MOJ Food Processing & Technology

Review Article Open Access

Role of plasticizers in bioplastics

Abstract Volume 7 Issue 4 - 2019
Currently, a variety of petroleum based plastic materials are dominating the packaging
industries owing to their durability, versatility, light-weight and most importantly
Varee Tyagi, Bhaswati Bhattacharya
Department of Basic and Applied Sciences, National Institute
their cost-effectiveness. This trend is being overcome by the growing concern towards of Food Technology Entrepreneurship and Management, India
environmental pollution caused by the production as well as the disposal of these
materials and the presence of toxic substances that could migrate from the packaging Correspondence: Bhaswati Bhattacharya, Department of Basic
material to the product causing potential risk to human health while using the product. and Applied Sciences, National Institute of Food Technology
Biopolymers, is a promising green alternative to synthetic, non-degradable polymers. Entrepreneurship and Management, Kundli, Sonepat, India,Tel
These natural polymers (polysaccharides, proteins and lipids) are much more suitable +91-9253613641, Email
components for food as well as non-food packaging applications due to their qualities of
renew-ability, degradability and edibility. However, poor water vapour barrier properties Received: November 18, 2019 | Published: December 13,
of carbohydrates (polysaccharides) and proteins, and low elasticity of lipids are the main 2019
limitations for their use as commercial packaging materials. In this regard plasticizers
provide the necessary workability to biopolymers. This review gives a brief insight into
their plasticization effects, types, properties along with their effect and recent applications
on bio-based materials, with special reference to a new class of plasticizers, Ionic liquids.

Keywords: degradability, elasticity, plasticizers, Ionic liquids, biopolymers

Introduction polymers. These plasticizers are not chemically attached to polymer

Over the last few years, there has been a gradual shift in focus chains by primary bonds, although, there is interaction between the
from petroleum based plastics to biopolymers. Though, biopolymers two. Since they are not chemically bound they are easily lost by
are considered best biodegradable and green alternative, they still extraction, migration or evaporation. Conversely, internal
have a long way to go in terms of various characteristics to be able to plasticizers are integral part of the polymer chain, which can be
replace plastics in market. The fragility and brittleness exhibited either be reacted with the native polymer or co-polymerized into the
during thermo-formation leads to poor mechanical properties with polymer arrangement. These plasticizers eventually become a part of
regards to process-ability and end-use application thereby limiting the final product. The bulky structure of the internal plasticizers offer
their potential for various packaging applications. In order to more space for the polymers to move and also prevents them from
overcome this limitation of biopolymers, the use of various types of coming close together, thereby softening the polymers by reducing
plasticizers has gained momentum quite recently. Plasticizers have the glass transition temperature (Tg) and ultimately elastic modulus.
been widely used in the modification of polymers since the early Although, more prominent for internal plasticizers, a strong
1800s. These are a class of low molecular weight, relatively non- temperature dependence of material properties is observed for both
volatile organic molecules that improve workability and durability of internal as well as external plasticizers. Compared to internal
polymers since they help in the reduction of polymer-polymer plasticizers, the use of external plasticizers gives the opportunity to
contact leading to decrease in rigidity of the three dimensional choose the right material according to the desired product
structure of polymers thereby enhancing the deformation ability properties.1,3
without rupture.1 Primary and secondary plasticizers
Plasticization When a polymer, at high concentration, is soluble in a plasticizer,
it is considered as a primary plasticizer. These plasticizers gel
In general, this process denotes a change in the mechanical and
the polymer rapidly in the normal processing temperature range
thermal characteristics of a polymer, involving:2
are considered the sole plasticizer or as the core component of the
a. lowering of inelasticity at room temperature plasticizer and they should not leach out from the plasticized
material. Whereas, secondary plasticizers have restricted
b. lowering of temperature- at which substantial distortions can be compatibility with the polymer and reduced gelation capacity. They
achieved without needing enormous forces are, generally, combined with primary plasticizers to reduce the cost
c. enhanced elongation to break at room temperature or improve product properties.

