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Synthesis of Acrylic Superabsorbents

Umendra Dayala; Sanjay K. Mehtaa; Manjeet S. Choudharya; Ramesh C. Jaina


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Research Center, Indian Petrochemicals Corporation Limited, Dist. Vadodara, India
Online publication date: 08 December 1999

To cite this Article Dayal, Umendra , Mehta, Sanjay K. , Choudhary, Manjeet S. and Jain, Ramesh C.(1999) 'Synthesis of

Acrylic Superabsorbents', Polymer Reviews, 39: 3, 507 525


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J.M.S.REV. MACROMOL. CHEM. PHYS., C39(3), 507525 (1999)

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Synthesis of Acrylic
Superabsorbents
UMENDRA DAYAL, SANJAY K. MEHTA,
MANJEET S. CHOUDHARY, and RAMESH C. JAIN
Research Center
Indian Petrochemicals Corporation Limited
P.O. Petrochemicals 391 346
Dist. Vadodara, India

1. INTRODUCTION.................................................................................. 507
2. PREPARATION OF SUPERABSORBENT POLYMERS .................. 508
2.1. Solution Polymerization............................................................... 509
2.2. Suspension Polymerization .......................................................... 512
3. MODIFIED SUPERABSORBENT POLYMERS ................................ 515
4. NEW TRENDS IN SUPERABSORBENT POLYMER
PREPARATION..................................................................................... 518
REFERENCES ....................................................................................... 519

1. INTRODUCTION
Superabsorbent polymers (SAPs) are characterized by their ability to absorb
and retain unusually large amounts of water and body fluids [1]. As these materials are dry substances and act as gelling agents, sometimes they also are referred to as xerogellents or xerogels [2]. Their affinity for water makes
them especially useful for personal hygiene products; the disposable diaper in507
Copyright 1999 by Marcel Dekker, Inc.

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dustry alone accounts for 8085% of the market share [3]. Their use for agricultural applications [4] has shown encouraging results as they have been observed
to help reduce irrigation water consumption, lower the death rate of plants,
improve fertilizer retention in the soil, and increase plant growth rate. Their use
for additional applications (i.e., communications cables, industrial absorbents,
antiredeposition agents for detergent formulations, artificial snow for winter
sports, absorption/release of humidity, gel actuators, toys, medicines, cosmetics,
and prevention of moisture ingress into walls and ceilings) is in the experimental
stage [57].
The first-generation SAPs were developed in the late 1950s. They were
mainly based on hydroxy alkyl methacrylate and related monomers [8]. These
materials, with a swelling capacity of 4050%, were used in contact lenses for
ophthalmologic applications. To improve on their quality and the rising demand
for medical applications, absorbents with 7080% swelling capacity were developed. This widened the scope of application areas, and their use in treating
burns, as nutrient media for microorganisms, and as moisture-absorbing coatings
was investigated. The development of ultrahigh absorption materials, known as
SAPs, started in the late 1970s. They were prepared by radical grafting of acrylonitrile on starch or cellulose using cerium nitrate initiators [911]. The absorption capacity of these materials was a function of the type of starch, the extent
of hydrolysis of grafted polyacrylonitrile, and the component ratio.
The majority of present-day SAPs for health care applications are prepared
from partially neutralized acrylic acid (AA) and a bidentate cross-linking agent.
An alkali metal is generally used for varying the AA-acrylate ratio. The polymerization reaction initiated by free radicals results in a three-dimensional network structure that is responsible for the unique absorption characteristics of
SAP. The absorbency, however, decreases with the increase in cross-linking
density [12, 13], while absorption under load or gel strength varies in the opposite direction [14]. Unfortunately, the health care products demand both properties to be at their best. This requires postreactor treatment of SAPs or other
specialized techniques that can produce the desired result. Further, the presence
of ions in water also affects the absorption characteristics adversely, with the
effect more pronounced with increasing concentration. This requires modifications for a specific application [1517]. As a consequence, the science and technology of SAP preparation has grown considerably, justifying the need for the
present review, which deals exclusively with the various aspects of their synthesis.
2. PREPARATION OF SUPERABSORBENT POLYMERS
Acrylic SAPs are generally terpolymers of AA-co-sodium or potassium acrylate-co-cross-linking agent. The reaction is initiated by a free-radical [18], redox
[1921], or a mixed initiator system [2224]. The use of -ray, ultraviolet (UV),

