811-97-2 Usage
Uses
Used in Refrigeration Industry:
1,1,1,2-Tetrafluoroethane is used as a refrigerant for fridges, freezers, and automotive air conditioning due to its stable quality and non-flammable properties.
Used in Pharmaceutical and Cosmetics Industry:
1,1,1,2-Tetrafluoroethane is used as an aerosol propellant for medicine and cosmetics, providing a safe and effective means of dispensing products.
Used in Animal Health Industry:
1,1,1,2-Tetrafluoroethane is used as an animal-used antibiotic with stable quality, high antibacterial activity in vivo, and low propensity to produce drug resistance and cross-resistance. It is mainly applied to the treatment of E. coli disease in livestock and poultry, cholera, dysentery, and chronic respiratory infections.
Used as a Blowing Agent:
1,1,2-Tetrafluoroethane is used as a blowing agent for foams, providing a stable and non-irritating alternative for foam production.
Safety Information:
Inhalation of 1,1,1,2-Tetrafluoroethane at high concentrations can be harmful and may cause heart irregularities, unconsciousness, or death without warning. Liquid contact may cause frostbite, and vapors can replace the available oxygen.
Physical and Chemical Properties
1, 1, 1, 2-Tetrafluoroethane is commonly known as R134a, HFC134a and HFC-134a. It is a kind of colorless, non-toxic and non-burning chemical. It is insoluble in water (67mg/L, 25 ℃ ) but soluble in ether with its potential value of ozone depletion being 0. Its thermodynamic property is very similar as CFC-12 while having its security being comparable to CFC-12, and thus has been recognized as the best substitute of CFC-12. Although there are some greenhouse effect for HFC-134a (HGWP = 0.28), this doesn’t affect it to become the primary-choice ODS (Ozone Depleting Substances) substitute. 1, 1, 1, 2-tetrafluoroethane (HFC-134a or HFA-134a) is a new generation of non-chlorofluorocarbon compounds as pharmaceutical excipients. It is mainly used as the propellant agent contained in the mist agent during the treatment of asthma and chronic respiratory disorders disease. Compared with the traditional CFC class pharmaceutical propellant, the advantage of HFC-134a is free of chlorine atom and thus having zero ODP (ozone depletion potential) value and GWP value (global warming potential) without depleting ozone and generating photochemical smog and is chemically inert and toxicologically safe. It is also a kind of environmental friendly pharmaceutical excipients and is also currently used as the major substitute of CFC contained in aerosol that is ozone-depleting.
Figure 1 is the chemical structure formula of tetra-fluoroethane.
Environmental friendly refrigerants
Tetrafluoroethane (R-134a) is the most widely used low or moderate-temperature refrigerant. Owing to the excellent overall performance of the tetrafluoroethane (HFC-134a), it has become a very effective and safe substitute for CFC-12 products. It is mainly applied to various areas taking advantage of R-12 (R12, Freon 12, F-12, CFC-12, Freon 12, dichlorodifluoromethane) refrigerant including: refrigerators, freezers, water dispensers, auto air conditioning, central air conditioning, dehumidifiers, cold storage, commercial refrigeration, ice machines, ice cream machine, refrigeration condensing units and other refrigeration equipment. It can also be applied to fields of aerosol propellants, medical aerosols, pesticides propellant, polymer (plastic) physical foaming agent, and protection gas of magnesium alloy.
While tetrafluoroethane refrigerant (R-134a) is the most popular choice as alternative of the feron R12 for being applied to the newly installed refrigeration equipment, owing to that R134a is different from R12 in physical and chemical properties, theoretical cycle performance as well as the applied compressor oil, for the after-sales repair of the refrigerated equipment with initial installation of R12 refrigerant refrigeration equipment repairs, if you need to add or replace the refrigerant, you have no choice but still add R12. Usually people can‘t directly apply tetrafluoroethane refrigerant (R-134a) to replace R12 (That is usually called “no cataclysmic replacement”).
Synthetic route
Synthetic route of the raw material of 1, 1, 1, 2-tetfluoroethane: it has been reported of as much as several dozens of major synthetic routes. Among them, the major synthetic route is shown as the figure. For various synthetic routes, considering comprehensively of the sources of raw materials, production processes and waste treatment and other factors, only two routes of raw materials, trichlorethylene and tetrachlorethylene have practical value of industrial production. In the actual industrial production, trichlorethylene raw material routes, due to its simple reaction step and small amounts of by-products, is preferentially recommended.
