CN105237332A - Method for preparing 1,1,1,3,3-pentachloropropane - Google Patents
Method for preparing 1,1,1,3,3-pentachloropropane Download PDFInfo
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- CN105237332A CN105237332A CN201510769505.9A CN201510769505A CN105237332A CN 105237332 A CN105237332 A CN 105237332A CN 201510769505 A CN201510769505 A CN 201510769505A CN 105237332 A CN105237332 A CN 105237332A
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- pentachloropropane
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Abstract
The invention discloses a method for preparing 1,1,1,3,3-pentachloropropane. According to the method, due to the fact that a telomeric catalyst exists, telomeric reaction is conducted on tetrachloromethane and chloroethylene, and the 1,1,1,3,3-pentachloropropane is prepared, the reaction temperature ranges from 25 DEG C to 100 DEG C, and the reaction time ranges from 0.5 h to 5 h; the telomeric catalyst is composed of a main catalyst, an auxiliary catalyst and an organic activation agent, wherein the main catalyst adopts halogenated copper salt or halogenated iron salt, the auxiliary catalyst adopts alkylphosphonate or diisopropyl phosphite or organic tertiary amine, the organic tertiary amine adopts azodiisobutyronitrile or 2,2-azobis(4-methoxyl-2,4-dimethylvaleronitrile) or 1,1-azobis-cyclohexanecarbonitril or 2,3,4,5,6-pentacarbonyl-2-hexenic acid-4-lactone or 2,3,4,5,6-pentacarbonyl acetaldehyde or phenylhydrazine or metoxyphenol, and the molar ratio of the main catalyst to the auxiliary catalyst to the organic activation substance is 1 to 0.5-20 to 0.1-20. According to the method for preparing the 1,1,1,3,3-pentachloropropane, the telomeric catalyst has the advantages that the telomeric catalyst exists in a reaction system in a homogeneous mode, the reaction condition is mild, and the telomeric catalyst is stable to air; the telomeric catalyst can be used for catalyzing the tetrachloromethane and the chloroethylene to conduct the telomeric reaction to prepare the 1,1,1,3,3-pentachloropropane.
Description
Technical field
The present invention relates to the method that one prepares 1,1,1,3,3-pentachloropropane, specifically refer to Primary Catalysts, promotor and organic activator composition telomerize catalyzer exist under, tetracol phenixin and vinylchlorid telomerize the method for preparation 1,1,1,3,3-pentachloropropane.
Background technology
1,1,1,3,3-pentachloropropane (HCC-240fa) is the intermediate of preparation 1,1,1,3,3-pentafluoropropane (HFC-245fa).The latent value (ODP) of atmospheric ozone consumption of HFC-245fa is zero, environmental-protecting performance is excellent, is 1, and 1, the ideal substitute of 1-chloro fluoroethane (HCFC-141b) and dichloromonofluoromethane (CFC-11), is widely used as whipping agent, solvent and clean-out system.
In existing HCC-240fa technology of preparing, main employing tetracol phenixin and vinylchlorid are raw material, lower to aggregate into obtain in the effect of catalyzer.US Patent No. 6313360 reports a kind of method of catalysis tetracol phenixin and VCM synthesis HCC-240fa, the method with iron powder, iron trichloride, tributyl phosphate for catalyzer, wherein iron powder is as the composition of catalyzer, in operation easy occluding device and pipeline.Chinese patent CN1986507A reports tetracol phenixin and vinylchlorid carries out telomerizing synthesis HCC-240fa in 80 ~ 115 DEG C under iron powder and phosphoric acid ester effect, reaction product need by settlement separate removal crude iron powder, and by washing the thin iron powder removing and be suspended in reaction product further, add complicacy and the production cost of aftertreatment.In the preparation HCC-240fa technology of above-mentioned bibliographical information, use iron powder in catalyst system, in operating process there is the problem of easy occluding device and pipeline, aftertreatment complexity in iron powder, and the easy oxidation by air of iron powder itself simultaneously, storage requirement is high.
Chinese patent CN1335291A reports tetracol phenixin and vinylchlorid under the combination catalyst of cuprous chloride and thanomin, and 120 DEG C of reactions 4 hours, HCC-240fa yield is 86.5%.Chinese patent CN104230648A reports tetracol phenixin and vinylchlorid under the combination catalyst of cuprous chloride and TERTIARY BUTYL AMINE, is warming up to 75 DEG C, is incubated about 30 minutes, is warming up to 110 DEG C subsequently, stirring reaction 8h, HCC-240fa yield 82.3%.All there is the shortcoming that temperature of reaction is higher or the reaction times is longer in the preparation HCC-240fa technology of above-mentioned bibliographical information, the easy oxidation by air of cuprous chloride, not easily stores simultaneously.
