EP0874795A1 - Process for producing 1,1-difluoroethane - Google Patents
Process for producing 1,1-difluoroethaneInfo
- Publication number
- EP0874795A1 EP0874795A1 EP97903762A EP97903762A EP0874795A1 EP 0874795 A1 EP0874795 A1 EP 0874795A1 EP 97903762 A EP97903762 A EP 97903762A EP 97903762 A EP97903762 A EP 97903762A EP 0874795 A1 EP0874795 A1 EP 0874795A1
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- Prior art keywords
- chloroethene
- tin catalyst
- hfc
- additive
- ofthe
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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
- 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
Definitions
- the present invention relates to processes for selective and high yield preparation of 1 , 1 -difluoroethane and more particularly to such successes which comprise contacting chloroethene with hydrogen fluoride in a liquid phase while in the presence of a tin catalyst and an oxygen, nitrogen, or phosphorous-containing additive.
- HFCs hydrofluorocarbons
- HCFCs hydrochlorofluorocarbons
- HCCs hydrochlorocarbons
- HF hydrogen fluoride
- the examples reveal that the additives reduce the activity ofthe tin catalyst and thus compromise the efficiency of this process towards forming useful yields of higher fluorinated hydrocarbons.
- Komatsu et al. in Japanese Kokai publication number SHO 62[1987]-246528, disclose a process for manufacture of HFCs and HCFCs, characterized by allowing a hydrogen-containing halogenated hydrocarbon to react with HF in a liquid phase in the presence ofthe reaction product from a compound acting as a base in HF, a tin catalyst, and HF.
- Komatsu teaches the invention in a single example where 1,1,2- trichloroethane is allowed to react with HF in the presence of tin tetrachloride and sodium fluoride.
- the reaction was carried out as a batch process at 90 to 98°C and 980 kPa for three hours, and the charged mole ratio of reactants was 1,1,2- trichloroethane (16.7) : HF (33.3) : SnCl 4 (1.0) : NaF (1.0).
- the isolated product mixture was 32% (wt) 1,2-dichloro-l- fluoroethane (HCFC-141), 1% 1 -chloro- 1,2-difluoroethane (HCFC-142a), and 67% recovered starting material (1,1,2- trichloroethane) with no dimers observed.
- all additives discussed in this Kokai publication, used in a process otherwise identical to U.S. Patent No. 4,766,258 issued to these same authors, are proposed to provide similar benefits.
- HFC- 152a or 152a 1,1-Difluoroethane, hereinafter referred to as HFC- 152a or 152a, is a compound of considerable utility. It may be used either alone or in blends with other materials as a refrigerant, blowing agent, propellant, cleaning agent, or as an intermediate for other fluorocarbon compounds, such as fluoroethene.
- HFCs such as HFC- 152a are environmentally acceptable replacements for chlorofluorocarbons (CFCs), since they have no known effect on the earth's stratospheric ozone.
- HFC- 152a has been manufactured in this manner using liquid and gas phase processes.
- the literature reveals that HFC- 152a has been prepared by allowing chloroethene to react with HF in the presence of salts of various oxidized metals such as tin(IV), titanium(IV), antimony(III), and antimony(V).
- HFC- 152a is prepared from chloroethene comprise 1 -chloro- 1 -fluoroethane (HCFC- 151 a, or 151 a) and 1,1- dichloroethane (HCC- 150a, or 150a).
- Byproducts of such conventional procedures include an assortment of oligomeric and polymeric materials; low molecular weight halogenated dimers and oligomers through higher molecular weight halogenated polymers taking the form of oils, tars and dark carbonaceous solids.
- These byproducts are typically higher molecular weight, e.g., predominately 50,000, with standard weight fraction distribution from 2,000 to 75,000 number averaged molecular weight, branched, polymeric, halogenated hydrocarbons, which may contain metal species acquired from catalyst and other additives, if present.
- Such higher molecular weight materials can be formed by polymerization of lower molecular weight dimers, trimers, and oligomers with themselves or with the halogenated carbon-containing reagents and their fluorinated adducts.
- These byproducts are detrimental to the halogen exchange process as they interfere with catalyst activity, reduce reactor volume, decrease the yield of HFC- 152a, and are a disposal concern.
- the ideal additive for the exchange process is one which minimizes byproduct formation while enhancing the reaction rate and increasing selectivity towards the desired product.
- This invention is a process for the selective preparation of HFC- 152a from chloroethene while minimizing formation of oligomeric and polymeric byproducts.
- the process comprises: providing a liquid phase mixture containing chloroethene, HF, at least one tin catalyst, and at least one compound from the families consisting of oxygen, nitrogen, and phosphorous-containing compounds; heating the mixture; and isolating the HFC- 152a formed.
- the reaction components may be charged to a reaction vessel in any order, but preferably, the vessel is first charged with tin catalyst, HF, and the nitrogen, oxygen, or phosphorous-containing additive.
- the temperature of this mixture is maintained from 20 to 160°C over the reaction period.
- chloroethene is added and is converted to 1 -chloro- 1 -fluoroethane (HCFC-151a) under the reaction conditions.
- This HCFC-151a then undergoes fluorine for chlorine halogen exchange under the reaction conditions and product HFC- 152a distills out of the reaction mixture.
- the process ofthe present invention can be operated as a batch process. It is preferable to operate a continuous process by the continuous addition of HF, tin catalyst, and oxygen, nitrogen, and phosphorous-containing additive to the reaction vessel along with chloroethene accompanied by the removal of HFC- 152a and HCl.
- Figure 1 Schematic ofthe continuous process used to produce HFC-152a.
- This invention is a process for the selective and high yield synthesis of HFC- 152a from chloroethene while minimizing the formation of byproducts.
- the process comprises: providing a liquid phase mixture comprising chloroethene, HF, at least one tin catalyst, and at least one compound selected from the group consisting of oxygen, nitrogen, and phosphorous-containing compounds, heating the mixture, and isolating the HFC- 152a formed.
- Results obtained in this study are summarized in Table 1 and reveal the benefits of employing an oxygen, nitrogen, or phosphorous- containing additive in the tin(IV) mediated synthesis of HFC- 152a from chloroethene and HF.
