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Controlled release agrochemicals formulations: A review

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Journal of Scientific DUBEY
& Industrial
et alResearch
: CONTROLLED RELEASE AGROCHEMICALS FORMULATIONS: A REVIEW 105
Vol. 70, February 2011, pp. 105-112

Controlled release agrochemicals formulations: A review

Saurabh Dubey*, Vishal Jhelum & P K Patanjali

Institute of Pesticide Formulation Technology, Sector 20, Gurgaon 122 016, India

Received 30 July 2010; revised 23 December 2010; accepted 04 January 2011

This study reviews controlled release formulation (CRF) of agrochemicals (fertilizers, pesticides, herbicides, plant growth
regulators etc.). Synthetic as well as naturally occurring polymers have been used for preparation of these formulations. Dual
applications of polymer supported herbicides have also been attempted. This strategy would open new areas for prevailing
registered pesticides in India. Scope of CRF in controlling other pests like mosquito is also visualised.

Keywords: Agrochemicals, Controlled release formulation (CRF), Pesticides, Polymers

Introduction CRF has following advantages 8,9: 1) Activity

Applied conventional agrochemicals (90%) never
reach their objective to produce desired biological
response at the precise time and in precise quantities
required, due to nonspecific and periodic application of
active agents. Both factors, besides increasing treatment
cost, produce undesirable side effects to plant or
environment1. Widespread application of different
polymeric materials as reactive molecules is based on
potential advantages of specifically active functional
groups and characteristic properties of polymeric
molecules2,3. Conventional application of agrochemicals
results in groundwater contamination 4. Also, over
application and point source contamination increase
pollution potential 5. Replacement of conventional
agrochemical formulations by controlled-release systems
not only helps to avoid treatment with excess amounts
of active substances, but also offers, besides ecologic
and economic advantages, the most suitable technical
solution in special fields of application (in aquatic weed
control and pest management in paddy fields).
Controlled-release formulations (CRF) are used to
maintain effective local concentration of active ingredients
in the soil and to reduce runoff6. Conventional application
of agrochemicals provides an initial concentration far in
excess than required and cause toxicity problems for
organisms7 and also produces undesirable side effects in
the environment.
*Author for correspondence
E-mail: drsaurabh_dubey@rediffmail.com
prolongation by providing continuously low amount of
pesticide, a level sufficient to perform its function over a
long period; 2) Reduced number of applications by
achieving a long period of activity duration through a
single application; 3) Cost reduction by eliminating time
and cost of repeated and over applications; 4)
Environment pollution reduction by eliminating the need
for widespread distribution of a large amount of pesticide
one time, thereby reducing undesirable side effects of
agrochemical losses by evaporation and degradation or
leaching by rain into the soil or waterways; 5) Extending
activity duration of less persistent pesticide, which is
unstable under an aquatic environment; 6) CRF converts
technical pesticide liquid into solid formulation, resulting
in easily transported material with reduction of
flammability; and 7) Mammalian and phytotoxicity
reduction by lowering high mobility of pesticide in soil
and hence reducing their residue in food chain. High cost
involved in manufacturing of these formulations, excessive
amount of polymer used and polymeric herbicide is the
fate of polymer matrix¤:10-12.
This review presents CRF of agrochemicals,
particularly pesticides.
Controlled Release Formulations (CRF)
Technology
CRF technology is based on interaction of pesticides
with polymers. Developed methods are classified as per
106 J SCI IND RES VOL 70 FEBRUARY 2011
the material or technology used for their preparation as
follows:
Diffusion of Pesticide in Polymeric Medium
This technology includes two types of products: i)
Monolithic system, where pesticides are dispersed
uniformly in polymeric or elastomeric matrices; and (ii)
Reservoir system, where pesticides are covered by
membranes, laminate, capsule, coating, liposome etc.
Polymeric Pesticides
Pesticide is bound via covalent or ionic bonds to
polymers or pesticide formulation may also be obtained
by binding pesticide to monomers, followed by
polymerization. Pesticide is released from polymeric
matrix by hydrolysis of polymer-pesticide bond in the
