CN1128253A - 甲基乙二醛二甲基缩醛的制备方法 - Google Patents
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Abstract
一种在催化剂存在下从甲基乙二醛和甲醇制备甲基乙二醛二甲基缩醛的方法中,所形成的甲基乙二醛二甲基缩醛是在水中经共沸蒸馏得到的。
Description
本发明涉及在酸催化剂特别是在酸离子交换剂下通过甲基乙二醛(2-氧代丙醛)和甲醇反应制备甲基乙二醛二甲基缩醛(1,1-二甲氧基-2-丙酮)的方法。
在以前阐述的由甲基乙二醛(MG)和甲醇制备甲基乙二醛二甲基缩醛(MGDA)的方法中,经常设法在反应过程中使用共沸剂除去水水可能来自起始甲基乙二醛溶液、反应本身和反应混合物(例如Braude等人,J.Chem.Soc.3321(1955);Hoechst AG,DE2947383)。这要求使用易挥发但常有毒的辅助剂如苯,为此可能污染产物。另外,上述的产量最高仅是67%。作为废产物的是1,2,2,2-四甲氧基丙烷。
此外,日本专利申请(JP59199651A)描述了甲基乙二醛和甲醇在悬浮液中经离子交换剂缩醛化,通过利用作为溶剂的二氯甲烷萃取作用完成。因为甲基乙二醛二甲基缩醛广泛用于制造药品,所以使用这种毒性辅助剂显然是不能接受的。尚未得到关于离子交换剂和蒸馏残留物的信息。并且,我们自己的试验(参见对比实施例)表明用工业中可得的甲基乙二醛(约40%浓度水溶液)不能重复JP59199651A中所述的产量。而且,在公开的实施例中所用甲醇过量1∶23,反应时间长达16小时,这些都不利于工业甲基乙二醛二甲基缩醛的合成。
本发明的目的是克服上述从甲基乙二醛和甲醇制备甲基乙二醛二甲基缩醛的缺点。
我们已经发现,通过如权利要求1所述的甲基乙二醛二甲基缩醛的新颖和改进的制备方法能达到上述目的,其中甲基乙二醛和甲醇在有催化剂存在的情况下反应后,经和水共沸蒸馏得到产物甲基乙二醛二甲基缩醛。
本方法可以连续完成,但最好间歇进行。为完成上述方法,水含量大于40%(重量)的甲基乙二醛最好在减压下蒸掉水份,浓缩到水含量小于40%(重量)。在从属权利要求中进一步描述优选的实施方案。
本发明所用的甲基乙二醛一般是含有大约60%(重量)水的工业甲基乙二醛。甲基乙二醛的水溶液优选被浓缩到水含量小于40%,最好小于20%(重量)方法是在20-1013mbar特别优选50-150mbar下蒸馏去掉水,当把水含量降到小于5%时,可以加入略微挥发的溶剂,例如沸点比较高的醇(如癸醇或二甘醇)或沸点比较高的醚(如二甘醇丁基醚)或类似的高沸溶剂,以改善搅拌性能。
进行甲基乙二醛和甲醇的实际反应最好是甲基乙二醛与甲醇的摩尔比从1∶2~1∶50,优选从1∶8~1∶15。
反应的催化可用常规的方法,如在强酸性pH下完成。作为这种酸性催化剂优选使用商业上可得的固定床或悬浮液形式的酸性离子交换剂(例如Baykat 2611,Amberlyst 15等)。有催化剂的反应过程的温度优选从20℃~120℃,特别优选50℃~90℃。反应无需一定达到100%转化,因此用离子交换剂的反应时间可以变化。
优选反应时间是4~7小时,特别是5~6小时,优选反应温度是50~100℃,特别是60~80℃。
为了得到产物,把水加到反应混合物中;然后进行分馏,惊奇的是尽管反应器排放物是酸性的(例如pH2.0),但加水并没有使甲基乙二醛二甲基缩醛水解;而且,同时形成的且不希望有的副产物1,1,2,2-四甲氧基丙烷被水解,得到需要的产物甲基乙二醛二甲基缩醛。在反应产物的分馏中,分离掉低沸物和过量甲醇以后,就能有利地开始提出MGDA-H2O-甲醇的单相混合物直到甲醇从反应混合物中被基本分离。进而馏出的甲基乙二醛二甲基缩醛和水的共沸混合物(可能还含有一点甲醇)在上部分离成两相,结果是用简单的方法能得到粗的甲基乙二醛二甲基缩醛。
如上所述,反应可以连续进行,但最好是间歇进行。在反应过程中,被引入反应的、还含有甲基乙二醛缩醛,甲基乙二醛或可转为甲基乙二醛的产物的全部物质进行连续循环直到多步反应后,例如12步反应,最终得到粗甲基乙二醛二甲基缩醛,一般产量多于80%。
图1表示的是间歇完成本发明方法的合适的装置。搅拌罐10设有搅拌器30、温度感应器40、排放线路70、填料装置50和进料线路60。排放线路70通过流量计80和泵90通到反应器110a、110b和110c,它们是固定床酸性离子交换器,用恒温器130维持要求的温度。反应所需时间后,在搅拌罐中的排放料经柱140蒸馏。蒸馏装置为传统型,设有回流冷凝器170、温度用恒温器220调整的水冷却装置210、泵150、接受器160、回流分配器180、冷汽水阀190、压力控制器200和真空泵240。装有阀65的循环线路55使柱底部产物循环到搅拌罐。