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or other high-energy radiation, however, has been reported [2528]. The polymer network is adequately cross-linked to maximize water absorption, but prevent dissolution of the SAP. The cross-linking agent generally has two double
bonds. Initially, one of these reacts with a growing radical, while the pendant
one anchors another growing radical, forming a three-dimensional cross-linked
network structure. The concentration of the cross-linking agent, therefore, has a
significant effect on the absorption characteristics [29]. Nevertheless, other variables (i.e., type of cross-linking agent, AAsodium acrylate [SA]) mole ratio,
initiator type, temperature, and method of polymerization) also affect the SAP
properties.
The SAPs are prepared either in aqueous medium by solution polymerization
[30] or in a hydrocarbon medium in which monomers are dispersed as an emulsion or suspension [31, 32]. In the former case, the resin is obtained as a lump
that has to be cut, dried, and pulverized before use. The reaction is generally
carried out in a suitable reactor. Saotane [33], however, has developed a process
in which monomercross-linking agent slurry is purged with nitrogen and polymerized in a flat container in the presence of ammonium persulfate (APS) and
sodium bisulfite. The suspension process yields granules, the size of which depends on the viscosity of monomers and a number of other factors [34]. To
improve the porosity and network structure of SAPs, sometimes special additives such as blowing agents, chain transfer agents, complexing agents, metal
ions, and radical scavengers are also used [5]. The postreactor modification of
SAPs for surface cross-linking [24], which results in improvement of absorption
characteristics, has been reported [35].
2.1. Solution Polymerization
The polymerization of an AA-SA system is an exothermic reaction, and the
related kinetics is primarily a function of a number of variables. This, coupled
with the role of the cross-linking agent, make this system a complex one. To
prevent boiling of the aqueous medium, Mori et al. [36] recommended a process
for preparing SAP at a pressure of 4 kg/cm2. The monomers (AA-SA) were
cross-linked by diethylene glycol diglycidyl ether, and the reaction was initiated
by an APSErbit N mixture.
Scott and Peppas [37] have reported that the kinetic constants of AA polymerization depend on the system temperature, solution pH, chain conformation,
monomer concentration, cross-linking agent concentration, and double-bond
conversion. Peppas and Scott [38] used a calorimetric technique for studying
AA kinetics and determined the effect of varying the solution pH. Nishino et
al. [39] studied the dissociation behavior of SAP using Fourier transform infrared (FTIR) methods and observed that the polyacrylate salts, polymerized in
distilled aqueous solution, have a higher dissociation tendency than the conventional samples.

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Arriola et al. [40] determined the reactivity ratios of AA at different concentrations using [13]C-labeled trimethylolpropane triacrylate (TMPTA) using nuclear magnetic resonance (NMR). It was concluded from the measurements that
all the double bonds of TMPTA were incorporated into the gel network; earlier
models predicted reaction of two double bonds only. It was observed that a graft
copolymer formed later in the polymerization reaction onto the cross-linked gel
formed earlier. This graft copolymer was a major component of the gel.
The monomer feeding skills and effective utilization of the heat of acid neutralization can be used to prepare porous absorbents with an absorption capacity
as high as 12001400 g/g [31]. Cutie et al. [41] determined the activation energy
for the rate of AA polymerization using 1H-NMR, which was found to be 3/2
the power of monomer and 1/2 the power of sodium persulfate (SPS) concentration. The activation energies for partially neutralized AA and 100% acrylate
were found to be 913 kcal/mol and 18 kcal/mol, respectively. Qian, Pu, and
Ye [42] have reported that poly(SA)-based resin can absorb over 1400 g/g water
and 150 g/g of 0.9% sodium chloride solution (saline) under optimized conditions.
The rate of AA solution polymerization has been reported to vary as the
square root of initiator concentration [37]. Since the decomposition of persulfates is accelerated in the presence of AA, the choice of initiator is important.
Buchholz, Graham, and Johnson [43] employed a sodium erythorbateSPShydrogen peroxide system for polymerization of partially neutralized AA. TMPTA
was used as the cross-linking agent in this process. Sakakibara, Okada, and
Koyama [44] employed APS, organic peroxides (Perbutyl H), and reducing
agents to prepare SAP with low amounts of unreacted monomer. Ishizaki, Motono, and Harada [45] prepared AA-SA-TMPTA terpolymer in the presence of
78.581.5% saponified poly(vinyl acetate), heating at 150C, that absorbed 47.0
g/g saline. Funk et al. [46] used the reaction products of 4,4azobis(4-cyanovaleric acid) and 2,5-dihydroperoxy-2,5-dimethyl hexane as the free-radical initiator system for the preparation of AA-SA-N,N-methylenebisacrylamide (MBA)
terpolymer. Stockhausen et al. [47] used a mixture of hydrogen peroxide, SPS,
and AIBN (azobisisobutyronitrile) for preparing AASPSpolyethylene glycol
(PEG) monomethyl ether methyacrylatemonoallyl ether methacrylate copolymer, which had improved liquid retention and absorption characteristics.
The cross-linker type, certain comonomers, and the initiator system have a
significant effect on SAP properties. The effect of MEHQ, generally added to
inhibit polymerization of AA during storage, has been studied by Cutie et al.
[48]. It has been reported to reduce the rate of polymerization of AA, but does
not reduce the molar mass of the resin. Harada et al. [49] used 2-sulfoethylmethacrylate sodium salt as a comonomer, TMPTA as a cross-linker, and APSascorbic acid initiator for improving saline absorption. The use of sodium hypophosphite, thiourea, and other additives like phosphoric acid have been reported to

