CN105237332B - A kind of method for preparing 1,1,1,3,3 pentachloropropanes - Google Patents
A kind of method for preparing 1,1,1,3,3 pentachloropropanes Download PDFInfo
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- CN105237332B CN105237332B CN201510769505.9A CN201510769505A CN105237332B CN 105237332 B CN105237332 B CN 105237332B CN 201510769505 A CN201510769505 A CN 201510769505A CN 105237332 B CN105237332 B CN 105237332B
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- carbon tetrachloride
- telomerization
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Abstract
The invention discloses a kind of method for preparing 1,1,1,3,3 pentachloropropanes.For this method in the presence of telomerization catalyst, carbon tetrachloride prepares 1,1,1,3,3 pentachloropropane with vinyl chloride telomerisation, and reaction temperature is 25~100 DEG C, and the reaction time is 0.5~5h；Telomerization catalyst is made up of major catalyst, co-catalyst and organic activator, wherein major catalyst is halo mantoquita or halo molysite, co-catalyst is alkylphosphonate, alkyl phosphite or trimethylamine, organic activator is azodiisobutyronitrile, 2, double (4 methoxyl groups 2 of 2 azos, 4 methyl pentane nitriles), the cyclohexanenitrile of 1,1 azo two, 2,3,4, the lactone of 5,6 penta hydroxy group, 2 hexenoic acid 4,2,3,4,5,6 penta hydroxy groups aldehyde, phenylhydrazine or metoxyphenol, the mol ratio of major catalyst, co-catalyst and organic activator is 1:0.5~20:0.1~20.The telomerization catalyst that the present invention uses has is present in the advantages of reaction system, reaction condition are gentle, to air-stable in a manner of homogeneous, and 1,1,1,3,3 pentachloropropane is prepared available for catalysis carbon tetrachloride and vinyl chloride telomerisation.
Description
Technical field
The method of 1,1,1,3,3- pentachloropropane is prepared the present invention relates to one kind, in particular in major catalyst, co-catalysis
In the presence of the telomerization catalyst of agent and organic activator composition, carbon tetrachloride prepares 1,1,1,3,3- pentachloro- with vinyl chloride telomerization
The method of propane.
Background technology
1,1,1,3,3- pentachloropropanes (HCC-240fa) are prepared in 1,1,1,3,3- pentafluoropropanes (HFC-245fa)
Mesosome.The HFC-245fa latent value (ODP) of atmospheric ozone consumption is zero, and environmental-protecting performance is excellent, is 1,1,1- chloro fluoroethane
(HCFC-141b) and monofluorodichloromethane (CFC-11) ideal substitute, be widely used as foaming agent, solvent and cleaning agent.
It is main to use carbon tetrachloride with vinyl chloride for raw material in existing HCC-240fa technologies of preparing, in the work of catalyst
Aggregate into obtain with downward.United States Patent (USP) US6313360 reports a kind of catalysis carbon tetrachloride and VCM synthesis HCC-240fa
Method, this method is using iron powder, ferric trichloride, tributyl phosphate as catalyst, and wherein composition of the iron powder as catalyst is operating
During easily occluding device and pipeline.Chinese patent CN1986507 A report carbon tetrachloride and vinyl chloride in iron powder and phosphoric acid
Telomerization synthesis HCC-240fa is carried out under ester effect in 80~115 DEG C, reaction product need to remove crude iron powder by sedimentation separation, and
The thin iron powder being suspended in reaction product is removed by further washing, adds the complexity and production cost of post processing.On
In the preparation HCC-240fa technologies for stating document report, iron powder is used in catalyst system, iron powder, which exists, in operating process easily blocks
Equipment and pipeline, the problem of complicated, while iron powder easy oxidation by air in itself are post-processed, memory requirement is high.
Chinese patent CN1335291A reports carbon tetrachloride and vinyl chloride and is catalyzed in the combination of stannous chloride and monoethanolamine
Under agent, 120 DEG C of 4 hours of reaction, HCC-240fa yields are 86.5%.The A of Chinese patent CN 104230648 report tetrachloro
Change carbon and vinyl chloride under the combination catalyst of stannous chloride and tert-butylamine, be warming up to 75 DEG C, be incubated about 30 minutes, then heating
To 110 DEG C, stirring reaction 8h, HCC-240fa yield 82.3%.The preparation HCC-240fa technologies of above-mentioned document report are present
Reaction temperature is higher or the shortcomings that the reaction time is longer, while the easy oxidation by air of stannous chloride, is not easy to store.
