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THE M.W.KELLOGG COMPANY

"1

THE M. W. KELLOGG COMPANY Petroleum & Chemical EEWiSS

Research Dept. Jersey City. N. j. Report No. RL-5V289

Petroleum and Chemical Research Department

PROGRESS REPORT

ARCTIC RUBBER

U.S. Army Contract DA-U4-109-qm-222 Project No. 7-93-15-60U

For the Period April-July, 1933

August 1, 1953

Copy No. lu Report RL-53-289

Petroleum and Chemical Research Department Laboratory Division, Jersey City, New Jersey

1

:

t

THE M. W. KELLOGG COMPANY Patrolaum I Chemical

Research D«pt J«rs»y City, N. J.

BE^BD

RtportNo. RL-53-289

Subject:

Staff:

PROGRESS REPORT

Arctic Rubber - U.S. Army Contract DA-UU-109-qm-222 Project No. 7-93-15-60*+ For the Period April-July, 1953

J.W. Copenhaver, F.J. Honn, A.N. Bolstad, J.M. Hoyt, A.G. Davis, B.F. Landrum, M.E. Conroy, L.E. Robb

Authors: J.M. Hoyt and F.J. Honn

:

Period Covered: April 1, 1953 to July 31, 1953

L.O. No. D-122; Job No. 5531

Previous Reports on this Subject:

RL-50-139 dated November 1, 195-' RL-51-1U6 11 February 1, 1951 RL-51-156

H April 1, 1951 RL-51-163

11 July 1, 1951 RL-51-171*

n October 1, 1951 RL-52-183

11 February 1, 1952 RL-52-195

ti May 1, 1952 RL-52-209

11 August 1, 1952 RL-52-2U8 11 October 1, 1952

RL-53-259 11 January 1, 1953

RL-53-27^ 11 April 1, 1953

I

Approved:

THE M. W. KEUOGG COMf ANY Pttroltum & Chamico!

Rtstorch D«p» Jtrity City, N. J.

05^21

R.portNo. RL-53-289

CONTENTS

I. Introduction

A. Purpose of the Project B. Research Program C. Past Progress

II. Summary of Current Progress

III. Experimental Section

A. Monomer Synthesis B. Monomer Analysis C. Polymer Preparation

1. Copolymers of CH^CHF 2. Copolymers of CFn-CHoCH-CH-CHg 3. Copolymers of CF^CCCH^-CH-CHg k. Copolymers of CF3-CHs=CF2 5. Vinyl Ether and Vinyl Ester Copolymers 6. CFg^CFCl/CFg-CHg/X Terpolymers 7. Reactivity Ratios for the CF^Fg/CH^CFCl Syste 6. Miscellaneous Exploratory Copolymerizations 9- Extreme High Pressure Polymerization

10. Polymerization Recipes

D. Polymer Evaluation

1. Properties und Uses of X-300

a. Vulcanization b. Softeners and Fillers c. End Items

2. Screening of Raw Polymers

IV. Pilot Plant Operations

V. Final Report - Plans for Future Work under New Contract

m

Page No.

k

k k 5

7

6

6 11 1?

13 13 13 13 ll* 11* 15 it 16 17

16

18

16 19 19

19

21

21

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THE M. W. KELLOGG COMPANY Pttrolaum & Chemical '^w

r<es»arch D«pt j.n.y City, N. J. Report No. RL-S^-PRQ

Introduction

A. Purpose of the Project

The primary purpose of this project is the development of a fluorine containing oil- and fuel-resistant elastomer which will retain its rubbery properties between -70°F. and +l60°F. A more recent objective is the pilot plant production and large scale evaluation of the more promising elastomers, with special emphasis on the polymer currently designated by M.W. Kellogg as "X-300 Rubber."

B. Research Program

To achieve this goal, the M.W. Kellogg Company has been authorized by the Quartermaster Corps to conduct a broad investigation of fluoro- carbon polymers involving (l) monomer synthesis; (2) polymer preparation; and (3) polymer evaluation. Emphasis has been placed upon polymer preparation and especially upon the copolymerization of fluoroolefins and fluoro-chloro-olefins among themselves and with olefinic and diolefinic hydrocarbons.

Monomer synthesis at Kellogg has been restricted to products arising from the thermal dimerization of CF^CFCl, namely, CF2=CF-CF=CF2, CFg-CF=CF-CF2, and CF^-CF^Fg. Where feasible, the preparation of other monomers, e.g., CF^CF^ and CF2=CHF, has also been undertaken in these laboratories. For the most part, however, monomers not available commercially have been requested from Dr. Paul Tarrant of the University of Florida, Dr. Aldrich Syverson of the Ohio State University, and Dr. W.T. Miller of Cornell University, or obtained on an exchange basis from Minnesota Mining and Manufacturing Company.

Polymer preparation has proceeded through four phases: (a) exploratory copolymerization of new monomer pairs; (b) determination of the relative reactivities of monomers successfully copolymerized into elastomers; (c) synthesis of pound batches of these elastomers in several comonomer ratios for evaluation; and (d) pilot plant production of one elastomer (Kellogg "X-300 Rubber") which is of interest to the Quarter- master not so much as an Arctic Rubber but more precisely as an acid- and oxidant-resistant elastomer for protective suits, gloves, and boots. A new phase, initiated during the present quarter, will involve the testing of small samples of unvulcanized, rubbery polymers, obtained from exploratory work, for oil-resistance and low temperature flexibility. This testing program will be carried on at the Quartermaster Depot in Philadelphia.

HI

THE M. W. KELLOGG COMPANY ••trol.um & Ch.m.col BtVL^

Ressorch Dapt. J.rs.y City, N. J Report No. RL-5V289

Recently, a program has been initiated for comparing all rubbery products obtained in exploratory work as to oil- and fuel-resistance and low temperature flexibility. Small samples (l-2 g.) of the raw polymer will be subjected to the Gehman torsional stiffness test and the solvent swell test in ASTM Reference Fuel No. 2.

Polymer compounding, testing, and evaluation has been carried forward most capably by Mr. C.B. Griffis and his staff at the Philadelphia Quartermaster Depot. The development of uses for X-300 has been the Joint responsibility of Mr. Griffis and the Kellogg Applications Laboratory.

C. Past Progress

1. Quarters completed as of April 1, 1953: H 2. Monomers available for copolymerization: <+¥

a. Purchased: 18 b. Minnesota Mining & Mfg. Co: 3 c. Dr. Tarrant: 10 d. Dr. Syverson: 7 e. M.W. Kellogg Co: 6

3. Copolymer systems investigated: 236 (where the numbers refer to the monomers listed in section III-A, below):

1-2, 1-2-U, 1-2-9, 1-2-11, 1-2-lU, 1-2-21, 1-2-22, 1-2-23, 1-2-2U, 1-2-29, 1-2-33, 1-2-31, 1-2-35. 1-2-1*0, 1-3, l-h, 1-5, 1-6, 1-7, 1-8, 1-9, 1-12, 1-13, 1-lU, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-25, 1-27, 1-28, 1-30, 1-35, 1-36, 1-37, I-39, 1-1*1, 2-3, 2-U, 2-6, 2-8, 2-9, 2-12, 2-13, 2-15, 2-16, 2-17, 2-18, 2-19, 2-21, 2-22, 2-23, 2-Ph, 2-28, 2-29, 2-30, 2-32, 2-3fc, 2-35, 2-37, 2-38, 2-39, 3-1*, 3-7, 3-9, 3-Ht, 3-18, 3-19, 3-20, 3-21, 3-22, 3-23, 3-2U, 3-25, 3-30, 3-32, k, U-5, 1+-6, U-8, k-9, ^-10, U-ll, U-12, U-lU, U-15, U-17, U-19, U-20, U-21, U-22, k-2h, U-25, ^-28, U-29, U-32, U-35, ^-37, U-39, ^1, 5-9, 6-3, 6-9, 6-30, 6-37, 6-1+1, 7-35, 7-37, 1-hl, 8-13, 8-2U, 8-35, 8-37, 8-Ui, 9, 9-12, 9-13, 9-i1*, 9-16, 9-17, 9-18, 9-22, 9-23, 9-27, 9-28, 9-35, 9-36, 9-37, 9-39, 9-M, 10-lU, 10-28, 11-Ul, 12-2U, 12-35, 12-37, 12-Ul, 13-17, 13-18, 1U-22, 11+-28, 11+-35, 1U-37, 1U-U1, 16-18, 16-2U, 16-35, 16-37, 16-Ul, 17-18, 17-2U, 17-35, 17-37, 17-^1, 18-21, 19-22, 19-28, 19-35, 20-22, 20-28, 20-35, 20-37, 20-Ul,

ugRMnHMBMSMMi

THE M. W. KELLOGG COM*ANY Patrolcum I Chcmkol

RasaarcK D»pt J«rjty City, N. J.

BE^S) Report No. RL-53-289

21, 21-22, 21-28, 21-30, 21-35, 21-37, 21-1*1, 22, 22-2**, 22-28, 22-30, 22-32, 22-35, 22-36, 22-37, 22-38, 22-1*1, 23-28, 23-35, 23-37, 23-1*1, 2U-28, 2U-31, 2U-35, 21*-36, 2»*-37, 2U-39, 2l*-l*l, 25-28, 25-35, 25-37, 25-1+1, 27, 27-37, 27-38, 27-1+1, 27-35, 28, 28-30, 28-32, 29-35, 29-37, 30, 30-35, 30-37, 30-1*1, 31-35, 32-35, 32-37, 32-1*1, 33-35, 33-37, 33-1+1, 31+-37, 31+-1+1, 35, 35-36, 35-37, 35-1*1, 37, 37-38, 37-39, 37-1+0, 37-1+1, 38-1*1, 39, 39-1+1, kl, and 1+1-1+2.

