CN1252784A - 一步法由链烯制备二醇单醚的方法 - Google Patents
一步法由链烯制备二醇单醚的方法 Download PDFInfo
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- CN1252784A CN1252784A CN98804365A CN98804365A CN1252784A CN 1252784 A CN1252784 A CN 1252784A CN 98804365 A CN98804365 A CN 98804365A CN 98804365 A CN98804365 A CN 98804365A CN 1252784 A CN1252784 A CN 1252784A
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- Prior art keywords
- catalyst
- alkene
- mixture
- epoxidation
- acid
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Abstract
一种用于从链烯制备二醇单醚的方法,包括链烯与环氧化试剂在同时存在含羟基有机化合物的情况下在环氧化催化剂和烷氧化催化剂的混合物上进行反应。
Description
本发明涉及一种从链烯制备二醇单醚的改进方法。本发明进一步涉及用于本发明方法的催化剂混合物。
二醇单醚在工业上大量用作溶剂、涤气过程中的吸收液体、防冻液、水力系统用流体、润滑剂、增塑剂、表面活性剂、用于纤维产品如聚酯或者尿烷的前体、用于油墨和在化妆品和护肤品中的添加剂。
最重要的产品是乙烯和丙烯的相应二醇醚。这些二醇醚通常是通过母体链烯的环氧化物与相应的醇反应来制备。
这种方法的缺点是需要一个多步工艺,它包括先从链烯制备环氧化物,接着在高温下采用例如硫酸进行环氧化物与醇的开环反应。
本发明的目的是提供一种制备二醇单醚的更简单方法。
我们出乎意料地发现可以通过简单地一步合成达到这个目的并克服上述缺点,所说合成包括将链烯与常规环氧化试剂在合适的环氧化催化剂上反应,并同时允许存在含羟基有机化合物,例如醇,和酸性或者碱性烷氧化催化剂。环氧化物中间体就地在所加入的烷氧化催化剂上反应,生成二醇单醚。
本发明提供了一种从链烯制备二醇单醚的方法,该方法包括链烯与环氧化试制在同时存在含羟基有机化合物的情况下在环氧化催化剂和烷氧化催化剂的混合物上反应。
在催化剂混合物中的优选环氧化催化剂是含钛硅酸盐或者含钛、钒、锗或者锡的沸石,特别是钛或钒的硅质岩(silicalite),它们具有通过X射线衍射测定的沸石结构:MFI、MEL、BEA、MTW、TON、FER或MFI/MEL混合结构。这类环氧化催化剂记载在例如DE-A4425672中。根据DE-A4425672,上述钛或钒的硅质岩可含有贵金属,例如0.01~20%重量的金属铂,这在所采用的环氧化试剂是氢/氧混合物时特别有利。
在催化剂混合物中优选的烷氧化催化剂是无机酸形式的或者固体酸性多相催化剂形式的酸性催化剂和固体碱性催化剂。
无机酸的例子是硫酸、氢氯酸和原磷酸;基于本发明的目的,无机酸包括有足够酸性的有机磺酸和羧酸,例如对甲苯磺酸、甲磺酸或者三氟乙酸。
固体烷氧化催化剂是特别适合的,即不溶解在反应介质中并且在反应过程中以固相(作为多相催化剂)存在的那些。
优选给出的是固体酸性多相催化剂,它基于所负载的无机酸、聚合的酸性离子交换树脂、酸性离子交换树脂在无机物中的复合物、酸性金属氧化物或者酸性沸石。这类多相催化剂的例子是K10型酸性片状硅酸盐、Arata记载在Appl.Catalysis A:General 146(1996),3~32的酸性金属氧化物和结构类型为MFI(例如H-ZSM-5沸石)、MEL、MFI/MEL、BEA(例如H-B-β-沸石)、MOR、FER、NES、ERI、OFF、MAZ、FAU、TON、CHA、RUT、BOG、LTA、NON、MTN、HEU、AFI、MTM、DOH、EUO、MTT、RHO、CAN、LTL、GIS、GME、VFI、EMT、DDR、SGT、CON、ZON或MFS的酸性沸石。
