New chlorotrifluoroethylene telomers and process for preparing them.

The present invention relates to new telomers of chlorotri­fluoroethylene. Particularly, it relates to new telomers pre­pared by reaction of chlorotrifluoroethylene with perhalo­fluoroxy compounds.

Chlorotrifluoroethylene telomers are utilized in particular as hydraulic fluids. In general, they are prepared by reacting chlorotrifluoroethylene with chlorinated telogens, such as e.g. CCl₄ and SO₂Cl₂. The telomers so obtained contain poly­chlorinated end groups, for example -CFCl₂ and -CCl₃ which, in appliances where high temperatures or oxidizing media are used, can be hydrolysed or oxidized and result in corrosive acid groups.

Due to the above drawbacks, the telomers so obtained require a stabilizing fluorination treatment for the conversion of the polychlorinated end groups to groups having a higher fluo­rine content. This treatment is complex and expensive.

US-A- 4,577,044 describes a new type of chlorotrifluoro­ethylene telomers obtained by reaction of CF₂CFCl with CF₃OF. The following telomeric species were obtained: F(CF₂-CFCl)_nF, CF₃O-(CF₂CFCl)_n-F and CF₃O-(CF₂CFCl)_n-OCF₃, in which n usually ranges from 1 to 10 and telomeric units (CF₂-CFCl) are random­ly distributed: i.e. they can be linked to one another both in head-to-head and head-to-tail fashion.

Since said telomers have a low degree of telomerization, it is assumed that the nature of the end groups and the type of bond (namely oxygen-carbon or carbon-carbon) by which these groups are bound to the monomeric units, may exert a consider­able influence on the physical and chemical properties of the telomers, due, in particular, to different binding forces, dif­ferent sizes of the groups and differences in the steric en­vironment of said groups and in the flexibility of the type of bond (oxygen-carbon or carbon-carbon).

Consequently, the telomers of chlorotrifluoroethylene with CF₃OF cannot exhibit a large variety of properties as they possess only the CF₃O- and F- end groups. On the other hand, it is well known that an optimum property for a particular application of the chlorotrifluoroethylene telomers may be a handicap for another application.

Thus, it is an object of the present invention to provide a process for the production of chlorotrifluoroethylene telomers with inert end groups both of the perhaloalkyl type (which consequently bind to the monomeric units by means of a carbon-­carbon bond) and of the perhaloalkoxy type, i.e. of the ether type (which bind to the monomeric units by means of an oxygen-­carbon bond).

Another object is that of providing a process which allows to vary, over a wide range, both distribution and nature of the end groups which are present in the telomers.

A further object is that of providing a process which allows to vary, over a wide range, the F/Cl ratio in the telomers. This embodiment has two important aspects. On the one hand, a higher F/Cl ratio, achieved by means of ether and non-ether perfluorinated end groups, leads to a modification of the phy­sical and chemical properties of the telomers, which makes it possible, for example, to obtain lower pour point tempe­ratures, lower heat of combustion values, a lower surface ten­sion and a different variation of the viscosity as a function of temperature. On the other hand, for certain uses, a low F/Cl ratio, achieved through end groups containing Cl and F atoms, of the ether and non-ether type, results in special properties such as, for example, a decrease in the compressi­bility.

A still further object of the present invention is to provide a process which allows, within certain limits, to control the telomerization reaction so as to obtain telomeric species ha­ ving a low telomerization degree or, on the contrary, a higher telomerization degree.

It is therefore apparent that the present invention provides a very flexible process capable of yielding a very broad range of products, with different physical and chemical characteri­stics, which makes it possible to meet various applicative requirements.

These and still other objects are achieved by the process of the present invention for preparing chlorotrifluoroethylene telomers. This process is characterized in that chlorotrifluo­roethylene is reacted, at a temperature ranging from -100 to +40°C, with a perhalofluoroxy compound of formula R_x-CF₂OF, wherein R_x is a perhalogenated alkyl radical, a perhaloalkyl­monoether radical or a perhaloalkylpolyether radical, either linear or branched, having from 1 to 10 carbon atoms and con­taining fluorine atoms or fluorine and chlorine atoms, but being free of vicinal chlorine atoms and -CCl₃ groups.

It is assumed that the reaction mechanism involves in part the homolytic rupture of the O-F bond of the fluoroxy compound according to the equation: R_x-CF₂-OF → R_x-CF₂-O^.+F^. wherefore radicals R_x-CF₂-O^. and F^. can act as telomerization starters and terminators. It is likewise assumed that the above radicals can also undergo further fragmentation and re­arrangement reactions with formation of other radicals which, in turn, can act as telomerization starters and terminators. In the case of radicals R_x containing Cl atoms, it is further­more supposed that one or more chlorine atoms can be substi­tuted by fluorine atoms.

When starting from a perfluorofluoroxy compound, R¹ radicals derived from R_x form, in which R_x having at least two carbon atoms has lost one or more carbon atoms and/or R_x having at least three carbon atoms has undergone a re-arrangement. More frequently, radical R¹ is a radical R² which contains a lower number of carbon atoms with respect to R_x. Thus, when R_x con­tains from 2 to 10 carbon atoms, R² contains from 1 to 9 car­bon atoms. Starting from a perhalofluoroxy compound which con­tains chlorine, radicals R³ derived from R_x are formed, in which R_x having at least two carbon atoms has lost one or more carbon atoms and/or R_x having at least 3 carbon atoms has un­dergone a re-arrangement and one or more chlorine atoms of R_x have been substituted by fluorine atoms.

