DE2130378A1 - Process for the preparation of alpha-omega-diiodoperfluoroalkanes - Google Patents

Description

nio jirfindun "relates to a process for the production of v> - W -Όijodpe ^ f'uorn1 can and especially a new process 711 ^" instead of such perpluorni inside in a ¹ '"high bulge.

ΆΗ is known to ciai3 FI uorkoh 1 ens boffe aus.qe / eichnee i-heiii see and therTii -ehe St;> bi Ii tnt own and ween 'li "S (! T' ij i f'eriMoha f» -. En iin ^ ewöbnl icli usable for a multitude of \ nwöndun ^ sr »eb ie t.en are. So they were ili ο as ^ eM ^- -urirl 'iliibivei'ieri'le means for textiles and Pai ior im · ¹ <uiii lib« v / i fih «n von '■! <» tr »| 1 en vorwejnde t. Klni / ^ e dor T ¹ M iiorl: oh 1 on-H t.ofTpf) I»' iiiisro have low rails I vv i. skos 1 step, din

; , C ΐί 8 5/1 9 6 6

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make them useful as adhesives. Also a! 'Became a high-molecular flno ^ cohi enstoffpolyniere produced, which are elastomers and therefore in fields of application are useful where synthetic Π-uinmis with especially good chemical properties and fire resistance required are.

Among the various starting materials used in the synthesis of high molecular weight fluorocarbon polymers can be used, are found dxe ^ V - £ (^ - Diiodoperfluoroalkanes. These Dijodperfluoralkane can with Ethylene reacted and forming the terminal Ethylene groups are dehydroiodinated. Such terminal ones Ethylene groups can be divided into various functional groups be converted, for example by oxidation into carboxyl groups, via which high molecular weight polymers can be produced. The use of Di iodoperfluoroalkanes as starting materials in such syntheses but was delayed because of the unsatisfactory Nature of the processes that have been used to date to produce this Materials were suggested, and in particular \\ rain of the very low yields known with such Procedures have been received.

It is accordingly one of the aims of the present invention to obtain an improved process for the preparation of O \ - CO - diiodopperf luoralkanes;

10 9 8 8 5/1966 ~ ■ ³ "

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which has a relatively high conversion to the perfluoroalkane and / or obtain a relatively high yield thereof. Other objects of the invention are in part apparent aTis of the description and are partly expressly below listed.

The objects and advantages of the present iürfindun ^ is generally achieved by telomerizing 1,2-Di j odäthan in (rain waiting a Feie-radical catalyst and Tinter using tetrafluoroethylene as a taxogen. The reactants are known products, which are prepared by known methods It has been found that the telomerization process can be carried out effectively under autogenous pressure at temperatures in the range of 30 to 150 C. In order to obtain good conversion and yield of the telomerization products, a molar ratio of tetrafluoroethylene to 1 should desirably be carried out , 2-diiodoethane of at least 1: 1 and preferably 3s1 or greater can be used

In general, any free radical generating catalyst can be used in the present process, such as di-tert-butyl peroxide, tert-butyl hydroperoxide, Diisopropyl percarbonate, tert-butyl perbenzoate, Acetyl peroxide, lauroyl peroxide, benzoyl peroxide and azobisieobutyronitrile. Particularly good results were obtained when using benzoyl peroxide and di-tert-butyl peroxide used. The optimal temperature is evidently

109885/1966 BAD, ORIGINAL _c

In relation to the half-life decomposition of the catalyst, if benzoyl peroxide is used, the temperature can be kept at about 80 ° C. With di-tert-butyl peroxide a satisfactory temperature is 120 to 130 C. With diisopropyl percarbonate one can
Use a temperature of around 60 C. The catalyst will
It is used in an amount in the range from 0.1 to 10 mol ^S 5, based on the diiodotetrafluoroethane. The preferred range is 0.5 to 5 mole- "i.

The reaction can either be in bulk or in the presence
carried out an inert liquid Reaktdonsmediums
will. Preferred liquid media are perhaloalkanes, such as, for example, fluorotrichloromethane or 1,2-dihrointetrafluoroethane.

The reaction time can vary from, for example, 1 to 30 hours or more, depending on factors such as the catalyst used, the ratio of the reaction partnerships.
and especially the. desired molecular weight distribution in the product telomers, in most cases is a
Response time of 10 to 2k hours is suitable. The reaction pressure depends on factors such as the reaction temperature,
the nature of the reaction medium, if one is used, and the ratio of tetrafluoroethylene / C FT
and can, for example, be between 13 »6 and CP> aii ^; (
up to 10ΠΟ psig).

