R. R. TURNER, D. W. CARLSON, AND A. G.

ALTENAU

The Firestone Tire and Rubber Company

Central Research Laboratories
Akron, Ohio 44317

DETERMINATION OF UNGRAFTED RUBBER IN ABS POLYMERS

(Recemed August 10, 1973~-

ABSTRACT: A method has been developed for determining the amount of

ungrafted rubber in ABS polymers. First the styrene-acrylonitrile (SAN)
resin is removed by extraction with ethyl acetate. The composition of the
SAN resin was determined by NMR analysis. The ethyl acetate insoluble
material which consists of graft polymer and ungrafted rubber is then
extracted with a mixture of hexachlorobutadiene and ethyl acetate The
ungrafted rubber dissolves in the extraction solvent mixture while the graft
polymer remains insoluble Filtration, concentration of the filtrate by
vacuum distillation and NMR analysis of the concentrated filtrate using an
internal standard technique provided the amount and composition of the
ungrafted rubber. The data also permitted the amount and composition of
the graft polymer to be calculated.

INTRODUCTION

N THE LAST 20 years a class of thermoplastic polymers has been developed

and are known as ABS polymers. These polymers can exhibit a wide range of
desirable properties. The ABS polymers are composed of styrene-acrylonitrile
copolymer (SAN) as a continuous phase and a dispersed phase of either butadiene-
acrylonitrile rubber (called type B - ABS polymer), or a butadiene containing
rubber onto which styrene and acrylonitrile monomers have been grafted (called
type G - ABS polymer). Type G is now the most commonly produced ABS
polymer and consequently was chosen for investigation in this paper. Type G
polymers are probably mixtures of polybutadiene, polybutadiene grafted with
styrene and acrylonitrile and SAN copolymer [1, 2] . Mere mixtures of polybuta-
diene and SAN copolymer are extremely weak and it is the graft polymer which
provides the link between the two other components. A correct balance between
grafted and ungrafted rubber is essential and this is achieved by controlling the
polymerization conditions within certain limits [1, 2]. The rubber component
should be gelled [1, 2] . This can be accomplished during the rubber preparation or
during the grafting. If no gellation occurs the final blend would have poor impact
strength properties. Since some rubber remains ungrafted, ABS polymers possess
good low temperature impact strength [1, 2] .
The amounts of SAN copolymer, graft and rubber in ABS polymers are very

J of Elastomers and Plastics, Vol. 6 (April 1974), p. 94

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critical for optimum properties. The amount of SAN copolymer can be determined
by extraction with a variety of solvents, e.g., ethyl acetate, acetone and methyl
ethyl ketone, but unfortunately a satisfactory method for determining the amounts
of rubber and graft has not been previously found.
This is mainly the result of the rubber being gelled and solvents such as xylene
and cyclohexane have been unable to extract all the ungrafted rubber [3].
The composition of ABS polymers has been studied by electron microscopy [4] .
Although some conclusions were made about the arrangement and function of the
SAN, graft and rubber, no conclusion was made about the amount of each com-
ponent.
This paper describes a solvent system composed of hexachlorobutadiene and
ethyl acetate which is capable of extracting the ungrafted rubber from commercial
ABS polymers after the SAN copolymer has been extracted with ethyl acetate.
NMR and infrared analyses were used to characterize the composition of the ex-
tracted ungrafted rubber. Knowing the amount of SAN copolymer and ungrafted
rubber and the overall composition of the graft and ungrafted rubber fraction, the
amount and composition of the graft was determined.

PROCEDURE

Part A - Separation and Identification of

the Resin Content of ABS Polymers

5.0 grams of ABS polymer were weighed into a pint jar. Four hundred milliliters
of ethyl acetate were added, the jar was sealed with a teflon lined lid and the
sample stirred on a magnetic stirrer until completely dispersed. The contents of the
jar were transferred to 150 milliliter centrifuge bottles and centrifuged at 13,000
rpm’s for 90 minutes at 0°-5° C. The supernatant was decanted into pre-weighed
crystallizing dishes, and air dried at room temperature. The weight of the residue
was the amount of styrene-acrylonitrile copolymer in the ABS polymer. NMR

spectra confirmed that only styrene-acrylonitrile copolymer (Figure 1) was present.

The ratio of styrene to acrylonitrile was calculated from the NMR spectra.