environment. Pesticide that contains very reactive
functional groups (carboxyl, hydroxyl, and amino etc.)
can react with monomers or polymers directly. In case
pesticides do not have any functional groups, some
bridging agents are needed in order to bind pesticide to
monomers or polymers13. By this method various kind
of pesticides are bound to natural polymers (kraft, lignin,
and bark and saw dust) as follows: i) Erosion of
Polymers –Pesticide is released by chemical or biological
erosion of polymers from monolithic or reservoir system;
ii) Porous Materials – This technique, where pesticide
is retained in capillary channels (hollow fibres, porous
plastic, and foam and so on), is used only for insect
pheromones; iii) Adsorptive Carriers – Montmorillonite
clays and attapulgite clays have adsorptive ability for
various compounds including pesticides. The formulation
thus obtained is released under controlled conditions and
longer residual activity is expected. Activated charcoal
may also be used for this purpose; iv) Propesticide – A
modified molecule release active pesticide under certain
conditions. One of the examples of propesticide for
controlled release is pyrazolate; and v) Osmotic
Pump – Pesticide is covered by semipermeable
membrane with small holes14-16.
Chemical and Physical Methods of Controlled
Release Agrochemical Formulations
Chemical Bonding of Pesticide to Polymer Matrix
One of the basic methods to prepare CRFs of
pesticides is via synthesis of polymer with pesticides as
pendent substituent. Generally, there are two ways for
preparation of polymers chemically bonded with
pesticides17 : i) pesticide reacts with polymerizable
monomer to give macromolecular combination; and ii)
preformed synthetic or natural polymers are chemically
modified with herbicide or herbicide derivatives.
Polymerization of Herbicide-Containing Monomers
Polymerization of herbicide-containing monomers
depends on functional groups of both pesticide as well as
monomer. Polymerization of herbicide containing
monomers requires high monomer purity in order to obtain
reasonable molecular weight. McCormick et al 18,19
synthesized a controlled-release system by polymerization
of vinyl ester of 2, 4-dichlorophenoxy acetic acid
(2, 4-D). Neogi & Allan20,21 prepared polymerizable
monomers containing 2-methyl-4-chlorophenoxyacetacid
and pentachlorophenol. Copolymer of monomer containing
2-methyl-4-chlorophenoxy acetic acid with acrylic acid
(AA) was found biologically activet22.
Various controlled-release pesticide-polymer
formulations have been developed23-27. Harris’s group28,29
synthesized vinyl 2, 4-dichlorophenoxyacetate and vinyl
2-(2, 4, 5-trichlorophenoxy) propionate by
transvinylations29,30. 2-Acryloxyethyl ester of 2, 4-D was
copolymerized with triethylamine methacrylimide. Linear
polymeric pesticides31 containing a pentachlorophenol
moiety were synthesized by radical polymerization of vinyl
monomers containing pentachlorophenol pesticide via
ester linkage unit. Release of pentachlorophenol from
these systems was reported to be mainly dependent on
degree of hydrophilicity and temperature. Other systems
were synthesized32 from vinyl monomers by introducing
an oxyethylene moiety via ester group as a space between
pentachlorophenol and vinyl moieties. These systems
containing pentachlorophenol pesticide were polymerized
under free-radical conditions and cross-linked using
different ratios of divinyl benzene. Acryloyl chloride
monomer carrier or its methyl derivative was reported to
be useful in controlled release of niclosamide
molluscicide33. Polymers containing niclosamide were
obtained either by homoporymerization or
copolymerization of monomer with styrene or
oligo-(oxyethylene) vinyl monomers in different molar
ratios. Synthesis of N, N-diacryloyl metribuzin (DAMB),
and herbicide-containing monomer34 was co-polymerized
with acrylamide (AM) and AA. Co-polymerization of
monomer in aqueous buffer systems indicated that
hydrolysis of labial bond to release metribuzin was slow.
 DUBEY et al : CONTROLLED RELEASE AGROCHEMICALS FORMULATIONS: A REVIEW
McCormick et al35,36 synthesized and characterized
co-polymers with pendent esters of plant growth
regulators. Hydrolytic release behaviour36 for above
formulations shows that it is dependent on nature of
monomer structure and its composition. Another
polymeric herbicide formulation was prepared using oligo-
(oxyethylene) methacrylates loaded with either 2, 4-D
or MCPA (2-methyl-4-chlorophenoxyacetic acid).
Herbicide-containing monomer was homopolymerized or
copolymerized with AM and other hydrophilic
co-monomers such as 4-vinylpyridine37.
CRF systems are of special interest because of their
