Starch/Stärke 58 (2006) 131–139 DOI 10.1002/star.

200500407 131

Fengwei Xiea Starch Modification Using Reactive Extrusion

Long Yua,b
Hongshen Liua
This paper presents a review of the principle and technologies in reactive extrusion and
Ling Chena
their application in starch modification and preparation of starch derivatives, such as
a
CPFRR, School of Light starch graft copolymers, glycosides, cationic starch, or oxidized starch. The applica-
Industry and Food, SCUT, tions of reactive extrusion in producing other biopolymers are also touched. Flexibility
Guangzhou, P. R. China and efficiency of reactive extruders as reactors for biopolymers are particularly note-
b
Commonwealth Scientific and worthy.
Industrial Research Organization,
CMIT, Keywords: Reactive extrusion; Starch modification; Starch derivatives; Graft polym-
Melbourne, Australia
erization

1 Introduction reported about the synthesis of molar mass epoxy pre-

polymers containing rubber preformed particles by reac-
Starch, as a natural polymer, has received great attention tive extrusion. Hu et al. [4] reported a two-step method of
recently as a possible alternative to petroleum-based synthesizing pure graft copolymers with polyamides as
polymers. It has the advantages of being renewable, bio- grafts. Natov et al. [5] have recently investigated the
degradable, abundantly available and low in costs. How- chemical transformation of the nitrile groups occurring
ever, the microstructure of starches is much more com- during the extrusion of composites of PA-6 and the poly-
plex than that of conventional polymers, because butadiene-acrylonitrile (PBAN) elastomer, which can be
starches are synthesized to meet the natural require- used for producing polyamide products with increased
ments of plants. In practice, native starches are not sim- impact strength. All these examples show that the em-
ply suitable for any specific application. Various modified phasis in the use of extruders in the last two decades has
starches have been developed for non-food applications. shifted from studying the preparation and modification of
For example, sodium hypochlorite oxidized starch which polymers for the plastics industry towards creating new
has the advantages of bright white color, easy gelatiniza- and unusual resins, thermoplastics, and other synthetic
tion, and high solubility, is more suitable than native star- polymers for industrial uses by reactive extrusion, where
ches for application in papermaking and textile industries. such processes as viscosity-breaking, grafting, cross-
Cationic starch that has positive charges can more easily linking and coupling reactions as well as polymerization
be attracted by negative charges on fibers, hence it is processes are carried out [6, 7].
more efficient than native starches in the application of
papermaking and in textile industries. Superabsorbent
The application of extrusion in starch was initially studied
polymers, prepared by grafting acrylonitrile onto starch,
in food processing. Food extrusion has been practiced for
can be used in various fields such as hygiene, cosmetics,
more than 50 years with early developments in the prep-
and agriculture.
aration of ready-to-eat cereals [18]. The use of twin-screw

Review
Reactive extrusion (REX) has been defined as the con- extruders (TSE’s) for food processing began in the 1970s
current reaction in extrusion processing of polymers in an and expanded dramatically in the 1980s. During these
extruder [1]. Reactive extrusion was developed in the periods, TSE’s became more widely studied as reactors
1980s, primarily for the modification of synthetic poly- for the modification of biopolymers with acids, alkalis,
mers. Since then the technology has been developed and enzymes [12]. Then some primary works were pub-
quickly and has been applied in various areas, such as lished in the preparation of modified starches using the
polymerization, grafting, cross-linking, etc. One of the extruder as a continuous reactor [9–47].
early examples was the bulk polymerization of capro-
lactam to polyamide (PA)-6 [2]. In 1996, Taha et al. [3] The purpose of this paper is to provide a brief review of
the development and application of reactive extruders as
reactors for starch modification and preparation of some
Correspondence: Long Yu, Commonwealth Scientific and
starch derivatives. The application of reactive extrusion in
Industrial Research Organization, CMIT, Gate 4, Normanby
Road, Clayton South, Melbourne, Australia. Phone: 161–3- producing other biopolymers has also been touched
95452797, Fax: 161–3-95441128, e-mail: long.yu@csiro.au. upon.

