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QUARTERLY REPORT NO. 7

CONTRACT NO. DA 19-129-AMC-152(N)(0I9116)

WITH

U. 8. ARMY NATICK LABORATORIES

Report Period» 1 January 1965 - 31 March 1965

SYNTHESIS AND POLYMERIZATION OP

FLUORINATED SULFUR MODIFIED

NITROSO RUBBER

I ».

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By

Eugene C. Stump, Ward H. Oliver, and Calvin D. Padgett

23 April 1965

Peninaular ChemReeearch, Inc. Poet Office Box 14318 Gaineeville, Florida

i

I !

QUARTERLY REPORT NO. 7

CONTRACT NO. DA 19-129-AMC-152(N)(019H6)

WITH

U. S. ARMY NATICK LABORATORIES

Report Period: 1 January 1965 - 31 March 1965

SYNTHESIS AND POLYMERIZATION OF

FLUORINATED SULFUR MODIFIED

NITROSO RUBBER

By

Eugene C. Stump, Ward H. Oliver, and Calvin D. Padgett

23 April 1965

Peninsular ChemResearch, Inc. Post Office Box 14318 Gainesville, Florida

t

FOREWORD

This report was prepared by Peninsular ChemResearch, Inc. /SX'

under Contract No. DA 19-129-(AMC)-P&?-(N) (OI 9116) for the U. S. Army

Natick Laboratories with Mr. C. B. Griffis as Project Officer. This is the

seventh Quarterly Report under this contract and covers the period 1 January

1965 through 31 March 1965.

Personnel engaged in this research are Dr. Eugene Stump,

Project Supervisor (27.5%), Dr. W. H. Oliver, Senior Research Chemist (90%)

Calvin Padgett, Research Chemist(97. 6%).Analytical work was performed under

the supervision of Van May. Drs. Paul Tarrant and George Butler are acting

consultants.

It is estimated that 90% of the work is completed and that 89. 9%

of the estimated costs have been incurred to date. To the contractor's best

knowledge the funds remaining unexpended are sufficient to complete the work

called for in the contract.

- i

*

ABSTRACT

Perfluorobutadiene has been reacted with oxygen in sunlight to

give a mixture of products possibly containing perfluorobutadiene monoxide.

Reaction of tetrafluoroethylene with nitrosyl bromide gave CF^BrCF^NO and

a lower boiling nitroso compound, as yet unidentified. Perfluorosuccinic

anhydride did not react with nitrosyl chloride at room temperature. Pyrolysis

of CH^OOCCF^CF^COONO gave a blue product believed to be CH^OOCCF^CF^NO.

A larger reactor for the pyrolysis of CF^COONO was constructed. About

120 g. of CF^NO is produced in 8 hours. The addition of nitrosyl chloride to

CF^NO/CF2=CFCF=CF2 copolymer gives a blue polymer containing nitroso

groups and having a Tg of -85°. CF^OF was added to CF^NO/CF^CF^/

CF2=CFCH=CH2 terpolymer. A gum copolymer having a Tg of -48* has been

prepared from CF NO/CF SCF=CF Copolymers of CF =CFBr with CF NO j ó £ Cd j

and terpolymers with CF NO/CF =CF have been prepared. CF =CFBr j Cd C* Cd

apparently has a higher reactivity ratio than CF^CF^ in this polymerization.

An attempt to incorporate p-trifluorovinylbenzoic acid as a termonomer was not

successful.