The content of the invention
It is insufficient present in background technology it is an object of the invention to overcome, there is provided one kind is present in reaction in a manner of homogeneous
System, reaction condition are gentle, the telomerization catalyst to air-stable, and use the catalyst carbon tetrachloride and vinyl chloride
The method that telomerization prepares 1,1,1,3,3- pentachloropropanes.
In order to realize the purpose of the present invention, the method for the pentachloropropane (HCC-240fa) of preparation 1,1,1,3,3- of the invention,
The telomerization catalyst being made up of major catalyst, co-catalyst and organic activator is constructed, and applies the catalyst four
Chlorination carbon prepares HCC-240fa with vinyl chloride telomerization.
Described major catalyst is the halo mantoquita or halo molysite of high-valence state, and specific preferable halo mantoquita is chlorination
Copper, copper bromide, preferable halo molysite are iron chloride or ferric bromide, and preferred halo mantoquita is copper chloride, preferred halogen
It is iron chloride for molysite.
Described co-catalyst dissolves in major catalyst the organic ligand of reaction system for that can be coordinated with major catalyst,
Suitable co-catalyst is alkylphosphonate, alkyl phosphite or trimethylamine.Specific preferable alkylphosphonate is phosphoric acid
Triethyl, tributyl phosphate or triphenyl phosphate, specific preferable alkyl phosphite is triethyl phosphite or phosphorous acid three
Butyl ester；Specific preferable trimethylamine is 2,2'- bipyridyls, three (2- (methylamino) ethamine, N, N, N', N', N "-pentamethyls
Diethylenetriamines, 1,1,4,7,10,10- hexamethyl triethylene tetramines or three (2- pyridylmethyls) amine.
Described organic activator, which is, to be the lower valency metal salt with telomerization catalytic activity by major catalyst activation,
And reaction system is dissolvable in water, and the compound being stabilized at the reaction temperatures.Specific selected organic activator is azo
Bis-isobutyronitrile, 2,2- azos double (4- methoxyl group -2,4- methyl pentane nitriles), the cyclohexanenitrile of 1,1- azos two, 2,3,4,5,6- pentahydroxy-s
Base -2- hexenoic acid -4- lactones, 2,3,4,5,6- pentahydroxy-s ethylhexanal, phenylhydrazine or metoxyphenol.
The mol ratio of major catalyst, co-catalyst and organic activator is 1 in the telomerization catalyst:0.5~20:0.1
~20, preferable mol ratio is 1:1~5:0.5~10.The major catalyst of addition and the mol ratio of carbon tetrachloride be 0.001~
0.5:1, preferable mol ratio is 0.005~0.1:1.
The present invention carries out telomerisation using the excessive method of carbon tetrachloride, and the mol ratio of vinyl chloride and carbon tetrachloride is
0.1~1:1, preferable mol ratio is 0.3~0.8:1.
The reaction temperature of telomerisation is 25~100 DEG C, and the reaction time is 0.5~5h.Preferable reaction temperature is 50~
80 DEG C, the reaction time is 1~3h.
The telomerisation of carbon tetrachloride and vinyl chloride can in organic solvent or solvent-free middle progress, when using organic molten
During agent, optional organic solvent is acetonitrile, ethylene glycol, ethanol, acetone, petroleum ether, toluene, DMF or diformazan
Sulfoxide.The usage amount of solvent is the 10%~200% of carbon tetrachloride mass fraction.
The telomerisation of carbon tetrachloride and vinyl chloride be able to can also be operated continuously with intermittently operated, and reaction is in itself to reacting shape
Formula requires without obvious.
A kind of preferable method for preparing 1,1,1,3,3- pentachloropropanes：With iron chloride, the cyclohexanenitrile of 1,1- azos two and phosphorus
In the presence of the telomerization catalyst of sour tributyl composition, carbon tetrachloride prepares 1,1,1,3,3- pentachloro- third with vinyl chloride telomerisation
The mol ratio of alkane, wherein iron chloride, the hexamethylene of 1,1- azos two and tributyl phosphate is 1:1:3, iron chloride and carbon tetrachloride rub
You are than being 0.01:1, the mol ratio of vinyl chloride and carbon tetrachloride is 0.5:1, reaction temperature is 80 DEG C, reaction time 1h.