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improve saline absorption of AA-SA-MBA polymer [50]. Yano et al. [51] prepared SAP with improved resistance to aging by using polyethylene glycol diacrylate as the cross-linking agent for 75% sodium hydroxideneutralized AA.
Isomi [52] developed a process for preparing SAP with high gel strength and
saline absorption by using a special cross-linking agent that was prepared from
epichlorohydrin, ammonia, and methanol. The polymerization of partially neutralized AA was initiated by potassium persulfate (PPS) and potassium metabisulfite in the presence of glyoxal. Ito and Kadoi [53] improved the saline absorption capacity of the resin by copolymerizing 3-acrylamidopropyltrimethyl
ammonium chloride and SA, which was cross-linked by MBA. Kato, Kadoi, and
Higaki [54] used 2,2,6,6-tetramethyl-piperidyl acrylate as a comonomer with
potassium hydroxideneutralized AA for preparing SAP with improved heat and
light stability. The polymerization was done by spraying a solution of L-ascorbic
acid over monomers containing hydrogen peroxide. Okamura and Shioji [55]
used (PEG) methyl ether methacrylate and (PEG) diacrylate as cross-linking
agents for AA-SA. The SAP had better salt resistance and a lower soluble component. Houben [56] used two cross-linking agents for obtaining SAP with a
reduced amount of soluble material. Thus, partially neutralized AA was crosslinked with polyethylene glycol acrylate ester allyl ether and SR351.
The neutralization of carboxylic groups of AA can be done after polymerization, which affects water absorption and other characteristics of SAP. Liu, Wu,
and Ju [57] have reported that a suitable degree of neutralization for AA polymerization was 8085% when using PPS initiator. Yarbrough, Short, and Harland [58] prepared poly(AA) cross-linked with MBA using SPS as the initiator.
The resin was neutralized by potassium hydroxide to get an absorbent with high
absorption efficiency for blood and physiological saline. Tanaka et al. [59, 60]
have described a process for the polymerization of AA-MBA in the presence of
allyl mercaptan using hydrogen peroxide, ascorbic acid, and an azo catalyst
as initiators. The resin was later neutralized with sodium hydroxide. The thiol
compound offered resistance to polymer degradation during exposure to body
fluids, thus resulting in gel stability. The SAP prepared also had improved water
retention. Other polymerizable thiols (i.e., triethylene glycol dimercaptan acrylate and p-mercapto styrene) have also been demonstrated to be effective for
similar applications [61]. The thiol compounds can be added during drying or
pulverizing steps [62]. A diphosphonic acid of the type RC(OH)(PO3H2)2, where
R = C523 hydrocarbyl or a salt thereof, has been used to resist metal ioncatalyzed degradation of SAP by free-radical precursors. The process developed
by Watanabe et al. [63] involves cross-linking of partially neutralized AA by
polyglycerolpolyglycidyl ether (Denacol EX512), which has been reported to be
effective even after considerable absorption time for body fluids [64]. Igarashi
[65] used a mixture of Denacol EX512 and a dihydroxy bislactatotitaniummonoammonium compound (TLA-A-50) for partially neutralized AA polymeriza-

