Formulation of citric acid crosslinked PVA-CS-LNC hybrid film with improved hydrophobic

nature: Influence of ZnO-ABC catalyst on crosslinking reactions

CHAPTER 1 INTRODUCTION
Introduction: Industrial Revolution has radically changed human life to dynamic. Human
demands have been increased beyond to limit. The unprecedented prosperity of science and
technology flourished multidimensional enrichment in human history. Packaging industry also
has become an important part in our lives to store, protect as well as transport of various goods.
In prehistoric time, it has been mainly used to carry something goods. But due to rapid growth of
industrial development, the excessive usage of numerous amounts of non-degradable synthetic
polymer has become an environmental concerning[1]. Moreover, a daily mass disposal of these
packaging films are now a serious global trash. The most common daily used packaging films
are like as plastics, glass, cardboard, aluminum foils etc. In past few decades, it has been seen a
remarkable increase in the use of plastic materials as food packaging film. Now there are several
types of plastics packaging films available in the market [1-2]. Many trading companies are
producing huge number of plastics films which are not coherent for environment. Plastic
packaging films such as plastic bag is a byproduct of petroleum crude oils that remains
unchanged and needs many centuries to decay in natural condition. Now a days, not only in food
packaging aspect but also in the field of medical, mechanical, agriculture that plastic packaging
films is using regularly in an indiscriminate manner. Synthetic plastic polymer molecules form a
strong intertwisted intermolecular bonding force that is not biodegradable at normal conditions.
So, these materials need many decades to take up by environment. Moreover, in this plastic
materials, many harmful elements are existed[1].
Further that, it creates many toxic elements when gets broken down by various influential
factors. Admittedly, the petroleum-based packaging materials cause serious environmental
impacts such as depletion of natural resources, energy crisis, global warming and ecological
problems. At present, the concern ‘white pollution’ caused by plastic waste has become a serious
global tension. Basically, packaging of goods is used to for storing, distributing, retailing,
preserving as well as tempering of the quality of commodities. But these alarming disposal rate
as well as negative impact on ecosystem compelling to think biodegradable and sustainable
packaging technology. Because these non-degrading and nonrenewable source originating
plastics and microplastics also possess hazard element like as pigments, dye, plasticizers,
aromatic compounds that can migrate air-soil-water lives[2]. Moreover, usage of old-fashioned
technology for dumping, burning or landfilling these materials contaminate ecosystem besides
creating serious health risk. At present it is about >2% as gross national product that contributes
packaging industry in developed country. As packaging materials, todays various materials are
introduced according to required features. Suppose glass is popular for its transparency, inertness
where biopolymers (protein, lipid, polysaccharides) are attracted for its safety and ecofriendly
features. On the other hand, PU, PVC, PE etc. petroleum-based polymers hold demand for its
availability and mechanical superiority. Metal oxides are also nowadays catching high appealing

1
due to possessing excellent microbials property. So, many metal and its oxides such as ZnO,
TiO2, Cu, Ag, Au and other nanoparticles are incorporated with packaging materials to enhance
antibacterial characteristics and other required properties. In order to overcome these burden of
‘white pollution’ and making the world free of plastics, most scientists are now getting attracted
on biocompatible and biodegradable natural polymer for researching in the field of food
packaging technology[2-3]. In this case, many naturals polymer such as cellulose, hemicellulose,
starch, polylactide, lignocellulose are top in the choice. However, unlike many of the synthetic
polymers which are non-deteriorated, polyvinyl alcohol(PVA) is less hazard and perfectly
biodegradable both in aerobic and nonaerobic condition. Even it does not break down or shed
into microplastics at any points. So, PVA is frequently used as a typical adhesive, packaging film
or opto-sensorial devices.
Biodegradability process generally involves some important steps that influent the acceleration
of degradation. Biotic and abiotic factors associate in that case. For example, microbial action,
bio-fragmentation, enzymatic degradation, mechanical, chemical, hydrothermal, radiation or
photodegradation maintain for polymer deterioration. Figure1.0; demonstrate the factors that
are basically responsible for polymer degradation and the mechanism of PVA degradation under
hydro and acidic environments[3-4]. PVA, due to unique properties, it is being applied widely as
a food packaging film as well as adhesive materials. However, PVA shows extremely
hydrosoluble. So, it sometimes limits applicability as a packaging film[5].
Hence, many scientists are trying to improve its hydrophobicity nature
through modifying surface activity via incorporating or linking several
es