-li¬

li

TABLE OF CONTENTS

I. INTRODUCTION.

II. DISCUSSION .

A. Monomer Synthesis . ..• *

B. Synthesis of CF^NO.

C. Reaction of CF„OF and C1NO with Unsaturated Polymers.

D. Polymerization.

III. EXPERIMENTAL.

A. Monomer Synthesis.

1. Pyrolysis of Perfluoro(2-methyl-3, 6-dihydro-l, 2, 2H-oxazine

2. Reaction of Perfluorobutadiene with Oxygen.

3. Reaction of Tetrafluoroethylene with Nitrosyl Bromide.

4. Reaction of Perfluorosuccinic Anhydride with Nitrosyl Chloride.

5. Pyrolysis of CH^OOCCF^CF^COONO.

6. Synthesis of 4-Methyl- a. , ß, ß-trifluorostyrene

B. Synthesis of CF^NO.

C. Reaction of CF OF and C1NO with Unsaturated Polymers.

1. Reaction of CF OF with cf3no/cf2=cf2/cf2=cfch=ch2

Terpolymer.

2. Reaction of C1NO with CF NO/CF =CFCF=CF Copolymer.

3 2 ¿ D. Polymerization.

1. General Procedures for Polymerizations Described in the Tables.

iii -

1

2

2

4

4

6

14

14

14

14

15

15

15

15

16

16

16

16

17

17

#

IV. MONOMER PROCUREMENT.. 18

V. SAMPLES SUBMITTED. 19

VI. MONOMER LIST 20

TABLES

Table 1 Copolymerization with CF^NO. 9

Table 2 Terpolymerization . .. 10

Table 3 Miscellaneous Polymerizations. 13

FIGURES

Figure 1 Infrared Spectrum of Unidentified Nitroso Compound . 23

Figure 2 Infrared Spectrum of Volatile Products from Perfluorobutadiene-Oxygen Reaction. 23

Figure 3 Infrared Spectrum of CF^NO/CF^CFCF^F^

Copolymer after Reaction with C1NO. 23

Figure 4 Infrared Spectrum of CF^NO/CF^CF^/

CF2=CFCH=CH2 Terpolymer after Reaction

with CF3OF. 24

Figure 5 Infrared Spectrum of CF^NO/CF^SCF^F^

Copolymer. 24

Figure 6 Infrared Spectrum of CF3NO/CF2=CFBr

Copolymer. 24

- IV -

#

CORRECTIONS TO QUARTERLY REPORT NO. 6

Page 25, Figure 5 should read "Infrared Spectrum of

cf3no/cf2=cf2/cf2=cfcf=cf2/cf2=cfch=ch2. "

(t

I. INTRODUCTION

The research described in this report is part of a continuing

program sponsored by the U. S. Army Natick Laboratories and concerned with

the development of so-called "nitroso rubber", a 1:1 copolymer of trifluor

nitrosomethane and tetrafluoroethylene. A list of references describing

prior research was given in the First Quarterly Report.

The primary objective of this contract was to enhance the

desirable properties, in particular the low-temperature flexibility, of nitroso

rubber by the incorporation of sulfur atoms in a modified polymer structure.

Secondary objectives included the synthesis of desirable monomers, including

monomers not containing sulfur, and their polymerization in the nitroso rubber

system. This research has been described in previous reports.

Recently, the objectives of the contract were modified and

increased in scope. During this quarter major emphasis was placed upon

the incorporation of termonomers in the nitroso polymer system. The

objective of this work is to provide a cross-linking site along the polymer

chain which would not require the use of the ususal diamine cure.

1 -

#

IL DISCUSSION

A. Monomer Synthesis

Concurrent with our polymerization effort we are carrying out

research on the synthesis of several ccmpounds of potential interest as

termonomers.

Since nitroso-substituted perfluoroacids have been shown to

terpolymerize in the nitroso system to give a polymer which may be cured

through the carboxy group, * the synthesis of an ester derivative,

CH OOCCF CF NO, has been initiated. This synthesis involves the conversion 3 ù Cà

of perfluorosuccinic anhydride to its half-acid ester by reaction with methanol,

followed by formation of the silver salt and its conversion to the nitrite with

nitrosyl chloride.

CF C = O I > + CH OH

CF C = O > CH3OOCCF2CF2COOH

i AgzO

CH3OOCCF2CF2COONO < C1NQ- CH3OOCCF2CF2COOAg

The final step consists of pyrolysis of the acid nitrite to the desired product.

