DE2250344B2 - PROCESS FOR THE PREPARATION OF DERIVATIVES OF TETRAFLUORAETHYLENE OLIGOMERS - Google Patents

Description

Carbonic acid, one and the normal salts of stronger y

Acids such as orthophosphoric acid. Under λ "- /

sair salts are salts of di- and polybasic f \ or [ \

Understood acids in which only part of the acidic / ^ \ / ^ - \

Hydrogen portion is replaced by the cation of the metal 65 CH ₃ CH ₃ CH ₃ CH ₃ . Under normal salts are such salts

understood, in which the acidic hydrogen content is reacted with a Tetrafluoräthylcnoligomer,

the cation of the metal is replaced. to give a compound of the formula R / OC ₆ H ₃ (CH ₃ ) ₂

result, the two methyl groups can be oxidized by the action of gaseous oxygen in the presence of a suitable catalyst. This gives a dicarboxylic acid of the formula R / OC ₆ H ;, (COOH) ₂ , which is a useful intermediate for the preparation of a condensation polymer which has perfluorocarbon side chains.

The reaction of the hydroxy compound and the perfluoroolefin is preferably an anhydrous Solvent carried out, with approximately equimolecular proportions of the reactants with each other Can be mixed when a reaction of a monohydroxy compound with one mole of the oligomer is desired. The proportions should of course be changed to 2: 1 mol if there are two molecules of the oligomer should react with a dihydroxy bond. The molar parts of the metal salt and the organic hydroxy compounds should be essentially the same, however, the use of a Excess, for example an excess of »o up to 100% of the metal salt is preferred if good yields are to be obtained.

The reaction temperature can be from room temperature up to 200 "C, and it should preferably 40 to 120 ° C. The temperature is expediently regulated by the fact that the reaction takes place during the The reflux temperature of the solvent is carried out. Suitable solvent media are polar Solvents, preferably ketones, nitriles. Amides and particularly preferred are aprotic solvents, such as dimethylformamide, acetonitrile, acetone and methyl ethyl ketone.

The use of the salt in the solid form is advantageous because here the excess salt and the Metal fluoride by-product of the reaction can be filtered off, the oligomer ether product in the solvent medium remains from which it. if it is mixable. extracted by distillation or if it is immiscible. by phase separation

(ic i game 1

To 125 g of the pentamer of tetrafluoroethylene and 25 g of anhydrous sodium carbonate in 350 cm ^{; 1} dry acetone, a solution of 24 g of phenol in 50 cm ^{3 of} acetone was slowly added with stirring. The mixture was held at 50 ° C. for 4 hours, then cooled and filtered. Most of the acetone was distilled off and the remainder was washed first with dilute sodium hydroxide solution and then with water. There remained 105 g of a pale yellow liquid, which was identified as tetrafluoroethylene pentamine phcnylether of the formula C ₁₀ Fi ₉ OC ₆ H ₅ .

Example 2

A solution of 9.4 g of phenol in 20 cm ^{3 of} dimethylformamide was slowly added with stirring to 50 g of pentamer and 14 g of anhydrous potassium carbonate in 130 cm ^{3 of dimethylformamide.} The mixture was kept at 50 ° C. for 4 hours with constant stirring, then cooled and filtered. The filtrate was poured into water and the lower layer was deposited, washed and identified as tetrafluoroethylene pentamer phenyl ether of the formula C ₁₀ F ₁₉ OC ₆ M ₅ . The yield was 43 g.

Example 3

To 50 g of the pentamer of tetrafluoroethylene and 17 g of anhydrous sodium bicarbonate in 130 cm ^{3 of} dimethylformamide, a solution of 9.4 g of phenol in 20 cm ^{3 of} dimethylformamide was slowly added with stirring. The mixture was kept under constant stirring for 4 hours at 6O ⁰ C, then cooled and filtered. The filtrate was poured into water and a lower layer was separated. This was washed and identified as a mixture of 30 g of unreacted tetrafluoroethylene pentamer (70%) and tetrafluoroethylene pentamer phenyl ether (30%) of the formula C ₁₁₁ F ₁₀ OC ₆ H ₅ .

Example 4

To 50 g of the pentamer of tetrafluoroethylene and 6.6 g of anhydrous lithium carbonate in 130 cm ^{3 of} dimethylformamide, a solution of 9.4 g of phenol in 20 cm ^{3 of} dimethylformamide was slowly added with stirring. The mixture was heated and stirred for 4 h at 60 "C, then cooled and filtered. The filtrate was poured into water and a lower layer was separated. This was washed with water and treated as a mixture (43g) of unreacted pentamer (35%). ) and tetrafluoroethylene pentamer phenyl ether (65%) of the formula C ₁₀ F ₁₉ OC ₆ H ₅ identified.

Example 5

To 50 g of the pentamer of tetrafluoroethylene and 14 g of anhydrous potassium carbonate in 130 cm ^{3 of} dimethylformamide, a solution of 10.8 g of p-cresol in 20 cm ^{3 of} dimethylformamide was slowly added with stirring. The mixture was heated and stirred at 60 ° C. for 4 h, then cooled and filtered. The filtrate was poured into water and the lower layer was separated. This was washed with water and identified as 45 g of a tetrafluoroethylene pentamer p-cresyl ether of the formula C ₁₀ F ₁₉ OC ₁ ) H ₄ CH ₃ .