也优选固体碱性催化剂,它基于碱金属或者碱土金属氧化物或者氢氧化物、被承载的碱、聚合的碱性离子交换树脂、dendrimeric胺、滑石(talcites)或氢滑石(hydrotalcites)。
上述催化剂混合物通常含有1~99重量份的环氧化催化剂和99~1重量份的烷氧化催化剂,此时烷氧化催化剂以固体形式存在,即作为多相催化剂。这两类催化剂的优选份额范围为5~95重量份/95~5重量份,特别是20-80重量份:80-20重量份。上述催化剂混合物可以另外含有其它常规添加剂。当游离无机酸作为烷氧化催化剂存在时,环氧化催化剂与烷氧化催化剂的比例通常为90~99.999重量份:10~0.001重量份,特别是90~99.99重量份:1~0.01重量份。
由于固体环氧化催化剂和固体烷氧化催化剂的上述混合物是新的,本发明还提供了一种用于一步环氧化和烷氧化链烯的催化剂混合物,它含有1~99重量份的环氧化催化剂和99~1重量份的固体烷氧化催化剂。
用于本发明方法的特别有效的环氧化试剂是过氧化氢水溶液或者氢/氧混合物。采用氢/氧化合物用于环氧化反应记载在例如DE-A4425672中。但是,有机过酸或者过氧化氢作为环氧化试剂也是有效的。
含羟基有机化合物主要是所有具有足够的O-H酸性的一羟基和多羟基化合物。优选给出线性或者支链化的C1-到C20-链烷醇、C5-到C8-环烷醇和C7-到C20-芳基烷醇。这类醇的例子是甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、仲丁醇、叔丁醇、戊醇、异戊醇、仲戊醇、叔戊醇、新戊醇、己醇、庚醇、辛醇、2-乙基己醇、壬醇、异壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、异十三烷醇、十四烷醇、十五烷醇、十六烷醇、十七烷醇、十八烷醇、二十烷醇、环戊醇、环己醇、环庚醇、环辛醇、苄醇、2-苯基乙醇、3-苯基丙醇和4-苯基丁醇。也可以采用上述醇的混合物。特别优选给出C1-到C8-烷醇。
含羟基的有机化合物可以基于链烯的烯键不饱和双键的当量以化学计量的量或者过量使用,并且还可作为溶剂。如果含羟基化合物也与链烯的其它官能团反应,含羟基化合物的量要增加。
所采用的链烯可以是含有至少一个烯键不饱和双键的任何有机化合物。它可以是脂肪的、芳香或者环脂的并可由线性或者支链化结构构成。链烯优选为2到30个碳原子。可以存在多于一个链烯不饱和双键,例如在二烯或者三烯中。链烯可另外含有官能团,例如卤原子、羧基、羧酸酯官能团、羟基、醚桥、硫桥、羰基官能团、氰基、硝基或者氨基。
这类链烯典型例子是乙烯、丙烯、1-丁烯、顺和反-2-丁烯、1,3-丁二烯、戊烯、异戊二烯、己烯、辛烯、壬烯、癸烯、十一碳烯、十二碳烯、环戊烯、环己烯、二环戊二烯、亚甲基环丙烷、乙烯基环己烷、乙烯基环己烯、烯丙基氯、丙烯酸、甲基丙烯酸、巴豆酸、乙烯基乙酸、烯丙基醇、烷基丙烯酸酯、烷基甲基丙烯酸酯、油酸、亚油酸、亚麻酸、这些不饱和脂肪酸的酯和甘油酯,苯乙烯、α-甲基苯乙烯、二乙烯基苯、茚和茋。所说的链烯的混合物也可用于本发明的方法中。
本发明的方法特别适用于从线性或者支链化的C2-到C5-链烯,特别是丙烯制备二醇单醚。
本发明方法所采用的反应条件涉及温度、压力、加入原料的方式和反应时间,它们随着原料的结构而改变。原则上讲,体系的反应性随着所采用的链烯和含羟基有机化合物增加链的长度或者增大分子量而降低,因此需要更强烈的反应条件。
用于线性或者支链化的C2-到C5-烯烃(在标准条件下大多呈气态)与过氧化氢水溶液在存在C1-到C8-链烷醇(通常为过量)的情况下的反应的典型反应条件如下:在反应温度的自生压力下,温度为-30℃到+80℃,特别是-10℃到+50℃,反应时间为1到10个小时。
本发明的方法可以在实验室规模和工业规模上以批式或者连续操作的方式进行。可以将反应物与催化剂混合物在浆料和固定床步骤中接触。反应可以在气相、液相或者超临界相中进行,优选给出液相。
另一个优点是采用多相环氧化和烷氧化催化剂使失去活性的催化剂可通过采用反应中用的醇洗涤或者在氧化条件下加热进行再生。
在许多情况下,本发明的方法可以使链烯基本上全部转化成二醇单醚。如果在最终产物中仍存在大量的环氧化物中间产物,它们可以通常可以通过简单的方法完全去除,例如通过蒸馏或者脱气(在挥发性环氧化物,例如氧化丙烯的情况下)。