图2表示完成本发明新方法的可能的间歇反应的基本流程图。在第一步中,工业甲基乙二醛(MG)被蒸掉水浓缩。第二步前,加入新鲜甲醇,如需要,加入循环甲醇,在第二步中进行缩醛化作用。优选在缩醛化作用后加水到反应排放料中,然后上述排放料进行分馏。在蒸馏步骤3中,被去除的低沸点馏分4A以及主要含有甲醇并循环到下批的馏分4B被蒸掉。由甲醇、MGDA和H2O的单相混合物组成的中间馏分5与被蒸掉。此馏分在缩醛化作用后循环到下一反应步骤。然后,在步骤6中经共沸蒸馏分离甲基乙二醛,共沸混合物在蒸馏柱上部分成两相,即在蒸馏过程循环到蒸馏3底部的水相7和作为产物8(MGDA)提取的粗甲基乙二醛二甲基缩醛。在间歇过程步骤结束后,如果需要,蒸馏的底产物9循环到下步的起始物料,且起始物料必须脱水(脱水(1))。
完成本方法的条件是,例如压力约100mbar,从工业甲基乙二醛水溶液(约60%重量的水)蒸掉大部分存在的水。加入甲醇后,然后优选在65℃-75℃、例如51小时、泵送混合物至商业酸性离子交换器(例如BayKat 2611,Amberlyst15)。在高于甲醇的沸点温度下,于系统自压下进行本操作。首先,蒸掉甲醇和其它低沸馏分,直到柱的上部产物发生相分离,使得甲基乙二醇二甲基缩醛作为杂共沸混合物被分出。剩下的底部产物实际上不含有甲基乙二醛二甲基缩醛(小于0.3%重量);它们回流到下一步骤。惊奇的是,甲基乙二醛二甲基缩醛的产量因此而提高,因为底部产物中所含的物质也和甲醇形成了甲基乙二醛二甲基缩醛,从反应步骤中未加入新的甲基乙二醛即可看出这一点。
下面的实施例阐述本发明。
实施例1A
开始,438g二甘醇(4.125mol)进入6升的搅拌罐,加入986.5g40.1%浓度的甲基乙二醛(5.5mol)。
在100mbar,馏分被蒸馏直到底部温度达到80℃。底部产物的水含量是3~5%wt。冷却后,加入17609(55mol)甲醇,然后在70℃、于系统自压下泵送反应混合物5小时,经过三个反应器110a,110b,110c中的离子交换剂床。整个装置中主要的自压(柱阀关闭)约为0.8巴。
反应器的阀关闭后,往搅拌罐中的反应混合物中加入500ml水,然后进行蒸馏。蒸馏掉图3的低沸馏分4A,直到上部温度达到60℃。
然后可变回流蒸馏掉甲醇(馏分4B),直到底部温度达85℃,上部温度保持在65℃。维持可变回流比高达5∶1。
然后进行减压500mbar,进一步在可变回流比高至10∶1下蒸馏出甲醇(馏分4c;最高沸点温度=49℃)。混合4B和4C馏分,作为循环甲醇(4=(4B+4C))在催化进行的反应前循环到下一批。此后,上部温度限制到74.5℃,由单相甲基乙二醛二甲基缩醛/水/甲醇混合物组成的中间馏分5在500mbar下被分出。当达到74.5℃时,甲醇已基本去除,流过的基本上是含甲基乙二醛二甲基缩醛/水的共沸混合物进行相分离。充分分离甲基乙二醛二甲基缩醛相(8),回流较低的水相直到甲基乙二醛二甲基缩醛相(8)不再增加。
降低压力至100mbar,从搅拌罐蒸馏掉(7)500ml水相,在蒸馏出产物前,所述水相循环到下次反应步骤中的底部。
如实施例1B中详述的,中间馏分(5)和底部产物(9)也循环到反应中。
实施例1B
本实施例描述一种间歇反应步骤的操作,但它不是第一步反应。开始加入前批的底部产物(9)和5.5mol甲基乙二醛。如实施例1A那样蒸掉水,冷却后,加入回收的甲醇4并补加新甲醇根据GC分析,使存在的甲醇总量是1760g=(55mol)。然后和实施例1A,上述混合物经离子交换器反应。随后,前批的中间馏分(5)和水相(7)加到搅拌罐中,按实施1A进行蒸馏。
实施例1C
进行两批反应,其中仅最后步骤蒸馏的底部产物(9)进一步反应,不加入新的甲基乙二醛,其它操作和实施例1B相同。
完成如实施例1A所述的一个反应步骤后,再按实施例1B所述的九个步骤和实施例1C所述的两个步骤进行,得到总量是4474.7g86.5%浓度的粗甲基乙二醛二甲基缩醛,相应粗甲基乙二醛二甲基缩醛的总产量是84.4%。下面表1表示批反应的组成和产物的组成。MGDA2或MGDA∑2相(已被去除的甲基乙二醛二甲基缩醛)含有86.5%的甲基乙二醛二甲基缩醛、9.1%水和1.6%甲醇(或86.5%浓度)。
表1
循环 | 0(g/%) | 1st(g/%) | 2nd(g/%) | 3rd(g/%) |
MG∑1nMGDA1MGTA1MGTA∑1MGDA∑1MGDA2MGDA∑2 | 5.5mol296.2/45.638.0/4.238.0/4.2296.2/45.692.1/14.292.1/14.2 | 11.0 mol450.6/69.435.3/3.973.3/4.1746.8/57.5479.6/73.9571.7/44.0 | 16.5mol482.9/74.433.7/3.7107.0/4.01229.7/63.1514.8/79.31086.5/55.8 | 22.0ml543.7/83.828.3/3.1135.3/3.81773.4/68.3492.6/75.91579.1/60.8 |