1+. Rubberlike systems: 89

1-2, 1-2-lU, 1-2-21, 1-2-22, 1-2-23 1-2-31*, 1-3, 1-5, 1-13, 1-17, 1-22, 2-1+, 2-6, 2-13, 2-17, 2-22, 2-2U, 2 2-3!+, 3-1*, 3-9, 3-ik, 3-18, 3-19, 3 3-21+, 1+-5, I+-28, i*-37, 1+-1+1, 5-9, 6 8-1*1, 9-12, 9-13, 9-17, 9-28, 9-37, 12-37, 12-1+1, 13-18, 11+-22, lU-28, 17-21+, 17-35, 17-1*1, 20-22, 21, 21- 21-1+1, 22, 22-2U, 22-28, 22-32, 22- 21+-U1, 27-28, 27-37, 27-1+1, 28, 28- 30-37, 31-35, 37, 37-39, 37-1+1, 39-

, 1-2-2U, 1-2-29, 1-28, 1-37, l-i+l,

-28, 2-30, 2-32, -21, 3-22, 3-23, -1*1, 7-1+1, 8-37, 9-1+1, 12-28,

16-1+1, 17-18, 22, 21-28, 21-37, •1*1, 2U-28, 21+-31, 30, 28-32, 28-35, 1+1, and 1+1.

5- Monomer reactivity ratios determined:

System

1-3 1-5 1-2 5-9 3-9 3-1+ 1+-5 3-2U

22-21+

_Mj_

CF2-CFCI CFp«=CFCl CF2-CFCI CF2-CCI2 CFp-CClg CF2»CF-CF=GF2 CF2»CF-CF=CFo CFS=CF2 CHg-CFCl

Mp

Butadiene Isoprene CFp-CHp Isoprene Butadiene Butadiene Isoprene Butadiene CFp-CFp

0.0 0.1 0.52 0.0 0.0 0.0 0.0 0.0 2.8

12..

1-35 1.1+1

0.17 0.1*5 0.80 1.35 0.75 1.75 0.1

6. Status of rubberlike systems:

a. Most promising, in pilot plant and undergoing extensive tests: 1-2.

b. Evaluated and rejected as unpromising: 1-3, 1-5, 1-17, 3-9, 5-9, 21, 22 and 28.

THE M. W. KELLOGG COMPANY Petroleum & Chemical KEViftS

Research Dept Jersey City. N. j. Report No. RL-5^-28Q

c. Promising, to be tested: 1-2-14, 1-2-21, 1-2-22, 1-2-24, 1-2-29, 1-13, 1-22, 1-28, 1-37, 1-41, 2-22, 9-24, 2-30, 2-32, 2-34, 3-4, 3-24, 4-28. 4-37, 4-41, 6-41, 7-41, 8-37, 8-41, 9-13, 9-28, 9-37, 9-1+1, 12-28, 12-37, 12-41, 16-41, 17-24, 17-35, 17-41, 21-22, 21-37, 21-41, 22-24, 22-41, 24-28, 24-31, 24-41, 27-37, 27-41, 28-32, 28-35, 30-37, 37-39, 37-41, 39-41 and 4l.

d. Interesting, but better recipes needed to increase yields or to increase proportion of fluorocarbon combined: 2-4, 2-28, 3-lU, 3-lS, 3-19, 3-21, 3-23, 14-22, 14-28, 21-28, 22-28, 22-32, 27-28, 28-30,

31-35, and 37.

e. Relatively uninteresting (low F content or negligible amount of third monomer in 1-2-X systems: 1-2-23, 1-2-31+, 2-6, 2-13, 2-17, 3-22, 4-5 (isoprene copolymers no longer of interest), 9-12, 9-17, 13-18. 17-18, and 20-22.

II. Summary of Current Progress

During the final period of this contract, the number of monomers available for copolymerization studies hus increased to 54, the number of copolymer systems investigated to 357 and the number of rubberlike systems to 145.

Initial results have been received from the screening of a number of raw polymers for oil-resistance and low temperature properties. The indications are that CFp-CH-CCCH^CHg and its copolymers and copolymers of CFg-CH-CH-CHo have fair oil-resistance (25-125$ is volume swell in ASTM Reference Fuel No. 2) and reasonably good low temperature properties. The incorporation of a third monomer into the CF2=CFCl/CF2=CH2 (X-300) system fails to improve its low temperature properties or oil-resistance and, in some cases, harms tnese properties.

The monomers CF2-C(CH3)-CH=CH2 and CF3-CH=CH-CH«=CH2 have been screened for copolymerizability with many other available monomers. The copolymers obtained, most of them rubbery, have been submitted to the QM Depot as raw polymers to be screened for oil-resistance and low temperature flexibility.

Vinyl butyrate and several vinyl ethers were copolymerized with a number of representative fluoro-olefins. The copolymers with CFg—CFg and CF2-CF-CF=CF2 were in nearly all cases rubbery; the CF2=CF2 copolymers appeared to be more rubbery. Samples have been sent for screening.

I *

THE M. W. KELLOGG COMPANY Patrolaum & Chemical

Research D»pt j.r,.y City. N. j. Report No. RL-5V289

BE^Sl

The isocyanate vulcanization of X-300 rubber lacks reproducibillty, although strong organic polyamines seem to overcome this difficulty. A number of alternate curing systems are being investigated at Kellogg.

A comparative study of 50/50 and 30/70 molar CF^-CFCl/CF^CHg (X-300) copolymers has confirmed earlier indications that the 30/70 product has superior low temperature properties and greater resistance to a variety of swelling agents. QM and Kellogg have agreed to consider shifting the composition at X-300 to the 30/70 molar CFg-CFCl/CFg-CHg level as soon as practicable.

X-300 has been successfully softened at the QM Depot by the addition of various plasticizers, viscous resins and oils.

Forty-five more pounds of X-300 rubber (50/50) have been shipped to the QM Depot during this period.

Ill. Experimental Section

A. Monomer Synthesis

Fifty-four monomers are now available for copoiymerization studies:

mmam*

THE M. W. KEUOGG COMPANY Petroleum I Ch«rmtol

Research D«pt. Jtr».y City, N. j. Report N o. RL-S^-?8Q

1.

2.

CFg-CFCl

CF2*CH2

28.

29-

CH^CF-CH-CHg

/CF3

CF3 CF^CFBr 3- CH2=CH-CH»CH2 30.

k. CF2-CF-CF=CF2 31- CHg-CHg

5- CH2-C(CH3)-CH=CH2 32. CF2-CC1-CF3

6.

7-

(CH3)2OCH2

CF2-CF*CF-CF2

33-

3^.

CF3-C(GH3)rCH-COOH

CHg-CH-C-NHg

8. CHg-CHCl 35- CF3-CH^CH2

9- CF^CC^ 36. CHg-CHBr

10. CHo-CH»CHo 37- CFg-CH-CH-CHg

11. C/-Hr- — CH^CHQ 38. CF3-CC1»CC12

12. CH2-:CC12 39- CF3-CC1=CH2

13- CH2-CC1-CH-CH2 1+0. CH2-CHF

Ik. CF2-CF=CF2 Ul. CF?=CH-C(CH3)=CH2

15- CF2=CF-CN k2. CF3-CH-CF2

16. CH2-CH-CN U3. CF3-CH*CH-CH»CH2

17- CH2««CH-C02 -C^H^n) W+. CF2-C(CH3)-CH»CH2

17a CH2»CH-C02-CH3 «*5. CH2«CH-0-C0-CH3

18. CFg-CHCl USa. CH2«CH-0-C0-CH2-CH2-CH3

19- CF3-CCI-CCI-CF3 U5b. CHg-CH-O-CO-CHpCl

20. CFo-CiC-CF3 U6. C£,H5-CH»CH-C02CH3

21. CF2=CFH U7- CH2-=CH-0-CH2-CH3

22. CH2-CFC1 kQ. CH^CH -0-CH2-CH2-Cl

23- Cls-CF3-CH>«CH-CF3 k9. CH2=CH-0-CH2CH(CH3)2

2k. CF2=CF2 so. CF2-C(CH3)-CF-CH2

25- trans - CF3-CH-CH-CF3 51. CF2=CH-CF«CH2

26. CH2»CH-C6H5-CH=CH2

/CF3 CHo=C

52. trans - CpHsOpC-CH-CH-COpCpHs

27: 53. els - C2H502C-CH=CH-C02C2H5

^CH3 5U. CH2-CH-Si(0C2H5)3

THE M. W. KEUOGG COMPANY Pttroleum 4 Chemical

Research 0«pl J«rj»y City, N. J.

•ft" Report No. RL-53-289

10

Dr. Tarrant of the University of Florida prepared two of the twelve new monomers:

#50. CF2-C(CH3)-CF=CH2 Received as the precursor

CF2Br-CH(CH3)-CFBr-CH3, 700 g., b.p. 65-66°/29-5 mm.

Preparation: CH, I benzoyl . '

CF2Br2 + CH2-CH-CF-CH3 per0xlde * CFgBr-CH-CFBr-CR^

#51. CF^-CH-CF-CI^ Received as the precursor

CF2Br-CH2-CFBr-CH3, U00 g., b.p. 55-57°AO mm.

The other new monomers were obtained as samples or by purchase.

No.

#^5

#U5a

#^5b

#^6

#W

#U8

#^9

#52

#53

#5^

Monemer Source

CH2=CH-0-CO-CH3

CH2=CH-0-C0-CH2-CH2-CH3

CH^CH-0-CO-CHpCl

C6Hc,-CH=CH-C02CH3

CH2-CH-J-CH2-CH3

CH2-CH-0-CH2-CH2Cl

CH2=CH-0-CHo-CH(CH3)2

trans - C2Hc,02C-CH=CH-C02C2H5

Cis - C2H502C-CH=CH-C02C2H5

CH2=CH-Si(OC2H5)3

Matheson Co.

