CN1149043A - 烯属不饱和化合物的加氢甲酰化方法 - Google Patents
烯属不饱和化合物的加氢甲酰化方法 Download PDFInfo
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Abstract
这里描述了烯属不饱和化合物的醛化方法,该化合物的醛化产物不溶于或微溶于水。反应在作为反应介质的极性有机溶剂中在均相中进行。由羰基铑化合物和磺化或羧化有机膦的盐组成的催化剂体系既可以溶于极性有机溶剂又可溶于水。对于后处理,极性有机溶剂从均匀的反应混合物中蒸除,催化剂体系通过使用水从蒸馏残余物分离。
Description
本发明涉及烯属不饱和化合物的加氢甲酰化方法,它们的加氢甲酰化产物是不溶于或微溶于水。该反应在作为反应介质的极性有机溶剂中在均相中进行。由羰基铑化合物和磺化或羧化有机单膦或多膦的盐组成的催化剂体系既可以溶于极性有机溶剂又可溶于水。
近年来对于烯属不饱和化合物的加氢甲酰化已建立两种方法。一种是在均相中进行,即原料烯烃、催化剂体系(羰基铑和有机膦)和反应产物一起作为溶液存在。通过从反应混合物蒸馏分离出反应产物。其它方法突出表现于存在含水催化剂相,它与反应产物分离并包括羰基铑和磺化或羧化有机膦。这一反应的变化形式使得无需使用热处理步骤就可分离出加氢甲酰化产物,它简化了催化剂的再循环和当使用端烯烃时得到特别高比例的未支化醛类。
较高级的、烯属单不饱和或多不饱和化合物的加氢甲酰化是十分有价值的。这种好处不仅延伸到烃的反应,而且延伸到不仅含有双键而且含有其它反应活性官能团的化合物。具有工业意义的此类化合物的例子是不饱和脂肪酸酯。它们通常是天然的或可以从天然原料制备并且能够大量获得。加氢甲酰化的反应产物,单甲酰基羧酸酯或多甲酰基羧酸酯,也可以含有仍未反应的双键,是供不应求的中间体,它可进一步被加工成广泛使用的产品,如聚胺、聚亚胺酯、醇酸树脂、增塑剂和合成润滑剂。
由使用羰基铑/膦催化剂的均相方法加氢甲酰化较高级的、烯属不饱和或多不饱和化合物已经被反复研究过。这一方法的经济上的利益只有当均匀溶解的催化剂体系能够无损失地从反应产物中分离出来并以活性形式返回加氢甲酰化反应器时才被确保。迄今,只能从由单不饱和脂肪酸酯的加氢甲酰化反应衍生而来的含有甲酰基脂肪酸酯的反应混合物中除去催化剂。然而,除了催化剂以非活性形式获得和催化剂体系的膦组分被完全损失以外,该操作程序还要求耗费的措施(J.Amer.Oil Chem.Soc.vol.50,455(1973))。
当使用具有分开的、相互不靠近的双键的多不饱和化合物时,尽管能够避免双键的异构化而进行加氢甲酰化,但以均相形式溶于反应产物中的催化剂的分离和再循环(例如通过蒸馏)是不可能的。
亚油酸和亚麻酸的甲基酯能够在基于聚硅氧烷的多相化羰基铑/膦配合物催化剂存在下被加氢甲酰化(Chemiker-Zeitung,115(1991,S.39ff))。当使用亚油酸甲酯时,该方法以高达79%的收率得到单甲酰基硬脂酸酯,以所使用的双不饱和的酯为基础计。在上述催化剂体系存在下的加氢甲酰化反应中,亚麻酸得到最大50%的二甲酰基化合物,而三甲酰基产物至多以从属的量(低于10%)获得。所携带的铑的量平均是最初所使用的贵金属的约0.5%。还不能排除部分催化剂金属存在于均相溶液中以与固定金属平衡,这样,加氢甲酰化不仅在固定床催化剂上,而且在溶液中发生。
在含水催化剂溶液存在下在较高级烯属不饱和化合物的加氢甲酰化反应中不会存在反应产物与催化剂体系相互分离的困难。然而,由于烯烃在水中的低溶解性,转化率通常不能令人满意。这一缺点能够避免,如果根据EP-B-157 316,在分子中具有6个以上碳原子的烯烃的加氢甲酰化反应是在包含作为催化剂的铑配合物和作为增溶剂的季铵盐的含水溶液存在下进行的话。这一方法的其它进展是EP-B-163 234的主题。根据该专利,C6-C20烯烃与氢气和一氧化碳在铑和磺化芳基膦的盐(它的阳离子是季铵离子)存在下进行。这里,膦的季铵盐不仅用作催化剂组分,而且同时用作增溶剂。两种方法只涉及不含官能团的单不饱和化合物的反应。
