SYNOPSIS

Polymers and Polymer Composites are increasingly gaining

importance as substitute materials for metals in applications within the
aerospace, automotive, marine, sporting goods and electronic industries. Their
light weight and superior mechanical properties enhance their application to
different applied fields.
Again bio-based grafted polymers are a class of polymer that seeks to
remedy the issues regarding raw material sources as well as disposal at the end
of the product life cycle. In particular, lignocelluloses bio-based grafted
polymers represent a large and renewable source of polymeric raw materials.
Cellulosic polymers serve as both thermoplastic matrix and fiber
reinforcement. The different properties like brittleness, lengthy curve cycles,
tensile strength, biodegradability, dyeing properties and viscosity etc. of the
homopolymer, copolymer and graft copolymer on natural fiber are mostly
dependent upon the principle of production and their modification.
The present research topic of the thesis is mainly aimed at to develop
new, novel, simple, low cost and rapid non-conventional complex initiating
surfactant free emulsion system consisting of metal ions coupled with
chelating ligands which stabilizesv the emulsion latex leading to high
conversion in much the same way as a surfactant does in the conventional
emulsion system. Using these complex initiating systems, adhesive based
homopolymers of MMA, AN are prepared, and the graft copolymers of acrylic
monomers like MMA, AM, BA onto natural polymers like jute, pineapple leaf
fiber (PALF) and rice straw fibers are synthesized by complex catalyzed
peroxo initiating system for their tremendous industrial applications.

The so prepared polymers and copolymers are characterized by IR,

NMR, GPC, TGA, DTA, SEM, TEM, viscosity and solubility measurements.
Again the different physical and chemical properties including viscosity,
density, tensile strength, molecular weight, ultrasonic velocity and related
acoustic parameters, adhesive strength, biodegradability, dyeing properties etc.
are studied. In addition to this, the kinetics and conceptual mechanism model

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for polymerization process are proposed. The systematic work done in
different chapters are as follows:
Chapter-1, Section-I: In this section the characteristics of nonconventional
(soap-free) aqueous emulsion polymerization reactions of methyl methacrylate
were evaluated by the catalytic effect of in situ developed different transition
metal (II) chelate complex with amino acids initiated by different peroxo salts
like potassium monopersulfate (KMPS, KHSO5), potassium persulfate (KPS,
K2S2O8), ammonium persulfate [APS, (NH4)2S20g]. From the comparative
data, the Q1SO4/ histidine chelate complex was selected as a novel catalyst for
a detailed kinetic and spectrometric study of polymerization. Both kinetic and
thermodynamic aspects of the polymerization dictate which initiator and
particle morphology are obtained. The complex catalyzed polymerization
proceeded smoothly until high conversion and yielded stable emulsions. The
apparent activation energies (Ea) for the complex catalyzed emulsion
polymerization were computed for different initiators to be 34, 38 and 46
kJ/mol, each a very low value. Use of these values and activation energies of
propagation and termination for MMA gave unexpectedly low activation
energies (Ed, 26, 34 and 51 kJ/mol for KMPS, KPS and APS respectively) to
the decomposition of different persulfate initiators in the complex catalyzed
system. The emulsion polymer latex was characterized through the
determination of average molecular weights of the purified polymers by GPC
and viscosity methods and the morphology by Scanning Electron Microscopy
(SEM). The coordination complex catalytic system shows excellent industrial
performance characteristics in preparing micro- to nano-scale latex particles.
Chapter-1, Section-II: Radical polymerization of acrylonitrile was carried
out in an emulsifier free condition initiated by KHSO5 catalysed with Cu
(II)/bis-salicylidene ethylene diamine (H2 Salen) complex. The Cu(II) salt
alone, Cu(II)/Salicylaldehyde and Cu(II)/ ethylene diamine have a retarding
effect on the polymerization reaction, while the chelate of Cu(II) with the
tetradentate Schiff base ligand, H2 salen has a catalytic effect. Prior to this, the
catalytic effect of various bivalent transition metal salts and their couple with
the Schiff base, H2 salen on the polymerization reaction has been examined to
be not significant. The in situ developed complex produces the stable emulsion
leading to high conversion. In the polymerization, the variables studied were