Summary of the invention
The object of the invention is to overcome the deficiency existed in background technology, there is provided a kind of with homogeneous phase mode be present in reaction system, reaction conditions gentle, catalyzer is telomerized to air-stable, and use this catalyst tetracol phenixin and vinylchlorid to telomerize preparation 1,1,1, the method of 3,3-pentachloropropane.
In order to realize object of the present invention, preparation 1 of the present invention, 1,1,3, the method of 3-pentachloropropane (HCC-240fa), construct be made up of Primary Catalysts, promotor and organic activator telomerize catalyzer, and apply this catalyst tetracol phenixin and vinylchlorid and telomerize and prepare HCC-240fa.
Described Primary Catalysts is halo mantoquita or the halo molysite of high-valence state, concrete preferred halo mantoquita is cupric chloride, cupric bromide, preferred halo molysite is iron(ic) chloride or iron bromide, and preferred halo mantoquita is cupric chloride, and preferred halo molysite is iron(ic) chloride.
Described promotor be can with Primary Catalysts coordination, and Primary Catalysts is dissolved in the organic ligand of reaction system, suitable promotor is alkyl phosphate, alkyl phosphite or trimethylamine.Concrete preferred alkyl phosphate is triethyl phosphate, tributyl phosphate or triphenylphosphate, and concrete preferred alkyl phosphite is triethyl-phosphite or tributyl phosphate; Concrete preferred trimethylamine is 2,2'-dipyridyl, three (2-(methyl amido) ethamine, N, N, N', N', N "-five methyl diethylentriamine, 1, Isosorbide-5-Nitrae; 7,10,10-hexamethyl triethylene tetramine or three (2-pyridylmethyl) amine.
Described organic activator is by Primary Catalysts activation for having the lower valency metal-salt telomerizing catalytic activity, and can be dissolvable in water reaction system, and the compound of stable existence at the reaction temperatures.Concrete selected organic activator is Diisopropyl azodicarboxylate, 2,2-azos two (4-methoxyl group-2,4-methyl pentane nitrile), 1,1-azo two cyclohexanenitrile, 2,3,4,5,6-penta hydroxy group-2-hexenoic acid-4-lactone, 2,3,4,5,6-penta hydroxy group acetaldehyde, phenylhydrazine or methoxyphenol.
The described mol ratio telomerizing Primary Catalysts in catalyzer, promotor and organic activator is 1:0.5 ~ 20:0.1 ~ 20, and preferred mol ratio is 1:1 ~ 5:0.5 ~ 10.The Primary Catalysts added and the mol ratio of tetracol phenixin are 0.001 ~ 0.5:1, and preferred mol ratio is 0.005 ~ 0.1:1.
The method that the present invention adopts tetracol phenixin excessive carries out telomerization, and the mol ratio of vinylchlorid and tetracol phenixin is 0.1 ~ 1:1, and preferred mol ratio is 0.3 ~ 0.8:1.
The temperature of reaction of telomerization is 25 ~ 100 DEG C, and the reaction times is 0.5 ~ 5h.Preferred temperature of reaction is 50 ~ 80 DEG C, and the reaction times is 1 ~ 3h.
The telomerization of tetracol phenixin and vinylchlorid can in organic solvent or solvent-free in carry out, when with an organic solvent, optional organic solvent is acetonitrile, ethylene glycol, ethanol, acetone, sherwood oil, toluene, DMF or methyl-sulphoxide.The usage quantity of solvent is 10% ~ 200% of tetracol phenixin massfraction.
The telomerization of tetracol phenixin and vinylchlorid can periodical operation, also can operate continuously, reaction itself to reaction formation without obvious requirement.
A kind of preferred preparation 1,1,1, the method of 3,3-pentachloropropane: with iron(ic) chloride, 1,1-azo two cyclohexanenitrile and tributyl phosphate composition telomerize catalyzer exist under, tetracol phenixin and vinylchlorid telomerization prepare 1,1,1,3,3-pentachloropropane, wherein iron(ic) chloride, 1, the mol ratio of 1-azo two hexamethylene and tributyl phosphate is 1:1:3, and the mol ratio of iron(ic) chloride and tetracol phenixin is 0.01:1, and the mol ratio of vinylchlorid and tetracol phenixin is 0.5:1, temperature of reaction is 80 DEG C, and the reaction times is 1h.
