CN101665404B - 制备2,3,3,3-四氟丙烯的方法 - Google Patents
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- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/204—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being a halogen
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
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- C07—ORGANIC CHEMISTRY
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Abstract
一种制备2,3,3,3-四氟丙烯的方法,所述方法包括在可以有效的产生包含CF3CF=CH2的反应产物的条件下,将包含CCl2=CFCH2Cl的反应物与氟化剂(例如HF)接触。
Description
相关申请的交叉引用
本申请是2007年1月3日提交的美国专利申请No.11/619,592的部分继续申请,其公开的内容在此引入参考。
技术领域
本发明涉及制备氟代有机化合物的新方法,更具体地,本发明涉及制备氟代烯烃的方法。
背景技术
氢氟烃(HFCs),包括特定的氢氟烯烃如四氟丙烯(例如,2,3,3,3-四氟-1-丙烯(HFO-1234yf)),是有效的制冷剂、灭火剂、传热介质、推进剂、起泡剂、发泡剂、气相绝缘介质、杀菌剂载体、聚合反应介质、除颗粒流体、传递液、抛光磨料、置换干燥剂和动力循环工作流体。与潜在破坏地球臭氧层的氯氟烃(CFCs)和氢氯氟烃(HCFCs)不同,HFO-1234yf不含氯,因此,其对臭氧层没有威胁。而且,与绝大多数CFCs和HCFCs相比,HFO-1234yf具有相对低的全球变暖潜在性(GWP)。
合成某些HFOs的方法是已知的。例如,有人报道了由三氟乙酰丙酮和四氟化硫制备HFO-1234yf。参见Banks等人,Journal of Fluorine Chemistry,Vol.82,Iss.2,p.171-174(1997).另外,美国专利No.5,162,594(Krespan)公开了一种由四氟乙烯和另一类氟代乙烯在液相条件下反应制备聚氟烯烃产品的方法。上述这些起始原料昂贵、难于处理、和/或导致产率低。然而,CCl2=CClCH2Cl可以作为一种廉价、易得的起始原料用于通过下述三步法制备CH2=CFCF3:
CCl2=CClCH2Cl→CF3CCl=CH2→CF3CFClCH3
→CF3CF=CH2
但是,相比于更短的合成路线,这样的多步过程显得比较复杂和不经济。因此,仍然需要一条可以将廉价易得的起始原料直接转化的路线。而这种用于合成HFO-1234yf的起始原料迄今为止是未知的。
发明内容
申请人发现了一种包括氟化CCl2=CFCH2Cl的合成HFO-1234yf的新方法。在本发明中,CF3CF=CH2的中心碳原子上的氟原子是在制备CCl2=CFCH2Cl(例如,通过将HF加成到CH2=CClCH2Cl或CHCl=CClCH2Cl,或通过CH2=CClCH2Cl的氯氟化反应)时引入的。这使得整个合成过程比现有技术中的路线要短。尽管CCl2=CFCH2Cl是一种已知化合物,但是它作为合成HFO-1234yf的反应物的优越性是未被认识到的,尽管也确实需要这样一种反应物。
因此,一方面本发明提供了一种制备2,3,3,3-四氟丙烯的方法,所述方法包括使包含CCl2=CFCH2Cl的反应物在能有效产生包含CF3CF=CH2的反应产物的条件下与氟化剂接触。
另一方面,本发明提供了一种制备2,3,3,3-四氟丙烯的方法,所述方法包括:提供一种包含至少一种四氯氟丙烷的前体组合物;将至少一种四氯氟丙烷脱氯化氢生成第一批至少一种选自CCl2=CFCH2Cl和CH2=CFCCl3的三氯氟丙烯;任选地,将上述CH2=CFCCl3与异构化催化剂接触得到第二批CCl2=CFCH2Cl;和使包含上述第一批三氯氟丙烯以及任选地第二批CCl2=CFCH2Cl的反应物与氟化试剂在能有效产生包含CF3CF=CH2的反应产物的条件下接触。
具体实施方式