dual function in utilization as herbicide and fertilizers.
Dual applications of polymer-supported herbicides are
based on a combination of herbicide-fertilizer, in which
polymer contains elements like nitrogen or phosphorus
to act as a fertilizer in the soil after polymer degradation.
Polymeric herbicides were synthesized by condensation
of tartrate monomer with a series of diamines
(ethylenediamine, triethylenetetramine, tetraethy
lenediamine, diethylenetriamine, triethylenetetramine).
Akelah et al12 prepared CRF based on polyureas and
poly schiff bases. These systems were synthesized by
polymerization of monomer either with
hexamethylenediisocyanate to yield polyurea or with
terephthaldehyde to yield poly (Schiff bases). Akelah et
al38 also reported CRF from monomeric herbicides of
diethanol amine using 2, 4-D or 2-methyl-4-chlorophenoxy
acetic acid (DCPA). Use of natural and acid- treated
bentonite39 as modifying agents for CRF development
(sodium alginate-atrazine-water) reduces release rate of
herbicide as compared with technical atrazine and with
alginate CRFs. Clay-based formulations of herbicides
can yield slow release and consequently reduce herbicide
leaching in soil. El Nahhal et al40 used hexadecyltrimethyl
ammonium (HDTMA) as herbicide for the combination
of montmorillonite as an adsorbent for controlled release.
This application generates structural similarity between
exchanged organic cation and herbicide molecules. This
similarity may enhance interactions between herbicide
and adsorbed organic cation and increase herbicide
adsorption on organo-clay complex.
Cespedes et al41 studied encapsulation efficiency of
alginate - based controlled release granules of chloridazon
and metribuzin activated carbon as sorbent. Kinetic
experiments of release in water show that: i) release
rate is higher in metribuzin formulation than in those
prepared with chloridazon; ii) use of bentonite, anthracite
and activated carbon samples as modifying agents of
107
alginate formulations reduce the release rate of
chloridazon and metribuzin in comparison with technical
product and with alginate formulation without modifying
agents; and iii) highest decrease in release rate
corresponds to the formulations prepared with activated
carbon. Moreover, diffusion causes release of
chloridazon and metribuzin from various alginate-based
CRFs into water and in this diffusion sorption capacity
of modifying agents for herbicides is the most influential
factor42-47. Gressel et al48 successfully used imidazolinone
resistant maize seed dresses with imazapyrh to control
parasitic weed striga. A series of slow release
formulations were synthesized based on binding imazapyr
to high capacity anion exchangers and using them to coat
maize seed.
Chemical Modifications of Preformed Polymers with Pesticide or
Pesticide Derivatives
Combination of pesticides with natural and synthetic
polymers are comprehensively described49,50. Similar
systems were synthesized 19 using 2, 4-D herbicide.
Schacht et al51 synthesised cyclic six member acetyl
ring by reacting 2, 4-dichlorobenzaldehyde with PVA.
Hartman & Wemann 52,53 synthesized polymeric
herbicides from modification of poly (acrylic acid).
Wilkins & Blackmore 54 modified kraft lignin with
propachlor to produce polymeric, in which availability of
active agent was extended to more than 9 weeks .Similar
systems were prepared by Cho et al55 using rice husk
lignin and 2, 4-D. McCormick et al56-58 reported a number
of modifications of naturally occurring polymers with
herbicides, and also reported a series of polymeric
herbicides by modifying metribuzin with diisocyanate,
which were further modified with PVA. Release studies
from these systems using bioassay indicated phytotoxicity
for Sida spinosa L59. A series of preformed polymers
modified with pesticides has been reported2. 2, 4-D or
its salt was modified with either sawdust60,61, bark62, or
pine kraft lignin 63. Ikladious & Messiha 64 reported
controlled release from an antifouling system based on
treatment of copolymer of maleic anhydride and
methylmethacrylate with tributyltinoxide. Chitin was used
as a carrier for herbicide metribuzin 65, and system
showed slow release when polymer was directly attached
to metribuzin. Polyphosphazene66 containing 2, 4-D was
of great interest because of its biodegradability with
nitrogen and phosphorus-containing products in addition
to active ingredients. Degradation products were found
to be very useful as fertilizers.
108 J SCI IND RES VOL 70 FEBRUARY 2011
Polymeric molluscides67 were prepared by chemical
modifications of preformed cross-linked polyacrylic acid
(Amberlite resin IRC-50) or by modification of anion
