DE1518699A1 - Process for the production of perfluorocarboxylic acids - Google Patents

Description

Patent attorneys

Diving, by Kreisler Dr.-ing. Schönwald Dr.-lng.Th.Meyer Dr.Fues Dipl.-Chem. Alek von Kreis! Dipl.-Chem. Carole Keller Dr.-Ing. Klöpsch Cologne, Delchmennhau

Daikin Kofiyo Kabushlkl Kalshn, Shin-hankyu Bullding, 3 Umeda, Klta-ku, Osaka-shl (Jnpan). Process for the preparation of perfluoroorbonic acids

The invention relates to a process for the formation of aliphatic (J _t > J-Di-Ctrifluoromethyl) -porfluorocarbon-

eäurt? n, which is an end-to-end group of the formula

contain·

It was found that the straight-chain perfluoro- carbonoäuron and the branched PerfluoroarbonsUuron, the

3 \ an endogenous group of the formula ^ -CP- containing,

CP ₃

There are considerable differences, and that the latter are far superior to the more erotic ones. Contrary to the invention, there is a method for the heratellun ^vr "n verbose aliphutiochen" J _f ^ -J) i- (trifluoromethyl) -prriuorcurbona acids, which are used as a side chain one ends permanently containing irioluomethyl group and the following properties on weleeni oils have the remarkable ability to reduce the surface tension considerably in liquid media. Their surface tension in watery media is at most 18 Iyn / cm at or approximately at the critical concentration of them are advantageous AuB £ jan; eEiaterlallen

209817 / U96

BATH ORIGINAL

for the production of valuable water and oil repellants Hittoi and surface-active agents as well as for al »Horetstellung vorfiohledenci * Types of fluorine-containing compounds ·

VXn invention compounds have the general formula

CP,

cp ".

(CP ₂ ) _n C00H

where η «in · integer from 2 bio 21 · under dien · Formula drop the following compounds!

link

ßiedo- connection Period. C ______

Oie-de-

pun? ct> C.

¹⁵⁷

CP,

CP (CP ₂ ) ₄ C00H

CP (CPg) ₃ COOH

CP ₃

_cp / CP (CPg) ₅ COOH

CP,

205

• ⁱ J> CP (CP ₂ ) ₆ C00n 218 ^ CP (CPg) ₁₄ COOH 315

C * ·> CP ^

^ CP (CPg) ₇ COOH

CP,

240 /

50 Ba H <

0P (0P ₂ ) ₀ C00H

CP, CP,

228 /

30th

3 ^

^l ^> CP (CP ₂ ) ₉ C00n

CP,

258 /

50 at the H |

/ CP (CPg) ₁₀ COOH 27.0

CP

> CP (CPg) ₁₈ COOH

264/50 na H |

282

CP

CP,

209817 / U96

BATH ORIGINAL

268 /

50 aa H |

* ^ CP (CP ₉ K ₉ COOH 295 - ^ CP (CP ₃ ) P _n COOH 274 / ^ ^{2 ΊΖ} CP ^ * ^d0 50 on

y (o) \ * 305 - ³ ^ P (CP ₂ U ₁ COOH 284 / _cp / 2 13 _cy x- <: «n 50 ism Hg

Pie compounds of the above form in which η is a If the temperature ranges from 2-6, the ramperatures are liquid, while in cases where η has a value of 7-21, at Baust * are temperature resistant · All compounds of these formulas are acidic and have excellent tfärrae-, chemical and Cousin resistance. On their low surface tension in aqueous media has already been pointed out

As with the usual straight-chain aliphatic perfluorocarboxylic acids, the ability of the branched aliphatic, jnj-T'i-itrifluonaethyD-porfluorocarboxylic acids to reduce their surface tension in liquid chemicals decreases with increasing chain length Perfluoroarboxylic acids, however, the pre-bonds produced by the invention with the same chain length or the same carbon number have a significantly higher surface tension branched compounds of the formula _{cp prepared according to the invention}

³ > CF (CF ₉ ) ₉ COOH,

CP ₃ ⁴ ^

which are tait A boseichret in the figure, depending on the concentration in iräoorigen I'edien compared to usual straight-chain aliphatic perfluorocarboxylic acids dt? r Ponaeln CP ₃ (CP ₂ ) ₃ COOH and CP ₃ (CP ₂ ) .COOH, the ait B. and C are shown is · Pig · 2 is a graphic

209817 / U96 BATHROOM ORIGlNAt

Establishment of the invention-related connection of the Porxael

³ / CP (CP ₂ ) ₄ C00n _{f the CP 3} marked in the figure with D

lot, depending on the concentration in comparison SEU the straight-chain aliphatic, forfluorocarboxylic acids of the Pornein CP ₃ (CP ₂ J ₅ COOH and CP ₃ (CP ₂ ^ COOH, which are denoted by S and?

You can now clearly see these figures the non-inventive compounds A and D in comparison now the usual straight connections B and E, which the the same length as the connections A and D, always a lower surface tension »below 16 dynes / is approx. at concentrations above and below the critical micron concentration Compounds A and D always have a lower surface tension, in particular a slightly lower surface tension at a concentration below the critical one Kizc & concentration, as the straight-chain compounds C and P, which has the same C number as compounds A and IV and have a greater chain length than these compounds.

The properties described in the Toroto show that that the branched compounds prepared according to the invention and the salts, esters, amides derived from them, Nitriles and polymers have a far higher V / Na and CO release capacity and a far higher surface activity have straight-chain aliphaticheη as dio entapreohonden Perfluorocarboxylic acids and their torivate · At Vorouohen in this direction was a raised one üntersohiod between the known pre-bindings and connections according to the invention found "Selnpiolsv / ise a propanollus arose, the 0.1 Gβw, - ^ dos Chrookomplexoe one exactly of the invention

established connection of the Poxzael

CP ^

contains, a gas · the ability to de »Sindringen of Uaaohi-

2098Ί7 / 1Α96

BATH ORIGINAL '

