CN1036915C - 用钯/膦催化剂进行的羰基化方法 - Google Patents
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- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 35
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- 238000005810 carbonylation reaction Methods 0.000 title claims description 25
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及烯属或炔属不饱和烃化合物的羧基化方法，其中在包括阳离子钯源，膦源和质子酸的催化剂存在下将其与一氧化碳和羟基化合物反应，其特征是反应在自由基抑制剂存在下进行。
Description
本发明涉及炔属不饱和烃化合物的羧基化方法，其中在包括阳离子钯源，膦源和质子酸的催化剂存在下将其与一氧化碳和羟基化合物反应。
这些方法提供了用易得到的不饱和烃原料生产各种化学品的灵活有效的办法，羧基化反应如下式：
其中A为不饱和烃化合物，BOH为羟基化合物，如水(B＝H)，醇(B＝R)及羧酸(B＝RCO)一般来说，烯属前体可提供饱和产品，而炔属前体提供烯属产品，而且并不排除多次羰基化如用炔属前体生产饱和产品。根据羟基化合物BOH的性质，可得各种官能化产品，包括羧酸，酯和酸酐。
最近，已发现可用包括阳离子钯，膦配位体，质子酸的催化体系构成极适宜的催化剂，这些催化体系可在中等温度和一氧化碳压力条件下使羰基化反应以极高速度下进行。精心选择膦种类和质子酸性质，可达到对要求具体产品达到极高选择性，至于这样催化的具体羰基化反应细节可参见EP-106379，EP-186228，EP-190473，EP-271144，EP-282142，EP-386833，EP-386834，EP＝441446和EP-441447。低温对羰基化反应极其有利，因为通常在制备和/或提纯过程中涉及乙烯基类前体或产品的聚合副反应问题可在很大程度受到抑制。
一般来说，这些催化体系应包括相当高的膦摩尔与钯克原子之比以保证在低钯浓度下达到高转化率，而高膦含量又会不利地造成废物流并且上述方法，尤其是在将精心安排取代的膦用于具体选择性方法时的经济性会下降，因此在不影响这些催化体系时要求尽可能降低膦/钯比。
已报道将抑制剂用于其它羰基化反应和/或甲基丙烯酸甲酯(MMA)制备方法，但这种情况下加抑制剂的众所周知的功能是抑制乙烯基化合物的聚合反应，因为这些方法在约100℃或更高温度下进行，其中US-4447640公开了在带载体钯催化剂和抑制剂存在下150-300℃下将1，2-二卤代烷羰基化制备MMA的方法，该说明书提到也可用包括VIII族金属盐与三有机膦组成的均相催化剂，但未提供进一步的细节，其中声称的加抑制剂的效果如第4栏第7-37行所述是阻止MMA产品的聚合并且通过阻止因碳沉积使催化剂结垢而提高催化剂的活性寿命，很清楚这后一问题似乎仅限于多相催化剂。US4480116说明了MMA制备方法，其中在50-3000ppm特定抑制剂存在下将丙酮氰醇酸解，尤其是在加工过程中进行。该文献强调的效果是防止MMA产品聚合，而该文献根本未谈到对催化剂寿命的效果。在EP-A-386833的例22中是在氢醌存在下将3-丁炔醇羰基化，其中加氢醌的目的是防止形成的methylenolacton产品聚合。US-4416823又说明了在钯/膦/硫醇稳定催化剂存在下80-120℃优选温度下将1，3-二烯二聚加氢酯化。优选的是，反应在乙烯基聚合抑制剂存在下进行以避免1，3-丁二烯不断转变为聚合副产品而丧失。但这些文献没有一篇提到在通常羰基化反应中降低膦/钯比，就便不用说本发明的羰基化反应类型了。
为解决上述问题，本发明提出一种炔属不饱和烃化合物的羰基化方法，其中，在包括阳离子钯源、膦源和质子酸的催化剂体系下使其与一氧化碳和羟基化合物反应，其特征在于，所述反应在自由基抑制剂的存在下进行，其中自由基抑制剂的浓度为0.0005-1％(重量)并且自由基抑制剂选自芳族羟基化合物、芳族酮基化合物、苯醌、萘醌、吩嗪、吩噁嗪和吩噻嗪。
据信，在上述羰基化反应中某些膦失活并要求催化体系中膦/钯比要高以在整个羰基化反应过程中提供足够的可应用膦。因此，换一种说法，本发明提出将自由基抑制剂用于烯属或炔属不饱和烃化合物的羰基化方法，其中在包括阳离子钯源，膦源和降低膦消耗速度的质子酸的催化体系存在下将其与一氧化碳和羟基化合物反应。
已惊人发现本发明羰基化反应中自由基抑制剂提供了不同于其通常的抑制乙烯基聚合的作用的有利效果，结果是可用膦/钯比低于现有催化剂的催化体系，同时又不会对催化剂寿命带来不利影响并且在相同条件下进行的羰基化过程中不影响转化率。因此本发明可降低膦配位体的费用并降低已知工艺中废物流的膦成分排放量。
