N·m-2和特别是在5×105-50×105N·m-2下进行。
适宜的VIII族金属包括Co、Ni、Pd、Rh和Pt。特别优选的是Pd。这些VIII族金属的适宜化合物包括这些金属，或包括弱配位阴离子衍生的化合物与硝酸、硫酸；低碳链烷(达C12)酸如乙酸和丙酸；磺酸如甲磺酸、氯磺酸、氟磺酸、三氟甲磺酸、苯磺酸、萘磺酸、甲苯磺酸，如对-甲苯磺酸、叔丁基磺酸和2-羟基丙磺酸；磺化的离子交换树脂；全卤酸如全氯酸；全氟化羧酸如三氯乙酸和三氟乙酸；正磷酸；膦酸如苯膦酸和Lewis酸与Broensted酸间相互反应得到的酸的盐。可以提供适宜阴离子的其它的源包括硼酸四苯酯的衍生物。因此，可以使用易变配位体如三(二苄基茚基丙酮)二钯的零价钯化合物。
本发明的催化剂体系可以均相或多相使用。本发明的催化剂体系优选以均相使用。
本发明的催化剂体系优选通过一种或几种反应物生成的液相，或使用适宜溶剂的液相构成。
可以与本发明的催化剂体系一起使用的适宜的溶剂包括一种或几种非质子传递溶剂，如醚类例如乙醚、二甲醚、二乙二醇的二甲醚、茴香醚和二苯醚；芳烃化合物，包括这些化合物的卤素的变体如苯、甲苯、乙苯、邻二甲苯、间二甲苯、对二甲苯、氯苯、邻-二氯苯、间-二氯苯和对-二氯苯；链烷类，包括这些化合物的卤素变体，例如己烷、庚烷、2，2，3-三甲基戊烷、二氯甲烷和四氯化碳；腈类例如苄腈和乙腈；酯类例如苯甲酸甲酯、乙酸甲酯和邻苯二甲酸二甲酯；砜类例如二乙砜和四氢噻吩1，1-二噁烷；酰胺类，包括这些化合物的卤素变体，如二甲基甲酰胺和N-甲基吡咯烷酮。
本发明的催化剂体系特别适合于乙烯的羰基化反应，令人惊奇地是，已经发现难于羰基化达本发明催化剂体系程度的丙烯可视为不能羰基化的丙烯。
反应的最终产品至少部分由所使用的羟基源决定。使用水产生了相应的羧酸，而使用链烷醇产生了相应的酯。适宜的链烷醇包括C1-30链烷醇，可以被一个或几个取代基如卤原子、氰基、羰基、烷氧基或芳基取代的C1-30链烷醇。适宜的链烷醇包括甲醇、乙醇、丙醇、2-丙醇、2-丁醇、叔丁醇和氯癸醇。特别有用的是甲醇和乙醇。
在反应中所使用的乙烯的量与提供羟基的化合物的量的摩尔比并不重要，可以在很宽的范围例如0.001∶1-100∶1mol/mol改变。
通过任何适合的方法都可以将反应产物从其它的组分中分离出来。但是，本发明催化剂体系的优点是生成很少的付产物，因此在产品初步分离后，就减少了必须的进一步纯化，这可以由非常高的选择性来证明。其它的优点是包含其它组分的催化剂体系补充最小量的新鲜催化剂后，在进一步的反应中可以循环和/或再用。
用下面的实施例进一步说明本发明。
实施例1
在这个实施例中，使用甲醇作羟基源，从CO和乙烯制备戊酸甲酯。
容积为2升的机械搅拌的高压釜用空气排空后，加入如下组成的催化剂体系：甲醇           300cm3乙酸钯         0.1mmol二齿配位体*   0.3mmol甲磺酸         0.24mmol*双(二叔丁基膦基)-邻-二甲苯
CO和乙烯按等摩尔加入高压釜，至到达到30×105N·m-2的压力为止。反应器的温度升高到100℃并保持在100℃。当反应充分进行后，加入附加量的甲醇，以补充甲醇的消耗，同时添加附加量的CO和乙烯(按等摩尔添加)。没有发现钯的沉淀。
实施例2(比较例)
重复实施例1，只是使用邻-二甲苯二齿配位体的丙烷相似物。在两小时内发现了Pd的沉淀，因此催化剂体系减活。
对实施例1和2所述的催化剂体系的每一种的反应速率(以molC2H6/molPd·时表示)、对丙酸甲酯的选择性(％由气相色谱法测定)和按膦计(以mol丙酸甲酯/mol膦表示)的周转数示于表1。表1
    膦配位体 反应速率   选择性   周转数
  双(二叔丁基膦基)-邻-二甲苯   40000   99.55   ＞50000
  双(二叔丁基膦基)-丙烷   15000   98.00   1700
因此，可以看出，与传统的二齿配位体催化剂体系相比，本发明的催化剂体系更稳定、更活泼和选择性更高。
实施例3
在方法结束时提取出的实施例1的催化剂体系与新鲜甲醇和甲磺酸一起再使用。再使用的催化剂体系的活性与原来的相同。实施例2的催化剂体系由于钯的沉淀，不能再使用。
实施例4
使用二齿配位体的4-硝基取代的相似物，重复实施例1，所述的相似物通过适当的仲膦与相应的芳烃二齿化物反应产生的磷盐制备的。