Trichlorethylene route, the main production process are liquid, gas and gas-liquid method. Take trichlorethylene (TCE) and hydrogen fluoride (HF) as raw materials, upon the action of catalyst, perform addition and substitution reaction in the first step to generate 1,1,1-trifluoro-2-chloroethane (HCFC-133a ); then, at higher temperatures, perform the second step to generate 1,1,1,2-tetrafluoroethane (HFC-134a). The reaction equation is as follows:
The advantage of liquid Freon is following the traditional production methods with simple production process and relatively mature technology. In 1982, DuPont ha applied liquid fluorination for the manufacturing of HFC-134a. However, at high temperature, due to the emergent corrosion of the equipment and the difficulty in conducting continuous production, this method is still in the stage of small-range laboratory test. Shanghai Institute of Organic Chemistry Research has applied Cl (CF2CF2) 4OCF2SO2F (perfluoroalkoxy sulfonyl fluoride) as a catalyst and have reaction in the KF solution at the pressure of 230e and 12.5MPa for 2h to give HC-134a with the yield being 88%. The reaction equation is: CF3CH2Cl + KF---CF3CH2F + KCl, compared with the DuPont method, the CAS Shanghai Institute of Organic Chemistry had achieved lower reaction temperature so that corrosion and byproducts have been effectively controlled, making it possible to conduct the continuous production. However, it is still difficult to achieve industrial production using this method in short term.
The above information is edited by the lookchem of Dai Xiongfeng.
Gas - liquid phase and gas-phase synthesis of tetra-fluoroethane
The advantage of gas-Liquid method is that at the first-step reaction, it can almost take advantage of all the equipment and technology, liquid-phase washing, alkaline washing and drying processes for the original production of Freon products. This can effectively reduce the energy consumption. This process, for the old plant of the original production of CFCs, it is a doable route. However, the second step is equilibrium reaction with low gas one-way conversion rate and short duration life of the catalyst and other shortcomings. Therefore, this step restricts the vapor-liquid phase process for being applied to process route for large-scale production.
Gas phase method applies trichlorethylene (TCE) and anhydrous hydrogen fluoride (HF) for reaction in the action of a chromium-containing catalyst. The first step of addition and substitution reactions generates HCFC-133a, and then it is further reacted with HF in the presence of chromium-based catalyst to generate the finished product, tetrafluoroethane (HFC-134a) at a temperature of 350~380 ℃. The second-stage reaction of gas-phase method is relative difficult with the conversion rate being generally only about 20%. Therefore, in the industrial production, people mostly adopts continuous cycle method to have the large amount of raw materials be recycled to reduce the toxic and hazardous intermediate products as well as improve the overall yield.
Gas-phase method has a lot of advantages including easily controllable reaction process, small amount of waste pollution and easily being applied for large-scale continuous production. Currently gas-phase method has gradually replaced liquid-phase method and gas phase-liquid phase method to become the mainstream of the world's production of tetrafluoroethane (HFC-134a).
Precautions for manipulation
Technical measures: it should be manipulated in a well-ventilated place. Upon high pressure condition, make sure that the internal pressure of the reaction apparatus does not exceed the cylinder pressure. For safety purpose, the gas flow path should be installed with a check valve. Do not remove the check valve before running out of the content. Wear protective equipment when handling. Wash hands and face thoroughly after handling.
Handling Precautions: Avoid contact with skin, eyes and clothing.
Storage conditions: Avoid the sunshine. Store it in a well-ventilated place. Do not expose it to environment above 40 ℃. Locked up the place where it is stored. Store it away from incompatible materials such as oxidants.
Production Methods
Tetrafluoroethane can be prepared by several different routes;
however, the following routes of preparation illustrate the methods
used:
Isomerization/hydrofluorination of 1,1,2-trichloro-1,2,2-trifluoroethane
(CFC-113) to 1,1-dichloro-1,2,2,2-tetrafluoroethane
(CFC-114a), followed by hydrodechlorination of the latter.
Hydrofluorination of trichloroethylene, via 1-chloro-1,1,1-
trifluoroethane (HCFC-133a).
Air & Water Reactions
Insoluble in water.
Reactivity Profile
1,1,1,2-Tetrafluoroethane is chemically inert in many situations, but can react violently with strong reducing agents such as the very active metals and the active metals. Can react with strong oxidizing agents or weaker oxidizing agents under extremes of temperature.