Nine oil and liquid paraffin to withstand more every 24 hours, while the compound dor formula CP ^ (CP ₂ ) 4COOII, which has the same carbon number, but a longer period of time, protects the oasis under the same conditions at most 10 minutes A compound of the Poraol CP-j (CP ₂ KCOOn, which has the same Xotten length "does not prevent the binding of liquid paraffin under the same soilingson''T> In this way, the compounds according to the invention do not only have excellent Abv / oisungavepotigen for Waaner and oil In the form of the chron complexes, but also in the form of the zirconium salt, aluainium, or the polyesters obtained by etherification of polyvinyl alcohol or the chewing-like "poly" crystallization of substances made from any number of inventions, aliphatic perfluorocarboxylic acids and allyl unsaturated alcohols (β · · allyl unsaturated alcohols) as well as in pom of polymers, which by unsaturated meters atopiele-

CP, weis · der Poratl ^^ CPCCP ^ J ^ CONIICcH ;,) OOCH'-CHj »derived

are where η is said; "Q a" has a meaning as a whole number is from 2-4 and R * for T / aooeratoff or a Hothylrest stands,

The compounds prepared according to the invention and their · rorivato have fornor in considerable IUaOe the ability » Polyfluorovinyl pre-bonds, polyfluoroalkenes and their poly zaore to emulsify in nilnorigen media, making them very advantageous agents for the emulsion polymerization of these represent unsaturated polyfluorocompounds · For example, with the compound of the invention

(see Example 1) where it achieves a higher reaction rate and polymer concentration than with the straight connection of the formula CP- * (CP ₂ ) ^ COOKa, which has the gloioh · C number, but «in · a longer chain when the connections

al · Emulsifiers for the polyetherization of tetrafluoroethylene

209 817/1496 BAD ORIQINAt. <

In other words, it is not exposed to the action of ionizing agents Rays are used. As beneficial · emulsifiers laooon eich, the carboxylic acids and those derived from them

Sale dor Po na el ^> CP (CP) _n , COOLI ₁ where U is sodium,

Kaliua or Annoniun otcht and n »a whole number from 2-21 * inabcoonder · from 3-10 is, use. Iiio connections These porael not only have a very high level of emulsification, but also of high levels of chemicals, chemicals and chemicals Weather resistance, eo that watery Eauloionen of ir.it Ihiion «mulgiortott fluorine content polymers valuable · product · of versatile applicability are · Boiopiolswoiee laooen the anionaktivon compounds of Porael

³ ^ CP (CP ₂ J _n CQO (CH ₂ ) ₂ 0 (CHgCHgO) ^, where η di · called · CP ₃

Has meaning and r is a gan & o number of 1 * 12 let, and the cation-active compounds from Porael

Ultimately, more beneficial as a surface-active agent insert·

The gcn & Q of the invention ;; "eotollten aliphatic u)"U> X) i- (trlfluoraothyl) -perfluorocarbon acids can also be found in the form of the original carboxylic acid or the ßUurectnhydrlds In advantageous Y / oiso aloodor accelerator for the dinination reaction of the foliation reaction Use silicone. I) Io derivatives of the Poxael

CP

where η dl · named · has meaning are also special effective amphibious agent for cockroaches

209817 / 1A96 BATH ORIGINAL

The found 3 compounds and their derivatives have thus not only very fourfold properties as such, but can also be used as output products for manufacture of water and oil repellants, surface-active agents Agents, anti-fouling agents, dyes, insect attractants, insecticides, heat-resistant resins and rubbers and the like can be used.

The pre-binding requirements of the invention also have one lower melting point and higher solubility in solvents al3 the straight-chain aliphatic Perfluorcarbon3üuron with the corresponding C number, so that they are easier to handle than the usual carboxylic acids For example, the compound according to the invention is the formal

CP (CF ₂ ) ^ COOH a liquid at room temperature because

its melting point is about -10 ⁰ C, while the compound of the formula CF (CF ₂₎ ^ COOH with the corresponding number of carbon atoms is solid at room temperature because their amounts melting point 55 ° C.

The derivatives of the compounds according to the invention are also in Solvents are easily soluble. A polyester, the one Has ester number of $ 90 and has been made ^. by a Polyvinyl alcohol with a degree of polymerisation of 500 and a saponification number of about 100 in dimethylformamide with an inventive acid chloride of the formula

CP (CP ₂ ) ^ COOH is esterified, for example

wise easily dissolved in acetone or trifluorotrichloroethane to form a homogeneous solution, while a polyester with an ester number of 90 ^, which under the same conditions with a compound of the formula CP »(CP ₂ ) ^ COOH, which has the corresponding carbon number , has been produced, is difficult to dissolve in trifluorotrichloroethane and takes a long time

209817 / U96
BATH ORIGINAL

VI \ J V- / \ J

must be stirred before it is completely dissolved. Floodplains this confirms that the compounds and their derivatives prepared according to the invention are easy and versatile are applicable «

As already mentioned, the inventions show u> »u> -Di- (trifluoromethyl / perfluorocarboxylic acids with increasing chain lung a gradual decrease in surface tension However, this property almost disappears when η has a value reached by 10 or achr, sSMffaQ. the synthesis of the compounds as such / behaving more difficult ulcd. Most beneficial are also those compounds according to the invention of named continuity, where η is in the range of 3-10

The carboxylic acids according to the invention are oxidized any compounds of the following formulas produced!

CP 3 (II)

(III)

³ ^ CP (CP CP) (CH-CX.) _O X ₆ (IV)

Y m -Br or -J

X ₁ and X _5. «-H, -P, -Cl, -Br or r« 7 »but not equal to · ^{1 Λ} leading to -P;

Xj and X ₄ - -H, -P, -Cl, -Br, -J, -OH, -R, -OR, -OCR,

-OOCn, -ROH, COOR or -COOH; R «alkyl with 1-5 C atoms;

Xc and Xg m -H, -Cl, -Br or J, but not equilateral ³ ° -Hj

α ·· an integer from 1-10

ρ «2 or)

209817 / 143G

BATH ORIGINAL

.'JIs examples of connections dor Poraeln Ι-Γ7 # boi donon ^J J>" ^ötr E ¹¹ ^ ^00111103 · * for the sake of me called Rj

is called »bo ion

E ₁ CP ₂ CCl ₂ J

dor Pormel Is

K _x CP ₂ CPClBr

R _f CF ₂ CClEJ

2) Connections of the Pornel Ils
RjCH ₂ CHCIJ RjCII ₂ CH ₂ J RjCH ₂ CH ₂ Br RjCHClCPClBr RjCH ₂ CnJOOCCH ₃

