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Publication numberUS3226449 A
Publication typeGrant
Publication dateDec 28, 1965
Filing dateJun 6, 1962
Priority dateJun 6, 1962
Publication numberUS 3226449 A, US 3226449A, US-A-3226449, US3226449 A, US3226449A
InventorsBlanchard Wesley Alva, Rhode Judson Cyrus
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for preparing perfluoroalkyl iodides
US 3226449 A
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Description  (OCR text may contain errors)

United States Patent 3,226,449 PRQCESS FOR PREPARTNG PERFLUORCALKYL IODTDES Wesley Alva Blanchard, Newcmtle, and Judson Cyrus Rhode, Wilmington, DeL, assignors to E. l. (in Pont de Nernonrs and Company, Wilmington, Del, 21 corporation of Delaware No Drawing. Filed June 6, 1962, Ser. No. 200,299 2 Claims. (Cl. 260--653.1)

The present invention is directed to a novel process for telomerization of perlluoroalkyl iodides with tetrafluoroethylene to obtain higher perfiuoroalkyl iodides.

The thermal and photochemical telomerization of pertluoroalkyl iodides with tetrafluoroethylene to form higher perfluoroalky'l iodides is known. For example, Haszeldine, J. Chem. Soc. 1949, 2856; 1953, 3761; Nature, 167, 139 (1951), has described the thermal and photochemical telomerization process as follows:

where R and 12 respectively are: C1 11:140; C 1 n=l7; n-C F n=l2; rzC F n=12; n-C F 11:1 and greater. These thermal and photochemical processes have distinct disadvantages of being time-consuming and tedious. Also, these thermal and photochemical processes ol'fer rather poor control of product composition and low productivity of reaction equipment. While the 1:1 addition product can usually be produced by these processes in relatively high yield, higher telomers are obtained by these processes either in poor yield and conversion or a very wide range of products is obtained. Thus, if a particular range of telomers is desired by the known thermal and photochemical processes, it can be obtained only in relatively low yield along with considerable quantitles of undesired and less useful products. Since both perfiuoroalkyl iodides and tetrailuoroethylene are relatively expensive as commercial chemicals go, it is economically undesirable to use processes which give poor utilization of these materials in forming useful products.

It is, therefore, an object of this invention to provide a novel telomerization process capable of giving high yields of a desired range of telomers.

it is a further object to provide a novel process for telomerization of perfluoroalkyl iodide with tetrafluoroethylene which is convenient to operate, and which uses conventional equipment at high production rates.

These and other objects will become apparent from the following description and claims.

It has now been found that the telomerization of perfiuoroallryl iodides with tetraiiuoroethylene in the presence of certain free radical generating catalysts is capable of high production rates and leads to good yields of relatively narrow ranges of telomers.

More specifically, the present invention is directed to a process for preparing pertluoroalkyl iodides containing from six to twelve carbon atoms which comprises injecting gradually during the reaction cycle a quantity of tetrafiuoroethylene and a free radical generating catalyst into a mixture containing initially (1) a perfiuoroallryl iodide chosen from pcrlluoroethyl iodide and mixtures of pertluoroethyl iodide and n-perfluorobutyl iodide and (2) a portion of free radical generating catalyst, said The present process consists of reacting perfiuoroethyl iodide or mixtures of perfluoroethyl iodide and n-perfiuorobutyl iodide with tetrafluoroethylene and obtaining products of structure F(CF l containing from six to twelve carbons. These products are produced in yields of better than 70% by this process.

Any free radical generating catalyst which has a useful decomposition rate within the range of Sit-170 C. may be used. Examples of useful catalysts are ketone peroxides such as methyl amyl ketone peroxide, di-tert-alkyl peroxides such as di-tertbutyl peroxide, alkyl azo .compounds such as a,iz-azobis(isobutyronitrile), a,a'-azobis(a -dimethylvaleronitrile) and perfiuoroazomethane, aromatic diacyl peroxides such as benzoyl peroxide and the like. The preferred free radical generating catalyst is di-tert-butyl peroxide. Inorganic peroxides such as potassium persultate are generally not useful due to their insolubiiity in the reaction mixture.

The reaction temperature depends primarily on the catalyst used. The ketone peroxides, the azo compounds and the aromatic diacyl peroxides are generally used in the range of 120 C., while the di-tert-allryl peroxides such as di-tert-butyl peroxide require l70 C. reaction temperatures. The preferred reaction temperature, with the preferred catalyst, is about C. Temperature causes an undesirable yield loss when it exceeds C. The main function of temperature is to control the rate of decomposition of the free radical generating catalyst. T he present reaction is somewhat exothermic and should rapid initiation occur, control of the temperature and control of the reaction become ditlicult. Several reactions which are difficult to control and which are hazardous occur when tetrafiuoroethylene is heated above about 250 C. under pressure.

