3033

Sonderdruck aus der Zeitschrift "die starke - starch"

Internationale Zeitschrift fur die Erforschung, Verarbeitung und Verwendung von
Kohlenhydraten und deren Derivaten
International Journal for Research, Processing, and Use of Carbohydrates and their Derivatives
23. Jahrgang Heft 10 Seite 350-359 Verlag Chemie GmbH, Weinheim/Bergstr.
"Purchased by U.S. Department of Agriculture for Official Use."
Starch in Rubber
Influence of Starch Type and Concomitant
Variables in Reinforcement of Styrene-Butadiene Rubbers
By R. A. Buchanan, W. F. Kwolek, H. C. Katz, and C. R. Russell, Peoria, Illinois (USA)
These swdies allowed selection of four starch derivative styrene butadiene elastomer (SBR)
masterbatch compositions for futlire optimization swdies. The main factor remaining to be opti-
mized is level of resorcinol-formaldehyde (RF) incorporation; btlt fine adjllstment of such factors
as stanh loading and plasticizer incorporation is needed also.
Results in these experiments suggest that further swdy of certain high-amylose starch composi-
tions might lead to masterbatches gi'uing vulcanizates with both low adsorption and gooe!
strength properties. Fmther work is also needed on oil-extension of starch derivative-SBR
masterbatches.
Properties of selected starch-SBR masterbatches met requirements of the rubber indllstry for many
end-lise applications.
(ZusammenfaSSlmg siehe Seite 357; ReSt/me ala page 358)
Introduction
Certain crosslinked resinlike starch derivatives are effective
reinforcing agents for rubber when incorporated by latex
masterbatching procedures [1, 2]. Further studies have
extended this technology [3, 4, 5Jand have delineated large
areas of potential commercial interest.
A number of compositional and operational variables have
been treated in the work cited above. However, there are
no published results showing the influence of starch molec-
ular size and structure on resultant reinforced rubbers.
Further, the only comparisons of reinforcing agents from
cereal flour derivatives with those from starch derivatives
are with a few powdered elastomer compositions [5J.
This paper reports research results which relate starch
characteristics to properties of corresponding starch-rein-
forced rubbers. Because of the large number of variables
and possible interactions involved in the complex master-
batching process, statistical experimental designs were used.
Also, these studies were limited to two styrene-butadiene
(SBR) elastomers representative of the major synthetic
rubber in domestic usage.
Experimental
Materials
Types 1502 and 1713 SBR latices were the untreated emul-
sion polymerization products of about 20 % total solids
content supplied by manufacturers of the conventional
elastomers [6J.
Starch xanthates were prepared from pearl corn starch
(unmodified corn starch), 37 fluidity acid-modified corn
starch (intrinsic viscosity 0.98), 75 fluidity acid-modified
corn starch (intrinsic viscosity 0.54), waxy maize starch,
and high-amylose corn starch (71 % apparent amylose,
intrinsic viscosity 1.07). Flour xanthates were prepared
from edible yellow corn flour, soft wheat flour and hard
wheat flour. These starches and flours were used as pur-
chased from domestic processors.
Starch and flour xanthates were made at 10 % concentra-
tion, based on dry starting materials, by a procedure [7J
which causes little reduction in starch intrinsic viscosity.
The desired xanthate degree of substitution (D.s.) was
achieved with 0.5 mole sodium hydroxide per mole starch
or flour (taken as 162 unit molecular weight) and with
variable amounts of carbon disulfide. Xanthates for each
starch-elastomer masterbatch preparation were made indi-
vidually and used after overnight storage in a refrigerator.
Technical grades of resorcinol and paraformaldehyde were
used. Vulcanizing agents, accelerator, antioxidants and
other rubber compounding ingredients were common com-
mercial materials. Fillers were a rubber-reinforcing grade
of hydrated silica and a white kaolin clay designated a
"hard clay" by rubber compounders.
The extender oil incorporated into SBR 1713 was a stain-
resistant naphthenic oil of about 31 % aromatic coment
and about 1200 SUS at 100 OF (= 38 0q.
Sulfuric acid, zinc sulfate, sodium nitrite and other reagents
were analytical grade.
Preparation of Starch-Elastomer jllasterbatches
All preparations were nude by slight modification of pre-
viously described procedures [3J as schematically diagram-
med in Figure 1. Batch size was generally based on 400 g
latex solids. Xanthate solution was mixed with latex to
give either 30 or 45 parts starch per 100 parts (phr) latex
solids. In those SBR 1713 preparations containing extender
oil, the oil was emulsified in xanthate solution before mixing
with latex. Also, in preparations containing fillers, the in-
organic pigment was suspended in xanthate prior to mixing
with latex. Styrenated-phenol antioxidant emulsion was
added to a level of 1.25 phr. When resorcinol and form-
aldehyde (RF) were coreacted with xanthate, the level of
resorcinol addition was 0.03 mole per mole starch with a
formaldehyde to resorcinol mole ratio of 3. All mixtures
were stirred continuously for 30 min before and during
coprecipi tation.
Xanthate-latex mixtures were coprecipitated with zinc by
slowly adding an amount of M sulfuric acid calculated to
~
~ g
-=====, ....--- _h_____ Filtration
Drying \::\====, t
ICurd Serum,
t discarded
\::====::::1
1
Partial
C:::=:::=:::=:::l' Drying
WetExtrusion ~
Processed Masterbatch,
Product
Curing characteristics were obtained with an oscillating
disk rheometer operated at 10 cpm frequency, 3 arc ampli-
tude and 150C by ASTM D2705-68T method [8]. Opti-
mum cure time, to' (90), was taken as time for the torque
to increase to 90 % of its total increase or increment.
In wet-extrusion processing, the starch-elastomer coprecipi-
tate was partially dried at 70C in a forced draft oven to
moisture levels of 10, 20 or 300/0. Moist coprecipitate was
stored in air-tight plastic bags for at least 24 hr and then
processed to dryness by repeated extrusions from small
laboratory extruders at temperatures above 100C. In
these studies, the best process employed a Brabender Plasti-
corder
l
) equipped with a 25/1, length to diameter ratio,
vacuum vented extrusion-head. This extruder had three
independent temperature-controlled barrel zones and was
operated at 100 rpm. to give a product temperature near
150C. An unheated "spaghetti" die with 24 holes of
1/32 in. diameter was employed. Up to four extrusion
passes were required to completely dry the products.