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tion initiated by PPS. The reaction was carried out at 75C in cyclohexane that
contained ethyl cellulose (N-100).
Engelhardt and Ebert [66] prepared SAP for hygiene products and horticulture applications by polymerizing AA. The reaction was initiated by PPS and
ascorbic acid using N,N-(1,2-dihydroxyethylene)bisacrylamide as the crosslinking agent. The polymer was obtained as foam after neutralization with
sodium bicarbonate. Kaledkowska et al. [67] have described a process for producing SAP for use as a soil stabilizer. AA was partially neutralized with sodium and calcium hydroxide in the presence of ethylene glycol monomaleate in
the process. The compositions decreased water leakage when polymerized
with MBA.
SAP with lower residual monomer/water-soluble content, higher gel strength,
and improved absorption characteristics can be synthesized in an aqueous system using special preparation techniques. Sumiya, Date, and Kenji [68] prepared
SAP with a 2.5% water-soluble fraction and 500 ppm residual monomer content
by first polymerizing aqueous AA at 5560% using tetrakis(allyloxy)ethane and
Peroyl SA. The resin was dried, powdered to 20 mesh, and heated with ethylene
glycol diglycidyl ether (EGDE) to give the desired product. Tanioku, Kitagawa,
and Takeuchi [69] developed a process for producing SAP with 8% water-soluble matter by dispersing a cross-linked poly(AA) with MBA, AA, sodium hydroxide, and an azo initiator. The contents were UV irradiatated to give the
desired cross-linked resin. Lind and Smith [70] developed a method for treating
the resin with an aqueous solution containing a surfactant and vinylic addition
compound comprised of a reactive double bond. The AA-SA resin was sprayed
with sodium bisulfitepotassium stearate solution that reduced the unreacted AA
content below 50 ppm. Brehm, Dahmen, and Mertens [71] developed a process
for producing SAP with less extractable fraction and residual monomer content
by first dispersing cross-linked polyacrylate, a nonswelling monomer, in an
aqueous phase containing monomers. Later, AApotassium acrylateMBA mixture was polymerized by stirring with an azo compound, SPS, and hydrogen
peroxide.
2.2. Suspension Polymerization
The preparation of SAP by dispersing monomers in a suitable hydrocarbon
phase is termed suspension or emulsion polymerization. The two terms are used
for large or small droplet sizes of the dispersed phase, respectively [72]. Unlike
solution polymerization, the resin in this process is obtained as a powder [73],
thus avoiding the need for subsequent grinding. The monomers and initiator are
dispersed in the hydrocarbon phase as a homogeneous mixture [74]. The resin
particle size and shape are governed mainly by the viscosity of the monomer
solution, agitation speed, rotor design, and dispersant type. Benda, Snuparek,