The mole ratio of tetrafiuoroethylene to perfiuoroalkyl iodide may vary from about 0.25 to about. 1.2. Ratios higher than 1.2 cause excessive yield losses due to formation of reaction products where m is greater than 12. The ratio also has an effect on the composition of the product. The preferred mole ratio is from 0.4 to 1.1, depending on conditions and whether recycle material is being used.

The total weight of free radical generating catalyst added to the reaction mixture may vary from about 0.25% to about 0.9% by weight of the reaction mixture. The concentration of catalyst present at any time, as well as the total amount of catalyst used, should be kept as low as possible consistent with a desirable reaction rate. Excessive initiating agent (greater than 0.9% by weight total) has an undesired efiect on yield, causing by-product formation.

The reaction pressure may be varied from about 225 p.s.i. to about 700 p.s.i. The actual pressure will depend on the reaction temperature and the concentration of tetrafiuoroethylene. In the present process, the perfiuoroalkyl iodide and a portion of the free radical generating catalyst (generally less than one-half of the total catalyst to be used) are placed in a pressure vessel and heated, usually with agitation. Tetrafluoroethylene and further catalyst are added to the mixture until the desired amount of each has been added. Heating is then continued until the tetratluoroethylene has been consumed. but no further, since excessive heating also can cause by-product formation. The initial reaction pressure will vary with the temperature and other reaction conditions, but usually does not exceed about 450-600 p.s.i. The final pressure will generally be about 200300 p.s.i. The rate of addition of tetrafiuoroethylene and catalyst will depend on such factors as the rate of consumption of these materials and the ability of the reaction vessel for removing heat from the reaction mixture. It has been found that the time taken for the addition may vary from one-half to about two hours depending on these factors. The heating time required after the addition is complete is usually rather short. Over-all, reaction times of from one to two hours are the general rule.

Tetrafiuoroethylene is added over the period of the reaction for two reasons: first, because if added all at once it generally leads to high pressures, and second, if added all at once it seems to have an effect on the composition and yield of the desired product. The catalyst is added over the period of reaction because it allows better control of the reaction and because the presence of excess catalyst can lead to larger amounts of byproducts.

Conversion of tetrafluoroethylene is essentially complete. Conversion of the perfluoroalkyl iodides, since they are often used in some excess, particularly under the preferred conditions, is incomplete. However, with recycle, complete conversion of the perfluoroalkyl iodides is obtained.

The perfiuoroalkyl iodides are well known to the art. Although it is preferred to use perfiuoroethyl iodide, mixtures of perfiuoroethyl iodide and n-perfluorobutyl iodide may also be used. In commercial practice, nperfiuorobutyl iodide will usually result from recycle of products containing less than six carbon atoms. Mixtures of perfluoroalkyl iodides require slight modification of reaction conditions, for instance, less tetrafluoroethylene.

The best source of perlluoroethyl iodide seems to be the reaction of tetrafluoroethylene with a mixture of iodine and iodine pentafluoride in the presence of an aluminum-aluminum iodide catalyst, as described by Hauptschein et al. in J. Amer. Chem. Soc. 83, 2383 (1961), U.S. Patent 3,006,973 (Oct. 3l, 1961) and Belgium Patent 594,145 (Aug. 17, 1960). Of course, other, more expensive methods are known for preparing this material.

Tctrafluoroethylene is a commercial material. It is usually stored containing d-limonene inhibitor. While it is often desirable to remove the inhibitor before use in free radical initiated reactions and can be done in the subject invention if desired, it is unnecessary to do so in the present process. This is a distinct advantage since it removes one source of potential hazard.

The products of the present invention have the structure F(CF )I. The value of m is from six to twelve. The range of reaction conditions described produce the best yields of products containing six to twelve carbons. Products containing less than six carbons are formed, but they are recycled by combining with pertluoroethyl iodide for further reaction with tetrafluoroethylene. As noted earlier, the composition of the product varies with the reactant mole ratio of tetratluoroethylene to perfiuoroalkyl iodide. As the ratio increases, so does the relative amount of products containing more than twelve carbons. As the value of the ratio decreases, the relative amount of product containing less than six carbons (which must be recycled) increases also. Since a large recycle is undesirable, the range of mole ratios cited is also critical in limiting this factor. The surprising feature of this invention is that a mole ratio range exists which not only limits the amounts of products containing more than twelve carbons but also the amount of products containing less than six carbons. The present process limits the amount of product containing more than twelve carbons and other by-products to less than 30%. Hence, the yields of useful products are in excess of 70% and usually nearer 90% The major by-products of the present process, in addition to those iodides containing more than twelve carbons, are F(CF I-I, apparently produced by the reaction of intermediate radicals with the catalyst or catalyst fragments by hydrogen abstraction. (Of course, such products are not formed when perfiuoroazomethane is used as the catalyst.) The yield of these by-products increases with the amount of catalyst and catalyst fragments present. Smaller amounts of other, unidentified materials may also occur but they are readily separated from the desired products. These unidentified materials are also quite inert and can be allowed to remain in the product, if so desired, since they will not enter into any of the reactions in which the product iodides may be used.