下面的实施例说明本发明,而不是对它的限定。制备条件、转化率和产率并不是最佳的。
实施例
实施例1:制备环氧化催化剂
将455克原硅酸四乙酯放入一个2升四口烧瓶中,并用30分钟的时间从滴液漏斗加入15克原钛酸四异丙酯,同时搅拌(250rpm,桨式搅拌机)。形成无色澄清的混合物。最后,加入800克20%重量的四丙基氢氧化铵溶液(碱金属含量<10ppm),并再持续搅拌一个小时。在90℃~100℃蒸馏水解形成的醇混合物(约450克)。加入1.5升去离子水之后,将稍微不透明的溶胶转移到搅拌着的2.5升不锈钢高压釜中。
将密封的高压釜(锚式搅拌器,200rpm)的温度以3℃/分钟的加热速度升高到175℃。92小时后停止反应。将冷却的反应混合物(白色悬浮液)离心,用水洗涤几次生成的固体,呈中性。将所得到的固体在110℃下干燥24个小时(所获得的重量为149克)。最后,将仍存在于沸石中的样板在550℃在空气中燃烧5个小时(焙烧失重:14%重量)。
按照湿化学分析,纯白产物的钛含量为1.5%重量,残留的碱金属含量小于100ppm。基于所用的SiO2的产率为97%。结晶的大小约为0.05~0.25微米,产物在约960cm-1具有典型的红外谱带。
实施例2:制备烷氧化催化剂
在烧杯中将60.0克硼酸溶解在343.8克四乙基氢氧化铵(在水中为40%重量)和206.2克去离子水的溶液中。将该溶液转移到搅拌的2.5升不锈钢高压釜中。将550.0克胶态硅溶胶(LudoxAS40)在搅拌的同时加入到该混合物中。
将该混合物在150℃用216个小时结晶,分离、用去离子水洗涤并在120℃干燥24个小时。得到的重量是279克。最后,将该产物在500℃在空气中焙烧5个小时,生成H-B-β-沸石。
实施例3:一步法从丙烯和甲醇制备二醇单醚
将45毫升甲醇、1.5克从实施例1得到的钛硅质岩粉末和1.5克沸石H-ZSM-5放置于一个250毫升的玻璃高压釜中,并采用磁力搅拌器搅拌悬浮液。接着将密封的玻璃高压釜冷却到-30℃,并用20.7克丙烯加压。接着将该玻璃高压釜升温到0℃,量取加入30克30%重量浓度的过氧化氢溶液。将反应混合物在0℃自生压力下搅拌5个小时。接着通过离心去除催化剂,并通过气相色谱分析该溶液。该溶液含有9.7%重量的氧化丙烯和8.2%重量的甲氧基丙醇。
实施例4:一步法从丙烯和乙醇制备二醇单醚
将45毫升乙醇、1.5克从实施例1得到的钛硅质岩粉末和1.5克沸石H-ZSM-5放置于一个250毫升的玻璃高压釜中,并采用磁力搅拌器搅拌悬浮液。接着将密封的玻璃高压釜冷却到-30℃,并用20.7克丙烯加压。接着将该玻璃高压釜升温到0℃,量取加入30克30%重量浓度的过氧化氢溶液。将反应混合物在0℃自生压力下搅拌5个小时。接着通过离心去除催化剂,并通过气相色谱分析该溶液。该溶液含有4.5%重量的氧化丙烯和2.2%重量的乙氧基丙醇。
实施例5:一步法从丙烯和丁醇制备二醇单醚
将45毫升丁醇、1.5ml从实施例1得到的钛硅质岩粉末和1.5克H-B-β-沸石放置于一个250毫升的玻璃高压釜中,并采用磁力搅拌器搅拌悬浮液。接着将密封的玻璃高压釜冷却到-30℃,并用20.7克丙烯加压。接着将该玻璃高压釜升温到0℃,量取加入30克30%重量浓度的过氧化氢溶液。将反应混合物在0℃自生压力下搅拌5个小时。接着通过离心去除催化剂,并通过气相色谱分析该溶液。该溶液含有0.3%重量的氧化丙烯和3.8%重量的丁氧基丙醇。
实施例6:一步法从丙烯和乙醇制备二醇单醚
将45毫升乙醇、1.5ml从实施例1得到的钛硅质岩粉末和1.5克聚合的酸性阳离子交换剂(Lewatit.,由Bayer提供)放置于一个250毫升的玻璃高压釜中,并采用磁力搅拌器搅拌悬浮液。接着将密封的玻璃高压釜冷却到-30℃,并用20.7克丙烯加压。接着将该玻璃高压釜升温到0℃,量取加入30克30%重量浓度的过氧化氢溶液。将反应混合物在0℃自生压力下搅拌5个小时。接着通过离心去除催化剂,并通过气相色谱分析该溶液。该溶液含有4.5%重量的氧化丙烯和2.2%重量的乙氧基丙醇。
对比实施例A:一步法从丙烯和甲醇制备二醇单醚