Part B - Separation and Identification of

the Ungrafted Rubber in ABS Polymers

The ethyl acetate insoluble portion of Part A was transferred into a 28 oz

polymerization bottle with 100 milliliters of ethyl acetate. One hundred and fifty
milliliters of hexachlorobutadiene were then added to the bottle. The bottle was
capped with an aluminum lined cap. The bottle was placed in an 80° C polymeriza-
tion bath for approximately 16 hours, then removed, cooled to room temperature
and filtered into a two hundred and fifty milliliter round bottom distillation flask.
With one of the samples it was necessary to use 100&dquo; C (steam bath) rather than the
80° C polymerization bath for extraction of the rubber. The sample was not

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 Figure 1. NMR spectrum of styrene-acrylonitrile (SAN) copolymer extracted
from ABS polymer. Signals around 7 ppm - styrene aromatic protons
Signals between 1 to 3 ppm - aliphatic protons of styrene and acrylonitrile

agitated on the steam bath but was tumbled using the polymerization bath. After
extraction, the sample was vacuum distilled to a volume of 10 to 20 milliliters.
After measuring the volume an aliquot (usually 0.5 ml) was syringed into a NMR
spinning tube. Ten microliters of dioxane were added to the spinning tube and the
NMR spectrum was recorded and integrated.
The amount of ungrafted rubber in the NMR tube was determined by comparing
the NMR integral response of the known amount of dioxane with the response of
the ungrafted rubber.
If 15 ml remained when the distillation was stopped and 0.5 ml of the 15 ml was
put in the NMR tube along with 10 microliters of dioxane, the following would be
the calculation.
The total rubber response was 210 units while the dioxane response was 84 units
(Figure 2). The quotient of 210 divided by 84 is 2.50. The ratio of the response of
1 mole of butadiene to 1 mole of dioxane is 0.75 since there are 6 protons per mole
of butadiene and 8 protons per mole of dioxane. Therefore 2.50 divided by 0.75
equals 3.33 which are the moles of rubber per mole of dioxane. The 3.33 moles of
rubber per mole of dioxane times the moles of dioxane in 10 microliters, which is
0.000117, gives 0.000389 moles of rubber in the 0.5 ml. Multiplying 0.000389
moles of butadiene by 54, its molecular weight, gives 0.021 grams of butadiene in
the 0.5 ml. Then 0.021 grams is multiplied by 30 to give 0.63 grams of butadiene in
the 15 ml as well as in the entire sample that was weighed. The factor of 30 was
determined by dividing 15 ml by the 0.5 mi aliquot taken for NMR analysis. Since
5 grams is our standard sample weight, 0.63 times 100 divided by 5 gives 12.6%
ungrafted rubber in the ABS polymer.

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Figure 2. Typical NMR spectrum of extracted ungrafted rubber from Samples 1 through 6.
Signal at 5.4 ppm - olefinic protons of 1,4-polybutadiene
Signal at 5. 1 ppm - olefinic protons of 1,2-polybutadiene
Signal at 3.5 ppm - dioxane (internal standard)
Signal at 2.0 ppm - aliphatic protons of 1,4-polybutadiene
Signal at 1.2 ppm - methylene protons of the soap
Signals between 6 and 7 ppm - impurities in hexachlorobutadiene

RESULTS AND DISCUSSION

Various commercial ABS polymers were extracted with ethyl acetate to remove
the SAN copolymer. NMR analysis of the SAN portion did not show any butadiene
(Figure 1). The ratio of styrene to acrylonitrile was calculated from the NMR
spectra. Table 1 shows the amount and composition of the SAN copolymers found
in the commercial ABS polymers that were investigated.
Since the ethyl acetate insoluble portion was not completely soluble in any
solvents we studied, NMR could not be used to determine the overall composition
of this fraction. Therefore infrared and nitrogen analysis were used to determine
the composition of this fraction. Nitrogen analysis provided the amount of acrylo-
nitrile while infrared provided the ratio of butadiene to styrene. The nitrile band
from acrylonitrile was seen in the infrared spectrum at 4.5 microns but we did not
have any calibration to quantitatively measure the amount of acrylonitrile. For
infrared analysis, the ethyl acetate insoluble portion was either run as a film or
sandwiched between salt plates. In both cases the sample was swelled with carbon
disulfide before film preparation or sandwiching between salt plates. Usually there
was more than the normal amount of scatter because the sample was never per-

fectly clear. Infrared spectra clearly showed the vinyl content of the butadiene
portion to be about 20% which is typical for emulsion polybutadienes. No good

