Process for the Manufacture of Perfluoroalkyl Iodide-Olefine Adducts

The subject of the invention is a process for the manufacture of perfluoroalkyl iodide-olefine adducts which possess a perfluoroalkyl radical with 6 to 24 carbon atoms and an optionally substituted aliphatic or cycloaliphatic radical with at most 12 carbon atoms, characterised in that (a) at least one perfluoroalkyl iodide with 6 to 24 carbon atoms is reacted with (b) at least one optionally substituted linear or cyclic olefine which contains at most 12 carbon atoms, in the presence of (c) at least one amine and (d) at least one metal salt of a metal of Groups Ia to IVa or Ib to VIIIb of the periodic system, optionally in the form of an amine-metal salt complex, at 0 to 350.degree. C and 0 to 200 atmospheres gauge, and the product is deiodised if required.

The ratios of the quantities of the components (a), (b), (c) and (d) vary within rather wide limits, depending on the reactivity of the individual components and on the intended properties of the end products. The preferred procedure is that 1 mol of the component (a) is reacted with 1 to 10 moles of the component (b) in the presence of 0.05 to 10 mols of the component (c) and 0.003 to 20 mols of the component (d).

The perfluoroalkyl iodides to be used according to the invention can be either in the form of monoiodides or in the form of diiodides. These perfluoroalkyl iodides of the component (a) are preferably branched or unbranched perfluoroalkyl iodides with 6 to 18, especially 6 to 14, carbon atoms.

As the component (b), alkenes optionally substituted by functional groups and containing 2 to 6 carbon atoms, or at most olefines which contain 6 to 12 carbon atoms, or an optionally substituted styrene, are preferably used.

The functional groups which are optionally present as substituents of the component (b) are, for example, hydroxyl, halogen, epoxide, ester or amide groups. The substituents of the styrene can, for example, be halogen, alkyl, alkoxy or hydroxyl; in particular, methylstyrene may also be mentioned. All components (b) contain at least 2 hydrogen atoms in the olefinic double bond.

Amongst the alkenes which can be used as component (b), ethylene or propylene are particularly suitable.

Alkenes substituted by functional groups are, for example, allyl alcohol and also vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate and 1,2-dichloroethene; esters, for example lower alkyl esters, and amides of acrylic, methacrylic, crotonic, maleic, fumaric or itaconic acid, and in particular allyl formate and allyl acetate, diallyl fumarate and diallyl itaconate and divinyl fumarate and divinyl itaconate. Further, appropriate epoxides, for example of the formula ##STR1## are also suitable. Cyclic olefines of particular interest correspond, for example, to the formula ##STR2##

The adducts obtained according to the invention are frequently isomer mixtures, in that the perfluoroalkyl radical can add onto either the .alpha.- or the .beta.-carbon atom of the ethylenically unsaturated bond of the olefine. For reasons of simplicity, only one isomer form is mostly mentioned in the present instance.

The amines which can be used as component (c) are especially primary, secondary or tertiary aliphatic, heterocyclic or aromatic amines. Amines which contain at least one oxygen atom in the molecule are preferred. Amines which contain at least one hydroxyl group in the molecule are here particularly suitable. Amines which are capable of assuming an amphoteric configuration, such as the alkanolamines, are of particular interest. Such alkanolamines preferably contain 2 to 6 carbon atoms.

The following amines may, for example, be mentioned individually: N-ethylethanolamine, aminoethylisopropanolamine, diethylethanolamine, N-(2-hydroxyethyl)-ethylenediamine, isopropanolamine, triisopropanolamine, N-ethylethanolamine and N-methylethanolamine, and in particular diethanolamine, triethanolamine and preferably monoethanolamine. Furthermore, amines such as N-hydroxyethylmorpholine, morpholine, N-hydroxyethylpiperazine, 3-diethylamino-phenol, glycine or diethylamine can also be used.

Amongst the metal salts to be used according to the invention as component (d), metal salts of a metal of Groups Ib to VIIIb, especially of the 4th to 6th period of the periodic system, are above all suitable. Metal salts of metals of Groups Ib and IIb are at the same time particularly suitable, such as, for example, cuprous, silver, gold, zinc, cadmium or mercury salts. Other preferred metal salts are derived from metals of Groups IIIb or VIIIb, especially of the 4th or 5th period, or from metals of Groups IVb or Vb, especially of the 4th to 6th period of the periodic system. These are yttrium, titanium, zirconium, niobium, tantalum, manganese, iron, ruthenium or rhodium salts.