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132 F. Xie et al. Starch/Stärke 58 (2006) 131–139

2 Reactive Extrusion
The use of an extruder as a chemical reactor allows high-
viscosity polymers to be handled in the absence of sol-
vents. It also affords a large operational flexibility, as a
result of the broad range of processing conditions in
pressure and temperature (0–500 bar and 70–5007C), the
possibility of multiple injection and the controlled resi-
dence time (distribution) and degree of mixing [10].

Though some co-rotating parallel multi-screw extruders

have been reported [11], the most widely used reactive
extruders until now are still single-screw extruders (SSE’s)
and twin-screw extruders (TSE’s), which are manu- Fig. 1. Schematic representation of a reactive extrusion
factured world-wide [12]. SSE’s are manufactured with system used for starch modification: (1) weight feeder for
and without grooved barrels and with either single-piece starch; (2) and (3) metering pump; (4) vacuum pump; (5)
twin-screw extruder; (6) forced strand pelletizer with “dry”
screws or individual slip-on screw elements of various
cut.
designs. Single-screw extruders are generally considered
to have three basic zones including a primary feed zone, a
melt zone, and a pump zone. As material is conveyed by tures at separately controlled zones and to feed solids or
the flights of the screw, drag flow results due to the liquids at many points along the entire length of the barrel.
reduced slip of material at the barrel wall. An opposite, Screw speeds range up to 700 rpm. In general, the capital
pressure-induced flow occurs due to the back pressure at investment and the maintenance costs are relatively high
the die where shaping takes place. Leakage flow results for the TSE’s, whereas the pressure and torque cap-
between the tips of the screw flights and the barrel wall, abilities are greater for the SSE’s. Mixing, conveying, heat
while laminar flow occurs within channels of the screw transfer, shear rate uniformity, RT distribution, and versa-
[18]. tility of TSE’s exceed those of SSE’s [17]. In addition,
TSE’s are generally classified as co-rotating or counter- intermeshing co-rotating twin-screws provide a better
rotating and as intermeshing or non-intermeshing. The basis for pressure build-up at a relatively short screw
twin parallel screws fit into a horizontal barrel housing, length [7].
resembling a Figure eight on its side. An analysis of the Fig. 1 shows a schematic representation of a reactive
complex mixing and flow mechanisms of these extruders extrusion system used for starch modification. The weight
has been discussed [13]. The most popular type of TSE’s feeder for starch needs a twin extruder providing self-
are those with co-rotating, intermeshing screws, which wiping operation. The first metering pump provides
have been found to be suitable for many REX processes chemicals for modification and the second metering
because of the wider control of the residence time dis- pump usually provides chemicals to neutralize the reac-
tribution, the good mixing intensity, the superior heat tive system. Water turns into steam well inside the closed
transfer and the self-wiping operation [14]. Potente et al. barrels and is routed through the axially open screw
[15] have studied the morphology development of poly- channels in the up- and down-stream directions where a
blends in co-rotating twin-screw extruders. In general, portion of the steam is removed through vent opening to
non-intermeshing, counter-rotating mixers have relatively reach the final level of residuals. Since starches and
poor pressure build-up and torque capability. Some starch derivatives are water-soluble a forced strand pel-
advantages of non-intermeshing and counter-rotating letizer with “dry” cut is required.
screws have also been discussed [16], [17]. Individual,
slip-on screw elements are designed for conveying, mix-
ing, kneading, flow restriction, and pumping. Kneading
3 Starch Modification
elements are used to increase mixing, shear, and heat
transfer. Reverse pitch screw elements are useful to 3.1 Extrusion cooking
restrict material flow in order to fill starve-fed screws,
increase residence time (RT), improve mixing, and Extrusion cooking has been practiced for more than 50
increase shear in locations preceding the restriction. years with early developments in the preparation of
Reverse pitch screws are also used for devolatilization, ready-to-eat cereals [18]. There are numerous papers and
cooling, and feeding purposes. Most TSE’s are designed books discussing and reviewing the science and tech-
to heat, cool, and measure barrel and material tempera- nologies in this area. Nout and Ngoddy [19] have dis-