The product iodides F(CF I may be separated from the reactants and by-products by any conventional means, for instance by fractional distillation. The product may also be recovered in sufficient purity for most purposes by stripping off the unreacted starting materials and recovering the product as still residue. The principal use of the products of this invention is as intermediates for preparing oil and water repellents for textiles and the like. To obtain oil and water repellents from the subject iodide products, a minimum range of six to twelve carbons is necessary. While iodides with more than twelve carbons may be used, they are more expensive since they contain more fluorine with no benefit derived therefrom. Hence it is desirable to produce iodides which contain near the minimum required and no more. The present process does this. One method for preparing oil and water repellents for textiles is via the following series of reactions:


Methyl acrylate, when used in place of methyl methacrylate above, gives the corresponding acrylate polymers. If a comonomer is used in the above polymerization step, copolymers are obtained which are also useful as oil repellents for textiles.

Other uses for the perfiuoroalkyl iodide products of this invention include conversion of the perfluoroalkyl iodides to the corresponding acids by way of reacting the perfiuoroalkyl iodide with acetylene to form the 1- perfluoroalkyl-2-iodoethylene, which is in turn oxidized to form the desired perfiuoroalkyl carboxylic acid. The perfluoroacids are useful as surface active agents. Their acid chlorides may be converted to other surface active agents such as those described in U.S. Patent 2,764,602 and for perfluoroalkylating aromatic compounds as described in U.S. Patent 2,957,031. The perfluoroalkyl iodides may also be used to perfluoroalkylate aromatic compounds as described in British Patent 840,725.

It should be particularly understood that, while the present process is defined for certain perfluoroalkyl iodide reactants, it could equally well be applied to other perfluoroalkyl iodides if so desired. A different range of products would naturally be obtained by changing reaction conditions while still remaining within the heretofore described scope of the invention. The limitations on desired product size in the definition of the invention are based on utility as heretofore pointed out and are not based on limitations of the process itself. It is not to be assumed, however, that the process as defined is equally well applicable to olefins other than tetrafiuoroethylene or to fiuoroalkyl iodides other than perfluoroalkyl iodides. The reaction conditions outlined earlier are applicable only to the combination of tetrafluoroethylene and perfiuoroethyl iodide or mixtures of perfiuoroethyl and perfluorobutyl iodides to produce the results described. For example, if the present process is applied to tetrafluoroethylene and CFgClCFClI, the 1:1 adduct is obtained as the primary product and little or no other reaction products are formed.

The following examples are representative and illustrate the present invention and show preferred embodithe conditions shown in the table. The results are shown ments thereof. The object of all of the following illusin the table.

Table Percent yield: Total Cilifift- Ratio of CsFrsI-CrzFzaI Example Parts 1 C F I Catalyst lyst used, Temp, C. Time, min. C2114 added Wt. percent to initial iodide moles Based on Based on 21 4 iodide 800 800 Ditertiary 0.9 165 so 0. 654 93.9 74.5

1, 200 0.89 165 60 0. s01 98 so. 1 1, 200 0. 78 165 so 0. 67 98+ 73. 6 1, 200 0.85 165 60 0.767 90. 7 81. 9 l, 200 0. 91 165 60 0. 80 c, 60 1, 200 0. 78 17s 00 1. 2 65 65 trative examples is to prepare n-perfluoroallryl iodides containing from six to twelve carbons. All parts are by weight unless stated otherwise.