This series of reactions was started by reaction of the silver salt (from PCR

stock) with nitrosyl chloride. The yellow, liquid acid nitrite was not isolated

but was heated under vacuum to give a blue vapor. This product has not yet

been isolated as a pure compound for identification but is thought to be the

(1) 3M Co. , Research Report on Contract DA-19-129-QM-a684, "Arctic Rubber", 23 December 1962.

- 2 -

é

desired nitroso ester. An attempt to isolate the nitrite by extraction with

ether resulted in its complete decomposition. Since a vigorous reaction also

occurs when sodium-dried ethyl ether is added to CF^COONOi it is apparent

that another solvent must be found if the nitrite is to be extracted from the

silver chloride by-product.

An attempt was also made to prepare the nitroso propanoic acid

by the sequence below. No reaction occurred,

GF G = O I ¿ + C1NO cf2c o

ONOOCCF2CF2COCl

A

ONCF2CF2COOH H2°

ONCF2CF2COCl

however, when perfluorosuccinic anhydride and nitrosyl chloride were mixed

at room temperature.

The reaction of tetrafluoroethylene with nitrosyl bromide in the

vapor phase with ultraviolet radiation has also been carried out to give

CF BrCF NO. About 69 g. of product boiling in the reported range were ù Câ

obtained but, of more interest, about 10 g. of a blue gas boiling at 0° was

obtained as a forerun. This compound is undoubtedly a lower molecular

weight nitroso compound. Its infrared spectrum (Fig. 1) is simple, exhibiting

No-O absorption at 6. 25 microns and C-F absorption at 8. 08 and 8. 75 microns.

This sample is being purified by GLC prior to NMR analysis and molecular

weight determination.

Since attempts to epoxidize perfluorobutadiene by the method

used to prepare perfluoropropylene epoxide were not successful, we are

3

«

investigating its reaction with oxygen in sunlight. After 5 days irradiation

a clear, colorless liquid had formed. The infrared spectrum (Fig. 2) of the

overgas exhibited a distinctive peak at 6.6 microns (similar to perfluoropropylene

epoxide) as well as a CF^CF peak at 5. 66 microns. The desired product,

CF =CFCF - CF , would be used as a c ross-linkable termonomer. ¿ 2

Since oxazetidines can be pyrolyzed to give interesting 2

intermediates such as I^N = CF^ and since a supply of perfluoro(2-methyl-

3, 6-dihydro-l, 2, 2H-oxazine) was available as a Diels-Alder by-product-5 of

our CF^NO/CF^CFCFiiCF^ copolymerization, we have pyrolyzed this oxazine

at 550°. Since the volatile mixture has not been separated the results of this

reaction will be described in the next report.

B. Synthesis of CF^NO

Increased scale polymerizations have necessitated scaling up 4 5

the pyrolysis reaction of CF^COONO ’ to supply sufficient monomer. The

apparatus currently in use is described in the Experimental section and

produces about 125 g. of pure CF^NO in an 8-hour day. This capacity is at

present adequate for our demands.

C. Reaction of CF^OF and CINQ with Unsaturated Polymers

The reaction of CF OF with CF NO/CF =CFCF=CF ■j 3 2 2

copolymer was described in the last Quarterly report. During this quarter

the copolymer was reacted in solution with nitrosyl chloride. The product

after precipitation was a light blue gum whose infrared spectrum (Fig. 3) is

very similar to that of the copolymer with the exception of a peak at 6. 2 microns,

(2) D. A. Barr and R.N. Haszeldine, J. Chem. Soc, , 1881 (1955) (3) Quarterly Report No. 6, this contract

(4) Thiokol Chemical Corp. , "Nitroso Rubber Research, Development and Production", Quarterly Report No. 5 on Contract DA-l9-129-AMC-69(x) for the period 1 March 1964 to 31 May 1964 and earlier reports.

(5) G. H. Crawford, Jr., U. S. Patent 3, 162, 692 (22 Dec. 1964). (6) See Fig. 9, Quarterly Report No. 5, this contract.