exchange resins Amberlite IRA-401 and IRA-400.
Niclosamide from polymers indicated that release rates
were strongly dependent on the nature of hydrolyzing
medium and type of binding group, as well as degree of
cross-linking. Two CRFs containing copper sulphate as
a molluscicide loaded onto natural clays as binding agent
have been reported68. Release of copper ions in water
follow a zero-order release kinetics with a theoretical
lifetime of 270-350 days. Lignin was used as a carrier
for 2,4-D69, chloramben, metribuzin, alachlor70 carbofuran
and diuron71.
Mair et al72 reported CRFs of pentachlorophenol
using cellulose as a carrier. Chiellini & Akelah 73
synthesized polymeric herbicides containing 2,4-D and
MCPA by modification of oligoethyleneoxylated styrene/
divinyl benzene (DVB) resins. Other systems were
synthesized using various either linear or cross-linked
poly [oligo (oxyethylene) methacrylate]s as main
polymer74,75. From release kinetics it was concluded that
release profiles cannot be easily correlated with structural
parameters (degree of cross-linking and distance of
herbicide from polymer backbone). Cross-linked
polysaccharides76 containing covalently bound 2,4-D
were prepared by reacting alkaline water solutions of
semisynthetic polymers (hydroxyethyl cellulose and
dextrans) with epichlorohydrine in toluene, using an
epichlorohydrin/glucose unit. 1-Naphthyl acetic acid
(NAA), as a plant growth regulator, was synthesized
using poly [oxytartaroyloxy poly (oxyethylene)]s
[PTEGs] to give polymeric plant growth regulators. No
release studies of these systems are reported77,78.
Controlled-release Bayluscide systems were
prepared by chemical reactions of commercial
chloromethyl styrene (2% DVB) and Amberlite IR-120
(8% DVB) with Bayluscide79,80. Resulting polymeric
molluscicides contain Bayluscide active group attached
via covalent bond or through physical interaction with
diethanol amine group of modified polymers. Release
rates of niclosamide were found strongly dependent on
medium pH and structure of composition of polymers81,82.
Kenway et al83 prepared CRFs based on cross-linked
polyacrylamide derivatives. Acrylamide gel derivatives
were prepared by transamidation of cross-linked
polymers with various diamines of different structures
(ethylenediamine, hydrazine hydrate, jeffamine 148, bis-
(3-aminopropyl)-polytetrahydrofuran 750, and
bis-(3-aminopropyl)-polytetrahydrofuran 1100).
Transamidated polyacrylamide gels were reacted with
2, 4-dichlorophenoxy acetyl chloride to produce
polyacrylamide derivatives containing 2, 4-D.
Kulkarni et al84 reported experimental results on
successful encapsulation of a natural liquid pesticide
‘Neem’ seed oil or NSO, using sodium alginate
(Na-Alg) as a polymer. SEM photographs indicate a
spherical and smooth surface of the beads. Particle size
was found to be independent of increasing exposure time
to cross linking agent or on increasing percentages of
loading of active ingredient. Higher release rates for NSO
were observed for higher loading of NSO. An increase
in degree of cross linking of precipitated Na-Alg polymer
resulted in a significant decrease of NSO release from
beads85. Novel polymeric sodium alginate (Na-Alg)
interpenetrating network (IPN) beads were prepared by
cross linking Na-Alg blend with gelatine or egg albumin
with glutaraldehyde as a cross linking agent. These beads
were used for controlled release of chlorpyrifos86. IPN
polymeric beads of poly (vinyl alcohol) - grafred-
acrylamide with Na-Alg have been prepared by cross
linking with glutaraldehyde87. Cypermethrin, a widely
used pesticide, was loaded with 80% efficiency in these
hydro gel beads. Diffusion of pesticides through polymeric
beads decreases with increasing cross linking as well as
increasing cypermethyrin loading88,89.
Clay minerals have been used as a inert material for
development of CRFs of pesticides90,91 because of their
larger specific surface area and considerable ion-
exchange capacity, which attribute to their ability to
absorb/desorbs pesticides. Besides controlling release of
pesticides from CRF, clay minerals also help in supplying
nutrients towards plants92. Modification of alginate with
kaolin and bentonite was found to reduce the release
rate of pesticides from formulations93. Singh et al94
developed starch-alginate beads for controlled release
of pesticides and release has been observed to increase
with increase in starch concentration. Release of active
was found to be dependent on percentage of Kaolin and
bentonite in starch-alginate based bead formulation.
Release of pesticides from these beads occurred in a
controlled manner, a primary requisite for use of