Flammability and Explosibility
Nonflammable
Pharmaceutical Applications
Tetrafluoroethane is a hydrofluorocarbon (HFC) or hydrofluoroalkane
(HFA) aerosol propellant (contains hydrogen, fluorine, and
carbon) as contrasted to a CFC (chlorine, fluorine, and carbon). The
lack of chlorine in the molecule and the presence of hydrogen reduce
the ozone depletion activity to practically zero. Hence tetrafluoroethane
is an alternative to CFCs in the formulation of metereddose
inhalers (MDIs). It has replaced CFC-12 as a refrigerant
and propellant since it has essentially the same vapor pressure. Its
very low Kauri-butanol value and solubility parameter indicate that
it is not a good solvent for the commonly used surfactants for MDIs.
Sorbitan trioleate, sorbitan sesquioleate, oleic acid, and soya
lecithin show limited solubility in tetrafluoroethane and the amount
of surfactant that actually dissolves may not be sufficient to keep a
drug readily dispersed. Up to 10% ethanol may be used to increase
its solubility.
When tetrafluoroethane (P-134a) is used for pharmaceutical
aerosols and MDIs, the pharmaceutical grade must be specified.
Industrial grades may not be satisfactory due to their impurity
profiles.
Safety
Tetrafluoroethane is used as a refrigerant and as a non-CFC
propellant in various aerosols including topical pharmaceuticals
and MDIs. Tetrafluoroethane is regarded as nontoxic and
nonirritating when used as directed. No acute or chronic hazard
is present when exposures to the vapor are below the acceptable
exposure limit (AEL) of 1000 ppm, 8-hour and 12-hour time
weighed average (TWA). In this regard it has the same value as
the threshold limit value (TLV) for CFC-12. Inhaling a high
concentration of tetrafluoroethane vapors can be harmful and is
similar to inhaling vapors of CFC-12. Intentional inhalation of
vapors of tetrafluoroethane can be dangerous and may cause death.
The same labeling required on CFC aerosols would be required for
those containing tetrafluoroethane as a propellant (except for the
EPA requirement).
Carcinogenicity
The results from three lifetime
inhalation carcinogenesis studies with HFC 134a have been
published. The first one involved exposure of groups of
80 male and 80 female rats to levels of ≤50,000 ppm 6 h/
day, 5 days/week for 2 years.An increase inLeydig cell tumors
was seen in themale rats at 50,000 ppm(30%) compared to the
air-exposed controls (12%). Likewise, therewas an increase in
Leydig cell hyperplasia. No effects were seen at 10,000 ppm
(370). The second study with rats involved snout-only inhalation
exposures to levels of ≤50,000 ppm 1 h/day, 7 days/week
for 108 weeks. The same investigators conducted a lifetime
study withmice. In this study, groups of mice were exposed to
snout-only levels of ≤75,000 ppm 1 h/day, 7 days/week for
104 weeks. No adverse effects were seen in either rats or
mice. Since the total dose received by the rats in the high
exposure level of this study was lower than in the Collins’
study, this report supports the observation that 10,000 ppm,
6 h/day, 5 days/week for 2 years was a NOEL.
Rats were given 300 mg of HFC 134a in corn oil 5 days/
week for 52 weeks and held for a total of 125 weeks.
There was no evidence for carcinogenicity.
storage
Tetrafluoroethane is a nonreactive and stable material. The liquified
gas is stable when used as a propellant and should be stored in a
metal cylinder in a cool dry place.
Incompatibilities
The major incompatibility of tetrafluoroethane is its lack of
miscibility with water. Since it has a very low Kauri-butanol value,
tetrafluoroethane is considered to be a very poor solvent for most
drugs used in MDI formulations. It also shows a low solubility for
some of the commonly used MDI surfactants.
Regulatory Status
Included in the FDA Inactive Ingredients Database (aerosol
formulations for inhalation and nasal applications). Included in
nonparenteral medicines licensed in the UK.
Check Digit Verification of cas no
The CAS Registry Mumber 811-97-2 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 8,1 and 1 respectively; the second part has 2 digits, 9 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 811-97:
(5*8)+(4*1)+(3*1)+(2*9)+(1*7)=72
72 % 10 = 2
So 811-97-2 is a valid CAS Registry Number.
