CN103508841A - Method for preparing 1,1-difluoro-1,2-dichloroethane - Google Patents
Method for preparing 1,1-difluoro-1,2-dichloroethane Download PDFInfo
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- CN103508841A CN103508841A CN201210197746.7A CN201210197746A CN103508841A CN 103508841 A CN103508841 A CN 103508841A CN 201210197746 A CN201210197746 A CN 201210197746A CN 103508841 A CN103508841 A CN 103508841A
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- hydrofluoric acid
- trieline
- anhydrous hydrofluoric
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Abstract
The invention discloses a method for preparing 1,1-difluoro-1,2-dichloroethane. The method uses trichloro ethylene and anhydrous hydrofluoric acid as raw materials, under action of a fluorination catalyst, to prepare 1,1-difluoro-1,2-dichloroethane by liquid phase catalysis and fluorination reaction. The method has advantages of mild reaction condition, simple method and easy implementation of industrialization production.
Description
Technical field
The invention belongs to organic fluorine chemical technology field, especially relate to a kind ofly 1,1-bis-is fluoro-1, the preparation method of 2-ethylene dichloride.
Background technology
1,1-bis-is fluoro-1, and 2-ethylene dichloride is commercial referred to as HCFC-132b or R132b, mainly for the preparation of polymer monomer with as the intermediate in fluorine Lyons.For the preparation of polymer monomer, from HCFC-132b, under the effect of alcohol alkali, can prepare the fluoro-2-vinyl chloride monomer of 1,1-bis-; As the intermediate in fluorine Lyons, by HCFC-132b, set out that through chlorination, can to prepare 1,1,2-tri-chloro-2,2-C2H4F2 C2H4F2 (R122) and 1,1,1,2-tetrachloro-2,2-C2H4F2 C2H4F2 (R112a), and R122 and R112a are the important intermediate in agricultural chemicals medicine fluorine Lyons.
About the preparation method of R132b, patent documentation has two kinds of preparation methods in recording.US4766259A is reported in MnCl
2/alF
3or FeCl
3/ AlF
3under catalyst action, trieline and anhydrous hydrofluoric acid generation gas and solid phase catalyzing fluoridation generate R132b, wherein temperature of reaction is controlled at 120～200 ℃, anhydrous hydrofluoric acid and trieline raw materials components mole ratio are controlled at 0.5:1～15:1, reaction time 20 seconds～80 seconds, trieline transformation efficiency is 10%～20%, R132b selectivity 60%～70%.US2399024A report trieline and anhydrous hydrofluoric acid are under existing without any catalyzer, 150～250 ℃ of temperature of reaction, anhydrous hydrofluoric acid and trieline charging total amount ratio are controlled in 1:2～2:1 situation liquid phase reaction 9～10 hours, and R132b selectivity is 50% left and right.Above two kinds of R132b patent system Preparation Methods all exist temperature of reaction high, the low shortcoming of reaction conversion ratio and selectivity.
Summary of the invention
The invention provides that a kind of temperature of reaction is low, reaction conversion ratio and selectivity higher 1,1-bis-is fluoro-1, and 2-ethylene dichloride (R132b) preparation method fluoridizes preparation 1 by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, 1-bis-is fluoro-1,2-ethylene dichloride (R132b).
Theoretical foundation of the present invention is as follows:
CHClCCl
2 + HF
CH
2ClCFCl
2 （I）
CH
2ClCFCl
2 + HF
CH
2ClCF
2Cl + HCl （II）
CH
2ClCF
2Cl + HF
CH
2ClCF
3 + HCl （III）
Reaction is under fluorination catalyst exists, under certain temperature and pressure condition, first there is addition reaction and generate 1 in trieline and anhydrous hydrofluoric acid, 1, the chloro-1-fluoroethane of 2-tri-(R131a) (as reaction formula (I)), and then 1, 1, there is substitution reaction and generate 1 in the chloro-1-fluoroethane of 2-tri-and HF, 1-bis-fluoro-1, 2-ethylene dichloride (R132b) (as reaction formula (II)), under excessive HF exists, there are small portion R132b and HF to continue to react simultaneously and generate by-product 1, 1, 1-trifluoro-2-chloroethane (R133a) (as reaction formula (III)), there is above-mentioned reaction simultaneously, under fluorination catalyst exists, trieline generation self-polymeric reaction and addition reaction occurs with HCl, make reaction process have the high boiling material such as polychloride to generate.