3) Connections of the Γοηαοί Ills

B ^ CH-CIICOOH

RjCIi-CHCOOCH ₃ RjCH »CHCH ₃

4) Pre-binding on the Porxael IVi

Rj (CH-CCl) ₂ Cl

RjCP ₂ CPHJ RjCP ₂ CH ₂ J

RjCHClCHClJ ßjCII ₂ CHJ000CH ₃ RjCn ₂ CHJCH ₂ OH

RjCH) -CPCl RjCH-CHOOCCH ₃

Ala Uittel been for the oxidation of compounds of Pornein I-IV Kaliumdioüroaat and and ore Tiichronate, Kaliunpcmang ana to and similar Pornansiinato, smoking © SChv / cf eloüur · or Sauerotoff vorwcndöt · Gccignote Oxydationnbedingungen in Ab inßigkoit on the type of Ausgangonaterialo and su Ycraanaenuon Osydationsmittel su eruittcln. 1, 'aohetehond oind oSÄSadvantageousoten BesinSangen for dleeo Oxydation listed as an example

209817/1496 BAD ORIGINAL

Α) Oxidation dor V ^ rblndu n / ton ^ cr . "Formula I.

The beneficial cotonic oxidizer for oxidation the connections of the lOnaol I aind Sauorotoff and smoking « Sulfuric acid.

i \) Oxidation nlt fjouemtofft

Daa Auoßanssnaterial is nit Cauerntoff, the llenge in oinor vorwendet of 3-7 moles per haul doo Auc angGnateriala ^ T / _t ird at I>; atrahlung nit light inabeaondere oichtbarem light odor Ultraviolottlicht oxidized. Dor AnfunßBdruck the Keaktion reads crr / iochon llornaldruck and 20 KSS / anr and di · KerJctior.ßtciaperatur sr.7iachon Rauntenperatur and OTWA 50 ⁰ C. As Beaouleunigcr chlorine can "iodine or Vaoncrdanpf in β in tr lüonco of 1.10 EUR am. 'iiuinolar lleng · vcrv / cndot be. Ala source dos oxygen was.! En beneficial oxygen or eauorotoffhaltiße Gaoo, wio air, used »

h) Oxidation ,, HJ t ₁ ..rauohnn <* rr ^ ch

fuming black folic acid is used in a water that is 2 to 6 times the doo uruprünlichen Cov / ichta the Ausassanßciaatorialo, calculated alo SO ,, speaks. the Reaction is carried out at a temperature of 90-170 ° C or above boi · lioraaldruok or, if applicable, eienenfallo increased ^ jruok carried out.

B) Oxidation <Ior Vftrbindunnon der Foracl II am IVt

In addition to the oacyiation agents described above under A, Pernansanate or Dichroaate in an amount of 1.5-5 Hol per oil can be used in combination with organic acid, e.g. Hatriuohydroxyd odor j: - '»liunhydroxyd, dorcn Lon ^ e je.v · ile £ v / l8ohon einor eq, uiiao laren Uonge and 10 KoI per UoI doa Oxydationcaittele left, be used. Pio reaction is conducted at a Ttnperatur of Raimtenperatur to about 15O ⁰ C and a Pniak of Korsialdruck are too oxy- to Pa & pfdruck <5or

? Υ? r ^ lndujig. carried out at the reaction period _for 2Ö9817 / 149T6

BATH ORIGINAL

44 "

C) Synthesis of Au3pgnr; snritcrial3

The preliminary bindings of the form I to IV, dlo goaSas of the invention are used as Ausgonssnateriol, can be produced by various methods. Most advantageously they will be eu3 compounds of the formula * -

CP (CF ₂ CP ₂ ) _m Y (V)

where Y and rs have the given meaning, produced *

1 ) Synthesis of the compounds of the formula I :

The compounds of the formula I are prepared by the addition reaction of a compound of the formula V and a compound of the formula CP ₂ -CX ₁ X ₂ * ^{in which χ} χ and ^x g have ^the meaning 8 ^βηβηη & · in the following white t

, CF (CP ₂ CF ₂ ) _n Y + CF ₂ -CX _x X ₁ γι

^? V

Addition reaction

2.) 5yntho3o dor connection of the Fornel II

The compounds of the formula II are obtained by the addition reaction of a compound of the formula V and a prebond of the formula CHg-CX ^ X ^, where X, and X ^ have the meaning given, manufactured as follows!

: CF (CF ₂ CP ₂ ) _B Y + CH ₂ ^ X ₃ Xi _m

* V

CF
Addition action

II

209817 / 149B

BAD ORiGINAL

3) Synthooe flor compounds dor Pomel III

Tic compounds dor Porr: ol III throw through addition reaction of a compound of formula V and acetylene or by pehydrohalo £ onlorung (-12Y ₉ where Y has the meaning mentioned) tinor compound of formula II prepared as follows!

^{3 T} V.

Addlt ionoronlct lon > CP (OP ₂ CP ₂ ) _a CH «CHY

cp,

⁰ IHa

VIII

T (-ΠΥ).

he _y

• III

4)! Synthesis of Vorblndunnon dor Pomel IV

The pre-binding of Pornol IV are horgcatollt through rehydrohaloßoniGrunc (-KXg and -HY, τ / obei Xg and Y dia Have mentioned meaning) a connection of the Poraol

Xg) PY, in which Y, α and ρ are called

³ IX Bodeaneut have, and Uie alo by-product at dor IIcratellun | From compounds of formula II obtained using an uneeBättistcin compound άβτ Pormel χ CH ₂ «CX ^ Xg, where Xe and Xg have the meaning mentioned, takes place ·

209817/1496 \

BATH ORIGINAL

"> CF (C.