因而,本发明的目的是开发一种方法,它能使较高分子量的烯属不饱和化合物被加氢甲酰化,其中多不饱和起始原料不是仅部分地,而是全部地转化成甲酰基化合物。此外,反应产物和催化剂体系应容易相互分离,大大避免贵金属的损失。
上述目的可由烯属不饱和化合物的加氢甲酰化方法实现,该化合物的加氢甲酰化产物不溶于或微溶于水。它包括在极性有机溶剂中和在包括羰基铑化合物和磺化或羧化有机单膦或多膦的盐(该盐既可以溶于极性有机溶剂又可以溶于水)的催化剂体系存在下,让烯属不饱和化合物在60-180℃和1-35MPa下与一氧化碳和氢气在均相中进行反应,从反应混合物中馏去极性有机溶剂以及通过使用水从蒸馏残余物分离出催化剂体系。
该新方法结合了均相中的加氢甲酰化的特性和在异相的(即含水的)催化剂相存在下加氢甲酰化的优点,从而得到新的、具有前景的操作方法,它非常适合于让较高分子量的烯属单不饱和或多不饱和化合物参与反应。特别成功的是它用于不饱和、优选多不饱和脂肪酸的酯的加氢甲酰化。
令人惊奇的是,本发明的方法能够使存在于酯分子中的多个双键(它们也可以处在非端部位置)被同时被加氢甲酰化,以使,例如,双不饱和化合物得到二甲酰基产物和三不饱和化合物得到三甲酰基产物。此外,该新方法取代了多相反应体系,该体系包括烯属不饱和的化合物和含水催化剂溶液,该方法对于如EP-B-167 316和EP-B-163 234所述的反应来说特征表现在起始原料和催化剂的均相的溶液,结果是反应速率被提高和转化率被改进。
适合作为本发明的起始原料的较高分子量的烯属不饱和化合物必须可溶于作为反应介质的极性有机溶剂和必须得到不溶于或微溶于水的加氢甲酰化产物。因此,在分子中具有6个或6个以上碳原子的无环单烯烃类,尤其C10-C30单烯烃如三和四丁烯类和三和四异丁烯能够根据该新方法进行反应。在分子中具有至少6个碳原子的多不饱和无环或环状烯烃,尤其包括单环和双环烯烃,也能够由本发明的方法很好地加氢甲酰化。这些类别的化合物的例子是二环戊二烯,1,5-环辛三烯,1,5,9-环十二碳三烯,1,5-己二烯,1,7-辛二烯,1,9-癸二烯。如上所述,这一新型方法特别适合于不饱和脂肪酸酯的加氢甲酰化。这些酯类尤其是从分子中具有8-25个碳原子、优选10-20个碳原子的双不饱和或三不饱和脂肪酸和从分子中具有110个碳原子的饱和脂族单元醇(优选甲醇)衍生而来。这些酯类可从天然油通过酯基转移获得,如果需要,该天然油可以预先被精制和蒸馏。作为起始酯的酸组分的基础的天然油是棉籽油、蓟子油、花生油、南瓜子油、亚麻子油、玉米油、大豆油和葵花油。
在作为权利要求的方法中使用催化剂是可溶于极性有机溶剂和可溶于水的体系并包括作为一个组分的羰基铑化合物和作为另一组分的既可以溶于水又可以溶于极性有机溶剂的磺化或羧化有机膦的盐。
羰基铑和膦反应形成配合物,在羰基铑化合物中的一部分一氧化碳分子被作为配体的膦分子取代。此时,铑/膦配合物的溶解性由膦的溶解性决定。膦通常相对于铑过量存在,即催化剂体系不仅含有铑/膦配合物而且含有游离膦。
对于本发明的目的,术语有机膦是指其中烷基和/或芳基键接于三价磷原子的单膦或多膦,这些烷基和/或芳基中至少一个被单或多磺化或羧化。脂族基的例子是在分子中具有2-8个碳原子的饱和烃和在分子中具有5-8个碳原子的环状烃的直链或支化基团。典型的芳基是苯基、苄基和萘基。脂族基和芳族基能够进一步被诸如烷基、羟基或卤素的基团或原子取代。所述有机膦还包括三价磷的这样一些化合物,其中磷原子是杂环的组成部分。