EXAMPLE 1 A stainless'steel autoclave of 1500 parts water capacity was charged with 1200 parts of periluoroethyl iodide and 400 parts of pcn'iuorobutyl iodide and heated to 116 C. An initiator solution (30.3 parts) containing 20% by weight di-tert-butyl peroxide in perliuorobutyl iodide was quickly added to the autoclave. The autoclave was then quickly heated to 165 C. and tetrafluoroethylene was added at the rate of six parts per minute while initiator was added at the rate of 0.83 part solution per minute. The initial reaction pressure was 440 p.s.i.g., which decreased during the course of the reaction to 285 p.s.i.g. After one hour, 402 parts of tetrailuoroethylene and 89.3 parts of initiator solution had been added (final ratio of added C 12, to initial ioclide=0.86, total catalyst used=0.78 wt. percent). The reaction mixture was cooled and the product (2107 parts, 100%) was discharged into receivers cooled to 50 C. The crude product was analyzed by vapor phase chromatography with the following results.

Component: Weight-percent C F l 35.9 F(CF I 19.7 F(CF I 15.1 F(CF l 11.6 F(CF I 7.2 F(CF l 3.7 Gthers 6.8

These results indicate that the apparent conversion of perfiuoroethyl iodide was about 37%, the apparent conversion of pertluorobutyl iodide was about 12%, the yield of F(CF l, where 111:6-12, was 76.3% based on periiuoroallryl iodide converted and 92.6% based on tetrafiuoroethylene which was completely converted. Distillation gave the following typical results.

Component: Boiling point (2 1 1 12 /7s0 F(CF ).;I 60-71/760 F(CF l 50-59/98 F(CF 1 75-90/5O F(CF I 105125/50 When the process above is repeated using 1600 parts of periluoroethyl iodide in place of the mixture of iodides used above, the conversion of perlluoroethyl iodide was about 50% and the yields are approximately the same as the above case.

Repeating this example using the same amount of a by weight solution of a,ct-azobisisobutyronitrile in perfluorobutyl iodide and a reaction temperature of 80- 90 C. gave essentially the same results.

The following examples shown in the table below were carried out in the same manner as described above under To illustrate the present invention, a comparison test was carried out using the prior art thermal process hereinbeiore described.

A mixture of 800 parts of perfiuoroethyl iodide (3.25 moles) and 800 parts of n-perfiuorobutyl iodide (2.31 moles) was heated to 194 C. in an autoclave and about parts of totrafluoroethylene was added. The temperature rose to 218 C. and the pressure rose to p.s.i. from 450 psi. When the temperature and pressure had decreasde, further tetrafluoroethylene was again added and the process repeated until a total of 192 parts (-1.92 moles) had been added (mole ratio of tetrafiuoroethylene added to the initial pertluoroalkyl iodide=0.345). The maximum pressure observed was about 800 psi.

Vapor phase chromatographic analysis of the crude product gave the following results.

Compound: Weight-percent C F I 36.2 F(CP I 37.9 F(CF l 11.4 F(CP T 4.4 F(CF l 1.7 F(CF l 0.6 Others 7.8

This analysis indicates an apparent conversion of perfluoroethyl iodide of 18.9%, an apparent conversion of pertiuorobutyl iodide of 15%, a yield of C(CF I, m=612, of 69.2% based on perfiuoroalkyl iodide converted and a yield of 61.8% based on tetrafiuoroethylene converted.

The ratio of tetrafluoroethylene to perfluoroalkyl iodide of the above thermal process is within the range of Examples 1-5. However, because it is a thermal process, the temperature is much higher than Examples 15. In comparing the above test illustrating the art recognized thermal process with the present invention, it will be noted that the yields of perfiuoroalkyl iodides containing from 6 to 12 carbon atoms is much lower in the thermal process than in the process of the present invention hereinbefore described in Examples 1-5.

There are several particular advantages of the present process over the thermal and photochemical processes. First, the process of the present invention is capable of producing a desired range of perfiuoroalltyl iodide products in high yield. Second, the yields are far better than the thermal and photochemical processes for the desired range of products. Third, the process is less hazardous especially when compared with the thermal process. Fourth, no unusual equipment is required, particularly when compared with the photochemical process. Fifth, the preent invention is less expensive than the photochemical process, since the photochemical process is very expensive to operate clue to the electrical power consumed by the light source (the eificiency of utilization in the reaction of light energy is usually poor). Sixth, the present process is considerably more rapid than either the photochemical or thermal processes. The present process usually requires one to two hours, whereas the '7 thermal process requires a large number of hours and the photochemical process times can be measured in days. Thus, the present process allows considerably higher productivity which lowers both investment and labor costs, both important commercial considerations. For the above reasons, this process is a valuable addition to the art.

It is to be understood that the preceding examples are representative and that said examples may be varied within the scope of the total specification, as understood by one skilled in the art, to produce essentially the same results.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.