Compounding and Curing
Usual test compound contained 1 phr stearic acid, 4 phr
zinc as zinc oxide, 2 phr sulfur, 1.5 phr alkylated diphenyl-
amine, 1.5 phr benzothiazyl disulfide and 0.1 phr tetra-
methylthiuram disulfide. Note that zinc oxide, per se, was
only added to xanthide preparations since zinc xanthate
preparations were coprecipitated with the required 4.0 phr
zinc as zinc oxide for cure activation. Compounds were
mii! mixed by slight modification of the procedure described
in ASTM D15-68a [8].
Extrusion
Drying
Vacuum
Vent
t
Mixing
t
~ Coprecipitation
W
Zinc Sulfate or Sodium
Nitiite and Acid
~
MiIli"0
~
OryMili Processed
Masterbatch.
1550Y Product
ResorcinolFormaldehyde,
Extender Oil and Fillers
Starch Xanthate
Solution
give final serum pH about 7.0, followed by M zinc sulfate
solution equivalent to 4.0 phr zinc as zinc oxide in the
coprecipitate. The crosslinked starch derivative in these
products was zinc starch xanthate, and those products con-
taining resorcinol and formaldehyde were designated zinc
starch xanthate RF.
In subsequent discussion, individual preparations (master-
batches) are mainly characterized in terms of their vulcan-
izate physical properties. Since all preparations were com-
pounded alike and cured to the same degree, vulcanizate
properties are considered derivative from masterbatch prop-
erties.
Xanthate-latex mixtures were also coprecipitated by adding
1.25 moles of sodium nitrite per mole of xanthate group,
followed by slow addition of M sulfuric acid to reduce pH
of the mixture to 4.5 and to maintain that pH for 10 min.
The crosslinked starch derivative in these products was
starch xanthide, and those products containing resorcinol
and formaldehyde were designated starch xanthide RF.
Coprecipitates were recovered on Buchner funnels with
cloth filters. Xanthide products were washed by suspension
in water, but zinc xanthate products were not washed be-
cause they tend to become sticky upon washing. Volumes
of serums and wash waters were measured and analyzed for
starch content. Processing of wet coprecipitates was by one
of the two methods outlined in Figure 1. Weights of dry
masterbatch products indicated that there was generally no
loss of elastomer.
In dry-mill processing, the starch-elastomer copreClpltate
was dried at 70C in a forced draft oven to less than 2
0
/0
moisture content. Then the dry crumb product was con-
solidated, banded onto a laboratory differential roll mill
and milled for a few minutes at roll temperatures below
65C.
Vttlcanizate Testing
Specimens for physical testing were made by press curing
at 150C for the optimum cure time as determined by
rheometer measurement. Physical properties of rubber spec-
imens were measured by ASTM methods [8]. Measured
properties were indentation hardness ASTM D2240-68, im-
pact resilience ASTM D2632-67, tensile properties ASTM
D412-68, tear resistance ASTM D624-54 die C, compres-
sion set ASTM D395-67 method B, change in properties
resulting from water immersion for 70 hr at 72 OF (=22C)
ASTM D471-68 and abrasion resistance ASTM D394-59.
Design of Experimental Program
The total number of preparations required to examine all
the factors and interactions was reduced from several
thousand to 144 by dividing the problem into four stages
[9] and utilizing fractional factorial experimental designs
The mention of firm names or trade products does not imply
that they are endorsed or recommended by the Department of
Agriculture over other firms or similar products not mentioned.
Die Starke 23. Jahrg. 1971 / Nr. 10
351
Table 1. Experimental Program for Selection of Starch Types and Preparative Conditions Giving Best Masterbatch Properties.
Stage
II
III
IV
Processing method
Dry-mill
\'\/et-extrusion
\\7et-extrusion
\\7et-extrusion
Number of
preparations
60
28
40
16
Factor
Starch type
SBR type")
Xanthate D.S.")
Crosslinking reaction
Starch loading
Silica loading
Clay loading
Method of filler addition
:Milling procedure
Starch type
Cereal flour
Crosslinking reaction
Starch loading
Moisture content
Starch type
Loading-crossJinking
reaction interaction
Extruder variables
Starch type
Loading-crosslinking
reaction interaction
Resorcinol-formaldehyde
coreaction
Oil extension
Xanthare D.S.
Levels
6 Starches
l
)
SBR 1502, SBR 1713
3
)
0.06,0.23
Zinc xanthare, xanthide
30 phr, 45 phr
ophr, 20 phr
ophr, 26.2 phr
Coprecipitation, mill mixing
Dry mill, hot-wet milP)
4 Starches
3 Flours
Zinc xanthate, xanthide
30 phr, 45 phr
10%,30%
Starch and corn flour
{
30 phr zinc xanthate }
45 phr xanthide
Many
Starch and corn flour
J 30 phr zinc xanthate
t 45 phr xanthide
0,0.03
SBR 1502, SBR 1713
3
)
0.06, 0.10
Selected for
further study
4 Starches
BOth
0.06,0.10,0.12
Both
Both
ophr
ophr
No filler addition
\\7et-extrusion
Unmodified corn starch
Yellow corn flour
30 phr, zinc xanthate
45 phr, xanthide
20%
Both
Both
Extrusion conditions')
Both
Both
0.03
SBR 1502
f 0.06 D.S. starch
l 0.10 D.S. corn flour
1) Unmodified corn starch (pearl corn starch), 37 and 75 fluidity acid-modified corn starches, waxy maize starch, high-amylose corn starch and
yellow corn flour;
2) SBR = styrene-butadiene; D.S. = degree of substitution;
3) SBR 1713 employed \vithout oil-extension in Stage I, with 50 phr napthenic oil in Stage IV. In Stage IV studies starch loadings were based
on oil plus elastomer;
4) An unsuccessful attempt to duplicate wet-extrusion processing using steam-heated open rolls for mastication of moist starch-elastomer
coprecipitate during drying;
5) Extrusion conditions were uncritical within the range of variables accessible to our laboratory equipment.