- Table 1 summarizes typical results obtained by employing at least one oxygen, nitrogen, or phosphorous-containing compound in the tin(IV) mediated synthesis of HFC- 152a from chloroethene. Holding all other process variables constant and increasing the mole ratio of nitrogen-containing additive to tin catalyst from about 0 to 6 through the addition of a nitrogen-containing compound causes a corresponding increase in the product HFC-152a/HCFC-151a mole ratio which varies in a non-linear fashion with the amount and exact chemical composition ofthe nitrogen-containing additive employed.
- Tin catalysts for use in the process ofthe present invention may be selected from the families of tin halides, tin oxyhalides, and organotins. Ofthe three families, the tin halides are preferred, and ofthe tin halides, tin(IV) chloride (SnCl stannic chloride) is most preferred.
- Other acceptable tin(IV) halides include SnBr4 ⁇ d e series of SnC ⁇ F, SnCl2F2, SnClF3, and SnF4; such species as are generated when SnC-4 is allowed to react with HF.
- tin oxyhalides compounds such as SnC ⁇ O, SnF2 ⁇ , and SnClFO are acceptable.
- organotins are compounds in which the tin atom is bonded to from one to four carbon atoms.
- Organotin compounds such as tetramethyl tin (Sn(CH3)4), oxydiethyl tin (OSn(C2H5)2), and dichlorodimethyl tin (SnCl2(CH3)2) are useful in the process.
- the nitrogen-containing compounds ofthe present invention are ammonia (NH3) and nitrogen-containing primary, secondary and tertiary organic compounds such as amines.
- acceptable amines include heterocyclic amines such as pyridine, 2-picoline; saturated and unsaturated aliphatic amines such as trimethylamine, triethylamine, sec-butylamine, hexamethylene diamine; aromatic amines such as aniline, toluidine; and triethanolamine, with t-alkyl amines such as trimethylamine and triethylamine being preferred.
- the oxygen-containing compounds which may be used in the present invention include H2O, H2O2 and other oxygen-generating compounds, and oxygen-containing organic compounds such as alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, sulfones, and epoxy compounds.
- the oxygen-containing compounds may be poly-oxygenated and may contain unlike oxygenated functional groups selected from hydroxyl, carbonyl, carboxyl, ester, ether, and epoxy groups.
- Preferred from the family of oxygenated compounds are the aliphatic alcohols such as ethyl alcohol.
- the phosphorous-containing compounds which may be used in the present invention are selected from the families of organic phosphites, phosphines, and phosphates.
- tri-lower alkyl phosphites such as triethyl phosphite, trimethyl phosphite, tri-n-butyl phosphite, and triisopropyl phosphite; and phenylphosphines such as chlorodiphenylphosphine, and triphenylphosphine oxide.
- the quantity of oxygen-containing additive used in the process ofthe present invention is generally between from about 0.1 mole to 1.5 moles per mole of tin catalyst employed. Preferably, such a process is carried out using between from about 0.6 to 0.9 mole oxygen-containing additive per mole of tin catalyst.
- the quantity of nitrogen-containing additive used in the process ofthe present invention is generally between from about 0.1 mole to 6.0 moles per mole of tin catalyst used. Preferably, such a process is carried out using between from about 0.6 to 0.9 mole nitrogen- containing additive per mole of tin catalyst.
- the quantity of phosphorous-containing additive used in the process according to the invention is generally between from about 0.05 to 0.5 mole per mole of tin catalyst. Preferably, such a process is carried out using between from about 0.2 mole to 0.35 mole phosphorous-containing additive per mole of tin catalyst.
- one or more ofthe aforementioned oxygen, nitrogen, and phosphorous-containing additives and tin catalysts can be combined prior to being contacted with chloroethene.
- ethanol and SnCl4 can be premixed to form a mixture comprising ethanol/SnCl4.
- the premixed combination can be employed in any suitable batch or continuous process described herein.
- the process is performed in a batch
- any suitable autoclave such as a 450 cc Parr Se ⁇ es 4560 Mini Reactor constructed of Hastelloy C can be used.
- the autoclave is typically fitted with a turbine impeller for agitating the liquid contents ofthe autoclave, a septum port for introducing or withdrawing liquids from the autoclave by syringe or cannula technique, valved ports for introducing or withdrawing gaseous or liquid materials, a jacketed 0.25 inch diameter tube reflux condenser topped with a valved takeoff port, and an external heating jacket.
- the inventive batch method generally can be carried out on any scale desired.
- the equipment and associated feed lines, effluent lines, and associated units should be constructed of materials resistant to HF and HCl.
- Typical materials of construction include stainless steels and high nickel alloys, such as Monel nickel-copper alloys, Hastelloy nickel-based
- a dry autoclave is transferred into a dry-box and the desired amount of at least one tin catalyst and at least one compound selected from the group consisting of oxygen, nitrogen, and phosphorous-containing compounds are charged to the autoclave.
- the tin catalysts are normally loaded into the autoclave while within a dry- box in order to minimize any reaction between the tin compounds and moisture present in the air.
- the autoclave is sealed, and removed from the drybox.
- a port ofthe autoclave is then attached to a vacuum pump and the lower portion cooled by being placed into liquid nitrogen, and the autoclave is evacuated.
- Liquid nitrogen facilitates transfer of HF by condensing gaseous HF in the autoclave.
- the autoclave is then attached to an HF cylinder and the desired amount of HF is vacuum transferred into the autoclave.
- the quantities of chloroethene, HF, and tin catalyst present in the autoclave may vary over a broad range of effective operation.
- the quantity of materials used in the process ofthe current invention is generally between about 0.1 to at least about 10 (kg chloroethene fed/hour)/kg catalyst, usually about 0.2 (kg chloroethene fed/hour)/kg catalyst when the tin catalyst comprises SnCl4.
- the initial amount of catalyst charged with HF is generally between about 5 to at least about 35 weight %, for example, SnCl4 in HF, normally from about 10 to about 20 weight % tin catalyst in HF.
- the autoclave is then detached from the vacuum and HF sources, and allowed to warm to ambient temperature.