在催化剂体系中存在的膦不必是单一的化合物,而是可以具有不同的化学组成。因此,它们可以在连接于磷原子的基团的类型和键接方式上,在磺化度或羧化度上或在阳离子类型上不同。它们是否适合作为催化剂成分的决定因素是它们在水和在极性溶剂中的溶解性。这一要求尤其可以由这样的磺化或羧化膦的盐满足,它们的阳离子是锂离子或结构式N(R1R2R3R4)+的铵离子。R1,R2,R3和R4可以相同或不同,并且是氢或直链或支化的烷基,尤其具有1-4个碳原子的烷基。
磺化或羧化单膦的阴离子优选对应于结构式(1):这里,Ar1,Ar2,Ar3各自是苯基或萘基。X1,X2,X3各自是磺酸根(-SO3 -)和/或羧酸根(-COO-),Y1,Y2,Y3各自是直链或支化的具有1-4个碳原子的烷基,烷氧基,卤素,OH,CN,NO2或(R5R6)N,其中R5和R6各自是直链或支化的具有1-4个碳原子的烷基,m1、m2和m3是0-5中的相同的或不同的整数,其前提条件是至少一个m1、m2或m3是大于0,n1、n2和n3是0-5中的相同的或不同的整数。
特别合适的盐是从其中Ar1,Ar2,Ar3各自是苯基和X1,X2,X3各自是处在磷的间位的磺酸根的结构式(1)的阴离子衍生出的,即,三(间-磺酸根苯基)-膦(缩写为TPPTS)的盐。
已发现适合作为催化剂组分的其它盐类是二苯基(间-磺酸根苯基)-膦(缩写为TPPMS)的那些盐,特别是锂盐(Li-TPPMS)。
已发现适合作为催化剂组分的单膦阴离子的其它基团是结构式(2)的那些:
A2P-(CH2)n-CH(R)-SO3 - (2)
其中A是相同的或不同的烷基和/或芳基,n是0,1或2和R是氢或烷基。这些化合物通过用1,2-,1,3-或1,4-磺酸内酯将二烷基膦类或二芳基膦类磺烷基化(sulfalkylation)获得的:(其中n=1,2或3和R=H,烷基),例如根据
碱金属盐能够由常规方法转化成铵盐。
它被至少一个磺酸根(-SO3 -)或羧酸根(-COO-)取代。在该结构式中,R7是相同或不同的烷基、环烷基、苯基、甲苯基或萘基,R8可以相同或不同并且是氢,具有1-14个碳原子的烷基或烷氧基,以及具有6-14个碳原子的环烷基、芳基或芳氧基或者被稠合的苯环,各m4可以相同或不同并且是0-5中的整数和n4同样可以相同或不同并且是0-4中的整数。优选磺化化合物,它们能够由普通方法获得。已发现有用的这一类化合物的代表物是由2,2’-双(二苯基-膦基甲基)-1,1’-联苯基或2,2’-双(二苯基-膦基甲基)-1,1’-联萘基的磺化反应获得的。可提及的杂环磷化合物的阴离子的例子是3,4-二甲基-2,5,6-三(对磺酸根苯基)-1-磷杂降冰片二烯。
烯属不饱和起始化合物与氢气和一氧化碳的反应是在60-180℃的温度下,尤其100-140℃下,和在1-35MPa的压力下进行的。对于烯烃的加氢甲酰化,2-35MPa的压力已发现特别有用;不饱和脂肪酸的酯类优选在15-25MPa的压力下反应。
反应是在作为反应介质的极性有机溶剂中进行的,该溶剂不仅溶解烯属不饱和起始化合物而且溶解反应产物和催化剂体系。合适的溶剂是在分子中具有1-4个碳原子的低分子量脂族醇类。代替纯溶剂,有可能使用这些醇类中的两种或多种的混合物,如甲醇/乙醇,甲醇/异丙醇混合物。已发现特别有用的反应介质是甲醇和乙醇,它们可以含有至多5重量%的水,但优选以无水形式使用。
催化剂在加入到反应体系中之前被预成形。然而,在反应混合物(即烯属不饱和化合物和溶剂)中,在反应条件下从组分铑或铑化合物和磺化或羧化膦的溶液同样能够成功地制备催化剂。除了极细散形式的金属铑以外,有可能使用无机铑盐如氯化铑,硫酸铑,有机酸的铑盐如乙酸铑,2-乙基己酸铑或氧化铑作为铑源。
在反应溶液中铑的浓度是100-600ppm(按重量),优选300400ppm(按重量),以溶液为基础计。膦以这样一种量使用:至少20摩尔,优选40-80摩尔的P(III)/摩尔铑.