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and Cermak [75] developed a procedure for the preparation of high molar mass
SAP by allowing monomer droplets to fall through a long, vertical, nonstirred
reactor containing continuous phase. Each droplet, therefore, acts as a microreactor in which the polymerization reaction takes place. Wan and Jing [76] have
determined the effect of dispersion medium, ratio of oil to water, and dispersant
on the particle size of AA-MBA polymer. It was found from FTIR, X-ray diffraction, and scanning electron microscopy (SEM) studies that potassium acetate, when added to the system, improves the surface contact area, thereby increasing water absorption.
The polymerization initiators generally are dispersed in the aqueous phase,
but those soluble in the oil phase base also have been employed to give resins
with different characteristics [77]. Yamamoto and Nakajima [78] used hydrogen
peroxide and sodium hypophosphite to improve the absorption and whiteness of
SAP. The suspension polymerization process generally results in reactor scale
formation. Differential thermal control [79] and use of certain polymers, which
act as suspending agents [80], have been reported to reduce the problem.
The coalscence of the droplets produced by vigorous agitation is prevented
by using a suitable stabilizer. The net effect of a stabilizing agent is to reduce
aggregation of polymer particles formed during the reaction. Sakakibara et al.
[81] recommended use of N-acylated disodium glutamate (Amisoft HS21),
which acts as a chelating agent. Brooks and Liu [82] studied droplet behavior
by SEM and with freeze fracture equipment using a water-soluble redox initiator. They concluded that the breakup and coalescence phenomena take place
simultaneously with some polymerization occurring in the reductant drops. A
large number of workers [8389] have used sorbitan monostearate (SMS) as a
dispersant due to its low HLB value, needed for the water-in-oil-type dispersions. The use of anionic [90] and nonionic [9193] surfactants other than SMS
has been reported. A mixture of surfactants has been found to be useful for
preparing SAP with better performance characteristics. Shimada and Miyoshi
[94] used SMS, glycerin polyglycidyl ether, and PEG for polymerization carried
out in the presence of acetone.
The surfactant system used for polymerization bears an important correlation
to the SAP particle size and distribution. Other variables that influence particle
size are the hydrocarbon phase, monomer concentration, and reaction temperature. Askari et al. [95] concluded that micromolecular surfactants such as sorbitan monooleate yield SAP particles that are 50500 m in size and are obtained
as lumplike 23-mm beads. Ethyl cellulose (substitution degree of 2.42 to 2.53),
which acts as macromolecular stabilizing systems, results in polymer particles
with an average diameter of about 300 m and safe processibility characteristics.
A coating of ethyl cellulose on resin particles also prevents agglomeration.
Mallo, Morean, and Cabestany [96] obtained SAP microspheres by polymerizing AApotassium acrylate1,4-butanediol diglycidyl ether in the presence of

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ethyl cellulose. The reaction was initiated by SPS4,4-azobis(4-methyl pentanoic acid) in cyclohexane. A mixture of monomersbisacrylamide acrylic acid,
diethylene-triaminepenta acetic acid, [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride, and SPS on gradual addition to the continuous phase containing ethyl cellulosehas been reported to give SAP useful for absorption of
aqueous salt solutions [97]. The copolymerization of finely divided silica with
other monomers has been reported to be useful for improving absorption capacity for urine and blood [98].
SAP with large particle size can be obtained by using a suitable combination
of dispersants. Thus, Kimura, Nagasuna, and Namba [99] prepared 100600m particles of AA-SA-MBA by dispersing a monomer mixture containing hydroxyethyl cellulose. The continuous phase (cyclohexane) contained a sucrose
fatty acid ester (DK Ester F-50). Chosakon [100] used a mixture of sucrose and
sorbitan fatty acid esters for preparing SAP with an average particle size of 300
m. For partially neutralized AA polymerization initiated by APS, sucrose fatty
acid ester (DK Ester F-70) and SMS were used with MBA as a cross-linking
agent. Ito and Tanaka [101] employed a mixture of SMS, C2838 alkenes, and
C2838 alkene maleic anhydride copolymer for AA-MBA polymerization using
PPS as the initiator. A mixture of ethyl cellulose, sucrose esters, and C1016 synthetic fatty acids was used as a dispersant by Klyuzhin et al. [102] for preparing
SAP with high water absorption capacity. Nagasuna, Suminaga, and Shimomura
[103] titrated monomer solution containing poly(oxyethylene)nonyl phenyl ether
having an HLB value of 12.5 into a cyclohexane-containing SMS (HLB 4.7).
This ultimately resulted in phase inversion, and SAP particles with a 6.3 m
average diameter were obtained in a distribution range of 115 m.
Sucrose fatty acid esters and their mixtures have been reported to give fine
particles that are useful as antiperspirants [104, 105]. Monoalkyl phosphates are
reported to be used as dispersants for SAP preparation [106]. He, Xiao, and Luo
[107] reported that SA-acrylamide copolymers, cross-linked with MBA, had
enhanced absorption in aqueous solutions containing Ca2+, Mg2+, and Fe3+ ions
when monohexadecyl phosphate was used as the dispersant. The average particle size was 100350 m, and the resin had more than 70 g/g saline absorption.
Hitomi, Harada, and Shimomura [108] prepared AA-SA-TMPTA copolymers
that produce sound while absorbing water. Ethylene carbonate was used as the
dispersant in this process. Large-size particles (average diameter 3062 m) have
been reported to be prepared as agglomerates in a two-step reaction [109]. AASA-MBA copolymer was first prepared at 60C70C in the presence of sodium
hypophosphite as the disperant, and then a solution of 2-hydroxyethyl methacrylate was added gradually to get the desired resin.
The absorbency of an SAP depends on the concentration and the type of ions
present in the aqueous phase. While cross-linking density and the network structure of gel determine the swelling behavior, the salt solution reduces the osmotic