- the autoclave is then heated to a temperature of about 20 to about 160°C, preferably from about 50 to about 95°C, and the total pressure within the autoclave is maintained between about 60 kPa and about 3000 kPa, preferably about 350 kPa.
- the pressure within the autoclave can be maintained by using any suitable means such as a back-pressure regulator.
- Gaseous chloroethene is then added to the autoclave at a rate that varies as a function ofthe amount of HF and tin catalyst within the autoclave, e.g., adding chloroethene at a rate of about 10 to about 100 seem (about 0.01 to about 0.5 kg/hr/kg-catalyst).
- a gaseous effluent exiting a reflux condenser, which is in fluid communication with the autoclave, is collected by condensation and monitored. The composition ofthe effluent is monitored by using an on-line gas chromatograph (GC).
- GC on-line gas chromatograph
- the autoclave is vented of excess gaseous and liquid materials by a nitrogen purge.
- the solid contents ofthe autoclave are then removed, drowned with water and filtered.
- the filtrate is rinsed with 10% aqueous hydrochloric acid, water, and dried in a vacuum oven to a constant weight.
- composition ofthe dried mass is also analyzed in order to determine the amount of tar that is formed.
- Figure 1 is a schematic diagram for a continuous HFC- 152a manufacturing process.
- a reactor 1 is in fluid communication with a reflux column 2-
- the reflux column 2 will have a reflux ratio of between about 2 to about 20 when operated at a pressure of about 340 to about 3000 kPa and a temperature of about 50 to about 150°C.
- Predetermined amounts (ratios as previously discussed for batch process) of HF, at least one tin catalyst and at least one compound selected from the group consisting of oxygen, nitrogen, and phosphorous-containing compounds are added to the reactor 1.
- the contents of the reactor 1 are agitated by using a dual bladed agitator with pump down action 3_, heated, and brought to reflux at the desired operating temperature/pressure.
- HF and chloroethene are fed continuously to the reactor via one or more feed lines 4_.
- the gas stream leaving the reflux column 2 typically consists essentially of HFC- 152a and HCl, e.g., about 60 to about 70 wt % HFC- 152a.
- a liquid return line 6 is connected to the bottom ofthe reflux column 2. Line 6.
- the gas stream leaving the reactor 1 or reflux column 2 can be purified by any suitable manner such as by using two conventional distillation steps (not shown in Figure 1).
- the first distillation step removes HCl.
- the second distillation step removes any unreacted intermediates and HF that are recovered and, if desired, recycled to reactor 1.
- the continuous production equipment and its associated feed lines, effluent lines and any handling units should be constructed of materials resistant to HF and HCl.
- the inventive process can also be operated in a manner which produces other desirable compounds. That is, the inventive process can produce HFC- 152a alone or co-produced with one or more of HCFC-141b (1,1-dichloro-l -fluoroethane), HCFC- 142b ( 1 -chloro- 1,1- difluoroethane), HFC- 143a (1,1 -trifluoroethane), among others, e.g., from a hydrochlorocarbon such as 1 , 1 -dichloroethene.
- the co-produced product can be recovered and employed as a useful mixture, or separated into its individual components.
- chloroethene was supplied by Fluka Inco ⁇ orated, Ronkonkoma, NY. and HF was supplied by Air Products (Allentown, PA.). All compounds employed in the following examples were commercially available.
- Tin tetrachloride (SnCl4, 37.5 g, 0.144 mol) was added to a Hastelloy C 450 cc Parr Series 4560 Mini Reactor in a dry box.
- the reactor head which was equipped with a 0.25 inch diameter tube reflux condenser, was attached then the reactor removed from the dry box and connected to a stainless steel vacuum line.
- the base ofthe reactor was immersed in liquid nitrogen and HF (150 g, 7.5 mol) was vacuum transferred into the reactor.
- the liquid nitrogen cooling bath was removed and triethylamine (N(C2H5)3, 8.71 g, 0.861 mol) was charged to the reactor via syringe through a septum port.
- the temperature ofthe reactor was raised using external heating until the internal temperature was near 25°C, and cooling water (3.7°C) was begun circulating through the condenser.
- a heating jacket was placed around the reactor, and the internal temperature of the reactor was brought to 50°C while maintaining the internal pressure at 350 kPa by use ofa back pressure regulator.
- flow of chloroethene (50.1 standard cubic centimeter/minute or seem, 8.4 x IO"? m ⁇ /sec) and internal standard methane (9.5 seem, 1.6 x 10"? m ⁇ /sec) were begun.
- the gaseous effluent was monitored every hour for the 17 hours of chloroethene addition.
- the molar yield of HFC- 152a based on the chloroethene fed was measured to be 85%.
- the HFC- 152a was measured by on-line gas chromatography (GC) to be 98% of the effluent.
- the ratio of HFC- 152a/HCFC- 151a (averaged from the 4 m to the 17 m hour ofthe experiment) measured by GC was 58.
- the reactor was vented to atmospheric pressure to drive off volatiles (HF and organics). Further removal of volatiles was assisted by a nitrogen purge.
- the solids remaining in the autoclave were drowned in water and filtered on a Teflon ® (PTFE) membrane filter. The filtrate was washed with 10% HCl and then with water and dried in a vacuum oven to constant mass.
- the tars formed over this run averaged 0.36 g per 100 g chloroethene fed.
- the HFC- 152a product was measured by on- line gas chromatography to be 98% of the effluent.
- the ratio of HFC- 152a/HCFC- 151a (averaged from the 4 th to the 17 tn hour ofthe experiment) was measured to be 40. After 18 hours of operation, the reaction was stopped and worked-up as in Example 1. The tars formed over this run averaged 2.30 g per 100 g chloroethene fed.
- Example 2 through 13 employed a procedure substantially identical to that disclosed in Example 1
- Comparative Example 2 employed a procedure substantially identical to Comparative Example 1.
- the reaction products and process variables which were altered or varied from the standard procedure of Example 1 are reported in Table 1. Process variables which remained constant throughout the runs are listed in the Note following Table 1.
- Table 1 Notes a: As in Example 1, Examples 2-13, Cl, and C2 used 0.144 mole SnCl4, 7.5 moles HF, and were carried out at 50°C and 350 kPa.