More commonly, radical R³ is a radical R⁴ which contains a lower number of carbon atoms with respect to R_x (i.e. when R_x contains from 2 to 10 carbon atoms, R⁴ contains from 1 to 9 carbon atoms) and in which one or more chlorine atoms have been substituted by fluorine atoms.

It has been found that the telomerization product consists of a mixture of telomers having different end groups.

When starting from a perfluorofluoroxy compound, the telomers obtained are the following (in each telomer, the monomeric unit CF₂-CFCl is schematically represented by the letter M): R_x-CF₂-O-(M)_n-F      (A) wherein R_x has the meaning defined above and "n" ranges from 2 to 20. R_x-CF₂-O-(M)_n-O-CF₂-R_x      (B) R_x-(M)_n-F      (C) R_x-(M)_n-R_x      (D) R_x-CF₂-O-(M)_n-R_x      (E) R_x-O-(M)_n-F      (F) R_x-O-(M)_n-O-CF₂-R_x      (G) R_x-O-(M)_n-R_x      (H) R_x-CF₂-(M)_n-F      (I) R_x-CF₂-(M)_n-O-CF₂-R_x      (J) R_x-CF₂-(M)_n-R_x      (K) R¹-O-(M)_n-OCF₂-R_x      (L) wherein R¹ is a radical derived from R_x, in which R_x having at least two carbon atoms has lost one or more carbon atoms and/or R_x having at least three carbon atoms has undergone a re-arrangement. R¹-O-(M)_n-R_x      (N) R¹-(M)_n-F      (O) CF₃-O-(M)_n-F      (P) F-(M)_n-F      (Q).

The telomers from (A) to (E) and from (G) to (O) are new com­pounds. The telomers (F) are new when R_x is different from -CF₃.

When starting from a perhalofluoroxy compound which contains chlorine, the telomers obtained are the following (in each of the telomers, the monomeric unit CF₂-CFCl is schematically represented by M: (A), (B), (C), (D), (E), (P) and (Q), indicated above R³-O-(M)_n-OCF₂-R_x      (R) wherein R_x and n have the meaning defined above while R³ is a radical derived from R_x, in which R_x having at least two carbon atoms has lost one or more carbon atoms and/or R_x ha­ving at least three carbon atoms has undergone a re-arrange­ment and one or more chlorine atoms of R_x have been substitu­ted by fluorine atoms R³-O-(M)_m-R_x      (S) R³-CF₂-O-(M)_n-F      (T) R³-CF₂-O-(M)_n-O-CF₂-R_x      (U) R³-CF₂-O-(M)_n-R_x      (V)

Telomers (R), (S), (T), (U) and (V) are new products. In the telomer chain (M)_n the monomeric units CF₂-CFCl are bonded to each other at random, i.e. they follow one another both in a head-to-head and a head-to-tail fashion.

It has to be borne in mind that in the indicated telomer for­mulae (M) can be either (CF₂-CFCl) or (CFCl-CF₂). So, with telomers R_x-CF₂-O-(M)_n-F (A) there are two corresponding se­ries of products represented by the formulae: 1) R_x-CF₂-O-(CF₂-CFCl)_n-F      (A₁) in which the end group R_x-CF₂-O- is bound to the group CF₂, while the end group F is bound to the group CFCl, independent­ly of the linkage of the intermediate monomeric units when n is higher than 2. 2) R_x-CF₂-O-(CFCl-CF₂)_n-F      (A2) in which the end group R_x-CF₂-O- is bound to the group CFCl, while the end group F is bound to the group CF₂, independently of the linkage of the intermediate monomeric units when n is higher than 2.

In the telomer mixtures obtained from perfluorofluoroxy com­pounds or from perhalofluoroxy compounds containing chlorine, small amounts of telomers having a formula different from those indicated above can be present.

Examples of R_x are perhalogenated methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. Said groups may have e.g. one or two interspersed O atoms, such as e.g. methoxy­ethyl, ethoxyethyl, ethoxyethoxyethyl etc.

When R_x is a perhaloalkylpolyether radical, it preferably con­tains two oxygen atoms. Preferably, the radical R_x contains from 1 to 5 carbon atoms.

As already mentioned herein, when R_x contains chlorine, it is free of vicinal chlorine atoms and -CCl₃ groups; further­more it is preferably free of -CCl₂- groups. In the preferred products, n generally ranges from 2 to 10.

The telomer mixtures prepared by the process of the present invention are useful in particular as hydraulic fluids and as service fluids (operating fluids).

To carry out the reaction, a gaseous or liquid flow of per­halofluoroxy compound is generally fed to a reactor containing chlorotrifluoroethylene in the liquid state or dissolved in a solvent. When operating under pressure, the reaction can be conducted at a temperature which is higher than the chlo­rotrifluoroethylene boiling point (-27.9°C). If the reaction is carried out in solution, a solvent for chlorotrifluoroethy­lene is used which is inert under the reaction conditions, in particular a chlorofluorohydrocarbon, such as for example 1,2-dichlorotetrafluoroethane, fluorotrichloromethane and di­chlorodifluoromethane; usually, the chlorotrifluoroethylene content in the solution ranges from 20 to 80% by weight.

