New pentafluorothio(SF5)fluoropolymers

Journal

of Fluorine Chemistry, 35 (1987) 653462

653

Received:August7, 1986;accepted: November2, 1986

NEW PENTAPLUOROTAIO(SF5)FLUOROPOLYMERS

ROBIN 3. TERJESON and GARY L. GARD

Department of Chemistry, Portland State University, Portland, Oregon 97207 (U.S.A.)

SUMMARY

New fluorinated polymers containing the pentafluorothio group have been prepared from SF5Br and the appropriate fluoroolefin under reaction temperatures of 90fS*C and autogeneous pressures of up to 90 atmospheres for periods of four days to two weeks. With ethylene, FCB2CH2Br and SF5CB2CR2Br were formed. A new monomer addition product, SF5CF2CF2Br, is also reported for the first time.

In our continuing studies of pentafluorothiocarbonsystems, we have found that upon reacting SF5Br with fluoroolefins not only monomeric liquids but polymeric solids are produced under proper conditions of heat and pressure. Prior to our studies, other workers have prepared SF5 containing polymers and telomers via the reaction of CF24F2 SzFlo[41,

with SF5C1[1,2,3], CF_,CF=CF2

with

SF5CF=CF2 with CF2=CF2[5] and with CF2=Ca2[6]. Many of these polymers

have not been well characterized. 0 Elsevier Sequoia/Printed inThe Netherlands

654 RESULTS

AND DISCUSSION

We have found incorporating

that

SF5Br

reacts

with

the SF5- group according

fluoroethylenes

to the following

to form

polymers

equations:

(1)

SF5Br + XS CH2=CBF --> SF5(CB2CAF)10Br SF5Br + XS CB2=CF

SF5Br f XS CFA=CF2 -> SF5Br + XS CF2=CF

With ethylene, polymers CF2=CF2)

--> SF5(CF2CF2)16Br0

2

l-41,

are formed.

have been previously The key factor with a 90+5OC atmospheres

the

findings

reported

The empirical

Other

in Table

variety

of chain lengths

termination chains

end

groups

CA2=CF2,

above

CHF=CF2,

of SF5CF2CF2Br

possibly

pressure

along

go as high

as the number

coincide

Additional

as 90

with

of fluorines

the

i) an increase

found acids

increasing in melting

in solubility.

qualitative

polymers

of concentrated

tests

that

with

they

(ACl, AN0

3'

These

were

the not

H2S04)

or

of 1OO'C.

As with end

(SF5,

to be high

and 3i) a decrease

of the polymers

and

also

and include:

other

groupings

in each case: possibilities

with

resulting

trends

I.

with a variety

formulas

to the

here.

in stability,

analyses.

can

are waxy and become whiter

(6N, NaOH) at temperatures

upon elemental

route seems

7 and SF5(CF2CF2)16Br0.3

soluble or reactive

(R is CH2=CHF,

pressures

in the structure;

are summarized

SF5(CFHCF2)30Br0

base

calculated

increases.

In addition

adducts with the exception

in this preparative

2i) an increase

formed.

[71.

reported

for reactions

number of fluorines

was

SF5RBr

The monomeric

All of the polymers

point,

adducts

(4)

3

no polymer

temperature;

in the structure

(3)

SF5(CFHCF2)3,3Br0 7 .

essentially

(eqs.

(2)

--> SF5(CH2CF2)BBr

2

SF51

are given in Table polymer

systems,

depending

are

we would

upon

for termination

I and

expect

a

nature

of the

include coupling

of two

or termination

with

in end groups of (SF5, SF51 or (SF5, Br).

Chain

SF

the

based

5

or Br

termination,

radicals either

655 TABLE

1

Melting Range ("C)

Composition*

Decomp. ("C)

Solubility Acetone

A20

SF5(CA2CRF)10Br

100-110

190

insol.

sol.

SF5KH2CF2)8B'

118-150

330

insol.

sol.

130-160

460

insol.

slightly

310-318

>510

insol.

insol.