Carbon & Carbide Chemicals Corp.

Monomer-Polymer, Inc.

Matheson Co.

Matheson Cc.

Monomer-Polymer, Inc.

Monomer-Polymer, Inc,

Matheson Co.

Matheson Co.

Linde Air Products Co.

Additional supplies of three monomers already on the list were received from Dr. Gyversuu of The Ohio State University.

No.

28. 35. 22.

Monomer Amount B.P.

CH2-CF-CH-=CH2 CF3-CH=CH2 CH2=CFC1

71 g. ca. 100 g. 10.8 lb.

11.3 - 12.0°C

-27 to -21°C.

I

THE M. W. KELLOGG COMPANY Patrolaum & Chemical

Research 0»pt J«rs«y City, N. J. R.portNo. RL-5V28Q

11

Monomers shipped to Bureau of Standards

An additional 10 g. of CF2=CFBr were sent to Dr. D.E. Mann of the Thermodynamic Section of the National Bureau of Standards for study of its Raman spectrum. Previously, 50 g. of CFg^CFBr along with several other fluorocarbons, had been sent for a vibrational spectrum study.

B. Monomer Analyses

The following monomers have been analyzed during this period with the mass spectrometer:

CF3-CH«=CH-CH=CH9

Approximate analysis: C6H7F3

Tank No. D-122M-U3-1

<J-1*

6 or more K compounds (not C/rH^Fo) - probably small concentrations. Chlorine (cannot identify any chlorine-containing compound from spectrum) - trace

CFQ-C(CH3)-CH=CHP

Approximate analysis:

C5H6F2 C5H7F3 C6F4HQ

CF3-CH=CH?

Approximate analysis:

87* 9*

Tank No. D-122M-UU-1

Tank No. D-122M-35-2

C3H3F3 97* C^FgH^ 2* CUF3H5 0.3* Chloro compounds trace -CgHc -containing

compounds 0.6*

Believed to contain appreciable quantities of isomers of CF^-CIWCHg, but this cannot be established.

I

THE M. W. KEUOGG COMPANY Petroleum L Chemical

i

Re»«orch D«pt. Jtri.y City, N. j. Report No. BT-^3-PflO

12

C. Polymer Preparation

Copolymerizations have now been attempted with 357 systems (where the numbers refer to the monomers listed in section III-A, above):

1-2, 1-2-4, 1-2-8, 1-2-9, 1-2-11, 1-2-14, 1-2-21, 1-2-22, 1-2-23, 1-2-24, 1-2-29, 1-2-30, 1-2-31, 1-2-32, 1-2-35, 1-2-1+0, 1-2-1+5, l-2-45a, l-2-45b, 1-2-52, 1-2-53, 1-3, 1-4, 1-5, 1-6, l-T, 1-8, 1-9, 1-12, 1-13, 1-14, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-27, 1-28, 1-30, 1-35, 1-36, 1-37, 1-39, 1-40, l-4l, 1-42, 1-43, 1-44, l-45a, 1-47, 1-48, 1-49, 1-54, 2-3, 2-4, 2-6, 2-8, 2-9, 2-12, 2-13, 2-15, 2-l6, 2-17, 2-l8, 2-19, 2-21, 2-22, 2-23, 2-24, 2-28, 2-29, 2-30, 2-32, 2-34, 2-35, 2-37, 2-38, 2-39, 2-40, 2-42, 2-43, 2-44, 3-4, 3-7, 3-9, 3-14, 3-l8, 3-19, 3-20, 3-21, 3-22, 3-23, 3-24, 3-25, 3-30, 3-32, 3-44, 4, 4-5, 4-6, 4-8, 4-9, 4-10, 4-11, 4-12, 4-14, 4-15, 4-17, 4-19, 4-20, 4-21, 4-22, 4-24, 4-25, 4-27, 4-28, 4-29, 4-32, 4-35, 4-37, 4-39, 4-40, 4-41, 4-42, 4-43, 4-44, 4-45a, 4-47, 4-48, 4-49, 5-9, 5,44, 6-8, 6-9, 6-30, 6-37, 6-41, 7-35, 7-37, 7-41, 7-42, 7-43, 7-44, 8-13, 8-24, 8-35, 8-37, 8-40, 8-4l, 8-42, 8-44, 9, 9-12, 9-13, 9-14, 9-16, 9-17, 9-18, 9-22, 9-23, 9-27, 9-28, 9-35, 9-36, 9-37, 9-39, 9-40, 9-41, 9-42, 9-43, 9_U4, 9-45a, 9-47, 9-48, 9-49, 10-14, 10-28, ll-4l, 11-42, 11-44, 12-24, 12-35, 12-37, 12-40, 12-41, 12-42, 12-44, 13-17, 13-18, 14-22, 14-28, 14-35, 14-37, iU-40, 14-41, 14-42, 14-43, 14-44, 16-18, 16-24, 16-35, 16-37, 16-41, 16-44, 17-18, 17-24, 17-35, 17-37, 17-41, 17-44, 18-21, 19-22, 19-28, 19-35, 20-22, 20-28, 20-35, 20-37, 20-40, 20-41, 20-42, 21, 21-22, 21-28, 21-30, 21-35, 21-37, 21-40, 21-41, 21-42, 21-43, 21-44, 21-45a, 21-47, 21-48, 22, 22-24, 22-28, 22-30, 22-32, 22-35, 22-36, 22-37, 22-38, 22-40, 22-41, 22-42, 22-43, 22-44, 23-28, 23-35, 23-37, 23-40, 23-41, 23-42, 23-44, 24-28, 24-31, 24-35, 24-36, 24-37, 24-39, 24-40, 24-41, 24-42, 24-43, 24-44, 24-45a, 24-47, 24-48, 24-49, 25-28, 25-35, 25-37, 25-40, 25-41, 25-42, 25-44, 27, 27-37, 27-38, 27-41, 27-35, 27-40, 27-42, 27-44, 28, 28-30, 28-32, 29-35, 29-37, 29-40, 29-42, 29-43, 30, 30-35, 30-37, 30-40, 30-41, 30-42, 30-44, 31-35, 31-42, 32-35, 32-37, 32-40, 32-41, 32-42, 32-43, 32-44, 33-35, 33-37, 33-40, 33-41, 33-42, 33-44, 33-37, 34-41, 34-42, 34-44, 35, 35-36, 35-37, 35-40, 35-41, 35-42, 35-43, 35-44, 37, 37-38, 37-39, 37-40, 37-43, 38, 38-40, 38-41, 38-42, 38-44, 39, 39-40, 39-41, 39-42, 39-43, 39-44, 4o, 40-42, 4l, 41-42, 41-43, 41-44, 42, 42-44, 43 and 43-44.

Of these systems, 145 can be considered rubber-like:

7_44, 8-37, 8-41, 8-44, 9-12, 9-13, 9-17, 9-28, 9-37, 9-4l, 9-43, 9-44, 12-28, 12-37, 12-41, 13-18, 14-22, 14-28, 14-43, 14-44, l6-4l, 16-44, 17-18, 17-24, 17-35, 17-41, 17-44, 20-22, 21, 21-22, 21-28, 21-41, 21-43, 21-44, 2l-45a, 22, 22-24, 22-28, 22-32, 22-41, 22-42, 22-43, 22-44, 23-44, 24-28, 24-37, 24-41, 24-43, 24-44, 24-45a, 24-47, 24-48, 2'i-49, 27-28, 27-37, 27-41, 27-44, 28, 28-30, 28-32, 28-35, 30-37, 30-44, 31-35, 32-43, 32-44, 33-44, 35-37, 35-40, 35-43, 35-44, 37, 37-38, 37-41, 37-43, 38-44, 39-41, 39-44, 41, 41-43, 41-44, 42-44, 43, and 43-44.

THE M. W. KELLOGG COMPANY Patrolaum k Chamicol

I

Research D«pt. vu

J.rs.y City, N. J. R.port No. RL-5V289

Experimental data relative to the exploratory work carried out during the current period are set forth below:

1. Copolymers of CHp»CHF

A series of copolymerizations were run with CHp=CHF to complete the screening of this monomer with all monomers currently available. It was found that CH2«CF is relatively unreactive, and that only the CFo-CH=CH2 copolymer was rubbery (#1112, Table l). All runs are summarized in Table 1.

2. Copolymers of CF3-CH=CH-CH=CH?

Results from the copolymerization screening of CF3-CH=CH-CH=CH2 appear in Table 2. A more complete screening was not possible because of the short supply of this monomer. The hnmopolymer of CFT-CH=CH-CH=CH2 is rubbery but not very snappy. The copolymers are also rubber-like.

3. Copolymers of CFg=C(CH3)-CH=CHg

A fairly complete screening of this monomer has been carried out. The results are shown in Table 'j. The homopolymer itself is rubbery, as are a number of the copolymers.

Both CF2=C(CH3)-CH=CH2 and CF^-CH-CH-C^CHg behave like reactive dienes; in copolymerization, they resemble butadiene and isoprene rather than perfluorobutadiene .

The copolymers of CF3-CH=CH-CH=CH2 and CF2=C(CH3)-CH=CH2 to be screened for lew temperature flexibility and oil resistance are listed in Table 11.

h. Copolymers of CFj-CH-CF?

