Blowing Agent Decomposition in Vinyl Foams

R. A. MARSHALL
Chemical Research & Development
The Goodyear Tire & Rubber Company
Akron, Ohio 44316-0001

Azodicarbonamide has been widely used for many years as the blowing agent
of choice for expansion of vinyl foams. It has been especially useful in chemically
embossed flooring because the sensitivity of the blowing agent to various factors
affecting its decomposition temperature permits control of the degree of expansion
of the foam. Considerable work has been done by a number of investigators to
elucidate these factors. Mechanisms for the decomposition of azodicarbonamide
have been proposed in the literature to explain the activating or retarding effect
of many compounds on the decomposition temperature. The use of Differential
Scanning Calorimetry with a n active reference is shown to be a n extremely useful
tool in determining small effects of various additives on the decomposition tem-
perature of the blowing agent.

INTRODUCTION cited different activation energies as evidence for

ecomposition of azodicarbonamide has long been differing mechanisms in the solid state and in a
D the method of choice to produce vinyl foam. The
recognition that the decomposition could both be ac-
silicone dispersion (11).
To better understand the effect of inhibitors and
tivated and deactivated with various additives led to activators on the blow temperature of the foam proc-
the technique of chemical embossing (1, 2). It has ess, the decomposition was studied using Differential
been observed that activators both decrease the tem- Scanning Calorimetry (DSC) in which a n active ref-
perature at which azodicarbonamide decomposes erence was employed to distinguish differences in
and increase the yield of gas produced (3,4). decomposition temperatures (12).
Although there has been general agreement that
inhibitor compounds reduce the quantity of gas EQUIPMENT AND PROCESS
formed (5),there is uncertainty whether the inhibitor For this work a Perkin-Elmer DSC-1B was used.
increases (6)or decreases (7)the decomposition tem- DSC measures the difference in heat absorbed or
perature. emitted from a sample compared to a n inactive ref-
To understand the effect of activators and inhibi- erence, such as an empty pan. In this work, following
tors, work has been done by several groups to define the suggestion of May (12). a n active reference was
the mechanism of the decomposition. Studies on the used. If identical samples of plastisol containing azo-
decomposition in solution using photochemical (8) dicarbonamide were placed in both pans, the DSC
and thermal (9) techniques suggest dual pathways signal for the decomposition exotherm from the ref-
after isomerization from the trans to the cis config- erence pan would be the mirror image of the signal
uration (see Chart I ) . Path 1 involves cyclization of from the sample pan, thus exactly canceling the
the cis-azodicarbonamide to 1,2,4-triazoline-3,5- output and resulting in a straight line. However, if
dione and ammonia with subsequent formation of the decomposition temperatures were slightly differ-
carbon monoxide and nitrogen. The alternate path ent, a discontinuity would result in the signal output
describes the decomposition of the cis azo compound because the exotherms would be shifted. An initial
to nitrogen and a carbonamide radical. Trisforma- positive exotherm would indicate that the sample’s
mylhydrazine, biurea, cyamilide, cyanic acid, and exotherm began before that of the reference. An
cyanuric acid are formed from the reactions of the initial negative exotherm would indicate the exo-
carbonamide radical. therm of the active reference began before that of
Prakash noted that in the solid state the isomeri- the sample. This technique was found to be highly
zation to cis-azodicarbonamide is blocked by limita- effective in detecting small differences between tem-
tions imposed by the crystal structure (10).Neverthe- peratures of decomposition exotherms.
less, he also proposed a mechanism with two paths, Pastisols were prepared and a n additive was placed
one of which involves the formation of urazole, the in a n aliquot of the plastisol. The untreated portion
saturated analog of 1,2.4-triazoline-3,5-dione. Sec- was used as the active reference.
ondary reactions of isocyanic acid are responsible for A typical plastisol formulation is shown in Table
carbon monoxide formation. Other workers have 1. In some of the work a masterbatch was used which

144 JOURNAL OF VINYL TECHNOLOGY, SEPTEMBER 1991, Vol. 13, No. 3

 Blowing Agent Decomposition in Vinyl Foams

contained all of the ingredients except the paste

resin. The masterbatch was obtained from a com-
mercial flooring company. The masterbatch permit-
ted testing different resins and additives in the res-
ins.

RESULTS AND DISCUSSION

The effect of a n activator on the decomposition
temperature of azodicarbonamide can be seen in Fig. TEMPERANRE, DEG C
1 which shows a DSC scan of two commercial blow-
ing agents. The activated blowing agent decomposes Fig. 2. Ink inhibited plastisol (RP) u s . control (LP).
about 150°C nearly 70°C lower than the unactivated
material. Thus it is clear that some materials dra-
TREATED SAMPLE: RIGHT PAN, UNTREATED: LEFT PAN
matically lower the temperature of decomposition of
azodicarbonamide. However, in plastisol formula-
tions there are compounds present which may affect
the temperature of decomposition both positively and
negatively (11).
The effect of 1 phr of a printing ink containing a
proprietary inhibitor on the decomposition tempera-
ture of a plastisol composed of Pliovic DR-450 in a
masterbatch is shown in Fig. 2. The initial exotherm
is in a negative direction, indicating the plastisol in TEMRRANRE. DEG C -D
the left pan (LP), the untreated sample, foamed first.
Thus the printing ink increased the decomposition Fig. 3. DR-450 resin treated w i t h Versene 100.
temperature.
The results of adding Versene 100 to a plastisol
made from the recipe in Table I are illustrated in TREATED RESIN (RP) VS UNTREATED (LP)
Fig. 3. Once again the untreated sample foamed be-
fore the treated sample, indicating that Versene 100
also raised the decomposition temperature.
Figure 4 shows a series of DSC scans of plastisols
made from a commercial foam masterbatch to which
a paste resin was added. Each plastisol was treated
with a small amount of butylated hydroxy toluene
[BHT),p-benzoquinone, phosphoric acid, or Versene
100. The phosphoric acid had little or no effect on TEMPERANRE. OEG C -D