> CF (CP ₂ Cr ₂ ) ϊ + CH ₂ -CX ₅ X ₆
CP · »

IX

Denydrohalogenation (-HXg and -HY) \; WcP CP)

CP ₃

IV

The addition reaction of equations VI, VII and VIII is carried out by the previous reactionon under the action of light, heat or some other free radical-forming initiator Appearance connected. In order to improve the addition product oline formation of unorv7ünoohtor byproducts, the number of unsaturated compounds to be used is in view of the properties that can be used One example is a prebond with high propriety polyraerionation, β CII ₂ -CHCl, Cn ₂ -CHOOCCH ₃ , CH ₂ »CH ₂ , Cn ₂ « CHCOOCH ₃ or CH = CH, wi * d preferably in a UoiißQ of 0 , 1-0.9 KoI per haul of the pre-binding of Pomol V is used. With an increase in the uni3atzoo t / o, the uncontrolled compound is not added all at once, but in portions or continuously. An unsaturated compound with little self-polymerization, such as CHCl-CHCl, CP ₂ * CC1 ₂ or CP ₂ -CHP, is used or can be used in equiiaolar henge In the tjbercohuß about the connection of the Pomel V been told.

With the application of Lioht in the beginning of the reaction Visible light or ultraviolet light is preferred

2 0 9-8 1 7 / U 9 6

BATH ORIGINAL

at a temperature of Eauiaten: temperature bio about 1 '"> 0 ° C used · Tor Rcaktlonodruck varies with the tank pressure the Einoatsnateriale · Eoiopi & Gveioe can be C] Xj ⁰ CIiCl, CIU ⁰¹ OIIg, CILiCH oiler CFg ¹⁵ CIiH Vur £ u £ ov A reaction component with a higher boiling point is placed in a central orfenon vessel with cooling and a flow cooler Reaction by w'ärno auocelöat Tfird "is carried out a preference, ο ie β in a c ^cac hloo: 5onen vessel at a temperature of 150-250 ⁰ C or above. When using a free jjadilcalo-forming initiator" the reaction is zv. OcknliDig with a 2enporatur of er.below temperature to "et \ 7a 150 ⁰ C carried out under a Γ-ruok of 1-50 k3 / om" Suitable free radical initiators for the purposes of the invention are t-Butylhyclroperoxidf Pi-t-Butylperosycl, Bon2oyl peroxide, left isopropylporoxydioarbonate and similar orsaniccho peroxides or azobiaioobutyronitrile and ährllcho or ^ cmincho azo compounds

DchydiOhalogenation reaction according to Gloichunß IX and X can be carried out in different ways. Xthanol or Ioopropylalkohol _t in an open or Geochloaaonon vessel at a temperature of Eaunitenperatur to etv / a 100 ⁰ C performed «£ io Kinlialtunß cana beetirjator Reaktioncbedinßunsen is not orioruerlich in this Pcbydrohaloßonierung, you can by any known Met ho .lon be performed ·

209817 / U96
BATH ORIGINAL

CF, ^

D synthesis of

The compounds of the Fornsel V, nSalich

) _1n Y 0 in which η and Y have the meaning mentioned

have, and used as the starting material for the manufacture of the Compounds of the formulas 1 to IV used have been made by reacting perfluoroisopropyl halides of the formula

CFY # where Y has the meaning mentioned, with tetra-

fluorethylene produced by various processes. Eo However, the reaction under the action of carry out ionizing radiation (as described in the Japanese application 6569/1964 of Anrcelderin). the The reaction can also advantageously be carried out in the presence of an initiator which forms free radicals (as in the applicant's Japanese patent application 6570/1964 described)

For irradiation in the first-mentioned method, α-rays, Q-rays, y-rays, X-rays, neutrons, protons, neutrons and similar ionizing rays are suitable, with 7-rays, especially 7-rays emitted by Co, being the most advantageous «Die Dosage is in the range from 1 10 r / hour to 1 χ 10 r / hour, in particular from 1 χ 10 ^ r / hour to 3 1 χ 10 ** r / hour, preferably in the range of a Gcsacit dose of 1 χ 10 ^ to 1 χ 10 r. The Reaktionsteraperaturen and reaction pressures may be within a wide range · The reaction temperature is between the temperature of liquid nitrogen and about 150 ° C, in particular between -90 ⁰ C and 100 ° C · The reaction can warden at verninderte "or elevated pressure performed, but the reaction proceeds perfectly at normal pressure or pressures up to 50 kg / cm. The porfluoroisopropyl halide used is preferably in a 20 9-81 7 / U 96

BATH ORIGINAL

1518099

-a-

Amount of 1 to 10 hol per 10 to 1 mole of that to be used with it Tetrafluorüthylena used.

Benzoyl peroxide is suitable as free radical initiators for the last-mentioned execution of the reaction, Di-t-butyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide and similar organic peroxide and azobisobutyronitrile and andoro organic azo compounds, These initiators are used in amounts of 0.05 bi3 XO Gaw, £, in particular from 0.5 to 5% by weight, based on the feed material, The reaction conditions vary with the properties of the initiator used, however tile advantageous with a temperature ira Boreich from 50 to 200 C and a pressure of 5 to 200 kg / cm. In this reaction, the perfluoroisopropyl ha logenide in an amount of 1 to 5 moles per 5 to 1 mole Tetrafluoroethylene, preferably used in an amount of 1 to 3 moles per mole of betrafluorlithylcn. Regardless of dtjv whether it is ionizing rays or free radicals Initiators are used, the reaction can properly be carried out in batches or if the reaction components are added in portions or be carried out continuously

The desired aliphatic <v, << -Di- (trifluoraothyl) -perfluoroearboxylic acids According to the invention can be easily by converting the readily available perfluoroisopropyl halides with tetrafluoroethylene to form the compounds of formula V and subsequent conversion of these compounds to produce the compounds of the formulas I bl3 IV «

The following are the preferred processes employed by the invention for preparing the compounds of the formula ^ "^ -. *.

^ - CF (CF ₀ CP ₀ ) _M J * in which m the mentioned badoutung CFj < d. 4L xa

has to be applied.

