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Synthesis of Bio Based Polymers and Its Applications

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 Review Article
THE INTERNATIONAL JOURNAL OF GLOBAL SCIENCES
(TIJOGS) ISSN Online: 2663-015X
Vol. 2(4) Oct-Dec. 165-184; 2019
http://www.rndjournls.com

Synthesis of Bio Based Polymers and Its Applications

Muhammad Tahir Khalil1, Ishrat Fatima2, Faheem Abbas3, Muhammad Usman Tahir3
1
New campus chemistry laboratory center, Zhengzhou university 203 College of Chemistry & Molecular Engineering,
Zhengzhou University No.100 science Avenue Zhengzhou 450001, Henan, P.R, China
2
Department of physics, Islamia University Bahawalpur
3
Department of chemistry, university of Agriculture Faisalabad, Pakistan
*
Corresponding author’s email: honestchemist786@gmail.com
_________________________________________________________________________________________________
Abstract
Biological based polymers are defined as polymers made from biological source. Some of these polymers are formed
directly as polymers in the producing organism such as micro-organism, plants or algae while others are made by ex vivo
from biological-based monomers. The simplest starch-based polymers, cellulose, are known and extensively used for
centuries. However the use of these novel compounds was limited to a few applications such as packing, textiles, and
construction. In recent years, advanced in chemical processing and biotechnology have led to allow the production of
new biological-based polymers like polyhydroxyalkanoate and polylactic acid that have attracted the attention from
many industrial players. Many people felt that these new bio-based polymers could potential to replace petroleum based
polymers and help to solve some of the most urgent problems caused by the excessive use of the petroleum based
polymers like water and soil pollution, harmful influence to human health, and excessive on oil. However others believe
that biologically based polymers deficiencies, both in the economic and technically, prevents their rapid adoption in the
near future.
_________________________________________________________________________________________________
1 Introduction
A chemical compound that is made up of small molecules which are arranged in a simple repeating structure to form a
large molecule is called polymer (Lopez and Villisca, 2012). Polymers are large class of materials consists of many small
molecules called monomers that can be linked together to form long chain thus they are known as macromolecules. A
typical polymer may be includes tens of thousands of monomers, because large size polymers are classified
macromolecules. Humans have taken many advantages of the usefulness of polymers in the form of oils, tars, resin and
gums. However it was not pending the industrial revolution that the modern polymer industry begins to develop. In the
late 1830s Charles Goodyear succeeded to produce a useful form of natural rubber through a process known as
"Vulcanization."
“Vulcanization” is a chemical process for converting natural rubber or related polymers into more durable materials via
the addition of sulfur. Celluloid a hard plastic formed from nitrocellulose was effectively commercialized. In spite of these
advance movement in polymer science was measured awaiting the 1930s.
1.1 Structures of polymers
The introduction of these radical materials began a fit in polymer research that is still going on today. Some polymers are
different in verity of their properties, such as cotton, wool and rubber (Morale and Pulido, 2011). Natural and synthetic
polymers can be produced with a large range of hardness, strength, heat resistance, density, and even price. With
continued research into the science and applications of polymers, they are playing an ever increasing role in society the
following sections provide an introduction to the science of macromolecules.
1.2 Primary structure
Primary structure is the sequence of monogenic residues in the covalently linked biopolymer. This arrangement is linear
for nucleic acids and proteins, but may be branched in polysaccharides
1.3 Secondary structure
Secondary structure is the local regular structure of a macromolecule or a specific region of the molecule these are helical,
pleated and coil structures.

1.4 Tertiary structure

Tertiary structure describes the global three-dimensional fold or topology of the macromolecule, relating the positions
of each atom and residue in three dimensional spaces.
1.5 Quaternary structure
Quaternary structure is the special arrangement of multiple distinct polymeric chains subunits that form a functional
complex refers to the association of one class of bio-macromolecules with another class of bio-macro molecule to form
complexes of cellular components such As his tone (DNA-protein), ribosome (RNA-protein) and Glycol protein
oligosaccharide protein (Thompson and swan, 2009

Fig. 1 Structure of polymers

Polyvinyl chloride is a plastic of which the properties can be adjusted by means of additives such as plasticizers. PVC
without or with very little amount of plasticizer is a hard material. Drain pipes, sewage pipes and synthetic window frames
are made of PVC. The fact that PVC is extremely sustainable has been proven in present PVC frames last over 40 years,
and sewage pipes around 100 years. Plasticized PVC can contain up to 60% of plasticizer and be made so flexible that it
can be used for e.g. rainproof clothing. Familiar products that are made from plasticized PVC include vinyl flooring,
electricity cables and shower curtains. The main application market for PVC nowadays is the construction of sector.
Although PVC has a negative image it receives high scores in environmental impact studies due to low energy
consumption in the production process and its very long natural life. Increasing the sustainability of renewable PVC
involves both the polymer PVC and plasticizers. In bio based polymer rubbers are elastic material that adapt under the
pressure before returning to their original dimensions or geometric shape. This elastic behavior is caused by the long
polymer chains that are cross-linked, making deformations reversible (Tabone and Cregg, 2010).
Rubber is elastic at normal application temperatures and becomes hard at lower temperatures. The global production of
rubber is approximately 22,000 ton per year of which around one-third is natural rubber. Natural rubber such as poly
isoprene is mainly produced in South East Asia and is a polymerization product of cis-1,4-isoprene. Although poly isoprene
can also be produced synthetically, natural rubber has maintained a substantial market share as a result of the
dependence on latex from the heave tree as the only source of natural rubber, bio based processes for the synthetic
rubbers poly isoprene, poly isobutene and poly butadiene. Polyesters are polymers in which the monomers are connected
via an ester linkage they can be produced via poly condensation of a di acid and a di alcohol, hydroxyl acid, or via ring-
opening polymerization of lactones this chapter provides further information on the building blocks for polyesters.
Polymers are also good components for bio based blends with other polymers like poly (lactic acid. These are underlined
by a recently announced collaboration between nature works and bio amber. In a joint venture called amber works. The
companies will work together on the production of bio-based PLA and PBS blends. Metabolic recently sold a license to
Nature Works for the production and sale of PLA and PBS blends. Bio amber foresees a rapidly growing market with PBS
composites.
Biopolymers come in many different forms that they can be derived from renewable resources and may not be defined
within the traditional plastics classification numbering system like polylactic acid or they can be partially made from
renewable and synthesized like traditional plastics as in the case of bio-based PET. Biopolymers offer a renewable
alternative to traditional petroleum-based plastics and can be derived from a wide variety of feedstock’s including
agricultural products such as corn or soybeans and from alternative sources like algae or food waste. Biopolymers can
replace petroleum-based polymers in nearly every function from packaging and single use to durable products
Biopolymers are being designed with features such as biodegradability and compost ability (Miller and Landis, 2007).
Bio-polymers offer the opportunity to reduce fossil resources required to produce the 21 million tons of plastic annually
consumed for packaging and nondurable goods, as well as divert the 16.7 million tons of plastic Waste entering landfills.
However, being derived from renewable resources does not guarantee that biopolymers will perform favorably when
compared to petroleum-based polymers and as such as sustainability assessments like life cycle assessment are
conducted to compare and improve the environmental impacts of biopolymers. This review presents a broad summary
of the current status of environmental impact assessments for biopolymers. We begin with an overview of biopolymers
and an introduction to life cycle assessment. Then we review the output data from the commonly used life cycle inventory
database, convent, and impact assessment tool. We review and analyze the findings of life cycle assessment studies on
biopolymers that have been published within the peer reviewed literature. The studies reviewed in this paper focused
on the life cycle assessment results of PLA, PHA, and thermoplastic starch. These are the biopolymers currently
represented in life cycle literature. The publicly available data and life cycle assessment results were not available at the
time of this review The applications of PLA include clear and opaque rigid plastics for packaging, disposable goods,
durable goods, and bottles, as well as films and fibers for a variety of purposes (Philip and Keshavarz, 2010 ). PLA is made
from lactic acid, which is produced through the fermentation of dextrose typically sourced from corn. However any
starch-rich Feed stock could be used. Lactic acid can be polymerized in a number of different ways to create granules that
are used to make commercial products. PLA can be blended with petroleum based polymers or fibers, either synthetic or
natural, to improve the heat resistance or durability of the plastic. PLA-based plastics can be biodegradable and
compostable and features that offer a wider Variety of options for disposal. PHA had a short history of use in packaging
and bottles but is not widely used in these applications today. PHA is increasingly being used in more niche applications
in a variety of industries from medicine to agriculture. PHA is produced through the bacterial fermentation of renewable
feed stocks containing monomers such as glucose, sucrose, and vegetable oil, resulting in the formation of the polymer
similar to PLA and PHA can also be combined with other materials to form composites with improved properties PHA is
also biodegradable and can be used to create compostable plastics another biopolymer included in the studies reviewed
herein is TPS it is created using the starch polymers from renewable sources, primarily corn, which is then processed and
combined with additives and formed into shape. TPS is generally incorporated into composites with synthetic polymers
to create materials appropriate for the market. These materials can be used in making films, rigid materials, such as plates
and cutlery, packaging, and foams, and, depending upon the constituents may be biodegradable and compostable
(Shiramizu and Toste, 2011). Current research efforts are focused on creating new TPS based composites by incorporating
fibers or nano-materials to improve or completely change the characteristics of starch products. Two other important
plant-based materials in the polymer industry are bio-based 1; 3-propanediol and bio-based polyethylene terephthalate
however these polymers are not well represented in the LCA literature and thus were not included in the subsequent
review. PDO is made through biological fermentation processes in conjunction with petroleum products to create
materials comparable with nylon. The primary biological feedstock used in the fermentation process is corn grain, which
makes up 37% of the Polymer by weight. The remaining content is derived from fossil based products. Current
applications of polymers made with PDO include carpeting, apparel, and films, which are reported to outperform
traditional petroleum-based materials (Fang and Liu, 2012).
2 Synthesis of bio based polymer
The study of polymer science begins with category the methods in which these materials are synthesized. Polymer
synthesis is a compound system and can take place in a selection of ways. Addition polymerizations describe the method
where monomers are added one by one to an active site on the growing chain. Addition Polymerization The most
common type of addition polymerization is free radical polymerization. A free radical is simply a molecule with an
unpaired electron. The tendency for this free radical to gain an additional electron in order to form a pair makes it highly
reactive so that it breaks the bond on another molecule by stealing an electron left that molecule with an unpaired
election which is another free radical.