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pressure at the interphase. The absorption characteristics of an SAP, therefore,


can be modified according to the desired application by careful selection of
comonomer and cross-linking agent. Lee et al. [110112] reported that SA-2hydroxymethacrylate-MBA gel has the same degree of swelling in aqueous solutions of lithium, sodium, and potassium chlorides at the same ionic strengths,
while calcium, strontium, and barium chlorides absorb less, respectively, in that
order. The absorption characteristics are related to the ability of metal ioncarboxylate group complex formation. The order for some common metal ions has
been reported as Fe3+ > Ca2+ > Cu2+. The swelling behaviors of SA3-[dimethyl(methacryloyloxyethyl)]ammonium propane sulfateMBA and SA-MBA for
various ions have been reported at different concentration ranges in this study.
Kim et al. [113] used AA-SA as monomers and ethylene glycol dimethacrylate and glycol polyglycidyl ether as the cross-linking agents for SAP preparation. The reaction, carried out in the presence of 1050 mol% sorbitol, employed
cyclohexane as the dispersion medium and PPS as the initiator. The spherical
SAP particles had a diameter of 177707 m and 5083 g/g saline absorption.
Mizutani [114] used poly(ethylene glycol) diacrylate or divinyl benzene as the
cross-linking agent for AA polymerization. A polymer complex was prepared
using sodium silicate powder, which showed higher absorptivity toward water.
3. MODIFIED SUPERABSORBENT POLYMERS
The absorption characteristics and gel strength reach a crossover point for a
given system. Beyond this point, a given property will show improvement at
the expense of other properties. To synthesize SAP with properties superior to
this optimum value, further modification in the process becomes essential [114,
116]. One approach for achieving the objective is to incorporate reactive groups
on the polymer surface during initial polymerization and additional cross-linking
during a subsequent step.
Matsumura et al. [117124] have done extensive work on sulfoacetic acid
substituted branched -1,3-glucans (-g), which are synthesized from Aurobasidium Sp. K-1 FERM P12989 by a shakeculture process. In the first step, AA,
partially neutralized by sodium hydroxide, is polymerized in the presence of g and MBA in cyclohexane medium that contains SMS and sucrose fatty acid
ester (DK Ester F-70). The reaction is initiated by APS, and the resin obtained
is treated with sodium tripolyphosphate and thiourea. Alternatively, the resin
could be treated with poly(vinyl alcohol), sodium hypophosphite/urea, or polyethylene glycol diglycidyl ether. Water is removed from the reaction mixture, if
required, by azeotropic distillation to get SAP. The process is claimed to reduce
scale formation in the reactor.
Wada, Ishizaki, and Nagasuna [125] first prepared AA-SA-TMPTA copolymer using APS/L-ascorbic acid divided into fine particles (average diameter 400