Results from the exploratory copolymerizations of CF3CH=CF2 (monomer 1+2) appear in Table h. This monomer was disappointingly inert, and no interesting rubbery materials were obtained. The copolymers were either non-rubbery or did not contain appreciable amounts of this comonomer. It had been hoped that this monomer would introduce trifluoromethyl groups into the polymer chain as points of irregularity, thus leading to better low-temperature properties. The trifluoromethyl groups should also reduce the solubility of the polymer- In general the available fluorinated propenes, CF3«CF=CF2, CF3CH=CH2, and CF3CH«CF2 have been unreactive or have not given rubbery products. Of the chlorofluoropropenes, CF3CC1=CC12 and CFoCCl-C^ have proved inert and uninteresting as far as we have explored these systems, but CF3CC1=CF2 has formed several copolymers in fair yield, some of which may be interesting as rubbers.

I THE M. W. KELLOGG COMPANY

Pctroltum & Chtmical Restore^ D«pt

J.rsty City, N. j. Report No. RL-53-289 11*

5. Vinyl Ether & Vinyl Ester Copolymers

Results from the exploratory copolymerization of representative fluorooleflns with vinyl ethyl ether, vinyl 2-chloroethyl ether, vinyl isobutyl ether, and vinyl butyrate ure summarized in Table 5- It was observed that the copolymer with CF2-CF2 gave the most rubbery product in each case. Copolymers of perfluorobutadiene were rubbery, but somewhat stiffer and shorter than the CF^CFg copolymer.

The CF^CFCl copolymers were very slightly rubbery at room temperature.

No attempt was made to determine in each case whether, and to what degree, side-by-side horaopolymerization took place. Generally, vinyl ethers produce only balsam-like, low-molecular weight products with radical catalysts. It has been observed that in bulk copolymerization of vinyl ethers and fluoroolefins that some homopolymerization of the vinyl ether occurs. (R.M. Adams and F.A. Bovey, J. Polymer Sci., £, WBl (1952)).

The copolymers which were obtained in runs 1333 ^nd 1339, in which a 25/75 CFg^CFCl/vinyl ether charge was used, show a high CFg-CFCl

J content. A simple calculation shows these analyses cannot represent the composition of all the copolymer formed since appreciably more CFg^CFCl would have to be present in the copolymer than was charged. This may point to a lack of homogeneity and possibly some side-by-side homopolymer- ization.

6. CF>>-CFCl/CF2-=CH2/X Terpolymers

In an attempt to improve the low temperature properties of the CF2=CFCl/CF2="CH2 copolymers designated as X-300 rubber, a series of terpolymerizations has been carried out, wherein the CFg^CFC1/CF2=CH2 ratio was to be held as closely as possible to 50/50 molar and the third monomer admitted to the system up to 20 mole per cent of the total. A summary of all terpolymerizations carried out during this period appears in Table 6. Of these, Runs 1297, 1315, lUl6, 1278, and H38 are to be screened for oil resistance and low temperature flexibility (Table ll).

Terpolymerization of vinyl acetate to the extent of 20 mole per cent of the whole product results in the disappearance of the rubber- iness characteristic of X-300. (Run 1195, Table 6). If the vinyl acetate combined is dropped to 7 mole per cent, the product is still rubbery, but inferior in this respect to X-300 (Run 1278, Table 6). If vinyl butyrate is terpolymerized, however, the product is still rubbery at 20 mole per cent vinyl butyrate, although not extremely so (Run 1316, Table 6). At k mole per cent vinyl butyrate (Run 1315), the product is similar to

M X-300 as far as apparent rubberiness is concerned.

THE M. W. KELLOGG COMPANY Pctroltum & Chtmicol

Research D»pt J«ri»y City, N. J. R.portNo. RL-53-P89

Vinyl chloride as a third monomer in this system has proved disappointing. Amounts up to 20 mole per cent appear to inhibit polymer- ization, and at best only powdery materials are obtained.

Based on the evaluation of terpolymers 909, 970, 955, 987, 1088 and 1190 where X of system CFgsCFCl/CF^CHg/X is CH^CFCl, CHg-CFCl, CF2=CFBr. CH2-CH2, CH2=CHF or CF2=CHF respectively, (see Table 10 and Figure 3); this approach to improved low temperature properties for X-300 rubbers has been unrewarding. The terpolymers tested have been no better and in some cases poorer than X-300.

Consequently, CF2=CFCl/CF2»CH2/X terpolymerization is being abandoned for the present, and efforts concentrated on arriving at this optimum CF2»CFCl/CF2=CHp ratio for low temperature flexibility, oil- resistance, and processibility.

7. Reactivity Ratios for the CF2=CF2/CHp=CFCl System

This system is of importance not only because some of its ratios are rubbery, but because it may provide an alternate route to the manufacture of X-3'00 rubber. A 50/50 molar copolymer of each system contains the same -CFo-, -CHg- and -CFC1- groups in the same proportions. Differences should arise only through the arrangement of these groups, i.e., through the mode of addition of the monomer units to each other during copolymerization. As yet, there is no definitive evidence on this point.

Monomer reactivity ratios have been computed for CH2=CFC1 (ML) and CF2=CF2(M2). The parameters found (rx= 2.8 ± 3-3, rg = 0.1 t O.l) are based on the following data:

Run Charged Found * Hours /l/ No. CHo=CFCl/CFo=CFp

50/50 82/18

Conversion Polymerization

2h

Appearance

689 5U rubber

809 30/70 26M 98 78 11

810 10/90 9/91 96 78 powder

1117 50/50 5lA9 97 23 ti

1118 30/70 32/68 99 23 rubber 1119 30/70 28/72 92 23 powder 1120 10/90 32/68 20 2.5 rubber 1206 50/50 80/20 8 0.3 11

1207 70/30 87/13 12 0.3 11

1208 30/70 67/33 10 0-3 11

/!/ Persulfate-bisulfite-iron suspension recipe at 20°C.

I THE M. W. KELLOGG COMPANY

Patrolium A Chtmicol

f

c

Research D»pt. •" J.rs.y City, N. J. Rtport No. RL-53-289 l|

The instantaneous composition diagram for this system is presented in Figure 1. The reactivity parameters show that the radical -CF2CF2- prefers M^ (CH^CFCl), whereas the radical -CH2-CFC1- is not as selective, preferring to homopolymerize very slightly. In order to maintain homogeneity in such a system the conversions must be kept very low as the CH^CFCl disappears rapidly (cf. Figure 2).

Several CF^CF^CH^CFCl copolymers have been submitted for low temperature flexibility and oil resistance screening tests (Table ll).

8. Miscellaneous Exploratory Copolymerlzations

A number of miscellaneous exploratory copolymerizations are summarized in Table 7. Only two of these produced rubbery materials (Runs 1203 and 1277).

Run 1277 yielded a rubbery copolymer of CF2«CF2 and n-butyl aerylate, presumably of the grafted type. A sample of the raw polymer has been sent for evaluation (Table ll). The corresponding CF2=CFC1 copolymers have not been outstanding in oil resistance and have been difficult to vulcanize. (Progress Report RL-53-259, P- 16).

Run 1203 is the designation of a rubbery material found in a tank in which CF2=CF-CF=CF2 distillation "tails" had been stored at dry-ice temperature for ab.iut three months.

analysis indicates this material is not polyperfluorobutadiene, and no alternative structure has as yet been assigned.

An attempt to polymerize CF2=CF-CF=CF2 using azobisisobuty- ronitrile at 1+0-60° was a failure, again emphasizing the unreactivity of this monomer (Run 1219). Perfluorobutadiene could not be induced to copolymerize with S02 at 60° (Run 1300).

The system CF^FCl/CH-CH-SUOCgH^ was unreactive (Run 1236).

9. Extreme Pressure Polymerization

The necessary equipment for running high pressure (10,000 atm) polymerizations has been received from J. Unertl Co., Pittsburgh, Pa. This unit consists of a heavy-walled cylinder and plunger in which a few grams of monomer will be subjected to extreme hydraulic pressures by concentrating the force applied to a large ram on the small diameter plunger. The first experiments will be carried out with CF2=CF-CF=CF2 in an effort to duplicate W.T. Miller's early work.

THE M. W. KELLOGG COMPANY Petroleum t, Chemical

Research Dept. Jeney City, N. J. R.portNo. RL-53-289

IT

10. Polymerization Recipes

For reference purposes the recipes commonly used by the Arctic Rubber Group in exploratory polymerization work are included in this report.

1. Mutual Recipe Temperature 50 C.

Water Monomers KORR Soap K2S2°8

pH

200 parts by weight 100

5 0.3 0.3 10.2

KORR is the designation for a saturated fatty acid potassium soap supplied in flake form by Proctor and Gamble.

Company. DDM is tertiary dodecyl raercaptan sold by Phillips Petroleum

I

Mutual-F Recipe Temperature 50°C.

Water 180 parts by weight Monomers 100 " C7F1,-C00NH1+ 2.5 "

J.3 " DDM 0.15 " pH 10 Concentrated buffer sol. -20

Cumene Hydroperoxide Redox Recipe (CHP - Redox)

Temperature 20°C.

Water 200 parts by weight Monomers 100 " " KORR Soap 5 " CHP (100#) 0.15 " NauP207-H20 FeSOu•7H26

1.00 " " 0.10 "

Dextrose 1.00 " " DDM 0.3 "

CHP is supplied by Hercules as a 75$ solution.

THE M. W. KELLOGG COMPANY Patrolaum & Ch»micol

Resaarcfc D«pl. J«rj«y City, N. J. RtportNo. RL-53-28Q 18

k. Persulfate-Bisulfite-Iron Suspension Recipe Temperature 20°C.

Water Monomers (NHU)2S208) Na2S20c FeS0^.7H20

200 parts by weight 100 " 1.0 " O.k " 0.1 "

The parts by weight of catalysts are frequently varied. The above recipe is typical.