InChI:InChI=1/C2H2F4/c3-1-2(4,5)6/h1H2
811-97-2Relevant articles and documents
MICROWAVE SPECTRUM, BARRIER TO INTERNAL ROTATION, STRUCTURE, AND DIPOLE MOMENT OF 1,1,1,2-TETRAFLUOROETHANE
Ogata, Teruhiko,Miki, Yasuhiro
, p. 49 - 56 (1986)
The microwave spectrum of CF3CH2F has been studied in the 8 to 26 GHz region, with b-type, Q- and R-branch transitions being assigned for the ground vibrational state and first excited torsional state.Relative intensity measurements give a torsional frequency of 108 +/- 18 cm-1, which lead to a barrier to internal rotation V3 = 3.3 +/- 0.8 kcal mol-1.The dipole moments determined from the observed first-second order Stark effect are μa = 0.411 +/- 0.009 D, μb = 1.75 +/- 0.22 D, and μtotal = 1.80 +/- 0.22 D.Observed moments of intertia suggest that the CF3 group is not symmetrical or its axis and the C-C bond are not collinear.The distance rF'...F' is obtained 2.1594 +/- 0.0006 Angstroem, where F' refers to the outer plane fluorine atoms in the CF3 group.
Electroreduction of a Chlorofluoroethane on a Solid Polymer Electrolyte Composite Electrode
Inaba, Minoru,Sawai, Ken,Ogumi, Zempachi,Takehara, Zen-ichiro
, p. 471 - 472 (1995)
The dechlorination of 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124) was carried out electrochemically on a solid polymer electrolyte composite electrode (Pd-Neosepta).As the sole product 1,1,1,2-tetrafluoroethane (HFC-134a) was obtained.Irradiation with light of a xenon arc lamp enhanced the dissociation of C-Cl bond of the reactant adsorbed on Pd, resulting in an increase in the rate for HFC-134a formation.
Effect of acid strength of co-precipitated chromia/alumina catalyst on the conversion and selectivity in the fluorination of 2-chloro-1,1,1-trifluoroethane to 1,1,1,2-tetrafluoroethane
Madhusudana Rao, Jampani,Shanthan Rao,Vijayakumar,Venkata Rao,Narsaiah,Narayan Reddy,Leela Krishna,Srinivas,Radhakrishnan,Patil
, p. 177 - 180 (1999)
Different fluorinated catalysts based on co-precipitated Cr2O3/Al2O3 and doped with compounds of Zn and/or Mg are prepared and their total acidity determined by TPD of ammonia. The influence of acidity of the above catalysts on the conversion and selectivity in the fluorination of HCFC-133a to give HFC-134a was studied. It was found that the selectivity for HFC-134a increases with a fall in the relative percentage of strong acid centres.
Effect of calcination temperature on CrOx-Y2O3 catalysts for fluorination of 2-chloro-1,1,1-trifluoroethane to 1,1,1,2-tetrafluoroethane
He, Jun,Xie, Guan-Qun,Lu, Ji-Qing,Qian, Lin,Zhang, Xue-Liang,Fang, Ping,Pu, Zhi-Ying,Luo, Meng-Fei
, p. 1 - 10 (2008)
A series of CrOx-Y2O3 catalysts were prepared by a deposition-precipitation method and tested for the fluorination of 2-chloro-1,1,1-trifluoroethane (CF3CH2Cl) to synthesize 1,1,1,2-tetrafluoroethane (CF3CH2F). The highest activity was obtained on a pre-fluorinated catalyst calcined at 400 °C, with 19% of CF3CH2Cl conversion at 320 °C. The effect of the calcination temperature on the CrOx species was investigated. X-ray diffraction and Raman results indicated that the CrOx species (Cr(VI)) were well dispersed on the catalyst surface when the catalyst was calcined at 400 °C. With increasing calcination temperature, most of the CrOx species changed from high oxidation state Cr(VI) to low oxidation state Cr(V) or Cr(III) species, which resulted in difficulty in pre-fluorination of the catalyst. It was also found that the CrFx, CrOxFy or Cr(OH)xFy phases originated from high oxidation state Cr(VI) species were the active sites for the fluorination reaction.
Efficient regioselective labelling of the CFC alternative 1,1,1,2-tetrafluoroethane (HFC-134a) with fluorine-18
Aigbirhio, Franklin I.,Pike, Victor W.,Waters, Stephen L.,Tanner, Richard J. N.
