CN1063736C - 1,1,1,3,3-五氟丙烷的制备方法 - Google Patents
1,1,1,3,3-五氟丙烷的制备方法 Download PDFInfo
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C17/206—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及含氢氟烃(HFCs)的制备。具体地讲,它涉及下式化合物与氟化氢进行的氟化反应:
CFyCl3-yCH2CHFwCl2-w
其中w=0或1,y=0-3,反应在氟化催化剂的存在下进行,反应条件足以生成式CF3CH2CF2H化合物。
CF3CH2CF2H或HFC-245fa可用作发泡剂、推进剂和传热剂。
Description
发明背景
本发明涉及一种制备1,1,1,3,3-五氟丙烷CF3CH2CF2H的新方法,CF3CH2CF2H在本领域中被称为HFC-245fa。具体地,本发明涉及下式化合物与氟化氢进行的氟化反应:
CFyCl3-yCH2CHFwCl2-w其中w=0或1,y=0-3,反应在氟化反应催化剂的存在下进行,生成HFC-245fa。
HFC-245fa的物理性质,包括沸点为约14℃,使之特别适于用作发泡剂。(参见Ger.Offen,DE3,903,336,1990 CEP 381,986A))。它还具有以类似于三氯氟甲烷的方式用作喷雾剂的推进剂(授予Smith和Woolf的U.S.P.2942036)以及用作传热剂的性能。本领域中将三氯氟甲烷称为CFC-11。(114《化学文摘》125031q(1991)上Jpn.Kokai Tokyo KohoJP 02,272,086。)
传统上,诸如CFC-11和二氯二氟甲烷(CFC-12)的含氯氟烃已被用作制冷剂、发泡剂和推进剂。但是,据信,这些材料是同温层臭氧消耗的原因之一。因此,含氟烃工业已将其注意力集中于最尖端的技术领域,即开发更为安全的替代材料。由于HFC-245fa的作用方式与CFC类基本相同,但其臭氧消耗为零,所以它是一种候选的替代材料。由于对此类及其它臭氧消耗低或无臭氧消耗的材料的需求在未来时期将急剧增加,具有商业价值的制备方法成为必需。
本领域中仅报道过两种制备HFC-245fa的方法(它们不是氢氟化作用)。但是,这些方法不无缺陷。Knunyants等人在55《化学文摘》349f(1961)中《全氟烯烃的催化加氢》一文公开了1,1,1,3,3-五氟丙烯还原为HFC-245fa。由于该方法包括多个步骤,所以效率低下而且不经济。Burdon等人在英国《化学会志》(C),1739(1969)中的《用三氟化钴对四氢呋喃进行部分氟化反应》一文公开了四氢呋喃初步氟化反应制备HFC-245fa。该方法的缺点是产生许多其它副产物,因此降低了所需产物的产率。
就氢氟化反应而言,本领域中没有此类制备HFC-245fa的方法报道,更不用说用1,1,1,3,3-五氯丙烷(CCl3CH2CHCl2)作为起始原料制备HFC-245fa的氟化反应了。尽管-CCl3基团转化为-CF3基团在本领域中众所周知,但将含有两个以上碳原子的化合物(特别是其中X是Cl或Br,R是含有至少1个碳原子的烷基的式RCH2CHCl2和RCH2CHFX化合物)中的端基-CHCl2或-CHClF基团氟化为CHF2基团的努力尚未成功。参见Henne等人58美国化学会会志889(1936)《氟代乙烷和氟代乙烯》。
Tarrant等人在77美国化学会会志2783(1955)中的《涉及氟化合物的自由基加成Ⅳ.将二溴二氟甲烷对氟代烯烃的加成》一文报道了在诸如SbCl5和TaF5的Sb(V)盐催化剂的存在下用氟化氢(HF)将CF2BrCH2CHFBr类化合物氟化。但是,该方法在125℃下制备CF3CH2CHFBr的产率仅为14%,在170℃下产率仅有有限的改进。即使在高温条件下也没有HFC-245fa生成。
发明描述
我们已经发现,存在于现有制备1,1,1,3,3-五氟丙烷或HFC-245fa的方法中的弊端,可以用本发明的方法加以消除。也就是说,我们已经发现一种在工业规模上制备HFC-245fa的有效和经济的方法,该方法采用易得的原材料,生产出高产率的HFC-245fa。
本发明涉及一种制备1,1,1,3,3-五氟丙烷的方法,包括:
1)在氟化催化剂的存在下,在足以产生式CF3CH2CF2H化合物的反应条件下,使下式化合物与氟化氢反应:
CFyCl3-yCH2CHFwCl2-w其中w=0或1,y=0-3;和
2)任选回收式CF3CH2CF2H化合物
对应于式CFyCl3-yCH2CHFwCl2-w的有机起始原料,其中w=0或1,y=0-3,包括CCl3CH2CHCl2、CF3CH2CHCl2、CFCl2CH2CHCl2、CF2ClCH2CHCl2、CFCl2CH2CHClF、CF2ClCH2CHFCl和CF3CH2CHFCl。优选的起始材料是CCl3CH2CHCl2。
这些材料在市场上买不到。但是,它们可以用本领域熟知的方法制备。例如,参见B.Boutevin等人在97《化学文摘》182966C(1982)上的18 Eur.Polym.J.675(1982)《单官能乙烯基氯调聚物Ⅰ.乙烯基氯调聚物标准物的合成与特征》一文,和Kotora等人在44(2)React.Kinet.Catal.Lett.415(1991)中的《用铜络合物作催化剂将多卤代化合物对氯代乙烯的选择性加成》一文。也可参见下列实例1和2中公开的方法。当起始材料是CCl3CH2CHCl2时,优选按照下列实例1中提供的方法制备。可供选择地,CCl3CH2CHCl2还可通过CCl3CH2CCl3(参见实例2)还原以及CCl3CH2CH2Cl的感光氯化作用来制备。
存在于HF中的任何水份都将与氟化催化剂反应并使之失活。因此,优选基本上不含水的HF。“基本上不含水”指HF中含有低于约0.05wt.%的水,优选含有低于约0.02wt.%的水。但是,本领域中普通技术人员懂得,催化剂中水份的存在可以通过增加催化剂的用量加以抵消。适用于本反应的HF可以从新泽西州Morristown的联合信号公司购得。
按照反应化学计量,所需的HF与有机物(即CFyCl3-yCH2FwCl2-w)的摩尔比是5-y-w(或有机起始原料中氯原子的数目)至1.0。HF的优选用量为HF对有机物化学计量用量的约1至约15倍,更优选地,为HF对有机物化学计量用量的约6至约15倍。
可用于本发明方法的氟化催化剂包括:(Ⅰ.)五价锑、铌、砷和钽的卤化物;(Ⅱ.)五价锑、铌、砷和钽的混合卤化物;和(Ⅲ.)五价锑、铌、砷和钽的卤化物催化剂的混合物。(Ⅰ.)组催化剂的实例包括五氯化锑和五氟化锑。(Ⅱ.)组催化剂的实例包括SbCl2F3和SbBr2F3。(Ⅲ.)组催化剂的实例包括五氯化锑和五氟化锑的混合物。
五价锑、铌、砷和钽的卤化物可商业购得,其混合卤化物通过与HF反应现场生成。由于其成本低和易于得到,五氯化锑优选。式SbClnF5-n的五价锑混合卤化物更为优选,其中n是0至5。本发明所用氟化催化剂优选具有至少约97%的纯度。尽管所用氟化催化剂的量可以在宽范围内变化,我们推荐使用有机物重量的约5%至约50%,或优选约10%至约25%的催化剂。
由于五价催化剂随时间推移会发生离解作用,周期性地再生催化剂是有利的。这种再生可以通过本领域熟知的任何方法实现。例如,催化剂可以通过向含有式CFyCl3-yCH2CHFwCl2-w有机物的物流和含有氟化不足的材料和HF的循环物流的合并物流中,加入氯(加入量为初始存在于反应器中五价催化剂量的约1%至约10%(摩尔))加以再生。连续式操作时连续加入本发明工艺中(间歇式操作时周期性加入)的氯将催化剂从三价态氧化到五价态。本领域普通技术人员不必做过多实验便能容易地确定加入氯的量,以优化催化剂的使用。
氟化反应进行的温度和反应时间取决于使用的反应材料和催化剂。本领域普通技术人员不必做过多实验便能容易地优化反应条件,以得到所要求的结果,但温度通常在约50至约175℃的范围,优选约115至约155℃,反应时间例如为约1至约25小时,优选约2至约8小时。
压力不重要。方便的操作压力范围为约1500至约5000KPa,优选约1500至约2500KPa。
氟化反应的设备优选用抗腐蚀性材料制成,例如Inconel或Monel(蒙乃尔)。
HFC-245fa可以用本领域所知的任何方法从未反应的起始材料、副产物和催化剂的混合物中回收,例如蒸馏和萃取法。如实例3所表示的,在加热阶段结束时,即间歇式操作完全反应的时间结束后,氟化反应产物和残余HF可以经由高压釜盖上的阀门排出,该阀门的另一端连接至酸洗涤器和冷阱以收集产物。可供选择地,未反应的HF和有机物可以排出和冷凝,HF层循环至反应器。然后处理有机层,即用碱水洗涤,以除去溶解的HF,再蒸馏。这一分离步骤特别适用于连续的氟化工艺。氟化不足的原料,如CF3CH2CHFCl,可以在后续运行中循环。