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Starch/Stärke 58 (2006) 131–139 Starch Modification Using Reactive Extrusion 133

cussed the requirements and manufacturing procedure of of monomers onto starch have been published [31–35].
complementary (weaning) foods and verified that extru- Most of them, however, were still carried out in typical
sion cooking is a promising technique that can be feasible batch processes with a very long reaction time e.g., 2 h
at medium and larger-scale production levels. Ilo et al. for grafting AN [31].
[20] have studied the optimal conditions for extrusion
cooking of rice flour and amaranth blends suitable for a In order to develop a more efficient way to produce starch
puffed snack food. Mouqueta et al. [21] have investigated graft copolymers, Carr et al. [36] studied the feasibility of
the ability of a “very low-cost extruder” to produce instant graft-polymerizing various types of monomers onto
infant flours at a small scale in Vietnam. Recently Brüm- unmodified corn starch in the presence of aqueous ceric
mer et al. [22] reported the effect of extrusion cooking on ammonium nitrate (CAN) as the free radical initiator using
molecular parameters of corn starch using a systems continuous twin-screw extrusion. Results of reacting corn
analytical model and a fuzzy logic control software. The starch (CS) with AA and AAm in the presence of CAN,
molecular size of extruded starch, expressed as the using a ZSK 30 as reactor, are shown in Tab. 1. The starch
weight average of the molecular weight (Mw), decreased (10% moisture), monomers, and aqueous solutions of
exponentially when the specific mechanical energy input CAN/nitric acid were fed into barrel blocks 1, 3, and 5,
increased. respectively. An intense mixing screw was used at 200
rpm. Reaction temperature was 707C and starch con-
Extrusion cooking, in general, is a processing of starch centration (starch/starch plus water) was 35%. The CS
gelatinization under shear stress. It is well known that and monomer feed rates were 75 g/min. The pH of the
the gelatinization under shearless conditions is con- samples was neutralized with NaOH and unreacted
trolled by water diffusion. Previous research has shown monomer was extracted from the samples in about 5–7
that full gelatinization under shearless condition requires min after initiation of the reaction. The results showed that
a molar ratio of water/starch .14, which is a ratio in 74% of the AN polymerized within the short reaction pe-
weight of starch/water about 33: 66 [23–25]. Gomez and riod. Acrylamide was much less reactive (16% conver-
Aguilera [26, 27] studied in detail the gelatinization of sion) with a 26% conversion only after aging the sample
corn starch under shear stress during extrusion. It was for 16 h at 307C. It also showed that the extrusion process
found that the maximum gelatinization was observed at with AN was as effective as a conventional laboratory
about 28–29% moisture which is about half as much as batch reaction process in which conversion for AN was
under shearless condition. Below 20% moisture, dex- 72%.
trinization becomes predominant during high-shear
cooking-extrusion. Yoon, Carr and Bagley [37] made a comparison between
a continuous reactive extrusion process and a typical
batch reaction process in which the AN was graft poly-
3.2 Starch graft copolymers merized onto unmodified corn starch. Processing times in
the twin-screw extruder (ZSK) were 2–3 min, and the total
Chemically modified starches with improved properties reaction time was about 7 min before reaction of the
in non-food applications have gained increasing impor-
tance in industry not only because they are low in cost,
but also mainly because the polysaccharide portion of Tab. 1. Preparation of starch graft copolymers by reac-
the product is biodegradable. In the last few decades, tive extrusion.
the chemical modification of starch via graft copolymer-
ization of vinyl monomers onto it has been a subject of Preparation Starch % Reaction Time Conver-
academic and industrial interest. Much work has been method concen- CAN temp. [h] sion [%]
reported on the grafting of acrylic acid (AA), acrylonitrile tration [%] [7C]
(AN) and acrylamide (AAm) onto starch, the graft poly-
mers are useful as flocculating agents, retention aids, Extrusion/AN 35 3.5 70 0.08 74
Batch/AN 5 3.5 30 2.00 72
thickening agents, absorbents, and adhesives. In 1958,
Extrusion/AAm 35 4.4 70 0.08 16
graft polymerization of AN onto poly(vinyl alcohol) by Extrusion/AAm 35 4.4 70 16.00 26
ceric ion initiation led to an expansion of research on
graft polymerization of various vinyl monomers onto cel-
Starch/monomer feed rate ratio = 75:75 g/min (d.b.).
lulose and starch [29]. High-capacity water absorbent Conversion =% of monomer converted to polyacryl-
products from saponified starch-g-polyacryonitrile (St-g- amide. 16.0 h reaction time = 16 h aging at room temper-
PAN, Super Slurper) have been developed and commer- ature after sample collection. Intense mixing screw =
cialized [30]. Numerous reviews on graft polymerization 2.00 rpm.% CAN = starch weight basis [36].