将45毫升甲醇、1.5克从实施例1得到的钛硅质岩粉末放置于一个250毫升的玻璃高压釜中,并采用磁力搅拌器搅拌悬浮液。接着将密封的玻璃高压釜冷却到-30℃,并用5.8克丙烯加压。接着将该玻璃高压釜升温到0℃,量取加入32克30%重量浓度的过氧化氢溶液。将反应混合物在0℃自生压力下搅拌2个小时。接着通过离心去除催化剂,并通过气相色谱分析该溶液。该溶液含有8.65%重量的氧化丙烯、0.04%重量的甲氧基-2-丙醇和0.09%重量的甲氧基-3-丙醇。
Claims (10)
1.一种从链烯制备二醇单醚的方法,它包括链烯与环氧化试剂在同时存在含羟基有机化合物的情况下在环氧化催化剂和烷氧化催化剂的混合物上反应。
2.一种权利要求1所述的方法,其中用于催化剂混合物中的环氧化催化剂是含钛硅酸盐或者含钛、钒、锗或者锡的沸石,特别是钛或者钒硅质岩,它们具有通过X射线衍射为MFI、MEL、BEA、MTW、TON、FER或者MFI/MEL混合结构的沸石结构。
3.权利要求1或2的方法,其中用于催化剂混合物中的烷氧化催化剂是无机酸形式或者固体酸性多相催化剂形式的酸性催化剂,或者固体碱性催化剂。
4.权利要求3的方法,其中用于催化剂混合物中的酸性烷氧化催化剂是基于承载的无机酸、聚合的酸性离子交换树脂、酸性离子交换树脂在无机物中的复合体、酸性金属氧化物或者酸性沸石的固体多相催化剂。
5.权利要求3的方法,其中用于催化剂混合物的碱性烷氧化催化剂是基于碱金属或者碱土金属氧化物或者氢氧化物、承载的碱、聚合的碱性离子交换树脂、dendrimeric胺、滑石(talcite)或氢滑石(hydrotalcite)的固体碱性催化剂。
6.权利要求1到5的任意一个的方法,其中所采用的环氧化试剂是过氧化氢水溶液或者氢/氧混合物。
7.权利要求1到6的任意一个的方法,其中所采用的含羟基有机化合物是线性或者支链化的C1-到C20-链烷醇,C5-到C8-环烷醇或者C7-到C20-芳基烷醇。
8.权利要求1到7的任意一个的方法,其中所采用的链烯是具有2到30个碳原子和一个或者几个烯键不饱和双键的链烯。
9.权利要求8的方法,其中所采用的链烯是线性或者支链化的C2-到C5-烯烃,特别是丙烯。
10.一种用于一步法环氧化和烷氧化链烯的催化剂混合物,它含有1到99重量份的环氧化催化剂和99到1重量份的固体烷氧化催化剂。
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DE19717320A DE19717320A1 (de) | 1997-04-24 | 1997-04-24 | Einstufiges Verfahren zur Herstellung von Glykolmonoethern aus Olefinen |
DE19717320.9 | 1997-04-24 |
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EP (1) | EP0977721B1 (zh) |
JP (1) | JP4059927B2 (zh) |
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CN (1) | CN1140489C (zh) |
AU (1) | AU8013998A (zh) |
CA (1) | CA2286340A1 (zh) |
DE (2) | DE19717320A1 (zh) |
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CN109704921A (zh) * | 2019-02-01 | 2019-05-03 | 淄博诺奥化工股份有限公司 | 邻二元醇的经济绿色制备方法 |
CN115806488A (zh) * | 2022-12-28 | 2023-03-17 | 南京工业大学 | 一种对环烷醇进行开环烯丙基化的方法 |
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DE19717320A1 (de) * | 1997-04-24 | 1998-10-29 | Basf Ag | Einstufiges Verfahren zur Herstellung von Glykolmonoethern aus Olefinen |