biodegradable polymer Such as chitosan, lignocellulose, citric acid etc.

ob
ic r
M
Decom

Enzy
posers

s me

N2, S, CO2, CH4….

Biodegradable polymer

ass Organic
Biom elements

Organic
Minerals compou Biodegradati
on
nds

Polymeric Depolymerization
modification

Monomers
Microorganism e rs
(Soil stock) Oligom

2
Assimilation
 Figure-1.0: A workflow of polymer biodegradation

1.1. Material and structure

-Polyvinyl alcohol(PVA): The date of invention of PVA is 1924. Polyvinyl alcohol solution was
first obtained by saponification of polyvinyl ester with caustic soda. According to its preparation,
PVA can be categorized into two groups a). Perfect hydrosoluble b). Partial hydrosoluble.
Unlike many other polymers, PVA is not usually synthesized from its precursor(monomer) rather
from polyvinyl acetate(PVAc) through dissolving into an alcoholic solution and treating with an
alkaline catalyst(NaOH). As a result alcoholysis or hydrolysis reaction removes the acetate group
from the molecules of PVAc keeping unchanged of the structure of long hydrocarbon backbone.
Though it is readily water soluble but in practice, not soluble in all organic solvents practically.

Figure-1.1: (a) Vinyl alcohol and (b) PVA

Whether, the reaction of PVA synthesis is taken perfectly complete, that PVA is readily
hydrosoluble. But incompletion of the removal of acetyl groups makes PVA less hydrosoluble
and more soluble in several organic solvents. Basically the primary condition(initial length) of
PVAc and degree of hydrolysis controls the nature of PVA such as water solubility, flexibility as
well as adeshivity. PVA is a colorless readily hydrosoluble resin that has a wider usage in sizing
paper, textile, packaging, coating fibre, adhesive, synthesis of poly(vinyl butyral) as well as
emulsifier industries[6].

- Chitosan(CS): Chitosan is the second most abundant natural polymer after cellulose. It is
found from the derived of chitin. Chitin is a fibrous compound that obtained from cell wall of
fungi as well as outer skeleton of crustaceans. Chitosan is usually derived by deacetylation of

3
 Chitin. Traditionally, chitosan is synthesized from chitin of crustacean sources followed by
deacetylation reaction. However, due to having some basic advantages, at present it is
popularly produced from fungi at a commercial scale. But in some fungi such as
Mucoraceae, natural occurrence of chitosan is poorly frequent. Chitosan from fungi
demonstrates better control of lower viscosity, high degree of deacetylation. Besides fungi,
cuticles of insects also a good source of extracting chitosan.

Figure-1.2: Structure of Chitosan

More highlightly, the characteristic of chitosan tightly relates with the physicochemical
properties of polymer such as degree of deacetylation, weight of molecules etc.

Chitosan is a biodegradable nontoxic highly fire retardant polysaccharide that contains

varying amounts of (β1→4) linked residues of N-acetyl-2 amino-2-deoxy-D-glucose
(glucosamine, GlcN) and 2-amino-2-deoxy-D-glucose (N-acetyl-glucosamine, GlcNAc)
residues. It is soluble in acidic solution due to having protonated ammino groups. But it
also has acetylated pendants which is not soluble in acidic solutions.
It is only natural polycation which charge density mainly relies on the pH of media and
the degree of acetylation. As usual oligomers of chitosan are soluble in wide rage of basic
or acidic solution but the high molecular weight chitosan is only soluble in some acid and
basic solvent even having higher degree of deacetylation.