[10]. From five to mne factors and their interactions were
examined in each stage of the study. At the end of each
stage, conditions for best starch-elastomer masterbatch prop-
erties were selected for inclusion along with other variables
needing further study in the design for the next stage [9,
10]' An outline of the experimental program, showing
selections made at the end of each stage is given in Table 1.
This table presents a detailed listing of factors included in
the experimental design for each stage of the study. Details
of statistical analysis are not given in this paper.
For Stage I studies, an experimental design with six starch
types and seven other factors at twO levels each was em-
ployed (Table 1). This design allowed measurement of var-
iations associated with starch type, main effects of the seven
factors and interactions between starch type and each of
the seven factors. Stage I studies also included a comparison
between a hot-wet-mill processing procedure and dry-mill
processing. Dry-mill processing was employed in Stage I
studies because this process is related to the process for
preparation of powdered starch-elastomers [5].
For Stage II studies, an experimental design with four
starch types and three other factors at two levels each was
selected (Table 1). Confounding [10] a difference between
352
pairs of starch types with an interaction provided a design
requiring only 16 preparations and allowing estimation of
several interactions. Twelve additional runs were then
added to allow comparison of yellow corn flour with soft
wheat and hard wheat flours. Previous work [4] had in-
dicated that wet-extrusion processing, as employed in
Stage II studies, gave better masterbatch properties than
did dry-mill processing. However, data from Stages I and
II did not provide a direct comparison between the two
processing methods because of differences in xanthate D.S.
In Stage III studies, extruder variables involved in wet-
extrusion processing were examined using three extrusion
heads and a variety of screws available as standard items
for the Brabender Plasticorder with several nonstandard
spaghetti extrusion dies. However, the full factorial experi-
mental design was not completed when it became evident
that extrusion conditions were noncritical within the range
of variables being studied.
Primary objective of Stage IV studies was to determine
effects from coreaction of starch xanthate derivatives with
RF and of oil extension. A fractional factorial experiment
was employed to examine five main effects and their 10
two-way interactions (Table 1).
Die St"rke 23. jahrg. 1971 I Hr. 10
Table 2. Means and Standard Deviations, by Measurement.
Starch Mini- Opti- Hard- Re- lvlodu-
recovery mum mum ness bound Ius at
( ~ 6 ) rheo- cure (Shore resi- 300%
meter time at A) lience elon-
torque 150
c
C (%) gation
(in.-Ib) (min) (psi)
After 70 hr water immersion
Elon- Tensile Tear Com- Abra- Volume Tensile Elon-
gation strength resi- pression sion increase strength gation
at break (psi) stance set, B rate (%) (psi) (%)
(%) (lb/in.) (%) (cm
3
1
hr)
Stage I
J'vlean value 95.00 20.95 17.55 77.56 43.50 1050 485.6 1517 201.0 0.99 14.14 1123 523.6
Standard deviation
l
) 3.86 3.79 4.27 3.20 2.50 215 77.5 278 24.0 0.32 4.99 265 69.3
Stage II
Mean value 97.43 6.05 20.91 63.54 53.15 851.7 392.7 1069 152.8 1.01 6.77 878.5 430.1
Stage IV
Mean value 97.96 8.21 22.66 64.81 46.79 346.9 1269 137.5 24.91 2.68 11.86 837.8 402.5
Standard deviation
2
) 1.69 9.28 2.14 2.21 53.4 261 18.1 2.37 0.18
3
) 1.63 163 46.4
1) Forty degrees of freedom; 2) Pooled Stage II and IV, 15 degrees of freedom; 3) Four degrees of freedom.
Results and Discussion Selection of Starch Type for Best Masterbatch Properties
Estimation of Variance
A measure of random run-to-run variation was obtained at
each stage in the study as illustrated by data in Table 2.
Variation estimates included some interaction effects and
preparative, analytical, testing and random run variations.
Therefore standard deviations and standard errors required
for evaluating the significance of effects tend to be larger
than precision estimates for physical testing of rubber vul-
canizates as an isolated step.
A main purpose of this research was to relate starch charac-
teristics to properties of resultant starch derivative-SBR
masterbatches. Table 3 gives only those analytical and test
values significantly influenced by starch characteristics.
Comparison in Stage I studies of pearl (unmodified) starch
with starches having fluidity of 37 and 75 showed that low
starch molecular weight (high fluidity) had a deleterious
effect on starch recovery, i.e., on completeness of coprecipi-
tation of crosslinked starch with latex solids. Tensile
Table 3. Relation of Starch Type to Masterbatch Properties.
Starch type Starch Minimum Optimum Hardness Tensile
recovery rheometer cure time (Shore A) strength
(%) torque at 150
c
C (psi)
(in.-Ib) (min)
Tear
resistance
(lb/in.)
Abrasion
rate
(cm
3
/hr)
After 70 hr water immersion
Tensile Elongation
strength at break
(psi) (%)
501.8
485.3
608.1
523.5
493.8
529.1
69.1
1046
937
1250
1122
1039
1345
236
1.02
0.86
1.23
0.99
0.85
0.98
0.36
21.52
25.84
15.16
20.48
22.40
20.29
3.08
Stage I, means of eight dry-mill preparations
16.14 80.38' 1615 204.8
15.60 80.25 1814 217.8
23.40 72.37 1134 175.0
14.90 76.00 1378 191.9
16.88 77.62 1365 195.0
18.41 78.75 1796 221.9
4.05 3.09 286 34.1
Stage II, means of four wet-extrusion preparations
65.0 1498 179.8 0.98 1040
65.0 1375 176.0 0.98 905
61.2 709 133.2 1.21 745
65.5 1398 177.8 1.01 974
3.5 443 31.8 0.21 278
Stage II, means of two preparations showing interaction of starch type with crosslinking reaction
98.12
97.25
96.25
96.13
86.62
95.63
3.06
Pearl corn starch
\\faxy maize starch
71 % Amylose starch
YellO\v corn flour
LSD
Pearl corn starch
\\faxy maize starch
71 %Amylose starch
37 Fluidity starch
75 Fluidity starch
Yellow corn flour
LSDl)
\'7axy maize starch-zinc
xanthate 61 1015 156.5
71 % Amylose starch-zinc
xanthate 61 840 147.5
\\faxy maize starch-
xanthide 69 1735 195.5
71 % Amylose starch-
xanthide 61.5 577 119.0
LSD 4.9 626 44.9
1) Least significant difference between the respective means at the 95 % probability level.