- Tin tetrachloride SnCl4, 100. g, 0.383 mol
- potassium fluoride KF, 13.4 g, 0.230 mol
- the reactor head was equipped with two ports for feed or sampling, a reflux column with port for collection of exiting vapors, and an agitator.
- the reactor was sealed, the base cooled, and HF (300 g, 15 mol) followed by ethanol (5.3 g, 0.12 mol) were charged to the reactor.
- the resulting liquid mixture was allowed to sit for 15 hours.
- the contents ofthe reactor were then heated to 80°C and agitation and chloroethene feed begun.
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Abstract
This invention is a process for the selective and high yield preparation of 1,1-difluoroethane (CHF2-CH3, HFC-152a) from chloroethene while minimizing formation of oligomeric and polymeric byproducts. This process comprises providing a liquid phase mixture containing chloroethene, HF, a tin catalyst, and one or a combination of compounds from the families of oxygen, nitrogen, and phosphorus-containing organic compounds, heating the mixture, and isolating the HFC-152a formed.
Description
TITLE
PROCESS FOR PRODUCING 1.1-DIFUJOROETHANE
FIELD OF THE INVENTION
The present invention relates to processes for selective and high yield preparation of 1 , 1 -difluoroethane and more particularly to such successes which comprise contacting chloroethene with hydrogen fluoride in a liquid phase while in the presence ofa tin catalyst and an oxygen, nitrogen, or phosphorous-containing additive.
BACKGROUND OF THE INVENTION Komatsu et al., in U.S. Patent No. 4,766,258, disclose a process for the manufacture of hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons (HCFCs) by allowing hydrochlorocarbons (HCCs) to react with hydrogen fluoride (HF) in the presence of a tin catalyst and an additive chosen from compounds containing oxygen or nitrogen. In most cases, the examples reveal that the additives reduce the activity ofthe tin catalyst and thus compromise the efficiency of this process towards forming useful yields of higher fluorinated hydrocarbons.
Komatsu et al., in Japanese Kokai publication number SHO 62[1987]-246528, disclose a process for manufacture of HFCs and HCFCs, characterized by allowing a hydrogen-containing halogenated hydrocarbon to react with HF in a liquid phase in the presence ofthe reaction product from a compound acting as a base in HF, a tin catalyst, and HF. Komatsu teaches the invention in a single example where 1,1,2- trichloroethane is allowed to react with HF in the presence of tin tetrachloride and sodium fluoride. The reaction was carried out as a batch process at 90 to 98°C and 980 kPa for three hours, and the charged mole ratio of reactants was 1,1,2- trichloroethane (16.7) : HF (33.3) : SnCl4 (1.0) : NaF (1.0). In this example, the isolated product mixture was 32% (wt) 1,2-dichloro-l- fluoroethane (HCFC-141), 1% 1 -chloro- 1,2-difluoroethane (HCFC-142a), and 67% recovered starting material (1,1,2- trichloroethane) with no dimers observed. Based on this single example, all additives discussed in this Kokai publication, used in a process otherwise identical to U.S. Patent No. 4,766,258 issued to these same authors, are proposed to provide similar benefits.
Franklin et al., in U.S. Patent No. 4,968,850, disclose a process for the preparation of HFCs and HCFCs by allowing an unsaturated HCC to react with HF in
a liquid phase in the presence of a tin catalyst and an organophosphorous additive. These additives are described to lead to an efficient halogen exchange process in which the activity ofthe catalyst used is increased and/or the stability ofthe additives is improved, and in which few oligomers are formed and the selectivity for worthwhile products is high. However, while exhibiting a decrease in the amount of oligomers formed, the examples reveal a process in which the selectivity for formation of higher fluorinated hydrocarbons is decreased or changed in a negligible manner.
1,1-Difluoroethane, hereinafter referred to as HFC- 152a or 152a, is a compound of considerable utility. It may be used either alone or in blends with other materials as a refrigerant, blowing agent, propellant, cleaning agent, or as an intermediate for other fluorocarbon compounds, such as fluoroethene. HFCs such as HFC- 152a are environmentally acceptable replacements for chlorofluorocarbons (CFCs), since they have no known effect on the earth's stratospheric ozone.
Processes for preparing HFCs and HCFCs from HCCs and HF by metal mediated halogen exchange have found wide industrial utility. The overall process is one in which carbon to chlorine bonds ofthe HCC are broken and carbon to fluorine bonds are formed in their place. The metal acts in a catalytic capacity leading to a more productive exchange process requiring milder reaction conditions. HFC- 152a has been manufactured in this manner using liquid and gas phase processes. The literature reveals that HFC- 152a has been prepared by allowing chloroethene to react with HF in the presence of salts of various oxidized metals such as tin(IV), titanium(IV), antimony(III), and antimony(V).
Intermediates in the conventional procedures in which HFC- 152a is prepared from chloroethene comprise 1 -chloro- 1 -fluoroethane (HCFC- 151 a, or 151 a) and 1,1- dichloroethane (HCC- 150a, or 150a). Byproducts of such conventional procedures include an assortment of oligomeric and polymeric materials; low molecular weight halogenated dimers and oligomers through higher molecular weight halogenated polymers taking the form of oils, tars and dark carbonaceous solids. These byproducts are typically higher molecular weight, e.g., predominately 50,000, with standard weight fraction distribution from 2,000 to 75,000 number averaged molecular weight, branched, polymeric, halogenated hydrocarbons, which may contain metal species acquired from catalyst and other additives, if present. Such higher molecular weight materials can be formed by polymerization of lower molecular weight dimers, trimers, and oligomers with themselves or with the halogenated carbon-containing reagents and their fluorinated adducts. These
byproducts are detrimental to the halogen exchange process as they interfere with catalyst activity, reduce reactor volume, decrease the yield of HFC- 152a, and are a disposal concern.
Modification ofthe metal catalyst through addition of compounds which are inert to fluorination but reactive with the metal species in HF, leads to catalysts with different properties from the parent. The ideal additive for the exchange process is one which minimizes byproduct formation while enhancing the reaction rate and increasing selectivity towards the desired product.
Conventional processes for making HFC- 152a are undesirable due to the high amounts of tars produced. The inventive process solves the problems associated with conventional processes by reducing the tar formation rates.