There ^! n der Tel 'imerisierutiR received «'"ealct'on = '

109 8 85/1966

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comprises a mixture of telomers with varying numbers of tetrafluoroethylene units and unreacted tetrafluoroethylene. The unreacted tetrafluoroethylene can be recovered by evaporation and recycled.
The telomeres can, if desired, according to known methods
chromatographic methods and by fractional
Distillation can be separated off at reduced pressures.

In the present method can be yields of telomeric Produkcen of bxs zii 50 J * s or more sustaining. Total Conversions to Eligible Products of $ 90 or more
more are available,

ran its tendency to polymerize, becomes tetrafluoroethylene often stabilized or inhibited by adding a material such as limonene, dipentene, or pinene. It it has been found that such inhibitors do not interfere with the present Telouerisierungsrealction and that either inhibited or non-inhibited tetrafluoroethylene is used can be.

The following examples serve to further explain the nature of the bond.

example 1

A stainless steel reactor of 20 liters, equipped with a stirrer, was filled with 700g (1.97 mol) TCP CF I,
this beforehand with 10% aqueous sodium hydroxide solution

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-G-

and was washed with barrel, and charged with 10 g (0.16 mol) of benzoyl peroxide. The autoclave was closed, flushed with nitrogen and evacuated. It was then heated to 80-3 C with agitation and 4250 grams (42.5 moles) of inhibited tetrafluoroethylene was added to give a pressure of 44 atmospheres (^ 50 psig). During the remainder of a period of 6 hours, a solution containing 2840 g (8 moles) of 1,2-diiodotetrafluoroethane and 50 g (0.21 mole) of benzene peroxide was introduced into the autoclave under pressure. The molar ratio of tetrafluoroethylene to TCF CF I was 4.25 / 1 and the concentration of benzoyl peroxide, apart from the TCF ₀ CF I _{1, was} 2.5 molar. Telotierisierung was continued for an overall reaction time of 26 hours. During this time, '''e trafl uorethylene was added, if necessary, in order to maintain the original pressure of hl \ atü. The autoclave was then cooled / 4uF room temperature and the umumgesetzte Tetraf luorä thyl-s f off bubbles. The remaining material, a cloudy, purple-colored oil, weighed 35 ^ 3 g and had the following composition, which was determined by chromatographic analysis:

Component weight ^r C

CF ₀ ) I (starting material 62.9

CF ₂ ) ₃ TH ₁ -.

CF _O ) _. T + unknown substances 5, ^

2 5

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The T ^T conversion to telomer oil, iodine, based on CF ₂ T, was 35%.

iL, i η Peakt ionsprodukt, the ^r in substantially the same H else wiu above htjrpestel It was, was removed by washing mild aqueous sodium sulfate decolorized, then washed with water and dried at Hnftnesiuinsulf. 150O g of the washed product were fractionally distilled at reduced pressure through a Widner Kotonne of 2, ^r > χ 75 cm, whereby the results listed in Table T below were obtained:

103885 / 196G BAD ORlQlMAL

Table I.

Fraction by weight, distillation in grams of piston temperature

temperature, ° 0 steam temperature _f

Pressure, mm / Hg

T 812 TT 5k Cold trap 319 TTI 5h TV 25th V kl VT 10 Cold trap 11 Residue 55

42 • 81

89 58

103 115 30

37

71

31-36
50-55
57-63

27 hk

51 3 3

(Continued)

109885/1966

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Table I (continued)

⁰ 6 ^F 12 ^T 2 ° 8 ^F 16 ^T 2 ⁰ IoW ₂ > ^C l _O ^F 2o ^T 2

95 , 3 4.2 0, 4th ο, 7th 0, 2 94 ,1 5.9 6, 6th 0, 2 97 , 6 2.1 0, 3 4th , 0 92.2 3, 7th 76.9 23, 1 6.0 92, 4th 1.5 89 6th 5 , 5 63.8 28, 1

12.6 5.9 42.5

109885/1966

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The residue was a brown solid which was almost completely soluble ^{in hot 1} CF _{0 ClCFCl.} When 351 / * residue, which had been collected from other distillations, was _{extracted in a Soxhlet apparatus with hot CFCIOFCi 2 for} 18 hours, there was thus obtained 120 g of crude telomer which remained undissolved. The soluble material consisted of C _n to C -diiodoperfluoroalkanes,