5. Mass Polymerization Recipe Temperature -15 C.

Monomers 100 parts by weight Bis-trichloroacetyl 0.037 "

peroxide Freon-11 <0.93 "

The catalyst is handled in Freon-11 solution. Some of this solvent is cautiously evaporated before adding monomers. The amount of catalyst is only illustrative; it may be varied considerably.

D. Polymer Evaluation

1. Properties and Uses of X-300 Rubber

a. Vulcanization

It was found during this period that the high tensile strength formerly obtained from the diisocyanate vulcanization of X-300 rubber could not be duplicated. However, it has since been shown that the diisocyanate cure can be accelerated with strongly basic organic amines such as triethylene tetramine (TETA). These latest findings are summarized in Tables 8 and 9. The addition of the amine to the MDl/ZnO recipe increases the tensile strength from 700 psi to > 1500 psi. Both TETA and hexamethylene tetramine (HMTA) have been used successfully. None of the curing agents synthesized at Kellogg appears to be superior to MDI.

Strongly basic organic diamines (alone) can also bring about X-300 vulcanization, as illustrated by the high tensiles observed for stock 13FU8. However, high levels of amines (e.g., 5 parts per 100 parts of X-300) tend to scorch the rubber during milling and to prevent easy flow during molding.

THE M. W. KELLOGG COMPANY Pttroltum I Ch.mical ISttiSiS

Research D«pt J.rs.y City, N. j. R.port No. RL-53-289

= 19

An intensive search for curing agents other than iso- cyanates and amines is being carried out at Kellogg. The results of this study will be reported when more data are available.

b. Softeners & Fillers

An increase in the plasticity of X-300 is highly desirable, especially for 6tocks which are to be calendered or extruded.

The QM Depot has attempted to soften X-300 rubber by incorporating plasticizers, viscous resins and oils. Such additives as over-modified X-300, telomer broad cut, Flexol TOF, Reogen, Vistanex B-100, dibutyl sebacate and Mercoflex 600 have been used in quantities up to 20 parts per 100 parts of X-300 to produce smooth sheets with the X-300/Zn0/ MDI/TETA (lOO/5/5/l) recipe. The softening of X-300 stock by other means, such as changes in copolymer ratio (50/50 to 30/70) and molecular weight modification during polymerization is also being considered.

c. End Items for QM

Protective suits, boots, and gloves are the end items ^ of greatest interest to QM. Work has been delayed on these applications ' for X-300 rubber because of difficulties encountered in reproducing the

isocyanate cure. However, some of the newer curing systems look promising enough for end item development to be resumed during the next period.

2. Screening of Raw Polymers

In an attempt to evaluate rapidly the large number of copolymers prepared in our exploratory work, it was decided after con- sultation with Mr. Griffis of the QM Depot, that small unvulcanized samples of each copolymer should be subjected to the Gehman stiffness and volume swell test (see previous progress report, RL-53-27i+, p.i6). It is hoped that this procedure will enable us to arrive at a useful comparison of the low temperature and oil-resistance properties of all rubbery materials prepared to date in a minimum of time.

It is difficult to predict how reliable a comparison of this type will be, based as it is on raw polymers and not on the final, cured and compounded rubber. However, it appears to be a realistic approach and should serve as a guide to future work.

The results of the screening tests on the initial lots of rubbery polymers have been received (cf. Table 10). In the table are listed all rubbery systems prepared up to the end of this period and their status with regard to evaluation, primarily from the point of view of raw polymer properties. Copolymers tested as vulcanizates are not treated in detail

f in this table. Monomers are referred to in Table 10 by their code numbers;

THE M. W. KELLOGG COMPANY /a PVroiaum * Ch.micol E&L0S3

Reiaarch D«pt. •" j.r,ey City, N. J. Report No. RL-53-289

20

these are identified at the foot of the table. The Gehman stiffness data temperatures, i.e., the and 100 times stiffer than

are expressed in terms of T2, Tc, 1-,Q an(^ ^100

temperatures at which the specimen Is 2, 5, 10 at 25°C. The per cent volume increase was determined in ASTM Reference Fuel No. 2, which consists of isooctane (60$ by vol.), benzene (5$), toluene (20$) and xylene (15$)- These swelling values are subject to some error because of the small samples used. The Gehman test samples were molded from raw polymer. The right hand columns in Table 10 give the molding temperature and appearance of the raw polymers after molding.

Many rubbery systems are labeled "no test" in Table 10. This generally means that the samples available were judged unsatisfactory or were not deemed interesting enough on inspection to warrant further screening.

Some preliminary conclusions from the screening tests:

a. Copolymers of CF2=CH-CH=CH2 and CF2=CH-C(CH^)=CH2) seem to have surprisingly good oil resistance. Compare Figures U, 5 and 6. In addition, it appears that CF2=CH-CH=CH2 copolymers are more oil resistant than those of CF2«CH-C(CH3)i=CH2.

b. Few data are available for comparison of the low-temper- ature properties of the 1,1-difluorodiene copolymers with butadiene copolymers. Runs 515 and 1013 (Figures h and 5) suggest that the butadiene copolymer of CF2=CF-CF=CF2 is more flexible than the copolymer of CF2=CH-CH«CH2 with CF2=CF-CF=CF2. However, the CF^CFg copolymers of the three dienes (Runs 573, 1129 and 1130) at approximately the same CF2=CF2 level have very similar low-temperature properties.

c. The screening test revealed that the Gehman stiffness of a 35/65 CF^C^/CF^CFg copolymer changes very little as the temperature decreases. (See Run 572, Table 10, and Figure 3-) Unfortunately, this copolymer is virtually non-rubberlike at room temperature. An attempt will be made, however, to determine whether other ratios are rubbery and whether the introduction of a third monomer such as CF^CFCl will produce a rubbery product.

d. Raw polymer samples of X-300 and X-300, 30/7O ratio, have been screened as reference points (Figure 3)- Hycar 0R-15, a commercially available oil resistant rubber, is also included for reference. X-30J containing 70 mole % CH^CFg is somewhat superior to Hycar OR in both oil resistance and low temperature properties.

t

THE M. W. KELLOGG COMPANY Petroleum I Chemical EftiiS

Research Dept. Jersey City, N. J. Rtport No. RL-53-289

21

e. X-300 is still not the answer to the Arctic Rubber problem, despite its apparent utility in other applications (e.g., for acid resistance). During the next contract year, commencing Aug. 1, 1953> emphasis will be placed on further screening of exploratory polymers and on the polymerization of unreactive monomers (e.g., CFo-CF=CF2) by unusual means (e.g., extreme pressure, see below).

3. Raw Polymers Shipped for Screening during this Period

The products described in Table 11 were shipped to the QM Depot for evaluation during the current period.

IV. Pilot Plant Production of X-300 Rubber

During this period, 1+5 lb. of X-300 were made for the QM account and shipped to the Philadelphia Depot.

V. Final Repnrt - Plans for Future Work under New Contract

A final report covering all work done under DA-UU-109-qm-222 from July 1, 1950 through July 31, 1953 is being prepared.

A new contract, with the same objectives as the old, is being negotiated with QM. Under this new contract, the plans for future work will include:

1. Pilot plant production of X-300 for thorough evaluation in a variety of end items (of immediate interest: protective suits, hoods, gloves, and boots).

2. Filler, Softener, Vulcanization studies on X-300.

3. Improved X-300 polymer.

k. Screening the more promising rubbers noted in the "past progress" section by means of Gehman stiffness and volume swell measurements on pressed sheets of the raw polymers.

5. Exploratory polymerization of new monomer pairs and development of better recipes where needed to improve yields,

6. High pressure polymerization of unreactive fluorc-olefins.

::

I

THE M. W. KEUOGG COMPANY P.troleum & Ch.micol ^Mf*

Rejsarch D»pt. J.ney City, N. J. Rtport No. RL-53~289

22 I

Reference to Original Records

Notebook #135 (A.N. Bolstad), p. 188-199, incl.

Notebook #23*+ (A.N. Bolstad), p. 1-53, incl.

Notebook #202 (F.N. Roberts), p. 159

Notebook #226 (J.M. Hoyt), p. 1-112 incl.

tHt M W KELLOGG COMPANY Petroleum & Chrmical

Research Dept Jersey City N J Report No. RI-l'j-

*3

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IHt M W UUOGG COMPANY Petfolcurn JL Chemicnl

Research Dept Jeriey City. N J

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THE M W KEUOGG COMPANY Peiroteum g, Chemical

Research Depi Jersey City. N J

fKfTuOGGl

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Rettorch D«pt. J«ri«y Ciry, N. J. Report No. PT-S^-PAQ

-22, f

TABLE 1

CHp=CHF COPOLYMERIZATIONS

Recipe: Persulfate-bisulfite suspension, 23 hr., 20°C, Molar Charge Ratio: 50/50

Run No. Comonomer (x)

0

1093 1091+ 1095 1096 1097 1098 1099 1100 1101 1102 1103 110U 1105 1106 1107 1108 1109 1110 1111 1112 1113 111k 1115 1116

CF2=CFC1 CF2-CH2 CFc*=CFCF*CF? CF2CF=CFCF2

CH2=CHC1 CF.2=CC12

CH^CClg CF3CF=CF2 CF3OSCCF3 CFgaCHF CH2=CFC1 CF3CH=CHCF3(cis) CF2=CF2

CF3CH«CHCF3(trans) CH3C(CF3>aCH2 (CF3)2C=CF2

CF^CFBr CF3CCL=CF2

CH3C(CF3)=CHCOOH CHj-CHCF. CF3CCL=CC12

CF30CL»CH2

none CF 3CH=CF2

FILE NO. LAS-106 FJH-.SB 1/7/5^

C :,n version

96 trace zero trace

16 k

2r; 1+0

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87 trace

5 zero zero zero 12 21 trace

2 zero zero trace zero

Moles CH2=*CHF/X Combined Appearance

53A7

8/92 60/'to 12/88 71/29

O/lOO UU/56

6V36

55/U5 58/U2

29/71

powder

white solid powder powder crumbly solid

powder powder si. rubbery

powder

crumbly solid papery solid

hard, tough rubber

THE M. W. KELLOGG COMPANY Petroleum & Chemical

Research Dept. Jeney City, N. J. Report No. tJT-m_p8Q

c J9

TABLE 2

CF3-CK=CH-Cft=CHP COPOLYMERIZATIONS

Recipe: Mutual-F, 90 hours, 50°C. flf Molar Charge Ratio: 50/50

*

T.