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134 F. Xie et al. Starch/Stärke 58 (2006) 131–139

extruded material was terminated, compared to a reac- period of 2 or more hours. A degree of substitution (DS) of
tion time of 2 h used in the typical batch procedure. The about 0.02–0.05 is suitable for most widely used applica-
continuous reactive extrusion process was found to be a tions such as papermaking and sizing, while DS levels of
rapid and efficient means of preparing St-g-PAN with high 0.2–0.7 are more effective for flocculation applications
add-on (% PAN of the grafted product). For example, [42, 43]. A reaction efficiency (RE, i.e.% of monomer
42% add-on was achieved within the 7 min reaction peri- reacted with starch) of 85% is considered a very good
od using an AN/starch weight ratio of 1.0 (3.5% CAN, result for the reaction mentioned above. Previously, a
starch weight basis), as compared to 38–49% for the 2 h maximum RE of 88% was achieved in a study that used a
batch process (0.75–1.5 AN/starch ratio). The experiment typical laboratory batch procedure with a reaction period
showed that percentages of homopolymer contained in of several hours [44].
the copolymers were low for both extrusion and batch
processes. Grafting frequencies were substantially higher A similar reaction has been investigated by Della Valle et
while molecularsweights were significantly lower for al. [45] for wheat starch using a Clextral BC 45 twin-screw
grafts from the extrusion process. Water absorbency of extruder as a reactor. An reaction efficiency of up to 82%
the saponified St-g-PAN products was somewhat greater was obtained in extrusion processing for only few minutes
for the products prepared by the batch process. when aging the extrudate for 24 h. In Carr’s study [46], an
unusually high reaction efficiency of up to 90% or more
was obtained for the system of unmodified CS reacting
with Q188 using NaOH as catalyst in a ZSK 30 twin-screw
3.3 Cationization of starch extruder. Starch with 10% moisture was fed into barrel
section number 1 (BS-1). An aqueous solution of NaOH
Cationic starches with amino, ammonium, sulfonium, was metered into BS-3, while Q188 (65% active mono-
phosphonium and other groups have been developed for mer in aqueous solution, used as shipped) was metered
decades [38–40]. A number of monomers with these into BS-5. Reaction temperatures were either 70, 80, or
groups are useful for preparation of cationic starches. The 907C in all zones (8 zones) except zone 1, which was kept
most widely used monomer, however, is probably 3- at 707C for all experiments.
chloro-2-hydroxypropyltrimethylammonium chloride
(CHPTMA) under the trade name of QUAT 188 [41]. The Tab. 2 shows the effect of some of the extrusion proces-
reaction of QUAT 188 (Q188) with starch in the presence sing variables on RE within a reaction period of approxi-
of an alkaline catalyst yields a quaternary ammonium mately 6–8 min. Reaction of each sample was quenched
cationic starch ether [starch-OCH2CHOHCH2N1(CH3)3]. immediately after pH neutralization with methanol/HCl.
This reaction occurs slowly with ungelatinized starch Total feed mass streams rates (including water) ranged
granules but relatively rapidly with gelatinized starch. from 8 to 16 kg/h. A 100% RE would represent a DS of
Conventional batch reaction procedures employ tem- 0.05. The combined effect of the high temperature (907C),
peratures of about 35–407C, starch in water concentra- intensive mixing, high-starch solids (65%), and appropri-
tions of 25–35%, and generally, a salt such as Na2SO4 to ate level of catalyst contributed to the unusually high RE
maintain integrity of the unswollen granule over a reaction values (90%) exceeding maximum values previously

Tab. 2. Preparation of cationic cornstarch from QUAT 188 monomer by reactive extrusion.