Generally, the fluoroxy compound is fed to the reactor as a gas stream. Preferably, the gaseous fluoroxy compound is dilu­ted with a gas which is inert under the reaction conditions. Examples of inert diluting gases are nitrogen, argon, helium and a gaseous chlorofluorohydrocarbon selected, for example, from 1,2-dichlorotetrafluoroethane and dichlorodifluorome­thane. Usually, the fluoroxy compound concentration in the gaseous mixture ranges from 5 to 80% by volume.

If the fluoroxy compound is fed to the reactor in the liquid state, it is subjected to mixing with a liquid which is inert under the reaction conditions, in particular a chlorofluoro­hydrocarbon, for example 1,2-dichlorotetrafluoroethane, fluo­rotrichloromethane and dichlorodifluoromethane, or it is car­ried, in the form of an aerosol, by a gas which is inert under the reaction conditions, for example nitrogen, argon or he­lium.

It is also possible to feed to the reactor containing a sol­vent for chlorotrifluoroethylene a gaseous or liquid fluoroxy compound flow, according to one of the feeding methods indi­cated herein-before, and, separately, a gaseous or liquid chlorotrifluoroethylene flow: in this case, chlorotrifluoro­ethylene is preferably fed in the liquid state.

The temperature at which the reaction is conducted ranges from -100 to +40°C. For each fluoroxy compound it is necessary to work at a temperature which is at least equal to the threshold temperature of its reaction with chlorotrifluoroethylene, this temperature varying from telogen to telogen. Furthermore, as will be explained below, the variation of the temperature makes it possible to vary, over a wide range, both distribu­tion and nature of the end groups which are present in the telomers, and to adjust, to a certain extent, the telomeriza­tion degree. Preferably, the temperature ranges from -30 to -80°C.

By means of the process of the present invention it is pos­sible to control the reaction in such way as to obtain pre­vailingly the telomers of formula: R_x-CF₂-O-(M)_n-F      (A) R_x-CF₂-O-(M)_n-O-CF₂-R_x      (B) and F-(M)_n-F      (Q).

The result can be achieved by employing conditions which re­duce the amount of heat generated in the reaction medium and promote an effective dispersion thereof.

If the telomerization is effected by adduction of a telogen gaseous flow to the chlorotrifluoroethylene, either as a li­quid or in solution, this result is obtained by following one or more or all of the following procedures: <ul id="ul0001" list-style="none"><li>1) according to the first procedure, the reaction is conducted in a lower temperature range, provided the temperature is still higher than the threshold temperature of the reaction;</li><li>2) another procedure consists in the precooling of the telogen before it is fed to the reactor. In this case, the telogen is employed in the gaseous or in the liquid state: if it is introduced in the liquid state, the feeding is carried out according to the previously described procedure;</li><li>3) a further procedure consists in decreasing the telogen flow rate or in increasing its dilution in the inert gas.</li></ul>

Effective stirring in the reactor also helps to obtain the desired result. Obviously, the lower the temperature of the reaction medium and the more effective the stirring and the lower the precoo­ling temperature of the telogen, the higher is the telogen flow rate which can be used.

By operating according to the above procedures and starting from CF₃CF₂OF it is possible to obtain said telomers (A), (B) and (Q) in amounts which can reach or exceed 90% by weight of the total weight of the reaction products.

Conversely, if higher temperatures of the reaction medium and/­or higher telogen flow rates and a less effective stirring are employed, telomers different from (A) and (B) will predo­minantly be obtained. More precisely, in the case of perfluo­rinated telogens, for example, the following telomers are pre­dominantly obtained: R_x-(M)_n-F      (C) R_x-(M)_n-R_x      (D) R_x-CF₂-O-(M)_n-R_x      (E) R_xO-(M)_n-F      (F) R_x-CF₂-(M)_n-F      (I) F-(M)_n-F      (Q).

In the case of chlorine-containing telogens there are prevai­lingly obtained, for example, the following telomers. R_x-(M)_n-F      (C) R_x-(M)_n-R_x      (D) R_x-CF₂-O-(M)_n-R_x      (E) F-(M)_n-F      (Q) R³-O-(M)_n-R_x      (S)

When working according to the last mentioned procedures and starting from CClF₂-CF₂OF, the above telomers are obtained in amounts which can reach or exceed 90% by weight of the to­tal weight of the reaction products.

According to another embodiment of the process of the present invention, using conditions which make it possible to direct the telomerization reaction prevailingly to the desired te­lomeric species, it is also possible, by reducing the amount of heat evolved in the reaction medium and by promoting an effective dispersion thereof, to direct, within certain limits, the telomerization degree towards low values. This is achieved with low telogen flow rates and with a low temperature of the rection medium and, optionally, by pre-cooling the telogen. Another measure which helps to obtain this result consists in carrying out an effective stirring in the reactor. It is possible to obtain, e.g., up to 80% or more of telomers having a value of "n" ranging from 3 to 6.