A kind of preferred preparation 1,1,1,3, the method of 3-pentachloropropane: with cupric chloride, Diisopropyl azodicarboxylate and three (2-(methyl amido) ethamine composition telomerize catalyzer exist under, tetracol phenixin and vinylchlorid telomerization prepare 1,1,1,3,3-pentachloropropane, wherein (mol ratio of 2-(methyl amido) ethamine is 1:1:1, and the mol ratio of iron(ic) chloride and tetracol phenixin is 0.01:1, and the mol ratio of vinylchlorid and tetracol phenixin is 0.5:1 for cupric chloride, Diisopropyl azodicarboxylate and three, temperature of reaction is 60 DEG C, and the reaction times is 1h.
Advantage of the present invention: (1) use be made up of Primary Catalysts, promotor and organic activator novelly telomerize catalyzer, this catalyst dissolution is in reaction system, formed homogeneous catalysis system, do not exist use iron powder exist occluding device and pipeline, aftertreatment complexity problem; (2) the novel catalyzer that telomerizes has very high catalytic activity, temperature of reaction is 25 ~ 100 DEG C, reaction times is 0.5 ~ 5h, temperature of reaction is 50 ~ 80 DEG C under the preferred conditions, reaction times is 1 ~ 3h, react under certain conditions and even can at room temperature carry out, also namely compare documents reaction conditions milder; (3) the novel Primary Catalysts telomerized in catalyzer is the metal-salt of high-valence state, and compare iron powder, the cuprous chloride of the lower valency that documents uses, not easily oxidation by air, more easily stores.
Embodiment
Followingly the present invention to be described in further detail in conjunction with the embodiments, but not to limit the scope of the invention.
Embodiment 1
Primary Catalysts iron(ic) chloride 8.13g (0.05mol), promotor tributyl phosphate 39.9g (0.15mol), organic activator 1,1-azo two cyclohexanenitrile 12.2 (0.05mol) and tetracol phenixin 770g (5mol) are added to 1L stainless steel autoclave successively.Enclosed high pressure still, opens and stirs, with the air in nitrogen replacement autoclave, replace three times.Disposablely subsequently add vinylchlorid 156.25g, temperature of reactor is heated to 80 DEG C, react after 1 hour and terminate.Treat that room temperature is down to by autoclave, unload still and take out material.Get liquid sample by pipette, analyzed by chromatographic process, the transformation efficiency of vinylchlorid is the selectivity of 95.5%, HCC-240fa is 96.1%.
Embodiment 2
The operating process of embodiment 2 is similar to embodiment 1, and difference is Primary Catalysts is iron bromide.Product is analyzed by chromatographic process, and the transformation efficiency of vinylchlorid is the selectivity of 96.5%, HCC-240fa is 93.1%.
Embodiment 3 ~ 9
The operating process of embodiment 3 ~ 9 is similar to embodiment 1, and difference changes promotor and organic activator, and regulates temperature of reaction to telomerize the activity of catalyzer with coupling.Reaction result is as shown in table 1.
Table 1
Embodiment 10
By Primary Catalysts cupric chloride 6.73g (0.05mol), (2-(methyl amido) ethamine 11.52g (0.05mol), organic activator Diisopropyl azodicarboxylate 12.2 (0.05mol) and tetracol phenixin 770g (5mol) are added to 1L stainless steel autoclave to promotor three.Enclosed high pressure still, opens and stirs, with the air in nitrogen replacement autoclave, replace three times.Disposablely subsequently add vinylchlorid 156.25g, temperature of reactor is heated to 60 DEG C, react after 1 hour and terminate.Treat that room temperature is down to by autoclave, unload still and take out material.Get liquid sample by pipette, and analyzed by chromatographic process, the transformation efficiency of vinylchlorid is the selectivity of 96.5%, HCC-240fa is 97.1%.
Embodiment 11
The operating process of embodiment 11 is similar to embodiment 10, and difference is Primary Catalysts is cupric bromide.Product is analyzed by chromatographic process, and the transformation efficiency of vinylchlorid is the selectivity of 94.5%, HCC-240fa is 94.8%.
Embodiment 12 ~ 21
The operating process of embodiment 12 ~ 21 is similar to embodiment 10, and difference changes promotor and organic activator, and regulates temperature of reaction to telomerize the activity of catalyzer with coupling.Reaction result is as shown in table 2.
Table 2
Embodiment 22 ~ 27
The operating process of embodiment 22 ~ 27 is similar to embodiment 10, and difference changes reaction conditions.Reaction result is as shown in table 3.
Table 3
Embodiment 28
The operating process of embodiment 28 is similar to embodiment 10, and difference adds 200g acetonitrile as solvent.Product is analyzed by chromatographic process, and the transformation efficiency of vinylchlorid is the selectivity of 93.5%, HCC-240fa is 93.8%.