Die Stiirke 23. Jalng. 1971 I Nr. 10 353
strengths given in Table 3 suggest that high-fluidity starches
give poorer vulcanizates than unmodified starch.
The comparison of waxy maize starch, pearl corn starch
and 71 0/0 amylose corn starch showed that starch molecular
structure had a definite effect on properties of resultant
starch derivative-SBR masterbatches. Vulcanizates rein-
forced with high-amylose starch derivatives gave generally
poorer physical properties than those given by either pearl
corn starch or waxy maize starch, but exhibited less change
in properties after water immersion. The interaction be-
tween crosslinking reaction and starch type in Stage II
studies may indicate that masterbatches containing 30 phr
zinc high-amylose starch xanthate are worthy of further
investigation because their vulcanizates have respectable
physical properties and change very little during water
ImmerSIon.
Yellow corn flour gave results equivalent to those obtained
with pearl corn starch in each stage of the study except that
it imparted a darker color to the masterbatch. This darker
color would be a serious consideration in some rubber
applications.
Effect of Filler Addition on Masterbatch Properties
Incorporation of two representative nonblack fillers into
starch-reinforced SBR masterbatches was considered in
Stage I studies. These fillers, incorporated at equal volume
loadings, were a low-cost, hard-clay extender and a higher
cost rubber-reinforcing grade of hydrated silica. Filler was
incorporated either by coprecipitation with starch and latex
solids or by mixing on the mill during dry-mill processing.
The effects of filler addition and the method of incorpora-
tion are presented in Table 4, which lists only those master-
batch properties significantly influenced by these variables.
Data in Table 4 show that starch reinforced-SBR master-
batches respond to filler addition by exhibiting increased
vulcanizate strength as expected. The only effect associated
with the method of incorporation was a small difference
in ultimate elongation. Studies on the effect of filler addi-
tion were discontinued after Stage 1.
Relation of Xanthate D.S. to Masterbatch Properties
Target xanthate D.S. levels 0.06 and 0.23 were employed
in Stage I studies, D.5. 0.12 in Stage II and III studies and
Table 4. Effect on Masterbatch Properties of Fillers and Their Method of Incorporation.
12.41 880 482
15.87 1366 565
1227
1019
2.32 136 40
Filler type and Minimum Optimum Hardness Rebound Modulus Elonga- Tensile Tear
method of rheometer cure dme (Shore A) resilience at 300%, don at strength resistance
incorporation torgue at 150
a
C (%,) elongation break (psi) (lb/in.)
(in.-lb) (min) (psi) (%,)
Stage I, means of 24 dry-mill preparations
Hydrated silica,
ophr 18.32 15.48 44.84 961 454 1206 176
Hydrated silica,
20 phr 23.58 19.63 42.17 1137 517 1828 226
Hard clay, 0 phr 17.10 20.60 74.96 46.46 929 1431
Hard clay, 26.2 phr 24.80 14.51 80.16 40.54 1170 1603
LSD 1.79 2.34 1.78 1.48 145 32 165 20
Coprecipitation 462
Dry-milling 510
LSD 32
After 70 hr Water immersion
Volume Tensile Elongation
increase strength at break
C%') (psi) (%,)
Table 5. Relation of Xanthate D.S. to Masterbatch Properties.
Xanthate D.S. or Starch Minimum Optimum Hardness Tensile Compression Abrasion After 70 hr
interaction recovery rheometer cure time (Shore A) strength set rate water im-
(%,) torgue at 150
a
C (psi) (%,) (cm
3
/hr) mersion,
(in.-Ib) (min) volume in-
crease (%,)
D.S.0.06
D.S.0.23
LSD
D.S.0.06
D.S.0.l0
LSD
D.S. 0.06-starch
D.S. 0.06-eorn flour
D.S. 0.10-starch
D.S. 0.10-eorn flour
LSD
Stage I, means of 24 dry-mill preparations
93.21 22.15 19.43 1734
96.79 19.75 15.68 1300
1.77 1.79 2.34 165
Stage IV, means of eight wet-extrusion preparations
25.19 23.27 2.48
18.75 26.55 2.88
9.89 3.29 0.20
Stage IV, means of four preparations showing interaction of xanthate D.S. with starch type
66.25 1.86
62.50 3.10
62.25 3.48
68.25 2.28
3.22 0.28
12.71
9.65
1.74
354 Die Starke 23. ]ahrg. 1971 I Nr. 10
Table 6. Effect on Masterbatch Properties of Crosslinking Reaction, Starch Loading and Their Interactions.