实施例5
使用4-甲氧基取代的相似物重复实施例4。实施例4和5的结果如下：
  膦配位体   反应速率     选择性     周转数
    4-硝基     36000     99.9     ＞25000
    4-甲氧基     37000     99.9     ＞25000
实施例6
除了使用的钯源改变外，其它均相同重复实施例1。按摩尔比为2∶1∶3，将二齿膦配位体、称为dba的三个(二苄基茚基丙酮)二钯和磺酸混合制备催化剂体系。在加入酸之前，将膦配位体和dba混合。
使用等摩尔的甲醇和丙酸甲酯的混合物，在总压为15巴g(使用1∶1的CO与乙烯的混合物)下进行反应。反应温度为80℃。
实施例7
除了配位体中在每个磷原子上的叔丁基被环己基取代外，其它均相同重复实施例6。
实施例8
除了配位体中的叔丁基被环己基取代外，其它均相同，重复实施例6。
实施例9
除了配位体中的叔丁基被异丙基取代外，其它均相同，重复实施例6。
实施例10
除了配位体中的叔丁基被苯基取代外，其它均相同，重复实施例6。
实施例11
除了连接基亚甲基都被氧原子取代外，其它均相同，重复实施例6。次膦酸盐是从芳烃二醇和氯代二叔丁基膦合成。
实施例12
除了使用配位体的4-丁基取代的相似物外，其它均相同，重复实施例11。
实施例6-12的结果如下：
  膦配位体   反应速率     选择性     周转数
    实施例6     12000     99.95     ＞25000
    实施例7     500     30     ＞1500
    实施例8     200     25     ＞600
    实施例9     200     20     50
   实施例10     400     20     ＞1200
   实施例11     100     30     ＜300
   实施例12     100     30     ＜300

Claims (5)

1.一种用于乙烯羰基化作用的方法，该方法包括在羟基源和催化剂体系存在下，使CO与乙烯进行反应，其中催化剂体系是通过(a)和(b)的结合而制得，所述的(a)和(b)是：
(a)一种VIII族金属或VIII族金属的化合物；和
(b)通式(1)的二齿膦配位体
Figure A9519705000021
其中R0是一个叔碳原子；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12的每一个是独立地可以取代的侧有机基，它带有一个连接相应R0的碳原子：
L1和L2的每一个是选自可取代的连接相应磷原子与基X的低碳亚烷基链的独立地连接基；和
X是一个包括可以取代的在可利用的相邻碳原子上连接磷原子的芳基的桥连基。
2.一种能够催化乙烯羰基化反应的催化剂体系，该催化剂体系是由(a)和(b)生成，所述的(a)和(b)是：
(a)一种VIII族金属或VIII族金属的化合物；和(b)通式(1)的二齿膦
Figure A9519705000031
其中R0是一叔碳原子；
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12的每一个是独立地可取代的侧有机基，它带有一个连接相应R0的碳原子：
L1和L2的每一个是选自可以取代的连接相应磷原子与基X的低碳亚烷基链的独立地连接基；和
X是一个包括可取代的在可利用的相邻碳原子上连接磷原子的芳基的桥连基。
3.按权利要求1或2的方法或催化剂体系，其中可取代的侧有机基R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12都是独立地，选自可取代的低碳烷基。
4.按前述权利要求任一项的方法或催化剂体系，其中有机基R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11和R12是与它们相应R0碳原子相联系，以便生成至少像叔丁基空间位阻那样的复合基。
5.按前述权利要求任一项的方法或催化剂，其中L1和L2都是亚甲基。
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