ΰ dd

Example 2

A stainless 300 ml steel autoclave was charged with 55 g (0.16 mol) 1,2-diiodotetrafluoroethane and one gram (θ, Οθ4 mol) benzoyl peroxide, cooled in liquid nitrogen and evacuated. Inhibited tetrafluoroethylene (43 s) i (0.43 mol) was added by vacuum transfer and gave a molar ratio of CF = CF to IC F, I of 2.7 s 1. The autoclave was placed on a shaker and at 85 ° C. for 21 hours heated. The initial pressure was 42 atmospheres (620 psig) and the final pressure 39 atmospheres (575 psig). It was then cooled to room temperature and the unreacted tetrafluoroethylene was blown off to a trap with liquid nitrogen. The residual material weighed 64.9 g. Chromatographic analysis showed the presence of

64.9 ° h ICF ₂ CF ₂ I, 13.8 $ I (CF ₂ CF ₂ ) ₂ T, 12.5 #! (CFgCFg) 3.6 io 1 (CP ₂ CP ₂ J ₄ I, 1.6 $ 1 (CF ₂ CF ₂ J ₅ I, 1.0 < I (CF ₂ CF ₂ ) ₆ I and 1.7 $

Example 3

A 300 ml reactor was as in Example 2 with 2 g of benzoyl

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peroxide, 0.28 mol of KIF ₂ CF I and 0.9 mol of non-inhibited tetrafluoroethylene charged. After two hours at 80 ° C., the reactor was ventilated. The product was analyzed by chromatography. Ink contained 17.1 * ?? ifCF) .I, 11.1 «-; T (0F ₂ ) ₆ T, 5.9 3 I (CF ₂ ) _S T, 1 ^ TfCF ₂ ) ₁₀ T and 6 "'telomeres of higher molecular weight.

example

Example 2 is repeated with 45 g (0.13 mol) ICF ₂ CF ₂ T, 45 g (0.45 mol) ^ 2 ^ k ^{and 1 ß Ben7O} ^ ^rl '" ^ierox " V ^<i . The reaction time was 5 hours . The product weighed 56 F, contained S ¹ S *, ICF ₂ CF ₂ T, 7 % T. (CFgCF ₂ ^ I, 5 <

CF ₂ ¹ I ₃ I, 1.3 ^c o T (CF ₂ CF ₂ ) J ₁ T, 0.5 «-i TfrF ₂ CF ₂ ) ₅ T and telomeres with a higher molecular weight.

Example 5

Tn this example, which was most TCF ^ CF ^ T and Ben7oylperoxv (3 for a period of several hours: ugesetzt Jiin stainless 20 liter steel reactor was charged with 700 g (l, Q8 mole of ¹ »TfP CF T and 10 g (0, 0 * 1 mol) Ben?: Oylperoxide charged, flushed with nitrogen * and evacuated. It was heated to 3 ° C., and 4250 g (42.5 mol) of tetrafluoroethylene, which contained no inhibitor, were added. The pressure was 44 atu (65 psig), 1,2-diiodotetrafiluoroethane (240 ft, 8 JIoI) and 50 g (0.21 mol) of benzoyl peroxide were replaced over hours while leading to the reactor. After 20 hours the reactor cools and ventilates. Composition of the residue material in Oe-

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weight percentage was as follows: 74.6 ^{c F} .T, ¹² > 7 ⁰ Zi ¹ ^ s ¹ O '

7.8 C ₆ F ₁₂ I ₂ , 1.4 C ₈ P ₁₆ I ₂ , 0.4 C ₁₀ F ₂₀ I ₂ , 3, ο> c., ^ F ₂₀ T

Example 6

This example illustrates the use of fluorotrichloromethane as a reaction medium.

A 4 liter stainless steel reactor was charged with Ij g of benzoyl peroxide, 742 g of ICF CF ₃ I and 500 ml of CFCl 2. Et was evacuated, flushed with nitrogen, evacuated again and charged with 600 g of tetrafluoroethylene which had previously been treated to remove the inhibitor. The reactor was then heated to 80 ° C. with agitation and held at 80 ° C. for 20 hours. The reactor was then cooled to room temperature and ventilated in order to remove unreacted tetrafluoroethylene and CFC1. Chromatographic analysis of the residue material showed, in addition to the solvent, the presence of 14 fo l (CF Kl, 12.4 ^C 5 4.6 ^£! S l (CF ₀ ) ₀ I, 3 4> 1 (CF -). ,,.! and about 4 <* Ό higher molecular weight telomeres.