No. Ccmonomer-(X) Conversion

12^3 CF2=CF-CF=CF2 Ul

12UU CF^CClg 38

12^5 CF3-CF=CF2 »i2

12 U6 CR2=CFC1 51

121+7 (CF3)2C=CF2 0

12 U8 CF3-CC1=CF2 36

12 k9 CF2=CH-C(CH3)= CH2 92 /2/

1250 CF3-CC1=CH2 trace

1251 CF2=CH-CH=CH2 100 I2I

1252 CF3-CK=CH2 1+0

1253 none 91* /2/

125^ CF2=C(CH3)-Cft=CH2 80 /2/

1255 CF2-CF=CF-CF9 10

Moles CF3-CH=CH-CH=CH2/X Combined

82/18

89/11

79/21

81/19

95/5

90/10

90/10

86/lU

100/0

97/3

96/6

1215 CF2=CH2

1216 CF2=CF2

1217 CF2CFH

1218 CFjeCFCl (l/

Recipe: CRT - Redox, 21* hours, 20°C. flf Molar Charge Ratio: U8/52

trace

he

2h

37

a

(If See section on recipes elsewhere in this report. /2/ Polymerization time 2k hours. flf Molar ratio 50/50 fkf Fluorine content too low for either homopolymer; product

probably loses HF.

Appearance

stiff rubber

slow rubber

stiff rubber

slow rubber

Stiff rubber

rubber

rubber

stiff rubber

rubber

rubber

rubber

86/lU slow rubber

N slow rubber

99/1 fast rubber

FILE NO. LAS-109 FJH:SB 1/7/5^

TMf M. W, <IUOOO COMMNY

Jwu? City. N. J. •.•port No. ft s53a3fla 31

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r TABLE 3

COPOUTMERS OF CFp-C(CH3)-CH-CH2

Recipe: Mutual, 2k hours, 50°C. /l/ Molar Charge Ratio: 50/50

0

0

No, C omcnomer

1221 CF^CFCl

1222 CH2-CH-CH.CH2

1225 CH3-C(CF3)-CH2

1226 CHj-CHCl

1227 CH2-C(CH3)-Cft.CH2

1228 CH2-CCI2

1229 CH2-CH-CN

1230 CF3-Cd-CF^

1231 CF3-CH.CH2

12 32 CF3-CCVCH2

1233 CF2»CH-C(CH3)-CH2

123>» CF3-CR.CF2

1237 CF3-CCIJ.CCI2

1238 CH2-CR-C-NH2

1239

12 UO

•TH2-CFC1

N-CHa-CH-C-OCuHg

12U1 CF2-CFBr

12 U2 Styrene

1272 CFg-CF-CF-CFj

1273 CF^CClg

1289 cls-CF^-CH-CH-CF^

1290 CH3-C(CF3)-CH-C00H

1291 CFj-CF-CFg

1292 trans-CF^-CJWCH-CF:,

1293 CF2-CFWCF-6F2

* Convers Ion

Moles CFg-CtCHjl-CIWCH^/X Combined Appearance

rubber 5U 75/25

83 U8/58 soft rubber

33 91/9 rubber

U9 82/18 soft rubber

86 50/50 8lightly tacky rubber

1 - soft, sticky rubber

79 88/12 stiff rubber

23 97/3 soft rubber

38 99/1 soft rubber

35 81/19 slow rubber

,U - rubber

32 82/18 soft rubber

UO 111 96/U soft, weak rubber

96 III 80/20 /a/ hard, blulsh-whlte resin

rubber

suft, slightly tacky rubber

55 m 93/7

91 in 52/W

15 m 96A soft, slightly tacky rubber

92 in 6U/36 paper-like solid

2Q 88/12 slow rubber

5C 78/22 rubber

20 99/1 slightly tacky rubber

0.2 - rubber

22 98/2 slow rubber

17 trace F only •low rubber

16 99/1 •low rubber

111 Bun length UO hours. lil May Indicate that product Is not homogeneous.

Recipe: CHP Redox, 2U hours, 20*C.

Wo.

1211

1212

1213

Cononomer-(X)

CH2-CF2

CF2-CF2

CF2-CFH

* Conversion

Mole* CFj-CCCHjJ-C^CHa/X Combined Appearance

38 90/10 rubber

U9 90/10 rubber

U9 90/10 rubber

FILE NO. LA3-108 FJH:SB 1/7/51*

THE M W KELLOGG COMPANY Prirolei.m & Chemical

Research Dept Jersey City, N. J. Report No. RT-s^-289

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TABLE 5

VINYL ETHER & VINYL ESTER - FLUOROOLEFIN COPOLYMERS

Vinyl Ethyl Ether (VEE) CopolymerB

Recipe (parts by wt. Water 180; Monomers 100; KORR soap 5.0; K2S2O8 0.3; cone, buffer soln. 2'; pH - 10.0; Temp. - 50°C.

No.

1331 1332 1333 1331* 1335 1336 13L8

Comonomer (X)

CF^CFCl CFg-CFCl CF2-CFCI CF2=CF-CF=CF2

CF2-CCI2 CF2-CFK CF2=CF2

Moles Moles Hrs. VEE/X VEE/X * Polymer

Charged Combined Conversion Izatlon

50/50 1*9/51 89 2 25/75 1*1*/56 5C 22 75/25 33/67 57 2 50/50 1*7/53 89 22 50/50 38/62 32 2 50/50 - trace 22 50/50 52/1*8 1*1 k

Vinyl 2 -Chloroethyl Ether (VCEE) C r.pclymers

Appe

Tough, very slightly rubbery Hard, Inelastic Brittle, very slightly rubbery

N Brittle

Soft, rubbery crumb

Recipe (parts by wt .): Water 200; Monomers 100; KORR sot-.p 5.0; KgSjOs 0.3; cone, buffer soln. 20; pH = 10.0; Temp. = 50°C.

••

M?les Moles Hrs. VCFE/X VCFE/X \ t:oiymer-

Ho. C omon OBW r (X1

CF^CFCi

Charged

25/75

Combined C nvers on izatlon Appearance

1337 Ui/5t ^5 \. Tough, inelastic 1338 CF2=CFC1 50/50 1*8/52 71 3 Toi'gh, Inelastic 13 3-> CF2=CFC1 r5/25 1*0/60 52 3 Hard, slow rubber ". \~ CF2=CF2 50/50 51/1*9 do 2 Rubber 131*1 CF2=CF-CF=CF2 50/50 86/11* 50 5 Rubber 131*2 CF2=CCi2 50/50 1*5/55 23 5 Brittle

13**3 CF^CFH 50/50 - 1 5 Short., slow rubber

VI nyi Isobutyl Ether (VIE) Ccpolytners

Rec'.pe (parts Dy wt,); Water l80; Mot.omers 100; KORR soap 1*.5; ^SgOg 0.3; eonc. buffer soln. 16.1*; pH » 10.2. Temperature- 50*C.

No. Comonomer (X)

1301 CF^CFCl 1302 CF2-CFC1 1307 CF2-CFCI 1301* CF2-CF2 1305 CF2»CCl2 1306 CF2-CF-CF-CF2

Mcles Moles Hr. VIE/X VIE/X * Polymer-

Charged Combined Conversion ization

75/25 50/50 25/75 50/50 50/50 50/50

1*8/52 1*7/53 1*5/55 1*8/52 56/1*1* 1*8/52

52 78 37 1*1

9 96

1 1/U 1 1/U 1 1/3 1 1/U 1 1/U

18

Vinyl Butyrate (VB) Copolymers

Appe

hard, very slightly rubbery hard, very slightly rubbery hard, very slightly rubbery rubber hard, very slightly rubbery short rubber.

Recipe (parts by wt.) Water 200; Monomers 100; KORR soap 5.0; KgS^Q 0.3; cone, buffer soln. 20; pH « 10.0; Temp. » 50°C.

No. 13T7- 131B 1319 1320 1323 132** 1325

Comonomer (X) CF2-CF2 CF2-CFCI CF2-CPCI CF2-CFCI CF2-CF-CF-CF2 CF2-CCI2 CF2-CFH

Moles Moles Hr. VB/X VB/X * Polymer-

Charged Combined Conversion ization 50/50 65/35 16 i/3 75/25 70/30 Ik 1/3 50/5C 55A5 31* 1/3 25/75 1*5/55 1*6 1/3 50/50 - 15 26 50/50 28/72 23 2-1/2 50/50 75/25 6 1-1/2

Appea Rubber Soft, slow rubber Hard, slightly rubbery Hard, slightly rubbery Brittle Paper-like, transparent Rubber

717 Product consists of a small amount of rubbery material (O.U£) and a major portion of granular material. The analysis applies to the granular material. This latter material has not been further Investigated.

FILE NO. LAS-105 FJH:SB 1-5-51*

THE M. W. KELLOGG COMPANY P«trol«um & Ch»micol

Rataarch Dapt. Janay City, N. J.