Example 6

To 40 g of the tetramer of tetrifluoroethylene and 10.6 g of anhydrous sodium carbonate in 130 cm ^{3 of} dimethylformamide, a solution of 9.4 g of phenol in 20 cm ^{3 of} dimethylformamide was added with stirring. The mixture was then stirred with heating at 60 ° C. for an additional 4 hours, then cooled and filtered. The filtrate was poured into water and the lower layer was separated, washed with water and identified as 33 g of tetramer phenyl ether of the formula C ₈ F ₁₅ OC ₆ H ₅ .

Example 7

A solution of 3.1 g of phenol in 5 cm ^{3 of} acetonitrile was added to 12 g of tetrafluoroethylene and 3.2 g of anhydrous sodium carbonate in 16 cm ^{3 of acetonitrile.} The mixture was stirred for an additional 5 hours with heating at 450 ° C., then cooled and filtered. The filtrate was then washed in water and the lower layer was separated, washed with water and identified as a mixture of unreacted tetramer (40%) and tetrafluoroethylene tetramer phenyl ether (60%) of the formula C ₈ F ₁₅ OC ₆ H ₆ .

65

Example 8

A mixture of 55 g of the pentamer of tetrafluoroethylene, 14 g of potassium carbonate and Γ.5 g of methoxy

polyethylene glycol-350 in 150 cm ^{3 of} acetone was stirred and refluxed for 8 hours. It was then cooled, filtered and the solvent was distilled off from the filtrate on a rotary evaporator. The remaining pale yellow liquid was then analyzed, it consisted of a major portion of a compound of the formula

C ₁₀ F ₁₉ O (CH ₂ CH ₂ O) ^ H ₃ .
in which η had a mean value of 7. .
Example 9

A mixture of 55 g of the pentamer of tetrafluoroethylene, 14 g of potassium carbonate and 50 g of a sample of a polyethylene glycol which is commercially available under the name Carbowax 1000. in 150 cm ^{3 of} acetone was stirred and stirred under reflux for 8 h. The mixture was then cooled, filtered and the solvent was distilled off from the filtrate on a rotary evaporator. A pale yellow liquid remained as residue, which slowly solidified on cooling. Analysis has shown that this product consists of a major proportion of a compound of the formula

C ₁₀ F ₁₉ O (CHXH ₂ O) _n C ₁₀ F ₁₉
where #i has a mean value of 23.

Example 10

To 50 g of tetrafluoroethylene pentamer, 14 g of potassium carbonate and 130 cm ^{3 of} methyl ethyl ketone, a solution of 9.4 g of phenol in 20 cm ^{3 of} methyl ethyl ketone was slowly added with stirring. The mixture was stirred at 50 ° C. for 5 hours, then cooled to room temperature, filtered and washed in water. A lower layer which formed was deposited, washed with water and 95% tetrafluoroethylene pentamer phenyl ether of the formula by gas chromatography and infrared spectroscopy

C ₁₀ F ₁₉ OC ₆ H ₅

identified. The rest consisted of non-implemented Pe η tu in er.

Example 11

A mixture of 60 g of tetrafluoroethylene hexamer (C ₁₂ Fo,). 60.3 g of phenol and 10.6 g of sodium carbonate were stirred ^{in 60 cm 3 of dimethylformamide at 70 ° C. for 5 hours.} The inorganic solids were filtered off and the two liquid layers were separated. The lower layer was washed with water and dried to give, in 96 "yield, a product which was identified by analysis to be a compound of the formula Ci ₂ F ₂₃ OC ₆ H _5. The structure of this compound was determined by infrared - and NMR spectra confirmed.

Example 12

A solution of 9.4 g of phenol in 20 cm ^{3 of} acetone was slowly added to a stirred mixture of 50 g of tetrafluoroethylene pentamer, 60 g of trisodium orthophosphate and 130 cm ^{3 of acetone.} The mixture was stirred under reflux for 4 hours, then filtered and the filtrate poured into water. A lower ^a 5 layer separated and this was washed three times with water and identified by the infrared spectrum as tetrafluoroethylene pentamer phcnyl ether of the formula

yp
C ₁₀ F ₁₉ OC ₆ H ₅ identified. The yield was 24 g.

Example 13

A solution of 9.4 g of phenol in 20 cm ^{3 of} methyl ethyl ketone was added to a stirred mixture of 50 g of pentamer, 30 g of sodium metasilical and 130 cm ^{3 of methyl ethyl ketone.} The mixture was stirred for 5 hours at 50 ° C., then cooled, filtered and poured into water. A lower layer formed and this was deposited, washed and identified by its infrared spectrum as tetrafluoroethylene pentamer.

phenyl ether of the formula C ₁₀ F ₁₉ OC ₆ H ₅ identified. The yield was 40 g.