反应溶液的PH应不低于3的值。PH一般设定在4-11之间。当甲醇用作溶剂时,会发生由加氢甲酰化所形成的醛的乙酰化。如果希望保护羰基免受第二次反应,建议在PH4.5-6.5,优选5.5-6.0下进行。
在合成气中一氧化碳与氢气的比例能够在大范围内变化。一般来说,所使用的合成气是其中一氧化碳与氢气的体积比为1∶1或与这一值偏离很小的合成气。
该反应能够间歇或连续进行。
对于处理反应产物,极性有机溶剂首先被蒸除。蒸馏残余物然后用水洗涤,优选在室温下,以从醛类中除去催化剂体系。如果合适,这一处理可以重复进行几次。为了完全回收铑,已发现有利的是向洗涤水中添加能与铑形成配合物的膦,最好膦同时也是催化剂组分。
本发明的方法通过下面的实施例来进行说明,但并不限于所给出的实施方案。
实施例1
在一个已用氩气吹洗过的Schlenk管中装入15ml甲醇,60mg(0.05mmol)的8.5重量%的铑溶液(作为Rh2(SO4)3水溶液)和700mg(2mmol)的二苯基(4-磺酸根丁基锂)膦。P/Rh摩尔比是40。溶液的PH值被调节至5,然后该溶液借助于注射器被注入实验室压力釜中,该釜已用氩气吹洗过并填充了氩气。将15g 90重量%强度的亚麻酸甲酯(剩余物:亚油酸甲酯)装入压力釜的耐压滴液漏斗中。压力釜用用水煤气吹洗,随后设定反应压力20MPa和反应温度120℃。在1小时的预成形之后,滴加亚麻酸甲酯和然后由压力传感器和记录器调控压力下降。在10小时后完成气体的吸收。冷却压力釜,排气,它的内容物在排除空气的情况下(氩气)通过蒸馏除去甲醇。残余物用无氧水洗涤两次(每次15-20ml)来抽提催化剂体系,然后进行分析。亚麻酸和亚油酸酯的转化率是定量的,收率是:
5%的单甲酰基产物,以总起始原料为基础,
22%的二甲酰基产物,以总起始原料为基础,
82%的三甲酰基产物,以在起始原料中使用的亚麻酸甲酯为基
础。
实施例2-6
实施例2-6
按与实施例1的方式来进行,只是改变压力,催化剂溶液的PH值,和P/Rh比例。所得的结果在下表中给出。
表1实施例 P/Rh PH 温度 压力 时间1) MF2) DF3) TF4) 转化率
[℃] [MPa] [h] [mol%] [%]2 40 8.4 120 20 3 4 24 80 1003 20 5.0 120 20 3 14 44 47 1004 10 5.0 120 20 3 16 44 45 1005 10 5.0 120 7 3 20 50 34 1006 20 5.0 120 7 3 15 59 40 100
1)时间,在该时间后已吸收90-95%的气体
2)单甲酰基产物,以总起始原料为基础
3)二甲酰基产物,以总起始原料为基础
4)三甲酰基产物,以所使用的亚麻酸甲酯为基础
实施例7
在已用氩气吹洗并装有磁力搅拌器、耐压计量容器、热电偶底座和压力传感器(膨胀测量条)的一个100ml V4A不锈钢压力釜中,装入24mg铑(0.05mmol)(作为Rh2(SO4)3水溶液的形式)和2.2g(3mmol)的已溶于30ml甲醇的三(四甲基铵-间-磺酸根苯基)膦(P/Rh比:60)。封闭压力釜,用水煤气吹洗,设定反应温度120℃和反应压力2MPa。然后从计量器添加10g(50mmol)的10-十一碳烯酸甲酯。1小时后,反应完成。形成了97%的由71% 11-甲酰基十一羧酸甲酯和29% 10-甲酰基十一羧酸甲酯组成的混合物,以及3%的氢化产物十一羧酸甲酯。在蒸除甲醇之后,催化剂体系被吸收在水中,并通过相分离从反应产物中分离出来。
实施例8
在反应压力1MPa下,其它条件相同,重复实施例7。仅仅在30分钟后结束转化反应。除了99%的由70重量% 11-甲酰基十一羧酸甲酯和30重量% 10-甲酰基十一羧酸甲酯组成的混合物以外,只获得1%的十一碳酸甲酯。在蒸除甲醇之后催化剂被吸收在水中,并从反应产物中分离出来。
实施例9
在作为保护气的氢气气氛下,将15ml甲醇,0.05mmol Rh(以60mg的8.5%的铑溶液(作为Rh2(SO4)3水溶液)形式)和348mg(1mmol)的Li-TPPMS(P/Rh摩尔比:20)装入Schlenk管中。溶液的PH被调节至6和该溶液在氩气气氛中装入压力釜。在封闭压力釜和用水煤气吹洗压力釜之后,设定反应压力10MPa和反应温度120℃。从计量器加入12g(60mmol)的正十四碳-1-烯。1小时后,烯烃已完全反应。形成了98%的具有组成:72重量%正十五醛和28重量% 2-甲基-十四醛的加氢甲酰化产物,以及2%的氢化产物正十四烷。醛类主要以二甲基乙缩醛的形式获得(约70%)。在蒸除绝大部分的甲醇溶剂之后,反应产物与约10ml水混合以分离出催化剂配合物。有机相再次用约5ml水萃取。在合并含水萃取液之后,在减压下蒸去水,催化剂体系被再次溶于甲醇中。
实施例10-15
按实施例9中所述回收的催化剂体系被再次用于正十四碳-1-烯的加氢甲酰化。条件与实施例9中一样。实验结果在表2中给出。 实施例 转化率 收率 正十五醛 2-甲基十四醛 十四烷