4-

i

probably due to N-O absorption. Since less than an equivalent amount of

nitrosyl chloride was used, the polymer still exhibits CF2=CF- and -CF=CF-

absorption at 5. 61 and 5. 8 microns, respectively. The presence of pendent

nitroso groups in the polymer might allow cross-linking with a fluorodiene by

oxazetidine formation.

CF.CF -

2I F-C-NO CF =CF

I FCF

Cl

+ (CF ) ' 2 X

Cl FCF

I F - C - NO

! - CF2CF —

cf2-cf

CF.CF -

2| FC —N— O

I I I FCF CF -CF

Cl I F CF CF-CF

I ! 2 I F C - N - O

I CF2CF-

Another particularly interesting feature of the polymer is its

reduced glass transition temperature7. Tg of the copolymer is -43" while

that of the nitrosyl chloride adduct is -85°. The reason for this unusually

low Tg is not immediately apparent.

The addition of CF^F to the CF3NO/CF2=CF2/CF2=CFCH=CH2

terpolymer has also been carried out. A s in the addition to CF3NO/CF2=CFCF=CF2

copolymer, little (if any) residual unsaturation remained as indicated by the

infrared spectrum (Fig. 4) of the polymer.

The fact that additions of this type to double bond in the polymer

can be accomplished is encouraging and suggests that a cross-linking reaction

would occur with the proper difunctional agent.

(7) Determinations by U.S. Army Natick Laboratories

- 5 -

t

An attempt to cross-link a small sample of CF3NO/CF2-CFCF=CF2

copolymer by heaung a solution in refluxing FC-43 was not successful. The

reaction desired was a cyclization of the pendent trifluorovinyl groups to give

cross-link.

CF - CF

D. Polymerization g

An early attempt to copolymerize CF2NO with CF3SCF=CF2

produced a small amount of high-boiling liquid which appeared to be a mixture

of oxazetidine and low molecular weight polymer. This polymerization has

been repeated using larger quantities of the reac.ants in a smaller reactor and,

consequentially, higher pressure. Again, a viscous liquid was obtained but

upon removal of volatile material under vacuum a colorless gum copolymer

remained. The infrared spectrum (Fig. 5) shows a distinctive CF3S peak

at 13. 1. NMR analysis corroborates the copolymer structure. The glass

transition temperature of this sample9 was found to be -48°. Since the Tg

of nitroso rubber is -51°, it would appear that the incorporation of CF^ as

pendent groups in nitroso polymer will not enhance its low temperature

properties.

A copolymer of CF^O and CF^CFBr has been prepared in

order to investigate to possibility of curing by abstraction of a bromine atom.

This polymerization occurs readily to give a tough gum. Intrinsic viscosity of

this copolymer could not be obtained since it was insoluble in FC-43. An

infrared spectrum of this polymer is shown in Fig. 6. Preliminary NMR

analysis indicates that the alternating copolymer structure is formed.

Elemental analysis also indicates a 1:1 copolymer [Ãnal. caled. : %N, 5. 4;

%Br, 30.8. Fd. :%N, 5. 3; %Br, 30. <f| . Conversions were high, in the

(8) Quarterly Report No. 2, this contract (9) DTA analysis by Sadtler Research Laboratories

- 6 -

order of 90%.

Terpolymers with varying amounts of CF^CFBr were also

prepared. Samples containing up to 21. 7 mole% CF =CFBr were soluble

in FC-43. Intrinsic viscosities of these samples were low (see Table 2 for

data). As expected, the glass transition temperature rises with increasing

amounts of CF_ = CFBr as shown: ^ Q

Mole % CF2=CFBr Tg

in polymer

9.4 -45°

21.7 -35°

31.0 -21°

50. 0 (copolymer) + 3“

It is also interesting to note that the ratio of CF^CFBr/CF^-CF^ incorporated

in the polymer was greater than that in the monomer charge and that the total

mole % CF2=CFBr

Sample No. ^

2

3

4

+ CF2=CF2 in the terpolymers exceeds 50%.