SUMMARY OF THE INVENTION
This invention is a process for the selective preparation of HFC- 152a from chloroethene while minimizing formation of oligomeric and polymeric byproducts. The process comprises: providing a liquid phase mixture containing chloroethene, HF, at least one tin catalyst, and at least one compound from the families consisting of oxygen, nitrogen, and phosphorous-containing compounds; heating the mixture; and isolating the HFC- 152a formed.
The reaction components may be charged to a reaction vessel in any order, but preferably, the vessel is first charged with tin catalyst, HF, and the nitrogen, oxygen, or phosphorous-containing additive. The temperature of this mixture is maintained from 20 to 160°C over the reaction period. During this period, chloroethene is added and is converted to 1 -chloro- 1 -fluoroethane (HCFC-151a) under the reaction conditions. This HCFC-151a then undergoes fluorine for chlorine halogen exchange under the reaction conditions and product HFC- 152a distills out of the reaction mixture.
The process ofthe present invention can be operated as a batch process. It is preferable to operate a continuous process by the continuous addition of HF, tin catalyst, and oxygen, nitrogen, and phosphorous-containing additive to the reaction vessel along with chloroethene accompanied by the removal of HFC- 152a and HCl.
Analysis of this process reveals high and selective conversion of chloroethene to HFC-152a while minimizing the amounts of oligomeric and polymeric byproducts.
BRTEF DESCRIPTION OF THE DRAWINGS
Figure 1 — Schematic ofthe continuous process used to produce HFC-152a.
DETAILED DESCRIPTION OF THE INVENTION
This invention is a process for the selective and high yield synthesis of HFC- 152a from chloroethene while minimizing the formation of byproducts. The process comprises: providing a liquid phase mixture comprising chloroethene, HF, at least one tin catalyst, and at least one compound selected from the group consisting of oxygen, nitrogen, and phosphorous-containing compounds, heating the mixture, and isolating the HFC- 152a formed. Results obtained in this study are summarized in Table 1 and reveal the benefits of employing an oxygen, nitrogen, or phosphorous- containing additive in the tin(IV) mediated synthesis of HFC- 152a from chloroethene and HF. Employing the process ofthe present invention leads to a marked increase in selectivity for formation of HFC- 152a over HCFC-151a, increased molar yields of HFC- 152a from chloroethene, and decreased amounts of oligomeric and polymeric byproducts.
Table 1 summarizes typical results obtained by employing at least one oxygen, nitrogen, or phosphorous-containing compound in the tin(IV) mediated synthesis of HFC- 152a from chloroethene. Holding all other process variables constant and increasing the mole ratio of nitrogen-containing additive to tin catalyst from about 0 to 6 through the addition of a nitrogen-containing compound causes a corresponding increase in the product HFC-152a/HCFC-151a mole ratio which varies in a non-linear fashion with the amount and exact chemical composition ofthe nitrogen-containing additive employed. Further, this increase in the mole ratio of nitrogen-containing additive to tin catalyst is accompanied in all cases by a decrease in the mass percent byproducts formed and/or an increase in the molar yield of HFC- 152a. It was also discovered that in the tin (IV) mediated liquid phase synthesis of HFC- 152a from chloroethene, similar such benefits arise when employing an oxygen containing additive such as ethanol (C2H5OH), or a phosphorous-containing additive such as triethyl phosphite (P(OC2H5)3). The synergy of increased HFC- 152a selectivity and increased yield (decreased tar formation), together with the possibility of employing a wide variety of additives, leads to a valuable process.
Tin catalysts for use in the process ofthe present invention may be selected from the families of tin halides, tin oxyhalides, and organotins. Ofthe three families, the tin halides are preferred, and ofthe tin halides, tin(IV) chloride (SnCl stannic chloride) is most preferred. Other acceptable tin(IV) halides include SnBr4 ^d e
series of SnC^F, SnCl2F2, SnClF3, and SnF4; such species as are generated when SnC-4 is allowed to react with HF. Ofthe tin oxyhalides, compounds such as SnC^O, SnF2θ, and SnClFO are acceptable. For the purpose ofthe present invention, organotins are compounds in which the tin atom is bonded to from one to four carbon atoms. Organotin compounds such as tetramethyl tin (Sn(CH3)4), oxydiethyl tin (OSn(C2H5)2), and dichlorodimethyl tin (SnCl2(CH3)2) are useful in the process.
The following oxygen, nitrogen, and phosphorous-containing additives may be used alone or in any composition or mixture in the process ofthe present invention. The nitrogen-containing compounds ofthe present invention are ammonia (NH3) and nitrogen-containing primary, secondary and tertiary organic compounds such as amines. Examples of acceptable amines include heterocyclic amines such as pyridine, 2-picoline; saturated and unsaturated aliphatic amines such as trimethylamine, triethylamine, sec-butylamine, hexamethylene diamine; aromatic amines such as aniline, toluidine; and triethanolamine, with t-alkyl amines such as trimethylamine and triethylamine being preferred. The oxygen-containing compounds which may be used in the present invention include H2O, H2O2 and other oxygen-generating compounds, and oxygen-containing organic compounds such as alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, sulfones, and epoxy compounds. The oxygen-containing compounds may be poly-oxygenated and may contain unlike oxygenated functional groups selected from hydroxyl, carbonyl, carboxyl, ester, ether, and epoxy groups. Preferred from the family of oxygenated compounds are the aliphatic alcohols such as ethyl alcohol. The phosphorous-containing compounds which may be used in the present invention are selected from the families of organic phosphites, phosphines, and phosphates. Preferred from these families are tri-lower alkyl phosphites such as triethyl phosphite, trimethyl phosphite, tri-n-butyl phosphite, and triisopropyl phosphite; and phenylphosphines such as chlorodiphenylphosphine, and triphenylphosphine oxide.