Example 7

In this experiment the same amounts of reactants were used as in Example 6 and 500 ml of CF BrCF Br were used in place of CFCl. The residue product contained 14.5 # 1 (CF ₂ ) ^ I, 9.8 # 1 (CPg) ₆ T, 4.5 4 L (CF ₂ ) ₈ T, 2.6 ^ 1 (CF ₂ ) I and about 5.8 < high molecular weight telomeres.

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Example 8

This example illustrates the use of fluorotrichloromethane as reaction medium, repressurization of the reactor with tetrafluoroethylene and gradual Addition of ICFgCFgl.

Fluorotrichloromethane (744 g) was added to a 4 liter stainless steel autoclave which was then purged with nitrogen. Inhibited tetra-juoroethylene (600 g, 6 mol) was then added and the reactor was heated to 50.degree. The pressure was 29 atmospheres (430 psig). A solution of benzoyl peroxide (5 Bolumen- ^) in 260 ml of 1,2-diiodotetrafluoroethane was added to the reactor over 2 hours with the aid of a high pressure metering pump. Tetrafluoroethylene was added to bring the pressure to 29 atmospheres. The temperature was kept at 80-3 ° C. for a further 16 hours with stirring. The reactor was then cooled and the fluorotrichloromethane and the unused tetrafluoroethylene were removed by evaporation. Analysis of the contents of the reactor indicated that the following materials were present: 56.3 % l (CF_) ₂ T, 10.2 #

^ T, 9.6 i> 1 (CP ₂ J ₅ I, 5.8 # I (CF ₂ ) ₈ I, 4.3 1 " ₁

₂ ) ₈ I and 14 % higher molecular telomeres.

Example 9

In this example, the molar ratio of tetrafluoroethylene was to ICF CF I 1: 1. The tetrafluoroethylene was not inhibited. Telomerization occurred in one

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300 ml shake bomb for 20 hours at 8C ° C. The maximum pressure was 21.5 atmospheres (315 p ~ ± g). The total conversion to telomeric diiodides was 7t7 '' Si, i.e. 3.7 '-

8 ¹ 16 ¹ 2 '

PT 1 4 ° £ N. Π F T

Example 10

This example illustrates the manner in which telome conversion varies as a function of catalyst concentration. In the experiments listed below in Table TI, a molar ratio of tetrafluoroethylene of CF ₉ ICF I of 3.2: 1, a 3enzoylperoxydkatalvsator, a reaction temperature of. ^Q 0 C and one; Reaction time of 20 hours used. In the table, for convenience, the telomeres are identified by the number of carbon atoms they contained. The pressure used was kl to kk atu f £ 00 to 650 psig).

109885/1966 BAD OBiGiNAL

^T 'abe1 le .1 I.

Catalyst ^c . \ Conversion as Mo 3- ^

⁰¹ I ^ e ¹ omer rr

0.73 8th , 3 H, 1 1 , 9 O, 0 O, 8th 0.73 11 » , 3 6, 3 , '·' 1 , 0, 0 2.86 kl , 0 17, H 11 ,1 3. 1 , 6th k, 0 35 , 0 n, 8th 12th , 5 3, 6th ι, 2 7.3 36 , 3 12, 2 7th , 2 2, ? 2 7.3 43 , 3 15, 5 10 , / 1, 9 2,

10

unknown
Fabrics

1 , ί ¹ , 3 3 , 6 12th , 0 9 , 0

The above values show that the catalyst concentration and the molecular weight of the ebz1deten telomeres in one Relate to each other.

Example 11

This example illustrates the results obtained when different types of catalysts were used.

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Table TII MoI- temperature 125-130
125-130
125-130 Time , 2130378 veiiiältnis o_
Tetrafluoro
ethylene / 80
80 SM. catalyst 25-3O <?. Convert. Mon 1 - "'
Tel ofjen 2.6
3.1
3.6 80
80 6th
11
18th (approximately) Di-tert-bntyl
peroxvde 2.8
3.0 18th
20th 3.4
3.5
3.5
Azobi siso-
butyronitrile 3.0 22nd 4.4
7.6
19.9 3, '1
Di sisopropy.1 -
percarbonnt 3.5
2.8 5
21 5.2
2.9 5.0
Benzoyi
peroxide 10.1 3.2
4.0 14.5
35.1 (Continue.)

109885/1966 BAD ORfGINAL

-IS-

Table III (continued.

^c o Telomer

1 ο

2 Λ ο, _η 0 A. 0 , 16 ο. Me CO) '■ 3 5 ι, 2 0 ,H O , 2 ι, O 13th ,8th H, H 1 , 7 (· ^, 3 ^ί: -

, 0

2.5

0.2

0.3

3 , 0 2 ,1 1 , 5 ι, 0 2,! ,8th fl ., 7 ^f • i Tso-PrOH) 7th 5 , 0 1 , 3 0, 5 J / 13th 12th , 5 3 1, 6th

109885 / 19.66

At game 12

This example illustrates the effect of the molar ratio of einesVariierens Tetraf luoräthylen to ^c ₂ ^F 2 <- ^ 2 * ^ * ^{η ίθ} the table listed tests were bex 80 C using di-tert-butyl peroxide at the catalyst dureh- re Hihrt.

10988 5/1966 ORIGINAL BATHROOM *

- 2ο -

H i-l Φ

U O φ γ-1 ε α ο
r-t E- OO ο

H Φ

■ Ü E

C O

CO ι-Ι

S Φ

ε ε- ¹

10 ι G j— ~. CM • Η Φ Oi ϋ C. O H H -μ H ^ j : ce Ch -P CM CO : cö O μ «Η Φ -P • 3 Φ CO r-i C. ^ν - ' C. / ■ —- Φ CM ΜΗ O O • Ρ N CO Φ M. V-- r * i ι H H (P O -P CO W.

Jf 00 H ι-Ι

Γ- ι-Ι

Oi

σ- σ \ tr.

Cl VO C--

1-1 ι- »

VO
ι-Ι in O O r- σ. ^C ^ ο " γ-Η VO VC CM Jf σ, C. O VC O ι-Ι "1 CI r-1
H H
ι — i O H νο CM Oi CM H CO Jf
H σ ^ Γ- Jf W. Oil O
H ■ Η £>
H t — t
τ — ί

Jf

CO

ντ νο \ τ »γ

σ. ο,

ve ve vo

N in OO If »K ΙΛ CM Oi Oi CM CM Cl

109885/1966 ORIGINAL BATHROOM

The above values show that an increase in the molar ratio of tetrafluoroethylene to C ₃ FT ^ increases the value of higher molecular weight telomers.

109885/1968

Claims (7)

Claims Process for the preparation of ^ A - CO Di.jodperf luoralkanen, thereby gelcinnzeichntt that 1,2-Dijodtetrafluoroäthylen and Tetrafluoroäthylen in present & iner catalyt ι see amount of a free radical-forming catalyst to a telomeric product of the formula T (CF ₂ CF _? ) _N T converts, in which η is 2 to 10, and from the reaction mixture the telomere product wins. 2.) Process according to claim 1, characterized in that a molar ratio of tetrafluoroethylene to 1, Ζ-Ώ ± iodetetrofluoroethylene of at least 1: 1 is used. 3.) Method according to claim 1 and 2, characterized in that that one reacts at a temperature of 3O to 150 C. 4.) Method according to claim 1 to 3i, characterized in that that one reacts under autogenous pressure. 5.) Process according to \ nspruch 2 to k, characterized in that a molar ratio of tetrafluoroethylene to 1,2-dyododite-grafluorate of at least 1: 1 is used. 6 _S ) Method according to claim 1 to 5i thereby ^ ekennreichnet, one called the Uni ^ - · ι; "] n ^ in an inert liquid reaction 109885/1966 BATH ORIGINAL ' medium performs. 7.) The method according to claim 6, characterized in that daft one as an inert Reaktxonsmediuni exn perhalogenated Alkane used. ^5. ) Process according to Claims 1 to 7, characterized in that the catalyst used is benzoyl peroxide or di-tert-butyl peroxide. o _t ) Process according to Ansnnsoh 1 to 3, characterized in that a telomer is obtained enfcemi sch and the telomers are separated by fractional distillation. 109885/1 ^ 966 BATH ORIGINAL