Claims (3)

The weakly acidic hydrogen is preferably derived from a mineral acid, for example from carbon Patent claims: J - ^ - orthophosphoric acid, pyrophosphoric acid, kie ". r cpic acid and boric acid. It has been found that salts 1. A process for the preparation of derivatives of "·""" _{enclosed type} (ie such a weak Tetrafluoräthylenoligomeren, characterized overall aej * se _{k sin} d _{basjsch a} Dinatriumorthokennzeichnet ls, one DSSS a tetrafluoro- acid) ^ _{sjnd jn the implementation, Example} . Ethylene oligomer (C ₂ F ₁ ) ,,, worm η is an integer pnosp - sodium and potassium carbonates and greater than 1, with an alcoholic or ^w ' ^e ' ^S _n ^e ? t. _bonate sodium melasilicate and trisodium phenolic OH group-containing organic - ^ ^st > ^u '" ^r ° _{h The} particularly preferred salts are compounds in the presence of the alkali metal salt .o orthophosphate. ^ ^. ^ ^ ^. ^ an acid which has a pK value of 6 or more ^the ^ * ™ £ ^e _{0T & Lnic} compound more than one owns, implements. ., contains holic or phenolic OH groups, see above 2. The method of claim I, characterized marked Liquor ^lsc J ^s ° P _{k of each} hydroxyl group instead is characterized in that mt reacting a Ol.go- Un ^dle ^ ^ _n ^J _derivatives are prepared _so mer of the formula (C ₂ F ₄ ) ,,, in which «is equal to 4, 5 or 6 .5 ^" ^ £, ° is _{a residue} of tetrafluoroethylene., -, lim-niers. In general it is not desirable 3. The method according to claim 1 and 2. daourch oil g ^ ^{rs ent} jj ' _sjch ^ "^ _two oligomer residues characterized in that one de implementation, n counter- £ * ™ ^ _fcü , _{found <and it is the selection} , If the alkali metal salt of a mineral acid has one or two oligomer residues with a pK value of not less than 7. ^. ^ ^η ^ _{Γ dje properties} , which are promoted in the product 'ΤVerehren according to claim I to 3. and on the application _purposes , fQ characterized that the implementation at a ^^^^^^^^! ΓΖ ^ ^Τ Τ ^ ίΓη ^ Α ^ ί7ί ^ ¹ thereby> 5 ferment ^ the, ichte --g characterized by the fact that the implementation at Tenv Fonnstuckcn -n ^ -en ^ us.de "^ c _n temperatures within the range from 40 to 120 C ^^^ _Hy is droxyverbindung bound durchturirt. ^^ ^ _al jphatic, aromatic or cyclic 30 R _{esl se} jn. The remainder can by nature be a saturated or unsaturated hydrocarbon, In the German patent 16 18 523 and in that «^^ 2 ^ German Offenleeungsschrift 22 15 385 are reaction groups with other atoms than carbon ϊϋ, ΐη described by the ether derivatives of and hydrogen peat (but preferably only oxygen. TÄoÄnoSomcren can be produced- 35 atoms) contain ™ ^^. ^ ™ ^b ^^ hen it has now been found that when using Gruppe, d.e through the alkali metal allsal / akt v.erte Metal salts with basic properties similar um- nucleophilic reaction of the hydroxyl group does not Influences with organic 'hydroxy compounds. The substances should be inert towards scm can be carried out 'this salt, they are preferably ether or ^dU; f: haisom, "a method for manufacturing, 0 _re ste As Subs.ituenten the groups, uelche. hlli ih repeating Oxyathylcn- Oxyiiicti.y.cn- your The hrl development of derivatives of tetrafluoroethylene oligomers repeating Oxyäthylcn-. Oxymeiliyieii- or To the object that is characterized by it. that contain oxypropylene units, particularly preferably one is a Tctrafluoroäthylenoligomer (C ₂ F ₄ ) ,,. in which / ι because they have hydrophilic properties and with "An integer greater than 1" with an acodic hydrophobic peripheral group on the molecule as Iiolic or phenolic OH group-containing 45 give whole surface-active properties, organic compound in the presence of the alkali If the hydroxyl groups are only a non-sub- Metallsal7.es an acid, which contain a pK value of 6 or stiuiicrten hydrocarbon radical, for example not owns, implements. a benzene ring or another aromatic The value of /; is preferably greater than 3 and see the remainder, so substituents can be introduced is particularly preferably within the range of 50 den, for example by sulfonation, chloromethyl 4 to 6, as already in the German patent specification or nitration of the hydrocarbon residue, 16 18 523 executed. as ir. of German Offenlegungsschrift 22 15 385 The salt is preferably described as that of an alkali. This allows substituents. Which metal, and particularly preferred salts are those which have useful properties, for example poly- of the metals sodium and potassium. 55 merisable or hydrophilic properties, included Dic salts of alkali metals with weak acids lead to a number of compounds too are generally basic in character, and all of them result in the fluorocarbon group like salts are included for the process of the invention, which is derived from the oligomer, suitable. Suitable salts include both normal and If, for example, a xylenol, i.e. H. also acid salts from weak acids, for example ⁶⁰