(%) (%) (%) (%) (%)
10 100 98 72 28 2
11 100 96 70 30 4
12 100 98 71 29 2
13 100 99 70 30 1
14 100 98 71 29 2
15 100 97 70 30 3
实施例16
在作为保护气的氩气气氛下,将25ml甲醇,0.05mmol Rh(以60mg的8.5%的铑溶液(作为Rh2(SO4)3水溶液)形式)和348mg(1mmol)的Li-TPPMS(P/Rh摩尔比:20)装入Schlenk管中。溶液的PH被调节至11和该溶液在氩气气氛中装入压力釜。在封闭压力釜和用水煤气吹洗压力釜之后,设定反应压力10MPa和反应温度120℃。从计量器加入12g(60mmol)的正十四碳-1-烯。1小时后,烯烃已完全反应。形成了98%的具有组成:71重量%正十五醛和29重量% 2-甲基-十四醛的加氢甲酰化产物,以及2%的氢化产物正十四烷。只有3%的所形成的醛类是以二甲基乙缩醛的形式获得的(作为高PH值11的结果)。
实施例17
在作为保护气的氩气气氛下,将15ml甲醇,0.05mmol Rh(以60mg的8.5%的铑溶液(作为Rh2(SO4)3水溶液)形式)和348mg(1mmol)的Li-TPPMS(P/Rh摩尔比:20)装入Schlenk管中。溶液的PH被调节至6和该溶液在氩气气氛中装入压力釜。在封闭压力釜和用水煤气吹洗压力釜之后,设定反应压力20MPa和反应温度120℃。从计量器加入16g(50mmol)工业亚麻酸甲酯(55%的亚麻酸甲酯,剩余物约15%亚油酸甲酯,约20%油酸甲酯)。3小时后,烯烃已完全反应。反应混合物含有23重量%的单甲酰基产物,22重量%的二甲酰基产物和47重量%的三甲酰基产物。基于在工业产物中亚麻酸甲酯的比例为55%,基于三重加氢甲酰化产物的形成,这意味着85%的选择性。
Claims (26)
1、一种加氢甲酰化烯属不饱和化合物的方法,它的加氢甲酰化产物不溶于或微溶于水,该方法包括在极性有机溶剂中和在包含羰基铑化合物和磺化或羧化有机单膦或多膦的盐-该盐既可以溶于极性有机溶剂又可以溶于水-的催化剂体系的存在下,让烯属不饱和化合物在60-180℃和135MPa下与一氧化碳和氢气在均相中进行反应,从反应混合物中馏出极性有机溶剂以及通过使用水从蒸馏残余物分离出催化剂体系。
2、根据权利要求1所要求的方法,其中烯属不饱和化合物是在分子中具有10个或10个以上碳原子的无环单烯烃,在分子中具有至少6个碳原子的多不饱和无环或环状烯烃或不饱和脂肪酸的酯类。
3、根据权利要求1或2所要求的方法,其中烯属不饱和化合物是无环C16-C30单烯烃。
4、根据权利要求1或2所要求的方法,其中烯属不饱和化合物是在分子中具有至少6个碳原子的单环或双环烯烃。
5、根据权利要求1或2所要求的方法,其中烯属不饱和化合物是在分子中具有8-25个碳原子的双不饱和或三不饱和脂肪酸的酯类。
6、根据权利要求5所要求的方法,其中酯类是从在分子中具有10-20个碳原子的双不饱和或三不饱和脂肪酸衍生而来的。
7、根据权利要求2,5和6中一项或多项所要求的方法,其中酯类是从在分子中具有1-10个碳原子的饱和脂族单元醇衍生而来的。
8、根据权利要求7所要求的方法,其中脂族单元醇是甲醇。
9、根据权利要求1-8中一项或多项所要求的方法,其中极性有机溶剂是在分子中具有1-4个碳原子的低分子量脂族醇或这些醇的两种或多种的混合物。
10、根据权利要求9所要求的方法,其中极性溶剂是甲醇或乙醇。
11、根据权利要求1-10中一项或多项所要求的方法,其中磺化或羧化有机膦的盐-该盐可溶于极性有机溶剂和可溶于水-的阳离子是锂离子或结构式N(R1R2R3R4)+的铵离子,其中R1,R2,R3和R4可以相同或不同,并且是氢或直链或支化的烷基,尤其具有1-4个碳原子的烷基。
13、根据权利要求12所要求的方法,其中磺化有机膦的盐-该盐可溶于极性有机溶剂和可溶于水-含有三(间-磺酸根苯基)膦阴离子。
14、根据权利要求1-11中一项或多项所要求的方法,其中磺化有机膦的盐-该盐可溶于极性有机溶剂和可溶于水-的阴离子具有以下结构式:A2P-(CH2)m-CH(R)-SO3 -
其中A是相同的或不同的烷基和/或芳基,n是0,1或2和R是氢或烷基。
16、根据权利要求15所要求的方法,其中可溶于极性有机溶剂和可溶于水的盐的阴离子是从二芳基化合物衍生而来的,该化合物被至少一个磺酸根取代。
17、根据权利要求1-16中一项或多项所要求的方法,其中烯属不饱和化合物与氢气和一氧化碳的反应是在100-140℃下进行。
18、根据权利要求1-4和11-17中一项或多项所要求的方法,其中烯烃与氢气和一氧化碳的反应是在2-35Mpa范围内的压力下进行的。
19、根据权利要求1,2和5-17中一项或多项所要求的方法,其中不饱和脂肪酸酯与一氧化碳和氢气的反应是在15-25Mpa下进行的。