The selection of fluorination catalyst is one of key problem in technology of the present invention, is applicable to fluorination catalyst of the present invention and is selected from SbCl
5, SnCl
4, TiCl
4, HSO
3cl or HSO
3a kind of, more than two or three combination in F.
The concentration of fluorination catalyst directly affects the formation speed of target product R132b and by-product R133a and high boiling material, the concentration of fluorination catalyst is high, target product R132b formation speed is accelerated, but correspondingly the formation speed of by-product R133a and high boiling material is also accelerated, the concentration of contrary fluorination catalyst is low, the formation speed of by-product R133a and high boiling material slows down, but target product R132b formation speed also slows down, for guaranteeing reaction, carry out smoothly, reduce by-product and high boiling material growing amount as far as possible, keep again suitable speed of response simultaneously, in reaction system, fluorination catalyst concentration will be controlled in OK range, fluorination catalyst add-on is preferably and accounts for 5%～30% of the total weight of material of reaction, more preferably 8%～15%, the method of controlling fluorination catalyst concentration can react by control in trieline and anhydrous hydrofluoric acid content comprehensive adjustment in fluorination catalyst add-on and reaction system.
In the present invention reaction, temperature of reaction is another important factor of impact reaction, and temperature of reaction is higher, and R132b formation speed is accelerated, but in reaction system, by-product and high boiling material gather way also soon, and catalyzer also can be affected work-ing life; Temperature of reaction reduces, although by-product and high boiling material formation speed slow down in reaction system, target product formation speed also reduces, and considers speed of response and catalyst life, temperature of reaction of the present invention is preferably 0～100 ℃, more preferably 50～70 ℃.
Raw material anhydrous hydrofluoric acid and trieline raw materials components mole ratio can have influence on the transformation efficiency of trieline and generate target product R132b selectivity.Anhydrous hydrofluoric acid and trieline raw materials components mole ratio < 1.5, trieline and anhydrous hydrofluoric acid react not exclusively, are converted into R132b elective reduction.Anhydrous hydrofluoric acid and trieline raw materials components mole ratio > 3.5, although being conducive to R132b generates, but by-product R133a content in reaction system can increase, so anhydrous hydrofluoric acid and the suitable raw materials components mole ratio of trieline be preferably 1.5～3.5, more preferably 2.1～2.8.
In the present invention's reaction, reaction pressure is another important factor of impact reaction, and reaction pressure is controlled highlyer, and target product R132b formation speed is accelerated, under identical condensing temperature, reaction discharging R132b content is higher, carries hydrogen fluoride content secretly lower, but hypertonia, to equipment and corresponding material-transporting system, require also higher, facility investment expense is also high, so reaction pressure is preferably 0.1～1.0 MPa, is preferably controlled at 0.3～0.7 MPa.
Fluorination catalyst of the present invention is best activated processing before use, can use anhydrous hydrofluoric acid activation treatment, fluorination catalyst and anhydrous hydrofluoric acid mol ratio 1:5～1:20,60～70 ℃ of activation temperatures, soak time 2～5 hours.
Compared with prior art, R132b preparation method reaction conversion ratio provided by the invention, selectivity and productive rate are all higher, and method is simple and easy, is easy to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained all alternativess, improvement project and the equivalents that within the scope of claims, may comprise.
embodiment 1
Toward the antimony pentachloride fluorination catalyst that drops into 50Kg in 600L reactor, the disposable anhydrous hydrofluoric acid toward adding 50Kg in reactor, then input 4Kg anhydrous hydrofluoric acid per hour heats up to reactor, heating-up time is controlled at 5 hours, when temperature rises to 70 ℃ of left and right, constant temperature 3 hours, guarantees that catalyst activation is complete.Then opening reaction jacket refrigerating medium lowers the temperature 4 hours to reactor, while being down to 45 ℃ to temperature, toward reactor interior input trieline and anhydrous hydrofluoric acid, carry out bottoming, the rate of feeding of trieline is 100Kg/h, the rate of feeding of anhydrous hydrofluoric acid is 4 Kg/h, until trieline charging capacity while reaching 300Kg bottoming finish.Then by trieline: anhydrous hydrofluoric acid=60:24Kg/h carries out continuous dosing, control reaction liquid level 50%, temperature of reaction is between 55 ℃, and reaction pressure is at 0.3 ~ 0.4MPa.Reaction product gas obtains more than 99.5% R132b product after the purification systems such as washing, alkali cleaning, fractionation.