1.) In a 500 cnr-RUhrautoclave from "HasteUoy-C"

2 0 9817 / U9G

BATH ORIGINAL

1ü5 S (0.625 mol) perfluoroisopropyl iodide from Porrael CP,

CPJ , 0.7 & t-butylhydropcroxyd and Jf, ^ g di-t-butyl

peroxide given · After cooling, do 3 mixture with flUsai-S «r The air in the autoclave was reduced Pressure evacuated · After adding 35 S tetrafluoroethylene the mixture was stirred while steam was being introduced became. The reaction temperature rose to 100.5 ° C. The maximum pressure reached 10 minutes after heating with steam 20.5 kg / cm, but the pressure subsequently fell gradually · 5 hours after the start of heating with Water vapor, the pressure had fallen to 6 kg / cra. Thereupon the stirrer was shut down and the steam supply cut off The autoclave was cooled with water and the connection probe fell the pressure to almost 0 ks / eni · The reaction products obtained weighed 217 ß The following compounds were obtained by fractionation:

CP.

not implemented

CP,

CPJ

CP,

CP ₁ CP,

CP. CP

CP, CP

CP, CP

CP (CP ₂ CP ₂ ) J.

CP (CP ₂ CP ₂ ), J.

Graon (mol) boiling point in ⁰ C /

Ed

.6 (0.472)

20.9 (0.0528) 86-88.5 / 7 ^ 0

25 * 5 (0.0510) 7 ^ -76 / 92-94 15 * 1 (0.0264) 69-72 / 10-11.5 10.5 (0.0176) 91-91.5 / 4.5-5.0

> 5 ^J Z09817 / 1

4.2 496

oonstice connections 5.4

BATH ORIGINAL

125-123 / 4.5-5.0

Among other things, perfluoroisopropyl iodide 24.5 & tetrafluoroethylene 9δ.1 £

2.) On the Woico described above, 295 β fll, 00 mol) of P ^ riVu ^ isopropyl iodide, 100 ε (1.0Q mol) of tetrafluoroethylene and 1.9 β (0 , 04Sl KoI) given azobisisobutyronitrile. Daa Goaloch was converted 10 3tundan at 100 to HO ⁰ C. The following compounds were obtained during fractionation:

CP (CP ₂ CP ₂ ) ^ J 15.0 β (0.0252 moles) 3

25.8 ß (0.0371 mol)

CP (CP ₂ CP ₂ J ₅ J 20.2 g (0.0254 mol)

other connections 16.4 g

ttaaatz: perfluoroisopropyl iodide 11.0 Totrafluorilthylon

j5.) In a pressure-resistant 150 cnr glass cylinder were 242.4 g (0.819 mol) perfluoroisopropyl iodide and 1δ.4 g (0.164 mol) Given tetrafluoroethylene. The mixture became liquid Nitrogen cooled. The cylinder was hermetically sealed and the air in the cylinder was evacuated. The cylinder Was then connected to the liquid nitrogen and gradually warmed to room temperature with starting materials were mixed well by stirring. Hochdca the Temperature of the mixture approx Pressure reached 1.6 kg / approx., The pressure-resistant cylinder became

209817 / U96

BATH ORIGINAL

at a distance of 20 cm from a co-source one Intensity arranged by 2CCO Curie. The genic became 2 hours before exposure to y-rays, which emitted by this radiation source · By fractionation the following products were obtained:

CF (CP ₂ CP ₂ ) J 4.4 g. Boiling point 30 ° C / 92.5 mm Hs

CF (CP ₂ C? ₂ ) ₂ J 0.6 G; Boiling point 29 ° C / 57 # 5 Dia

additive: perfluoroisopropyl iodide 1.50 ^ tetrafluoroethylene 8.24 #

Preferred implementation of the method according to the invention are described in the following examples}

Ball game 1

Synthesis of CF (CP ₂ ) ^ CCOH

In a 150 cn ^ autoclave made of "Hastelloy-C" 150 g (0.303 mol) of the compound ^ CP (CP ₂ CP ₂ ) ₂ J, 7 ß (0.250 mol])

Ethylene and 1 g of azobisioobutyronitrile. The one in the autoclave Existing air was evacuated and the goal was csriüirt for 5 hours at 60 to 70 ° C. After separation of 2.5 g Ethylene that had not been released was then reduced in the Autoclave fractionated, with 63.3 g of an addition producta

^CP 3N,
dor Portael ^, CP (CP ₂ Cp2) ₂ CI ^ CE ₂ J, 5.9 g other fractions

CF

and 79.3 g of not unoccupied ".CF (CP ^ CP ₀ ) _o J was obtained

BATH ORIGINAL

the.

In a 100-crr Vierholokolbon Ic3 g Koliunihydroxyd and 20 Q of ethanol was added with stirring, liach cuter Verclichuns were added portionwise 63 g of the crude CF

P ₂ CF ₂ J ₂ CIJ ₂ CH ₂ J succsobcn, whereby the reaction

temperature triggered by the cxothoraen reaction » was kept at about 50 to 3 60 ° C by means of a cooling belt. tlach to succeed; In addition, the temperature was increased to 80 ° C * whereupon was stirred for a further 1 hour · The product was then in 200 cnr of water ccoO - ^^ n. After separation of the oil phase was the liquid phase is extracted from chloroform The extract and the ulphaso were then combined with anhydrous Magneaiura sulfate dehydrated and dea Chloroformo fractionated, with 49.5 S (0.125 KoI) CP.

", CF (CF ₂ CP ₂ J ₂ CH ^ CH _2. The yield.

betrus

C (0.121 mol) of the product thus obtained were then at 120-135 ° C for 8 hours with a mixture of 74 β potassium dichronate, 162 g concentrated sulfuric acid and 58 ß distilled water and stirred with water steam distilled. The extract was neutralized with a 5 # aqueous potassium hydroxide solution, evaporated and dried. The solid residue obtained in this way became k> SchwofeIs & ure ceßeben and concentrated in UberschüsslGo ° distilled under changed pressure, with 43 β

-J ^ CF (CF ₀ CF ₀ ) o COOH vöa boiling point S5 to 3 Öü ° C / 6 bia δ

* ^ - «^ Ct Cm ^ m

£ j mm ils were obtained.

AnnIy; q ; CFH

Found: 25, o; 5 6Q

calculated: 2 ^, 2; ί 63, £> 0.24; 'J

BATH ORIGINAL

l / citere germ count:

ο 2ζ tendon point -10.5 to -11.0 C, τι ^ =

d? ⁵ - 1.76

The compound obtained on the Iteice was treated with sodium hydroxide neutralized and made from anhydrous toluene-n-butanol

uncrystallized, being dry

recovered, that had a strong influence on the emulsion polymerization of Tctrafluorüthyleijln aqueous media exercised.

