-

adit+ by '
Denisan University
Granville. Ohio 43023

Synthesis and Decomposition of Zn12 The Preparation and Properties of Poiybutadiene

(Jumping Rubber)
Submitted by: Noojin Walker
Pensacola Junior College Bassam Z. Shakhashiri
Pensacola, F L 32504 Glen E. Dirreen
and Lloyd G. Williams'
Checked by: Richard F. Jones University of Wisconsin-Madison
Sinclair Community College Madison, WI 53706
444 West 3rd Street A violet suspension of an "alfin" catalyst is added to a pop
Dayton, OH bottle containing a solution of 1,s-hutadiene in pentane. The
Preparation bottle is corked and shaken for several seconds. The mixture
Obtain Zn dust (3 g), Iz crystals (2 g), water (10 ml), small sets to a gel and the contents erupt from the bottle within two
gauge insulated Cu wire (30 cm), two 100 mm watch glasses, minutes.
dropper, funnel, filter paper, stirring rod, and a DC power
source, (1.5 V AA dry cell is the minimum.)
Demonstration
1) Mix the Zn and 12 on a dry watch glass. No reaction.
I T H E CHEMICALS USED I N THIS
DEMONSTRATION ARE FIRE HAZARDS. 1
Materials
2) Add 10 ml of water drop by drop (hood).Copious violet vapors.
3) Stir the mixture well. Filter. Pour the filtrate into a watch glass. Jumping rubber kit available from Orgmet, Inc., Route 111, East
The solution should he relatively clear and colorless. Hampstead, NH 03282
The
....kit:
.....
4) Connect Cu wires to the DC source. An amber coloration of the
filtrate occurs immediately at the anode; Zn accumlatea on the Small pop b o k mntainii l$-hutadiene digsolved in dry pentane
cathode. War-sealed, screw capped bottle containing the alfin catalyst
Cork for pop bottle
Remarks Bottle opener
The simplicity, the controlled violence, and the visual ex- Glass stirring rod
citement makes ZnIp an excellent demonstration. In a very few Tonga
moments it can he used to show direct combination, decom- Procedure
position, the effect of a catalyst, recrystallization of sublimed WARNING! The alfin catalyst is extremely reactive with
1%and electrolysis. moisture. Perform this demonstration in a well-ventilated
The demonstration is enhanced by the use of an overhead room to minimize inhalation of pentkne vapor.
projector. The violet color is more dramatic, the silvery Open the catalyst vial and use the glass rod to stir its con-
sparkles of cjstalline I2 in the violet vapors are visible, amber tents. Quickly remove the crown seal from the pop bottle and
droplets of aqueous I p are apparent, and the produds accu- add all the catalyst. Immediately cork the bottle and shake.
mulating around the electrodes and the diffusion rates are The temperature increases slightly (to about 50°C) and the
easily observed ("Tested Demonstration," 6th ed., p. 161). pressure increases (perhaps 2-3 atm) until, within two min-
The reaction is reported to occur also when scrupulously utes, the cork is forced from the mouth of the bottle and a
clean and dry Al and Mg are used (Antelman, M., J. CHEM. polymer "snake" shoots out into the air. The hottle is left al-
EDUC., 30, 134 (1953)). What would he the electrolytic
products? ' Present address: Hampshire College, Amherst, MA 01002

788 1 Journal of Chemical Education

most dry and the liquid is trapped in the polymer. Use a pair mer consists mainly of trans-1,4 repeating units. Since one
of tongs to handle the polymer. Over a period of an hour or so ally1 group is incorporated into each polymer chain, the pro-
the trapped pentane will evaporate and the polymer will
shrink.

Hazards
This dramatic demonstration should be performed only by
individuals who understand the fire hazard and reactivity of
organosodium reagents. Under hot or extremely humid con-
cess resembles Ziegler-Natta catalysis (4).
nCIf2=CHeH=CH2
l,3-butadiena
a l f l n catalyst
CH
lH>c=C CHI