Mole Ratio Charged CF NO:CF =CF :CF =CFBr

J L* L* L*

6:5:1

6:4:2

6:3:3

Mole Ratio Found CF NO:CF =CF :CF =CFBr

•J ù Ct ù

6 : 5.6 : 1.2

6 : 4.1 : 2.8

6 : 2.7 : 3.4

Although the reaction of nitrosobenzene with tetrafluoroethylene 12

has been examined , no report of the reaction of CF2=CF2 with N-nitroso

compounds has been found. Since N, N'-dimethyl-N, N'-dinitrosoterephthalamide

is commercially available, an attempt was made to react this compound with

CF2=CF2. The nitroso compound was placed in acetone solution in a flask and

tetrafluoroethylene was admitted. After 5 days, however, there was no apparent

reaction.

(10) From Table 2. (11) By elemental analysis for N and Br (12) Quarterly Report No. 2, this contract

_ 7 _

An attempt was made to incorporate p-trifluorovinyl benzoic

acid as a termonomer by running both in solution and in suspension (using the

sodium salt). In neither case was a detectable amount of acid incorporated.

Similar results were obtained using 4-methyl- , ß, ß-trifluorostyrene,

perfluoroallyl trifluoroethyl ether and hexafluoroacetone as termonomers.

The polymerizations run during this quarter are summarized

in Tables 1, 2 and 3.

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- 13

III. EXPERIMENTAL

A. Monomer Synthesis

1. Pyrolysis of Perfluoro(2-methyl-3, 6-dihydro-l, 2, 2H-oxazine)

The oxazine used was first distilled on a spinning band column

and the fraction boiling at 52-53* (13.2 g. ) was taken for the pyrolysis.

A 2-neck flask was fitted with an addition funnel containing the

oxazine and a 1" x 15" Vigreaux column vented to a trap cooled to -183*. The

system was evacuated to a pressure of 5 mm. the flask was heated to 80-100*

and the column was heated to 550*. The oxazine was added dropwise to the

heated flask. After all but 4 g. of material had been reacted the column became

overheated and it collapsed. The product was transferred to a pressure ampoule

and allowed to warm to room temperature. It then deposited a yellow solid. The

remaining product has not yet been examined.

2. Reaction of Perfluorobutadiene with Oxygen

A 1-1. Vycor flask was charged with CF2=CFCF=CF2 (2.4 g. ,

0.015 moles) and (0.48 g. , 0.015 moles) and placed in sunlight for 5 days.

At the end of this time the flask contained a water-white liquid. An infrared

spectrum of the overgas showed some unreacted diene and a peak at 6. 6

(thought to be -Cf^^CF^ as well as other peaks. A spectrum of the liquid

also showed absorption at 6. 5 - 6. .

The reaction was repeated on a larger scale. A 12-1. flask

was charged with (20. 7 g., 0. 128 moles) and 02 (8. 19 g., 0. 256 moles)

and irradiated with a u. v. lamp through a Vycor immersion well. After 24 hr.

an infrared spectrum of the vapor phase showed a peak at 6. byU and the reaction

was stopped. The products were removed to a trap in liquid air and stored.

They have not yet been separated and examined.

- 14 -

*

3. Reaction of Tetrafluoroethylene with Nitrosyl Bromide

A 72-1. flask was charged with CF^CF^ (127 g. , 1.27 mole)

and BrNO (140 g. , 1.27 mole) and irradiated with u. v. light for 24 hours. The

mixture which was originally brown had now turned blue-green and was

transferred to a flask for distillation. The mixture was distilled on a glass-

packed column to give approximately 10 g. of a blue product boiling at 0* and

69 g. of blue product boiling at 13-20°.