20、根据权利要求1-19中一项或多项所要求的方法,其中在催化剂溶液中铑的浓度是100-600重量ppm,以溶液为基础计。
21、根据权利要求20所要求的方法,其中在催化剂溶液中铑的浓度是300-400重量ppm,以溶液为基础计。
22、根据权利要求1-21中一项或多项所要求的方法,其中在反应溶液中每摩尔铑存在至少20摩尔,优选40-80摩尔的P(III)。
23、根据权利要求1-22中一项或多项所要求的方法,其中反应溶液的PH是至少3,优选4-11。
24、根据权利要求1-8和10-22中一项或多项所要求的方法,其中反应溶液的PH是4.5-6.5,尤其5.5-6.0。
25、根据权利要求1-24中一项或多项所要求的方法,其中催化剂体系通过多次用水处理从蒸馏残余物中分离出来。
26、根据权利要求1-25中一项或多项所要求的方法,其中能够与铑形成配合物的膦被加入到用来处理蒸馏残余物的水中。
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DE19532393.9 | 1995-09-02 | ||
DE19532393A DE19532393A1 (de) | 1995-09-02 | 1995-09-02 | Verfahren zur Hydroformylierung olefinisch ungesättigter Verbindungen |
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CN1149043A true CN1149043A (zh) | 1997-05-07 |
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CN96111973A Pending CN1149043A (zh) | 1995-09-02 | 1996-08-30 | 烯属不饱和化合物的加氢甲酰化方法 |
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US (1) | US5756854A (zh) |
EP (1) | EP0761635B1 (zh) |
JP (1) | JP3042835B2 (zh) |
KR (1) | KR970015551A (zh) |
CN (1) | CN1149043A (zh) |
AT (1) | ATE182876T1 (zh) |
AU (1) | AU6439096A (zh) |
BR (1) | BR9603617A (zh) |
CA (1) | CA2184048C (zh) |
DE (2) | DE19532393A1 (zh) |
DK (1) | DK0761635T3 (zh) |
ES (1) | ES2137604T3 (zh) |
GR (1) | GR3031630T3 (zh) |
MX (1) | MX9603656A (zh) |
PL (1) | PL183632B1 (zh) |
TW (1) | TW389751B (zh) |
ZA (1) | ZA967228B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
CN101722048B (zh) * | 2008-10-31 | 2011-11-30 | 中国石油化工股份有限公司 | 一种两相催化氢甲酰化反应制备醛的催化剂及其应用 |
CN112570032A (zh) * | 2020-11-17 | 2021-03-30 | 广东仁康达材料科技有限公司 | 一种水溶性氢甲酰化催化剂及其应用 |
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ID21537A (id) * | 1997-12-22 | 1999-06-24 | Celanese Gmbh | Proses pembuatan aldehid |
KR100308731B1 (ko) * | 1998-06-17 | 2001-11-14 | 박호군 | 로듐촉매/염조촉매시스템을사용한이산화탄소의수소화방법 |
US6303829B1 (en) | 2000-03-15 | 2001-10-16 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6307110B1 (en) | 2000-03-15 | 2001-10-23 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6310260B1 (en) | 2000-03-15 | 2001-10-30 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6307109B1 (en) | 2000-03-15 | 2001-10-23 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6303830B1 (en) | 2000-03-15 | 2001-10-16 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