自由基抑制剂的应用浓度可在很宽范围内变化，这取决于许多因素，如羰基化时间，微量氧浓度，催化剂浓度和温度。对于经济效益好的羰基化反应，自由基抑制剂浓度优选0.0005-1％wt，更优选0.001-0.1％wt，以反应成分总量计。本发明另一优点是该抑制剂浓度还会极有效地抑制任何聚合反应。在约50℃的正常工艺温度下，这种附带的效果在理论上据说有利，但实践上其重要性是第二位的。
自由基抑制剂有时也称为聚合抑制剂，宜于本发明的例子已在聚合领域众所周知，事实上本发明方法中可用任何自由基抑制剂，代表性例子包括芳族羟基化合物，芳族酮基化合物，苯醌和萘醌，吩嗪，吩噁嗪和吩噻嗪，优选自取代酚，包括用另外羟基取代的酚，如氢醌。酚可带任何另外的惰性取代基，尤其是烷基，如甲基和叔丁基，包括羟基化稠合芳环体系，如萘酚。
非限制性具体自由基抑制剂代表包括一元酚，如4-甲基-2，6-二叔丁基酚(“丁基化甲酚”)，2，4-二甲基-6-叔丁基酚，β-萘酚，对甲氧酚(“甲基氢醌”)；二元酚，如氢醌，萘并氢醌，儿茶酚，如对叔丁基儿茶酚和三元酚，如焦格酚。
由于存在自由基抑制剂，用于本发明方法的催化体系在较低的初始膦比例下亻有效。因此可有利地用反应开始时膦摩尔数与钯克原子数之比2.5-50，优选5-30的催化体系，更高的膦比例不会干扰反应，但影响本发明达到的经济效益。
催化体系中与初始膦比例有关的质子酸比例宜在0.5-10范围内。已发现用约为1的酸/膦比膦消耗速度有利，因此质子酸与膦mol比优选为0.7-1.5。
被羰基化的烯属或炔属不饱和化合物，适宜阳离子钯源，膦和质子酸，反应条件和进一步的试验细节已广泛记述于上述欧洲专利申请中，这些申请作为本发明的一部分供参考。
总的说来，炔属不饱和化合物包括链炔，尤其是1-链炔，可为直链或支链并可包括多个叁键或另外的双键，如乙炔，丙炔和1-丁炔。适宜羟基化合物包括水，醇和羧酸，可为脂族，环脂族或芳族化合物，优选含不多于20碳，并可具有多于1个的羧基官能团。适宜醇例子包括甲醇，乙醇，异丁醇，丙醇，叔丁醇，硬脂醇，苯酚，乙二醇和甘油。适宜羧酸例子包括乙酸和丙酸。
适宜钯源包括钯化合物，如盐，如乙酸钯以及络合物，如四-(三苯膦)钯和双-(三苯膦)钯乙酸盐，但也可为金属钯，此时用催化体系的酸成分溶解。适宜膦一般包括三有机膦，其中有机取代基可分别为脂族，环脂族，芳族或杂环基并可含1-10碳，如三苯膦，乙基二苯膦，二环已基苯基膦，2-吡啶基苯基膦，双-(6-甲基-2-吡啶基)苯基膦，三对氯苯基膦和三对甲氧基苯基膦。优选膦包括至少一个必须时取代的2-吡啶基。适宜质子酸优选具有非配位或弱配位阴离子。一般来说，这些酸为强酸，其pka小于4.5，尤其是小于2(水溶液中18℃测定)，包括硫酸，磺酸、膦酸和某些羧酸。在本文中，质子酸可由路易斯酸，如BF3与质子供体，如HF反应产生，也可就地产生，还可为酸性离子交换树脂。
本发明方法可方便地在液相中进行，但单独的溶剂并不关键，必要时用于本发明方法的溶剂包括芳烃，酯，醚和砜。在优选浓度下，自由基抑制剂易溶于液态反应介质中。本发明方法可方便地在10-130℃进行，优选温度30-90℃，方便的压力100-10000kpa。烯属或炔属不饱和烃化合物和羟基化合物之mol比并不关键，可为0.01至100∶1。催化体系量也不关键，钯量可方便地定为10-7至10-1克原子钯/mol不饱和化合物。
本发明方法要求的一氧化碳可以基本上纯态或用惰性气体，如氮气稀释后应用。如在具体羧基化反应中氢基本上为惰性的，则也可存在氢。
用于本发明方法的催化体系可用任何方便的方法制得，因此可将单独的钯化合物，膦和质子酸组合而得。另一方面，又可将钯化合物和膦的酸加成盐组合而得。再一方面，还可用与膦呈络合物的钯化合物和质子酸制成。自由基抑制剂可用任何方便的方法引入反应中，如将其与催化体系混合，或加入原料前体之一中。
例如本发明可参考炔属不饱和化合物羰基化过程详细说明，尤其是将丙炔与一氧化碳和醇反应制取甲基丙烯酸烷酯。该方法已详见于EP-271144，其中应用由钯化合物，质子酸和式PR1R2R3的有机膦制成的催化体系，其中R1，R2和R3之一，之二或每一个代表包括至少一个氮杂原子的5或6个原子的杂环，该环必要时可被取代和/或构成更大且可被取代的稠环结构的一部分，而且其余的任何基团R1，R2或R3代表必要时取代的烃基。
若反应在升压下进行，在反应开始时，除了液化丙炔而外液态载体主要还包括甲醇。在反应过程中，甲醇被甲基丙烯酸甲酯取代，后者又成为反应混合物的液态载体或溶剂。在连续进行的方法中，部分反应原料由循环甲基丙烯酸甲酯/甲醇共沸物流组成，因此在反应的每一阶段均存在甲基丙烯酸甲酯。
实施例A
通过在指定重量比例的甲基丙烯酸甲酯(MMA)和甲醇(MeOH)或仅在MeOH中制备指定mol量的催化成分溶液而进行代表性稳定性试验。乙酸钯(pdAc)作钯源，二苯基2-吡啶基膦作为配位体，而甲磺酸作催化体系的酸成分。在试验1-3，5，6和8中加入指定量指定类型的自由基抑制剂，试验4和7作参考。溶液在气态介质中于指定温度下保存24小时，然后分析溶液中膦氧化物相对于磷化合物，膦和膦氧化物总量的含量。用于这些试验的膦样品的初始氧化物含量为2.4％mol。