SF5(CRFCF2)30Br0

7

SF5(CF2CF2)16Br0_3

*

Empirical

by coupling content

compositions

based on elemental

or reaction

with

SF5

analyses.

radicals

would

result

[81 reported

that for compounds

is bound to an aliphatic

hydrocarbon,

a very intense

or about 870 cm

-1

found.

stretching 845-899

and a less

For

cm

monomeric

-1

carbon

absorption

stretching

cm

-1

but

sharp

reported

bromine

with

C-F

located

fluorine

bands

in the

cm

cm

-1

-1

.

fragment

(CFBr)+,

paper,

we

for SF5CF2CF2Br

groupings, cm

-1

the

cm

-1

region

bands for

region,

For the new compounds

for SF5CF2CF2Br

peaks were,found:

(SF4)+,

(C2F4)+,

centered 600

cm

find

region

-1

the

in the

on are S-F

region

corresponding

It is known strong

group

C-F

that

for

stretching

of the

infrared:

bands are found for these new compounds.

2941-3010

cm

at or near

modes are located

in the 1000-1250

-1

band

are

attributed

fluoroalkyl

while

for

described

bromides

did not contain

(SF3)+, and Br .

C-E

191 are [lo]

in this paper,

the bands

a molecular

(C2F4Br) + , (C2F3Br)+, +

to

alkylbromides

region may well be due to the C-Br stretching

The mass spectrum appropriate

band

, respectively.

-CF2-

absorption

to be in the 740-770

in the 766-705

and

cm

The C-Br stretching

modes.

range is 515-680

609

-1

in which the SF5

infrared

in this

, respectively:

at 903 and

are usually

appropriate

(SF4C)+,

polymers

and 606-600

compounds

vibrations

reported

the

intense

mode and one of the S-F deformation

modes were located

The

in a lower

in the polymer.

Cross and coworkers

always

sol.

the

mode. ion but other

(CF2Br)+,

(SF5)+,

656 The nmr spectra complex multiplets

for all the polymers

from which representative

The lg F nmr pattern the B4 equatorial

fluorines

chemical

group consisted

The

chemical

monomeric

values

adduct

were present. resonances

doublet

shift

for

polymers

and

19

the

found

at 8-183

F chemical

shift

inversion

defects

depending

for

polymer,

values

for

C-F

in polyvinylidene

on the relationship

fluoride of the

CF2

equatorial adducts

fluorine

for

the

the

values

respective

two types of SF5 groups polymers,

ppm,

19F

the

respectively.

By are

shifts at g-190 to -200 ppm lg F chemical

The Wilson

of g-91.6,

with

in polyvinylfluoride

chemical

[ill.

the

axial

to 80 ppm

8-211

for the CF2 group vary from 8-93 to -130 ppm. of CF2 shifts

The

and

found.

AB4 pattern

for monomeric

ppm

in the chain

were

of

and the axial fluorine,

For the SF5(CH2CAF)lo Br and SF(CHFCF2)30Br0.7

at 8-178 to -185 ppm (broad peaks):

represent

861

In the trifluoroethylene

[7].

values

values

range from 844 to 67 ppm [71.

for C-F are

comparison,

shift

values

and Santee report

regions

-94.8, -113.6 and -115.6 ppm

to other

CA2

and

CF2

groups

in the

[121. The new monomeric

for CF2 groups SF5 group. axial

shift

3 consist

of the expected

split into a complex

pattern.

range from 871 to 83 ppm

chain

SF5(CF2CF2)16BrO

are found in a range of 854 to 66 ppm while

corresponding

located

SF5

for the

A, into a nine-line fluorine

except

The equatorial

respectively.

into

a nine-line

The coupling

(cl and

The

1

Ii nmr

characteristic chemical

spectra

chemical

pattern

for

with

Ja_b=146.6

Hz.

polymers

are

shift values are found.

ppm

For

and

the

8-66.5

adducts

complex

5'

The

for the and

861.5

ppm,

the

ppm, the

respectively at 4.5 Hz.