By operating under inverse conditions, i.e. with higher telo­gen flow rates and/or with a higher temperature of the reac­tion medium and, optionally, with a less intense stirring, the production of telomers having higher values of "n" is pro­moted.

For each telogen it is possible, therefore, to control the reaction towards the predominant production of telomers con­taining particular end groups, and to obtain, to a certain extent, a more or less low or a more or less high telomeri­zation degree. It is therefore evident that the process of the present invention allows to obtain a large variety of pro­ducts capable of meeting various applicative requirements.

Among the fluoroxy compounds utilizable in the process of the present invention, the following can be cited: fluoroxy pentafluoroethane 1-fluoroxy heptafluoropropane 1-fluoroxy nonafluorobutane 1-fluoroxy 2-chlorotetrafluoroethane 1-fluoroxy 2,2′-dichlorotrifluoroethane fluoroxy heptafluoroisopropane fluoroxy nonafluoroisobutane fluoroxy nonafluoro-ter.butane 1-fluoroxy-2-perfluoro n.propoxy-hexafluoropropane 1-fluoroxy-2-perfluoromethoxy-hexafluoropropane 1-fluoroxy-2-perfluoroethoxy-hexafluoropropane and 1-fluoroxy-3-chlorohexafluoro n.propane.

When CF₃CF₂OF is used as a telogen, the resulting telogen mixture is almost exclusively composed of the follow­ing species: F(M)_nF      (Ia) F(M)_nOCF₂CF₃      (IIa) CF₃CF₂O(M)_n-OCF₂CF₃      (IIIa) CF₃(M)_n-F      (IVa) CF₃(M)_n-OCF₂CF₃      (Va) CF₃O(M)_n-OCF₂CF₃      (VIa) CF₃CF₂-(M)_n-F      (VIIa) CF₃CF₂(M)_n-OCF₂CF₃      (VIIIa) CF₃O(M)_nF      (IXa) CF₃-(M)_n-CF₃      (Xa)

With exception of species Ia and IXa, all the above telomers are new products.

By reducing the amount of heat evolved in the reaction medium and by promoting its effective dispersion, according to the procedures specified hereinbefore, species Ia, IIa and IIIa may constitute more than 85% of the obtained telomer mixture.

Conversely, by increasing the amount of heat evolved in the reaction medium, according to the procedures indicated herein­before, species Ia and IVa through IXa may constitute more than 90% of the obtained mixture.

When CF₃-CF₂-CF₂OF is used as the telogen, the obtained telo­mer mixture is almost exclusively composed of the following species: F(M)_nF      (Ia) F(M)_n-OCF₂CF₂CF₃      (IIb) F(M)_n-CF₂CF₃      (IIIb) CF₃CF₂CF₂-O(M)_n-OCF₂CF₂CF₃      (IVb) CF₃CF₂CF₂O-(M)_n-CF₂CF₃      (Vb) CF₃CF₂-(M)_n-CF₂CF₃      (VIb) CF₃CF₂CF₂O(M)_n-OCF₂CF₃      (VIIb) CF₃CF₂CF₂O(M)_n-OCF₃      (VIIIb) CF₃CF₂CF₂O(M)_n-CF₂CF₂CF₃      (IXb) CF₃CF₂CF₂(M)_n-F      (Xb) CF₃CF₂CF₂(M)_n-CF₂CF₃      (XIb) CF₃CF₂(M)_n-OCF₃      (XIIb) CF₃CF₂O(M)_n-F      (IIa) CF₃O(M)_n-F      (IXa) CF₃CF₂(M)_n-OCF₂CF₃      (VIIIa) Except for species Ia and IXa, all the telomers obtained are new products.

By reducing the amount of heat evolved in the reaction medium and by promoting an effective dispersion thereof according to the previously indicated procedures, species Ia and IIb through VIb may constitute more than 90% of the obtained telo­mer mixture.

When ClCF₂-CF₂OF is used as the telogen, the obtained telomer mixture is almost exclusively composed of the following spe­cies. F(M)_nF      (Ia) F(M)_n-OCF₂CF₂Cl      (IIc) ClCF₂-CF₂O-(M)_n-OCF₂CF₂Cl      (IIIc) ClCF₂-CF₂O-(M)_n-CF₂Cl      (IVc) F(M)_n-CF₂Cl      (Vc) CF₂Cl(M)_n-CF₂Cl      (VIc) ClCF₂CF₂O-(M)_n-OCF₃      (VIIc) ClCF₂CF₂O(M)_n-OCF₂CF₃      (VIIIc) CF₃CF₂O(M)_nCF₂Cl      (IXc) CF₃O(M)_n-CF₂Cl      (Xc) CF₃CF₂O(M)_nF      (IIa) CF₃O(M)_n-F      (IXa) With the exception of species Ia and IXa, all the telomers obtained are new products. When reducing the amount of heat evolved in the reaction me­dium and promoting an effective dispersion thereof, according to the procedures indicated hereinbefore, species Ia and IIc through VIc may constitute more than 90% of the obtained telo­mer mixture.