Crosslinking reaction
and starch loading
Starch
recovery
(%)
Minimum Optimum
rheometer cure time
torque at 150'C
(in.-lb) (min)
Hardness Elongation Tensile
(Shore A) at break strength
(%) (psi)
Abrasion
rate
(cm
3
jhr)
After 70 hr water immersion
Volume Tensile Elongation
increase strength at break
(%) (psi) (%)
Stage I, means of 24 dry-mill preparations
Zinc xanthate 17.81 16.35 76.29 587.7 1391 1.30 16.22 614.8
Xanthide 24.09 18.76 78.83 383.5 1642 0.68 12.06 432.4
30 phr Loading 97.04 17.68 20.16 73.58 541.9 1686 8.64 1416 573.7
45 phr Loading 92.96 24.22 14.95 81.54 429.4 1348 19.64 830 473.5
LSD 1.77 1.79 2.34 1.78 32.0 165 0.21 2.32 136 39.9
Stage II, means of eight wet-extrusion preparations
Zinc xanthate 4.52 61.8 440.0 1054 1.33
Xanthide 6.63 66.6 339.4 1436 0.76
30 phr Loading 4.59 61.1 416.9 0.85 5.06
45 phr Loading 6.56 67.3 362.5 1.24 7.57
LSD 1.64 2.5 52.9 313 0.15 1.71
Stage II, means of seven preparations showing interaction of crosslinking reaction \vith starch loading
Zinc xanthate, 30 phr 98.91 4.64 59.1 461.4 1208 0.74 6.40 931 482.1
Xanthide, 30 phr 94.87 6.00 61.4 384.3 1150 0.57 4.37 890 394.3
Zinc xanthate, 45 phr 97.10 6.00 63.6 413.6 705 1.55 8.91 689 492.9
Xanthide, 45 phr 96.84 7.64 68.3 325.7 1301 1.17 7.46 993 355.0
LSD 4.05 1.75 2.6 56.6 335 0.16 1.83 211 52.3
Srage IV, means of eight wet-extrusion preparations
Zinc xanthate, 30 phr 99.66 5.68 29.69 55.12 418.7 3.40 6.05 476.2
Xanthide, 45 phr 96.26 10.75 14.25 74.50 272.5 1.96 16.31 328.7
LSD 3.79 1.80 9.89 2.28 56.9 0.20 1.74 49.4
D.S. 0.06 and 0.10 in Stage IV studies. In Stage I studies,
the higher xanthate D.S. gave better starch recovery, less
viscous masterbatches (indicated by lower rheometer torque),
and faster curing compounds but gave lower strength vul-
canizates as shown in Table 5. Stage IV studies indicated
that higher xanthate D.S. also had a somewhat deleterious
effect on compression set and abrasion resistance. However,
as shown in Table 5, there is an interaction requiring that
corn flour be used at higher D.S. than pearl starch for
equivalent vulcanizate hardness and abrasion resistance.
Stage II studies showed that low starch recoveries, as noted
for D.S. 0.06 preparations in Stage I (Table 5), were asso-
ciated with 30 phr starch xanthide coprecipitations (Table 6).
Thus in Stage IV studies, which included only the 30 phr
zinc xanthate and 45 phr xanthide preparations, the average
starch recovery at D.S. 0.06 was 98.5
0
/0.
For further examination of the influence of xanthate D.S.
on masterbatch properties, data from wet-extrusion pro-
cessed 30 phr zinc xanthate-SBR 1502 and 45 phr xanthide-
SBR 1502 preparations in Stage II, III and IV studies were
pooled. This gave a data pool with 28 individual prepara-
tions and a xanthate D.S. range 0.05 to 0.18 for each com-
position. Least-squares regression lines for various master-
batch properties as a function of xanthate D.S. were cal-
culated from this data. Even though a wide range of prepa-
ration variables were included, the regression lines provided
a significant fit of the data for several properties. Over the
xanthate D.S. range 0.05 to 0.18, starch recoveries improved
slightly with increasing D.S.; but vulcanizate properties in
general were adversely affected by increasing xanthate D.S.
Thus xanthate D.S. 0.06 appears to be about optimum. This
result has been confirmed in other studies [11].
Die Starke 23. Jalng. 1971 I Nt. 10
Selection of Processing Procedure
Previously published [4] and unpublished [11] results have
disclosed that mastication of wet starch-elastomer copreci-
pitates during extrusion drying gives large improvements in
masterbatch properties. In Stage I studies, a partially suc-
cessful attempt was made to achieve this advantage by
drying wet coprecipitate while masticating on an open
steam-heated differential roll mill. This hot-wet-milling
procedure gave some improvement in masterbatch proper-
ties, but the improvement was much less than expected for
wet-extrusion processing. No direct comparison of Stage I
preparations with wet-extrusion processed masterbatches in
Stages II - IV was permitted by the choices made in xan-
thate D.S. and crosslinking reaction.
Stage II studies employed wet-extrusion processing with
coprecipitate moisture levels of 10 and 30
0
/0. No significant
effects were associated with these levels except an inter-
action of 30 % moisture content and zinc xanthate cross-
linking to give a slight reduction in optimum cure at the
expense of slightly increased abrasion rate. Thus, 20
0
/0
coprecipitate moisture content was selected for remaining
wet-processing studies.
Stage III studies were devoted exclusively to extruder vari-
ables in wet-extrusion processing of two selected SBR 1502
coprecipitate compositions. A vacuum vented extruder was
compared with an unvented extruder. Three length-to-
diameter ratio extruders were employed with various screw
compression ratios, die configurations and temperature pro-
files.. However, variations in xanthate D.S. accounted for
most of the observed variation in experimental results as
discussed above. The wet-extrusion processing procedure
355
described in the experimental section of this paper was
used in Stage IV studies. This procedure employs best con-
ditions accessible to the Brabender Plasticorder equipment.
Optimum conditions for wet-extrusion processing of starch-
SBR coprecipitate by other machines will have to be estab-
lished by further experimentation.
Selection of Crosslinking Reaction Type and Starch Loading
Stage I studies indicated that both starch loading and cross-
linking reaction type affected most masterbatch properties
as shown in Table 6. However, the Stage I experimental
design did not allow estimation of certain interactions.
The interaction of starch loading and crosslinking reaction
was investigated in Stage II studies. As shown in Table 6,
30 phr starch xanthide preparations resulted in low starch
recoveries and 45 phr zinc starch xanthate preparations
gave low tensile strengths, high abrasion rate and high
water absorption. The remaining two compositions were
selected for further study and did not give significantly
different vulcanizate tensile strengths even in Stage IV
studies where the factors of oil-extension and RF coreaction
were included.
Effect of Coreaction of Resorcinol-Formaldehyde
with Xanthate
Resorcinol and formaldehyde can be employed at relatively
high levels as primary starch crosslinking agents in prepara-
tion of starch-reinforced rubbers [2]. In Stage IV studies,
RF was coreacted with starch xanthate at a level of 0.03
mole per mole starch and affected vulcanizate properties as
shown in Table 7. In general, incorporation of RF gave
increases in vulcanizate strength and abrasion resistance.