d. increase in impact strength (toughness) to the lowest temperature The first successful class of plasticizers to be used, dating back
of serviceability to the 1920s, were phthalic acid esters or phthalates. The most
commonly used phthalates are di(2-ethylhexyl) phthalate (DEHP),
These characteristics can be accomplished via: external and diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP),
internal plasticizers, as well as, primary and secondary plasticizers.3 which have been used until recently. However, the use of phthalates
is now regulated and restricted in various products when found to be
External and internal plasticizers
toxic to human health as well as environment due to their migration
External plasticizers are low volatile constituents added to ability.4

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Properties of plasticizers as sorbitol and glycerine are added. After addition of plasticizers
and application of thermal and mechanical energy, these constitute
Typically, plasticizers have linear or cyclic carbon chain with thermoplastic starch (TPS) which could be used as a substitute for
an average molecular weight of 300 to 600. These are high boiling polystyrene (PS). Starch works as an effective packaging material
point liquids with a low molecular size that helps them to penetrate when it is modified to form films that provide adequate mechanical
into the intermolecular spaces in the polymer chains leading to properties of high percentage elongation, tensile and flexural
lowering of secondary forces between the chains. This changes the strength. Starch can be modified by either plasticization, blending
three- dimensional network of the polymer chains which eventually with other materials, genetic or chemical modification or
gives higher mobility by increasing the free volume. Therefore, the combinations of different approaches.5
chemical structure of the plasticizer along with the molecular weight,
functional groups, chemical composition plays a vital part in Biodegradable films based on starch, sodium caseinate, glycerol
deciding the degree of plasticity of polymers.3 and lipids (oleic acid and/or a-tocopherol) have been formulated
and evaluated in terms of microstructure, mechanical behaviour,
The compatibility factor between the system that is the plasticizer barrier and optical properties and antioxidant capacity. The effect
and the polymer is of paramount importance which signify a key role of film storage time on these properties was also analysed. 6 Physical
in various parameters such as solubility, polarity, dielectric constant and mechanical properties of edible films based on blends of sago
and hydrogen bonding.3 starch and fish gelatin plasticized with glycerol or sorbitol have been
As commonly desired, plasticizers should have low vapour investigated by.7 The thermo-mechanical properties and oxygen
pressure and diffusion rate into the polymers. This permanence of permeability of sorbitol–starch–water films have been studied by. 8 The
plasticizers is related to volatility and resistance to migration and effect of plasticizers, glycerol, sorbitol and poly(ethylene glycol) 400
extraction in water, oil or any other solvents.2,3 (PEG 400), on mechanical and barrier properties of rice starch film
have been investigated. Sorbitol and glycerol-plasticized starch films
Another important factor is the ease or difficulty in processing appeared homogeneous, clear, smooth, and contained less insoluble
the polymers, which is majorly tackled by addition of plasticizers. particles compared to unplasticized rice starch films. 9 Another study
The plasticizer concentration and type not only aid in modifying investigated effects of plasticizer (sorbitol) contribution on
the properties of the polymer but also influence processing ability structural, barrier and mechanical properties of corn starch-based
by reducing viscosity, heat generation and power consumption and edible films.10 In a recent study, films from jackfruit seed starch have
enhance dispersion and flow characteristics.1,3 been developed with glycerol having low opacity, high mechanical
characteristics and average water vapour permeability.11 In another
Specific to bio-based coatings and films, plasticizers aid in
study, aliginate films with glycerol, tributyl citrate (TC) and their
reducing brittleness/ fragility and enhance flexibility in films making
blends have been made wherein films with glycerol were less
them easier to handle, along with preventing cracks and pores in
hygroscopic when compared to films with TC or their blends.
them.2
Meanwhile films with TC and their blends had were observed to
Overall, the selection of plasticizer for a particular polymeric be opaque and less homogenous in structure.12 Cassava starch and
system depends on their compatibility with each other, desired lentil protein based films have been developed with glycerol as
characteristics of the final product, plasticization properties, plasticizer, which showed reduced water vapour permeability and
migration/ permanence, toxicity and cost. improved breaking resistance due to extrusion.13 Elephant foot yam
starch, whey protein concentrate and psyllium husk have been used
Plasticization of bio-based materials to prepare biodegradable films wherein glycerol, used for
plasticization, overcame the imperfections in physicochemical,
The need for low migration as well as low toxicity is now of
mechanical, barrier, surface morphology, optical and thermal
paramount importance while choosing a plasticizer. Keeping in view
properties. These composite films had lower water vapour permeability,
the safety concerns as well as biodegradability, new alternatives to
higher tensile strength and uniform structural integrity as compared
the conventional plasticizers are being explored. With respect to,
to the control films having only the starch component.14
biopolymer-based films, they can be categorised into water soluble
and water insoluble plasticizers. The nature of the plasticizer and its
amount can vastly affect the film formation from polymeric aqueous
Ionic liquids
dispersions.2 Based on the nature of the plasticizers; they are Ionic liquids (ILs) are organic salts that are liquid at ambient
classified into two categories: hydrophilic and hydrophobic temperatures, preferably at room temperature (RTIL – room
plasticizers. Hydrophilic plasticizers when added to polymer temperature ionic liquids). These are composed of large organic
dispersions dissolve in the aqueous medium such as glycerol, cations and small inorganic or organic anions. Room temperature
polyethylene glycol (PEG), ethylene glycol. They can lead to ionic liquids have emerged as a new class of solvents with a unique
enhanced water diffusion in the polymer if added in higher combination of low volatility, chemical stability, high conductivity,
concentrations. Hydrophobic plasticizers such as phenyl ethers, and wide electrochemical window, ability to dissolve organic and
citrate esters, phenyl ester, stearyl esters, on the other hand, can lead inorganic solutes and gases, and tunable solvent properties. Due to
to a decrease in water uptake as they close the micro-voids in the these unique properties and their toxicity profile ranging from low
films.3 to hazardous, ionic liquids are finding applications in varied arenas,
such as in biological processes development (biotransformation
Applications of various bio-based processes, as active pharmaceutical ingredients, for lignocellulosic
plasticizers biomass and cellulose dissolution); in extraction, separation and
absorption of biomolecules, rare earth, vinyl chloride; in preparation
Majority of bio-plastics are starch-based biopolymers which are of nanomaterials; in modifications of wool; as herbicide, fungicide
storage polysaccharide of cereals, legumes and tubers and widely
available. For processing of starch, flexibilizer and plasticizer such