Representatives of metals of Group Ia are, for example, sodium and potassium and of Group IIa are, for example, magnesium, calcium, strontium or barium. The metals of Group IIIa include gallium, thallium and indium and of Group IVa include germanium, tin or lead.

All references to the periodic system are references to the periodic system according to Mendelejeff. In various systems the present groups VIIIa and VIIIb correspond to groups 0 and VIII respectively.

The halides, such as the bromides, iodides or preferably chlorides, of the appropriate metals have proved particularly advantageous. Additionally, however, appropriate phosphates, carbonates, nitrates, sulphates, cyanides, hydride, acetylacetonates or alcoholates, for example ethylates or methylates, can also be used. Salt mixtures can also be used, including mixtures of salts of metals of different valency.

Cuprous chloride has proved particularly suitable.

The components (c) and (d) are preferably employed as amine-metal salt complexes, to which an excess of the complex-forming amine can be added as a solvent. At the same time it is also possible for the amine-metal salt complex to contain an excess of unreacted metal salt.

To facilitate isolation and re-use of the amine-metal salt complex, binders and absorbents can also be conjointly used as carriers for the catalyst complex. Aluminum oxide, silicon dioxide, charcoal, kieselguhr or natural and synthetic molecular sieves are, for example, suitable for this purpose.

The reaction of the components (a) and (b) preferably takes place at 60.degree. to 250.degree. C or especially at 120.degree. to 180.degree. C.

Depending on whether the boiling points of the components (a), (b) and (c) are below or above 60.degree. C, the reaction is appropriately carried out in an autoclave or in a non-pressure apparatus, at atmospheric pressure. In the autoclave, a pressure becomes established which depends on the initially introduced amounts of the components (a) and (b). The pressures lie in the range of 1-200 atmospheres gauge, preferably at 1 to 160 atmospheres gauge, depending on the components undergoing the reaction. The reaction can be carried out continuously or batchwise.

The reaction takes place smoothly. In each case, mixtures of products of perfluoroalkyl iodides are obtained, mainly consisting of 1:1 adducts.

The reaction can be carried out in the absence or presence of a solvent. Suitable solvents are, for example, fluorinated alkanes, fluorinated halogenoalkanes, alcohols, ethers, aromatic hydrocarbons or cycloaliphatic compounds.

The perfluoroalkyl iodide-olefine adducts possessing functional groups are valuable intermediate products which can be used for the synthesis of products used for practical applications, for example for imparting oleophobic and hydrophobic properties.

By splitting off iodine by hydrogenation, or by splitting off hydrogen iodide, perfluoroalkylalkenes and perfluoroalkanes are obtained from the iodides. The perfluoroalkylalkenes can be converted into alkanes by subsequent hydrogenation. The following reaction routes may be mentioned as a possible selection: ##STR3##

In some cases, the splitting off of hydrogen iodide already occurs during the reaction of the perfluoroalkyl iodides with the olefine. The resulting products then contain a double bond.

The reactive functional groups X can be hydroxyl, halogen, epoxide, ester or amide groups.

After esterification of the hydroxyl group with acrylic, methacrylic, crotonic, itaconic, fumaric or maleic acid or with, for example, allyl isocyanate, reactive esters or carbanates are produced, which can be polymerised.

Reaction of an amine group with an acid chloride of the abovementioned acids yields a reactive amide which can be polymerised.

Carboxyl groups can be reacted to give vinyl esters. Epoxides can be used directly, or are reacted with the above unsaturated acids to give reactive esters which can in turn again be polymerised. Amides can be crosslinked as such or as methylolamides with aminoplasts.

The products for practical application manufactured from the intermediate products described above are very suitable for finishing textiles, paper and leather and also other solids, for example wood, metals or glass, but especially for rendering such substrates oleophobic or hydrophobic.

500 g of a perfluoroalkyl iodide telomer consisting of 30% of n-perfluorohexyl iodide, 46% of n-perfluorooctyl iodide, 20.5% of n-perfluorodecyl iodide + C.sub.4, C.sub.12 and C.sub.14 perfluoroalkyl iodides, together with 1 g of Cu.sup.I Cl and 5 g of ethanolamine are introduced into a 1 liter stainless steel autoclave. An excess of ethylene is then injected. The autoclave is heated to 140.degree. C over the course of 45 minutes and is kept at this temperature for 45 minutes. Shortly before reaching the reaction temperature, the pressure in the autoclave already begins to drop from 138 atmospheres gauge to 130 atmospheres gauge and remains constant thereat after 30 minutes.

530 g of solid white waxy substance are recovered from the autoclave and distilled in vacuo. Hereupon a total fracton of 484 g (boiling point 29 to 150.degree. C/5 mm Hg) of a semi-solid white substance are isolated.