800 ear were deoxidized in a 2 liter stirred autoclave given distilled V / 3sser, the 0.2 Gaw. $ of the compound

Ta and 6 Gow. £ η-cetane as stabilizer

gate contained. After evacuating the air present in the autoclave, gaseous tetrafluoroethylene was introduced in an amount of 6 kg / cra and stirred in completely. The mixture was then irradiated with 7 rays extracted from a Co source of 2000 Curie. As the polymerization proceeded, the reaction temperature gradually dropped. To compensate for the Tcmpcraturrückganges Tctrafluorfithylen was replenished in such a Konze, DAS3 the reaction pressure at 6 kg / ca was maintained. Nr.ch reaching a radiation dose of 8 χ 10 r liesa oan the mixture further

Post-polymerize for minutes. The dispersion obtained had a polymer concentration of 23.7% by weight. The maximum reaction rate was 4.1 mol / liter / hour. For comparison, when CF ^ (CP ₂ ) COONa was used as an emulsifier under the same conditions, a dispersion having a polymer concentration of 20% by weight was obtained, the axial reaction rate not exceeding 0.5 mol / liter / hour .

20981 7 / U96

BATH ORIGINAL

CP,

hesis of C? (CP ₂ ) _o CC0II

155 S (0.3> 2 KoI) CF ₂ J ^υηίί 1 # 7 2 azobialaabutyronitrile c

Since Cecil sch was tilted flüoaicor air oinsefrorcn After evaluation of the air present in the autoclave, 9 # 1 β (0.350 mol) of ßereinict03 Acefcylei ^ üsegobcn / what was 7 2tundan at 100 to 100 ⁰ C c, while heating with steam. 2.1 g of unreacted acetylene were then separated off. The reaction sora was fractionated, with 92.5 S (0.219 mol)
C? 2

CPCP ₂ CP ₂ CH «CHJ, 67 * 7 Z not know yet

CPCP ₂ CP ₂ ^ ^xm ^ * "t * S other substances were" rholtcn ·

92 g of the product 3 CFCP ₂ Cp ₂ CH-CIIJ were added

Cenisch of 175 £ Kaliu & dichromate oxidized yi & ζ concentrated sulfuric acid and 137 S doatilliertea Munster and · described dl "in case of game 1 Veiso worked" The erbmltenea product "contained 5 NC # 1 S (0, lß5 Hol)

^N CFCF ₂ CP ₂ C00H from boiling point 62 to 63 ⁰ CA * We 16 ca Hg.

The yield was 47.2 mol. Melting point -21.6 ° C, 1.2160, dp «1.65

209817 / U96 BATHROOM ORIGlNAt.

- 23 Example 3

Synthesis of CF (CF ₂ ) ^ COOH

he/

150 g. Of

CF,
(0.252 moles) - ^ CF (CF ₂ CF ₂ ) J, 12.5 g (0.200 moles) vinyl

Chloride and 1.9 g of azobislsobutyronitrile given. The mixture was frozen with liquid air. After the air had been evacuated from the autoclave, the mixture was ^{agitated for 90 minutes at HO 0} C while heating with superheated steam. The reactant pressure fell from the initial value of 7.8 kg / cm

to 2 kg / cm. With further cooling to room temperature the pressure in the autoclave fell to a value below normal atmospheric pressure, with unreacted vinyl chloride was deposited. The resulting liquid reaction mixture of 162.1 g was fractionated to give 38.1 g

CF ,. (0.064 moles) unreacted ^p CF (CF ₂ CF ₂ ), J, 118.5 g

CF, /

CF, _v ^p

(0.180 mol) ^p ^ CF (CF ₂ CF ₂ 5, CH ₂ CHCIJ and 5.4 g of other sub-

CF, ^/
punch were obtained. The yield was 95.8 molji.

CF
^Conversion : 5v CF (CF ₂ CF ₂ ), J: 7 ^, 6 MoIJi

CF, "

Vinyl chloride ι 100 mol *.

Into a 300cc four neck flask was 118.2 grams of the obtained

\ rvirT? _CF ₂ ), CH ₂ CHCU, 144 g of potassium dichromate and 113 g

given distilled water. Then 3 * 12 g of concentrated sulfuric acid were added in portions with stirring added within 2 hours. A very violent exotherm

^ 09817/1496

iSUe Below. ¹ lacan (■ ".. '..". Αι ... · ·· . - _Ί Λ - I tin Änoerungsges. V. 9/9/1967)

BAD ORIGINAU

Reaction took place. Here, the Tc temperature was lower Initial value held. After the addition, was still stirred for a further 2 hours at the reflux temperature. To The reaction was terminated with steam distilled, neutralized with diluted Ilatriur hydroxide, for removal <2e3 U -'- ssers evaporated, sur removal of Internal iodide extracted with ethanol and filtered. Kach. Removal of the ethanol, the filtrates were concentrated with Sulfuric acid is distilled, which is used in an amount which corresponded to about 2.5 times the original weight of the filtrate. This resulted in 81.1 g

^x CF (CF ₂ CF ₂ kCOOH voa boiling point 74 to 70 ° C / 1.5 to 3

2.5 mm K2 received.