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m) and cross-linked with glycerol polyglycidyl ether in the presence of ethylene glycol and ethanol. The resin was subsequently mixed further with silica,
and the resulting SAP was reported to have high absorbency and gel strength.
In another process [126], SAP from AA-SApolyethylene glycol diacrylate was
cross-linked with EGDE in the presence of glycerol and then treated with polyethylenimine hydrochloride salt for improvement in absorption characteristics.
Amiya, Mujanaga, and Hanada [127] used -thujaplicin sodium salt, a chelating
agent, in an SAP, which provided a site that could react with copper. Yoshinaga
et al. [128] prepared AA-SA polymer in cyclohexane that contained -glycidoxypropyltrimethoxy-silane. The resin was treated with zirconium dioxide to get
an SAP that showed good absorbency for urine and had a high gel strength.
Ito and Iida [129] prepared AA-SA-MBA polymer in the presence of silica
powder and then treated it with additional monomers and the cross-linking
agent. The SAP obtained had an average particle size of 810 m. Karasawa,
Yamaguchi, and Nagao [130] treated AA-SA-MBA resin, polymerized by an
APS/sodium bisulfite initiator system, with glycidol to get an SAP with improved properties. Takahashi et al. [131] used an open cylinder for spraying the
SAP-glycerin mixture for improvement of its properties. The AA-SA-TMPTA
copolymer was prepared in an earlier step. Kajikawa et al. [132] treated AASA-MBA copolymer with trimethalolpropane, sodium bisulfite, water, and isopropanol to reduce the monomer content and improve water absorption. Zastera,
Parizek, and Dzurny [133] reported a process for manufacture of SAP that was
first deposited on a textile support. Later, the resin was crushed and ground,
neutralized, and cross-linked with pentaerythritol triacrylate in the presence of
potato starch using APS as the initiator.
To increase the particle size and absorption characteristics of SAP, crosslinking of primary particles of a hydrogel is carried out along with monomers
and other additives [134]. Collette et al. [135] reported a method for producing
SAP with a core-shell structure. The procedure involves cross-linking a hydrocarbon suspension of powdered SAP with an aqueous solution of a cross-linking
agent. The dispersion of partially neutralized AA, PPS, carboxymethyl cellulose,
and EGDE was added to heptane that contained ethoxylated nonyl phenol, monomers, initiator, and carboxymethyl cellulose. The product had higher saline
absorption. Engelhardt et al. [136] prepared SAP with improved absorption
characteristics by adding granules of two different resins in the presence of a
surfactant (Tween 21). Another method for preparing composite polymers has
been developed by Fujikake et al. [137]. The procedure involves dispersion of
partially neutralized AA; an SAP (Aqua Keep); and PPS in cyclohexane, which
contains a nonionic detergent (Nonion LP 20R), sodium hydroxide, and PPS.
The porous structure of SAPs is sometimes blocked by the absorbed species
present in the fluid. This phenomenon is called gel blocking and restricts further
fluid absorption adversely, despite the SAP capacity remaining intact. Attempts

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have been made to prepare gels with a foamlike structure [138]. The method
involves incorporation of a blowing agent in the polymer matrix. The treatment provides a surface-to-weight ratio greater than 0.2 m2/g and an average
cell size of less than 100 m. The monomers and cross-linking agent expand in
the presence of the blowing agent, which is water insoluble. The SAP obtained
from AA-SA-MBA has been reported [139] to absorb 50 g/g synthetic urine
and to have a swelling rate of 28 g/g?s. Dahmen, Herrmann, and Pflneger [140]
synthesized AA-SA-triallylamine polymer in the presence of magnesium carbonate, which was employed as a blowing agent. The polymer was milled to a
size of 90850 m, mixed with ethylene carbonate, ethanol, and water, and
dried at 180C to get the final product. Smith and Lind [141, 142] improved the
performance of an SAP by incorporating a carbonate blowing agent in the matrix and finally treating it with a cross-linking agent. A method for preparation
of cellular articles that requires polymerization of AA-SA-MBA in the presence
of 2,2-azobis(2-amidopropane) dihydrochloride has been reported [143]. The
reaction, carried out in a mold, is initiated by UV radiation. Scholz and Ritzberger [144] used nitrogen containing blowing agents for improvement of gel
blocking and reduction of the residual monomer content of the SAP produced.
The process involves preparation of AA-SAtriacryloyl perhydro-s-triazine,
which is heated with ammonium carbonate in the presence of a catalyst. The
SAP is reported to absorb 76 ml/g synthetic urine with 930 ppm residual monomer content.
The surface cross-linking of SAPs is primarily aimed at improvement in fluid
absorption under load and increase in the particle size. However, other properties, such as improved handling of material, higher rate of absorption, and gel
stability, are also obtained. In the first step, the procedure [145, 146] involves
preparation of an SAP using an internal cross-linking agent. In the next stage,
the resin is treated with a solution containing surface cross-linking agent(s) and
is heated if necessary. Henderson, Tomlinson, and Lucas [147149] developed
a method for impregnation of an SAP with a past containing another crosslinking agent to form larger size particles with improved absorption capacity.
The surface-cross-linked particles were subsequently allowed to absorb water
and were heated and pulverized. Kajikawa, Hatsuda, and Nakamura [150] reacted AA-SA-TMPTA and polyamide-polyamine-epichlorohydrin polymers in
the presence of glycerin, water, and isopropyl alcohol to prepare an SAP composition.
Silica has been used as a surface cross-linking agent on SAPs. Hasegawa and
Chosakon [151] mixed the base SAP particles with a bifunctional epoxy compound (Celloxide 2021) and silica to get resins with low bulk density and less
fines. Johnson and Couldwell [152] used a diethylene glycol diether/silica mixture for surface cross-linking of AA-SAtriallyl ammonium chloride copolymer
with improved absorption under load. An SAP modified by an organsilane com-

