Background and Objective of the Study

Background of the Study

Scope of Search
Overprint varnish (OPV) is widely used in the printing industry to enhance the aesthetics and
durability of the printed materials. However, most OPVs are fossil fuel based such as acrylics, Literature Search
which raises concerns about their environmental impact and sustainability. There has been a
growing demand for bio-renewable and sustainable OPVs that can reduce CO 2 footprints. The
• Google Scholar
global market size of OPVs crossed 900 million USD in 2020, growing at 8.9% CAGR and
expected to reach over 2 billion USD by 2026. The market for bio-renewable and sustainable • Science Direct
OPVs is expected to grow significantly in the coming years, driven by the increasing demand for
eco-friendly printing practices and regulations. Starch is one potential renewable material for Patent Search
development of sustainable and eco-friendly OPVs. While Starch offers excellent gloss, scratch • Pat base
resistance and adhesion to various substrate, its hydrophilicity makes it susceptible to degrade. • Google patents

Objective of the Study Supplier Search

• Product Search
The objective of the study is to conduct a literature search to identify different methodologies • Capacity
and possible approaches to modify starch to enhance its water resistance at the same time
identifying different starch suppliers from India market with potential modified starch.

1 MODIFICATION OF STARCH FOR WATER FASTNESS 17TH APRIL'2023

 Approach
Scope of Search

Patent Literature ~ 80 Scientific Literature ~150 Secondary Search

(Patbase, Google patent) (Science direct, Google scholar, Springer) (Company website, Supplier Search)

Detailed assessment of all the shortlisted literature

Insights and summary of available literature

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 Modification of Starch
̵ Starch modification refers to changes made to the structure and properties of starch molecules to improve their functionality add
versatility in properties.

̵ Starch can be modified through physical, chemical and enzymatic methods.

• Physical modification involves mechanical or thermal treatment of starch, such as pre-gelatinisation, grinding or extrusion.

• Chemical modification involves chemical reactions with starch molecules such as cross-linking, esterification, acid hydrolysis,
etherification, graft polymerization, etc.

• Enzymatic modification involves the use of enzymes to catalyse specific reactions with starch molecules, such as hydrolysis or
phosphorylation, etc.

̵ Either alone or a combination of methods could be used to produce starch with specific properties such as using physical and chemical
methods or physical and enzymatic methods to modify starch.

̵ Physical and enzymatic modification of starch are not effective methods to modify starch for water resistance. Also, there is a limited
scope of properties like adhesion, viscosity and molecular weight of starch.

̵ Chemical modification is widely studied and the most suitable method to modify starch for water resistance. Several chemical methods
has been developed and available in literature to introduce specific chemical groups to modify the structure and properties of starch for
various application such as adhesives, coatings, etc.

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 Chemical Modification of Starch- consolidated

Acylation

Esterification Acetylation

Enzymatic
Reaction
Chemical
Modification of Graft Polymerization
Starch

Ionic modification

Etherification CM/HP/HE

Benzylation/Borylation

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 1. Esterification of Starch
Summary
Challenges of esterification
Routes of esterification
 Acetylation.  The properties of starch is greatly influenced by the degree of
 Succinylation substitution such as higher DS value starch or not soluble in
 Acylation water but there is a possibility of increase in molecular
 Enzymatic weight due to bulky ester groups.
 Maleylation  Reduced viscosity and solvent compatibility need to be taken
care.
Advantages of esterification
 Reduced gloss and transparency
 Simple and cost-effective method .
 Different types of starch including corn , potato, rice and
Application
wheat starch can be modified.
 Paper manufacturing
 Several routes to modify starch with a wide range of degree
 Coatings
of substitution(DS) to improve the water resistance.
 Adhesives
 Esterified starch has good adhesion properties allowing
 Food packaging
effective bonding to substrate and provide good film
 Textile
formation.
 Yield percentage is higher in esterification generally above
85%

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 1. Esterification of Starch
Most common routes in literature

Source: Polymers 2022, 14 (10), 2023

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 1. Esterification of Starch
Example: Acylation of Starch DS values & Yield% with different reagent

 Acylation of polysaccharides can be done by acid

chlorides in alkaline environment.
 Acyl groups contribute to hydrophobicity, but it
depends on the DS.
 Acylated starch with DS 1.5 or more are not soluble in
water.

Scheme of Acylation

Starch Butyrate + HCl

Source: Carbohydrate Polymers 47 (2002) 245 - 252

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 2. Graft Polymerization of Starch
Summary Mechanism of Graft Polymerization
 Grafting process is the covalent attachment of the
monomers on the backbone of starch.
 Grafting with hydrophobic monomers, such as acrylic
acid, MMA, vinyl acetate or styrene improves water
resistance.
 Film formation and adhesion increases with grafting Initiation
appropriate monomer onto the backbone.

Challenges in Graft Polymerization

 Complex and multi step process.

 Compatibility issues with starch
Propagation

Source: Starch/Sta¨rke 2012, 00, 1–9

Carbohydrate Polymers 48 (2002) 125-130
Starch/Stärke 56 (2004) 407–412
Carbohydrate Polymers 75 (2009) 71-78 Termination
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 2. Graft Polymerization of Starch
Example: Cationic acetylated starch-g-poly(styrene-butyl Effect of St/BA ratio on water absorption
acrylate)
 CAS-g-poly(St-BA) was synthesized in three stages in RBF.
 Maximum graft percentage of 55.68% was achieved St/BA
ratio is 1:1
 Surfactant free

Properties of CAS-g-poly(St-BA)
 Water absorption decreased from 89.23 to 27.85%
 Contact angle increased from 34 ◦ to 114 ◦
 Film formation is excellent
 Crystallinity of starch decreased from 30.03 to 25.24

Challenges.

o Un-grafted monomer is more than 40%

o Un-grafted monomers need to be separated,
which will require addition setup. Source: Starch/Sta¨rke 2012, 00, 1–9

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