The

[7,141.

multiplets

For SF5(CBFCF

respectively.

values

CF 2 groups,

)

2 30

shifts occur at 81.3 to 3 ppm and 65.5 ppm corresponding

the chain and the CA next to the SF

shift

the AB4 pattern

Es and Jc_d estimated

with other monomeric the

F chemical

844.3

at 8-93.5 ppm and

As. J b_d=11.3

shifts are consistent

19

are split into the typical doublet

constant

(d) are assigned

has

region and contains

fluorines

with Jb_c =14.4 Hz, Ja_c=4.23 chemical

SFaSF4bCF2CCF2dBr,

in the characteristic

fluorine

fluorines

adduct,

monomer

Br

in

which

0.7' the

lH

to the

CA in

adduct

has

a

657 value of

65.58 ppm next to the SF5 171.

shift is assigned

to the band at 64.74 ppm and overlaps

when the CH 2 is attached the CH2 value located

to the SF5 group;

is found at 64.27 ppm 171.

chloride,

are attributed protons

[131.

the chemical

to the CI protons In the polymer

The chemical

respectively.

shift

By comparison,

shift values,

1

SF5(CH2CF218Br,

monomeric of the

group

it is reported

that

in the 61.9-2.3

H chemical

adduct has a CH

2

adduct

CH2

ppm

region,

to the

B (CH2)

shift values are found

to the chain CH2 groups and

The monomeric

CA chemical

with the CH2 resonances

(CH) and the values at 64.2-4.5

at 62.8 and 64.5 ppm corresponding 5'

Br the

in the corresponding

in the chain is found at 61.8 ppm.

for polyvinyl

the SF

In SF5(CHZCHF)10

the

chemical

CH

next

2

shift

to

of 64.46

ppm [71. we find that for SF

In general, group is attached

to a CH2 group

containing

5

in the

fluoropolymers, the

chain,

proton

found near 64.5 ppm; for the rest of the CA2 in the values are located

in the 61.8-2.8

65.15 ppm for the C-H group when attached groups

in the chain, chemical

We

ppm region.

chain, find

to SF5, while

shift values are located

when

chemical the

the

the shift

chemical

chemical

for the

rest

SF5 is

shift

shift

at

of the

CH

in the range of

6 1.3-3.0

ppm. EXPERIMENTAL SF5Br was prepared purification.

CF2=CF

SCM Specialty

Chemicals

General apparatus

as previously

2'

with a Heise-Bourdon

Infrared

windows

or as solids between

spectra

spectra were recorded

trifluoroacetic determined

CH2=CF2,

CBF=CS2

Gases were manipulated

gauge.

90.0 MHz for proton

2'

[7] and

used

without

further

and CH2=CH2 were obtained

from

and used as received.

Procedure.

equipped

CFH-CF

reported

were

with and

tube gauge

obtained

by using

UBr disks on a Nicolet a Varian

84.67

MHz

Model for

capillary

and

a Televac

cell

with

KBr

The

nmr

operating

at

TPIS, F-11,

and

spectrometer resonances.

The melting

point apparatus.

vacuum

thermocouple

2ODX spectrometer.

standards.

melting

Pyrex

a Pyrex-glass

EM-390

fluorine

acid were used as external

using a Hel-Temp

in a conventional

points

were

658 The

mass

spectrum

spectrometer

equipped

Perfluorokerosene Elemental Gottingen,

was with

taken

on

a 6-kV

ion

was used as an internal

analyses

were determined

a CEC

21-110

B double-focus

accelerator

and

operated

at

70V.

standard.

by Beller Microanalytical

Laboratory

in

West Germany.

with SF5x

CF2M2F

To a 75 mu stainless

steel vessel

equipped

with a Whitey

(20-VF4) stainless

steel valve were added 64 mm01 of SF5Br and 75 mm01 of CF2=CF2. heated

The

for 5.8 days at 90fS'C.

leaving behind

6.44g of a white

The melting

observed

range

1244), 1152

the

Anal.

transferred

were

was Out

solid. solid is 310-318'C

white

with

In a second

no decomposition

1216

(6, with

SF5CF2CF2Br.

bp.

weight

The infrared (w), 1152

766 (vs), 684

741

(W).

(m), 606 (wm), 556 (m), 503 (s.b). calcd:

C, 21.95;

S,

1.83:

F,

74.87:

run, 61.0 mm01 of CF2=CF2 and 62.2 mm01 of SF5Br were heated at

60-62'C.

of

the

leaving

of SF5CF2CF2Br spectrum

(s), 1061

volatile

behind

material

8.91

grams

gave

3.71

of solid

mm01

polymer.

Of

The

(talc. 307.0, found 303.6).

had the following

(m), 1047

bands

(cm

-1

1216 (ms), 1194 (m),

):

(w), 934 cm), 903 (vs,b), 859 (VW), 831

(m),

(w), 609 (ms), 591 (w), 578 (w).