The effect of RF was relatively greater in corn flour prepa-
rations than in starch preparations. Also, the effect of RF
was relatively greater at 30 phr starch loading than at
45 phr starch loading. This latter interaction suggests that
the level of RF incorporation might have been better cal-
culated on a phr basis than on a starch content basis.
Effect of Oil-Extension on Masterbatch Propnties
High-molecular-weight SBR type 1713 was used without
oil extension in Stage I studies and gave vulcanizate
strengths higher than were obtained with SBR type 1502 as
expected. In Stage IV studies, SBR 1713 was used with its
normal oil-extension (50 phr naphthenic oil), and starch
loading for the oil-extended SBR 1713 compositions was
calculated based on elastomer plus oil. Under these con-
ditions, oil-extension had a severe deleterious effect on vul-
canizate properties. For example, average tensile strength
and abrasion rate for oil-extended SBR 1713 compositions
were, respectively, 766 psi and 4.59 cm
3
/hr compared to
1771 psi and 0.77 cm
3
/hr for SBR 1502 vulcanizates in
Stage IV studies. However, several interactions of oil-
extension with other factors occurred. In a separate com-
parison, the oil was incorporated into starch derivative-
SBR 1713 masterbatches by mill mixing after wet-extrusion
processing rather than before coprecipitation. This "late"
oil incorporation gave masterbatches having different pro-
perties than those obtained in Stage IV studies. Future
studies will consider oil-extension in much greater detail.
Properties of Select Masterbatches
Selection of factors leading to best masterbatch properties
gives four best compositions. These compositions are based
on nonoil-extended SBR elastomers, contain derivatives of
either pearl corn starch or corn flour and would be pro-
cessed by the wet-extrusion method. The starting xanthate
D.S. for corn flour preparations would be 0.10 and for
starch preparations 0.06. Crosslinking of starch or flour
would be by the zinc xanthate reaction at 30 phr loading
and by the xanthide reaction at 45 phr loading. RF would
be coreacted with xanthate in each preparation at an op-
timum level which will have to be determined in future
studies. Coreaction with RF imparts a darker color to the
masterbatch, and this effect would also have to be taken
into account in optimizing RF level for applications where
bright colors are desired.
Table 7. Effect on Masterbatch Properties of Resorcinol-Formaldehyde (RF) Coreaction ''lith Xanthate.
RF level (moles/starch
mole)
Hardness
(Shore A)
Rebound
resilience
(%)
Tensile
strength
(psi)
Tension set Tear Abrasion
at break resistance rate
(%) (lb/in.) (cm
3
/hr)
Compression After 70 hr
set, B Water im-
(%) mersion,
volume in-
crease (%)
None
0.03
LSD
None--eorn flour
0.03-Corn flour
None-starch
0.03-Starch
LSD
None-30 phr
0.03-30 phr
None-45 phr
0.03-45 phr
LSD
Stage IV, means of eight ,vet-extrusion preparations
60.70 48.60 1108 11.87 124.2 3.61
68.87 46.12 1430 26.00 150.7 1.76
2.28 2.35 278 19.3 0.20
Stage IV, means of four preparations sho"'ing interaction of RF level with starch type
59.3 49.5
71.5 44.3
62.2 47.8
66.2 48.0
4.2 3.3
Stage IV, means of four preparations showing interaction of RF level with starch loading
47.8 54.0 4.90
62.5 47.2 1.90
ll7 ~ 3 D1
75.2 45.0 1.62
3.2 3.3 0.28
23.00
26.38
26.22
24.05
4.65
8.50
12.40
12.50
11.32
2.45
356
Die Stiirke 23. ]ahrg. 1971 I Nr. 10
Table 8. Properties of Select Starch Derivative-SBR 1502 Master-
batches.
Starch derivative!) and loading
30 phr, 30 phr, 45 phr, 45 phr,
Zinc corn Zinc starch Corn flour Starch
flour xanthate xanthide xanthide
Property xanthate RP) RpJ RF5)
RP)
Starch recovery, % " 99.75 99.43 96.8 99.2
Mooney viscosity,
MLl + 4 (100
c
C) 66.5 70.2 97 107
Minimum rheometer
torque, in.-l b 6.0 7.2 13 13.5
Optimum cure, at
150
a
C, min 25.75 24.8 14 20.5
Specific gravity 1.093 1.097 1.115 1.122
Hardness, Shore A 65 69 81 80
Rebound resilience,
0""
49 50 46 45 /0
Modulus, at 300%
elongation, psi 1470 1553
Elongation at
break, psi 375 383 250 270
Tensile strength,
psi 1800 2000 1860 2140
Energy for tensile
break, relative 497 525 322 388
Tension set, at
break, % 22.5 21.7 26 32
Tear resistance,
lb/in. 149 136 191 183
Compression set, B,
Of
17.8 19.2 25.6 19.9
/0
Abrasion rate,
cm
3
/hr 0.87 0.44 0.67 0.56
Properties after 70 hr
water immersion:
Volume increase,
0/
4.7 4.3 6.8 6.2
/0
Tensile strength,
psi 1350 1213 1280 1390
Elongation at
break, % 455 417 340 350
1) RF level in all preparations, 0.03 mole/mole starch; 2) Average from
t\VO preparations, xanthate D.S. 0.06; 3) Average from three prepara-
tions, xanthate D.S. 0.10; 4) Individual preparation, xanthate D.S.
0.10; 5) Individual preparation, xanthate D.S. 0.06.
Table 8 gives properties for those Stage IV preparations
most nearly approximating the above best compositions.
From data in Table 8, the 30 phr zinc xanthate preparations
probably had a better overall balance of properties than
the 45 phr xanthide preparations. The 30 phr zinc starch
xanthate masterbatches had lower viscosities and gave vul-
canizates which were softer, more resilient, more elastic,
and about as strong as vulcanizates containing 45 phr starch
xanthide reinforcing agent. However, in practical applica-
tion, the properties of vulcanizates from starch derivative-
SBR masterbatches would be modified over a wide range
by compounding with conventional reinforcing agents,
fillers, plasticizers, etc. and by use of other curing systems.
