Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield

Newman, J.

Toy, M. S.

English

NASA Technical Reports Server

July 1970
	
.	 Brief 70-10131 
NASA TECH BRIEF 
NASA Tech Briefs announce new technology derived from the U.S. space program. They are issued to encourage commercial 
application. Tech-Briefs are available on a subscription basis from the Clearinghouse for Federal Scientific and Technical 
Information, Springfield, Virginia 22151. Requests for individual copies or questions relating to the Tech Brief program may 
be directed to the Technology Utilization Division, NASA, Code UT, Washington, D.C. 20546. 
Polymerization of Perfluorobutadiene 
.
A new polymer form of perfluorobutadiene and a 
new method of production has been developed. Pre-
vious methods required extremely-high pressures, on 
the order of 104 atmospheres, which placed severe 
limitations\on thequipment,\ besides\ increasin'haz\- 
ards and-production costs. 
The polyperfluorobutadiene obtained by this 
method has good chemical resistance and can be used 
where hard elastomers are required. It can also serve 
as a prepolymer to form high molecular weight ma-
terial with excellent temperature and other properties. 
In the new method, diisopropyl peroxydicarbonate 
is used as a catalyst to initiate the polymerization of 
polyperfluorobutadiene. The peroxydicarbonate is 
dissolved directly in the liquid perfluorobutadiene 
and the reaction conducted in a sealed vessel at'the 
autogenous pressure of polymerization. The reaction 
temperature, the ratio of catalyst to monomer, and 
the amount of agitation determine the degree of 
polymerization and product yield. With increased 
temperature (up to about 50°C) or amount of catalyst, 
the molecular weight of the polymer tends to decrease, 
while the yield tends to increase. 
Analysis of the polyperfluorobutadiene indicates 
that it is a copolymer of perfluoro-1, 2- and 1, 4-buta-
diêne. It has the advantage of two types of double 
bonds (terminal- and internal) which are easily sus-
ceptible to cross-linking reactions and graft copolym-
erizations.
One advantage of diisopropyl peroxydicarbonate 
as a catalyst is that it is miscible with the perfluoro-
butadiene monomer. At-leat 0.10 weight percent 
of the catalyst is .needed to obtain polymerization. 
Because it decomposes at 5°C, the solid catalyst is 
placed into a precooled pressure vessel which is 
attached to a vacuum line and evacuated. The vessel 
is further cooled in a liquid nitrogen or dry-ice/acetone 
bath and perfluorobutadiene is condensed into it. The 
vessel is then sealed and the materials mixed continu-
ously during the reaction period, which can last from 
24 hours to several weeks. 
Note: 
Requests for further information may be directed to:

Technology Utilization Officer - 
NASA Pasadena Office 
4800 Oak Grove Drive 
Pasadena, California -91103 
Reference: B70-10131 
Patent status: 
Inquiries about obtaining rights for the commercial 
use of this invention may be made to NASA, Code 
GP, Washington, D.C.. 20546. 
Source: M. Toy and J. Newman of

McDonnell Douglas Corporation
under contract to

NASA Pasadena Office 
(N P0-10863) 
Category 04 
This document was prepared under the sponsorship of the National 
Aeronautics and Space Administration. Neither the United States 
Government nor any person acting on behalf of the United -States
Government assumes any liability resulting from the use of the 
information contained in this document, or warrants that such use 
will be free from privately owned-rights.
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Polymerization of perfluorobutadiene

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