4. Reaction of Perfluorosuccinic Anhydride with Nitrosyl Chlorid^

In an attempt to prepare CIOCCF^CF^COONO, a 100-ml.

flask was charged with perfluorosuccinic anhydride (17. 2 g. , 0. 10 mole)

and C1NO (6. 5 g. , 0. 10 mole) and the contents stirred while the mixture warmed

to room temperature. The overgas was removed under vacuum and e. minaticn

of the liquid residue showed it to be only unreacted starting material.

5. Pyrolysis of CH^OOCCF-.CF^COQNO

A 20-ml. ampoule was charged with CH^OOCCF^CF^COOAg

(6. 5 g. , 0. 021 mole) and C1NO (6. 5 g. , 0. 1 mole) and shaken overnight at room

temperature. The ampoule was then opened to the vacuum system and the excess

C1NO removed. This left a solid wet with a light-yellow liquid. The ampoule

was now vented to a trap in liquid air and a vacuum was maintained while the

ampoule was heated with a heat gun. The yellow liquid began boiling and the

vapor phase turned blue. A blue product was trapped in the -183* receiver.

After heat had been applied for several minutes the material in the ampoule

detonated. The blue product has not yet been analyzed but may be the desired

ch3ooccf2cf2no.

The reaction was repeated on a larger scale with the intention

of washing the yellow liquid (proposed CH^OOCCF^F^OONO) free from the

solid (AgCl) with dry ether. However, the ethyl ether reacted vigorously with

the product resulting in complete decomposition.

6. Synthesis of 4-Methyl- a , ß, ß-trifluorostyrene

4-Bromotoluene (10 g. , 0.062 mole) was reacted with lithium

in ether to form the lithium reagent. The solution was placed in a 300-ml.

- 15 -

#

Fischer “Porter bottle and cooled in liquid nitrogen. The bottle was exhausted

and excess tetrafluoroethylene was condensed into the bottle. The bottle was

sealed and placed in a cold bath at -30° for 4 hours. The mixture was hydrolyzed

and the ether layer dried. Evaporation of solvent and vacuum distillation gave

4-methyl- a , ß, ß -trifluorostyrene (3 g. , 30%), B. p. 90-92B/70mm.

n(j = 1.478. Reported Bp=91. 5/70 mm, n^= 1.481.

B. Synthesis of CF^NO

Trifluoroacetylnitrite is added at a constant rate to a 5-1. flask

containing refluxing FC-43 (3000g. ). The FC-43 is refluxed through a

2" X 24" column topped by a water-cooled condenser. The products are passed

through the condenser to a wash column containing Raschig ring packing and

circulating 7% aqueous NaOH, then through a CaCl_ drying tube, Linde 4A Cá

Molecular Sieve, and finally into a trap immersed in liquid air.

In a typical run 352 g. of CF^NO was prepared from 945 g. of

a yield of 54%. About 120 g. of CF^NO is prepared per day using

this apparatus.

C• Reaction of CF^OF and CINQ with Unsaturated Polymers

1 • Reaction of CF^OF with CF^NO/CF^CF^/CF^CFCI^CIL.

Terpolymer

A 7 g. sample of CF3NO/CF2=CF2/CF2=CFCH=CH2 terpolymer

(3:2:1) was dissolved in Freon 113 and reacted with CF^F (2 g. ) as described

in Quarterly Report No. 6 (p. 18). Infrared (Fig. 4) and NMR analysis

indicated complete reaction of CF3OF with the double bonds.

2. Reaction of CINQ with CF^NO/CF^CFCFrrCF^ Copolymer

A 10 g. sample of copolymer was dissolved in 50 ml. of Freon 113.

About 0. 5 g. of C1NO was condensed into the tube, which was sealed and placed

in sunlight for 4 hours. The solution was green at this time. The polymer was

precipitated by addition of acetone. A blue polymer (9 g. ) was obtained upon

drying. The polymer had a Tg of -85° and decomposed upon heating. An

infrared spectrum of this sample is shown in Fig. 3.