在另一实施例中,本发明涉及一种制备1,1,1,3,3-五氟丙烷的方法,包括:
1.在一种调聚催化剂的存在下,在足以生成式CCl3CH2CHCl2化合物的反应条件下,使CCl4与乙烯基氯反应;
2.在一种氟化催化剂的存在下,在足以生成式CF3CH2CF2H化合物的反应条件下,使式CCl3CH2CHCl2化合物与氟化氢反应;和
3.任选回收式CF3CH2CF2H化合物。
乙烯基氯与四氯化碳反应生成CCl3CH2CHCl2的调聚反应在本领域中是已知的。参见例如B.Boutevin等人在97《化学文摘》182966C(1982),18Eur.Polym.J.675(1982)上的《单官能乙烯基氯调聚物Ⅰ.乙烯基氯调聚物标准物的合成和特征》一文;和Kotora等人在44(2)《反应动力学催化剂通讯》415(1991)上的《用铜络合物催化将多卤代化合物对氯代乙烯的选择性加成》一文。
调聚反应的起始材料,即四氯化碳和乙烯基氯可商业购得。CCl4与乙烯基氯的摩尔比为约0.5∶10,优选约1∶8(以将较高级调聚物的生成减少至最低),最优选约1∶5。
乙烯基氯的调聚反应可以用任何可商购的、本领域已知可用于引发和催化四氯化碳和乙烯基氯的调聚反应的催化剂引发。适用的催化剂包括但不限于有机过氧化物、金属盐和金属碳酰类化合物。铜和铁盐催化剂,如氯化亚铜(CuCl)、碘化亚铜(CuI)和氯化亚铁(FeCl2)为优选。调聚反应中催化剂的用量为每摩尔有机物(即CCl3CH2CHCl2)至少约0.1至约50mmol,优选约1至约20mmol。
可以任选使用一种胺助催化剂,如链烷醇胺、烷基胺和芳香胺,以使在调聚反应过程中采用较温和的反应条件成为可能。适用的胺助催化剂的实例包括乙醇胺、丁胺、丙胺、苄胺和吡啶。乙-丙胺是最优选的助催化剂。这类助催化剂可商购。使用助催化剂时,其用量应该为每摩尔催化剂,即,例如铜盐,约1至约10摩尔。
为了溶解催化剂,对反应物和所需产物呈惰性的一种溶剂可用于调聚反应中。适用的溶剂包括但不限于可商购的乙腈、二甲亚砜、二甲基甲酰胺、四氢呋喃、异丙醇和叔丁醇。乙腈由于易于处理和稳定被优选使用。溶剂用量在所用催化剂摩尔量的约5倍至总的调聚反应混合物(即溶剂、催化剂、助催化剂、四氯化碳、乙烯基氯化物)总体积的80%范围内,较优选在所用催化剂摩尔量的约10至50倍之间。
调聚反应的温度和反应时间取决于选用的催化剂、助催化剂的存在以及催化剂体系在溶剂中的溶解性。本领域普通技术人员不必过多实验便能容易地优化反应条件,以得到所要求的结果,但温度一般在约25至约225℃的范围,优选从约50至约150℃。反应时间一般在约3至约72小时,优选约10至约24小时。
压力不重要。
优选地,调聚反应在常规装置中进行,如用诸如聚四氟乙烯(Teflon)和玻璃等抗腐蚀材料制成的高压釜。
优选地,调聚产物在氟化反应进行前从副产物、溶剂、催化剂和肋催化剂中回收,以基本上消除氟化反应步骤中副产物的生成。调聚反应产物可以用诸如蒸馏和萃取的本领域熟知的任何方法回收。任选地,调聚产物可以通过进一步蒸馏而进一步净化。
由于乙烯基氯有毒,可以采用制备CCl3CH2CHCl2的其它步骤。参见实例2(CCl3CH2CCl3的还原)。可供选择地,CCl3CH2CCl3可以按照众所周知的二氯乙烯与四氯化碳的调聚反应制备。
实例1.由CCl4和CH2=CHCl制备CCl3CH2CHCl2
向600mL装有机械搅拌的蒙乃尔合金高压釜中加入1g CuCl、156.6gCCl4和75mL乙腈。内容物冰浴冷却,关闭高压釜并短时间抽空。然后加入36.7g乙烯基氯,内容物搅拌并加热至135℃16小时。常压下蒸馏除去挥发性物质。在23mmHg下蒸馏,得到90.0g无色液体(以所加乙烯基氯为基准,产率为71%),经质子核磁共振(“NMR”)证实,判明该液体为CCl3CH2CHCl2(沸点72-74℃。1H NMR(CDCl3):δ6.15(t,1H),3.7(d,2H)。实例2.CCl3CH2CCl3还原制备CCl3CH2CHCl2