Fig. 2 1, 3 Propanediol to n-polymer

Free radicals are often created by the division of a molecule known as an initiator into two fragments along a single bond
the stability of a radical refers to the molecules tendency to react with other compounds an unstable radical will readily
combine with many different molecules. However a stable radical will not easily interact with other chemical substance.
The stability of free radicals can vary widely depending on the properties of the molecule. In free radical polymerization
the radical attacks one monomer and the electron migrates to another art of the molecule. This newly formed radical
attacks another monomer and the process is repeated. Thus the active center moves down the chain as the
polymerization occurs. There are three significant reactions that take place in addition of polymerization:
 Initiation (birth)
 Propagation (growth)
 Termination (death)
These separate steps are explained below initiation reaction, the first step in producing polymers by free radical
polymerization is initiation this step begins when an initiator decomposes into free radicals in the presence of monomers
the instability of carbon-carbon double bonds in the monomer makes them susceptible to reaction with the unpaired
electrons in the radical. In this reaction the active center of the radical "grabs" one of the electrons from the double bond
of the monomer leaving an unpaired electron to appear as a new active center at the end of the chain. Addition can occur
at either end of the monomer in a typical synthesis between 60% and 100% of the free radicals undergo an initiation
reaction with a monomer the remaining radicals may join with each other or with an impurity instead of with a monomer.
"Self destruction" of free radicals is a major hindrance to the initiation reaction by controlling the monomer to radical
ratio this problem can be reduced. Propagation reaction after a synthesis reaction has been initiated the propagation
reaction takes over in the propagation stage the process of electron transfer and consequent motion of the active center
down the chain proceeds and refers to a chain of connected monomers and X refers to a substituent group a molecular
fragment specific to the monomer. For example, if X were a methyl group, the monomer would be propylene and the
polymer polypropylene in free radical polymerization the entire propagation reaction usually takes place within a fraction
of a second. Thousands of monomers are added to the chain within this time the entire process stops when the
termination reaction occurs. Termination reaction in theory the propagation reaction could continue until the supply of
monomers is exhausted. However this outcome is very unlikely most often the growth of a polymer chain is halted by
the termination reaction termination typically occurs in two ways: combination and disproportionate. Combination
occurs when the polymers growth is stopped by free electrons from two growing chains that join and form a single chain
(Wang et al., 2009).
Disproportionate halts the propagation reaction when a free radical strips a hydrogen atom from an active chain a
carbon-carbon double bond takes the place of the missing hydrogen. Termination by disproportionate can also occur
when the radical reacts with an impurity that is why it is so important that polymerization be carried out under very clean
conditions. Living polymerization exists as a type of addition polymerization that does not undergo a termination reaction
this called "living polymerization" continues until the monomer supply has been exhausted when this happen the free
radicals become less active due to interactions with solvent molecules (Bhardwaj and Kundu, 2012).
If more monomers are added to the solution, the polymerization will resume uniform molecular weights low poly-
disparity is characteristic of living polymerization because the supply of monomers is controlled, the chain length can be
manipulated to serve the needs of a specific application this assumes that the Initiator is 100% efficient. Statistical
analysis of polymers when dealing with millions of molecules in a tiny droplet, statistical methods must be employed to
make generalizations about the characteristics of the polymer. It can be assumed in polymer synthesis, each chain reacts
independently (Balamurugan and Sundarrajan, 2011).

Fig. 3 Natural types of bio based polymers

Therefore, the bulk polymer is characterized by a wide distribution of molecular weights and chain lengths the degree of
polymerization refers to the number of repeat units in the chain, and gives a measure of molecular weight. Many
important properties of the final result are determined primarily from the distribution of lengths and the degree of
polymerization in order to characterize the distribution of polymer lengths in a sample two parameters are defined:
Number average and weight average molecular weight the number average is just the sum of individual molecular
weights divided by the number of polymers (Suganya et al., 2014). The weight average is proportional to the square
of the molecular weight therefore the weight average is always larger than the number average the following graph
shows a typical distribution of polymers including the weight and number average molecular weights. The molecular
weight of a polymer can also be represented by the viscosity average molecular weight this form of the molecular weight
is found as a function of the viscosity of the polymer in solution viscosity determines the rate at which the solution flows
the slower a solution moves, the more viscous it is said to be and the polymer molecular weight influences the viscosity
(Wang et al., 2009).
3 Classification of bio based polymers
3.1 Bio based monomers
Instead of developing in new biotechnology routes to biopolymers with rather tedious polymer purification and difficult
tuning of processing properties, biotechnology and bio-refinery processes are employed to supply renewable monomers,
which are polymerized in highly effective conventional melt- or gas-phase polymerization processes. Compared to
polymers, monomers are much easier to purify. Moreover, the resulting bio-based polymers combine the advantages of
a low carbon footprint, typical for renewable feed stocks, with the recycling capability and high resource- and energy-
effectiveness of solvent-free melt-, and gas-phase polymerization processes (john and Anandjiwala, 2008).
Bio feed stocks such as agricultural and forestry wastes are used preferentially to order to avoid conflicts with food
production. Fermentation of glucose, obtained from lignocelluloses and starch, can be used to produce a great variety of
bio-based monomers. Selected examples are listed For example; bio ethanol is readily converted into ethylene,
propylene, and also butadiene that can be used to synthesize bio-based polyolefin’s and butadiene rubber (Inomata,
2010).
Bio based monomers are also available are diol, polyols, di-acids, hydroxyl alkanoic acids, amino alkanoic acids, and di-
amines that can be used in melt poly condensation reactions to produce bio-based polyesters, polyamides,
polycarbonates, as well as thermo set resins such as unsaturated polyesters and air-drying finishes. Starting from glucose,
it is possible to obtain sorption, isosorbide, and also a large variety of furans, most of which are not natural products.
Furan derivatives offer attractive opportunities for preparing bio-based thermo set and thermoplastic resins from furfural
alcohol, furfural aldehyde, hydroxyl methyl furfural aldehyde, and 2-5 furan di-carboxylic acids (Tokiwa et al., 2009). Side-
products of bio fuel production, such as glycerol, are also attractive bio resources for producing bio-based monomers
such as acrylic acids, epichlorohydrin, 1,3propanediol, and acrogenic. Selected examples for the production of bio-based
polymers are presented below. In 1997, Cargill and Dow formed a joint venture aiming at converting PLA into a
commodity plastic. The poly lactic acid monomer was produced by fermentation of dextrose from forage maize or other
plant sources for sugar without requiring genetically modified plants. In a separate step subsequent to fermentation,
lactide was formed and polymerized by ring-opening polymerization to produce PLA, which was globally marketed in
2003 by the newly formed company Nature Works under the trade name NGO. In contrast to the one-step biotechnology
route to PLA, the lactide ring-opening polymerization in the melt phase enables facile tuning of the PLA molecular
architectures to substantially improve PLA melt processing and property profiles. Incorporation of small amounts of the
D-isomer led to self-nucleation and very fast PLA crystallization during rapid cooling in injection-molding applications.
Long chain branching enable melt strengthening during foaming and extrusion coating. In 2009, Nature Works
established an annual nameplate production capacity of 140 000 tons of biopolymer. Going well beyond the scope of
biodegradable plastics, PLA applications include packaging, durable plastics, and fibers. Similar to paper, PLA does not
degrade in landfills. NIR probes can be used to detect PLA wastes so that they can be separated from plastics recycling
stream (Cooper et al., 2013).

Poly lactic acid from bacteria and by melt polymerization of lactide, prepared from bio–based lactic acid. In 2011, the
world's largest beverage company Coca-Cola Co. announced a partnership with three biotechnology companies with the
aim of producing plastic bottles made from 100% bio-based materials in 2009, the first generation of Plant Bottle was
introduced as the first recyclable PET bottle using up to 30% bio-based monomers. Bio-based ethylene glycol and recycled
PET are employed in PET production. In the new generation of 100% bio-based Plant Bottle the teri-phthalic acid will also
be bio-based at Variant and Gevo teri-phthalic acid is produced using bio-based p-xylene as an intermediate. This route
does not interfere with established PET recycling. At the Dutch company Avantium, R&D focuses on the development of
bio-based polyethylene furan ate (PEF) using bio-based ethylene glycol and furan di-carboxylic acid as monomers.
 Fig. 4 Plant based bottle process

3.2 Bio polymer

The rise of low cost synthetic polymers with far superior properties produced in highly energy a resource-efficient
polymerization processes, accounted for the declining use of the less competitive natural polymers which amount to less
than 1% of today's plastics production of 300 million tons per year (Son and Yeom, 2009). At the beginning of the 21st
Century, we are experiencing a renaissance of renewable polymers and a major thrust towards the development of bio-
based macromolecular materials. Is the future of plastics going to be green? There are several reasons for this paradigm
shift and for the envisioned transition from petro chemistry to bio economy. From the economic point of view, after
crossing the oil production peak, the dwindling oil supply is likely to further boost the oil price, especially in view of the
expected surge in worldwide energy demand. This could drastically impact the cost-effectiveness and competiveness of
plastics (Mather and Wardman, 2011).
When shifting of chemical raw material production to renewable resources or coal could safeguard plastics and
production against this expected new future oil crisis hence, another even more important reason is the growing concerns
of consumers regarding global warming resulting in a surging demand for sustainable and “green” products. Today the
world is facing mounting global crises, ranging from global financial market distress to extreme climate-induced weather
events and skyrocketing costs for energy. At present, the world population exceeds 7 billion people and is projected to
reach 9 billion people by 2050. People living in developing countries aspire to the living standards of the Western world
and claim their rightful part of the world's resources and plastics production. The resulting drastically increasing hunger
for energy, which is currently satisfied by consuming fossil fuels, will undoubtedly further increase emissions of the
greenhouse gases, water vapor, methane, and carbon dioxide.
 Fig. 5 Global warming on the basis of bio polymer
The limits of growth, as already pointed out by the club of Rome in 1972, are clearly visible at the horizon of our economy.
Continued reckless depletion of natural resources and progressive global warming could trigger a sudden collapse of the
biosphere. In excited visions, the path forward towards bio fuels and biomaterials based upon biomass utilization, genetic
engineering, and biotechnology is seen as the Holy Grail in a bright future. The UN Earth summit 2012 in Rio de Janeiro
endorsed the concept of building a prosperous and strong “greenish” world economy within the context of sustainable
development. The prime objective of sustainable development, as stated by the Brundtland Commission of the UN
General Assembly in 1987, “implies meeting the needs of the present without compromising the ability of future
generations to meet their own needs.” In European forestry, the concept of enabling a sustainable balance between
wood consumption and wood production for safeguarding the sustainable economic success of the forestry business has
a long tradition, dating back to the middle ages. Natural resources such as oil, gas, potable water, clean air, fertile soil,
rare metals, minerals, wood, and biodiversity are essential for human survival and for keeping the global economy
functioning .In green economy it is imperative to reduce the demand for resources and energy, minimize wastes, prevent
environmental pollution and hazards, reduce greenhouse gas emissions, optimize manufacturing processes, and establish
effective recycling of wastes. These elements are an integral part of sustainable chemistry which is also referred to as
green chemistry a term coined in the 1990s. Important green principles of polymer production address the following
issues
 High resource effectiveness and high atom economy, maximizing the content of raw materials in the product.
 Clean and lean production processes, preventing wastes and reducing greenhouse gas emissions.
 High safety standards.
 No use of auxiliary substances such as organic solvents, blocking groups etc.
 High energy efficiency of materials' manufacturing and applications.
 No health and environmental hazards by minimizing toxicity.
 Use of renewable resources and renewable energy.
 Low carbon footprint.
 Controlled product lifecycles with effective waste recycling (Saquing et al., 2013).
By this definition “green” is not equal with biomaterials and biotechnology. In fact, many existing polymers and
polymerization processes meet the demands of green chemistry. Prominent examples of successful sustainable materials
are polyolefin’s such as polyethylene and polypropylene, which amount to around half of the global polymer production.
In the 1930’s the first industrial process for making polyethylene required temperatures above 150°C and very high
pressures exceeding 1000 bar. Catalytic olefin polymerization was discovered during the 1950s.This enabled olefin
polymerization at low pressures below 10 bar and at temperatures below 100°C. During the 1980s aftermath of the first
oil crisis in 1973, the energy-efficient catalytic copolymerization of ethylene and 1-olefins for manufacturing linear low-
density polyethylene used in food packaging became a million ton business. Most likely, the marketing efforts by Union
Carbide stand for the first striking example of how the argument of improved energy effectiveness successfully triggered
substantial changes in the market place, with catalytic ethylene copolymerization progressing at the expense of energy-
intensive high-pressure ethylene polymerization (Jeong et al., 2010). In 1954, this tactic polypropylene became available
as a highly versatile hydrocarbon resin with an extraordinarily wide spectrum of applications ranging from automotive
bumpers to baby diapers, textiles, and food packaging. Since then, a chain of breakthroughs in catalyst and process
technology has greatly simplified polyolefin production, drastically enhancing energy- and resource-effectiveness. During
the early 1960s, polypropylene was produced in hydrocarbon slurry. Wasteful and costly purification was required to
recover the solvent and to remove corrosive catalyst residues together with tacky a tactic polypropylene byproduct
wastes that were deposited in a landfill. Today highly active and stereo specific supported catalyst generations polymerize
propylene in solvent-free gas phase and in liquid pool processes without byproduct formation and without the need for
waste disposition. Due to the extremely high catalyst activities, the very small amount of noncorrosive and nontoxic
catalyst residues can be left in the polymer. Moreover, polypropylene granules can be produced in the reactor, thus
eliminating the need for energy-consuming pelletizing melt extrusion (Marques and Renocret, 2010).
Modern olefin polymerization has set new standards for environmentally friendly polymer production. Polymer
properties can be readily tuned as a function of catalyst type and process conditions to meet the demands of specific
applications. Moreover, polypropylene is very effectively recycled either by remolding at temperatures around 230°C or
by facile thermal cleavage of the polypropylene backbone. At temperatures above 400°C, polymer chain scission accounts
for the quantitative recovery of the hydrocarbon feed stocks, which can be reused as a source of “renewable oil” for
producing ethylene monomer or as source of energy. Polyolefin’s meet the demands of sustainable development,
preserving resources for future generations. In terms of their favorable eco-balance, recycling, energy and resource-
effectiveness as well as their attractive cost performance ratio, polyolefin’s outperform all biopolymers and bio-based
plastics. In principle as will be discussed below it is feasible to switch from fossil resources to bio based feed stocks in
polyolefin manufacturing to meet the demands of green chemistry. Today, polyolefin technology stands for the most
effective and sustainable use of oil and gas, especially when compared with burning oil and gas in energy production. In
contrast, most biotechnology processes consume significant amounts of water, produce byproduct wastes, and require
energy intensive biopolymer purification (Masilela et al., 2013).

Fig.6 Types of bio polymers

An integral part of the green economy concept is fostering the use of renewable resources and bio-based products. The
environmentalists dream is using solar power in biological photosynthesis to convert greenhouse gas
carbon dioxide and water into biomass, which then serves as a feedstock for bio fuels, bio power, and bio plastics. Upon
thermal or biological degradation, water and carbon dioxide are recovered. In this perceived closed carbon dioxide cycle,
in contrast to fossil resources, no additional greenhouse gas emissions would occur, accounting for a very low carbon
footprint. From this extremely idealistic point of view, biodegradation appears to solve the littering problem encountered
when highly durable synthetic polymers are not recycled (Bhardwaj and Kundu, 2010).In the Northern Pacific Trash
Vortex, also referred to as the Pacific Garbage Patch, which is driven by converging maritime and wind currents, floating
plastic debris accumulates together with other garbage such as pesticides from agriculture and plentiful fishery wastes.
As polymers are nontoxic and inert, partially degraded polymer particles may accumulate in marine organisms. Owing to
their high porosity, which results from degradation and surface erosion, spongy polymer wastes are suspected to adsorb
and concentrate low-molecular-weight toxic wastes such as pesticides. When marine organisms settle on such debris,
they can travel far beyond their natural habitat (Frey, 2008).

Fig.7 Production of green chemistry

They should be durable synthetic materials, especially those used in packaging applications with a short product lifetime,
be banned and substituted by biodegradable bio plastics this issue has triggered a hot and ongoing battle of the bag,
fought by opponents of plastics bags and protagonists of paper. In order to address this question, a realistic disillusioned
view of the real world is needed. Although the vision for green technology is intriguing and inspiring severe
disillusionment sets in when facing reality. There is a growing recognition that “bio” does not automatically simply
“green.” Prospects and problems concerning the use of bio fuel and bio feed. First of all even the partial substitution of
fossil oil and gas for biomass would require intensify farming of energy crops in competition with food production.
Stepping positive energy crop production and intensifying production and worldwide trading of bio fuel and bio feed
stocks could severely threaten the biosphere. The skyrocket demand for bio fuel and bio feed stocks is likely to accelerate
deforestation of rainforests and cultivation of grasslands, both of which are very effective in carbon dioxide sequestering.
Due to intensified use of fertilizers, emission of the very potent N 2O greenhouse gas is expected to drastically increase
(Haghi et al., 2007).
Ultimately in spite of replacing fossil fuels, the rising and falling use of bio fuels will probably accelerate global warming
and biosphere collapse. According to recent modeling studies, the anticipated conversion of rainforest and grassland into
new cropland for producing biodiesel and bio ethanol could release 17 to 420 times more carbon dioxide greenhouse gas
for many decades and even centuries when switching from fossil to bio fuels. Intensify farming of energy crops, irrigation,
and the use of pesticides endangers the natural habitats of many plants and animals. Severe losses of biodiversity are
imminent together with alarming socioeconomic implications of bio feed stock competition with food production
(Ramakrishna et al., 2007).

Pro bio Contra bio

Renewable resources conserve renewable fossil raw Non Competition with food production
materials
 Lowering of carbon dioxide greenhouse gas emissions by Intensified farming, extensive use of fertilizers,
switching from fossil fuels to bio fuels deforestation, and grassland conversion cause drastic
increases of greenhouse gas emissions
Domestic energy supply and less
Energy crop monocultures threaten biodiversity
dependence on oil imports
Plant cells and bacteria serve as solar micro reactors for
Use of transgenic plants and genetically modified bacteria
producing compound
Energy crops as nonfood incentives for farmers in Rising costs of food because farmers abandon food
industrialized countries with surplus food production production in developing countries that are unable to feed
their rapidly increasing population
3.4 Biodegradation
No biodegradation in the absence of water and oxygen. Disintegration may cause nano particles emissions.
3.4 No toxicity and no health hazards
Spongy degrading biopolymer particles are food sources and breeding grounds for bacteria and spores which could be
inhaled. In an industrialized country like Germany, bio energy production could supply 9.1% of the electrical power, 13.1%
of the thermal energy, and 21.4% of the fuel used in transportation, including around 50% of imports from other
countries. Important pillars are biogenic wastes from forestry’s and farming (Thoppey and Bochinski, 2011). In contrast
to energy production, it would be easy to supply the much lower demand of biomass required for switching from fossil
to renewable raw materials in plastics production. However, although the demand for bio plastic is orders of magnitude
lower with respect to the demand for bio energy, both bio plastics and bio energy production are closely interconnected
because they compete for the same biomass feed stocks. The imbalance of demand and supply of biomass is likely to
trigger future “bio crises” similar to the oil crisis when the oil supply was low In order to avoid conflicts with securing
food supplies, it is imperative to focus on exploiting agricultural and forestry wastes for the production of bio plastics and
to avoid conversion of rainforests and grasslands (Thoppey et al., 2012).
Now a days it is recognized that “bio” does not simply quantitative and rapid degradation to produce exclusively carbon
dioxide and water. Biodegradation can also produce water-soluble and even toxic metabolites that are washed away by
rain and thus pollute groundwater. In landfills, cellulose of paper and other biodegradable materials do not degrade and
survive for many decades when oxygen and water are absent. Moreover, biodegradation and bio erosion render
polymers brittle so that they readily disintegrate when exposed to mechanical stresses (Abdel et al., 2011). Most likely,
they form much smaller dust-like micron- and nanometer-sized particles, which are carried away by wind or rain.
Although the biodegrading plastics are no longer visible to the human eye, the resulting fine and invisible particles can
accumulate in the air and cause inhalation hazards. Most biodegradable polymers are a coveted source of food for
bacteria, other microorganisms, for example fungal spores, and even small animals, such as insects, bugs, mice, and rats.
As a consequence, applications of truly biodegradable materials frequently require chemical lines of defense using rather
aggressive antimicrobial additives and poisons. Yet another consequence is that bacteria and spores can settle on such
particles, which may then be inhaled, causing severe health problems. At present, there is very little research addressing
such potential inhalation hazards and the role of climate-dependent bio degradation with respect to nanoparticles
emissions. The battle of the bag plastics against paper is a nuisance because both packaging materials represent a severe
source of pollution when recycling fails.
Whereas paper consists of the natural polymer cellulose, most synthetic packaging polymers are based on polyethylene,
which is still fossil-based but has a much lower weight, higher strength, and causes less pollution during production.
Moreover polyolefin as hydrocarbon resins have significantly higher energy efficiency (Eda and Shivkumar, 2007).
Polyethylene bags are produced in a blow-molding process by melt extrusion of polyethylene granules, which are
produced by highly energy-efficient catalytic polymerization of ethylene in solvent-free gas-phase processes. To produce
paper, trees are stripped of their bark, shredded, washed, and chemically digested for many hours at elevated
temperatures in aqueous sulfurous acid to separate cellulose and lignin. Pulp production requires a very large amount of
water. After bleaching and further washing, the suspension of cellulose fiber pulp is pressed into finished paper.
Polyolefin bags, on the other hand, have a low weight and high energy content, and are thus attractive for saving energy
due to weight savings in transportation and effective energy recovery in recycling.
On heating above 400°C, the high-molecular-weight hydrocarbon polymers degrade to produce low-molecular-weight
hydrocarbons, equivalent to crude oil that can be used as source for renewable oil and gas, and as a substitute for fossil
resources. As durable hydrocarbons, the non-biodegradable plastic wastes can be easily collected and stored, enabling
effective energy recycling without serving as a food source and a breeding ground for microbial organism. There is no
competition between polyethylene and other plastics. In fact, modern packaging of milk and fruit juices makes extensive
use of both materials, which are joined together with paper serving as the carrier and polyethylene as the barrier to
water and flavor permeation. Synthetic polymers are not marine villains that threaten marine life littering problems result
from a lack of recycling and illegal dumping of garbage, especially in shipping the issues of ineffective recycling and
intolerable burdening of the biosphere by wastes are not solved by banning non- biodegradable materials, but by
demands to change human attitudes (Teo et al., 2011).
4 Bio polymer strategies for renewable plastics
In principle, there are three different strategies towards renewable plastics that are useful in a green economy. In strategy
bio refining of biomass and chemical conversion of carbon dioxide are employed to produce synthetic crude oil renewable
oil and green monomers for highly resource- and energy-effective polymer manufacturing processes without impairing
established recycling technologies which goes well beyond the green routes of polymers living cells are converted into
solar power chemical reactor, exploiting genetic engineering and bio technology routes to produce bio polymer as well
as bio based polymer. Carbon dioxide is activated and polymerized discussed below. Whereas nature needs more than
300 million years to convert biomass into oil, there are several options for producing synthetic bio-based renewable oil
and even “green coal” on a large scale that require only a few minutes. Exploiting biomass as renewable resource for
making renewable oil, green coal, gas, monomers, and renewable polymers without a delay of many millions years typical
fossil raw materials. Recycling of polymer wastes can be used to recover oil and gas feed stocks from wastes in analogy
to petro chemistry, in which petroleum is refined to obtain monomers, in strategy bio refinery and bio fuel technologies
are developed to refine biomass to produce renewable oil and green monomers Inspired by coal liquefaction and
gasification, biomass-to-liquid conversion is based on the Fischer–Tropsch process to convert biomass into a mixture of
carbon monoxide and hydrogen (sun-gas) in which is an important feedstock for chemicals (Queiroz and Collares, 2009).
Although the entire plant can be gasified, this process is energy-intensive, especially when producing non polar olefin
monomers less favorable energy and problematic eco balances are typical for biodiesel, prepared by trans-esterification
of vegetable oils with methanol, accompanied by glycerol byproduct formation. Among emerging bio fuels, bio ethanol
is produced by fermentation of sugar obtained from sugarcane or cellulose. Bio ethanol represents a very versatile raw
biomaterial for producing olefin and di-olefin monomers such as ethylene, propylene, and butadiene. Both BtL and bio
ethanol processes possess rather poor atom economy because only part of the raw material is incorporated into the
polymer product. In recent research innovations, biomass is directly converted into renewable coal and oil in a single
process step. In the catalytic pressure less liquefaction of wood and plastics wastes (KDV, “katalytische Direktverolung”),
developed by Alpha Kat in Germany, high-quality diesel fuel is produced without requiring the high temperatures and
pressures typical for coal gasification and the Fischer-Tropsch processes. In hydrothermal carbonization, developed by
Antoinette, aqueous slurries of virtually any kind of biomass and agricultural waste are converted into “green coal” using
very moderate reaction conditions this process is exothermic and tolerates high salt contents, which are detrimental to
most other catalytic processes this carbonization enables highly effective and simultaneous dehydration of the biomass
several processes have been developed to convert carbon dioxide into carbon monoxide, methanol, formic acid, and
formaldehyde. In a recent advance, photo catalysis was employed to convert aqueous carbon dioxide into carbon
monoxide using in situ water splitting as a hydrogen source. Going well beyond the scope of biomass utilization, the
direct chemical fixation of carbon dioxide is commonly recognized as an attractive green feedstock and green solvent for
the chemical industry (Oksman, 2012). Bio based Renewable polymers are obtained either from natural biopolymers or
by polymerization of bio-based monomers carbohydrates, tarpon’s, proteins, and polyesters are prominent
representatives of biomaterials that are chemically modified in manifold ways to meet the demands of polymer
processing and applications. Cellulose is the most abundant biopolymer in the world serving as a renewable polymer and
as a sustainable carbon source for the green economy. Traditional applications of cellulosic materials include wood as
building materials, cotton for textiles, and hemp for ropes and sails of strategic importance in naval history natural fibers,
such as flax, jute, hemp, and sisal provide excellent fiber reinforcement for thermo sets and thermoplastics. The German
automotive company daimler has developed polypropylene composites reinforced with abaca fibers for interior
applications novel families of thermosetting and thermoplastic wood or plastics composites, such as injection-moldable
wood and plastic compounds, has been developed to reduce processing costs and improve performance. Over the last
decade, micro fibrillated cellulose from wood and cellulose nano-whisker has been developed as nano-fillers for polymer
nano-composites, including applications in medical implants. Wood is composed of cellulose that is chemically attached
to lignin as a phenol resin lignin protects cellulose against thermo-oxidative degradation and microbial attack. Most
chemical processes for separating cellulose from lignin are cost- and energy-intensive and do not meet all the
requirements of green chemistry the major market for purified cellulose is the paper industry in which hydrolysis of
lignocelluloses represents an attractive source of sugars, which are in demand as a food source for bacteria in various
biotechnology and bio refinery processes, including bio fuel production. Lignin is a million ton phenol byproduct from
pulping and serves as renewable energy source in paper manufacturing, as a dispersing agent for cement, and as a bio
feed stock for bio refining of aromatic compounds such as vanillin. In lignin with low sulfur content are of interest as
fillers for various polymers and rubbers (Inomata, 2010). Aiming at fulfilling the dream of injection-moldable wood, the
germen company tecnaro has introduced moldable lignin-based polymer compounds, marketed as Arbo form consisting
of a pelletized and moldable mixture of thermoplastic lignin with flax, hemp, and other natural fibers. This “liquid wood”
product is claimed to combine the advantages of wood materials with facile molding typical of synthetic thermoplastics.
Applications include furniture, automotive parts, and heels of the “Eco pump” shoe, commercialized by Sergio rossi gucci
starch formed as a granular energy reserve in plant cells, is highly water soluble, readily biodegradable, and consists of a
mixture of linear amylase and highly branched amylopectine present in maize, potatoes, wheat, and other plants, starch
are a major energy source for living organisms. Whereas most starch products are consumed in the food industry,
nonfood applications include cosmetics, adhesives, textile sizing, and provision of sugar and dextrose feed stocks for
biotechnology. In contrast to cellulose, amylase can be rendered thermoplastic by adding water, glycols, glycerol, or
sorption as a plasticizer for example thermoplastic high-amylase starch has been developed by cardia bio plastics for
injection-molding, blow-molding, extrusion, films, and coating applications. In view of the high water solubility of starch,
several companies have developed bio hybrids using starch as a blend component with hydrophobic non degradable poly
olefins and compostable polyesters such as teri-phthalic acid or adipic acid 1, 4-butanediol co-polyesters chitosan
contains glucose amine repeat units and is derived by partial or full de-acetylating of chitin, which is obtained from the
shells of shrimps, crabs, and lobsters its annual production quantity is very similar to that of cellulose applications of
chitosan include drug release, encapsulation, wound dressings, and water purification (Evans, 2010).
In the tarpene family, fats and oils are valuable intermediates for the chemical industry, especially for the production of
ionic and non-ionic surfactants hydroxyl-functionalized castor oils have been used for many years as poly components in
polyurethane syntheses. Unsaturated fatty acids are dimerized and trimerized to produce di-functional and tri-functional
carboxylic acids, also known as dimmer and trimmer acids they are used in polyester synthesis and in hot melt adhesives
as flexibility segments unsaturated fatty acids are modifiers for alkyd resins and air-drying finishes (Patey, 2010).
Transesterification of vegetable oils with methanol yields methyl esters biodiesel and glycerol as a byproduct, which can
be used as a bio feed stock for a variety of monomers such as 1, 3-propane diol and bio-based acrylic acid and even
epichlorohydrin for the production of epoxy resins. Proteins such as collagen are abundant in mammals protein fibers
such as silk and wool have been used in the textile industry for centuries Gelatin, which is denatured collagen, is one of
the preferred materials for drug encapsulation. Casein, produced from cow's milk, is used as a binder and as an adhesive.
Bio-polyesters such as polylactic acid (PLA), polyhydroxybutyrate (PHB), and other polyhydroxalkanoates, produced by
bacteria as chemical energy storage in cells, are fully biodegradable and decompose to produce water, carbon dioxide,
and humus when air and water are present. It is possible to tailor stiff, soft, and elastomeric polyesters as a function of
their molecular architecture. Bacteria and transgenic plants have been successfully used to produce bio-polyesters on a
large scale. For two decades, PLA, produced by bacteria and especially by lactide polymerization, has been the approved
material of choice for restorable sutures in surgery. As a function of the stereoisomer composition, PLA can be amorphous
or crystalline melting at temperatures up to 185°C. The thermal stability is rather low with degradation starting below
230°C. ICI introduced biodegradable polyhydroxybutyrate marketed as bipolar it targeted polypropylene, but failed to
match the attractive cost per performance ratio typical for polypropylene, even when taking into account today's
increased oil price although significant progress has been made in biotechnology since then, separation of polyesters
from cell proteins and purification is rather expensive and energy intense contrary to the demands of green chemistry,
bio polyesters are often extracted using chlorinated solvents it should be noted that biodegradation is not the domain of
biotechnology. Biodegradable PHB can also be produced by the catalytic conversion of propylene oxide with carbon
monoxide when account is taken of the entire product lifecycle, biopolymers are not always by definition superior in
terms of low carbon footprint, resource eco and energy efficiency when compared to the same polyesters prepared from
fossil feed stocks. In bacterial polyesters, it is rather difficult to fine-tune molecular polyester architectures with respect
to improving shear thinning and crystallization rate of polyesters in melt processing (Murali and Ratna, 2007).
5 Applications of bio based polymers
Bio-based polymers materials are applied in various fields ranging from packaging and agriculture to applications with
higher added value, i.e. electronics and automotive advanced biomaterials are also being used in increasing quantities in
biomedical applications in various forms. One of the main functions of these materials is to bridge the interface between
artificial and biological systems, i.e. they must be biocompatible. Bio polymer is also favorable in most cases, but a long
list of other important and specific requirements can also be provided using appropriate modification techniques, natural
and synthetic biopolymers are able to meet these requirements, while the biomedical field tolerates the rather high price
of these materials much better than other application areas, thus 10 for tissue engineering purposes. Macromolecular
science has had a major impact on the way we live it is difficult to find an aspect of our lives that is not affected by
polymers just 50 years ago materials we now take for granted were non-existent with further advances in the
understanding of polymers and with new applications being researched, here is no reason to believe that the revolution
will stop any time soon (Dartee, 2010).

Fig.8 structures of Rubber

This section presents some common applications of the polymer classes introduced in the section on polymer structure
these are by no means all of the applications but a cross section of the ways of polymer is used in industry (Haider and
Park, 2009). Elastomers Rubber is the most important of all Elastomers natural rubber is a polymer whose repeating unit
is isoprene this material obtained from the bark of the rubber tree, has been used by humans for many centuries it was
not until 1823 however that rubber became the valuable material we know today in that year Charles Goodyear
succeeded in "vulcanizing" natural rubber by heating it with sulfur. In this process sulfur chain fragments attack the
polymer chains and lead to cross-linking the term vulcanization is often used now to describe the cross-linking of all
elastomers. Much of the rubber used in the United States today is a synthetic variety called styrene- butadiene rubber
SBR researchers eventually found success using butadiene and styrene with sodium metal as the initiator this rubber is
called Buna "BU" from butadiene "NA" from the symbol for sodium and "S" from styrene. During World War II hundreds
of thousands of tons of synthetic rubber were produced in government controlled factories after the war private industry
took over and changed the name to styrene-butadiene rubber. Today the United States consumes on the order of a
million tons of SBR each year natural and other synthetic rubber materials are quite important Plastics Americans
consume approximately 60 billion pounds of plastics each year. The two main types of plastics are thermoplastics and
thermo sets (Cho and Lee, 2013). Thermoplastics soften on heating and harden on cooling while thermo sets on heating
flow and cross-link to form rigid material which does not soften on future heating thermoplastics account for the majority
of commercial usage. Among the most important and versatile of the hundreds of commercial plastics is polyethylene is
used in a wide variety of applications because, based on its structure, it can be produced in many different forms the first
type to be commercially exploited was called low density polyethylene or branch polyethylene this polymer is
characterized by a large degree of branching, forcing the molecules to be packed rather loosely forming a low density
material. LDPE is soft and pliable and has applications ranging from plastic bags, containers, textiles, and electrical
insulation, to coatings for packaging materials. Another form of polyethylene differing from LDPE only in structure is high
density polyethylene or linear polyethylene this form demonstrates little or no branching, enabling the molecules to be
tightly packed. HDPE is much more rigid than branched polyethylene and is used in applications where rigidity is
important. Major uses of HDPE are plastic tubing, bottles, and bottle caps other forms of this material include high and
ultra-high molecular weight polyethylene (Frenot and Henriksson, 2007). These are used in applications where extremely
tough and resilient materials are needed. Fibers represent a very important application of polymeric materials including
many examples from the categories of plastics and elastomers natural fibers such as cotton, wool, and silk have been
used by humans for many centuries. In 1885 artificial silk was patented and launched the modern fiber industry manmade
fibers include materials such as nylon, polyester, rayon, and acrylic the combination of strength, weight, and durability
has made these materials very important in modern industry. Generally fibers are at least 100 times longer than they are
wide typical natural and artificial fibers can have axial ratios ratio of length to diameter of 3000 or more. Synthetic
polymers have been developed that possess desirable characteristics such as a high softening point to allow for ironing
high tensile strength adequate stiffness and desirable fabric qualities these polymers are then formed into fibers with
various characteristics (Nie et al., 2008). Nylon a generic term for polyamides was developed in the 1930s and used for
parachutes in World War II. This synthetic fiber, known for its strength, elasticity, toughness, and resistance to abrasion,
has commercial applications including clothing and carpeting.
Nylon has special properties which distinguish it from other materials. One such property is the elasticity. Nylon is very
elastic, however after elastic limit has been exceeded the material will not return to its original shape like other synthetic
fibers, nylon has a large electrical resistance this is the cause for the build-up of static charges in some articles of clothing
and carpets from textiles to bullet-proof vests, fibers have become very important in modern life. As the technology of
fiber processing expands, new generations of strong and light weight materials will be produced processing polymers
Once a polymer with the right properties is produced, it must be manipulated into some useful shape or object (Jacobs
et al., 2011).There are various methods are used in industry to do this Injection molding and extrusion are widely used
to process plastics while spinning is the process used to produce fibers injection molding one of the most widely used
forms of plastic processing is injection molding basically plastics heated above its glass transition temperature enough so
that it will flow and then is forced under high pressure to fill the contents of a mold. The molten plastic is usually squeezed
into the mold by a ram or a reciprocating screw the plastic is allowed to cool and is then removed from the mold in its
final form the advantage of injection molding is speed this process can be performed many times each second (Dong et
al., 2009). Extrusion is similar to injection molding except that the plastic is forced through a die rather than into a mold
however, the disadvantage of extrusion is that the objects made must have the same cross-sectional shape plastic tubing
and hose is produced in this manner. Spinning the process of producing fibers is called spinning there are three main
types of spinning melt, dry, and wet melt spinning is used for polymers that can be melted easily dry spinning involves
dissolving the polymer into a solution that can be evaporated wet spinning is used when the solvent cannot be
evaporated and must be removed by chemical means all types of spinning use the same principle so it is convenient to
just describe just one (Moon and Farris, 2009). In melt spinning a mass of polymer is heated until it will flow the molten
polymer is pumped to the face of a metal disk containing many small holes, called the spinneret.
Tiny streams of polymer that emerge from these holes called filaments are wound together as they solidify forming a
long fiber speeds of up to 2500 feet and minute can be employed in spinning following the spinning process as noted in
the section on polymer morphology fibers are stretched substantially from 3 to 8 or more times their original length to
produce increased chain alignment and enhanced crystalline in order to yield improved strength (Patanaik and Jacobs,
2010).
5.1 Potential application of smart polymer
The application of smart polymers for drug delivery shows great promise due to modulated or pulsating drug release
pattern to mimic the biological demand. Another important thing is that these operate fully automatically, without the
need of additional sensors, transducers, switches or pumps. Stimuli occurring externally of internally include
temperature, electric current, pH etc. When an enzyme is immobilized in smart hydro gels the product of enzymatic
reaction could themselves trigger the gel’s phase transition. It would then be possible to translate the chemical signal
e.g. presence of substrate, into the environment signal e.g. pH change and then into the mechanical signal (shrinking or
swelling) of smart gel. This effect of swelling or shrinking of smart polymer beads in response to small change in pH or
temperature can be used successfully to control drug release, because diffusion of the drug out of beads depends upon
the gel state. These smart polymers become viscous and cling to the surface in a bio adhesive form therefore providing
an effective way to administer drugs, either topically or mucosa, over long timescales by dissolving them in solution,
which contains hydrophobic regions through this technique, efficiency and cost effectiveness is increased (Han et al.,
2010). Most extensive efforts in this area have been made for developing insulin release system in response to high
glucose levels. In an early approach, entrapped insulin was released from copolymers of alkyl glucose cross linked with
Concanavalin. In later designs, glucose oxidize has been used to generate H positive in response to the presence of
glucose and hence exploit pH sensitive hydro gels one common worry in all such cases is the slow response time. Thus,
use of super porous hydro gels with fast swelling-deswelling kinetics is a step in the right direction. A pH responsive
hydrogel composed of polymethacrylic acid grafted with polyethylene glycol has been evaluated in vitro for calcitonin
delivery this poly peptide is a therapeutic agent for bone diseases like Paget’s disease, hypocalcaemia and osteoporosis.
As the pH increased during the passage from stomach to upper small intestine, the ionized pendant carboxyl groups
caused electrostatic repulsion, the network swelled and the hormone was released the release behavior showed that
movement of polymer chains was a key factor that controlled the solute transport.
Qiu and Park have also reviewed various hydro gels responsive to various stimuli. Another example worth quoting from
their review uses the concept of release of antibiotics at the site and time of infection the antibiotic, Gentamycin, was
attached to the polyvinyl alcohol backbone through peptide linkers infected wounds produced a higher concentration of
thrombin which snapped the peptide linkers and accelerated the release of the antibiotic. Dextran is attached to the drug
molecules for the formation of a pro drug using various techniques like direct linkage, attachment through intercalated
spacer arm, use of modulator ligand and tissue specific receptor ligand. In the direct linkage model of dextran the drug
is directly linked to dextran, which will release the active agent in a predictable manner. The regeneration of the parent
drug would be exclusively governed by the pH dependent hydrolysis, as the bulky dextran matrix would be inaccessible
to enzymatic attack. Intercalation of a spacer arm between the drug and the carrier dextran may serve three purposes.
The terminal functional group of the spacer arm was different which allows the covalent drug fixation to be established
through a variety of chemical bonds.Steric hindrance of enzyme activation of the ligand drug is circumvented by
augmenting the distance between the drug and the dextran backbone. Sequentially labile dextran pro drugs are
constructed specifically in which the pH dependent hydrolysis only liberates the spacer-drug derivatives, which after
extravasations or diffusion from the site of injection is activated at the diseased tissue. The active drug is released from
the dextran pro drug by the cleavage of the covalent bond existing between drug and the carrier moiety dextran, enzyme
or pH. If the drug contains a hydrolysable chemical bond, it might deteriorate even attached to the polymer backbone.
The ability of the bulky dextran molecule to suppress catabolism of the attached drug or enzyme has been exploited
extensively. Partial enzymatic disrupture of the main chains of dextran pro drugs changes the molecular weight
distribution of the originally administered pro drug, making it susceptible to the attack of various hydrolyses (Greer,
2006).
5.2 Targeting tumor cells
Methotrexate conjugates have been synthesized by covalently linking extran through a short-lived ester bond and a
longer-lived amide bond. The ability of these agents to kill cells and to penetrate through tissue has been evaluated. The
cytotoxicity of ester dextran and MTX amide dextran was found equivalent to unmodified MTX. Intracranial polymeric
delivery of MTX or MTX amide dextran to rats with intracranial gliosarcoma produced modest but significant increases in
survival conjugation of MTX to dextran appeared to shift the dose-response curve to a lower dosage. Synthesis of dextran
conjugate of sodium phenyl acetate with substituted dextran like dextran-methyl-carboxyl ate-benzyl amide has been
reported, for better tumor inhibition effect against human tumor melanoma cells than napa alone. A dicarboxymethyl
Dextran conjugate of cisplatin is synthesized by immobilizing cisplatin to dextran through a six-membered chelate type
coordination bond, which shows longer half life and better tumor growth inhibitory activity than plain cisplatin in colon
26 cancer cells. A macromolecular pro drug of cisplatin using dextran carrier with branched galaxies units has been
synthesized for targeting to hematoma cells effectively.
5.3 Natural based polymers for biomedical applications
Clinically available camptothecins like irinotecan and topotecan represent one of the most prominent classes of
antitumor agents. A new macromolecular prod rug denoted was synthesized bearing a novel analog conjugated to
carboxymethyl dextran via a triglycine spacer to improve their pharmacological profile. This conjugate shows better
specificity and ten times better activity than its parent the conjugate of paclitaxel with carboxymethyl dextran via an
amino acid linker produces better antitumor activity than paclitaxel alone. The pharmacokinetic and therapeutic studies
of mitomycin-dextran conjugate shows better activity and prolonged action than plain mitomycin against walker-256-
carcinoma in rats. The effect was distinctly bitter in case of cationic conjugate which is attributed for the presence of a
high load of negatively charged silica acid residues on cancer cell surface accomplishing effective cationic conjugate
absorption. Over-expression of the epidermal growth factor receptor has been caused in bladder cancer and is a potential
target for therapy with radio nuclides. The intravesically administered EGF-dextran conjugate EGF-dextran selectively
accumulates in the tumor tissue and shows better activity.
5.4 Targeted antimycobacterial therapy
Tuberculosis treatment requires a long-term antibiotic therapy. Targeted antibiotic therapy improves the efficacy of
treatment by concentrating the drugs close to mycobacterium. Antibiotic norfloxacin has been linked to mannosylated
dextran using a peptide spacer arm for this purpose. This conjugate shows more efficiency against mycobacterium than
plain norfloxacin (Jung et al., 2010).
5.5 Improved in vitro physico-chemical
The tendency of enzymes to undergo autolytic degradation and thermal liability might be partly circumvented by coupling
with dextran. The thermal stability of various enzymes like adenosine deaminase a-amylase, peroxide hydrolases and a-
chymotrypsin has been increased by their conjugation with dextran of molecular weight 1000, 80000, 70000 and 10000
respectively. Possibly other bioactive peptide agents might be stabilized in the same way. Several carboxylic acid drugs
like NSAIDs are insoluble in water in the free acid form. Dextran prod rugs of such drugs may constitute an alternative
approach to provide reproducible bioavailability of water insoluble drugs by releasing the active agent in a soluble state
in the gastrointestinal tract. The water solubility of naproxen is increased by a factor of 500 when it is conjugated to
dextran.
5.6 Antifungal activity
Life-threatening fungal infections have become increasingly widespread, especially among immune compromised
patients, such as those undergoing cancer treatment or transplantation and those with AIDS. The current treatment of
severe systemic fungal infections is inadequate, due to limited availability of effective parenteral drug formulations and
the appearance of new opportunistic fungal infections resistant to the marketed drugs. The pattern of new or newly
resistant species emerging in response to widespread and prolonged drug treatment renders the development of new
effective parenteral antifungal drug delivery systems highly important. Synthesis of dextran conjugate with misstating
nays has been reported for producing a stable water-soluble polysaccharide conjugate of nays as antifungal treatment.
Nays, a tetraene-diene antifungal agent, possess a broad spectrum of activity problems associated with its insolubility in
inject able solvents and high toxicity in injections has precluded its systemic administration. A nay is unstable in aqueous
medium and is sensitive to oxidation and heat. The drug was conjugated by a schiff-base reaction with oxidized dextran.
High conjugation yield of active Nays was obtained the conjugates were highly water soluble and could be appropriately
formulated for injection. The conjugates showed comparable MIC values against Candida alb cans and crypt cocas
neoformans and were about 25 times less toxic than free Nays after a single injection in mice (Nagahiro et al., 2008).
5.7 Antileishmanial targeted therapy
Pyrimethamine is effective in antileishmanial therapy because of its ability to inhibit both the enzymes of leishmanial
foliate pathway. But in vivo this effect occurs only at high concentration, associated with toxicity. To overcome this
problem, a prod rug of pyrimethamine, namely carboxymethyldextran thiomannopyrannoside pyrimethamine, has been
synthesized and utilized with approximately 50% destruction of intracellular amastigotes with no detectable toxicity to
macrophage cells.
5.8 PH-controlled intracellular drug releases
Polymers like dextran, when entering the endosomal or lysosomal compartment, are exposed to an acidic medium (pH
4.5–5.5). Using acid cleavable spacers like hydrazones spacer and N-cis-aconite spacer between the drug and the 36
natural-based polymers for biomedical applications carrier, a pH controlled intracellular drug release can be obtained.
Streptomycin has been linked to dextran via a carboxylic hydrazones linkage for its intracellular delivery (Mwaikamno,
2009).
5.9 Modification of immunogenicity of peptides
When proteins or peptides are conjugated to macromolecules, the resulting conjugate colloid in most cases and the
protein core get protected from interaction with other macromolecular plasma components by a hydrophilic polymer
shield. Therefore the conjugation decreases the immunogenicity of the protein component and permits repeated
administration of foreign proteins. This approach is useful when the protein is an enzyme with a low molecular weight
substrate found in plasma. The antigen city of L-asparagines and catalane was substantially suppressed when they were
conjugated to oxidized dextran and dextran with molecular weight of 40 000, respectively. Spacer linked dextran
derivatives of pancreatic Raze showed decreased antigen city.
5.10 Pharmacokinetic applications
The profile of plasma concentration of drugs is an important determinant of their quantitative access to many targets.
The plasma concentration is usually measured as the area under the curve. In general and slow renal elimination and
metabolic in activation promote better access of drugs to remote the targets. The efficacy of various drugs is limited due
to their rapid renal excretion. Conjugation of drugs with hydrophilic macromolecular carriers like dextran prevents rapid
renal excretion and restricts the drug entry into cells, thus prolonging their plasma circulation time. Insulin dextran
complex when injected intraperitoneally in diabolized rabbits maintains blood glucose levels at normal value over several
days. Design of dextran pro drugs prolonged systemic concentration of the liberated drug after oral administration this
has been reported for guanidine ursodeoxycholic acid ibuprofen and analogs of aspirin.Isoniazid have been conjugated
to dextran to form dextran-isoniazid complex, which exhibits prolonged persistence in circulation and reduced acute
toxicity in guinea pigs as compared to the parent drug. Nicotinic acid is an effective hypolipidemic agent, but suffers from
the disadvantage of rapid elimination from the systemic circulation. When it is conjugated with dextran, the drug is slowly
released from the polymeric support and prolonged the presence of the active substance in the body to lower the
triglyceride levels (Sandeep and Alive, 2010).
6 List of abbreviation
Abbreviations Full names
PLA Polylactic acid
PA Poly amide
PHB Poly hydroxyl butyrate
PHA Poly hydroxyl alkanoates
PCL Poly capro lactone
PBS Poly butylenes succinate
PVC Poly vinyl chloride
PB Poly butylenes
PEF Poly ethylene furan

Summary
A chemical compound that is made up of small molecules which are arranged in a simple repeating structure to form a
large molecule is called polymer. The study of polymer science begins with category the methods in which these materials
are synthesized. Addition polymerizations describe the method where monomers are added one by one to an active site
on the growing chain. Addition polymerization the most common type of addition polymerization is free radical
polymerization. A free radical is simply a molecule with an unpaired electron. The tendency for this free radical to gain
an additional electron in order to form a pair makes it highly reactive so that it breaks the bond on another molecule by
stealing an electron left that molecule with an unpaired election which is another free radical.

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