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1-2-79 I-J.JO

1-7.57 i-7-5; !-».}» 1-2-40 1-2-41 l-2-4-« 1-7-4S. l-?-4»t

l-i 1-1 .-:> 1-1T :-i7« 1-71 .-.-2 i.?e 1-J7 1-41 1-45

!->»• 1-47

)<••)** 51-40

55-4 ) 51-44

)7-»

57-41 n-») >»-»i 16-44 59-41 59-44 • I 41-4} 41-4) 41-44 •i •)-44

Ho f

Ratio

10/10 50/70 «i'^3'4 44'40'1» •*'»/>> 59/50 "2* 11'o*-/?0 '?'

40/40/20 /?/ 49'M timct

1S/4»l*Tr»c» 4V»8/^ V5'4fc'4

41'5V?0

40'J?"?"

11/61 t>)')7

ll/* 11/89 1/99 71/1*

11/4 >

14/86 I'99 »4/lr> 80/70 /4/ 10/90 /4/ 1/99 k/9*

lo'84 19/Sl

*9/l 10/90 /4/

97/J /4/

st iffavM T,

a.

Be

)

•a 15

jo"

10

-?

f - jo II

104

rjtbtr rufcbvr

•^ort r jbbtr » •« r • r — -

•forl, f4H r .ooer

12 UflC

• i' -p (MI

- *IL

6 4 ) 9 " 6

1' II 10 15 e • *• t.p*i for t«at oo *#•*

!ncr«*a«, Tn» n rv«i

ia 5 8

>0C

S*a»l« Condition *ft*r

WoIdlot

•aft, flai. •oft, flri.

no trat no t«at ?• 19 :' i^ ««1 IhlDftJ fTT t*»* 10 6 6 0 3? no Uat ?0 1« 1* 1} )! • • rr-*1 for :#•«*

•l'OP*4 for •<••* • :<-n for Wat O" t«at

• . ?••*!-/ rr'aettd btetuN of »w ;1 -rfi iu-.rf • .r**dj r* *-*r-l MC4UM of noor -1" •m'ftMN "o U«t

lmrw> JO/70 oaten ( •oo. 7*e) no trat nc trat

• . ** r . ;•*•!•

• ft. t !-»ry •r a*

1 k* X-JOO »'• -m, tx ft r *b»r

•I'fTitiy r^bbrry

225 b*ro, fit*. 2?} •oft. n«. 225 soft, fir*.

225 »oft. *itr«-

??^> imrt, fl«.

??S t»ra, fln-

no t*«t: 91 could not • 1 ICMljr r iutr> • HChtlj rJ^&•ry no t««t Q3 t*St UrtfTf -~" • * r • , «»•« f -M*-t f&st rubber '*•* i jt • ' r

v. •. *xx.f rjbbrry

»! . riAMr no t*«t

•tiff ruobtr

•oft rdbfe*r

• oft rAbtr ••-.ft rjbbrr rvMw •oft, »-»ppj rjtb»r •oft, v««k r.twr •oft, ataw rubber • low r-Jtl»*r • .*f-. f»«T • At in

• oft , clow r dl-t

-? -16 -17 -^3 -< -1^ -19 -?5 -•O t«*t . tOC : i'T.r 1 • I,UI*I Tor t»»t no i««t • - ;;** for t*r«t

}00 •oft, fl«t. »1 «oft, fi««.

26

•tiff rutbtr

•hlpe«4 for trat no '-*•*.. ln«jfflcl«nt }^ rat'.wd 1? 0 -1 -16 60

-17 -?t> -?8 -3? 70 •Mpp«4 ft* (Nt oo tut, '.nauffIflmt vi roBtlnrd no t«Bt, tMMtfftelaot )0 coa61a*4 ln«iiff'.rlmt aaa^l* for 8rr*«nlnc ttst •hipe«4 f W teat

-H -21 -2^ -29 Ul no test, uuffl;)*nt -;•' roBtirx-r •blpp«4 for tr«t •htoprd for trat •h'.pprd for trst • r.ipp»a for t*»t

??': •oT., fin. ror »oft, rin.

2)0 soft, f Us

':' t*«t» co»4wct«« wltr ulc«nl(M i .'?'' Hol» ratio la aonoarr f««4-

/J/ /*/

Conat&ot prrM^* rjr«. R*«aon for mesprctro' »• tl/tica,! rvswlta lAdetrrmlnrd -

r 14n>tlfiftt.oc

roar Cod* lo.

12

13

"Fy-CICl

3 ri^ci^-^Cfls

CFj-Cf-Cf-Cfj

4^2^ 3« CH^CHCl

ctycci-c»ci,

^•:U6 9-*-*3

n cr,-cF^»

Ir CI^Cll-CI

i' CUf. c«-co» -CMM •)

17. IA

19

cFj.cn

Cfj-CCWCCl-Cfj

?>j CTJ^»C<TJ

?1

7?

2) 24

2".

CTy»CTt

ClyCKl

III - C?,-CfcC«<f j

c?rc?,

tr«m - Cf,^:^ci-C?

24 C^CK6l4-C»-Clj

rt. v, 76

7-i

CHy.-P-CfcClj

"5 50 51

Cfj-cmr

cv«, 52 CTj-OCbCFj

55 otj^cfjKci- 54

* 57

enj-exo-nj CT,-04>Clj

C^vClVir

CI>J.CI-C»-C«J

56 cr.-ccfecci;

59 CT)-CC4,c»j

41 C7j.C>-C(Cij4.Clj

42 Cf)-C!4-C7j

43 CTj-CfcCB-CfcCij

44 CTj. C(«,',-C»-Clj

41 CHj.CB-0-CO-Oj

4> cij.a-0-co-cig-cij-ctj

454 C«j.Cl^)-C0«jCi

46 C^^KI-COjCI]

47 Clj-O-OO jClj

48 C«j.CI-0-C«j-CIjCl

49 ctj-ci-o-Oj-cKctjIj

50 CTj-CfCljl-CF-Clj

11 C?j*C*-CT4>C^

THE M W KELLOGG COMPANY Petroleum & Chemical

Research Dept. Jersey City, N. J. Report No. RL-C;

CUTOPTT 3TATUB Of THJMPLIKZ KingXS (8M end if CtnaTa for IGMHr ?4«nt'feat tan)

Hew PO'jr—r Screening Tuti

Hoi* « mmm % Vol<«J> Hold S«BHtla Coad'.tlon Urn Nonoir *•' :oa- St.ffneaa, X - tncra*»e. Taa*. after lo. : at rwt-.or. - at'***

W/7O

...» ». AppMruc* T? T^ T10 T100

•» i » -?

Type II Fu»l

18

Holdlnc

J-)00 .. r if 6#r aoft , flM. 1-300 1-* 30/70 -- r jt>o*r -10 -1* -17 -2« S »oc aoft, , flbl. 1021 (1) i-2-ik »J*»V» 7\-«0 • ••ort r bb»r 6 » 3 -y 1 «• ., 1190 i-»-?i kk/ke'16 19 r jbb«r 9^6-1 ,-. •fi hart 1 flam. »• 1-2-22 */8'36 Jk •lOW f ''*r 1' 11 10 «•• ??'. aoft, , f.ei ?70 1-2-2? 39'36"2^ » iflMrt , f»«t r .Db»r IS 8 T * $a ??* aoft | , flex. II* 1-2-22

1-2-2) 1-2-2k 1-2-29

»V***o '?' '. ruttwr at-.'peed for teat 00 teat r tea* no t«t

•• 1-2-30 f#*i '- • 1-w - ** 19 l- 1? te; ?2S aoft , »*.tre-ua rx 1-2-3? kO/kO/20 /?' •" nMtf • • i(^- for teat -- *• 1-2-31 k9'*l'Tract kk r .t>n*r 10 8 6 0

no teat <* ??• hard, , flea.

. "• 1-2-«0 W/kATnc* 32 • L'.fhtly rubtary ?0 18 If 11 31 ^*- imrij, fltt. 12 "* 1-2-^ n'«a/7 < *»r4, rw<ttwry cna* at•-vpned fof teat IJM 1-?•»'• *>'kt'k .. 1'k* i-joo a^.•pp•4 for teat 1316 l-j.k-. kl'S9"?0 1- •l«w( at tr r Mar ai-.'peed for teat

a-2-n» 1-3

•I

W'32'2* ' 1 *. • <• • «• 1 • *• .

• »«•.. r*'*ct«4 MCI; -0 t**t

n" teat »' Of OOOr : rr-e •"•- -r ae of Door -*. '.rep1 at*r.ce

l-l no tttt: <#l could not larice JO/W *«ien ( r^oc. 7a -• 1-11* )5/6, -. » • *" . j ' • • •"• - no teat --. 1-21

.-.V 63/37 k

no •••* nc teat

. :/ ••> 17/* 38 • h~rt . *••• . • .-• -? -16 -17 ^3 V »f aoft. torn. • •- 11/89 ?3 '••- r>Aber -0 -15 -19 -4*^ 12? MS aort. flea. l-») 1/99 " f»«t r>jtt^r no teat, too little * •< « aar 1 coafelord

an -• 1-k*

2^/75 »k r«t,r>»r ahlpped for teat no teat

• "• 1-kT il/k9 99 v. •) nut 1/ rubbery • . . ' ' for teat

I3N .... - ....