向600mL装有机械搅拌的蒙乃尔合金高压釜中加入199.9gCCl3CH2CCl3、199.5g异丙醇和4gCuI。关闭高压釜并短时间抽空。内容物加热至120-125℃16小时。挥发性物质,包括副产物2-氯丙烷,用旋转蒸发法除去。剩下200g残余物。在装有填料塔的Varian气体色谱(“GC分析”)上分析表明,CCl3CH2CHCl2和CCl3CH2CCl3分别存在,比例为约1∶2。在29mmHg下蒸馏,得到107.9g起始原料(沸点约105至107℃),和36.9g(产率46%)CCl3CH2CHCl2(沸点约85至90℃)。实例3.用HF/SbCl5对CCl3CH2CHCl2进行氟化
向600mL装有机械搅拌的蒙乃尔合金高压釜中加入8.7g SbCl5并冷却至-27℃。然后高压釜抽空,并装以49.8g无水HF。内容物冷却至-40℃,加入44g CCl3CH2CHCl2。然后将反应器与一填料塔/冷凝器组合件相连。将冷凝器维持在-20℃。在2.25小时内将反应混合物加热至135℃,并维持在此温度下2小时。在此加热期间,高压釜的压力通过定期排压(HCl副产物),由2655KPa(400psig)以上的压力降至约1965KPa至2655Kpa(300-400psig)。排放物由冷凝器顶部排至与-78℃冷阱相连的冷KOH水洗涤器。然后将反应器完全排空至冷阱、收集到18.5g无色液体。GC分析判定该液体是84%的CF3CH2CHF2(相应的产率为57%)和11%的CF3CH2CHClF。实例4.用HF/SbF5对CF3CH2CHCl2进行氟化
重复实例3的实验,但用CF3CH2CHCl2作起始原料。向实例3所述装置中加入8.2g SbF5、41g HF和37g CF3CH2CHCl2。(由可商购的CF3CH2CH2Cl在室温下感光氯化作用获得CF3CH2CHCl2)。边搅拌、在最大操作压力3450KPa下将混合物加热至约130-135℃4.5小时。回收到18.1g(相应的产率为57%)无色液体。GC分析表明,该材料是纯度为94%的HFC-245fa。实例5.在150-160℃、低操作压力下用HF/SbCl5将CF3CH2CHCl2进行氟化
重复实例3的实验,但CF3CH2CHCl2用作起始原料。向实例3所述装置中加入9.5g SbCl5、47.9gHF和34.6g CF3CH2CHCl2。边搅拌边将混合物加热至约150-160℃3.5小时,再维持在此温度下2小时。通过定期排出副产物HCl,将最大操作压力控制在1280 KPa。对粗反应产物进行分析显示,其中含有71%HFC-245fa。
如上述实例显示,不采用高温、高压、不使用大量昂贵催化剂,可高产率生产出HFC-245fa。
Claims (10)
1.一种制备1,1,1,3,3-五氟丙烷的方法,包括:
a)下式化合物在氟化催化剂存在下,在足以生成式CF3CH2CF2H化合物的反应条件下,与氟化氢反应:
CFyCl3-yCH2CHFwCl2-w其中w=0或1,y=0-3。
2.权利要求1的方法,其中氟化催化剂选自五价锑卤化物、五价铌卤化物、五价砷卤化物、五价钽卤化物;五价锑混合卤化物、五价铌混合卤化物、五价砷混合卤化物、五价钽混合卤化物,及其混合物。
3.权利要求2的方法,其中氟化催化剂具有式SbClnF5-n,其中n是0至5。
4.权利要求2的方法,其中所述式CFyCl3-yCH2CHFwCl2-w化合物选自CCl3CH2CHCl2、CF3CH2CHCl2、CFCl2CH2CHCl2、CF2ClCH2CHCl2、CFCl2CH2CHClF、CF2ClCH2CHFCl和CF3CH2CHFCl。
5.权利要求2的方法,其中所述式CFyCl3-yCH2CHFwCl2-w化合物是CCl3CH2CHCl2。
6.权利要求1的方法,其中所述反应在温度为约50至约175℃下进行。
7.权利要求1的方法,其中所用HF的量为HF对所述式CFyCl3-yCH2CHFwCl2-w化合物的化学计量用量的约1至约15倍。
8.权利要求7的方法,其中氟化催化剂的用量为式CFyCl3-yCH2CHFwCl2-w化合物重量的约5%至约50%。
9.制备1,1,1,3,3-五氟丙烷的方法,包括:
a)在足以生成式CCl3CH2CHCl2化合物的条件下,使CCl4与乙烯基氯反应;和
b)在氟化催化剂的存在下,使式CCl3CH2CHCl2化合物与氟化氢反应,生成式CF3CH2CF2H化合物。
10.权利要求9的方法,其中所述CCl3CH2CHCl2在步骤b进行之前回收。