- 16 -

D. Polymerization

1. General Procedure for Polymerizations Described in the Tables^

Bulk polymerizations were run by condensing monomers into

ampoules or Fischer-Porter tubes. The tubes were evacuated, sealed at

liquid nitrogen temperature, and transferred to a cold bath for the time indicated.

The suspension polymerizations were run in a similar manner,

except the samples were shaken. The suspending medium was MgCC>3 in a

saturated LiBr-water solution.

In working up the products, the unreacted gases were vented

and the volatile materials recovered by vacuum distillation. The polymer was

then removed, washed and weighed after vacuum drying.

- 17 -

IV. MONOMER PROCUREMENT

During this quarter the following monomers were received from

outside sources:

25 g.

COOH

University of Florida

CF =CFCF OCH-CF L> L» U J

0. 7 g. University of Florida

Tetrafluoroethylene and perfluorobutadiene were obtained from

PCR stock. Trifluorobutadiene was prepared as described in previous reports.

- 18 -

V. SAMPLES SUBMITTED

During this quarter the following samples were submitted to the

U.5. Army Natick Laboratories for evaluation;

Designation

CQC 4. 3

CQC 8. 1

CQC 8. 2

CQC 8. 3

WD 46. 1

WD 51. 1

WD 54. 2

WD 56. 1

WD 57. 1

Charged Composition Amount (g.)

CF3NO(l)/CF2=CFBr(l) 5

CF3NO(6)/CF2=CF2(5)/CF2=CFBr(l) 5

CF3NO(3)/CF2=CF2(2)/CF2=CFBr(l) 5

CF3NO(2)/CF2=CF2(l)/CF2=CFBr(l) 5

CF3NO(3)/CF2=CF2(2)/CF2=CFCH=CH2( 1) 5. 5

CF3NO(3)/CF2=CF2(2)/CF2=CFCH=CH2( 1)+ 6.5

cf3of

CF3NO(l)/CF2=CFCF=CF2(l) + CINQ 2

CF3N0(6)/CF2CF2(5)/CF2=CFCF=CF2(1) 5

CF3NO(6)/CF2=CF2(5)/CF2=CFCH=CH2( 1) 5

- 19 -

#

VI. MONOMER LIST

The monomers listed below have been assigned the identification

numbers shown. These numbers will be used frequently throughout future

reports in place of cumbersome nomenclature or structures. A complete

list of monomer number assignments will be given in each report.

Number

400

401

402

403

404

405

406

407

408

409

Monomer

f2c=s

C6F5NO SF5CH=CH2

CF3SCF=CF2

(cf3)2c=s

CF3N=SF2

c6h5n°

[ICF3CF2CH2CH2Si(CH3)cQ 3

[CF3CF2CH2CH2Si(CH3)0] 4

cf3scf(no)cf2ci

F F F F

410

411

412

413

414

415

h2n

F F

F F

ON

F F

NH,

F F

F F

NO

F F

h2nnh

F F

O F F

NHNH,

NH„

HOOC

F F

COOH

F F

F F

416 SFgCF = CF2

#

417

418

419

420 (nc)2c = c(cn)2

4¿ 1

422 CF2BrC>¿nO

423 C: iOOCCF2CF2NO

- U -

i iirmr- 'iiwiniinmn rin irrrimrrir^f iijirwrflliwtiliïl1 iii 'lili i ' iii ^ ‘‘•IN1'H wlliBi'lillf",lll’Wfe ililiilHMIilliM

«

MrAVINUMftfk CM '

WOlNVMlti C

Figure 2. Infrared Spectrum of Volatile Products from Perfluorobutadiene -Oxygen Reaction

WAvtNUMMI CM

23

WAVINVMMI Cl«'

wâ*iiiNOn* M wcio*ii

Figure 4. Infrared Spectrum of CF^O/CF^CF^CF^CFCI^CI^

Terpolymer after Reaction with CF3OF

Figure 5. Infrared Spectrum of CF3NO/CF3SCF=CF2 Copolymer

Figure 6. Infrared Spectrum of CF3NO/CF2=CFBr Copolymer

24

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