US6307108B1 (en) | 2000-03-15 | 2001-10-23 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
US6294700B1 (en) | 2000-03-15 | 2001-09-25 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
KR100322617B1 (ko) * | 2000-08-29 | 2002-03-18 | 박호군 | 로듐 촉매/염 조촉매 시스템을 사용한 올레핀의카보알콕시화 및 카복실화 방법 |
KR100322616B1 (ko) * | 2000-08-29 | 2002-03-18 | 박호군 | 로듐 촉매/염 조촉매 시스템을 사용한 올레핀의하이드로포밀화 방법 |
UA86019C2 (ru) * | 2003-04-25 | 2009-03-25 | Доу Глобал Технолоджис Инк. | Альдегидные и спиртовые композиции, полученные из растительных масел, и способы их получения |
MY147009A (en) * | 2006-05-15 | 2012-10-15 | Dow Global Technologies Inc | Hydroformylation process and product separation with improved recovery of rhodium |
US9382180B2 (en) | 2012-12-06 | 2016-07-05 | Dow Technology Investments Llc | Hydroformylation process |
WO2015134769A1 (en) * | 2014-03-06 | 2015-09-11 | Elevance Renewable Sciences, Inc. | Renewably derived aldehydes and methods of making and using the same |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
JPS58216138A (ja) * | 1982-06-09 | 1983-12-15 | Kuraray Co Ltd | 1,8−オクタンジア−ルまたは1,10−デカンジア−ルの製造法 |
FR2571725B1 (fr) * | 1984-10-16 | 1987-09-18 | Rhone Poulenc Chim Base | Complexes rhodies, dinucleaires et hydrosolubles et leur utilisation comme catalyseur d'hydroformylation |
US4808756A (en) * | 1986-04-07 | 1989-02-28 | Kuraray Co., Ltd. | Method for production of α,ω-dialdehydes |
US4731486A (en) * | 1986-11-18 | 1988-03-15 | Union Carbide Corporation | Hydroformylation using low volatile phosphine ligands |
JP2775907B2 (ja) * | 1989-07-12 | 1998-07-16 | 三菱化学株式会社 | ヒドロホルミル化法 |
DE3942954A1 (de) * | 1989-12-23 | 1991-06-27 | Hoechst Ag | Verfahren zur herstellung von aldehyden |
-
1995
- 1995-09-02 DE DE19532393A patent/DE19532393A1/de not_active Withdrawn
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1996
- 1996-08-16 TW TW085109975A patent/TW389751B/zh active
- 1996-08-23 CA CA002184048A patent/CA2184048C/en not_active Expired - Fee Related