The main advantages of the present invention can be summarized as follows: <ul id="ul0002" list-style="none"><li>1) inert end groups are obtained which impart high chemical and thermal stability to the telomers;</li><li>2) it is possible to vary, over a wide range, both distribu­tion and nature of the end groups which are present in the obtained telomeric species and, to a certain extent, the telomerization degree, thus resulting in large variety of products having different physical and chemical properties, which are suited to meet various different applicative re­quirements;</li><li>3) it is possible to vary, over a wide range, the F/Cl ratio of the telomers obtained. Thus, it is possible to obtain products having a high F/Cl ratio and endowed with particu­lar physical and chemical properties. Furthermore, it is possible to obtain telomers with a lower F/Cl ratio which can impart particular properties to the products such as, for example, a low compressibility.</li></ul>

The following examples are given merely to illustrate the present invention and are not to be construed as a limi­tation thereof.

Example 1

A flow of 1.0 Nl/h of fluoroxypentafluoroethane and 3.0 Nl/h of N₂ was continuously bubbled through 450 g of liquid chlorotrifluoroethylene, cooled to -55°C, in a 1-liter glass reactor equipped with a reflux condenser, a thermo­meter and a mechanical stirrer. After 4 hours and 30 minutes the reaction was stopped and the unreacted CTFE (chlorotrifluoroethylene) was distilled off. There were obtained 71 g of product; by gas-chromatographic analysis, the composition was evaluated in terms of "n" values, whereafter it was possible to calculate a yield of about 50%, based on CF₃-CF₂OF, corresponding to about 15.8 g of telomers per liter of gaseous telogen. The product was subjected to further analysis via gas-mass spectroscopy by means of a capillary column SE-52. Moreover, ¹⁹F-N.M.R. spectra were recorded on a BRUKER appa­ratus AM 300, dissolving the samples in CDCl₃.

From these tests it was concluded that the product consisted of telomeric species Ia to Xa, out of which species Ia to IIIa proved to constitute more than 85% of the mixture. Species IXa was present in an amount lower than 1%. The gas-chromatographic analyses revealed that the telomers having a value of "n" from 3 to 6 represented about 90% of the crude product.

Said product was then subjected to fractionated distillation under reduced pressure. In this manner there were removed a head product consisting of CTFE residues and of non-telomeric by-products, and a tail product consisting of telomeric high-­boiling products and of telomeric waxy products. The thus ob­tained product was a colorless oil (designated as sample 1), whose distribution in terms of "n" values, as concluded from the gas-chromatographic analysis, was as follows: <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><u style="single">Sample 1</u></entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">value of "n"</entry><entry namest="col2" nameend="col2" align="center">area %</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">2 + volatile matter</entry><entry namest="col2" nameend="col2" align="char" char=".">27.2</entry></row><row><entry namest="col1" nameend="col1" align="left">3</entry><entry namest="col2" nameend="col2" align="char" char=".">16.4</entry></row><row><entry namest="col1" nameend="col1" align="left">4</entry><entry namest="col2" nameend="col2" align="char" char=".">36.0</entry></row><row><entry namest="col1" nameend="col1" align="left">5</entry><entry namest="col2" nameend="col2" align="char" char=".">18.1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">6</entry><entry namest="col2" nameend="col2" align="char" char=".">0.8</entry></row></tbody></tgroup></table></tables>

A second distillation under reduced pressure was then carried out in order to decrease the amount of telomers having a "n" value equal to 2. Thus, sample 2 having the following distri­bution of the "n" values was obtained: <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="center"><u style="single">Sample 2</u></entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">value of "n"</entry><entry namest="col2" nameend="col2" align="center">area %</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="char" char=".">2.3</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="char" char=".">25.4</entry></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="char" char=".">45.9</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="char" char=".">22.1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="char" char=".">4.3</entry></row></tbody></tgroup></table></tables>

On samples 1 and 2, the following physical and chemic­al properties were determined : - density according to method ISO R/758 - viscosity according to standard ASTM D445 - pour point according to standard ASTM D99 - vapour tension according to the method of the pressure trans­ducer as described in Journ. of Chem. and Eng. Data, vol. 13, No. 3, July 1969 - heat of combustion according to standard ASTM D240 - unsaturation according to the method illustrated in the tech­nical handbook by Halocarbon Product Corpora­tion - bulk modulus by measuring the propagation rate of the su­personic waves.