循环 | 4th(g/%) | 5th(g/%) | 6th(g/%) | 7th(g/%) |
MG∑1nMGDA1MGTA1MGTA∑1MGDA∑1MGDA2MGDA∑2 | 27.5mol522.7/80.531.9/3.5167.2/3.72296.1/70.8563.4/86.82142.5/66.0 | 27 5mol317.4/48.9*32.5/3.6*195.2/4.32613.5/80.5266.1/41.0*2408.6/74.2 | 330mol424.0/65.351.3/5.7246.5/4.63037.5/78.0581.1/89.52989.7/76.8 | 38.5mol500.7/77.133 0/3.7279.5/4.43538.2/77.9394.7/60.83384.4/74.5 |
循环 | 8th(g/%) | 9th(g/%) | 10th(g/%) | 11th*(g/%) |
MG∑1nMGDA1MGTA1MGTA∑1MGDA∑1MGDA2MGDA∑2 | 44.0mol493.0/76.052.3/5.8331.8/4.64031.2/77.6629.3/97.04013.7/77.3 | 49.5mol525.7/81.042.2/4.7374.0/4.64556.9/78 0513.9/79.24527.6/77.5 | 55.0mol555.1/85.543.1/4.8417.1/4.65112.0/78.8582.7/89.95110.3/78.7 | 55.0mol279.5/43.171.7/8.0488.8/5.45391.5/83.1364.4/56.25474 7/84.4 |
不加MG,假设MG是5.5mol,计算出产量
实施例2
在实施例2中,改变实验条件。没有任何高沸溶剂如二甘醇被加到反应物中。和实施例1一样,在100mbar下完成的脱水过程的底部温度调到70℃。底部产物的水含量约10%。全部十二步反应后,排放的粗甲基乙二醛二甲基缩醛的总产量约80%。下面表2详尽地给出实施例2的数据。
表2
实施例2的反应步骤 | 0 | 1 | 2 | 3 | 4 | 5 | 6 |
MG1n(累加,mol) | 5.5 | 11.0 | 16.5 | 22.0 | 27.5 | 27.5 | 33.0 |
MGDA4(每批,g) | 306.0 | 399.9 | 472.3 | 464.9 | 509.9 | 288.5 | 405.8 |
MGDA4(每批,mol%) | 47.1 | 61.6 | 72.8 | 71.6 | 78.6 | 44.5 | 62.5 |
MGTA4(每批,g) | 44.6 | 47.2 | 31.2 | 38.7 | 27.6 | 19.8 | 28.8 |
MGTA4(每批,mol%) | 4.9 | 5.2 | 3.5 | 4.3 | 3.1 | 2.2 | 3.2 |
MGTA4(累加,g) | 44.6 | 91.8 | 123.0 | 161.7 | 189.3 | 209.1 | 237.9 |
MGTA4(累加,mol%) | 4.9 | 5.1 | 4.5 | 4.5 | 4.2 | 4.6 | 4.4 |
MGDA4(累加,g) | 306.0 | 705.9 | 1178.2 | 1643.1 | 2153.0 | 2441.5 | 2847.3 |
MGDA4(累加,mol%) | 47.1 | 54.4 | 60.5 | 63.3 | 66.3 | 75.2 | 73.1 |
MGDA7(每批,g) | 217.4 | 393.6 | 421.2 | 531.3 | 497.8 | 341.9 | 394.1 |
MGDA7(每批,mol%) | 33.5 | 60.6 | 64.9 | 81.9 | 76.7 | 52.7 | 60.7 |
MGDA7(累加,g) | 217.4 | 611.0 | 1032.2 | 1563.5 | 2061.3 | 2403.2 | 2797.3 |
MGDA7(累加,mol%) | 33.5 | 47.1 | 53.0 | 60.2 | 63.5 | 74.1 | 71.8 |
不加MG循环 |
表2(续)
实施例2的反应步骤 | 7 | 8 | 9 | 10 | 11 | |
MG1n(累加,mol) | 38.5 | 44.0 | 49.5 | 55.0 | 55.0 | |
MGDA4(每批,g) | 459.5 | 467.1 | 520.0 | 513.1 | 331.5 | |
MGDA4(每批,mol%) | 70.8 | 72.0 | 80.1 | 79.1 | 51.1 | |
MGTA4(每批,g) | 27.6 | 54.2 | 28.6 | 32.9 | 33.6 | |