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the concentration of monomer, initiator, Cu (II), H2 salen and temperature.
The overall activation energy was computed to be 13.1 kcal/mol. From the
kinetic and spectral analyses, the mechanism of the initiator decomposition
and initiation of polymerization by Cu (II) H2 salen complex were suggested.
The rate of polymerization (Rp) was found to be dependent on the monomer,
initiator, Cu (II) ion, H2 salen concentrations to the 1.4, 0.3, 1.6, and 1.5
powers respectively. The polymers were characterized by IR and molecular
weight by viscosity and GPC methods.
Chapter-2, Section-IA: This section consists of two sub-sections. In this
section, the author has focused on to the natural fiber copolymers , prepared
by grafting hydrophobic monomer, methyl methacrylate (MMA), onto
chemically modified Pineapple Leaf Fiber (PALF) using a complex initiating
system: Cu (II) SO4 / histidine / ammonium persulfate (APS) in an aqueous
medium. The overall activation energy (Ea) of grafting was computed to be
21.8 kJ mol'1. The PALF-g-PMMA copolymers so obtained were
characterized by FT-IR, their thermal behaviour by TGA and their
morphology by scanning electron microscopy (SEM). Their tensile strength,
elongation and tenacity were measured. The extent of water absorption by the
grafted PALF showed that grafting of MMA imparts hydrophobicity onto
PALFs. The biodegradation of the copolymers was evaluated in sludge water
and soil and by using cultured microorganisms. Chapter-2 Section-IB: Here
we have concentrated on natural fiber composites, prepared by grafting
hydrophobic monomer, n-butyl acrylate (BA), onto chemically modified
Pineapple Leaf Fiber (PALF) using a complex initiating system: Cu (II) SO4 /
EDTA / ammonium persulfate (APS) in an aqueous medium without and with
additives like sodium silicate, (S.S) and taking N, N-methylenebisacrylamide
(MBA) as crosslinker. The polymerization reaction was studied under varying
temperature, time, and Cu (II), EDTA, APS, BA concentrations. The overall
activation energy (Ea) of grafting was found out to be 19.04 kJ mol'1 and the
optimum time period for the reaction was found to be 3h. The chemically
modified PALF, crosslinked PALF-g-PBA copolymer and (crosslinked
PALF-g-PBA) / S.S. composites so obtained were characterized by FT-IR.
Their morphology was studied by scanning electron microscopy (SEM). Their
thermal behavior and tensile properties were studied and compared along with

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their biodegradation and water absorption capacity. It was found that the
composites showed more water uptake capacity than the copolymers making
them suitable candidates for natural fiber based superabsorbents. These
composite superabsorbents show lower biodegradability in both sludge water
and soil as well as by using cultured microorganisms than the copolymer
alone.
Chapter-2, Section-II: In this part of the work we have taken Jute (Corchorus
capsularis) based natural fiber composites, prepared by a series of experiments
such as pulping, bleaching and grafting with butyl acrylate (BA) together with
a crosslinker, N, N methylene-bis-acrylamide (MBA) and finally embedding
the copolymer with sodium silicate (SS) additive using a complex initiating
system CuS04/histidine/potassium peresulfate (KPS). The (crosslinked jute
pulp-g-PBA)/SS composites so obtained were characterized by FT-IR, TGA
and their morphology by scanning electron microscopy (SEM). The tensile
properties, superabsorbency and biodegradability of the composites in soil and
sludge water were evaluated for their novel commercial importance as jute
based superabsorbents. The water absorption of the grafted composites with
SS was more than 35 times greater than that of the ungrafted fiber. While the
biodegradability of the grafted crosslinked composite with SS was lowered
than the other samples due to dispersed silicate layers in the composite matrix.
Chapter-2, Section-Ill: In this endeavor we have had a rigorous study on
Rice Straw Fiber (RSF), which is a major agro waste in India. The processed
RSF sample is grafted with two different monomers having hydrophilic
[acrylamide (AM)] and hydrophobic [methyl methacryalate (MMA)]
characterstics. A comparative study in change in concentration of monomers
(MMA, AM), initiators (APS), complexing reagents like [Cu (II)], [EDTA],
time, temperature etc was done. The % conversion RSF-g-PMMA is more as
compared to RSF-g-PAM due to hydrophilic nature of PAM. The (crosslinked
RSF pulp-g-PMMA and RSF pulp-g- PMA) composites so obtained were
characterized by FT-IR, TGA and their morphology by scanning electron
microscopy (SEM). The tensile properties, superabsorbency, biodegradability
and dyeing property were evaluated and compared. The water uptake increases
with the increases in the degree of grafting of monomers. This may be due to

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with the increases in the degree of grafting of monomers. This may be due to
the increase of the carbonyl groups in the grafted fiber due to their hydrophilic
properties. This is the reason why there is a comparatively better water uptake
by RSF-g-PAM in comparison to RSF-g-PMMA. It was also noticed that the
colour strength of dyed fabrics increases as the grafting percentage increases
to reach its maximum value and thereafter it levels off or shows a tendency to
decrease. The increase in colour strength of fiber with the increase in graft
yield can thus be attributed to the increase in the >C=0 functional group in the
fiber structure. The leveling off in the colour strength at higher degress of
grafting may be explained by the depletion of the aqueous solution from the
dye through the increasing number of active functional groups associated with
the grafted fiber while the dye concentration is kept constant, thus decreasing
the driving force for the diffusion of the dye into grafted regions.