- 1996-08-24 ES ES96113605T patent/ES2137604T3/es not_active Expired - Lifetime
- 1996-08-24 AT AT96113605T patent/ATE182876T1/de active
- 1996-08-24 DK DK96113605T patent/DK0761635T3/da active
- 1996-08-24 EP EP96113605A patent/EP0761635B1/de not_active Expired - Lifetime
- 1996-08-24 DE DE59602596T patent/DE59602596D1/de not_active Expired - Fee Related
- 1996-08-26 US US08/701,775 patent/US5756854A/en not_active Expired - Fee Related
- 1996-08-26 ZA ZA967228A patent/ZA967228B/xx unknown
- 1996-08-26 PL PL96315833A patent/PL183632B1/pl unknown
- 1996-08-26 MX MX9603656A patent/MX9603656A/es not_active IP Right Cessation
- 1996-08-26 KR KR1019960035491A patent/KR970015551A/ko not_active Application Discontinuation
- 1996-08-30 AU AU64390/96A patent/AU6439096A/en not_active Abandoned
- 1996-08-30 CN CN96111973A patent/CN1149043A/zh active Pending
- 1996-08-30 BR BR9603617A patent/BR9603617A/pt not_active Application Discontinuation
- 1996-08-30 JP JP8230636A patent/JP3042835B2/ja not_active Expired - Fee Related
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
CN101722048B (zh) * | 2008-10-31 | 2011-11-30 | 中国石油化工股份有限公司 | 一种两相催化氢甲酰化反应制备醛的催化剂及其应用 |
CN112570032A (zh) * | 2020-11-17 | 2021-03-30 | 广东仁康达材料科技有限公司 | 一种水溶性氢甲酰化催化剂及其应用 |
Also Published As
Publication number | Publication date |
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DE19532393A1 (de) | 1997-03-06 |
ATE182876T1 (de) | 1999-08-15 |
CA2184048A1 (en) | 1997-03-03 |
TW389751B (en) | 2000-05-11 |
KR970015551A (ko) | 1997-04-28 |
EP0761635A1 (de) | 1997-03-12 |
GR3031630T3 (en) | 2000-01-31 |
PL315833A1 (en) | 1997-03-03 |
PL183632B1 (pl) | 2002-06-28 |
JPH09124534A (ja) | 1997-05-13 |
JP3042835B2 (ja) | 2000-05-22 |
ZA967228B (en) | 1997-03-03 |
ES2137604T3 (es) | 1999-12-16 |
AU6439096A (en) | 1997-03-06 |
DE59602596D1 (de) | 1999-09-09 |
BR9603617A (pt) | 1998-05-19 |
MX9603656A (es) | 1997-03-29 |
DK0761635T3 (da) | 1999-12-06 |
EP0761635B1 (de) | 1999-08-04 |
CA2184048C (en) | 1999-05-25 |
US5756854A (en) | 1998-05-26 |
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