MGTA4(每批,mol%) | 3.1 | 6.0 | 3.2 | 3.6 | 3 7 | |
MGTA4(累加,g) | 265.5 | 319.7 | 348.3 | 381.2 | 414.8 | |
MGTA4(累加,mol%) | 4.2 | 4.4 | 4.3 | 4.2 | 4.6 | |
MGDA4(累加,g) | 3306.8 | 3773.9 | 4293.9 | 4807.0 | 5138.5 | |
MGDA4(累加,mol%) | 72.8 | 72.7 | 73.5 | 74.1 | 79.2 | |
MGDA7(每批,g) | 450.8 | 465.3 | 514.0 | 521.5 | 416.4 | |
MGDA7(每批,mol%) | 69.5 | 71.7 | 79.2 | 80.4 | 64.2 | |
MGDA7(累加,g) | 3248.1 | 3713.4 | 4227.4 | 4748.9 | 5165.3 | |
MGDA7(累加,mol%) | 71.5 | 71.5 | 72.4 | 73.2 | 79.6 | |
不加MG循环 |
对比实施例
45g 40%浓度甲基乙二醛水溶液(0.25mol甲基乙二醛)、185g甲醇(5.78mol)和Dow Chemical的12.5g强酸性离子交换剂Dowex 50WX8回流16小时。过滤掉催化剂后,分析过滤液(经气相色谱法测定百分重量,内标物:二噁烷)表明仅形成16.1g(0.14mol,56%,基于甲基乙二醛)的甲基乙二醛二甲基缩醛。
Claims (12)
1.一种在催化剂存在下从甲基乙二醛和甲醇制备甲基乙二醛二甲基缩醛的方法,其特征在于所形成的甲基乙二醛二甲基缩醛是在水中经共沸蒸馏得到的。
2.如权利要求1所述的方法,其中在方法开始时甲基乙二醛是以水溶液的形式存在,其水含量大于40%wt.,在进行进一步的步骤前通过蒸馏掉水而浓缩甲基乙二醛水溶液,使其水含量小于40%wt.。
3.如权利要求1或2所述的方法,其中催化剂是酸性离子交换剂,优选离子交换剂床。
4.如权利要求3所述的方法,其中在升高的温度下泵送甲基乙二醛和甲醇经过酸性离子交换剂床。
5.如权利要求2-4中任一项所述的方法,其中甲基乙二醛溶液浓缩到水含量小于20%wt.。
6.如权利要求1-4中任一项所述的方法,其中在有水存在下经共沸蒸馏回收甲基乙二醛二甲基缩醛时,在初馏物中的甲醇基本上完全被蒸馏掉。
7.如权利要求1-4中任一项所述的方法,其中进行间歇操作。
8.如权利要求1-4中任一项所述的方法,其中初馏物或蒸馏的底部产物再循环到操作中。
9.如权利要求7所述的方法,其中离子交换剂再循环到反应中。
10.如权利要求8所述的方法,其中离子交换剂再循环到反应中。
11.如权利要求1-4中任一项所述的方法,其中含有甲基乙二醛二甲基缩醛和水的气态共沸混合物经蒸馏冷凝,分成两个液相,即水相和甲基乙二醛二甲基缩醛相。
12.一种分离甲基乙二醛二甲基缩醛和水的混合物的方法,其特征在于蒸馏甲基乙二醛二甲基缩醛和水的共沸混合物,使蒸馏的和冷凝的混合物分成两个液相,即水相和甲基乙二醛二甲基缩醛相,两相互相分离。
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DE4435176A DE4435176A1 (de) | 1994-09-30 | 1994-09-30 | Verfahren zur Herstellung von Methylglyoxaldimethylacetal |
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CN102531864A (zh) * | 2011-12-15 | 2012-07-04 | 温州澳珀化工有限公司 | 一种制备丙酮醛缩二甲醇的方法 |
CN103242145A (zh) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | 乙二醛制备乙二醛单缩醛和二缩醛的方法 |
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US7700814B2 (en) | 2007-03-27 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Manufacture of alcohols |
DE102007022521A1 (de) * | 2007-05-14 | 2008-11-20 | Cognis Ip Management Gmbh | Verfahren zur Herstellung von Diolen |