22 g of starting material are isolated from the cooled trap. Analyses by gas chromatography and mass spectrography yield the following result:

Relative to converted starting material (M = 546), the yield of perfluoroalkylalkyl iodide (M = 574), calculated for the batch, is

500 g of a perfluoroalkyl iodide telomer consisting of 30% of n-perfluorohexyl iodide, 46% of n-perfluorooctyl iodide, 20.5% of n-perfluorodecyl iodide + C.sub.4, C.sub.12 and C.sub.14 perfluoroalkyl iodides together with 1 g of Cu.sup.I Cl and 5 g of ethanolamine are introduced into a 1 liter stainless steel autoclave. An excess of propylene is then injected. The autoclave is heated to 140.degree. C over the course of 45 minutes and left at this temperature for 45 minutes. As the reaction temperature is reached, the pressure drops over the course of 20 minutes from 20 atmospheres gauge to 15 atmospheres gauge and remains constant for the remaining duration of the reaction.

509 g of light brown, viscose substance are recovered from the autoclave and distilled in vacuo. Hereupon a total fraction of 460 g (boiling point 33.degree. to 150.degree. C/10 mm Hg) of fluid-solid, white substance is isolated.

33 g of starting material are isolated from the cooled trap. Analyses by gas chromatography and mass spectrography yield the following results:

Relative to converted starting material (M = 546), the yield of perfluoroalkyl iodide (M = 588), calculated for the batch, is

54.6 g of a perfluoroalkyl iodide telomer consisting of 30% of n-perfluorohexyl iodide, 46% of n-perfluorooctyl iodide, 20.5% of n-perfluorodecyl iodide + C.sub.4, C.sub.12 and C.sub.14 perfluoroalkyl iodides and 11.2 g of .DELTA..sup.3 -tetrahydrobenzyl alcohol are introduced into a 3000 ml stainless steel autoclave. 100 mg of Cu.sup.I Cl and 1 g of ethanolamine are used as the catalyst. The reaction mixture is heated to 100.degree. C, whereupon a reaction temperature of 150.degree. to 160.degree. C rapidly becomes established. The reaction mixture is kept at this temperature for 90 minutes. The pressure is 2 atmospheres gauge. After cooling the autoclave, 64 g of dark brown liquid substance are obtained. This crude product is dissolved in 250 ml of diethyl ether, the solution is washed three times with 50 ml of water and dried with sodium sulphate, and the ether is distilled off. A vacuum distillation of 58 g of purified substance gives the following:

By recording a mass spectrum of Fraction 2, compounds of the formula ##STR7## are identified by their "parent peaks" M = 558, 658 and 758.

The yield of the above compounds from Fractions 1 + 2 of the reaction described is

relative to an average molecular weight of 658.

13.2 g of distillate (boiling point 65.degree. to 70.degree. C, 3 mm Hg) are treated with 50 ml of 50% strength potassium hydroxide solution in a 100 ml round flask and a steam distillation is started immediately. Hereupon 6.6 g of a clear, colourless substance are obtained, having a boiling point of 45.degree. to 100.degree. C/12 mm Hg after distillation. The following compounds are identified by recording a mass spectrum: ##STR8## Relative to an average molecular weight of the starting material of 658 and an average molecular weight of the end product of 530, the yield is 66% of theory.

54.6 g of a perfluoroalkyl iodide telomer consisting of 30% of n-perfluoroalkyl iodide, 46% of n-perfluorooctyl iodide, 20.5% of n-perfluorodecyl iodide + C.sub.4, C.sub.12 and C.sub.14 perfluoroalkyl iodides, together with 48 g of an epoxide of the formula ##STR9## are introduced into a 300 ml stainless steel autoclave. 100 ml of Cu.sup.I Cl and 1 g of triethanolamine are used as the catalyst. The reaction mixture is kept at 140.degree. to 158.degree. C for 135 minutes and is then discharged. Pressure 1 atmosphere gauge. 97 g of brown crude product are dissolved in 250 ml of ether, the solution is washed three times with 50 ml of water until neutral and dried with sodium sulphate, and the ether is distilled off. Yield: 95 g = 93% of theory. Calculated with regard to a compound of the formula ##STR10## the epoxide content is 100%.

Recording a mass spectrum shows M + H = 643, 743, 843, M - H = 641, 741, 841, and a corresponding decomposition series, starting with M - I, = 515, 615, 715.