Starch derivative-SBR elastomers can be compounded to
give vulcanizate properties adequate for the wide variety
of end uses listed in Table 9. Table 9 compares hardness
and tensile properties of test vulcanizates from the above
selected starch-SBR masterbatches with properties of rep-
Die Starke 23. Jahrg. 1971/ Nr. 10
resentative commercial SBR rubbers as given in the Vander-
bilt Handbook [12J and industrial literature. Starch-rein-
forced rubbers are of particular interest in applications for
brightly colored rubbers.
Acknowledgements
idabel D. Swanson for analyses, "Wilbur C. Bury and Loyal D.
Miller for physical testing.
Summary
Xanthate derivatives of pearl corn starch, acid-modified
corn starches, waxy maize starch, high-amylose corn starch
and corn and wheat flours were evaluated in reinforcement
of styrene-butadiene (SBR) elastomers. Concomitant vari-
ables included in the experimental design were starch load-
ing, xanthate degree of substitution (D.5.), crosslinking
reaction, coreaction with resorcinol and formaldehyde (RF),
incorporation of fillers or extender oil, and processing con-
ditions.
Xanthate derivatives of high-molecular-weight starches
were quantitatively retained in resultant starch-SBR master-
batches, but analogous acid-modified starch products were
poorly retained. Vulcanized rubbers containing high-amy-
lose starch xanthate derivatives had lower water absorptions
but generally poorer physical properties than those con-
taining the same derivatives of pearl corn starch and waxy
maize starch. Corn and wheat flour xanthate derivatives
gave rubber reinforcement about equal to that obtained
from corresponding derivatives of pearl corn starch, but
produced vulcanizates of darker color.
Optimum starch xanthate D.S. was about 0.06 mole xan-
thate group per mole of anhydroglucose unit. There were
interactions between starch loading and crosslinking reac-
tion resulting in best rubber reinforcement at a loading of
30 parts zinc starch xanthate and 45 parts starch xanthide,
respectively, per 100 parts (phr) SBR elastomer. Coreaction
of RF with starch xanthate derivatives increased rubber
reinforcement. Reinforcing grades of hydrated silica and
hard clay were easily incorporated into masterbatches by
coprecipitation with starch derivatives. Wet extrusion meth-
ods for processing starch-elastomer coprecipitates gave bet-
ter results than hot-wet-mill or dry-mill processing. Incor-
poration of 50 phr naphthenic oil into high-molecular-
weight SBR by coprecipitation with starch derivatives gave
poor quality products.
Best masterbatch types contained 30 phr zinc starch xan-
thate RF and 45 phr starch xanthide RF, respectively, in
SBR 1502 elastomer. These masterbatches had properties
meeting requirements for many end-use applications.
Zusammenfassung
Starke in Gummi. EinfluB des Starketyps und der begleitenden
Variablen bei der Verstarkung von StyroI-Butadiengummi.
Xanthatderivate von Perlmaisstarke, sauremodifizierten Maisstar-
ken, amylosereicher Maisstarke und Weizenmehlen wurden fiir
357
Table 9. Comparison of Starch Reinforced SBR with Commercial SBR Rubbers.
Major reinforcing agent
Product Type Loading Modulus, at Tensile Elongation Hardness
(phr) 300 % elonga- strength at break (Shore A)
tion (psi) (psi)
(%)
Zinc starch xanthate RF-SBR 1502
1
) Starch 30 1553 2000 383 69
Starch xanthide-SBR 1502
1
) Starch 45 2140 270 80
Truck tire sidewall, SBR 1500 GPF black 60 1120 1980 550 58
Passenger tire sidewall, SBR 1500 GPF black 65 1200 2000 560 56
Third line passenger tire tread, SBR 1825 HAFblack 90 970 2150 640 60
Competitive orbitread, SBR 1808 & reclaim HAF black 75 960 2190 580 55
Heat resistant conveyor belt, SBR 1500 FEF & FT black 45 300 1450 800 41
V belt, base stock, SBR 1500 HLF (N724) black 132 1140 2130 280 74
Washing machine hose, SBR 1018, 1503 Whiting & Clay 200 180 320 550 52
Low cost hose compound, SBR 8754 SRF black, clay, talc 310 550 900 580 67
Molded goods, SBR 1500 FT black 125 1240 1360 400 70
Molded goods, SBR 1500 FT & EPC blacks 100 1920 2180 390 69
\XThite molded goods, SBR 1006 Clay, calcium silicate 140 670 1400 600 70
White molded goods, SBR 1006 Clay, calcium silicate 115 870 1410 530 80
Neutral extruded goods, SBR 1006 Silica, clay, "vhiting 200 450 930 600 70
Transparent molded shoe sole, SBR 1507 Silica 40 700 2000 900 57
Translucent molded shoe sole, SBR 1551,
8107 Silica 60 300 1200 925 57
Molded shoe sole, SBR 1507, 1703 Clay 170 500 1400 500 60
RHW wire insulation, SBR 1018,1503 Resin, ZnO, hydrocarbon 80 1360 490
1) See Table 8 for detailed properties and product description.
die Verstarkllng von Styrol-Blltadien-(SBR)-Elastomeren einge-
setzt. In die experimentelle Anordmmg wllrden als begleitende
Variablen die Starkeeinspeisung, der Xanthat-Sllbstitlltionsgrad
(D. S.), die Vemetzlmgsreaktion, die Coreaktion mit Resorcin lind
Formaldehyd (RF), der Einball von Fiillmitteln oder von Fiil!ol
lind die Verf,thrensbedingllngen aufgenommen.
Die Xanthatderivate von Starken mit hohem j\;Jolektdargewicht
wllrden qllantitativ in den resliltierenden Starke-SBR-Hallptchar'-
gen festgehalten, wogegen analoge saltremodifizierte Starkepro-
dllkte kaum festgehalten wurden. Vu'kanisiertes Gllmmi, das
Xanthatderivate ails amylosereicher Starke enthielt, zeigte gerin-
gere IVasserabsorption, jedoch im allgemeinen schlechtere physi-
kalische Eigenschaflen als diejenigen, die Xanthatderivate ails
Perlmaisstarke und IVachsmaisstarke enthielten. Derivate aus Mais-
und IVeizenmehl ergaben eine Verstarktmg des Gummis, die in
etwa der der entsprechenden Derivate aus Perlmaisstarke ent-
sprach. Allerdings fiihrten sie zu Vulkanisiemngsprodukten 'von
dtmklerer Farbe.