The results obtained are given in the following Table 1. <tables id="tabl0003" num="0003"><table frame="all"><title>TABLE 1</title><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="center"><u style="single">Physical and chemical properties</u></entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Properties</entry><entry namest="col2" nameend="col2" align="center">Sample 1</entry><entry namest="col3" nameend="col3" align="center">Sample 2</entry></row><row><entry namest="col1" nameend="col3" align="center">DENSITY (g/ml)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">20°C</entry><entry namest="col2" nameend="col2" align="char" char=".">1.8106</entry><entry namest="col3" nameend="col3" align="right">1.8522</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">40°C</entry><entry namest="col2" nameend="col2" align="char" char=".">1.7722</entry><entry namest="col3" nameend="col3" align="right">1.8129</entry></row></tbody></tgroup><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col3" align="center">VISCOSITY (cSt)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">-20°C</entry><entry namest="col2" nameend="col2" align="char" char=".">-</entry><entry namest="col3" nameend="col3" align="right">68.8</entry></row><row><entry namest="col1" nameend="col1" align="left">-18°C</entry><entry namest="col2" nameend="col2" align="char" char=".">10.55</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">-15°C</entry><entry namest="col2" nameend="col2" align="char" char=".">9.34</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">-10°C</entry><entry namest="col2" nameend="col2" align="char" char=".">7.40</entry><entry namest="col3" nameend="col3" align="right">31.1</entry></row><row><entry namest="col1" nameend="col1" align="left">0°C</entry><entry namest="col2" nameend="col2" align="char" char=".">4.95</entry><entry namest="col3" nameend="col3" align="right">16.4</entry></row><row><entry namest="col1" nameend="col1" align="left">20°C</entry><entry namest="col2" nameend="col2" align="char" char=".">2.86</entry><entry namest="col3" nameend="col3" align="right">6.7</entry></row><row><entry namest="col1" nameend="col1" align="left">40°C</entry><entry namest="col2" nameend="col2" align="char" char=".">1.99</entry><entry namest="col3" nameend="col3" align="right">3.4</entry></row><row><entry namest="col1" nameend="col1" align="left">60°C</entry><entry namest="col2" nameend="col2" align="char" char=".">1.34</entry><entry namest="col3" nameend="col3" align="right">2.1</entry></row><row><entry namest="col1" nameend="col1" align="left">80°C</entry><entry namest="col2" nameend="col2" align="char" char=".">0.99</entry><entry namest="col3" nameend="col3" align="right">1.4</entry></row><row><entry namest="col1" nameend="col1" align="left">100°C</entry><entry namest="col2" nameend="col2" align="char" char=".">0.87</entry><entry namest="col3" nameend="col3" align="right">1</entry></row><row><entry namest="col1" nameend="col1" align="left">120°C</entry><entry namest="col2" nameend="col2" align="char" char=".">0.71</entry><entry namest="col3" nameend="col3" align="right">0.8</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">135°C</entry><entry namest="col2" nameend="col2" align="char" char=".">0.51</entry><entry namest="col3" nameend="col3" align="right">0.67</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">POUR POINT, °C</entry><entry namest="col2" nameend="col2" align="char" char=".">-78</entry><entry namest="col3" nameend="col3" align="right">-58</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">VAPOR TENSION AT 121°C, TORR.</entry><entry namest="col2" nameend="col2" align="char" char=".">1030</entry><entry namest="col3" nameend="col3" align="right">270</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">COMBUSTION HEAT cal/g</entry><entry namest="col2" nameend="col2" align="char" char=".">1410</entry><entry namest="col3" nameend="col3" align="right">1640</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">UNSATURATION (min.)</entry><entry namest="col2" nameend="col2" align="char" char=".">140</entry><entry namest="col3" nameend="col3" align="right">415</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">BULK MODULUS</entry><entry namest="col2" nameend="col2" align="char" char=".">-</entry><entry namest="col3" nameend="col3" align="right">0.93083.10⁹Pa</entry></row></tbody></tgroup></table></tables>

To be noticed are the particularly low values of pour point, heat of combustion and unsaturation.

Example 2

Following the procedure of example 1, 1.0 Nl/h of CF₃-CF₂OF and 4.0 Nl/h of nitrogen were bubbled through 450 g of liquid CTFE, at -75°C, during 6 hours. After removal of the unreacted CTFE there were obtained 101 g of product with a yield of about 15.0 g of telomers per liter of gaseous CF₃-CF₂OF. The compounds Ia to Xa were present. About 90% of the mixture was composed of the species Ia to IIIa. The telomers having a value of "n" ranging from 3 to 6 amounted to about 93% of the total.

Example 3

Following the procedure of example 1, 2.0 Nl/h of CF₃-CF₂OF and 4.0 Nl/h of N₂ were bubbled through 260 g of liquid CTFE, at -40°C, for 3 hours and 30 minutes. After removal of the unreacted CTFE, there were obtained 63 g of product with a yield of about 9.0 g of telomers per liter of gaseous CF₃-CF₂OF. Compounds Ia to Xa were present. The species IVa to Xa repre­sented about 90% of the mixture.

After the unreacted CTFE was distilled off, the following dis­tribution of the "n" values resulted: <tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">value of "n"</entry><entry namest="col2" nameend="col2" align="center">area %</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="right">not determined</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="right">3.2</entry></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="right">6.7</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="right">11.1</entry></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="right">14.5</entry></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="right">14.5</entry></row><row><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="right">13.5</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="right">12.0</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="right">10.2</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="right">7.9</entry></row><row><entry namest="col1" nameend="col1" align="right">12</entry><entry namest="col2" nameend="col2" align="right">5.1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">&gt;12</entry><entry namest="col2" nameend="col2" align="right">not determined</entry></row></tbody></tgroup></table></tables>

Example 4

Following the procedure of example 1, 1.0 Nl/h of CF₃-CF₂OF and 3.0 Nl/h of N₂ were bubbled through 160 g of CTFE mixed with 160 g of CF₂Cl-CF₂Cl, at -55°C, for 6 hours.

After the unreacted CTFE and the solvent were distilled off, 71 g of product were obtained, the yield being about 11.3 g of telomers per liter of gaseous CF₃CF₂OF. Compounds Ia to Xa were present. About 90% of the mixture was composed of species Ia to IIIa. The telomers having a "n" value ranging from 3 to 6 amounted to 76% of the total.