Feed rate [g/min] Starch Reaction Screw REe DSf

conc. [%] temp. [7C] [%]
Starcha H2Ob NaOH Q 188c W/Sd [rpm]

90 141.4 2.0 4.7 35 70 S 200 8 0.004

90 34.6 2.0 4.7 65 70 S 200 36 0.018
90 141.4 2.0 4.7 35 90 S 200 42 0.021
90 34.6 1.0 4.7 65 90 S 200 50 0.025
90 34.6 2.0 4.7 65 90 S 200 92 0.046
180 69.2 4.0 9.4 65 90 S 200 86 0.043
90 34.6 2.0 4.7 65 80 W 100 69 0.035
90 34.6 2.0 4.7 65 80 S 100 76 0.038
a
Starch = as is moisture, 10%. bH2O = total in the system. cQ 188 = addition, active monomer basis.
d
W = weak intensity mixing and S = strong intensity mixing. eRE = reaction efficiency (% of monomer
bonded to starch). fDS = degree of substitution. Theoretical DS possible = 0.05 [46].

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Starch/Stärke 58 (2006) 131–139 Starch Modification Using Reactive Extrusion 135

reported using laboratory-batch reaction procedures. oxidants. Parovuori et al. [55] studied the oxidation of
These results are obtained using reactant molar ratios potato starch with hydrogen peroxide at 407C with metal
monomer/starch of 1:2. It is seen that the use of a rela- catalysts to yield carboxyl and carbonyl groups using
tively weak mixing screw, a slower screw speed (100 vs. acidic and alkaline reaction conditions respectively. Kru-
200), and a two-fold increase in all feed rates produced a ger [56] obtained an oxidized insoluble starch with
small but perhaps significant decrease in RE. improved properties using manganese ions in catalysis
with hydrogen peroxide. Blattner and Ferrier [57] eval-
Gimmler et al. [47] studied the influence of extrusion uated the effect of several metal catalysts on the oxidation
cooking conditions on the efficiency of the cationization of cellulose and Skibida et al. [58] studied several carbo-
and carboxymethylation of potato starch granules. A hydrate polymers. Floor et al. [59] oxidized maltodextrins
system analytical model for the extrusion of starches and and potato starch using a tungstate catalyst at low pH and
flours was modified to determine the optimal extrusion high peroxide level to yield highly degraded products of
conditions for the cationization and the carboxymethyla- moderate carboxyl content. Whistler and Schweiger [60]
tion of potato starch to determine the effect of the extru- oxidized amylopectin under ambient conditions with no
sion conditions, optimal for the RE and the desired DS, on catalyst over the pH range 3–11 at high peroxide levels. At
the rheological properties of the derivatives. Cationic pH . 7, extensive carbohydrate degradation was
starch as well as carboxymethyl starch can be produced observed, while at pH , 5 little oxidation occurred.
with high RE without using catalysis. A further study on
chemical and processing aspects of the production of Wing and Willett [61] introduced the reactive extrusion to
cationic starch using extrusion cooking was reported by prepare oxidized starches. Three types of cornstarches
Esan et al. [48]. These authors showed by extraction containing up to 70% amylose were oxidized by a reac-
experiments that the extractability of such substances tive extrusion-drum drying process with hydrogen per-
from ground cationic potato starches extrudates depends oxide and a ferrous-cupric sulfate catalyst. A ZSK 30 co-
on the penetration of the solvent through extrudates par- rotating twin-screw extruder, which had a temperature
ticles and the diffusion of the soluble substances in the profile of 88/115/88/77/71/65/54/487C (feed to die) and a
particles into the solvent. Optimized results for the RE screw speed of 110 rpm, with a starch feed of 180 g/min
were achieved by suspending one part ground cationic (10% moisture) was used. The results in Tab. 3 show data
potato starch extrudate in ten parts of a solvent consist- for waxy corn starch (WS), pearl corn starch (PCS), and
ing of 80% ethanol and 20% water (w/w). amylomaize VII (AM7) at three hydrogen peroxide levels
(0, 26, 35 mL, where 35 mL is full pumping capacity) and
constant catalyst concentration, two commercially avail-
3.4 Oxidization of starch