总体而言,利用HF催化氟化CCl2=CFCH2Cl制备CF3CF=CH2的反应可以在液相、气相或气液混合相中进行,并且该反应可以以分批、连续或其组合的形式进行。
此处使用的术语“直接转化”是指在单个反应中转化或在实质上一系列的反应条件下转化。
对于包含液相反应的实施方案,反应可以是催化的或非催化的。优选使用催化的方式。在某些实施方案中,优选路易斯酸催化剂,例如金属卤化物催化剂,包括卤化锑、卤化锡、卤化铊、卤化铁和两种或多种上述催化剂的组合。特别优选金属氯化物和金属氟化物。这类特别优选的催化剂的例子包括SbCl5、SbCl3、SbF5、SbClnF5-n(其中n为1-4的整数)、SnCl4、TiCl4、FeCl3和两种或多种上述催化剂的组合。
对于包含气相反应的实施方案,反应优选在至少是部分催化的条件下进行, 并且优选通过将反应物和氟化剂作为一股气流或多股气流通入到一个或多个反应容器中从而以连续方式进行。在某些实施方案中,通过将CCl2=CFCH2Cl气流(优选预热到约150℃)通入到反应器中,并在反应器中与催化剂和HF在约200-500℃(优选约250-450℃,更优选约300-400℃)下反应从而以连续的方式进行气相反应。HF和CCl2=CFCH2Cl的摩尔比可以从约3∶1(化学计量量)至约20∶1。优选的催化剂是铬基催化剂(例如Cr2O3,包括氟化的氧化铬)和铁基催化剂(例如FeCl3)或它们的组合。其它催化剂是活性炭和包含过渡金属盐(例如Co、Fe、Cu和Mn)的活性炭以及负载在惰性载体上的过渡金属盐(例如氟化铝)。
优选的接触时间是达到好的转化率的时间,这个时间会因催化剂活性的不同而改变。在某些实施方案中,选择接触时间以得到好的产率,这个接触时间通常从约1到约60秒,较优选约1到约10秒,更优选约2到约5秒。
液相和气相反应的容器由能抗HF和HCl腐蚀的材料构成,例如Hastelloy、Inconel和Monel。
反应压力可以在相当宽的范围内变化以调节接触时间,从而达到需要的转化率和产率水平。
本发明优选在如下条件下进行,包括利用一个或多个反应的情形,所述条件使HFO-1234yf的产率至少达到大约50%,较优选达到至少大约75%,更优选达到至少大约90%。在某些优选的实施方案中,转化率至少达到约95%,更优选达到至少约97%。
化合物CH3CFClCCl3可以通过脱氯化氢转化为CH2=CFCCl3,接下来异构化为需要的CCl2=CFCH2Cl。CH3CFClCCl3脱氯化氢可以是液相或气相的催化反应。根据脱氯化氢反应的条件,可以从CH3CFClCCl3得到两种异构产物CH2=CFCCl3和CCl2=CFCH2Cl。利用NaOH在低温下使CH3CFClCCl3脱氯化氢得到CH2=CFCCl3,而从液相和气相催化反应(例如,使用活性炭或FeCl3催化剂)产物是CCl2=CFCH2Cl。因此,在某些条件下,脱氯化氢反应和异构化反应可以在一个反应步骤中进行。
或者,CCl2=CFCH2Cl可以由CHCl2CFClCH2Cl脱氯化氢得到,而CHCl2CFClCH2Cl可以由CH2ClCFClCH2Cl氯化得到(参见,例如ZhurnalOrganicheskoi Khimii(1971),7(9),1181)。
实施例
实施例1气相氟化CCl2=CFCH2Cl制备CF3CF=CH2
将10cm3预先干燥过的氟代Cr2O3催化剂放入长50cm、直径为10mm的Monel管中,然后在管式炉中加热。将管的入口与HF气瓶及输送CCl2=CFCH2Cl的注射泵相连。管的出口与被干冰-丙酮冷却的阱相连,然后串联一个酸净气器。在反应过程中,温度控制在350℃,HF的加入速度控制在每小时5g(0.25摩尔),CCl2=CFCH2Cl的加入速度控制在每小时10g(0.06摩尔),接触时间为2.3秒。反应结束后,将冷阱中的粗产物缓慢升温,产物和HF一起被鼓泡通入水中,然后进入另一个冷阱中以冷凝产物CF3CF=CH2。
实施例2由CH2=CFCCl3异构化制备CCl2=CFCH2Cl
将50克CH2=CFCCl3和5克4.6%FeCl3/C催化剂在100℃下的烧瓶中搅拌。通过GC分析检测反应结束后,过滤除去催化剂,得到的CCl2=CFCH2Cl直接用于氟化反应。
实施例3利用NaOH使CH3CFClCCl3脱氯化氢制备CH2=CFCCl3