F i g . 4. DSC of f o a m plastisols.
Table 1. Plastisol Recipe.
Amount the decomposition temperature. However, in each of
Component (PW the other cases the additive lowered the decomposi-
Paste resin 100 tion temperature. In the plastisol recipe of T a b l e I ,
Dioctyl phthalate 50 Versene 100 raised the decomposition temperature.
Ferro 501 9 1.5 When Versene 100 was added to the masterbatch,
Azodicarbonarnide 5
the decomposition temperature was lowered. Thus
changing the formulation of the plastisol altered the
effect of Versene 100 on the decomposition temper-
LIBERATED HEAT VS TEMPERATURE ature. It is possible that differences in specific ingre-
dients or ratios of ingredients are responsible for
reversing the effect of Versene 100 on the decompo-
sition temperature.
When the pH of PVC resins was adjusted by adding
phosphoric acid to a portion of the latex before
drying, resins with various acidities were obtained
( T a b l e 2).These resins were added to a foam master-
batch. The DSC traces of the resulting plastisols [Fig.
5)indicated that the acid treatment of the latex low-
TEMPERAM. DEG C
ered the decomposition temperature, in disagreement
Fig. 1 . DSC of commercial blowing agents. with the general conclusion of Lally and Alter that

JOURNAL OF VlNYL TECHNOLOGY, SEPTEMBER 1991, Vol. 13, No. 3 145

 R. A. Marshall

the rate of blow is decreased by a n increase in acidity DENSITY, KGKUBIC METER

(3).
In a similar experiment, the pH values of latices
were adjusted with phosphoric acid before drying,
and plastisols were prepared by adding the resins to
a foam masterbatch. The plastisols were placed in
an oven at 195°C.The blow ratios and foam densities
were determined after 130 s. The data are shown in
Table 3. The foam density is plotted against pH in
Fig. 6. These data indicate that high pH increased
both gas formation and decomposition temperatures F4i

(Fig. 5). Fig. 6. Foam density us. latex PH.

CONCLUSIONS
Additive materials can affect both the amount of
gas generated in the decomposition and the temper-
ature of decomposition. Some materials, such as
phosphoric acid, have been shown to decrease the
decomposition temperature while also decreasing gas
0
evolution. H,N&. + N~
Additives can affect either or both of the reaction
pathways (refer to Chart 1 ) . Path 1 leading to the
generation of a mole of carbon monoxide, of nitrogen, lt BlUREA
I
and of ammonia from one mole of azodicarbonamide CYAMILIDE
will produce more gas than the path in which nitro- CYANIC ACID
I CVANURIC ACID
gen alone is generated. The path generating nitrogen 4 TRISFORMAMVL-
HYDRAZINE
and carbon monoxide involves a n equilibrium with NH,OCN + Nl + CO
ammonia. Therefore high pH would be expected to

BIURET
UREA
Table 2. Paste Resin Alkalinity’.
~ ~~~~~~~ Chart 1 Decomposition Mechanismfor azodicarbonamide.
PH
H3P04Treatment
Sample Before After
1 7.7 7.4 affect the equilibrium enhancing the amount of gas
2 9.3 7.0 generated.
3 9.0 7.7 Altering the temperature of decomposition will
‘The pH was measured as a slurry of 10 g of resin in 100 g of deionized water (pH change the rate of gas evolution. Additives which
5.3). retard the trans to cis isomerization, or complex with
the cis-azodicarbonamide, will slow the rate, or in-
crease the decomposition temperature.
This work has shown that compounds affecting
the blowing agent decomposition can alter both the
temperature of decomposition and the amount of gas
evolved. In some cases inhibitors can reduce both the
decomposition temperature and gas evolution. In
other instances, an inhibitor, e.g. Versene 100, can
raise the decomposition temperature in one system
and lower it in another.
EMPERANRE. DEG C -b

Fig. 5. Phosphoric acid treated plastisols (RP) u s . un-

ACKNOWLEDGMENTS
treated (LP). The author wishes to express his appreciation to
W. E. Hughes for providing the data correlating pH
with foam density, and to The Goodyear Tire & Rub-
Table 3. Effect of pH on Vinyl Foams. ber Company for permission to publish this work.
Latex pH 7.3 7.0 6.5 6.0
Density, kg/m3 206 223 246 307 REFERENCES
Blow RatioQ 5.54 4.97 4.68 3.75
*The ratio of the expanded thickness to the gelled thickness is known as the blow 1 . R. F. Nairn, J . C. Harkins, Jr., andF. E. Ehrenfeld. Jr.,
ratio (Ref 3). U. S. Patent 3,293,094 (1966).

146 JOURNAL OF VINYL TECHNOLOGY, SEPTEMBER 1991, Vol. 13, No. 3

 Blowing Agent Decomposition in Vinyl Foams

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JOURNAL OF VINYL TECHNOLOGY, SEPTEMBER 1991, Vol. 13, No. 3 147