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measure of the cis microstructure could be obtained because of the presence of

styrene. The trans band (10.35 microns) was sharp and easily measured. The ratio
of butadiene to styrene was determined by assuming the trans content of the
butadiene portion was 60%. This is about the average value of trans in emulsion
polybutadienes.
The percents of butadiene, styrene and acrylonitrile in the ethyl acetate insolu-
ble fraction (graft and ungrafted rubber) of the different commercial ABS polymers
studied are shown in Table 1. The ratio of styrene to acrylonitrile in the ethyl
acetate insoluble portion is similar to the ratio of the monomers in the SAN portion
of the ABS polymers. The similarity of the styrene to acrylonitrile ratios of the
graft and SAN portions was expected and shows that our infrared analysis of the
ethyl acetate insoluble was satisfactory.
The ethyl acetate insoluble portion was extracted overnight with the hexachloro-
butadiene-ethyl acetate solvent mixture. The soluble portion was the ungrafted
rubber as shown by NMR analysis while the insoluble portion was assumed to be
the graft. Infrared analysis of the graft portion was very difficult because of its
insolubility. However infrared analysis was able to show the presence of butadiene,
styrene and acrylonitrile and that the butadiene content was lower than before
extraction.
The amount of rubber extracted from the different ABS polymers is shown in
Table 1. The data show that about 60 to 80% of the butadiene in the entire sample
is present as ungrafted rubber except in Sample 3 which had 28%. Using the
compositional analysis of the ethyl acetate insoluble fraction (graft and ungrafted
rubber) and the amount of ungrafted rubber extracted (Table 1), one can calculate
the composition of the graft (Table 1). The compositions of the graft in the differ-
ent ABS polymers are similar to those of Smith [5], Hayes [6] , Childers [7] , and
Irvin [8] .
Figure 2 shows a typical NMR spectrum of the material extracted from the ethyl
acetate insoluble portion with the hexachlorobutadiene-ethyl acetate mixture for
Samples 1 through 6. No aromatic protons of styrene or acrylonitrile protons are
seen in the NMR spectra. The vinyl content of the polybutadiene is about 20%.

Figure 3 shows a typical NMR spectrum of the material extracted from the ethyl
acetate insoluble portion with hexachlorobutadiene-ethyl acetate mixture for
Samples 7 and 8. Both of these samples are from the same manufacturer. The
aromatic protons of styrene are seen around 7 ppm. The styrene content was 10%.
Numerous repeats always yielded the same results. We were unable to detect any
significant amount of nitrogen in these rubber fractions which indicate that there is
no acrylonitrile present. Infrared analyses also did not detect any acrylonitrile.

Therefore the styrene appears to be due to the manufacturer using a SBR rubber
rather than polybutadiene compared to the other possibility that the styrene is due
to the presence of graft.
Table 1 shows the amounts of ungrafted rubber, graft and the composition of
the graft based on the ungrafted rubber being polybutadiene as well as the actually

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Figure 3. Typical NMR spectrum of extracted ungrafted rubber from Samples 7 and 8. Signal at

7.2 ppm - sytrene aromatic protons. Other signals were identified in Figure 2.

determined SBR containing 10% styrene for Samples 6 and 7. Both numbers are
included so comparison of all the samples can be made on the basis of the rubber
being polybutadiene or on the basis that two of the samples contained SBR. Be-
cause of the low styrene content in the SBR, the differences are not large.

Only Sample 4 required the use of a steam bath rather than the 80°C polymer-
ization bath for extraction of the ungrafted rubber. Very little rubber was extracted
using the polymerization bath.
An ABS polymer prepared according to the British Patent [9] is considered to
be an example of a highly grafted polymer. The amounts of SAN copolymer, ethyl
acetate insoluble and the butadiene in the ethyl acetate insoluble portion are shown
in Table 1. The separation of the SAN copolymer from the ethyl acetate insoluble
portion is extremely difficult. Even after centrifuging at 13,000 rpm at 0°C, a small
amount of the graft was suspended in the ethyl acetate. None of the commercial
ABS samples behaved this way because the graft contents are much less. Only 3.2%
(calculated as polybutadiene) or 4.0% (calculated as SBR containing 25% styrene)
was extracted from the ethyl acetate insoluble portion with the hexachlorobuta-

diene-ethyl acetate mixture. An SBR rubber containing 25% styrene was used in
preparing this ABS polymer and NMR analysis of the ungrafted rubber actually
showed the rubber to contain 25% styrene. No significant amount of nitrogen was
found in the ungrafted rubber fraction and no acrylonitrile was detected by infra-
red. The amount of rubber extracted is considerably less than the amount of rubber
extractable from commercial samples. The small amounts of SAN copolymer and
ungrafted rubber extracted from this ABS polymer indicates that the sample is
highly grafted.

