CN1039706C - 癸醇混合物及由其获得的邻苯二甲酸酯 - Google Patents

癸醇混合物及由其获得的邻苯二甲酸酯 Download PDF

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CN1039706C
CN1039706C CN93103474A CN93103474A CN1039706C CN 1039706 C CN1039706 C CN 1039706C CN 93103474 A CN93103474 A CN 93103474A CN 93103474 A CN93103474 A CN 93103474A CN 1039706 C CN1039706 C CN 1039706C
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H·巴赫曼
W·哥乐伯
P·赫曼斯
P·拉普
J·萨迈塔特
T·姆勒
E·维布斯
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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    • C07C47/00—Compounds having —CHO groups
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Abstract

异构癸醇混合物是通过使丁二烯醛化为醛混合物、缩合从反应产物中分离出的醛混合物以形成醛醇混合物并分离及氢化醛醇混合物而获得。利用邻苯二甲酸酯化异构癸醇混合物后得到邻苯二甲酸癸酯异构混合物，它可用作增塑剂。

Description

癸醇混合物及由其获得的邻苯二甲酸酯
本发明涉及异构癸醇混合物，它们的制备方法，由这些醇获得的邻苯二甲酸酯，以及它们作为增塑剂的应用。
邻苯二甲酸酯被广泛用作增塑剂，对于聚氯乙烯尤其如此。所使用的主要醇成分是有8至10个碳原子的伯醇，其中最重要的是2-乙基已醇。短链醇的邻苯二甲酸酯将使得增塑剂具有良好的胶凝能力，但是，与长链化合物相比，其高挥发性是不利的。而另一方面，长链酯的胶凝极其缓慢且其抗冷性较差。
邻苯二甲酸酯增塑剂的性质不仅受醇分子大小的影响，而且也受碳链支化的影响。由分支较少的醇所产生的酯增塑剂尤其受到高度重视，因为它们具有很高的冷挠曲性。分子中有8至10个碳原子的基本上为线性的醇作为醇组分的重要性正在不断增大。使用它们的一个先决条件是它们能够以低成本大量得到。
按照德国专利2 855 421，用作增塑剂的C9醇的邻苯二甲酸酯是通过C8烯烃羰基合成、反应产物的氢化以及使用邻苯二甲酸酐酯化C9醇而制得。3-20％(重量)的起始烯烃在其每一分子链中具有异丁烷骨架，3％(重量)以下的烯烃具有季碳原子，且烯烃总重量90％以上是以正辛烯、单甲基庚烯和二甲基已烯的形式存在。另外，正辛烯和单甲基庚烯的总重量与二甲基已烯的重量之比大于0.8。
由C10醇制得的邻苯二甲酸酯是欧洲专利申请03 66 089的目的。所使用的C10醇是以混合物的形式存在，它是通过丁烯的加氢甲酰化、所得醛混合物的醛醇缩合以及随后的氢化而获得。
欧洲专利申请04 24 767叙述了获得邻苯二甲酸二癸酯混合物的另一种途径，该酯是通过多步骤方法制得，该方法包括使丁烯混合物二聚化、使所得辛烯混合物加氢甲酰化和氢化为壬醇混合物，使壬醇混合物脱水为壬烯混合物以及使壬烯混合物加氢甲酰化和氢化，从而形成癸醇混合物。
已知方法均没有满足工业规模实施过程中所有的经济和技术要求，它们或者是原材料不能大量得到和/或以理想的价格得到，或者是将原料转化为醇的方法成本太高。
因此，本发明的目的是要开发这样一种方法，其原料能够很便宜地得到并且能够按照简单的工业方法转化成所需的醇。
本发明包括异构癸醇混合物，它是通过如下方法获得：将丁二烯加氢甲酰化为醛混合物，从反应产物中分离出所产生的醛混合物，将醛混合物缩合成醛醇混合物，分离并氢化醛醇混合物，从而得到异构癸醇混合物。
作为制备本发明的异构癸醇混合物的原料的丁二烯不仅能够通过丁烷或丁烯的脱氢很容易地制得，而且在通过热裂解轻质石油或高级烃制备乙烯的过程中会不可避免地大量产生，它可采用选择性溶剂(如乙腈、二甲基甲酰胺或N-甲基吡咯烷酮)通过液—液萃取从热解产物的C4裂化片段中分离出来。