取一个250mL的三口烧瓶,装上搅拌棒、固体加料漏斗、蒸馏头、冷凝器和接收器。将CH3CFClCCl3(72g,0.36摩尔)加入到烧瓶中,固体NaOH粉末(15g,0.36摩尔)加入到漏斗中。将CH3CFClCCl3在油浴中加热至大约150-175℃,然后在搅拌下加入固态NaOH,加入时间约为1小时。在反应过程中,生成的CCl3CF=CH2被蒸馏出来。
实施例4液相催化CH3CFClCCl3脱氯化氢制备CCl2=CFCH2Cl
向装备有回流冷凝器和搅拌棒的250mL烧瓶中加入5克无水FeCl3和100gCH3CFClCCl3。在回流的顶部接酸净气器。油浴加热烧瓶并搅拌直至CH3CFClCCl3溶化,然后将上述混合物在该温度下(130-140℃)保温10h。然后蒸馏收集得到CCl2=CFCH2Cl产物,bp 129℃。
实施例5气相催化CH3CFClCCl3脱氯化氢制备CCl2=CFCH2Cl
将10克4.6%FeCl3/C催化剂放入直径为10mm的Monel管中,然后在管式炉中加热。管的入口连接流量计并与N2气源和CH3CFClCCl3源相连。管的出口与产物收集器相连,收集器在干冰中冷却并连接HCl净气器。在反应过程中反应管加热至200℃。N2气流速控制在10cc/min,CH3CFClCCl3的加入速度控制在0.2g/min。将冷阱中收集到的脱氯化氢粗产物蒸馏得到纯CCl2=CFCH2Cl。
实施例6 CHCl2CFClCH2Cl脱氯化氢制备CHCl=CClCH2Cl
制备方法同实施例5。
实施例7 CH2ClCFClCH2Cl氯化制备CHCl2CFClCH2Cl
将装备有搅拌棒、温度计和回流冷凝器的250mL三口瓶保持在-5℃。从氯气瓶中向烧瓶中通入氯气,并利用流量计控制Cl2的流量。在冷凝器的顶部接HCl和Cl2净气器。将CH2ClCFClCH2Cl(126g或0.76摩尔)加入到烧瓶中并用油浴加热到140-150℃。将氯气以10g每小时的速度通入到CH2ClCFClCH2Cl液面下。加入54g(0.76摩尔)Cl2后,将反应混合物分馏以分离CHCl2CFClCH2Cl。
实施例8液相条件下HF与CHCl=CClCH2Cl加成制备CHCl2CFClCH2Cl
将2摩尔(270g)CHCl=CClCH2Cl和2.2g(0.008摩尔)TaF5加入到500mL高压釜中。将反应器密闭并在干冰-丙酮中减压。加入40g(2摩尔)无水HF。将上述反应混合物在室温下搅拌24小时。然后将粗产物小心地倒入碎冰中,分离有机层,水洗,干燥。
以上描述了本发明的少数具体实施方案,但考虑到本文所包含的教导,对本领域技术人员显而易见的是未详细描述的各种变化、修饰和改进是可以得到的并且在本发明的范围之内。这些在本申请公开的内容的基础上所作的明显变化、修饰和改进虽未在此作特别地说明但意在作为本说明书的一部分,并且意在属于本发明的精神和范围之内。因此,前述的描述仅仅是例举而不是对本发明的限制。本发明仅根据下文的权利要求及它们的等价形式限定。
Claims (11)
1.一种制备2,3,3,3-四氟丙烯的方法,所述方法包括在催化剂的存在下,将CCl2=CFCH2Cl与氟化剂接触以产生CF3CF=CH2;
其中所述的氟化剂是HF;
其中所述的接触包括气相反应,其中所述的气相反应包括至少一种选自氧化铬(III)、氟化氧化铬、氯化铁(III)、活性炭和过渡金属卤化物的催化剂,或者其中所述的接触包括液相反应,其中所述的液相反应包括至少一种选自SbCl5、SbClnF5-n、SnCl4、TiCl4和FeCl3的催化剂,其中n为0-4的整数。
2.如权利要求1所述的方法,其中所述的接触直接将反应物转化为反应产物。
3.如权利要求1所述的方法,其中至少在一部分所述的气相反应中,所述HF和所述CCl2=CFCH2Cl以3∶1至20∶1的摩尔比存在。
4.如权利要求1所述的方法,其进一步包括:
提供一种包含CH2=CFCCl3的前体组合物;和
将所述前体组合物与异构化催化剂接触生成所述的CCl2=CFCH2Cl。
5.如权利要求4所述的方法,其中所述的异构化催化剂包含氯化铁(III)/碳催化剂。
6.一种制备2,3,3,3-四氟丙烯的方法,所述方法包括:
提供一种包含至少一种四氯氟丙烷的前体组合物;
将至少一种四氯氟丙烷脱氯化氢生成第一批选自CCl2=CFCH2Cl和CH2=CFCCl3的至少一种三氯氟丙烯;
任选地,将上述CH2=CFCCl3与异构化催化剂接触得到第二批CCl2=CFCH2Cl;和
使上述第一批三氯氟丙烯及,任选地,第二批CCl2=CFCH2Cl与氟化剂在催化剂的存在下接触以产生CF3CF=CH2;