Example 5

Following the procedure of example 1, 1.0 Nl/h of CF₃-CF₂OF and 5.0 Nl/h of N₂ were bubbled through 200 g of CTFE mixed with 200 g of CFCl₃, at -75°C, for 14 hours. After the unreac­ted CTFE and the solvent were distilled off, there were ob­tained 180 g of product with a yield of about 12.9 g of telo­mers per liter of gaseous CF₃-CF₂OF. Compounds Ia to Xa were present. Species Ia to IIIa represented about 90% of the mix­ture. The telomers having a "n" value ranging from 3 to 6 cor­responded to 66% of the total.

Example 6

Following the procedure of example 1, 1.0 Nl/h of CF₃-CF₂-CF₂OF and 8.0 Nl/h of N₂ were bubbled through 260 g of CTFE, at 50°C, for 8 hours. After the unreacted CTFE was distilled off, 72 g of product were obtained. A yield of about 9.0 g of telo­mers per liter of gaseous CF₃-CF₂-CF₂OF was calculated. The telomers IIb to XIIb, Ia, IIa, VIIIa and IXa were present. The species Ia and IIb to VIb represented about 90% of the mixture. Species IXa was present in an amount lower than 1%. The "n" values were distributed as follows: <tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">value of "n"</entry><entry namest="col2" nameend="col2" align="center">area %</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">2 + volatile matter</entry><entry namest="col2" nameend="col2" align="right">44.7</entry></row><row><entry namest="col1" nameend="col1" align="left">3</entry><entry namest="col2" nameend="col2" align="right">20.9</entry></row><row><entry namest="col1" nameend="col1" align="left">4</entry><entry namest="col2" nameend="col2" align="right">14.7</entry></row><row><entry namest="col1" nameend="col1" align="left">5</entry><entry namest="col2" nameend="col2" align="right">7.9</entry></row><row><entry namest="col1" nameend="col1" align="left">6</entry><entry namest="col2" nameend="col2" align="right">5.1</entry></row><row><entry namest="col1" nameend="col1" align="left">7</entry><entry namest="col2" nameend="col2" align="right">3.2</entry></row><row><entry namest="col1" nameend="col1" align="left">8</entry><entry namest="col2" nameend="col2" align="right">2.3</entry></row><row><entry namest="col1" nameend="col1" align="left">9</entry><entry namest="col2" nameend="col2" align="right">1.1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">≧ 10</entry><entry namest="col2" nameend="col2" align="right">not determined</entry></row></tbody></tgroup></table></tables>

Example 7

Following the procedure of example 1, 1.0 Nl/h of CF₃-CF₂-CF₂OF and 8.0 Nl/h of N₂ were bubbled through 260 g of CTFE mixed with 260 g of CF₂Cl-CF₂Cl, at -50°C, for 5 hours and 30 minu­tes. After having distilled off the unreacted CTFE and the solvent, 54 g of product were obtained. A yield of about 9.7 g of telomers per liter of gaseous CF₃-CF₂-CF₂OF was calculated. Compounds IIb to XIIb, Ia, IIa, IXa and VIIIa were present. More than 90% of the mixture was composed of species Ia and IIb to VIb. The telomers having "n" values from 3 to 6 amoun­ted to about 60% of the total.

Example 8

Following the procedure of example 1, 1.0 Nl/h of CClF₂-CF₂OF and 5.0 Nl/h of N₂ were bubbled through 260 g of CTFE, at -75°C, for 7 hours and 15 minutes. After distilling-off of the unreacted CTFE, there were obtained 80 g of product with a yield of 11.0 g of telomers per liter of gaseous CClF₂-CF₂OF. Telomers IIc to Xc, Ia, IIa and IXa were present. More than 90% of the mixture consisted of species Ia and from IIc to VIc. Species IXa was present in an amount lower than 1%.

The product was then subjected to fractionated distillation at reduced pressure. Thereby there were removed a head product prevailingly consisting of CTFE residues and a tail product consisting of high-boiling products and waxy products. A co­lorless oil (designated as fraction 3) was obtained which had the following "n" value distribution: <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">value of "n"</entry><entry namest="col2" nameend="col2" align="center">area %</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">2 + volatile matter</entry><entry namest="col2" nameend="col2" align="char" char=".">34.2</entry></row><row><entry namest="col1" nameend="col1" align="left">3</entry><entry namest="col2" nameend="col2" align="char" char=".">18.6</entry></row><row><entry namest="col1" nameend="col1" align="left">4</entry><entry namest="col2" nameend="col2" align="char" char=".">21.8</entry></row><row><entry namest="col1" nameend="col1" align="left">5</entry><entry namest="col2" nameend="col2" align="char" char=".">11.4</entry></row><row><entry namest="col1" nameend="col1" align="left">6</entry><entry namest="col2" nameend="col2" align="char" char=".">6.0</entry></row><row><entry namest="col1" nameend="col1" align="left">7</entry><entry namest="col2" nameend="col2" align="char" char=".">3.4</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">≧ 8</entry><entry namest="col2" nameend="col2" align="char" char=".">2.2</entry></row></tbody></tgroup></table></tables>