The quantity of oxygen-containing additive used in the process ofthe present invention is generally between from about 0.1 mole to 1.5 moles per mole of tin catalyst employed. Preferably, such a process is carried out using between from about 0.6 to 0.9 mole oxygen-containing additive per mole of tin catalyst. The quantity of nitrogen-containing additive used in the process ofthe present invention is generally between from about 0.1 mole to 6.0 moles per mole of tin catalyst used. Preferably, such a process is carried out using between from about 0.6 to 0.9 mole nitrogen- containing additive per mole of tin catalyst. The quantity of phosphorous-containing additive used in the process according to the invention is generally between from
about 0.05 to 0.5 mole per mole of tin catalyst. Preferably, such a process is carried out using between from about 0.2 mole to 0.35 mole phosphorous-containing additive per mole of tin catalyst.
In one aspect ofthe present invention, one or more ofthe aforementioned oxygen, nitrogen, and phosphorous-containing additives and tin catalysts can be combined prior to being contacted with chloroethene. For example, ethanol and SnCl4 can be premixed to form a mixture comprising ethanol/SnCl4. The premixed combination can be employed in any suitable batch or continuous process described herein.
In one aspect ofthe present invention, the process is performed in a batch
(ft) operation. Any suitable autoclave, such as a 450 cc Parr Seπes 4560 Mini Reactor constructed of Hastelloy C can be used. The autoclave is typically fitted with a turbine impeller for agitating the liquid contents ofthe autoclave, a septum port for introducing or withdrawing liquids from the autoclave by syringe or cannula technique, valved ports for introducing or withdrawing gaseous or liquid materials, a jacketed 0.25 inch diameter tube reflux condenser topped with a valved takeoff port, and an external heating jacket. The inventive batch method generally can be carried out on any scale desired. The equipment and associated feed lines, effluent lines, and associated units should be constructed of materials resistant to HF and HCl. Typical materials of construction, well-known to the fluorination art, include stainless steels and high nickel alloys, such as Monel nickel-copper alloys, Hastelloy nickel-based
(R) alloys, and Inconel nickel-chromium alloys.
A dry autoclave is transferred into a dry-box and the desired amount of at least one tin catalyst and at least one compound selected from the group consisting of oxygen, nitrogen, and phosphorous-containing compounds are charged to the autoclave. The tin catalysts are normally loaded into the autoclave while within a dry- box in order to minimize any reaction between the tin compounds and moisture present in the air.
The autoclave is sealed, and removed from the drybox. A port ofthe autoclave is then attached to a vacuum pump and the lower portion cooled by being placed into liquid nitrogen, and the autoclave is evacuated. By establishing a vacuum in the autoclave, potentially deleterious air is removed thereby permitting more efficient transfer of gaseous HF. Liquid nitrogen facilitates transfer of HF by condensing gaseous HF in the autoclave. The autoclave is then attached to an HF cylinder and the desired amount of HF is vacuum transferred into the autoclave.
The quantities of chloroethene, HF, and tin catalyst present in the autoclave may vary over a broad range of effective operation. The quantity of materials used in the process ofthe current invention is generally between about 0.1 to at least about 10 (kg chloroethene fed/hour)/kg catalyst, usually about 0.2 (kg chloroethene fed/hour)/kg catalyst when the tin catalyst comprises SnCl4. The initial amount of catalyst charged with HF is generally between about 5 to at least about 35 weight %, for example, SnCl4 in HF, normally from about 10 to about 20 weight % tin catalyst in HF.
After the starting materials are introduced into the sealed autoclave, the autoclave is then detached from the vacuum and HF sources, and allowed to warm to ambient temperature. The autoclave is then heated to a temperature of about 20 to about 160°C, preferably from about 50 to about 95°C, and the total pressure within the autoclave is maintained between about 60 kPa and about 3000 kPa, preferably about 350 kPa. The pressure within the autoclave can be maintained by using any suitable means such as a back-pressure regulator.
Gaseous chloroethene is then added to the autoclave at a rate that varies as a function ofthe amount of HF and tin catalyst within the autoclave, e.g., adding chloroethene at a rate of about 10 to about 100 seem (about 0.01 to about 0.5 kg/hr/kg-catalyst). A gaseous effluent exiting a reflux condenser, which is in fluid communication with the autoclave, is collected by condensation and monitored. The composition ofthe effluent is monitored by using an on-line gas chromatograph (GC). After the addition of chloroethene has ceased, the autoclave is vented of excess gaseous and liquid materials by a nitrogen purge. The solid contents ofthe autoclave are then removed, drowned with water and filtered. The filtrate is rinsed with 10% aqueous hydrochloric acid, water, and dried in a vacuum oven to a constant weight.
The composition ofthe dried mass is also analyzed in order to determine the amount of tar that is formed.
While the aforementioned batch process can be employed, a continuous process is particularly desirable from an industrial standpoint. Referring now to Figure 1 , Figure 1 is a schematic diagram for a continuous HFC- 152a manufacturing process. A reactor 1 is in fluid communication with a reflux column 2- Typically, the reflux column 2 will have a reflux ratio of between about 2 to about 20 when operated at a pressure of about 340 to about 3000 kPa and a temperature of about 50 to about 150°C. Predetermined amounts (ratios as previously discussed for batch process) of HF, at least one tin catalyst and at least one compound selected from the group consisting of oxygen, nitrogen, and phosphorous-containing compounds are added to
the reactor 1. The contents of the reactor 1 are agitated by using a dual bladed agitator with pump down action 3_, heated, and brought to reflux at the desired operating temperature/pressure. When the desired operating conditions have been established, HF and chloroethene are fed continuously to the reactor via one or more feed lines 4_. Gas exits from the reactor 1 and is transported to the reflux column 2 via one or more feed lines 5.- The gas stream leaving the reflux column 2 typically consists essentially of HFC- 152a and HCl, e.g., about 60 to about 70 wt % HFC- 152a. A liquid return line 6 is connected to the bottom ofthe reflux column 2. Line 6. returns high boiling intermediates such as 1,1-dichloroethane and HCFC-151a, among others, and any HF to reactor 1. The gas stream leaving the reactor 1 or reflux column 2 can be purified by any suitable manner such as by using two conventional distillation steps (not shown in Figure 1). The first distillation step removes HCl. The second distillation step removes any unreacted intermediates and HF that are recovered and, if desired, recycled to reactor 1.
Similar to operating a batch process as discussed earlier, the continuous production equipment and its associated feed lines, effluent lines and any handling units should be constructed of materials resistant to HF and HCl.