Analyzes C PH

found: 23.51 ^ '69, B8jä calculates:

The infrared absorption gave \} c »ο at 5 # δ7 · The yield was 08.2

₃
Synthesis of CF (CF ₂ ), -C00H

In a 500 cn ^ -Autolclav from stainless steel on

248 g (0.5 mole) ⁰ ^ v

CF (CF ₀ CF ₀ J and 2.4 g of di-t-butylproxide CF ^, '**

given. The Cecil sch was cit Sole a ^ girorcn, which was cooled fr.it Troclccneifl,!. "After evacuation of the air from the autoclave with nitrogen and gasfb'rnigca CF ₂ " CFC1 were ^S 40.6 g ( 0,4G0 mol) of CF zugogeban ₂ "= CFC1, whereupon daa Ceniisch voraichtis wurdo stirred ⁰ C at 120 to IJC. WShrenc3 represents oratcn ^ O minutes after the start of the found ftUhrcna

, ·. 209817 / U96

BAD ORIGJNAt

a courtly reaction took place, which gradually subsided. The ile action pressure was 3.5 hours after the start of stirring at a constant value of 2.2 ks / cn eci'allen. The reaction was then cooled to temperature with cold water. 295 g of a liquid product were obtained which contained almost no non-urseoctztea CP ^ -CPCl · The product thus obtained was then put into a two-necked flask and fractionated while nitrogen was passed through the capillary tubes · The following compounds were obtained:

12u, 8 s (0.256 moles) unreacted

Boiling point 75 to 70 ° C / 4.0 approx IZz, -

CP ₅ ^
90.6 g (0.143 Hol) ^ CP (CP ₂ C? ₂ ) ₂ CP ₂ C1J

48.1 β (0.066 moles)

and 26.9 & other substances. D03 C33 constant of the products was 156.6 s, dar Ubaatz

CP ₅

was 48, S MoI ^, the yield of ^X CP (C? ₂ CP ₂ ) ₂ CF ₂ CPC1J

CP ₅

60.7 Mo-Uli.

90 ζ (0.147 mol) of the obtained "" CP (C? ₂ C? ₂ J ₂ CP ₂ CI vurden then rnit fuming SChv / ofelsüuro 10 hours boi 150 ⁰ C oxidized · Da3 obtained CF (CP ₀ CP _{0) o} C? _o C0?

2 0 9 8 1 7 / U 9 6

BATH ORIGINAL

• - 26 -

CP,
was hydrolyzed, where ^ .CP (C? ₂ CP ₂ ) ₂ C? ₂ CöGH

from boiling point 15 to 70 ° C / 5.5 bia ^ * O κπι Hs obtained lrurdö · The Infrarctanalyaa resulted in ν c »ο at 5.66«

Synthesis of ^ CP (CP ₂ ^ CCOIi

210 g (0.302 mol) ^ .CF (CP ₀ CP ₀ KJ were rait Vk g

(0.250 KoI) CiJ ₂ = CHCH ₂ CH, and 2.5 g of di-t-butyl peroxide

4 'hours at 120 to 130 ° C unoccupied. After separation of 2.0 β (0.0 ^ 6 mol) not only CH ₀ = CKCH ₂ CH, and

S? _3v

66.8 s (0.036 moles) not only C

\ get other substances-1 nolarcn Additloncprodukts and 9.2 Zi U Aatz: vjurden 0.19 ^ "moles of a first:

J 68.2 K

ϊ € 5.6 KoIg
Yield of Itl-aolarca addition product: 9 ^, 2

The resulting addition product v ^ rde then with 2oQ s Ifctriucporinangsnat and I5OO β Eiceoais 10 hours> toi 100 ⁰ C under EUiU ¹ Cn unoccupied, llcch discoloration ait gasförciicar Ξαΐν.χΓοΙ-aSure were dlo Ecssis ^ aurcost · cKbaeatillicrt was separated in ^ ^ SO ^ ico zczzhzn and continuously old ether extracts · to Ktherlüsuns was ethanol-in .One

^Λ 2G9817 / U96.
BATHROOM ORIGINAL.

Γί ^ Ώ ^ ο given that roughly öerj. 2 times the original volume 6z ζ iithers corresponded · Ds wurde- mixture with a 20, vigen wlia-srisca Katruur-Jiydroxyd solution carefully neutralized, ÖIR odarnpft ^ ^ and dried to give 103 g cine hellbr lichon Fsststoffo obtained vrurdcn "Eel fractionation rjit concentrated weakness were 93 * 2 Q

from boiling point 70 to 75 ⁰ C / 1.0 to 1.5 ^ -nl-ä obtained »

Amlyaa s CPH

2j5, o $; » 70.09 / ^j 0.

2p, ^ 5 #

1 -lcular weight: gef undcn: 6l2.5

calculated:

Yield: 62.5

^CP 3 s
Synthesis of -, CF (CFg) ₂ COOH

In one 500 cm ^ four-necked flask, from which the air had been completely displaced with nitrogen, 596 q

(1.00 KoI) '3 "CFCFoCFoJ, 66 G (1.00 KoI) ßorelnl'stea Oly ^ ^

VinylacGtat and 1.2 s asobiaisobutyronitrile at the same time. That Geraiseii was kept at βθ to 75 ° C. for hours. Towards-

would there be a CPC of 53.6 g? ₂ C? ₂ J and 1.2 g asobisisobutyro-

Nitrile fa-urde the gohalfcon after 3 hours at 75 to £ 5 ° C.

'2098-17 / 1496
BATH ORIGINAL

After separation of unreacted and vinyl acetate became ^ 19 β crude C-I

CP,

Ann Iy se? CFJH found: 2 ^, 0 ^ 42.1 # 26.9> SO, 2 & 3 calculated: 22, '# 43>, 2 # 26.4 £ 0.21

400 ζ <2es obtained dicjso way crude product were "it 93 S Kn liurr.hydroxyd implemented in 100 cnr ethanol. The mixture vairdo in 600 cn ^ water geg03scn _# rnit Chloroforra extracted with 'kva ^ serfreiem magnesium sulfate getroctaiet and Sk Abtreib.2n de ο Chlorforras heated · Dsr brownish

slce: residue of 297 S was turned into a. 2 liter four-necked flask Given and while stirring with 700 g of potassium dichro.-ant and 17C0 a concentrated sulfuric acid in 567 S distilled V / a as © ρ S hours at 120 to 3-155 ° C. The mixture obtained was then distilled with steam, Kit 5 / ^ iSöra Potassium hydroxide neutralized and removed of the water heated, whereby 273 S one3 pale! Powders were obtained · By fractionation it was more concentrated Sulfuric acid with reduced duci; * .. urden

₃
99 # O g ^, CFCP ₂ Cp ₂ COOH from boiling point 55 to 5 & C / 10

CP ₅
bi3 11 οία Hg received · ·

Molokularsewlcht. g _G ? unden: 312.1, calculated:

Infrared absorption % ' r ¹ c ■ «ο at 5 * 63

Example 7 '

CP _x
Synthesis of CF (CP ₂ ) ^ COOH

a pressure-resistant 150 c ^ glass cylinder were 89.8 3,

2098 1 7 / U9G

ORIGINAL BATHROOM -

(0.20 Hol) CF (C? ₂ CF ₀ ) ₀ Er from boiling point 51 to

6ö na Ils and 9.7 S (0 * 10 mol) cIs-IjS-dichloroethylene sebon. The gene was frozen in liquid air. The cylinder was hermetically sealed, the air that was present was evacuated and the temperature was gradually increased, the ingredients being mixed well by stirring. Source of 2000 Curie and 5 hours 5 hours so that the 7 rays were emitted from this source. By fractionation, a lil-molar addition product (yield 21.5 mol) and an I i2-r.olar addition product (Auabeutö 10.3 ^ Jol ^) are obtained

Ana Iydo from C ^ F ^ qClgBrE · »; · CF Cl Br

Sefundens 20> 2 ^

calculated! 19 # S £

Analysis of C ,, P, cC1 ^ BrH ^ t

found! 20.4 ^ 45.1 ^ 2 ^, 8 ^ 11.7 *

calculated:

By oxidation with potassium chromate, concentrated sulfur siiura and distilled Vasasr to the .In Bsispiol 1 bs-. Schrebene V / eise became from 15 p

, the awakened ^

CF (CF ₂ CF ₂ ) ₂ CHCICHCIBp / In 84.7 yield

obtain·

he se from C? (CF ₂ ) -COOH

:; λ a 500 cnP * Autoldav made of stainless steel

209817/1498

BATH ORIGINAL

193 β (0.500 moles) ^ CP (CP ₂ CP ₂ ) J and>, 4 S di-t-butyl peroxide

Then the old brine, which had been cooled with dry ice, was frozen. The air in the autoclave was forced out with nitrogen, whereupon 46.6 g (0.00 KI) of CP ₂ CPCI were added During the first 20 minutes after the start of stirring, a violent reaction took place, which was then cloned all over the place. The pressure was 3.5 hours after the start of stirring to a constant fourth of 2.2 lcg / cra liked. After cooling dos obtained. Mixtures at eaucite color were obtained in 2 ^ 5 seconds of liquid Bc & ktioncscmläs which contained almost no converted CPgCFCl. By fractionation

_5x
«2 e (0.205 moles); ^ CP (CP ₂ CP ₂ ) J, 130g (0.254 KOl)

CP (CF ₂ Cf ₂ CP ₂ ) CFCU VO33 Boiling point 57 to 50 ° C / 2 to

CP ₅ '

3 cua Ils and ^ 1.9 g of other substances received *

In a 1500 ccr autoclave provided with a window, 51 # 3 B (Ο, ΐοο mol) of the aforementioned Ij! "Molar addition product": .10.1 g chlorine gas and 15.5 ß oxygen were added "The mixture was offered rauratoraturatur NLT 55 hours Ultraviolettstrahlexi bcstraHü ;, which is α by ά & incident window Hess · the volatile gases including chlorine were collected in a nlt fUlsslßor air-cooled trap. The liquid residue was fractionated, whereby the following products were obtained:

_5n
1 g CP (CP ₂ ) ₅ COF from boiling point 68 to 7O ⁰ C in

CP ₅

an Auobout® voa 71 * 3 Holja with a strong infrared absorption «sorptioa i c» o at 5.27 | 10.5 β (0 * 0205 moles) unreacted

* 2 0 98.17 / U || - ^, _. . ;

BATH ORIGINAL

C? (CF ₂ ) -, CFC1J mid 2.1 β others. Substances The usual

Borrowed hydrolysis of 10 g of this reaction product gave CF (CFo) -TCCQH voa ■ boiling point Sj up to 70 C / 10 tarn His

in a yield of 93> § 1-1

209817/149
BATH ORIGINAL

Claims (1)

Patent claims Process for the preparation of (J, U) -di (trifluoromethyl) -perfluorofatty acids the general formula (CF,) ^ CF (CF ₀ ) COOH
j c. t- η in which η is an integer from 2 to 21, characterized in that compounds of the general formulas \\ st} - * // - XrE \ ysF r \\ Jff n) i * / P rv ^ SL Λ X, ivr-iJnvf ΙΟΓηνΓΛΐ ulinuA Λ Χ, j <- tL (L m ei ever. d. c. X & c. (CF ₅ ) ₂ CF (CF ₂ CF ₂ ) _m CH «CX ^{: 5} X ⁴ or (CFJ ₂ CF (CF ₂ CF ₂ ) _m (CH = CX ⁵ ) X ⁶ , in which Y, X ¹ , X ² , X ⁵ , X ^, X ⁵ , X ⁶ , m and ρ have the following meanings: Y »-Br or -J X ¹ and X ² m -H, -F, -Cl, -Br or -J, but at the same time -F;
y? and X ^ «-H, -F, -Cl, -Br, -J, -OH, -R, -OR, -OCR, -OXR, -ROH, COOR or -COOH; R β alkyl with 1-3 carbon atoms; X ⁵ and X ⁶ - -H, -Cl, -Br or J, but not at the same time -Hj m >> 1 - 10;
ρ β 2 or 3, with oxygen, fuming sulfuric acid, bichromates or Oxidized permanganates. Process according to Claim 1, characterized in that the oxidizing agent used is oxygen in an amount of approximately 3 to 7 moles per mole of starting material used and the oxidation under irradiation with Lioht, optionally in the presence of accelerators. Process according to Claim 1, characterized in that the oxidizing agent used is 2 to 6 times the amount by weight of the starting material of 10 to 70% fuming sulfuric acid, calculated as SO ,, and the oxidation is carried out at a temperature of 90 to 170 ^° C performs. 209817 / UP6 BATH ORIGINAL Process according to claim 1, characterized in that the oxidizing agent used is alkali bichromate or permanganate in an amount of 1.5 to 5 mol per mol of starting material and the oxidation in a liquid acidic or
alkaline medium, the molar ratio of reaction medium to oxidizing agent being 1: 1 to 1:10. 209817 / U96 Blank page