Embodiment 29
The operating process of embodiment 29 is similar to embodiment 10, and difference adds 250gN, and dinethylformamide is as solvent.Product is analyzed by chromatographic process, and the transformation efficiency of vinylchlorid is the selectivity of 95.5%, HCC-240fa is 94.1%.
Embodiment 30
The operating process of embodiment 30 is similar to embodiment 10, and difference adds 250g toluene as solvent.Product is analyzed by chromatographic process, and the transformation efficiency of vinylchlorid is the selectivity of 82.5%, HCC-240fa is 95.1%.
Claims (5)
1. prepare the method for 1,1,1,3,3-pentachloropropane for one kind, it is characterized in that telomerizing under catalyzer existence, 1,1,1,3,3-pentachloropropane is prepared in tetracol phenixin and vinylchlorid telomerization, and temperature of reaction is 25 ~ 100 DEG C, and the reaction times is 0.5 ~ 5h, telomerize catalyzer by Primary Catalysts, promotor and organic activator composition, wherein Primary Catalysts is halo mantoquita or halo molysite, promotor is alkyl phosphate, alkyl phosphite or trimethylamine, organic activator is Diisopropyl azodicarboxylate, 2, two (the 4-methoxyl group-2 of 2-azo, 4-methyl pentane nitrile), 1, 1-azo two cyclohexanenitrile, 2, 3, 4, 5, 6-penta hydroxy group-2-hexenoic acid-4-lactone, 2, 3, 4, 5, 6-penta hydroxy group acetaldehyde, phenylhydrazine or methoxyphenol, Primary Catalysts, the mol ratio of promotor and organic activator is 1:0.5 ~ 20:0.1 ~ 20, the mol ratio of Primary Catalysts and tetracol phenixin is 0.001 ~ 0.5:1, the mol ratio of vinylchlorid and tetracol phenixin is 0.1 ~ 1:1.
2. the method for preparation 1,1,1,3,3-pentachloropropane according to claim 1, is characterized in that in described Primary Catalysts, halo mantoquita is cupric chloride or cupric bromide; Halo molysite is iron(ic) chloride or iron bromide.
3. the method for preparation 1,1,1,3,3-pentachloropropane according to claim 1, is characterized in that in described promotor, alkyl phosphate is triethyl phosphate, tributyl phosphate or triphenylphosphate; Alkyl phosphite is triethyl-phosphite or tributyl phosphate; Trimethylamine is 2,2 '-dipyridyl, three (2-(methyl amido) ethamine, N, N, N ', N ', N "-five methyl diethylentriamine, 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triethylene tetramine or three (2-pyridylmethyl) amine.
4. preparation 1 according to claims 1 to 3,1,1, the method of 3,3-pentachloropropane, is characterized in that with iron(ic) chloride, tributyl phosphate and 1,1-azo two cyclohexanenitrile composition telomerize catalyzer exist under, tetracol phenixin and vinylchlorid telomerization prepare 1,1,1,3,3-pentachloropropane, wherein the mol ratio of iron(ic) chloride, tributyl phosphate and 1,1-azo two cyclohexanenitrile is 1:3:1, the mol ratio of iron(ic) chloride and tetracol phenixin is 0.01:1, the mol ratio of vinylchlorid and tetracol phenixin is 0.5:1, and temperature of reaction is 80 DEG C, and the reaction times is 1h.
5. preparation 1 according to claims 1 to 3, 1, 1, 3, the method of 3-pentachloropropane, it is characterized in that with cupric chloride, three (2-(methyl amido) ethamine and Diisopropyl azodicarboxylate composition telomerize catalyzer exist under, tetracol phenixin and vinylchlorid telomerization prepare 1, 1, 1, 3, 3-pentachloropropane, wherein cupric chloride, three (mol ratio of 2-(methyl amido) ethamine and Diisopropyl azodicarboxylate is 1:1:1, the mol ratio of iron(ic) chloride and tetracol phenixin is 0.01:1, the mol ratio of vinylchlorid and tetracol phenixin is 0.5:1, temperature of reaction is 60 DEG C, reaction times is 1h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114349594A (en) * | 2021-12-16 | 2022-04-15 | 西安近代化学研究所 | Method and reactor for preparing polyhalogenated hydrocarbon |
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| CN114349594A (en) * | 2021-12-16 | 2022-04-15 | 西安近代化学研究所 | Method and reactor for preparing polyhalogenated hydrocarbon |
| CN114349594B (en) * | 2021-12-16 | 2024-02-20 | 西安近代化学研究所 | Method and reactor for preparing polyhalogenated hydrocarbon |
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