WO2000058252A1 (fr) * | 1999-03-31 | 2000-10-05 | Daicel Chemical Industries, Ltd. | Solvant derive de 1,3-propanediol tres pur, son procede de production et son utilisation |
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CN1310836C (zh) * | 2002-02-08 | 2007-04-18 | 住友化学工业株式会社 | 金属化中孔硅酸盐及用其进行氧化的方法 |
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US20060094893A1 (en) * | 2004-10-29 | 2006-05-04 | Darbha Srinivas | Process for preparing cyclic carbonates |
JP4790359B2 (ja) * | 2005-09-30 | 2011-10-12 | 日本乳化剤株式会社 | 水素イオン形態のメタロシリケート触媒を用いるグリコールエーテルの製造法 |
KR20120058559A (ko) | 2009-08-20 | 2012-06-07 | 바스프 에스이 | 폴리에스테르 알콜의 제조 방법 |
CN103012078B (zh) * | 2011-09-28 | 2015-07-01 | 中国石油化工股份有限公司 | 一种催化氧化丙烯制备丙二醇单甲醚的方法 |
CN103012077B (zh) * | 2011-09-28 | 2015-02-25 | 中国石油化工股份有限公司 | 一种催化环氧丙烷醇解制备丙二醇单甲醚的方法 |
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CN109704921A (zh) * | 2019-02-01 | 2019-05-03 | 淄博诺奥化工股份有限公司 | 邻二元醇的经济绿色制备方法 |
CN109704921B (zh) * | 2019-02-01 | 2022-01-04 | 淄博诺奥化工有限公司 | 邻二元醇的经济绿色制备方法 |
CN115806488A (zh) * | 2022-12-28 | 2023-03-17 | 南京工业大学 | 一种对环烷醇进行开环烯丙基化的方法 |
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EP0977721A1 (de) | 2000-02-09 |
ID22629A (id) | 1999-12-02 |
KR20010020164A (ko) | 2001-03-15 |
DE59803517D1 (de) | 2002-05-02 |
CN1140489C (zh) | 2004-03-03 |
KR100549674B1 (ko) | 2006-02-08 |
ES2174444T3 (es) | 2002-11-01 |
WO1998047845A1 (de) | 1998-10-29 |
AU8013998A (en) | 1998-11-13 |
US6239315B1 (en) | 2001-05-29 |
MX9908835A (en) | 2000-01-31 |
CA2286340A1 (en) | 1998-10-29 |
US20010011148A1 (en) | 2001-08-02 |
US6740616B2 (en) | 2004-05-25 |
JP2002508746A (ja) | 2002-03-19 |
MX211744B (en) | 2002-12-02 |
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DE19717320A1 (de) | 1998-10-29 |
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