Der optimale Xanthat-Sllbstitutionsgrad der Starke lag bei 0,06
Xanthatgmppen je Anhydroglucoseeinheit. Es wllrden IVechsel-
'wirkungen zwischen der Starkeeinspeisung tmd der Vemetztmgs-
reaktion festgestellt, die bei der Einspeisung von 30 Teilen Zink-
Starkexanthat bzw. 45 Teilen Starkexanthid je 100 Teilen (phr)
SBR-Elastomer zu hervorragender Gummiverstarktmg fiihrten.
Die Coreaktion von RF mit Starkexanthatderivaten erhohte die
Gummiverstarktmg. Die verstarkenden Qualitaten von Silicium-
dioxid-Hydrat Imd Hartton wurden durch gemeinsame Ausfallllng
mit Starkederivaten leicht in die HauptdJargen eingebaut. Nap-
extmsionsmethoden zur Gewinmmg von Starke-Elastomer-Co-
prazipitaten gaben bessere Ergebnisse als Heip-Napmahl- oder
Trockenmahlverfahren. Die Einarbeittmg von 50 phr Naphthenol
in hochmolekulares SBR durch gemeinsame Ausfalltmg mit Starke-
derivaten fiihrte ZIt qualitativ minderwertigen Produkten.
Die besten Hauptchargen enthielten 30 phr Zink-Starkexanthat-
RF, bzw. 45 phr Starkexanthid-RF in SBR 1502-Elastomer. Diese
Hauptchargen zeigten Eigenschaflen, die den Anfordemngen bei
zahlreichen Endanwendungen entsprechen.
358
Resume
L'amidon dans les gommes. Influence du type d'amidon et des
phenomenes variables concomitants au cours du renforcement
des gommes de styrene-butadiene.
derives des amidons suivan,ts ont ,ete testes qt;ant
a leurs proprzetes de renforcement des elastomeres de styrene-
blltadiene (SBR): amidon de mai's pede, amidon de mai's l'iche en
amylose, amidon modifif: par l'acide et farine de ble. Les pheno-
menes variables concomitants inchts au COllrs des hudes experi-
mentales haient: la dJar'ge en amidon, Ie degre de mbstitlltion
(D. S.) dll xanthate, la daction de rhicttlation, la coreaction avec
Ie resorcinol et Ie formaldehyde (RF), l'incorporation d'lmile ou
de charge et conditions teclmologiques.
Les derives xanthates des amidons de poids molewlaire eleve ont
pu etre retemts quantitativement dans les charges principales ami-
don-SBR reStlltantes, par contre les produits analogues des ami-
dons modifies par l'acide n'ont he que faiblement retenlls. Les
gommes vlllcanisees contenant des derives xanthates d'amidon riche
en amylose montraient tme absorption d'eau pllls faible, mais des
proprihes physiques inff:riellres acelles contenant les memes deri-
ves de l'amidon de .maYs perle et l'amidon de mai's cireux. Les
derives de farine de mai's et de ble provoquent tm renforcement de
la gomme analogue a ce que l'on obtient avec les derives corre-
spondants de l'amidon de maYs perle, mais if conduisent ades pro-
dllits vulcanises d'tme coulellr plus sombre.
Le degre optimal de mbstittttion du xanthate d' amidon est de
l'ordre de 0,06 groupement xanthate par IInite anhydroglllcose. Il
y avait des interactions entre la charge en amidon et la reaction de
rhiwlation donnant 1m meilleur renforcement pour une charge
de 30 parties de xanthate d'amidon au zinc et 45 parties de xan-
thate d'amidon respectivement pour 100 parties (pIn) d'elastomeres
SBR. La co-reaction de RF avec les derives xanthate d'amidon
augmente Ie renforcement de la gomme. Les qualites renforr;antes
de ['hydrate du dioxyde de silice et de l'argile dure ont pu etre
incorporees facilement dans les charges principales par co-precipi-
tation avec les derives d'amidon. Les methodes d'extmsion par
Die Starke 23. 1971 I Nr. 10
voie Immide pOllr la production de co-precipites amidon-elasto-
mhes ont donne de meillellrs resldtats qlle ceux obtenlls par les
procedes de mOIlWre hllmide achalld 011 sr;che. L'incorporation de
50 pin d'imile naphthenique dans les SBR de poids molecldaire
eleve par co-precipitation avec des derives d'amidon donne des
prodllits de qllalite mediocre.
Les meillelires charges principales contenaient 30 pin- de xanthate
d'amidon all zinc-RF et 45 phr de xanthide d'amidon-RF respec-
tivement dans l'elastomere SBR 1502. Les charges principales
montrent des proprihes qlli correspondent allX exigences de nom-
breuses applications finales.
References
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Rist: Ind. Eng. Chern. Prod. Res. Develop. 7 (1968), 155.
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Rubber. Reinforcement of Rubber by Starch-Resorcinol-
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Chemistry, ACS, Cleveland, Ohio, April 23-26, 1968. Ab-
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[3] Stephens, H. L., R. ]. kfurphy, and T. E. Reed: Rubber
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[4] Stephens, H. L., R. W. Roberts, T. F. Reed, and R. j.
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[10] Cocln-an, W. c., and G. lv!. Cox: "Experimental Designs",
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[11] Stephens, H. L., Institute of Polymer Science, Akron, Ohio.
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[12] lVinspear, G. G.: "The Vanderbilt Rubber Handbook"
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Address of authors: R. A. Bllchanan, H. C. Katz, and C. R. Rlissell,
Cereal Products Laboratory, Northern Regional Research Labo-
ratory"'), Peoria, Illinois 61604 (USA). W. F. Kwolek, Biometrical
Services, Agricultural Research Service, U.s. Department of Agri-
culture, stationed at Peoria.
". This is a laboratory of rhe Northern Marketing and Nutrition
Research Division, Agricultural Research Service, U.s. Department
of Agriculture.
(Received: May 3, 1971)