While the previous description has placed particular emphasis upon making a product stream wherein HFC-152a is the major component, the inventive process can also be operated in a manner which produces other desirable compounds. That is, the inventive process can produce HFC- 152a alone or co-produced with one or more of HCFC-141b (1,1-dichloro-l -fluoroethane), HCFC- 142b ( 1 -chloro- 1,1- difluoroethane), HFC- 143a (1,1 -trifluoroethane), among others, e.g., from a hydrochlorocarbon such as 1 , 1 -dichloroethene. The co-produced product can be recovered and employed as a useful mixture, or separated into its individual components.
The following examples are provided for the purpose of further illustrating the present invention without limiting the invention as defined in the appended claims. In the following examples, chloroethene was supplied by Fluka Incoφorated, Ronkonkoma, NY. and HF was supplied by Air Products (Allentown, PA.). All compounds employed in the following examples were commercially available.
EXAMPLES
Example 1 — Triethylamine as Additive
Tin tetrachloride (SnCl4, 37.5 g, 0.144 mol) was added to a Hastelloy C 450 cc Parr Series 4560 Mini Reactor in a dry box. The reactor head, which was equipped with a 0.25 inch diameter tube reflux condenser, was attached then the reactor removed from the dry box and connected to a stainless steel vacuum line. The base ofthe reactor was immersed in liquid nitrogen and HF (150 g, 7.5 mol) was vacuum transferred into the reactor. The liquid nitrogen cooling bath was removed and triethylamine (N(C2H5)3, 8.71 g, 0.861 mol) was charged to the reactor via syringe through a septum port. The temperature ofthe reactor was raised using external heating until the internal temperature was near 25°C, and cooling water (3.7°C) was begun circulating through the condenser. A heating jacket was placed around the reactor, and the internal temperature of the reactor was brought to 50°C while maintaining the internal pressure at 350 kPa by use ofa back pressure regulator. At this time, flow of chloroethene (50.1 standard cubic centimeter/minute or seem, 8.4 x IO"? m^/sec) and internal standard methane (9.5 seem, 1.6 x 10"? m^/sec) were begun. The gaseous effluent was monitored every hour for the 17 hours of chloroethene addition. The molar yield of HFC- 152a based on the chloroethene fed was measured to be 85%. The HFC- 152a was measured by on-line gas chromatography (GC) to be 98% of the effluent. The ratio of HFC- 152a/HCFC- 151a (averaged from the 4m to the 17m hour ofthe experiment) measured by GC was 58. At the end ofthe run, the reactor was vented to atmospheric pressure to drive off volatiles (HF and organics). Further removal of volatiles was assisted by a nitrogen purge. The solids remaining in the autoclave were drowned in water and filtered on a Teflon® (PTFE) membrane filter. The filtrate was washed with 10% HCl and then with water and dried in a vacuum oven to constant mass. The tars formed over this run averaged 0.36 g per 100 g chloroethene fed.
Comparative Example 1 — No Additive
The apparatus, procedure, and materials used for this comparative example were identical to those disclosed in Example 1 , with the exception that no triethylamine additive was used. The following discussion documents results obtained from this Example and deviations in procedure from that of Example 1.
The HFC- 152a product was measured by on- line gas chromatography to be 98% of the effluent. The ratio of HFC- 152a/HCFC- 151a (averaged from the 4th to
the 17tn hour ofthe experiment) was measured to be 40. After 18 hours of operation, the reaction was stopped and worked-up as in Example 1. The tars formed over this run averaged 2.30 g per 100 g chloroethene fed.
Table 1— Examples 1 through 15 and Comparative Examples 1 through 3.
Examples 2 through 13 employed a procedure substantially identical to that disclosed in Example 1 , and Comparative Example 2 employed a procedure substantially identical to Comparative Example 1. The reaction products and process variables which were altered or varied from the standard procedure of Example 1 are reported in Table 1. Process variables which remained constant throughout the runs are listed in the Note following Table 1.
IΔBLE1 Oxygen. Nitrogen, and Phosphorous-Containing Additives
Product Grams Tar
Mole % Mole per 100 g
Additive (moles used, mole Reaction Yield Ratio Chloroethene
Ex.a ratio to tin catalyst) Time (hr) 152a 152a/151a Fed
Cl None 18 85 40 2.30
C2 None 16.3 87 44 2.03
1 N(C2H5)3 (0.86, 6.0) 17 85 58 0.36
2 N(C2H5)3 x3HF (0.864, 6.0 16 97 76 0.45 )
3 N(C2H5)3 16 89 52 0.57 (0.043, 0.30)
4 N(C2H5)3 15 84 41 0.29 (0.144, 1.0)
5 2-methyl pyridine 16 87 69 0.56 (2-picoline) (0.086, 0.60)
6 P(OC2H5)3 (0.437, 3.0) 16 84 50 0.13
7 P(OC2H5)3 (0.087, 0.60) 14 83 28 0.05
8 C2H5OH (0.13, 0.90) 14 88 55 0.14
9 2-propanone (acetone) 16 87 63 0.49 (0.144, 1.0)
10 N(CH3)3 (0.096, 0.67) 16.5 89 75 0.49
11 N(CH3)3 (0.144, 1.0) 16.3 87 50 0.30
12 NH(C2H5)2 (0.144, 1.0) 16.5 90 66 0.14
13 tetramethylene sulfone 15.8 85 91 0.74 (0.144, 1.0)
Table 1 Notes a: As in Example 1, Examples 2-13, Cl, and C2 used 0.144 mole SnCl4, 7.5 moles HF, and were carried out at 50°C and 350 kPa.
b: These examples employed 0.383 mole SnCLj., 15 moles HF, and the reactions were carried out at 80°C. See following detailed procedural description for Examples 14, 15, and C3.