2-1) 2-17

60/kO -•. hard. 1 . * rutbe>r at.ipped f r tea*. no teat no teat r\. t e a"

no teat no teat .*•. 2-22 k«/« -. • ll«Ml)r rubbery 9 0 3 -» 2k ^^ baurd. •ttff

s\ 2-2k 2-2*

)V.>5 »T *- ii:(htl/ rutbrry -1J -70 <-7S <-7^ nc teat , «i r- ?6

1 «w hard, •tiff

' 2-29 38/ftf 2 • lightly rubier? ni- tebt

2-J0 ?•» 2-3*

H/k5 '« nMti ••-. - ahattered In djre no teat nc teat

Dil

Ull 2r») no teat 121 2-kk IP/9>- " rjtber atV.pped far teat •' ... TX.21 . ' r^tbe>ry rr«t -so •& -<>; <-66 " '• aoft. flea •-- )-* TfJ* i" r^tber* • J- -2) -51 -58 <-<X> J' aoft, flea. Ml •••

n 20 I. tAf*y fmt#r -IS -?9 -38 -V Jl» '• aoft, f*e«. ... o6/Jk •• r\*it*ry rnrnb -31 *M -*J -S* Tell apart, cheeay •Iliad 29 ftO. kO .- r^bt*r> rraM -17 -?9 *JJ -»• fell apart, cheeay not aclded

• • • lre*dy r»V~t«4, poor &'.» reatatance (... nc t**t

new >••! )-l* 1-1* (.1 .

3-2?

•>V31

teat no t*at

7 -10 -13 -17 32 aoft. flea.

• • )-?» 86/ik :•-

r *.r*ry -r at S -18 ->9 <-cC * !• aoft, flea. MJ >-2k 8./19 rubber -« -as -V -57 v " aoft. fiea

•-- 76/2k :* r itt*r>r cruab S -8 -?7 -S6 ... i- aoft. flea.

• )-V « .• -- rueb»r no teat 12? .... >*/k« 83 •oft rva>b«r ah-.pped for teat i^ •

• tbcor'.t ir»l

M* frrs * r. for

Cr>cr-c*-i:rs um cr>cr-c»>.cr? * -

• lfe»dj r»;Kt»4, poor no taal, lapor* ?6

ell reaiatbfl're

«-••* T

1 'i • ..)' »/«8 -• •t?fr, attort ri*o»r If! -10 -1? .?9 Jfl •M: : at Iff 1 »-.• k-n ik/86 f»«t » •- • rjtirr 0-10 -30 -?8 ..- :-;•. •oft, flea.

k-»J 19/82 k] at Iff ruebar •h'.ppad far teat k.kk 12/89 W • lov r**t*r •hipped for teat

•• - • 1^/81 so ruboar ahipped for teat ••• • •

*/k« - •bort rvAbrr already rejr-t«4, poor

ahlpped for teat oU-raaiatance

.. ,.kk JO/90 * a: t*cky rubber ahipped for teat ; ••• •1 1/99

1 aoft, alow rAbrr no te»t, low 6 content

. - ...1 15/6^ -- a .Tt . fairly altfa rubber no teat 10 31 •..; k/96 ?. hard r Jtber r.i/ teat , low 7 content • ••• •-. T/9) - e:f*.,anappy rubber teat aaaapit charred tn sold too ::••

-.<. <i/9k i r jbber ah:pped for tea*. u •• r-ki 1/99 i- alow rubber no teat, Inw 7 cTOtant . «-|7 21/79 aoft, alow r-bt-er JO 13 S -9 "- ?/• aoft, t*cH7 1.-. '.-•. 9/91 * • n , •napt/ r • •••' S ^ .12 -?3 .-. aoft. t*cky ....

9-12 -1' 9-IT 9-2«

is/ee «• aoft rubber no teat

•-»'

no t«t no taat, la*, or* ?8

*i;pped 'or tea*.

i i *•>' 16/8k -. •-OMfft, v. tlajt-.c rubber -l -U •' aoft, rie».

1 •• 9-*l > M faat, •nappy rueoer ^ -S -U -21 •• Bftj aoft, flai.

9-k) 11/99 ••- a low rubber ah-.pped for teat • 9-U 2?Arf> s.i - • • ^ .-• ahipped for taat

:>•• .... 12 -2* 12-37 :.-..: 1J-16 lk-22 lk-28

kk/56 • tiaird, •. al. rubbery no teat , tapure ?8 no teat n> teat uo teat r.•: teat

no teat

. •-- i.-n - « 2 .j»ra rubber no teat • ••• ..--. 2,9* •Oft, faat rsjbt^r no teat, low 1» c jr.ten*. - - ..... 21/79 at.ff robber • Mpped for teat ..-•. : 2/98 .< , ^ - .• • - r.o teat, low .» content

THt M w KIUOOO COMMNv aa • •-••»— 4 c HttrK

a rh Oat* w

*~» "»•" ' «epon l*> w- 53-28? 39

TABLE 11

C1P0LYMERS TO BE SCREENED AND LOW TEMPERATURE

EOF OIL RESISTANCE FLEXIBILITY

COPOLYNERS OF ( :F,.C(C,! ,)-CH.CHp (DFI)

Run No. C Lsonoawr

CFJ-CFCI

Mole # ratio DFl/Ccw:«iomer

75/25

* Converelon

12? 1 5»

1222 CHp.CH-CH.CHj U8/52 83

12? 1 Cr,-C(CH3)-CH? 91/9 S3

1226 CHp-CHC. 88/18 •9

1227 CHj-CfCHjl-CH-CBj ',0/50 86

1229 CHj-CH-CS 88/12 79

1232 CF3-CCWCHJ 81/19 35

1233 CFj-CH-C(CH3).CHo ! 9k

12 iU CF,-CH.CHj

n-0Hp.CH-C-0Cl.Ho,

82/18 32

121.0 52/1.8 91

1272 CFp.CF-CF.CFj 88/12 29

.. • CFp-CClj 78/2? 5<

1?;: CHp-CFp 90/10 38

1212 CFJ-CFJ 9C/10 "•9

1213 CFj-CFH 90/10 »9

COPOLYMER! 1 OF CFl-CH.CH-CH.CHj

121.3 CFp-CF-CF.CFj 82/18 »1

12WI. cr2-cci2 89/U 38

:?-' CF3.CF.CF2 79/21 -2

12 W CHp-CFCl 81/19 51

121.9 CFp.CH-C(CH3y.CHo 90/10 92

1251 CFj.CR-CH.CK? 90/10 10c

12S CF3-CH.CH2 86/11. .0

12c) nona 100/0 ~y

as* CFJ.:(CH3)-:H.:HJ 97/3 8c

1216 crj-ci-a B6/l« -8

Run !»:. Cocor.ooers

CFp-CFj/v'r.yi ethyl ether

Mola * COBb'.r.ed

lu3/52

* Conversion

13-5 -1

1317 CFp-CFj/vmyl butyrate 35/65 16

13-" CFj-CFj/vlnyl 2-chloroethyl ether U9/51 39

1323 CFj-CFj/CHp-CFCl 32/68 /•/ 1313 CFp-CFj/CRj-CFCi 50/50 /./ 13I.7 CFj-CFj/CBp-CFCl 65/35 /./ 1339 CFp-CFCl/vlnyl ?-chioraethyl ethei 60/W) 52

1331 CFp-CFCl/vlnyl ethyl ether 51/1.9 89

13"1 CFj.CF-CF.CF2/vlnyl 2-chloroethyl ether 15/85 50

770 CFJ-CFC1/CFJ.CHJ/CF3-CC1.CFJ "0/1.O/20 /b/ 78

1278 CFp-CFCl/CFp-CHj/vlnyl eceUte •5/W/7 30

1315 Crj-crCl/CFj-CHj/vlnyl butyrate 50/-6A M

1J1'. CFj-CFCl/CFp-CHj/vlnyl butyrate '•1/39/20 36

1203 Realdue froj» CFj-CF-CP-CF2 kl.?» F no Cl hi - 1277 CFj.CFj/n-butyl acrylate 18/82 6k

130* CFj-CFj/vlnyl laobutyl ether 50/50 \X

1306 CFp.CF-CP.CFp/vlnyl laobutyl ether 52/1*3 96

1138 CFj-CFCl/Cr>CH2/CHj.CFCl lil 56

1081 CFj-CHj/CHj-CPCl «8/5e 7»

96? CFj.CFClA.rp.CBo/CBp.CBj •.9/51/trece lib

1388 CTj.CFCl/CPj.CHj/CIij.CRT' 52/Wtrace 32

1190 CFp-crCl/Cr>CH2/Crj.CrH W./W/16 19

/a/ 7 onetent feed runs, /b/ Kola • ratio of leooomera charged. /c/ Thla material la of unkncem atructura. Tbaoratlcal % T tor poly-

perfluorobutadlana la 70.-. FILE NO. LAB-107 FJ«:SB l/7/5k

/d/ Charge ratio 15/65/20

firmed Services Technical Information Agency Because of our limited supply, you are requested to return this copy WHEN IT HAS SERVED YOUR PURPOSE so that it may be made available to other requesters. Your cooperation will be appreciated.

NOTICE: WHEN GOVERNMENT OR OTHER DRAWINGS, SPECIFICATIONS OR OTHER DATA ARE USED FOR ANY PURPOSE OTHER THAN IN CONNECTION WITH A DEFINITELY RELATED GOVERNMENT PROCUREMENT OPERATION, THE U. S. GOVERNMENT THEREBY INCURS NO RESPONSIBILITY, NOR ANY OBLIGATION WHATSOEVER; AND THE FACT THAT THE GOVERNMENT MAY HAVE FORMULATED, FURNISHED, OR IN ANY WAY SUPPLIED THE SAID DRAWINGS, SPECIFICATIONS, OR OTHER DATA IS NOT TO BE REGARDED BY IMPLICATION OR OTHERWISE AS IN ANY MANNER LICENSING THE HOLDER OR ANY OTHER PERSON OR CORPORATION, OR CONVEYING ANY RIGHTS OR PERMISSION TO MANUFACTURE, USE OR SELL ANY PATENTED INVENTION THAT MAY IN ANY WAY BE RELATED THERETO.

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