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- 1995-07-05 BR BR9508233A patent/BR9508233A/pt not_active Application Discontinuation
- 1995-07-05 KR KR1019970700157A patent/KR100240375B1/ko not_active IP Right Cessation
- 1995-07-05 DE DE0770048T patent/DE770048T1/de active Pending
- 1995-07-05 CN CN95194097A patent/CN1063736C/zh not_active Expired - Lifetime
- 1995-07-05 WO PCT/US1995/008404 patent/WO1996001797A1/en not_active Application Discontinuation
- 1995-07-05 JP JP8504369A patent/JP2818035B2/ja not_active Expired - Lifetime
- 1995-07-05 EP EP95924777A patent/EP0770048B1/en not_active Expired - Lifetime
- 1995-07-05 DK DK95924777T patent/DK0770048T3/da active
- 1995-07-05 CZ CZ9771A patent/CZ7197A3/cs unknown
- 1995-07-05 HU HU9700083A patent/HUT75954A/hu unknown
- 1995-07-05 DE DE69507034T patent/DE69507034C5/de not_active Expired - Lifetime
- 1995-07-05 ES ES95924777T patent/ES2104521T3/es not_active Expired - Lifetime
- 1995-08-25 US US08/519,857 patent/US5574192A/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
AU688925B2 (en) | 1998-03-19 |
EP0770048A1 (en) | 1997-05-02 |
CN1152904A (zh) | 1997-06-25 |
JP2818035B2 (ja) | 1998-10-30 |
CZ7197A3 (cs) | 1998-02-18 |
HUT75954A (en) | 1997-05-28 |
KR970704649A (ko) | 1997-09-06 |
BR9508233A (pt) | 1998-05-19 |
US5574192A (en) | 1996-11-12 |
GR970300031T1 (en) | 1997-09-30 |
KR100240375B1 (ko) | 2000-01-15 |
DE770048T1 (de) | 1998-01-02 |
GR3029809T3 (en) | 1999-06-30 |
EP0770048B1 (en) | 1998-12-30 |
JPH09508138A (ja) | 1997-08-19 |
DE69507034D1 (de) | 1999-02-11 |
ES2104521T1 (es) | 1997-10-16 |
ES2104521T3 (es) | 1999-05-01 |
DK0770048T3 (da) | 1999-08-30 |
DE69507034T2 (de) | 1999-07-01 |
AU2916095A (en) | 1996-02-09 |
ATE175180T1 (de) | 1999-01-15 |
WO1996001797A1 (en) | 1996-01-25 |
DE69507034C5 (de) | 2009-04-30 |
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