Because of excellent physicochemical properties (such as ecofriendly, biocompatible,

biodegradable, bioadhesive etc.) chitosan is used in a broad range areas like as water
treatment, biomedical, pharmaceutical as well as food and cosmetic industries[7].

- Lignocellulose(LNC): Lignocellulose also called word fibre is the first most abundant and
cheapest natural biodegradable polymer that is mainly a mixture of cellulose(40%-50%),
hemicellulose(25%-35%) and lignin(15%-20%). Lignocellulose is a natural biofuel that
mainly contains carbon, hydrogen as well as oxygen atoms which is found from several types
of woods, bamboos, grasses as well as agricultural residues. It is one of the most promising
in the production of eco-sustained biochemicals and biofuel for the utilization of the fields
such as biomedical, pharmaceutical, cosmeceutical, bio energy as well as packaging

4
 industries. In Lignocellulose, cellulose is the major component of that contains β1→1,4-
linked D-glucose units combined each other by glycosidic linkages, van der Waals forces and
hydrogen bonds. Admittedly, it is a hexose sugars which depicts as (C 6H10O5)n where ‘n’
represents number of glucose groups contain in a molecule. The range of the polymerization
degree of cellulose is about to 1510–5500. It is a long-chained polysaccharide commonly
comprises of glucose monomers with an often range of 7000–15,000 units. It is most
accessed renewable organic source that is about to 7.5×1010 tons of annual production in
globally. The cellulose microfibrils is the result of the aggregation of numerous cellulosic
chains with intramolecular hydrogen bonding between oxygen and hydroxyl group of the
adjacent molecules.

Figure-1.3: (a) structure of cellulose and (b) hemicellulose

Hemicellulose is the second major component of lignocellulose. In hemicellulose, the main chain
contains various pentose and hexose (C5 and C6) sugars like as glucose, galactose, mannose
arabinose or xylose and sugar acids(e.g. galacturonic acid glucuronic acid). Hemicellulose is
comparatively more degradable in acidic or basic solutions than cellulose due to possessing
lower polymerization’s degree as well as amorphous nature[8].
Lignin is the 3rd major compound in lignocellulose that mainly contains coniferyl alcohol(G), p-
coumaryl alcohol(H) as well as sinapyl alcohol(S) which are non-linearly and randomly
combined by ester bond with each others . Lignin is basically obtained by polymerization of
these alcohols. In the cell wall of various plants; cellulose, hemicellulose and lignin combinedly
form a microfibril structure for structural reinforcement and it is embedded in cellulose and
hemicellulose stake through hydrogen bond as well as Ven dar Walls force.

5
 Figure-1.4: Structure of lignin

The amount of the compositions of lignin usually varies with variation of lignocellulosic
biomass. For example methoxyl components are the major compounds in hardwood
lignin due to containing guaiacyl and syringyl units. Contrarily, guaiacyl units (almost
90wt%) are usually found in the softwood lignin.
In lignin, phenolic compounds generally bind with phenyl propane molecules that linked as C-C
and C-O-O connection and creating brunched macromolecules. Highly weighted
molecules are basically due to high degree of crosslink, highly brunched nature of the
compounds in lignin. However, normally molecular weight of lignin depends on several
internal and external influencing factor(e.g. separation and purification method,
biochemical compositions, inherent natures. The calorific value of lignin is about to
23.3–25.6 MJ/kg which is almost 30% greater than cellulose and hemicellulose
combinedly. Due to higher degree of oxidative value of both cellulose and hemicellulose
than lignin, so lignin processes higher energy density and calorific value[8].

- Citric Acid Crosslinker(CA): Citric acid is a weak organic acid. It is a crystalline, odorless
and colorless compound that molecular formula is C 6H8O7. Citric acid is an ecofriendly
natural organic compound that found in many fruits, leaves even in food from soft drinks to
canned stuffs. It contains three carboxyl groups and one hydroxyl group in the molecule.

Figure-1.4: Structure of citric acid crosslinker

Citric acid is considered as good solubility, low toxicity, strong chelating ability which is
widely used in the food processing purposes as an antioxidant, souring agent, buffer and
6
 so on[9]. It has also popular usage in sea food, frozen fruit, oils, meat, beverages, canning
industry, detergent, fertilizer, preservation, nanomedicine, water purification and so on.
Due to having unique carboxylic structure it is widely used as an efficient crosslinker in
many polymeric compounds. Citric acid is a safe, unexpensive as well as effective
crosslinking agent[10].

- Zinc oxide-Activated Brick Clay (ZnO-ABC) catalyst: After iron, ZnO is the second most
plenty metal oxide int the world[11]. ZnO is a white powder that almost insoluble in water.
On the owing of unique feature (high photochemical stability, wider range of the absorption
of radiation, higher electrochemical coupling coefficient) it is used in diversified fields. It is
less expensive, safe usually applied as a plethora of materials. It has a wider usage such as
glass, ceramic, cement, paints, lubricants, rubber, food, batteries, ointments, pigments,
sealant, adhesive, fire retardant as well as ferrites. ZnO generally found three different
polymorphs. These are Zinc blende, wurtzite and rock salt. In materials science, it is also
categorized as a (II-VI) semiconductor due to possession in 2nd (Zn) and 6 th(O) group in the
periodic tables[12].

As metal oxide, ZnO shows active catalytic activities such as acting both of hydrogenating and
dehydrating agent. It is found that ZnO can act as an oxidative agent of some selective
electrochemical reaction (e.g. water oxidation to H 2O2)[13]. Catalyst functions are basically to
accelerate the reactions by reducing activation energy of the overall reaction’s environment.
Catalysts makes reaction facile through physisorption and chemosorption of reactants onto its
surface that can alter reaction conditions by altering physical configuration of the reactants after
sorption(figure 1.5). Basically, transitional metal and its oxides are widely used as a catalyst for
various chemical reactions. As a dehydrating agent, various series of catalysts are used according
to reaction conditions, selectivity, yield as well as conversion. To catalytically dehydrate
alcoholic compounds, many homogenous or heterogenous catalysts are used. For example,
Gabriel J. B., et al. [14] have applied Niobium based catalyst to dehydrate Xylose to
2-Furfuraldehyde. Many inorganic based catalyst such as Pd(II), Si, Fe(II), Mg, Zn, Al and their
oxide are popular as a dehydrating catalyst. Again, zeolites and some other organic dehydrant
such as Acetonitrile are also used for dehydrating amino or alcoholic compounds [15].
ZnO also known as calamine or zinc white uses as a sunscreen for skin protection that one of a
very unique catalyst which can act both dehydrating and dehydrogenating agent. The catalytic
activity to dehydrogenate alcohol almost simile to alumina which catalytic activity basically
depends on its applicational conditions. It is found better dehydrating catalysicity for secondary
and tertiary alcohol (isobutanol) than n-alcohol above 300 0C at atmospheric pressure[16].

7
 As a catalytic activity brick clay basically red brick clay also found excellent dehydrating
activity for alcoholic compounds. Actually activated brick clay (ABC) shows superior
dehydrating catalytic properties on many selective alcoholic dehydrating reactions[17]. The
major chemical compositions of ABC catalyst often are SiO 2(48.7%), Al2O3(13.7%),
CaO(9.99%), Fe2O3(5.67%), MgO(3.74%), K2O(2.51%)[18]. Madduluri V. R. and
coresearchers[16] have found more superiority of the ABC catalyst then commercial silica
and α-Fe2O3 catalysts for the selective conversion of cyclohexanol to cyclohexene and 1-
phenylethanol to styrene at high temperature(~400 0C). Admittedly, ABC catalyst offers
good synergistic acidic properties as well as a combinatorial Lewis-Bronsted acidic sites[16].
So, over all consideration, in my research I intended to use ZnO as a catalytic promoter of
ABC catalyst.

1.2 Evolution of packaging:

Many raw materials or packaging of products are inevitable in our society. Human needs to
collect, transport or store their goods through packaging with suitable materials. But before
5,000BC the primitive peoples consumed their foods where it is found. So, in that time,
packaging was less necessary. But amid of 5,000BC to 3,500BC packaging system was invented.
The nomadic nature of prehistoric peoples need to collect food, store as well as protect and
carrying of their necessities. Prior to invention of glass packaging materials, primitives usually
used various leaves, animal skins as well as hollowed logs to protects their necessities. The
primitive Mesopotamians and Egyptians are considered to invent glass materials first during a
time zone about 3,500 BC. They have marked the pioneer of industrial glass invention since
1,500BC. As first flexible material, the Chinese are considered of the harbinger of paper which
was made by mulberry bark since 200 BC. More years later, flexible cellulose paper was enabled

8
to extract from several plant’s bark and leave. Nicholas Appert who was the troop of Napoleon
was regarded the first cane inventor to serve food shield to preserve[19-20].
On the other hand, metal was first started to use in the region of Bohemia during 1200AD. They
discovered tin plating techniques on Iron materials during 14 th century. Plastic packaging
materials are regarded first availability during 1800s but after discovered of cellphone since 19 th
century, plastic was began widely used as packaging materials. The prevailing of ‘LEVELs and
TRADEMARKs’ which means information of contents and company is an interesting history. In
1660s, the importers of England were often cheated. Impure and low-grade products were
disguised as solids to uniformed importers. So, they became unhappy for frequent deception with
them. And then began to mark their wares as “Let the buyer beware” to alert potential customers.
After decades of remarkable development, the industry of packaging film is now seeking to back
to primitive pattern where sustainable glass materials were used as packaging of various
goods[19-20].

1.3 Mechanism of the degradation of polymeric film:

In broad sense, degradation means the reducing or losing of original properties of polymer.
When polymer is exposed to environment it gets affected by various environmental influencers
which results a gradual reducing of polymeric materials. Polymer degradation is considerably a
complex process. But it always associates some unwanted impacts besides certain affirmative
sequels. Degradation of polymeric materials delivers various environmental hazards by exposing
toxic elements which pollutes air, soil and water life. On the other hand, controlled deterioration
of polymer is some kinds blessing which offers a clean recyclable and reprocessable as well as
natural decomposable of polymeric wastages. Actually, polymer degradation is the cleaving of
macromolecules into micromolecules (monomers or oligomers) via fragmenting at different
places of polymeric chains of macromolecules creating various size and structures. Polymeric
degradation may either reversible or irreversible. It can occur by various influences such as
mechanochemical, chemical, biological etc. Figure 3.0 shows below a brief figure of polymeric

Monomer

polymer
Depolymerization process
Oligomer (Reversible)
Thermal, chemical,
(Irreversible)
mechanical, enzyme, hv,
photon

9
 Degraded elements

Figure 3.0 Polymer degradation via several environmental influencers

degradation through various environmental influencers when exposed to workload.

- Mechanochemical degradation: It is an irreversible polymer degrading phenomena that
polymer undergoes degradation via physical stress. This degradation happens due to applying
higher mechanical load against polymer which can occur elongation deformation, shearing
deformation or breakdown of polymer. If any polymer deforms under mechanical stress that
have cleavage several chemical bonds of the compounds of this polymer. For instant, one
may break a cellulosic material, it means he actually breaks several chemical bonds of the
main chemical networks of cellulosic material. In many cases, the mechanochemically
breakdown linear polymer can fragment into several radical components through
intramolecular interactions. These polymers supposed to great loss of polymeric
viscosity[21]. When a polymeric macromolecule supposed to treat mechanochemical
deformation, its process basically involves three basic steps-
i. Undergo of original structural chains of polymer
ii. Breakdown of chemical bonds of the main valence chains
iii. Reorientation and reorganization of the broken chain of the molecules
This scenario is usually seen into long channid molecules. The event of fragmentation,
reorientation of fragmented molecular structure actually rely on the individual chemical bonds,
ions exchange tendency as well as electrochemical bonding ability of the next door bonds of
defected molecule. A perfect example of mechanochemical degradation could be cellulose
structural deformation

10
 i

ii

iii

Figure 3.1 Mechanochemical degradation of cellulose fibre(i. first step structural distress of main fibre ii. Separation
of polymeric structure iii. Breakdown and reorganization of fragmented elements of cellulose polymer

(Figure 3.1) where due to mechanical shearing force cellulose fibre undergoes deformation
physically. Afterword it is separated into single fibre. Gradually the cellulose polymer getting
deteriorate and fragmented in to two or more lower molecules and reorganization occurred
individually to make stable physically and chemically[21-22].

- Thermal degradation: As necessity of plastic packaging materials are increasing in the

modern day, so it is also simultaneously important to understand thermal behavioral
characteristics of polymers why may help to make people conscious about indiscriminate
outdoor disposal of plastic packaging materials. Thermal degradation is a heat induced
phenomena where temperature changes the conformity of structural or chemical behaviors of
the polymers. That means polymers undergo to changes it physical or chemical structure of
the molecular compounds and thereby a deterioration of polymer. To understand actual
phenomena during thermal degradation of polymers, several thermographic techniques such
as differential scanning calorimetry(DSC), thermogravimetry(TG), NMR, FTIR are now
available to access their transthermal properties. Investigating a large series of polymers by
many researchers at different times propose some essential phenomena during thermal

11
 degradation. Polymers such as polythene(PE), Polystyrene(PS), polyurethane(PU), polyvinyl
acetate(PVAs), polypropylene(PP) or polyvinyl alcohol(PVA) and so on that associate two
distinctive microscopic reaction mechanism which may occurs simultaneously during
thermal deterioration-
i. A random scission of bonded chains of polymer that occurs a weight loss of reduced
polymers
ii. β scission or chain end cleavage of C-C bonds whether volatile compounds are
basically generated.
It is explained[21] that the thermal cleavage which starts at backbone of the polymer usually
seen to get volatized compound with higher temperature. But if a cleavage starts between
backbone and side branch promotes to form crosslink or unsaturated bonds in the polymeric
chains. And the highly crosslinked polymeric compounds tend to form honeycomb like figure
during heat transformation.
Any thermal degradation, it involves three basic steps (Initiation of reaction, propagation of
reaction and termination of reaction[21]. For example- cellulose thermally degrades and
combusts upon 200-300 oC (figure-3.2).

Figure 3.2 a schematic figure of basic three steps of thermal degradation of polymer

In thermal degradation, polymer when undergoes to expose of heat start to segmenting by

producing many free radicals. The free radicals production is keeping on going thorough whole
the polymeric chains. Afterword, these free radicals terminate itself by interacting among each
others to produces lower chained molecules. But when temperature reaches above its boiling
point, the polymer starts to getting combustion producing CO 2, H2O, CO as well as many other
groups and free radicals too[21].

12
- Chemical degradation:The synthesis polymers which are non-biodegradable are the major
hazard on environment. It remains unchanged long decade and, in many cases, produce
various toxic elements by interacting with several environmental influencers. Chemically
alteration or degradation is basically fragmenting of big polymeric molecules into its
precursors such as monomers or oligomers. Chemically degrading process basically seen to
induced by four common types chemical degradation processes (adidolysis, alcoholysis,
aminolysis, hydrolysis as well as glycolysis). But for the environmentally friendly
management of these non-degradable synthetic polymer, either recycling or increase of the
use of ecofriendly polymer is the potential solution. Alcoholysis is one of the chemical
method to degrade and recycle of the polymer adding alcoholic element to the polymer for
chemically conversion in to monomer or oligomer which is similar to hydrolysis or
acidolysis process[23]. But in many conditions alcoholysis and acidolysis is faster than
hydrolysis degradation. Literally, hydrolysis is to split water by reacting with polymer. In the
time of hydrolysis the bonds onto the monomers of the polymer break down in presence of
water molecules. Again in acidiolysis degradation, acid dissociates to hydronium ion in
presence of moister in the cellulose polymer which breaks the β-1,4 glycosidic bonds to form
glucose monomer(figure-3.3). Then this monomer degrades to
hydroxymethylfurfural(Furan), formic acid or levulinic acid and other acidic compounds[23].

Figure-3.3 A graphical scheme of acidiolysis degradation of cellulose

13
The cleavage of β-1,4 glycosidic bond occurs very random manner in acidic solution. Actually
degradation which develop rapidly with the ability of chemical modification of cellulose with
reducing groups[24]. But it is found that in 40% hydrochloric acid solution, cellulose gets
fragmented first into oligosaccharides at 30 0C which produce glucose molecules after successive
dehydrolyzation[24].

- Microbial enzymatic degradation: The negative impact of petroplastic on environment first

described in early 1970[25]. In spite of various growing activities of reducing plastic waste
disposal into environment, plastic waste discharge is till a sizeable concern. Although various
efforts such as recovery of energy from plastic(incineration), recycling and so on are now a
regular basis of plastic reduction but it is still about 60% are remained into environment as a
domestic plastic waste where around 95% is landfills dispose and 5% is as a terrestrial and
ocean dispose[25]. Basis of degradation technique, petroplastic can be two kinds such as
carbatomic backbone(homogenous carbon backbone)(CAB) as well as heteroatomic
backbone (N, S, P, O,C) (HAB)petroplastic(PVC, PP, PS and PE). As a recycling pathway,
microbial enzyme degradation is one of the effective way to convert polymer into light
weight monomers. Basically, enzymatic base degradation of polymer can be comprised into
three steps- i. selective enzyme are adsorbed on the surface of polymer ii. Hydrolysis/hydro-
peroxidation takes place as well as ii. Release of light weights fragmented compounds[25].
Microorganisms can secrete enzyme to degrade polymer. Even biomaterials which are used
in biomedical purposes would be degraded via hydrolysis or oxidation with contacting body
tissue and fluids by enzyme secretions. Suppose oxidative enzymes such as catalase,
horseradish peroxidase as well as xanthine oxidase are responsible to occur enzymatic
degradation of polyurethane(PU)[26]. Now natural polymers such as cellulose, starch,
chitosan, chitin, alginate etc. are widely using in packaging purpose due to having intrinsic
characteristics. For example, chitosan which is obtained from chitin by alkaline deacetylation
process that undergoes hydrolysis through chitosanase and lysozyme like glycosidases
enzymes. The main compounds of chitosan are o-glucosamine (GlcN) and N-
acetyloglucosamine (GlcNAc). Whether cellulolytic enzymes (hydrolases) of cellulose
mostly categorized into three types[26]-
- For random cleavage of cellulose chain endo-1,4-β -glucanases is responsible
- For reducing and nonreducing cleavage of cellulose ( end of the polymeric chain) exo-
1,4-β-glucanases is responsible
- For the conversion of cellobiose to glucose β-glucosidases catalase is responsible which
main product is a mixture of endo- and exo-glucanase
On the contrary, there are about 90 types microorganisms comprising fungi and bacteria that can
decompose petroplastic such as PVA, PE[25]. PVA contains likely C-C bonds to PE but more
hydrophilic than PE due to containing many hydrophilic hydroxyl functional groups.
Pseudomonas sp. is more efficient to degrade PVA. Pseudomonas sp. can secrete oxidase and
hydrogenase enzymes to degrade PVA( figure-3.4). Not only Pseudomonas sp. but many other
bacteria such as Sphingopyxis sp., Alcaligenes sp. are capable to degrade PVA with their
extracellulose oxidase and dehydrogenase enzymes involving subsequent hydrolase and aldolase
reaction.
14
Figure-3.4 A schematic diagram of possible pathways of PVA degradation via microbial enzymatic
action[27]