The lg F nmr

spectrum

a doublet

contained

a multiplet

of multiplets

at 0 44.3

S-93.5 and -66.5 ppm (relative and

(W),

sh at

C, 21.42; S, 1.89; F, 72.8; Br, 1.38.

Distillation

(2d).

triplets),

(cm -1,..

of the solid has bands

SF5(CF2CF2)16Br0.3,

Found:

molecular

spectrum

(w), 640 (m), 625 for

Br, 1.35.

1.0:4-O

materials

(s), 899 (ms, with sh at 866), 847 (w), 825 (w), 781

719 (w), 688

9OiS'C

for

volatile

The mixture

up to 510°C.

The infrared

1173

mass

for

FaSF4bCF2CCF2dBr

E2Br

were J

to

a-b

band area

SF5cp2

=146.6,

was

for

at 8 61.5 ppm,

a pentet

SF to SF4 was

1.O:l.O).

J a_c=4.23,

(nine line pattern

Coupling

of

of multiplets 1.0:3.9,

theor.

constants

Jb c=14.4, Jb d=11.3,

al

Jc_,Q4.5

for Bs.

659

A molecular 179,181

(C2F4Brl+,

110,112

(CPBrl+,

ion "as

not

observed

160,162

(C2F3Brl+,

but

other

129,131

fragment

ions

were

found:

127 (SF5)+, 120 (sP4c)+,

(CF2B=)+,

108 (SP4)+, 101 tSF3C)+, 100 (C2F4) +r 89 (SF3)+,

79,81

+

(Br)

,

70 (SF2)+, 69 (CF3)+, 63 (SFC)+, 51 (SF)+, 50 (CF2)+. 44 (SC)+.

c.

Calcd for C2FgSBr:

Found:

C, 7.82; F, 55.70; S, 10.44; Br, 26.03.

C, 7.83: F, 55.40: S, 10.59: Br, 25.98%.

CFH=CF2 with SF5,. To a 75 mL stainless

steel vessel equipped

with a Whitey

(20~vF4) stainless

steel valve were added 93 am101 of SF5Br and 100 mm01 of CF2=CFH; this mixture

at 90f5"C

CF2=CFIi were

added.

volatile leaving

materials behind

The

of

reaction

mixture

The

run, 58.8

for

four

infrared

2994

(w),

1394

1112

(8).

991

mm01

days.

-129

(SF41

and

of SF5Br To this

Anal. Br. 2.11.

of

64 mmol

at 90fS°C

of SF5CF8CF2Br)

and

75.8

reaction

(3d).

were

The

removed

(ml, (w),

1350 978

mm01

of

mixture

CFH=CF2

an

were

additional

(3d); in this run 10.8 grams

The melting

of this (ml,

(w),

1281

875

solid

had

(ms),

1244

(ms with

sh.

range

of this polymer

"as

the

following

(ms), at 9221,

1197 834

bands (s), (ms),

(cm

-1

1:

1156

(81,

728

("1,

(w), 606 ("ml, 547 ("III),509 ("ml, 466 ("1, 438 ("1.

a multiplet

contained at 8 71

a complex doublet (SF):

multiplets

(CF2) and at -211 (CF) ppm are present.

multiplets

and

at 46O'C.

spectrum

The 1' F nmr spectrum 54

of SF5Br

heated

CF2=CFE "as added and heated at 90fS'C

with decomposition

669 ("1, 628

"as

(58 mm01

of the same white waxy solid "as formed. 130-16O'C

52 mm01

heating

9.0 grams of a white waxy solid.

at 90f5OC

69.7 mm01

an additional

at room temperature

In an additional heated

(4d)

after

centered

at

at 8 -120,

The LS nmr spectrum

5.5 and a series of peaks in the range of

for SF5(CBFCF2)30Br0 Found:

of doublets

7 calcd: .

-122.

-125.

has two

broad

1.3-3-O

C, 27.42; A, 1.14: F, 68.12;

C. 27.34; A, 1.19: S, 1.44;

F,

68.2; Br, 2.01%.

56 and

at 0

ppm.