用于加氢甲酰化的丁二烯为目前的市售形式，即其纯度至少为99.5％(重量)。共轭二烯烃的加氢甲酰化为本身已知的反应。该反应在钴催化剂和铑催化剂的作用下进行。钴催化剂反应在例如Ad-kins和Williams(J.Org.Chem.17，980(1952)中已有记载。所产生的是摩尔比为1∶1产率中等的正戊醛和异戊醛的混合物。
当使用铑催化剂进行丁二烯的加氢甲酰化时能获得有利得多的醛产率。铑与含有三价磷原子的多合配位体形成的复合物已被证明是有利的。在例如欧洲专利33 554中记载了依靠这类催化剂的方法。
在本发明中，优选的是在非均匀两相体系中进行丁二烯的加氢甲酰化。这一方法在例如德国专利26 27 354中已有记载。该方法的不同在于存在一有机相和一水相，其中有机相含有起始烯烃和反应产物，水相中渗解了催化剂。所使用的催化剂是铑与作为配位体的水溶性膦所形成的水溶性复合物。水溶性膦尤其包括三芳基膦、三烷基膦和烷基-、芳基-或烷芳基-二膦，其有机残基被磺酸基团或羧酸基团取代。它们的制备方法是已知的，例如见德国专利26 27 354和民主德国专利259194。该反应是在温度为60-150℃(优选90-120℃)、压力为0.4-30MPa(优选1-10MPa)的条件下进行。铑的浓度按催化剂水溶液的重量计为20-2000ppm，优选50-5000ppm；每摩尔铑使用4-100摩尔水溶性膦。水相与有机相的体积比为0.1至10∶1。
如果向催化剂水溶液中加入相转移试剂(加溶剂)则能显著增加丁二烯的转化，对式[A-N(R1R2R3)]+E-的阳离子加溶剂尤其如此，其中A为具有6-25个碳原子的直链或支链烷基，R1、R2和R3可相同或不同且为具有1-4个碳原子的直链或支链烷基，E尤其为硫酸盐、四氟硼酸盐、乙酸盐、甲硫酸盐、苯甲磺酸盐、烷基苯甲磺酸盐、甲苯磺酸盐、乳酸盐或柠檬酸盐。
利用铑作为催化剂对丁二烯进行加氢甲酰化，不论是在单相反应体系中还是在两相反应体系中均以高产率产生主要为饱和醛的混合物。通过改变合成气中的氢成分可使得饱和醛与不饱和醛的比在很宽的范围内变化。增加氢气气压有利于饱和醛的形成。
醛混合物含有90％或90％以上的正戊醛及少量的其它醛，包括异戊醛、二醛和其它副产物。通过选择膦配位体可改变醛混合物的组成。当使用含有水溶性烷基膦或烷基二膦或芳基二膦作为配位体的水溶性铑催化剂时，能够获得特别高的正/异比。
加氢甲酰化完成之后，从催化剂、未反应的反应物以及其它反应产物中分离出醛混合物。当反应在均相中发生时，通常的分离方法是蒸馏。如果加氢甲酰化是在两相体系中进行，产物和催化剂可采用简单的相分离方法彼此分离。在工业实施过程中，由于不存在热应力，该方法要简便得多，而且要比通过蒸馏分离醛混合物温和得多。不论使用何种方法，丁二醛的加氢甲酰化均可不连续进行或连续进行。如果所使用的丁二醛中仅一部分转化为醛而其余部分再用于循环，则能获得对正戊醛的高选择性。
按照常规途径通过碱性催化剂以作用可完成以混合物形式存在的醛醇缩合。对醛的预处理，如特别纯化是不需要的。所用催化剂是碱金属碳酸盐或碱金属氢氧化物，尤其是钠盐或甲盐，以及胺，优选的是叔胺，如三乙胺、三正丙胺和三正丁胺。所使用的温度为60-160℃，尤其是80-130℃，且所使用的压力为大气压或高达约1MPa的升高压力。反应时间为几分钟或高达几小时，它具体取决于催化剂的类型以及反应温度。由于其反应速率较高，正戊醛主要与其本身或与其它异构戊醛二聚化，产生癸醛；与此相反，分支的C5醛之间完全不出现缩合。
然后氢化通过缩合获得的醛混合物，得到癸醇混合物，加氢可按已知方法在催化剂存在的情况下进行。合适的催化剂是例如镍、铬或铜作为主要成分的氢化催化剂。氢化温度通常在100-180℃之间，压力在1-10MPa之间。癸醇混合物通过蒸馏纯化。它尤其适用作被用作增塑剂的邻苯二甲酸酯中的醇成分。邻苯二甲酸酯的制备方法是已知的[见Uumann，Encyclopaidie der TechnischenChemie[Encyclopeddia of Industral Chemistry](1979)，Volume18，page 536ff]。将邻苯二甲酸酐与癸醇混合物按1∶2的摩尔比一步进行反应较为有利。通过使用催化剂和/或通过提高反应温度可提高反应速率。为了使平衡向成酯方向转移，必须从反应混合物中除去形成的水。
按照本发明由癸醇混合物获得的邻苯二甲酸酯的不同之处在于在作为增塑剂时具有良好的抗冷性质。