The depolymerization of PVA occurs due to a cleave by oxidase or hydrogenase whether

compounds like acetic acid and hydroxyl fatty acids are produced through further cleaving by
hydrolase or aldolase reactions[27].

- Photochemical degradation: Photochemical degradation occurs by the adsorption of

photon form light. It is basically induced through adsorbing UV radiation via carbonyl
groups on the backbone or photo sensitive bonds of the atoms in the polymer. Polymer
when exposes in outdoor under high temperature it gradually losses service life which is
defined as weathering of polymer. Such as exposing under higher temperature, UV light
many synthetic and natural polymers like dyes, pigments, skin that lose its gloss, burnt,
weaken of mechanical durability, yellowing, weathering as well as cracking[28-29].
Yousif E., et al.[28] stated the main reasons that responsible for photochemical
degradation. According to them two main kinds are associated for photochemical
degradation of polymers-
i. Exo-impurities
- Additives, pollutant of foreign particles, trace of catalyst, metals, metal oxides as well as
solvent

15
ii. Endo-impurities
- Carbonyl groups, hydroperoxides, incoherent hybridized and unsaturation of chemical
bonds, transfer of charge, residue of catalyst
Photochemical reaction can take place in the present of oxygen (photooxidation) as well as
absent of oxygen such as crosslinking or breaking of chains. The mechanism of
photochemical reaction is basically stated by Norrish’s reaction (I & II). First photoinduced
ionization of polymer and transformation(Norrish’s reaction-I) and later Scission of the
polymeric chain (Norrish’s reaction-II)[29]. A Norrish’s photochemical degradation of poly
lactic acid(PLA) are demonstrated (figure-3.5) below-

16
 Figure-3.4(ii) Mechanism of UV light induced photochemical degradation of poly-L-lactide (PLLA)

In Norrish’s reaction-II, the main chain scission of polymer decreases the molecular weight
and chain length of the fragmented polymer. Geuskens G.[30] demonstrated the
mathematical model to count the average scission number of particular chain. Suppose, if
average number of initial molecular weight of a chain is M nW° and Mnw is the average number
of molecular weight of polymeric chain after scission by photoradiation then average number
of scission produced per chain-

N = ¿/ M wn ¿ – 1

Again, after cleaving randomly the relationship between average number of molecular
weight and viscosity of average molecular weight still a proportional. So, if initial viscosity
of average molecular weight is M °V and after scission that is Mv then it is described as-

N= ¿/Mv) -1
Afterwards, intrinsic viscosity of polymer ,µ is directly proportional to the power of average
viscosity Mv. So, it can be stated as follows-

[µ]= K M αv
[µ ° ]
Or, N= { }−1
[ µ]

Then we get quantum yield, [ðs] of the main chain scission,

[ðs] = N/ M wn ° r
Where r is the average Einstein’s energy absorbed by per gram of polymer

17
REFERRENCES
1. Nathalie Lucas, Christophe Bienaime, Christian Belloy, et al. Polymer biodegradation:
Mechanisms and estimation techniques [J]. Chemosphere, 2008,73:429-442
2. Iftikhar Ahmed Channa, Jaweria Ashfaq, Sadaf Jamal Gilani, et al. Sustainable and Eco-
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