S, 1.21;

660

CF2=CH with SF5E To a 75 nL stainless steel vessel equipped with a Whitey 120-VF4) stainless steel valve were added 96.2 mmol of SF5Br and 118.3 mmol of CF2=CH . 2

The

reaction mixture was maintained at 9025°C (12h), room temperature (5h), and 90t5OC (3d). The products, 69.4 mm01 of SF5CH2CF2Br (bp 86-87OC) and 3.0 grams of a waxy solid ware formed. The waxy solid (slightly discolored) melted in 118-15O'C range and decomposed at 330°C. The infrared spectrum of the solid had the following

bands

(cm

-1

1:

3010 (~1, 2984 (~1, 1422 (ml, 1399 (mf. 1384 (rn),1270 (m), 1209 (s), 1183 (~1, 1158 (s), 1077 (ml, 1012 Iw), 975 (ml, 941 fm), 871 (s), 838 Is), 796 (ml, 762 (ml, 727 (w), 657 fwm), 600 (WI), 576 (wf, 566 fwmf, 531 (wm), 509 iw), 493 fwm). The

19 F nmr spectrum contained a complex doublet at % 71 (SF41 and a

multiplet at % 81 (SF); multiplets at % -93 and 0 -98 (CF2) were present.

The

1 B nmr spectrum contained broad complex multiplets with the bands centered at

62.8 and

64.5 ppm.

Anal. for SF5(CE2CF2)8Br,calcd:

C, 26.70: Ii. 2.22; F, 55.40; S, 4.46:

Br, 11.10. Found: c, 26.83: ii,2.33; F, 54.2: S, 4.54; Br, 10.91%.

CFii=CH_with SF5& L The reactants, SP5Br (84 nunal)and CFH=CX2 (102.9 mmol) were condensed into the 75 mL reaction vessel. The reaction mixture was heated at 90f5°C (3dl and at 60°C fldf. The volatile materials, containing SF5CH2CHFBr were removed leaving behind 1.68 g of a waxy solid (slight discoloration>.

The waxy solid

melted in the 100-llO"~ range and decomposed at 190°C. The infrared spectrum of this solid bad the following bands (cm -1 ): 2970 (81, 2941 (81, 1446 (m), 1426 (~1, 1411 (~1, 1370 (ms), 1257 (m), 1067 (s with sh. at 10871, 845 (s), 830 (81, 824 (81, 720 (ml, 705 (ml, 642 601 cm), 565 (ml, 457 fmf.

(ml,

661

The lg F nmr

spectrum

contained

at 0 83; J8F_SF =155

multiplet centered

at 8 -183 ppm.

centered

at

61.8

4 The

(CH2) and

1

Hz,

a complex

the

A nmr

doublet

CF resonance

spectrum

at 8 66

was

contained

Q 64.7 (CA) ppm; relative

(SF41

a complex two

broad

and

a

multiplet multiplets

band areas 2.1:l.O

(theor.

2.O:l.O). Anal. Br, 11.97.

for SF5(CH2CFE)lo Br, calcd: Found:

C, 35.98;

R, 4.54:

S, 4.80:

F, 42.69;

C, 35.79; A, 4.39: S, 4.86; F, 43.0; Br, 11.95%.

CBq=CB2 with SF5E To the 75 mL reactor CA2=CE2 were added. heated at 55i2OC leaving

this

1.1

g of charred

gave a fraction

fraction

confirmed

The reaction

(2d) and 90fS°C

behind

materials

described

(137

boiling its

g/mole),

the material

earlier,

mixture

was warmed

(3d).

The

at 74-77OC

(16h). amount

Again,

used.

The

a volatile

reaction

fraction


mixture boiling

materials

(3.77 g).

the

(91%)

and

warmed

at 74-77OC

of

(16 h), removed

volatile

The molecular

weight

nmr

of

spectra

and SF5CIi2CH2Br (9%).

84.3 mm01 of SF5Br was

136 mmol

were

of

infrared

of FCE2CR2Br

and

to room temperature

Distillation

characteristic

to be a mixture

of SF5Br

volatile

material.

In a second run, under mild conditions, of CR =CH were 2 2

99 mmol

and

to room (3.06

109.2

mmol

temperature

g) and

a small

was formed.

ACKNOWLEDGEMENTS We wish (5084-260-1085)

to express

our

appreciation

for support of this research.

of Idaho obtained

the mass spectrum.

to

the

Gas

Research

Institute

Dr. G.D. Rnerr at the University

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4

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