agrochemicals to control environment system and health
hazards. Sanli & Isiklan95 successfully encapsulated
carbaryl in alginate polymer. Alginate beads appear to
be a good product for CRF for agrochemical formulation
applications to improve pesticide stability and to reduce
risk both to people who handle the product and to ground
 DUBEY et al : CONTROLLED RELEASE AGROCHEMICALS FORMULATIONS: A REVIEW
water. Pesticides (isoproturon, imidacloprid and
cyromazine) were incorporated in lignin based
formulations to obtain controlled release (CR)
properties96. Time taken analysis for 50% of active
ingredient to be released into water (T50), showed that
release rate were much higher in cyromazine CR
formulation than in isoproturan. However, imidacloprid
showed an intermediate release rate. Bajpai et al97
prepared biopolymer microsphere of sodium alginate and
starch by employing calcium chloride as a cross linker.
Prepared microsphere was loaded with an insecticide
chlorpyrifos and microsphere was characterized by FTIR
and SEM analysis. The result was further analyzed by
Ficks power law equation97. Singh et al98 prepared neem
leaf powder and alginate based beads by using calcium
chloride as cross linker. Maximum (78 ± 2.89%) swelling
was found in beads prepared with NLP (1.5%), alginate
(2.5%) and 0.1 M cross linker solution.
Physical Combination of Pesticides with Polymers
CRF systems based on stabilized natural rubber
masterbatch were reported for 2, 4-dichlorophenoxy acid
butoxyethanol99. Schacht et al100 reported systems based
on suspending dichlorobenil into urea-formaldehyde
prepolymer. These formulations were found to enhance
herbicidal activity towards Sagittaria pygmaea, bull rush,
and barnyard grass.
Choudary et al101 reported a novel technique for CR
of pesticides based on encapsulation of pesticides via
complexation with metals in interlamellars of
montmorillonite. Intercalated pesticides were released
in small amounts over a period of 7 to 8 weeks. Pesticides
diazinon, trifluralin, and alachlor were successfully
encapsulated into temperature-responsive interlamellar
microcapsules 102 . Prasad & Kalyanasundaram 103
reported a CRF of mosquito larvicide fenthion as
monolithic slabs by insolubilizing sodium carboxymethyl
cellulose by ionotropic cross-linking with ferric chloride
under ambient conditions of temperature and pH. Another
system 104 for herbicide Dicamba (DA) based on
polymeric microspheres was produced from ethyl
cellulose, polyarylsulfone, or a combination of the two.
Release rate of DA from ethyl cellulose microspheres
could be controlled using different viscosity grades,
molecular weights of ethyl cellulose; higher the viscosity,
lower the DA release rate. Metribuzin herbicide105-107
formulated with an alginate-clay system showed that
standard composition of formulation, which can act like
109
in controlled release product, is with formulation of:
alginate, 1; metribuzin, 1; clay, 10; and water, 88%.
Johnson & Pepperman 108,109 reported two CRFs of
attrazin based on Na-Alg (1%), kaolin, and Tween 20
(0.5%). First formulation was prepared with linseed oil
(4%), and second formulation was without oil. Leaching
potential of atrazine decreased with the use CRF; also,
CRF increased amount of atrazine retained on soil surface
horizon (58-93%) as compared with technical grade and
commercial liquid treatments. Singh et al110 explained
release of pesticide from CRFs is best strategy to reduce
agro-environmental pollution. They synthesized pesticide
delivery devices based on neem leaf powder, kaolin and
bentonite. Incorporation of clays in beads was found to
control release of thiram from formulations.
Conclusions
CRFs have various advantages such as labour-saving,
safety for workers, smaller dosage, fewer applications
and less environmental impact. Agrochemical-based
CRFs are highly efficient in sustaining release of
biological sense. A significant hurdle in promoting this
technology is the high cost of these formulations
developed but use of cheaper natural polymer waste
materials (sawdust, park, starch, rice husk, lignin, and
pine Kraft lignin) seems to be a viable way to provide
loading of active species. Other possible trends to reduce
cost are to increase weight efficiency by increasing
content of active ingredients and to use polymer itself in
a positive role rather than as an inert vehicle. One of the
possibilities of making formulations economically viable
is to make polymer backbone having a dual function as a
fertilizer and as a carrier for the active agent. Another
way is to use hydro gels as a carrier, which at the same
time, may play a role in water conservation.
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