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 The extraction of ungrafted rubber with the hexachlorobutadiene-ethyl acetate
mixture was done for 32 hours instead of the normal 16 hours with several of the
commercial samples. No increase in extractable rubber was observed. The longer
extraction time was studied to check the completeness of the extraction and,
incidentally showed the lack of degradation of the graft. The small amount of
rubber extracted from the British Patent ABS polymer is also indicative of the lack
of degradation of the graft.
Furthermore if graft degradation were occurring one would expect the NMR
spectra of the ungrafted rubber fraction to show some peaks other than rubber. The
NMR spectra are very normal and no unknown peaks are seen.
The dioxane internal standard method was used for measuring the amount of
ungrafted rubber instead of weighing the dried residue because it was extremely
difficult to evaporate all of the hexachlorobutadiene without oxidation of some of
the ungrafted rubber. Hexachlorobutadiene boils around 220°C. Upon complete
evaporation of the hexachlorobutadiene from the rubber extract, the sample
became very insoluble and we were not able to completely redissolve it. Infrared
analysis on the dried rubber extract did indicate that 2 to 5% styrene was present.
This is apparently due to some graft that was extracted with the rubber. Although
NM R analysis can detect 2 to 5% styrene, NMR analysis did not detect any styrene
in the 10-20 ml of the hexachlorobutadiene solution which was used with dioxane
to measure the amount of extractable rubber. The difference between infrared and
NMR in detecting styrene is best explained by the fact that the graft was not
soluble in the hexachlorobutadiene-ethyl acetate mixture but formed a very fine
dispersion. NMR only detects materials that are dissolved. (Actually NMR can
detect protons in solid materials, wide line NMR, but the signals are so broad
compared to dissolved materials, we can say for our purposes undissolved materials
are not detected by NMR.) Therefore the very small amount of graft that was in the
rubber extract was not measured by the dioxane internal standard technique.
Each of the rubber extracts from the ABS polymers were weighed after a great
deal of care was exercised to avoid oxidation during the evaporation of hexachloro-
butadiene. The entire drying was done under vacuum at 80°C. The dried extract
was washed with ethyl alcohol to remove most of the soap (emulsifier used in the

polymerization, e.g., stearate) that was present in the extract. The amount of
extracted rubber determined by the residue weight agreed within 15% (relative) of
those determined by the dioxane internal standard method. In each case the residue
weight percents were higher which is best explained by residual soap that was not
completely removed, residual hexachlorobutadiene and a very small amount of
graft. The residual soap is seen in the NMR spectrum at 1.2 ppm (f) (Figure 2). The
1.2 ppm (f) peak is from the methylene protons of the soap. The good agreement
between the residue weight and internal standard method demonstrates that the
very small amount of soap and graft that is extracted is negligible compared to the
amount of rubber extracted.

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 Attempts to extract the rubber with hexachlorobutadiene rather than the
hexachlorobutadiene-ethyl considerably less rubber. The
acetate mixture resulted in
function of the ethyl acetate appears to be to disperse the sample so a more
effective extraction by the hexachlorobutadiene can take place. Without ethyl
acetate the sample remains undispersed which does not allow optimum exposure of
the sample to hexachlorobutadiene.

ACKNOWLEDGMENTS
The authors wish to thank The Firestone Tire & Rubber Company for permis-
sion to publish this work and to Dr. R. A. Hayes for his many helpful suggestions
during the course of this work.

REFERENCES

1. C. H. Basdekis, "ABS Plastics,’ p. 62, Reinhold Publishing Corp , New York, 1964.
32, 549 (1959).
2. N E. Davenport, L. W. Hubbard, and M. R. Petit, Brit. Plastics
3. B. D. Gesner, J. Polymer Sci. A3, 3825 (1965).
4. M. G. Huguet, and T. R. Paxton, Polymer Preprints 11, (21, 548 (1970).
5. W. M. Smith, "Manufacture of Plastics," p. 453, Reinhold Publishing Corp., New York,
1964.
6. R. A. Hayes, U.S. Patent 2,802,808 (Aug. 13, 1957).
7. C. W. Childers, U.S. Patent 2,820,773 (Jan. 21, 1958).
8. H. H. Irvin, U.S. Patent 3,010,936 (Nov. 28, 1961)
9. T. A. Clayton, Brit. Patent 649,166 (Jan. 17, 1951).

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