54.6 g of a perfluoroalkyl iodide telomer consisting of 30% of n-perfluorohexyl iodide, 46% of n-perfluorooctyl iodide, 20.5% of n-perfluorodecyl iodide + C.sub.4, C.sub.12 and C.sub.14 perfluoroalkyl iodides, and 5.8 g of allyl alcohol are introduced into a 300 ml stainless steel autoclave. 100 mg of Cu.sup.I Cl and 1 g of ethanolamine are used as the catalyst.

The reaction mixture is heated to 100.degree. C, whereupon a reaction temperature of 140.degree. to 155.degree. C rapidly becomes established. This temperature is maintained for 120 minutes. The pressure is 2 atmospheres gauge. After cooling the autoclave, 50 g of brown viscous substance are discharged. This substance is distilled in vacuo.

According to a mass spectrum of Fraction 1, compounds of the formula ##STR11## are obtained. The yield is 29/60.4 = 48.0% with regard to an average molecular weight of 604.

Elimination of HI from the above compounds:

a. 26 g of distillate (boiling point 40.degree. to 110.degree. C, 2 mm Hg) are treated with 50 ml of 50% strength potassium hydroxide solution in a 100 ml round flask and a steam distillation is started immediately.

Hereupon, 12.7 g of a clear yellow liquid are isolated, which after distillation boils at 38 to 93.degree. C/15 mm Hg.

The following compounds are identified by recording a mass spectrum: (107) CF.sub.3 (CF.sub.2).sub.n --CH.dbd.CH--CH.sub.2 OH n = 5, 7, 9; M = 376, 476, 576. The yield is 12.2/20.4 = 62.25% of theory with regard to an average molecular weight of 476.

b. The procedure described under (a) is followed, but instead of the 50% strength potassium hydroxide solution 30 g of pulverulent potassium hydroxide in 100 ml of epichlorohydrin are employed. During the reaction, which lasts 5 hours, the water is removed azeotropically. An epoxide of the formula ##STR12## n = 5, 7, 9 is obtained. Yield 71.5%; epoxide content 93.7% of theory.

55 g of a compound of the formula ##STR13## wherein n is 5, 7, 9, are dissolved in a mixture of 100 ml of ethyl acetate and 20 ml of glacial acetic acid.

6 g of zinc dust are added to this solution and HCl gas is passed in for 5 minutes at the rate of 20 bubbles/minute. The reaction mixture is kept for 5 hours at the reflux temperature and is then cooled and filtered, and the solution is concentrated. The residue is distilled in a high vacuum and yields 18.6 g of a cream-coloured substance. Melting point 167.degree. - 204.degree. C/0.1 mm Hg. The yield is 42% of theory.

Recording a mass spectrum (M 420, 520, 620) confirms the following structure ##STR14## n = 5, 7, 9.

The above ester can be converted into the free acid by saponification.

Further esters are manufactured in accordance with the above example, for instance ##STR15##

The table which follows summarises the experimental conditions for carrying out Examples 7 to 72 and the results obtained. The calculation of the effective yield is shown for the case of Example 7.

In each case 150 g (0.3 mol = 100%) of a perfluoroalkyl iodide telomer consisting of 23.5% of n-perfluorohexyl iodide (M = 446), 44.9% of n-perfluorooctyl iodide (M = 546), 26.1% of n-perfluorodecyl iodide (M = 646), 2.0% of n-perfluorododecyl iodide (M = 746) + further perfluoro compound are reacted with 68 g (0.6 mol = 200%) of 1-octent in accordance with Example 1. 36.04 g of 1-octent (107%), 5 g of the perfluoroalkyl iodide (3.4%) and 141.25 g of reaction product are obtained.

The product is identified by gas chromatography and mass spectrum.

The effective yield from 145 g (150 - 5) of the perfluoroalkyl iodide is:

177.48 g is the theoretical yield at 100% conversion. The yields are calculated for an average molecular weight of the perfluoroalkyl iodide of 546.

The amount of the perfluoroalkyl iodide employed is always 96.6% and the percentages of the olefines employed are indicated in each case.

In the table the symbols furthermore have the following meaning:

Ea = ethanolamine

Dea = diethanolamine

Tea = triethanolamine

Al.sub.2 O.sub.3 = aluminum oxide for chromatography

SiO.sub.2 = silica gel for use for distribution chromatography or kieselguhr or molecular sieve

R.sub.f = perfluoroalkyl radical

Me = metal.

The ethanolamine present in excess is, in this case, capable of eliminating hydrogen iodide from the resulting alkyl iodide in the reaction mixture, and of forming an alkene. The yield was therefore calculated with regard to 1-perfluoroheptyl-2-dimethyl-ethylene.