On sample 3 there were determined the same physical and chemi­cal properties as in example 1. The results are given in the following Table 2. <tables id="tabl0007" num="0007"><table frame="all"><title>Table 2</title><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col2" align="center"><u style="single">Physical and chemical properties of sample 3</u></entry></row><row><entry namest="col1" nameend="col2" align="left">DENSITY , (g/ml)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">20°C</entry><entry namest="col2" nameend="col2" align="right">1.8444</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">40°C</entry><entry namest="col2" nameend="col2" align="right">1.8053</entry></row></tbody></tgroup><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">VISCOSITY , (cSt)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">-20°C</entry><entry namest="col2" nameend="col2" align="right">28.6</entry></row><row><entry namest="col1" nameend="col1" align="left">-10°C</entry><entry namest="col2" nameend="col2" align="right">15.6</entry></row><row><entry namest="col1" nameend="col1" align="left">0°C</entry><entry namest="col2" nameend="col2" align="right">9.7</entry></row><row><entry namest="col1" nameend="col1" align="left">20°C</entry><entry namest="col2" nameend="col2" align="right">4.5</entry></row><row><entry namest="col1" nameend="col1" align="left">40°C</entry><entry namest="col2" nameend="col2" align="right">3</entry></row><row><entry namest="col1" nameend="col1" align="left">60°C</entry><entry namest="col2" nameend="col2" align="right">1.9</entry></row><row><entry namest="col1" nameend="col1" align="left">80°C</entry><entry namest="col2" nameend="col2" align="right">1.2</entry></row><row><entry namest="col1" nameend="col1" align="left">100°C</entry><entry namest="col2" nameend="col2" align="right">0.9</entry></row><row><entry namest="col1" nameend="col1" align="left">120°C</entry><entry namest="col2" nameend="col2" align="right">0.74</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">135°C</entry><entry namest="col2" nameend="col2" align="right">0.63</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">POUR POINT, °C</entry><entry namest="col2" nameend="col2" align="right">-80</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">VAPOUR TENSION AT 121°C, TORR.</entry><entry namest="col2" nameend="col2" align="right">340</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">COMBUSTION HEAT cal/g</entry><entry namest="col2" nameend="col2" align="right">1810</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">UNSATURATION (min.)</entry><entry namest="col2" nameend="col2" align="right">250</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">BULK MODULUS</entry><entry namest="col2" nameend="col2" align="right">1,0263075.10⁹ Pa</entry></row></tbody></tgroup></table></tables>

It is to be noticed that the pour point value, the vapor ten­sion value and the unsaturation value are particularly low. Also the heat of combustion value is low. From a comparison of the bulk modulus value with the one of sample 2 (see ex­ample 1), a higher value can be observed, which is attributable to the presence of Cl in the end groups. Due to the high bulk modulus value, the sample is particularly suited for use in appliances where a low compressibility is required.

Example 9

Following the procedure of example 1, 1.0 Nl/h of CClF₂-CF₂OF and 5.0 Nl/h of N₂ were bubbled through 130 g of CTFE mixed with 160 g of CF₂Cl-CF₂Cl at -74°C for 9 hours. After having distilled off the unreacted CTFE and the solvent, there were obtained 59 g of product, with a yield of about 6.6 g of telo­mers per liter of gaseous CClF₂-CF₂OF. Compounds Ia, IXa and IIc to Xc were present. More than 90% of the mixture were com­posed of species Ia and IIc to VIc. About 40% of the mixture were composed of species Ia and IIc to IVc.

The telomers having a value of "n" ranging from 3 to 6 amoun­ted to 58% of the total.

Example 10

Following the procedure of example 1, 1.0 Nl/h of n-C₃F₇-O-­CF(CF₃)-CF₂OF and 5.0 Nl/h of N₂ were bubbled through 250 g of CTFE at -74°C for 10 hours. After having distilled off the unreacted CTFE, there were obtained 58.5 g of product. The following telomers resulted: F(M)_nF      (Ia) CF₃O(M)_n-F      (IXa) CF₃O(M)_nOCF₃      (3) C₃F₇O-CF(CF₃)-(M)_n-F      (4) C₃F₇O-CF(CF₃)CF₂O(M)_n-F      (5) C₃F₇O-CF(CF₃)-(M)_n-OCF₃      (6) C₃F₇O-CF(CF₃)-CF₂O(M)_n-OCF₃      (7) CF₃-CF₂-CF₂-CF(CF₃)-CF₂-O(M)_n-F      (8) CF₃-CF₂-CF₂-CF(CF₃)-CF₂(M)_n-OCF₃      (9) C₃F₇O-CF(CF₃)-(M)_n-CF(CF₃)-OC₃F₇      (10) C₃F₇O-CF(CF₃)-(M)_n-OC₃F₆-OC₃F₇      (11) C₃F₇O-C₃F₆O-(M)_n-OC₃F₆-OC₃F₇      (12) CF₃-CF₂-CF₂-CF(CF₃)-CF₂-(M)_n-CF(CF₃)-OC₃F₇      (13) CF₃-CF₂-CF₂-CF(CF₃)-CF₂-(M)_n-OC₃F₆-OC₃F₇      (14) where "n" ranges from 2 to 8. The telomeric species (4) to (14) are new compounds.