Claims (3)

1.异构癸醇混合物，它是通过如下方法获得：在水及含有作为配位体的磺化烷基膦或芳基膦的水溶性铑复合物催化剂存在下，于温度为70-150℃、压力为0.4-30MPa、水相与有机相的体积比为0.1-10∶1、催化剂水溶液中铑的浓度20-2000ppm且每摩尔铑使用4-100摩尔膦的条件下，醛化丁二烯，产生醛混合物，缩合醛混合物以形成醛醇混合物，使醛醇混合物分离并氢化，从而产生异构癸醇混合物。
2.根据权利要求1所述的异构癸醇混合物，其中丁二烯的醛化是在作为催化剂的水溶性铑复作合物存在下进行的，该催化剂含有作为配位体的磺化芳基二膦、烷基二膦或烷芳基二膦。
3.根据权利要求1所述的异构癸醇混合物，其中水溶性催化剂溶液含有相转移试剂。
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US5382716A (en) 1995-01-17
DE4210028A1 (de) 1993-09-30
KR100290220B1 (ko) 2001-05-15
JPH11222450A (ja) 1999-08-17
DE59309198D1 (de) 1999-01-21
TW241286B (zh) 1995-02-21
KR930019605A (ko) 1993-10-18
EP0562450A3 (en) 1994-11-23
ES2127227T3 (es) 1999-04-16
CN1122326A (zh) 1996-05-15
CN1076936A (zh) 1993-10-06
MX9301571A (es) 1993-11-01
EP0562450B1 (de) 1998-12-09
EP0562450A2 (de) 1993-09-29
JPH0739360B2 (ja) 1995-05-01
ATE174317T1 (de) 1998-12-15
AU659293B2 (en) 1995-05-11
DK0562450T3 (da) 1999-08-16
JPH0672924A (ja) 1994-03-15
AU3545393A (en) 1993-09-30
CA2092040A1 (en) 1993-09-28
ZA931988B (en) 1993-10-19
SG44987A1 (en) 1997-12-19
BR9301282A (pt) 1993-10-05

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