试验结果如下，从中可以看出加自由基抑制剂延长了催化体系寿命，而且即使在氮气氛下若反应溶剂包括MMA，则由于存在微量溶解氧，使效果尤为显著。
实施例B
在该例中给出了羰基化试验结果与经过催化剂溶液带入的氧量的关系。
羰基化试验在CSTR(连续进料的搅拌罐反应器)中进行。应用300mol Hastelloy蒸压釜，其中装有加热套和冷却盘管，用以控制温度，并设有中空轴搅拌器以改善CO传质效果。
例A中定义的催化剂组分和自由基抑制剂(甲基氢醌)常温常压溶于MeOH原料中(18ppmw pd/MeOH，pd/配位体/酸/抑制剂mol比1∶20∶15∶40)。气体环境可变(空气或惰性气，如N2或Ar)，丙炔经注射泵送入。
在试验开始时，反应器中填有催化剂/MeOH液，加热到45℃并用CO升压到1100kpa。然后1100kpa和45℃向反应器连续送入催化剂/MeOH液，丙炔和CO，用液体控制体系将反应器中液位恒定保持在220ml，通过改变加料速度而在不同停留时间达到稳定状态。连续取出的产品物流进行气—液色谱分析得活性和选择性。在所有情况下对MMA的选择性为99.2％主要副产品(0.8％)为丁烯酸甲酯。丙炔进料 催化剂溶液处理 不同停留时间
下丙炔转化率(％)
1.6h 4.4hA 用惰性气温和抽提 78 98A 空气饱和 63 80B 用惰性气温和抽提 69 88B 用惰性气严格抽提 79 90
性能上的差异是因氧使配位体氧化造成的，应用不同丙炔进料，其中一种经拨顶和截尾提纯(“A”)，另一种仅经拨顶提纯(“B”，含微量重质杂质)。从上述结果可以看出，存在氧而使配位体氧化会影响性能。
| 试验号 1 2 3 4 5 6 7 8 |
| MMA(％wt) 46.8 48.6 49.3 50.2 47.4 48.8 - -MeOH(％wt) 53.2 51.4 50.7 49.8 52.6 51.2 100 100介质 N2 N2 N2 N2 N2 N2 空气 空气Pd(mmol/kg) 0.23 0.12 0.11 0.11 0.12 0.11 0.21 0.23ligand(mmol/kg) 2.41 1.20 1.16 1.16 1.23 1.11 2.84 2.92acid(mmol/kg) 5.06 2.38 2.40 2.28 2.44 2.24 1.31 1.22H/L(mol/mol) 2.1 2.0 2.1 2.0 2.0 2.0 0.46 0.42L/Pd(mol/mol) 10 10 10 10 10 10 14 13引发剂类型* HQ HQ MEHQ - HQ BMP - MEHQ(mmol/kg) 4.94 4.68 9.02 - 0.97 2.25 - 3.01温度(℃) 45 45 45 45 45 45 20 20氧化物**t＝20hr(％mol) 13.1 10.4 14.5 90.0 21.7 15.3 16.5 6.8 |
*HQ＝氢醌；MEHQ＝甲基氢醌；BMP＝丁基化甲基酚
**磷氧化物相对于总P化合物的mol比；配位体的初始氧化物含量：2.4％mol。
Claims (8)
1.炔属不饱和烃化合物的羧基化方法，其中，在包括阳离子钯源、膦源和质子酸的催化剂体系下使其与一氧化碳和羟基化合物反应，其特征在于，所述反应在自由基抑制剂的存在下进行，其中自由基抑制剂的浓度为0.0005-1％(重量)并且自由基抑制剂选自芳族羟基化合物、芳族酮基化合物、苯醌、萘醌、吩嗪、吩噁嗪和吩噻嗪。
2.权利要求1的方法，其中，自由基抑制剂的浓度为0.001-0.1％(重量)。
3.权利要求1或2的方法，其中，自由基抑制剂选自取代酚。
4.权利要求1或2的方法，其中，膦的摩尔数与钯的克原子数的初始比为2.5-50。
5.权利要求4的方法，其中，膦的摩尔数与钯的克原子数的初始比为5-30。
6.权利要求1或2的方法，其中，质子酸的摩尔数与膦的摩尔数的初始比为0.5-10。
7.权利要求6的方法，其中，质子酸的摩尔数与膦的摩尔数的初始比为0.7-1.5。
8.权利要求1或2的方法，其中，使丙炔与一氧化碳和醇反应形成甲基丙烯酸烷基酯。
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| US5103043A (en) * | 1989-03-03 | 1992-04-07 | Shell Oil Company | Carbonylation catalyst system |
| KR0144567B1 (ko) * | 1989-03-03 | 1998-07-15 | 오노 알버어스 | 카르보닐화촉매시스템 |
| CA2034971A1 (en) * | 1990-02-05 | 1991-08-06 | Eit Drent | Carbonylation catalyst system |