embodiment 2
On the basis of embodiment 1, change trieline and anhydrous hydrofluoric acid continuous dosing velocity ratio is 60:16Kg/h, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 3
On the basis of embodiment 1, change trieline and anhydrous hydrofluoric acid continuous dosing velocity ratio is 60:20Kg/h, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 4
On the basis of embodiment 1, change trieline and anhydrous hydrofluoric acid continuous dosing velocity ratio is 60:28Kg/h, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 5
On the basis of embodiment 1, change trieline and anhydrous hydrofluoric acid continuous dosing velocity ratio is 60:32Kg/h, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 6
On the basis of embodiment 1, changing temperature of reaction is 50 ℃ of left and right, and remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 7
On the basis of embodiment 1, changing temperature of reaction is 60 ℃ of left and right, and remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 8
On the basis of embodiment 1, changing fluorination catalyst is SnCl
4, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 9
On the basis of embodiment 1, changing fluorination catalyst is TiCl
4, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 10
On the basis of embodiment 1, changing fluorination catalyst is HSO
3cl, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
embodiment 11
On the basis of embodiment 1, changing fluorination catalyst is HSO
3f, remaining reaction condition is identical with embodiment 1, and reaction result is in Table 1.
Table 1
| Embodiment | The transformation efficiency of trieline | The selectivity of R132b | The selectivity of R131a | The selectivity of R133a |
| 1 | 99.5% | 95.3% | 2.3% | 2.4% |
| 2 | 96.8% | 96.2% | 3.1% | 0.7% |
| 3 | 98.2% | 95.8% | 3.2% | 1% |
| 4 | 99.6% | 90.2% | 1.8% | 8% |
| 5 | 99.8% | 85.7% | 1.2% | 13.1% |
| 6 | 97.7% | 91.5% | 8% | 0.5% |
| 7 | 99.8% | 89.5% | 0.6% | 9.9% |
| 8 | 99.3% | 94.6% | 2.6% | 2.8% |
| 9 | 99.7% | 94.5% | 2.3% | 3.2% |
| 10 | 99.2% | 95.5% | 2.3% | 2.2% |
| 11 | 99.0% | 95.8% | 2.1% | 2.1% |
Claims (9)
1. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, fluoridize preparation 1 for one kind, 1-bis-fluoro-1, the method of 2-ethylene dichloride, it is characterized in that under fluorination catalyst exists, under 0～100 ℃ of temperature and 0.1～1.0 MPa pressure, anhydrous hydrofluoric acid reacts preparation 1,1-bis-with trieline fluoro-1,2-ethylene dichloride;
Described fluorination catalyst is selected from SbCl
5, SnCl
4, TiCl
4, HSO
3cl or HSO
3a kind of, more than two or three combination in F.
2. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, to fluoridize preparation 1,1-bis-fluoro-1 according to claimed in claim 1, the method for 2-ethylene dichloride, and the add-on that it is characterized in that described fluorination catalyst is 5%～30% of the total weight of material of reaction.
3. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, to fluoridize preparation 1,1-bis-fluoro-1 according to claimed in claim 2, the method for 2-ethylene dichloride, and the add-on that it is characterized in that described fluorination catalyst is 8%～15% of the total weight of material of reaction.
4. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, to fluoridize preparation 1,1-bis-fluoro-1 according to claimed in claim 1, the method for 2-ethylene dichloride, and mole proportioning that it is characterized in that described anhydrous hydrofluoric acid and trieline is 1.5～3.5:1.
5. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, to fluoridize preparation 1,1-bis-fluoro-1 according to claimed in claim 4, the method for 2-ethylene dichloride, and mole proportioning that it is characterized in that described anhydrous hydrofluoric acid and trieline is 2.1～2.8:1.
6. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, to fluoridize preparation 1,1-bis-fluoro-1 according to claimed in claim 1, and the method for 2-ethylene dichloride, is characterized in that described temperature of reaction is 50～70 ℃, and reaction pressure is 0.3～0.7 MPa.
7. according to claimed in claim 1, by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, fluoridize preparation 1,1-bis-fluoro-1, the method of 2-ethylene dichloride, it is characterized in that described fluorination catalyst is before use through anhydrous hydrofluoric acid activation treatment, fluorination catalyst and anhydrous hydrofluoric acid mol ratio 1:5～1:20,60～70 ℃ of activation temperatures, soak time 2～5 hours.
8. according to claimed in claim 1, by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, fluoridize preparation 1,1-bis-fluoro-1, the method of 2-ethylene dichloride, is characterized in that described reaction is successive reaction, and trieline and anhydrous hydrofluoric acid continuous dosing velocity ratio are 60:16Kg/h～60:32Kg/h.
9. by trieline and anhydrous hydrofluoric acid liquid-phase catalysis, to fluoridize preparation 1,1-bis-fluoro-1 according to claimed in claim 8, and the method for 2-ethylene dichloride, is characterized in that described trieline and anhydrous hydrofluoric acid continuous dosing velocity ratio are 60:16Kg/h～60:28Kg/h.
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|---|---|---|---|
| CN201210197746.7A CN103508841A (en) | 2012-06-15 | 2012-06-15 | Method for preparing 1,1-difluoro-1,2-dichloroethane |
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|---|---|---|---|
| CN201210197746.7A CN103508841A (en) | 2012-06-15 | 2012-06-15 | Method for preparing 1,1-difluoro-1,2-dichloroethane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299948A (en) * | 2020-12-01 | 2021-02-02 | 山东华安新材料有限公司 | Preparation method of 1, 1, 1-trifluoro-2-chloroethane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2719021A1 (en) * | 1977-04-28 | 1978-11-09 | Bayer Ag | 1,1,1-Tri:fluoro-2-chloro-ethane prodn. - from tri:chloro-ethylene and hydrogen fluoride using arsenic or antimony cpd. catalyst |
| US4374289A (en) * | 1980-10-01 | 1983-02-15 | Allied Corporation | Production of monofluorotrichloroethane |
| WO1989012614A1 (en) * | 1988-06-23 | 1989-12-28 | E.I. Du Pont De Nemours And Company | Catalyzed hydrofluorination of alkenes |
| CN1051349A (en) * | 1989-10-04 | 1991-05-15 | 纳幕尔杜邦公司 | The method of purification of fluorocarbon |
| CN1075709A (en) * | 1992-02-24 | 1993-09-01 | 中国科学院上海有机化学研究所 | 1,1, the preparation technology of 1-three fluoro-2-monochloroethane |
-
2012
- 2012-06-15 CN CN201210197746.7A patent/CN103508841A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2719021A1 (en) * | 1977-04-28 | 1978-11-09 | Bayer Ag | 1,1,1-Tri:fluoro-2-chloro-ethane prodn. - from tri:chloro-ethylene and hydrogen fluoride using arsenic or antimony cpd. catalyst |
| US4374289A (en) * | 1980-10-01 | 1983-02-15 | Allied Corporation | Production of monofluorotrichloroethane |
| WO1989012614A1 (en) * | 1988-06-23 | 1989-12-28 | E.I. Du Pont De Nemours And Company | Catalyzed hydrofluorination of alkenes |
| CN1051349A (en) * | 1989-10-04 | 1991-05-15 | 纳幕尔杜邦公司 | The method of purification of fluorocarbon |
| CN1075709A (en) * | 1992-02-24 | 1993-09-01 | 中国科学院上海有机化学研究所 | 1,1, the preparation technology of 1-three fluoro-2-monochloroethane |
Non-Patent Citations (1)
| Title |
|---|
| 黄志明等: "氯乙烯液相氟化生产HFC 一1 5 2 a", 《中国氯碱》, no. 1, 31 January 2001 (2001-01-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299948A (en) * | 2020-12-01 | 2021-02-02 | 山东华安新材料有限公司 | Preparation method of 1, 1, 1-trifluoro-2-chloroethane |
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Application publication date: 20140115 |