1. A process for preparing perfiuoroalkyl iodides containing from six to twelve carbon atoms which process comprises reacting tetrafiuoroethylene with a perfiuoroalkyl iodide selected from the group consisting of perfluoroethyl iodide and mixtures of perfiuoroethyl iodide and n-perfiuorobutyl iodide in the presence of an organic free radical generating catalyst at a temperature of from 80 C. to 170 C. and under a pressure from about 225 p.s.i. to about 700 p.s.i., said tetrafiuoroethylene and a portion of the free radical generating catalyst being injected gradually during the reaction to said perfluoroalkyl iodide containing a portion of said free radical generating catalyst until from about 0.25 to about 1.2 moles of tetrafiuoroethylene per mole of perfiuoroalkyl iodide and from about 0.25% to 0.9% by weight of free radical 8 generating catalyst per total weight of reaction mixture have been added, and recovering from the reaction mixture products having the structure (F(CE l, wherein m is from six to twelve.

2. A process for preparing perfiuoroalkyl iodides containing from six to twelve carbon atoms which process comprises reacting tetrafluoroethylene with perfiuoroethyl iodide in the presence of di-tert-butyl peroxide catalyst at a temperature of from 120 C. to 170 C. and under a pressure from about 225 psi. to about 700 p.s.i., said tetrailuoroethylcne and a portion of the total amount of di-tert-butyl peroxide being injected gradually during the reaction to said perfluoroalkyl iodide containing the remaining portion of said di-tert-butyl peroxide until from about 0.4 to about 1.1 moles of tetrafiuoroethylene per mole of perfiuoroethyl iodide and from about 0.25% to 0.9% by weight of di-tert-butyl peroxide per total weight of reaction mixture have been added, and recovering from the reaction mixture products having the structure F(CF l, wherein m is from six to twelve.

References Cited by the Examiner UNITED STATES PATENTS 2,562,547 7/1951 Hanford et a1. 260653.1

FOREIGN PATENTS 949,822 9/1956 Germany.

OTHER REFERENCES Haszeldine: J. Chem. Soc. (London), 1949, pp. 2856-61.

Haszeldine: Nature, 167, pp. 139-40-40 (1951 LEON ZITVER, Primary Examiner.

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US3525758 *Feb 5, 1965Aug 25, 1970Daikin Ind LtdPreparation of fluorine-containing carboxylic acids
US4001309 *Apr 16, 1973Jan 4, 1977Asahi Glass Co., Ltd.Method of preparing polyfluoroalkyl group containing compounds
US4058573 *Apr 4, 1974Nov 15, 1977Ciba-Geigy CorporationProcess for the addition of gaseous non-halogenated olefins and acetylenes to perfluoroalkyl iodides
US5268516 *Jan 13, 1993Dec 7, 1993Elf Atochem S.A.Synthesis of perfluoroalkyl iodides
US7038095Feb 5, 2002May 2, 2006Daikin Industries, Ltd.Method for producing fluoroalkyl iodide telomer mixture and method for producing mixture fluorine-containing (meth) acrylate esters
US7390917Mar 9, 2005Jun 24, 2008Daikin Industries, Ltd.Method for producing mixture of fluoroalkyl iodide telomers and method for producing mixture of fluorine-containing (meth)acrylate esters
US7888538Nov 4, 2009Feb 15, 2011E.I. Du Pont De Nemours And CompanyCatalyzed olefin insertion
US7951983Nov 4, 2009May 31, 2011E.I. Du Pont De Nemours And CompanyCatalyzed olefin insertion
US7981318 *Nov 6, 2007Jul 19, 2011Sagami Chemical Research CenterReaction reagent for trifluoromethylation
US7985286Nov 24, 2008Jul 26, 2011Xerox CorporationSolid inks with lower coefficient of friction
CN102041134BDec 25, 2010Aug 21, 2013锦州惠发天合化学有限公司Preparation method of lubricating oil containing fluorine
CN102154052BJan 29, 2011Jul 17, 2013锦州惠发天合化学有限公司Preparation method of fluorine resin
EP1364934A1 *Feb 5, 2002Nov 26, 2003Daikin Industries, Ltd.Method for producing fluoroalkyl iodide telomer mixture and method for producing fluorine-containing (meth)acrylate ester
EP2246324A1Apr 21, 2009Nov 3, 2010Maflon S.R.L.Sulphonic function fluorine compounds and their use
WO2011152499A1Jun 2, 2011Dec 8, 2011Asahi Glass Company, LimitedProcess for production of fluoroalkyl iodide
U.S. Classification570/139, 560/223, 585/502, 526/245, 252/8.62
International ClassificationC07C17/278
Cooperative ClassificationC07C17/278
European ClassificationC07C17/278