| GB9002521D0 (en) * | 1990-02-05 | 1990-04-04 | Shell Int Research | Carbonylation catalyst system |
| US5179225A (en) * | 1990-02-05 | 1993-01-12 | Shell Oil Company | Carbonylation catalyst system |
| US5166411A (en) * | 1990-02-05 | 1992-11-24 | Shell Oil Company | Carbonylation catalyst system |
| GB9014724D0 (en) * | 1990-07-03 | 1990-08-22 | Shell Int Research | Process for the preparation of alpha,beta-olefinically unsaturated compounds |
| GB9002491D0 (en) * | 1990-02-05 | 1990-04-04 | Shell Int Research | Carbonylation catalyst system |
| ES2088082T3 (es) * | 1991-01-15 | 1996-08-01 | Shell Int Research | Carbonilacion de olefinas. |
-
1993
- 1993-04-06 CN CN93103878A patent/CN1036915C/zh not_active Expired - Fee Related
- 1993-04-06 CA CA002093470A patent/CA2093470C/en not_active Expired - Fee Related
- 1993-04-06 SG SG1996001747A patent/SG49630A1/en unknown
- 1993-04-06 JP JP10183993A patent/JP3516405B2/ja not_active Expired - Fee Related
- 1993-04-06 EP EP93201017A patent/EP0565199B1/en not_active Expired - Lifetime
- 1993-04-06 KR KR1019930005729A patent/KR100277526B1/ko not_active IP Right Cessation
- 1993-04-06 DE DE69304386T patent/DE69304386T2/de not_active Expired - Lifetime
- 1993-04-08 US US08/045,290 patent/US5364957A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0271145A2 (en) * | 1986-12-05 | 1988-06-15 | Shell Internationale Researchmaatschappij B.V. | Process for the carbonylation of conjugated dienes |
| EP0447640A2 (de) * | 1990-03-20 | 1991-09-25 | Webasto AG Fahrzeugtechnik | Auf die feste Dachhaut eines Fahrzeugs aufsetzbare Rahmenspoileranordnung |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930021599A (ko) | 1993-11-22 |
| JP3516405B2 (ja) | 2004-04-05 |
| DE69304386D1 (de) | 1996-10-10 |
| CA2093470C (en) | 2003-12-09 |
| CA2093470A1 (en) | 1993-10-09 |
| CN1078230A (zh) | 1993-11-10 |
| EP0565199B1 (en) | 1996-09-04 |
| SG49630A1 (en) | 1998-06-15 |
| KR100277526B1 (ko) | 2001-02-01 |
| DE69304386T2 (de) | 1997-02-20 |
| EP0565199A2 (en) | 1993-10-13 |
| US5364957A (en) | 1994-11-15 |
| JPH0625086A (ja) | 1994-02-01 |
| EP0565199A3 (en) | 1993-12-29 |
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