A kind of preferable method for preparing 1,1,1,3,3- pentachloropropanes：With copper chloride, azodiisobutyronitrile and three (2-
In the presence of the telomerization catalyst of (methylamino) ethamine composition, carbon tetrachloride prepares 1,1,1,3,3- five with vinyl chloride telomerisation
(mol ratio of 2- (methylamino) ethamine is 1 by chloropropane, wherein copper chloride, azodiisobutyronitrile and three：1：1, iron chloride and four
The mol ratio of chlorination carbon is 0.01:1, the mol ratio of vinyl chloride and carbon tetrachloride is 0.5:1, reaction temperature is 60 DEG C, during reaction
Between be 1h.
Advantages of the present invention：(1) urged using the new telomerization being made up of major catalyst, co-catalyst and organic activator
Agent, the catalyst dissolution form homogeneous catalysis system, in the absence of occluding device and pipe existing for use iron powder in reaction system
The problem of road, complicated post processing；(2) new telomerization catalyst has very high catalytic activity, and reaction temperature is 25~100 DEG C,
Reaction time is 0.5~5h, and reaction temperature is 50~80 DEG C under the preferred conditions, and the reaction time is 1~3h, in some conditions
Lower reaction can even be carried out at room temperature, namely compared to documents reaction condition milder；(3) in new telomerization catalyst
Major catalyst be high-valence state metal salt, iron powder, the stannous chloride of the lower valency used compared to documents, be not easy by air
Oxidation, is more easy to store.
Embodiment
It is following that the present invention is described in further detail in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
By major catalyst iron chloride 8.13g (0.05mol), co-catalyst tributyl phosphate 39.9g (0.15mol), organic
The cyclohexanenitrile 12.2 (0.05mol) of activator 1,1- azos two and carbon tetrachloride 770g (5mol) are sequentially added to 1L stainless steel high pressures
Reactor.Enclosed high pressure kettle, stirring is opened, with the air in nitrogen displacement autoclave, displacement is three times.It is then disposable to add chlorine
Ethene 156.25g, temperature of reactor is heated to 80 DEG C, reaction terminates after 1 hour.Treat that autoclave is down to room temperature, unload kettle taking-up
Material.Fluid sample is taken with pipette, is analyzed by chromatographic process, the conversion ratio of vinyl chloride is 95.5%, HCC-240fa choosing
Selecting property is 96.1%.
Embodiment 2
The operating process of embodiment 2 is similar to Example 1, except that major catalyst is ferric bromide.Product passes through color
Spectral Analysis, the selectivity that the conversion ratio of vinyl chloride is 96.5%, HCC-240fa is 93.1%.
Embodiment 3~9
The operating process of embodiment 3~9 is similar to Example 1, except that change co-catalyst and organic activator,
And reaction temperature is adjusted to match the activity of telomerization catalyst.Reaction result is as shown in table 1.
Table 1
Embodiment 10
By major catalyst copper chloride 6.73g (0.05mol), (2- (methylamino) the ethamine 11.52g of co-catalyst three
(0.05mol), organic activator azodiisobutyronitrile 12.2 (0.05mol) and carbon tetrachloride 770g (5mol) add stainless to 1L
Steel autoclave.Enclosed high pressure kettle, stirring is opened, with the air in nitrogen displacement autoclave, displacement is three times.It is then disposable
Vinyl chloride 156.25g is added, temperature of reactor is heated to 60 DEG C, reaction terminates after 1 hour.Treat that autoclave is down to room temperature, unload
Kettle takes out material.Fluid sample is taken with pipette, and is analyzed by chromatographic process, the conversion ratio of vinyl chloride is 96.5%, HCC-
240fa selectivity is 97.1%.
Embodiment 11
The operating process of embodiment 11 is similar to Example 10, except that major catalyst is copper bromide.Product passes through
Chromatographic process is analyzed, and the selectivity that the conversion ratio of vinyl chloride is 94.5%, HCC-240fa is 94.8%.
Embodiment 12~21
The operating process of embodiment 12~21 is similar to Example 10, except that changing co-catalyst and organic active
Agent, and reaction temperature is adjusted to match the activity of telomerization catalyst.Reaction result is as shown in table 2.
Table 2
Embodiment 22~27
The operating process of embodiment 22~27 is similar to Example 10, except that changing reaction condition.Reaction result
As shown in table 3.