ditions the catalyst could ignite in air or ignite the butadi- trans-1,C
polybutadiene
ene-pentane solution. A carbon dioxide f i r e extinguisher
must be available. The predominance of 1,4-polymerization has been sug-
Pentane is a highly flammable and volatile liquid (b.p. gested as evidence for a free radical propagation mechanism.
36'C). Pentane can cause severe exolosions when ex~0Sed I t has heen proposed (4) that complexes such as
to heat, sparks, o r flame. Avoid inhiation of pentane vapors CH,-CH-CH, CH,-CH-CH,
- concentration Dentane
- toxic. I n hieh
since thev are sliehtlv I I
is a narcotic.
1.3-hutadiene ( b . ~ -. 5 W may be irritating to skin and
mucous membr&s and is a narcotic in high concen-
trations.
are formed and that adsorbed monomer displaces the aUyl
Disposal anion from the comolex to form an ion oair which then reacts
Since pentane is trapped in the product, the polymer should to form a radical pa'ir.
he kept away from flames. Pentane evaporates after several [CHI-CH-2CH-CHaaF-[CH2=CH=CH2]
hours and the shrunken polymer may be discarded. .CH2-CH=CH-CH,-Na+ +.CH,-CH=CHI
The empty screw capped bottle may he rinsed carefully
with water and discarded. The radical anion initiates polymerization which continues
until combination with an ally1 radical occurs. This does not
Discussion occur very readily hecause the allyl radical is bound to the
catalyst surface (4), and hence very high molecular weights
We have performed this demonstration over 100 times are obtained.
without a single accident. I t is a dramatic demonstration
which, along with other demonstrations, serves the purpose CHs CH, + CH,R CHI
of discussing polymers, their methods of preparation, their II
CH
I I II
CH
properties, and their uses. Polymer chemistry should become CH CH
an important aspect of general chemistry courses because of
6+CH
I
+ R- CH
II II
CH + ~'CH
I
its own richness and because of the importance of polymers + +

in our daily lives. We urge that this and other related dem- // / / //
6%H -CH, -CH, 6%H,
onstrations he used to focus attention on polymer chemistry
and to increase the students' knowledge and awareness of R- I 1
chemical systems. We discourage its use only as a magic 'Na+
trick.
Alfin catalysts are a class of heterogeneous catalysts which
cause rapid polymerization of hutadiene, isoprene, and other
1
~a+~l--Na+-oR .
4'"catalyst
surface
"7
catalyst
surface
monomers resulting in polymers with very high molecular CH,-CH,-CH=CH-CH,R
weights (1-2 million or higher). The alfin catalyst used in this I
demonstration is a solid surface catalyst developed by A. A.
Morton (1,2,3) and co-workers a t M.I.T. I t is produced by
reacting amyl chloride with sodium, which is then reacted with 1I
CH and so on
isopropyl alcohol. The resulting mixture contains amyl sodi-
um, sodium isopropoxide, and sodium chloride. Propylene is
added to produce ally1 sodium from amyl sodium. The fol-
lowing sequence (4) shows the necessary stoichiometry
1.5 CsHllCl 3 Na - 1.5 CsHllNa 1.5 NaCl
Nnt

1
catalyst
surface
Others have proposed an ionic mechanism for polymer-
ization with the alfin catalyst. Discussion of the ionic hy-
potheses may he found in the references cited, particularly in
The sodium isopn~poxide-allylaodiumcombination gives the Reich and Schindler (7).
highest polymer yields. The role of the sodium chloride is not
clear, although it could be acting as a support for the cata- Literature Cited
(1) MoMn, Avery A., Mwat,E., Leteinger, R. L., J Amen Chem. Sac, 69,950 (1947).
lyst. (2) Morton,AwryA.. Welehcr,R.P.,CoEns.F.,Penner.S.E..Comhi.RD.,
J A W . Chen.
The catalyst is the mixture of the three sodium compounds;
allyl sodium, sodium isopropoxide, and sodium chloride. All (3) ~ o m o s & ~ a & R:, and Campbell, Tod W. '"Preparative MeUlada of Polymer
Chemistry," SecondEdition. lntemienee, New York,1968. pp. 305307.
of these are essential constituents. The name, alfin, was taken (41 Stevens. Mdmlm P., "Polymer Chemia~y:An Intmduction:' Addilon-Wnley Pub-
from the fact that analcohol and an olefin are involved in the lishing Company, Inc., Reading, Massachwtta, 1915, pp. 179-180.
(5) Morton.AveryA. andlanpher.E.J.. J . Polymer Seiencea. 44.233(1960) andrrf.mneea
preparation of the reagent.
The alfin catalyst is believed (5,6)to adsorb and orient the
monomer prior to the chain-growth process. Surface effects
presumably influence the stereochemistry (4), and the poly-
Volume 57, Number 10, October 1980 1 739