, p. 279 - 288 (1995)
Efficient chemistry is described for the regioselective labelling of the CFC alternative 1,1,1,2-tetrafluoroethane with cyclotron-produced positron-emitting fluorine-18 (t1/2 = 109.7 min). 1,1,1,2-Tetrafluoroethane was prepared by nucleophilic addition of no-carrier-added fluoride to trifluoroethylene and 1,1,1,2-tetrafluoroethane by nucleophilic displacement of tosylate with fluoride in 2,2,2-trifluoroethyl p-toluenesulphonate.Each reaction was mediated by a potassium cation-Kryptofix 2.2.2 complex, with or without acetonitrile as solvent, in a sealed glassy carbon vessel.The selectivities were 97.2 +/- 0.4percent for labelling in the 1-position by nucleophilic addition and 91.2 +/- 1.2percent for labelling in the 2-position by nucleophilic substitution.GC separation afforded each labelled tetrafluoroethane in high radiochemical purity (>99.995percent) and high chemical purity (>99.6percent).Specific radioactivities of about 37 MBq (1 mCi) per μmol were obtained.Each synthesis was fully automated to cope safely with the high initial radioactivity and delivered purified product within one physical half-life of the fluorine-18.The products are suitable for pharmacokinetic studies in man. - Keywords: Regioselective labelling; 1,1,1,2-Tetrafluoroethane; Fluorine-18; Nucleophilic addition; Nucleophilic substitution; Mass spectrometry
METHOD OF PRODUCING HALIDE
-
Paragraph 0054; 0058, (2021/01/09)
PROBLEM TO BE SOLVED: To provide a novel method of producing a halide. SOLUTION: A method of producing a halide comprises reacting a halogen with a compound of general formula (1) in the figure, where X and Y each independently represent H, F or CF3. The halide is an unsaturated halide or a saturated halide. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
CATALYST AND PROCESS USING THE CATALYST FOR MANUFACTURING FLUORINATED HYDROCARBONS
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Page/Page column 10; 11; 12; 17, (2018/03/28)
A catalyst comprising one or more metal oxides, wherein the catalyst has a total pore volume equal to or greater than 0.3 cm3/g and a mean pore diameter greater than or equal to 90 ?, where in the pore volume is measured using N2 adsorption porosimetry and the mean pore diameter is measured using N2 BET adsorption porosimetry.
CATALYST AND PROCESS USING THE CATALYST FOR MANUFACTURING FLUORINATED HYDROCARBONS
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Page/Page column 11-13, (2018/03/28)
A catalyst comprising chromia and at least one additional metal or compound thereof and wherein the catalyst has a total pore volume of greater than 0.3 cm3/g and the mean pore diameter is greater than or equal to 90 ?, wherein the total pore volume is measured by N2 adsorption porosimetry and the mean pore diameter is measured by N2 BET adsorption porosimetry, and wherein the at least one additional metal is selected from Li, Na, K, Ca, Mg, Cs, Sc, Al, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, In, Pt, Cu, Ag, Au, Zn, La, Ce and mixtures thereof.
Device and method for preparing 1,1,1,2-tetrafluoroethane
-
Paragraph 0023-0024, (2017/06/20)
The invention discloses a device for preparing 1,1,1,2-tetrafluoroethane. The device comprises a preheater, a vertically-installed tubular reactor, a vertically-installed molten salt furnace, a buffer tank, a water scrubber, an alkaline tower, a drying tower and a rectifying tower; the preheater, the tubular reactor, the buffer tank, the water scrubber, the alkaline tower, the drying tower and the rectifying tower are sequentially connected, the tubular reactor comprises a reactor body, an upper sealing end and a lower sealing end, the upper sealing end and the lower sealing end are arranged at the two ends of the reactor body, and the reactor body penetrates the molten salt furnace. The invention further discloses a method for preparing the 1,1,1,2-tetrafluoroethane with the device. The device has the beneficial effects of being simple in structure, stable in operation, efficient, economical and long in running period.
Method for preparing fluorinated compound CH2F-R (R is H or CF3) through difluoromethane pyrolysis
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Paragraph 0034-0037, (2017/05/18)
The invention discloses a method for preparing a fluorinated compound CH2F-R (R is H or CF3) through difluoromethane pyrolysis. According the method, the fluorinated compound is obtained through a gas-phase reaction between difluoromethane and CH4, NH3, H2O or H under the circumstance that no catalyst exists. The following reaction conditions of the method are achieved: the reaction pressure is 0.1-1.5 MPa; the reaction temperature is 700-1000 DEG C; the mole ratio of difluoromethane to any one or more of CH4, NH3, H2O and H is 1:(0-40); and the residence time is 0.1-50 s. The method disclosed by the invention has the advantages that the raw material, namely difluoromethane, is easy to obtain; no catalyst needs to use; the operation and the control are easy; and the experimental repeatability is high.