Commercial oxidized starches are batch-prepared utiliz-

Tab. 3. Properties of extruded oxidized starches.a
ing room temperature conditions and low (, 3%) con-
centrations of an oxidant (usually hypochlorite) [38, 49,
50]. During product isolation (filtration and aqueous Starchb H2O2 COOH C=O Solu- Viscosity
[mL/ [mmol/ [%] bility [Pa?s6
washing) some of the product is solubilized (due to mo-
min]) g] [%] 1023]
lecular breakdown) and gets lost. Hypochlorite has been
the oldest and most frequently used oxidant. Other oxi- WS 0 0.27 0.17 99 4.0
dants such as permanganate, hydrogen peroxide, per- WS 26 0.64 2.58 100 1.2
sulfate, periodate and dichromate have also been used. WS 35 0.76 3.34 100 1.2
The different oxidation procedures result in variations in PCS 0 0.26 0.66 28 NT
molecular structure and properties. The annual con- PCS 26 0.69 2.64 98 NT
PCS 35 0.79 3.24 98 2.1
sumption of oxidized starches is about 88 6104 t with a
AM7 0 0.25 0.56 5 NT
predicted growth rate of 2.4% over the next decade, AM7 26 0.91 2.68 54 NT
mainly in the adhesive area [51]. AM7 35 1.13 3.77 66 NT
DAS – 0.79 6.64 6 NT
Maurer [52] reported the using of hydrogen peroxide A590 – 0.30 0.18 0 NT
(0.5%) at pH 4–5 in jet cooking starch for solubilization and
application in adhesive formulations. This procedure did a
Starch (180 g/min); ferrous sulfate (0.42 g/min); cupric
not promote oxidation, only a viscosity reduction. Ewing sulfate (0.33 g/min).
[53] obtained similar results using pH values of 6–7. Wing b
WS, waxy starch; PCS, pearl cornstarch; AM7, amylo-
[54] reported about the thermochemical oxidation of sev- maize VII; DAS, dialdehyde starch; A590, high oxidized
eral starches by jet cooking and drum drying with different starch. NT, not tested [61].

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136 F. Xie et al. Starch/Stärke 58 (2006) 131–139