Example 14 — Ethanol as Additive
Tin tetrachloride (SnCl4, 100. g, 0.383 mol) and potassium fluoride (KF, 13.4 g, 0.230 mol) were charged to a Hastelloy C 600 cc Parr Mini Reactor in a dry box. The reactor head was equipped with two ports for feed or sampling, a reflux column with port for collection of exiting vapors, and an agitator. The reactor was sealed, the base cooled, and HF (300 g, 15 mol) followed by ethanol (5.3 g, 0.12 mol) were charged to the reactor. The resulting liquid mixture was allowed to sit for 15 hours. The contents ofthe reactor were then heated to 80°C and agitation and chloroethene feed begun. HF feed was then started and adjusted so as to maintain a constant total weight of material in the reactor. Once this was attained, and once successive on-line GC analyses ofthe reflux condenser effluent were within experimental error, the process was consider to be at steady state. At a 19.6 g/hr (0.31 mol/hr) rate of chloroethene feed, the following steady state results were obtained by on-line GC analysis ofthe reflux condenser effluent: HFC-152a (96.7% by GC peak area integration), chloroethene (0.04%), HCFC-151a (2.2%), 1.1-dichloroethane (0.5%). The relative ratio of HFC-152a/HCFC-151a was measured by GC to be 44. At the end ofthe run. the reaction mixture was worked up by the procedure of Example 1. The tars formed over this run averaged 4.6 g per 100 g of chloroethene fed.
Example IS — Ethanol Additive
The apparatus, procedure, and materials used for this example were identical to those discussed for Example 14. The following discussion documents results obtained from this example and deviations in procedure from Example 14. The ethanol charge was 10.6 g (0.23 mol). At a 19.6 g/hr (0.31 mol/hr) rate of chloroethene feed, the following steady state results were obtained by on-line GC analysis ofthe reflux condenser effluent: HFC- 152a (95.2% by GC peak area integration), chloroethene (0.0%), HCFC- 151a (3.9%), 1,1-dichloroethane (1.0%). The relative ratio of HFC-152a/HCFC-151a was measured by GC to be 24. At the end ofthe run the mixture was worked- up by the procedure of Example 1. The tars formed over this run averaged 4.6 g per 100 g of chloroethene fed.
Comparative Example 3 - No Additive
The apparatus, procedure, and materials used for this example were identical to those discussed for Example 14, except that no ethanol additive was employed. The following discussion documents results obtained from this example and deviations in procedure from Example 14.
The SnCl4 charge was 140 g (0.54 mol) and the reaction was carried out at 76°C. At a 18.2 g hr (0.29 mol/hr) rate of chloroethene feed, the following steady state results were obtained by on-line GC analysis ofthe reflux condenser effluent: HFC- 152a (89.6% by GC peak area integration), chloroethene (0.0%), HCFC- 151a (7.8%), 1,1-dichloroethane (2.4%). The relative ratio of HFC-152a HCFC-151a was found by GC to be 11. At the end ofthe run the mixture was worked up by the procedure of Example 1. The tars formed over this run averaged 7.1 g per 100 g of chloroethene fed.
Claims
1. A process for the manufacture of 1,1-difluoroethane comprising: a) providing a liquid phase first mixture comprising chloroethene, hydrogen fluoride, at least one tin catalyst, and at least one additive selected from the group consisting of an oxygen, nitrogen, and phosphorous-containing compound; b) heating said first mixture, and; c) recovering a second mixture comprising 1,1-difluoroethane wherein said second mixture is substantially free of oligomeric and polymeric compounds.
2. The process of Claim 1 wherein said tin catalyst comprises at least one member from the group consisting of SnCLj, SnBr4, SnC^F, SnCl2F , SnClF3, SnF4, SnCl2O, SnF2O, SnClFO, Sn(CH3)4, OSn(C2H5)2, and SnCl2(CH3)2.
3. The process of Claim 1 wherein said additive is selected from the group consisting of H2O, peroxides, alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, sulfones, epoxides, ammonia, amines, phosphites, phosphines, and phosphates.
4. The process of Claim 3 wherein said additive is selected from the group consisting of H2O, H2O2, methanol, ethanol, propanol, isopropanol, butanol, tetramethylene sulfone, pyridine, 2-picoline, trimethylamine, triethylamine, tripropylamine, tributylamine, sec-butylamine, hexamethylene diamine, aniline, toluidine, triethanolamine, triethyl phosphite, trimethyl phosphite, tri-n-butyl phosphite, triisopropyl phosphite, chlorodiphenylphosphine, and triphenylphosphine oxide.
5. The process of Claim 1 wherein the mole ratio of said oxygen-containing compound to said tin catalyst is from about 0.1 to 1.5.
6. The process of Claim 1 wherein the mole ratio of said nitrogen-containing compound to said tin catalyst is from about 0.1 to 6.
7. The process of Claim 1 wherein the mole ratio of said phosphorous- containing compound to said tin catalyst is from about 0.05 to 0.5.
8. The process of Claim 1 wherein said heating is carried out at from about
2°C to 160°C.
9. The process of Claim 1 wherein said process is continuous process.
10. The process of Claim 1 wherein said tin catalyst is SnCl4 and said additive is at least one compound selected from the group consisting of ethanol, trimethylamine, triethylamine, and triethyl phosphite.
1 1. The process of Claim 1 wherein oligomeric and polymeric compounds formed is less than 0.5 weight % ofthe chloroethene fed.
Applications Claiming Priority (5)
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US987196P | 1996-01-05 | 1996-01-05 | |
US9871P | 1996-01-05 | ||
US77843997A | 1997-01-02 | 1997-01-02 | |
US778439 | 1997-01-02 | ||
PCT/US1997/000289 WO1997025301A1 (en) | 1996-01-05 | 1997-01-03 | Process for producing 1,1-difluoroethane |
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EP97903762A Withdrawn EP0874795A1 (en) | 1996-01-05 | 1997-01-03 | Process for producing 1,1-difluoroethane |
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EP (1) | EP0874795A1 (en) |
JP (1) | JP2000503300A (en) |
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FR2636941B1 (en) * | 1988-09-26 | 1991-02-01 | Solvay | PROCESS FOR THE MANUFACTURE OF FLUORINATED HYDROCARBON |
CN1037600C (en) * | 1992-01-15 | 1998-03-04 | 浙江省化工研究院 | Improving, separating and purifying method for 1,1-difluoroethane |
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- 1997-01-03 EP EP97903762A patent/EP0874795A1/en not_active Withdrawn
- 1997-01-03 CN CN 97192803 patent/CN1212679A/en active Pending
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