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US2421559A (en) * | 1944-01-14 | 1947-06-03 | Carbide & Carbon Chem Corp | Acetals of pyruvic aldehyde |
DE1252193B (de) | 1966-02-15 | 1967-10-19 | Badische Anilin- S. Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein | Verfahren zur Herstellung von Acetalen des Methylglyoxals |
DE2338665C2 (de) * | 1973-07-31 | 1975-04-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Gewinnung von Methylglyoxa lacetal |
US4158019A (en) * | 1975-08-13 | 1979-06-12 | Hoffmann-La Roche Inc. | Methylglyoxal dimethyl acetal production |
DE2947383A1 (de) * | 1979-11-24 | 1981-06-04 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von methylglyoxaldimethylacetal |
DE3019766A1 (de) * | 1980-05-23 | 1981-12-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur destillativen zerlegung von aliphatische alkohole enthaltenden fluessigkeitsgemischen |
US4473444A (en) * | 1981-02-09 | 1984-09-25 | National Distillers And Chemical Corporation | Extractive distillation of alcohol-ester mixtures |
DE3147320A1 (de) * | 1981-11-28 | 1983-06-01 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur gewinnung reinen methylals |
JPS59199651A (ja) * | 1983-04-26 | 1984-11-12 | Sumitomo Chem Co Ltd | メチルグリオキサ−ルアセタ−ルの合成法 |
DE3346266A1 (de) * | 1983-12-21 | 1985-07-11 | Lentia Gmbh | Verfahren zur herstelung von glyoxal, alkylglyoxalen und von deren acetalen |
HU203678B (en) * | 1988-09-26 | 1991-09-30 | Richter Gedeon Vegyeszet | Method for increased dewatering condensation reaction mixtures |
DE69327411T2 (de) * | 1992-04-24 | 2000-05-11 | Showa Denko Kk | Verfahren zur Herstellung von Acetaldehyddimethylacetal |
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- 1995-09-29 CN CN95118689A patent/CN1061642C/zh not_active Expired - Fee Related
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CN102531864A (zh) * | 2011-12-15 | 2012-07-04 | 温州澳珀化工有限公司 | 一种制备丙酮醛缩二甲醇的方法 |
CN103242145A (zh) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | 乙二醛制备乙二醛单缩醛和二缩醛的方法 |
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US6214172B1 (en) | 2001-04-10 |
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