Table 3
Embodiment 28
The operating process of embodiment 28 is similar to Example 10, except that adding 200g acetonitriles as solvent.Product
Analyzed by chromatographic process, the selectivity that the conversion ratio of vinyl chloride is 93.5%, HCC-240fa is 93.8%.
Embodiment 29
The operating process of embodiment 29 is similar to Example 10, except that adding 250g DMFs
As solvent.Product is analyzed by chromatographic process, and the selectivity that the conversion ratio of vinyl chloride is 95.5%, HCC-240fa is
94.1%.
Embodiment 30
The operating process of embodiment 30 is similar to Example 10, except that adding 250g toluene as solvent.Product
Analyzed by chromatographic process, the selectivity that the conversion ratio of vinyl chloride is 82.5%, HCC-240fa is 95.1%.
Claims (4)
1. the method that one kind prepares 1,1,1,3,3- pentachloropropane, it is characterised in that in the presence of telomerization catalyst, carbon tetrachloride
1,1,1,3,3- pentachloropropane is prepared with vinyl chloride telomerisation, reaction temperature is 25~100 DEG C, and the reaction time is 0.5~5h；
Telomerization catalyst is made up of major catalyst, co-catalyst and organic activator, and wherein major catalyst is halo molysite, co-catalyst
For alkylphosphonate, alkyl phosphite, organic activator is azodiisobutyronitrile, double (the 4- methoxyl groups -2,4- bis- of 2,2- azos
Methyl valeronitrile), the cyclohexanenitrile of 1,1- azos two, 2,3,4,5,6- penta hydroxy group -2- hexenoic acid -4- lactones, metoxyphenol, main catalytic
The mol ratio of agent, co-catalyst and organic activator is 1:0.5~20:0.1~20, the mol ratio of major catalyst and carbon tetrachloride
For 0.001~0.5:1, the mol ratio of vinyl chloride and carbon tetrachloride is 0.1~1:1.
2. the method according to claim 1 for preparing 1,1,1,3,3- pentachloropropane, it is characterised in that described main catalytic
Halo molysite is iron chloride or ferric bromide in agent.
3. the method according to claim 1 for preparing 1,1,1,3,3- pentachloropropane, it is characterised in that described co-catalysis
Alkylphosphonate is triethyl phosphate, tributyl phosphate or triphenyl phosphate in agent；Alkyl phosphite is triethyl phosphite
Or tributyl phosphite.
4. according to the method for any described pentachloropropane of preparation 1,1,1,3,3- of claims 1 to 3, it is characterised in that with chlorination
In the presence of the telomerization catalyst of iron, tributyl phosphate and the cyclohexanenitrile of 1,1- azo two composition, carbon tetrachloride and vinyl chloride telomerization are anti-
1,1,1,3,3- pentachloropropane should be prepared, the wherein mol ratio of iron chloride, tributyl phosphate and the cyclohexanenitrile of 1,1- azo two is 1:
3:1, the mol ratio of iron chloride and carbon tetrachloride is 0.01:1, the mol ratio of vinyl chloride and carbon tetrachloride is 0.5:1, reaction temperature
For 80 DEG C, reaction time 1h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021473A1 (en) * | 2003-08-26 | 2005-03-10 | Vulcan Chemicals A Business Group Of Vulcan Materials Company | Method for producing 1,1,1,3-tetrachloropropane and other haloalkanes with iron catalyst |
| CN1986507A (en) * | 2005-12-19 | 2007-06-27 | 浙江蓝天环保高科技股份有限公司 | Improved preparing process for 1,1,1,3,3-pentachloro propane |
| CN104447186A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane |
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| RU2010147002A (en) * | 2010-11-17 | 2012-05-27 | Е.И.Дюпон де Немур энд Компани (US) | CATALYTIC SYNTHESIS OF HALOGENED HYDROCARBONS |
| CN104230648A (en) * | 2013-06-18 | 2014-12-24 | 徐家乐 | Preparation method for synthesizing 1,1,1,3,3-pentachloropropane by carbon tetrachloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005021473A1 (en) * | 2003-08-26 | 2005-03-10 | Vulcan Chemicals A Business Group Of Vulcan Materials Company | Method for producing 1,1,1,3-tetrachloropropane and other haloalkanes with iron catalyst |
| CN1986507A (en) * | 2005-12-19 | 2007-06-27 | 浙江蓝天环保高科技股份有限公司 | Improved preparing process for 1,1,1,3,3-pentachloro propane |
| CN104447186A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane |
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