able oxidized starches, a dialdehyde starch (DAS) and speeds of 50–150 rpm, and barrel temperatures of 130–
Amaizo 590 (A590). Thermochemical oxidation of starch 1657C. Under optimum reaction conditions 88% of the
by reactive peroxide extrusion-drum drying is a rapid, starch was converted to a mixture of glycol a-D-gluco-
continuous procedure for making water-soluble products side, glycol b-D-glucoside, and a diglucoside in a ratio of
containing high carboxyl and carbonyl contents. Increas- 1.0:0.6:0.6. This was accomplished in a reaction period of
ing the peroxide level increased the carboxyl and the less than 1 min compared with about 20 min for small
carbonyl content, whereas increasing the amylose con- batch reactions also studied.
tent decreased the solubility. The carboxyl content of the
extruded products was greater at comparable peroxide
levels compared to the reaction under conditions where 3.6 Other applications
the granule structure is retained. The residual granule
structure was still present in high amylose starch extru- Starch has been investigated as an entrapment matrix for
dates with or without peroxide. Solution viscosities indi- a variety of pesticides prior to starch encapsulation by
cate a significant molecular degradation by reactive extrusion [70–79]. Various methods and procedures of
extrusion, with product molecular weights comparable to incorporating pesticides into the starch matrix, including
maltodextrins of DE 5–10. the use of various types of natural and modified starches,
cross-linking and/or coagulation chemicals, and combi-
nations of starch with other polymers have been devel-
3.5 Glycosides oped [70–73]. Various mechanical methods have been
Starch and ethylene glycol are still economically attractive used to form the starch encapsulated pesticides with
and readily available raw materials used for urethane limited processing flexibility, control, and efficiency. The
foams, alkyd resins, surface reactants, and other prod- most versatile, simple, and cost-effective method is by
ucts. The presence of an acid catalyst at elevated tem- using a continuous twin-screw processing [80–85]. Carr
perature can yield in a crude mixture of glycol glucosides [86] demonstrated the preparation of various types of
(GG’s) that have potential as chemical intermediates. The controlled-release starch-encapsulated pesticides by
obtained mixture is primarily composed of mono- and twin-screw processing. The studies were initially per-
diglucosides. Preparation and use of these products have formed with a ZSK 30 extruder. Barrel temperatures (7C)
been studied considerably in batch reaction processes were set at 70 in zone number one (Z-1), 90 (Z-2), 100 (Z-
[62–65]. In the batch preparation of the GG, however, high 6, 7), and 90 (Z-8). Total feed rates ranged from about 7–
viscosity, poor mixing and lack of uniformity are severe 14 kg/h, and, for example, metolachlor was pumped into
problems until the starch is sufficiently converted into a BS (barrel section)-5 (starch at BS-1 and water at BS-3)
flowable mass. using screw speeds ranging from 200–400 rpm. The
scale-up work on a ZSK 57 and a ZSK 58 [87] demon-
These problems can be eliminated by conducting the strated that materials did not need preblending; but could
reaction in an extruder [66]. Furthermore, the reaction rate be extruded through dies with holes as small as 0.7 mm.
can be greatly accelerated in an extruder under high Then the extruded materials was pelletized at the die
shear/temperature conditions. Carr and Cunningham [67] face, and continuously conveyed to a fluidized bed dryer
studied for example the acid-catalyzed starch/ethylene where the materials were dried for direct packaging. The
glycol transglycosylation reaction in a small, co-rotating, use of unmodified starch (or flour), without any need of
intermeshing twin-screw extruder. Although this reaction additional chemicals, provided the most effective low-
was previously investigated in a single-screw plastic cost substrate available for the extrusion process and for
extruder [68], little or no information was reported on obtaining a wide range of release characteristics.
reactive extrusion processing variables, capabilities, or
extent of starch converted beyond 60%. Later Carr and Other application of reactive extrusion in starch mod-
Cunningham [69] also demonstrated that the glucoside ification and preparation of starch derivatives and devel-
extrudates could be used as suitable chemical inter- opments in other areas have also been reported. A novel
mediates for the preparation of high-quality foams with- family of thermoplastic cellulose-2,5-acetate compounds
out separating product constituents. In their study, the was obtained by reactive processing when cyclic lac-
slurry had a starch concentration of 37.6% (w/w), a gly- tones were grafted in situ onto cellulose-2,5-actetate.
col-to-anhydroglucose unit (AGU) molar ratio of 4.0, and Hydroxyfunctional plasticizer and hydroxyfunctional fillers
an acid addition level of 0.75, 1.5, or 3.0% (dry starch were obtained by this route [88]. Kalambur and Rizvi [89]
basis), and a water concentration of 5%. After combining have demonstrated that the concept of nanocomposite
of the reactants for 1 h, the slurry was pumped into the technology could be applied in producing tougher blends
extruder feed port at rates of 50–210 mL/mm, screw of starch-polycaprolactone. The achieved results showed

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Starch/Stärke 58 (2006) 131–139 Starch Modification Using Reactive Extrusion 137

that addition of a modified nanoclay at 3% (w/w) level [3] M. Taha, V. Perrut, A. A. Roche, J. P. Pascault: Synthesis, by
increased the elongation of clay in the polymer matrix. reactive extrusion, of high molar mass epoxy prepolymers
containing rubber preformed particles. J. Appl. Polym. Sci.
The nanocomposites had better solvent-resistance prop- 1997, 65, 2447–2456.
erties because of the resistance to diffusion offered by [4] G.-H. Hu, H. Li, L.-F. Feng: A two-step reactive extrusion
clay platelets in the polymer matrix. Miladinov and Hanna process for the synthesis of graft copolymers with poly-
[90] developed starch esters by co-extruding starch and amides as grafts. Macromolecules 2002, 35(22), 8247–8250.
organic acid anhydrides in the presence of a sodium hy- [5] M. Natov, V. Mitova, S. Vassileva: On the use of extruders as
chemical reactors. J. Appl. Polym. Sci. 2004, 92, 871–877.
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