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pound has been reported to improve the gel blocking strength [153, 154]. Silicone surfactants (KF 353A) with an HLB of 718 and a viscosity of 10200
cSt at 25C were mixed with AA-EGDE-MBA-SA copolymer to achieve the
desired result. Tsubota et al. [155] first neutralized AA-MBA copolymer with
sodium hydroxide and then heated the resin with polyglycerol polyglycidyl ether
(average functionality 4), adipic acid, water, and diethylene glycol at 140C to
an SAP that had good dry feel. The base resin, when reacted with Denacol
EX810, methanol, and water, gave an SAP with improved gel strength [156].
Aayoma [157] repeatedly treated an SAP precursor with Denacol DX314 to
improve water absorptivity of the product. The precursor was prepared by copolymerizing, using APS initiator, a partially neutralized AA-MBA mixture in
cyclohexane that contained Denacol EX314. A process for treatment of an SAbased SAP by Denacol EX-512 and Epomine SP-006 has been developed by
Namba et al. that results in improved absorptivity [158].
Yanase et al. [159] developed a process for manufacture of an SAP having
resistance to urine and improved absorption under load. The precursor resin is
prepared for AA-SApolyethylene glycol diacrylate in the presence of sodium
phosphate using SPS as the initiator. The resin is surface cross-linked with
EGDE to get the SAP stability for urine absorption over 20 h.
4. NEW TRENDS IN SUPERABSORBENT
POLYMER PREPARATION
New trends in SAPs aim at production of resin in a different form so that its
application area may expand and it may give better performance during conventional use. Murase and Suzuki [160] have developed a process for producing
hollow fibers having microgrooves on the walls in which water-swellable gels
are filled. The polyester fibers containing titanium dioxide are first extracted
with sodium hydroxide solution to produce hollow fibers. Later, the modified
fibers are impregnated with an AA-SA-PEG monomer mixture, PPS, and water.
Heating the fibers in a vacuum gives the desired product. Okamoto et al. [161]
prepared water-absorbing composites by impregnating a solution of AA-SAMBA monomer mixture along with SPS on polyurethane foam. The porous
foam was squeezed and heated to obtain a dimensionally stable material with
3900 g/m2 water absorption and 900 ppm residual monomer content. Ishizaki et
al. [162] developed a process for manufacture of sheetlike absorbent material.
The monomer composition of AA-SA-TMPTA, glycerin, EGDE, and polyethylene terephthalate fiber was pressed on the dry drum of a press roller and heated
to give the target product.
Hahnle et al. [163] developed SAP foams by dispersion of a gas through
a mixture of monomers, cross-linking agents, foam stabilizers, polymerization

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regulators, fillers, and/or cell-nucleating agents. In a typical experiment, AASAethoxylated tallow fatty acidpentaneethoxylated glycerol triacrylate1,4butanediol diacrylate and 2,2-azobis(2-aminopropane) diydrochloride were used
to give a product with good storage stability and processability. SAP composites
consisting of starch, polyethylene glycol diacrylate, AA, and SA were prepared
[164] by dispersing them in benzene and heating at 40C. A method for preparing a high-performance absorbent particulate composition having a noncolloidal
solid core encapsulated in AA-SA-EGDE SAP has been developed by Pearlstein
[165]. Budlova and Vilesov [166] have reported the anomalous dependence of
absorbency on an SAP/alcohol/dye composition, rendering it useful as an optically active medium for lasers.
ACKNOWLEDGMENTS
The authors are thankful to Dr. M. Ravindranathan, DGM (Research), for
helpful guidance in preparing this article. The encouragement and permission
for publication of this article by Dr. S. K. Awasthi, General Manager (R&D),
are gratefully aknowledged.
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