其中所述的氟化剂是HF;
其中所述的接触包括气相反应,其中所述的气相反应包括至少一种选自氧化铬(III)、氟化氧化铬、氯化铁(III)、活性炭和过渡金属卤化物的催化剂,或者其中所述的接触包括液相反应,其中所述的液相反应包括至少一种选自SbCl5、SbClnF5-n、SnCl4、TiCl4和FeCl3的催化剂,其中n为0-4的整数。
7.如权利要求6所述的方法,其中所述的四氯氟丙烷选自CH3CFClCCl3、CHCl2CFClCH2Cl或它们的组合。
8.如权利要求7所述的方法,其中所述的异构化催化剂包含氯化铁(III)/碳催化剂。
9.如权利要求7所述的方法,其中所述的脱氯化氢反应包括将所述四氯氟丙烷与NaOH接触。
10.如权利要求7所述的方法,其中所述的脱氯化氢反应包括液相催化反应。
11.如权利要求7所述的方法,其中所述的脱氯化氢反应包括气相催化反应。
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US8129574B2 (en) * | 2009-08-31 | 2012-03-06 | Honeywell International Inc. | Hydrogenation process for fluorocarbons |
ES2547871T3 (es) * | 2009-12-23 | 2015-10-09 | Arkema France | Fluoración catalítica en fase gaseosa de 1230xa para dar 1234yf |
WO2011077191A1 (en) * | 2009-12-23 | 2011-06-30 | Arkema France | Catalytic gas phase fluorination of 1230xa to 1234yf |
WO2011099605A2 (en) * | 2010-02-12 | 2011-08-18 | Daikin Industries, Ltd. | Process for producing fluorine-containing alkene compound |
US8461401B2 (en) * | 2010-03-26 | 2013-06-11 | Honeywell International Inc. | Method for making hexafluoro-2-butene |
CN101913987B (zh) * | 2010-09-07 | 2013-04-17 | 西安近代化学研究所 | 2,3,3,3-四氟丙烯的制备方法 |
CN102001911B (zh) * | 2010-09-20 | 2013-09-25 | 西安近代化学研究所 | 2,3,3,3-四氟丙烯的制备方法 |
US8889930B2 (en) | 2013-01-22 | 2014-11-18 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons |
US9289758B2 (en) | 2013-01-22 | 2016-03-22 | Axiall Ohio, Inc. | Processes for producing chlorinated hydrocarbons and methods for recovering polyvalent antimony catalysts therefrom |
US8877991B2 (en) * | 2013-02-19 | 2014-11-04 | Honeywell International Inc. | Methods for the dehydrochlorination of 1,1,1,3-tetrachloropropane to 1,1,3-trichloropropene |
US9139497B2 (en) | 2013-10-23 | 2015-09-22 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons in the presence of a polyvalent bismuth compound |
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