Citation: Tyagi V, Bhattacharya B. Role of plasticizers in bioplastics. MOJ Food Process Technol. 2019;7(4):128‒130. DOI:
 Copyright:
Role of plasticizers in ©2019 Tyagi et 1

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impart and improve properties that are weak or not at all present in physicochemical properties of starch films. Carbohydrate Polymers.
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range needs to be scrutinized before their large scale applicability. In
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Funding 2009;34(12):1333–1347.
None. 18. Hajipour AR, Rafiee F. Recent Progress in Ionic Liquids and their
Applications in Organic Synthesis. Organic Preparations and
Acknowledgements Procedures International. 2015;47(4):1–60.

None. 19. Xie F, Flanagan BM, Li M, et al. Characteristics of starch-based

films plasticised by glycerol and by the ionic liquid 1-ethyl-3-
Conflict of interest methylimidazolium acetate: A comparative study. Carbohydrate
Polymers. 2014;111:841–848.
The authors declare that there was no conflict of interest.
20. Leroy E, Jacquet P, Coativy G, et al. Compatibilization of starch-zein
melt processed blends by an ionic liquid used as plasticizer. Carbohydr
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Citation: Tyagi V, Bhattacharya B. Role of plasticizers in bioplastics. MOJ Food Process Technol. 2019;7(4):128‒130. DOI: