chapter - i introduction - shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/24891/6/06...1998...

Chapter – I Introduction

Studies on Biopolyester Polymers from Renewable Resources 1

CHAPTER - I

INTRODUCTION

The development of polymers has a significant effect on everyday life.

Largely through engineering efforts, a series of commercially synthetic polymers

have been successfully modified, improved, fine-tuned for current and additional

needs and used in many applications in modern society. It is not surprising, that

much of the high technology in future from biotechnology to microelectronics

will depend on our ability to synthesize and manipulate polymers. Today

polymers are used as replacements for woods, glass and metals and for a wide

variety of applications in industries such as packaging, automobiles, building

construction, electronics, aerospace, electric equipments etc.

1.1. Natural Resources as Raw Materials for Biodegradable

Polymers

There is an increasing trend in the chemical industry to introduce new

processes that should meet requirements such as generation of nearly zero waste

chemicals, reduced energy input and use of raw materials derived from non fossil

primary sources.

Dependence on fossil fuels as the main energy sources has led to serious

energy crisis and environmental problems. The growing demand for polymeric

materials has increased our dependence on crude oil that left our highways,

beaches and landfills overflowing with these non-renewable, indestructible



materials. The decline of petroleum based resources for the polymer industry has

forced to explore the naturally available renewable resources as alternate raw

materials. The impact of raw material resources used in the manufacture of a

polymeric product and the ultimate disposal, biodegradability or recyclability of

the product when it enters the waste stream has to be considered while designing

the product. Designing these materials to be biodegradable ensures that they end

up in an appropriate disposal system that is highly relevant to protect the

environment and ecology.

Most conventional polymers derived from petroleum resources are

resistant to degradation [1, 2]. To facilitate their biodegradation, additives are

added. One method to degrade polyolefins consists in the introduction of

antioxidants into the polymer chains. Antioxidants will react under UV, inducing

degradation by photo-oxidation. Nevertheless the biodegradability of such

systems is still controversial. They are considered as oxo-degradable polymers.

Polyolefins are resistant to hydrolysis, to oxidation and to biodegradation due to

photo initiators and stabilizers [3]. The current interest in cheap, ready available

biodegradable polymeric materials has encouraged the development of such

materials from readily available, renewable inexpensive natural sources [4-6].

Two classes of biodegradable polymers can be distinguished: synthetic or

natural polymers. Natural polymers are produced from feed stocks derived from

renewable sources, while synthetic polymers are produced from non renewable

petroleum resources. The use of renewable resources as starting materials for the



synthesis of various polymers has been at the centre research activity for more

than 20 years [7-11]. These renewable resources hold beneficial characteristics

for being non-toxic, biodegradable and environmentally friendly. Natural

polymers are formed in nature during the growth cycles of all organisms and are

available in large quantities from renewable sources. These facts have helped to

stimulate interest in biodegradable polymers and in particular biodegradable

biopolymers. Biodegradable plastics and polymers were first introduced in 1980s.

Polysaccharides, as starch and cellulose, represent the most characteristic family

of these natural biodegradable polymers. Other natural polymers as proteins,

lipids, fats and oils from agricultural resources can also be used to produce

biodegradable materials. These are the two main renewable sources of

biopolymers. To improve the mechanical properties of such polymers or to

modify their degradation rate, natural polymers are often chemically modified.

Polymers with hydrolysable backbones are susceptible to biodegradation

under particular conditions. Synthetic polymers that have been developed with

these properties include polyesters, polyamides, polyurethanes and polyureas,

poly(amide-enamines) , polyanhydrides [12,13]. Biodegradation in natural

polymers takes place through the action of enzymes and chemical deterioration

associated with living organisms. This occurs in two steps. The first step is the

fragmentation of the polymers into lower molecular mass species by means of

either abiotic reactions, i.e. oxidation, photo degradation or hydrolysis, or biotic

reactions, i.e. degradations by micro organisms. This is followed by

bioassimilation of the polymer fragments by micro organisms and their



mineralisation. Biodegradability depends not only on the origin of the polymer

but also on its chemical structure and the environmental degrading conditions [14].

Biodegradable polymers can be processed by most conventional plastics

processing techniques, with some adjustments of processing conditions and

modifications of machinery. Film extrusion, injection moulding, blow moulding,

thermoforming are some of the processing techniques used.

The three main sectors where biodegradable polymers have been

introduced include medicine, packaging and agriculture. The applications of

biodegradable polymers include not only pharmacological devices, as matrices

for enzyme immobilization and controlled-release devices [13, 15-17] but also

therapeutic devices, as temporary prostheses, porous structure for tissue

engineering. Current applications of biodegradable polymers include surgical

implants in vascular or orthopaedic surgery and plain membranes. Biodegradable

polyesters are widely employed as porous structure in tissue engineering because

they typically have good strength and an adjustable degradation speed [18,19].

As biopolymers have appreciable water uptake, they could be used as

absorbent materials in horticulture, healthcare and agricultural applications [20].

Packaging waste has caused increasing environmental concerns. The

development of biodegradable packaging materials has received increasing

attention [21]. In everyday life, packaging is another important area where

biodegradable polymers are used. In order to reduce the volume of waste,

biodegradable polymers are often used. Besides their biodegradability,

biopolymers have other characteristics as air permeability, low temperature seal

ability and so on [22]. Biodegradable polymers used in packaging require



different physical characteristics, depending on the product to be packaged and

the store conditions. Due to its availability and its low price compared to other

biodegradable polyesters, poly(L-lactic acid) (PLA) is used for lawn waste bags.

In addition, PLA has a medium permeability level to water vapour and oxygen. It

is thus developed in packaging applications such as cups, bottles, films [23-25].

Poly caprolactone (PCL) finds applications in environment e.g. soft compostable

packaging.

To improve the properties of biodegradable polymers, a lot of methods

have been developed, such as random and block copolymerization or grafting.

These methods improve both the biodegradation rate and the mechanical

properties of the final products. Physical blending is another route to prepare

biodegradable materials with different morphologies and physical characteristics.

To provide added value to biodegradable polymers, some advanced technologies

have been applied. They include active packaging technology and natural fiber

reinforcements. Nano clay has been used with biodegradable polymers, especially

with starch and aliphatic polyesters to prepare nano-biocomposites.

1.1.1. Plant Oils Resources as Raw Materials

In recent years, environment friendly and biodegradable materials are

developed from agriculture products like plant oils [26,27]. The polymers

synthesized using plant oils exhibit appreciable properties at reduced cost [28].

Plant oils containing hydroxy fatty acids are important raw materials

for the production of polymers such as polyurethanes, polyesters, polystyrene,



poly(methyl methacrylate) and poly(ethyl acrylate) etc [19,22-29]. They can be

polymerized to form elastomeric networks and are used as alternative material

resources to petro-chemical derived resins [30]. The polymers obtained from

plant oils are biopolymers, they are often biodegradable as well as non-toxic.

Vegetable oils are abundant and cheap renewable resources which represent a

major potential alternative source of chemicals suitable for developing safe

environmentally and consumer friendly products.

The conversion of oilseed crops into bioplastics could be a sustainable

alternative which could compete with plastics obtained from petroleum

chemicals. Certain grades of vegetable oils and their derivatives, such as polyol

products, are already utilized industrially as an alternative feedstock to produce

additives or components for composites or polymers [31]. In recent years,

naturally functionalized triglyceride oils [32,33] as well as vegetable oil polyols

[34-36] have attracted attention for providing source materials for a multitude of

plastic products, including various PUs. Plant oils are triglycerides of fatty acids.

Seed oils containing hydroxy fatty acids are important raw materials. Hydroxy

fatty acids are used in the manufacture of polymers.

1.2 Cashew Nut Shell Liquid (CNSL)

The cashew tree (Anarcardium occidentale) is a native of Brazil and the

lower Amazons. The cashew has been introduced and is a valuable cash crop in

the Americas, West Indies, India and Malaysia. Casew nut is a high-value edible

nut. It yields two “Oils” of which one, found between the seed coat (or peri carp)



and the nuts, is called the cashew nut shell liquid. It is not a triglyceride and

contains a high proportion of phenolic compound. India is the largest producer

and processor of cashews in the world [37]. In India cashew cultivation covers a

total area of about 0.77×106 hectares of land, with annual production over

0.5×109 kg of raw cashew nuts. The average productivity per 100,000 m3 is

around 760 kg. The world production of cashew nut kernel was 907×106 kg in

1998 [38]. The cashew nut tree consists of the cashew nut fruit, the apple, leaf

and bark. The fruit consists of an outer shell, inner shell and the kernel. The

thickness of cashew nut shell is about 1/8 in (1 in. = 2.54 cm). The soft

honeycomb matrix, in between outer and inner shell, consists a dark brown liquid,

which is known as cashew nut shell liquid (CNSL). CNSL is a promising source

of unsaturated hydrocarbon phenol, an excellent monomer for polymer

production.

The major by-product of cashew nut is the liquid from the pericarp known

as cashew nut shell liquid. Cashew nut shell liquid (CNSL), an agricultural

renewable resource is the by-product of the cashew industry [39]. Cashew nut

shell liquid (CNSL) is one of the sources of naturally occurring phenols. CNSL

consist of four alkyl substituted phenols. Cashew nut shell liquid (CNSL) is an

amper – coloured, poisonous and viscous oil. Many researchers investigated its

extraction, chemistry, and composition [40,41]. The cashew nut shell liquid

contains four major components, namely, anacardic acid (1), cardanol (2), cardol

(3) and 2-methyl cardol (4) [42].



Where n=0 (C15 H31)

n=2 (C15 H29)

n=4 (C15 H27)

n=6 (C15 H25)

Chemical constituents of CNSL

Cardanol, cardol and anacardic acids are the major components

(respectively 10 and 63% of phenolic compounds) in cashew (Anacardium

occidentale sp.) nut shell oil [43]. Minor components include methyl cardol and a

small amount of polymeric materials. Due to the presence of the hydroxyl (OH)

group, the carboxyl (COOH) group and variable aliphatic unsaturation in the side

chain, CNSL is able to take part in several chemical reactions. Anacardic acid can

be decarboxylated to produce anacardol (5) which when hydrogenated yields

cardanol [44].

About 41% of the anacardic acids and cardanols are the tri-unsaturated

species (2-hydroxy-6- pentadeca-8, 11, 14 trienyl benzoic acid and 3-pentadeca-

anacardic and

(1)

cardanol

(2)

cardol

(3)

2-methyl cardol

(4)

OH COOH

C15 H31-n

OH

C15 H31-n

OH

C15 H31-n HO C15 H31-n

H3C

OH

HO



8, 11, 14 trienyl phenol), while 22% are diunsaturated, 34% mono unsaturated

and the remaining saturated.

(5)

Various methods have been reported in literature for the extraction of

CNSL from cashew nut shells (CNS), which include, open pan roasting, drum

roasting, hot oil roasting, cold extrusion, solvent extraction, etc. The extraction

through pyrolysis has been reported recently by Das et al. [45] and Tsamba et al.

[46]. The extraction of CNSL using supercritical carbon dioxide has also been

reported by Shobha and Ravindranath [47] and Smith et al. [38]. Granted that

supercritical fluid extraction (SFE) process involves high investment costs, yet

optimization of input energy for the process holds promise to improve the

production economics of existing extraction plants [48]. In the hot oil process, the

raw nuts are sent through a hot bath of CNSL (180-2000

C) when the outer part of

the shell bursts open and releases CNSL (50% recovery). By passing the spent

shells through an expeller, another 20% could be extracted. Remaining 30% is

recovered by solvent extraction technique. In the roasting process, the shells

mixed with sand, steel and wool are heated to 100-3000

C for an hour in a rotary

apparatus and then roasted to 400-7000 C in an inert atmosphere when the oil



comes out of the shell. The specifications for CNSL as per Indian standard (IS:

840-1964) are given in Table 1.1.

Table 1.1

Specification for CNSL

Characteristics Requirement

Colour Dark brown

Odour Smoky, mild phenolic

Specific gravity (g/c.c at 300C) 0.950-0.970

Viscosity at 300C(CPS) 550

Moisture % by weight (max.) 1.0

Matter insoluble in toluene % by weight (max.) 1.0

Loss in weight on heating % by weight (max.) 2.0

Ash % by weight (max.) 1.0

Iodine value (Wij's method) 250

Based on the mode of extraction and heat treatments, CNSL is classified

into two types, solvent-extracted CNSL and technical CNSL. A typical solvent-

extracted CNSL contains anacardic acid (60–65%), cardol (15– 20%), cardanol

(10%) and traces of methyl cardol. Technical CNSL is obtained by roasting shells

and contains mainly cardanol (60–65%), cardol (15– 20%), polymeric material

(10%), and traces of methyl cardol [49]. Depending on the conditions of the

roasting processes, the composition of the technical CNSL can change and reach



higher cardanol content (83-84%), less cardol (8-11%), polymeric material (10%)

and 2-melhyl cardol (2%) [50].

1.3 Applications of Cashew Nut Shell Liquid (CNSL)

1.3.1. CNSL In Phenolic Resins

The application of CNSL as a full replacement for synthetic resins may be

of immense interest in these days of diminishing petroleum reserves. The

versatility in polymerization, chemical modification and good impact resistance,

flexibility makes it industrially important one. CNSL is a source of unsaturated

hydrocarbon phenol and behaves as an excellent monomer for thermosetting

polymer production [39,41,51].

Phenolic resins are a class of synthetic materials developed continuously

in terms of volume and applications for several decades. Phenolic resins were the

first true synthetic polymers often referred to as Phenol-formaldehyde

condensation polymers and they have multifold applications in different areas.

Because of their excellent ablative properties and structural integrity, they can be

used as high temperature-resistant polymers [52]. Substituted phenols have been

used for the preparation of substituted phenolic resins. The substituted phenols

differ in their reactivity with formaldehyde. The phenolic nature makes it suitable

for polymerization into resins by formaldehyde using sodium hydroxide (NaOH)

as a catalyst and hexamethylenetetramine (HMTA) employed as a hardener [53].

The phenolic nature of the material makes it possible to react under a variety of

conditions to form both resols (condensation in presence of alkaline catalysts) and

novalcs (condensation in presence of acid catalysts). Lima et al. [54] condensed



cardol, cardanol and anacardic acid present in CNSL with formaldehyde, in

presence of NaOH catalyst to obtain liquid resols (6).

(6)

Studies have shown that the phenolic resins made from a mixture of

cardanol, phenol and formaldehyde have improved chemical resistance and

mechanical properties such as tensile, flexural, and Izod impact strengths than

those of pure phenol-formaldehyde resins [55]. The cardanol-formaldehyde resins

have been studied for producing protective varnishes with improved properties in

food industry [56]. Cardanol have been used for the manufacture of special

phenolic resins for coatings, laminates and friction materials [57]. The phenolic

resins made from cardanol can also be used for breaking crude oil emulsions and

as selective ion exchangers for certain metal ions [58]. Hydroxy alkylated

cardanol-formaldehyde resins have been used for the synthesis of polyurethanes

with good thermal and mechanical properties [59]. Certain base catalyzed

oxalkylated-cardanol alkyl phenol - aldehyde resins have been utilized in refinery

demulsification operations. These materials find particular utility in breaking



water-in-oil emulsions resulting from the water wash of crude oils. The materials

have also been employed to break other water-in-oil refinery emulsions.

Poly(vinyl formal) (PVF) was modified by phenol-cardanol-formaldehyde resins

(PCF) to improve properties of the insulating enamel varnish for copper wires

[60]. The varnish films prepared from modified PVF showed better physico-

mechanical properties, heat resistance and electrical properties.

1.3.2. CNSL In Coatings etc

CNSL are used for lacquers, paints, varnishes, waterproof materials etc

[61]. Bamboo surfaces are protected by CNSL based surface coatings. Lacquers

prepared from CNSL are used for insulation and as decorative coatings for

furniture, building materials and automobiles [62]. Speciality coatings prepared

from CNSL are used for wooden surfaces of fishing boats [63].The product of

enzymatic oxidative polymerization of thermally treated CNSL is an efficient

glossy coating material [64]. CNSL have been reported as a source of various

classes of surfactants [65].

1.3.3. CNSL in Friction Materials

About 90% of CNSL put on the market is, used to make resins for

clutches and disc brakes [44, 66]. The CNSL polymers with improved abrasion

resistance are used for friction materials. The CNSL is used in the manufacture of

special phenolic resins for coatings, for lamination, and as friction material [67,

68]. These polymers are synthesized from CNSL or cardanol either by

polycondensation with electrophilic compounds such as formaldehyde,



furfuraldehyde, or chain polymerization through the unsaturation present in the

side chain using acid catalysts, or by functionalization of the hydroxyl group and

subsequent oligomerization to obtain a functionalized pre polymer. The product

from CNSL based resins and cashew dust is used for corrosion and skid resistant

friction materials [69]. Brake lining and clutch facings based on CNSL resins

absorb the heat produced during friction and retain their braking efficiency longer

[70,71].

1.3.4. CNSL in Miscellaneous Applications

The CNSL based resins and their derivatives are used for the production

of laminates for electrical insulation and printed circuit boards. The CNSL are

also used in conducting composites [72]. CNSL and their derivatives are useful in

preparing detergents, plasticizers [73, 74], UV light absorbers [75], stabilizers

[76,77], dye sluffs. It has insecticidal, fungicidal and anti-terminate activities

[78]. The CNSL based composites are used as binder resin for particle boards.

1.4 Cardanol and Its Applications

Pure cardanol is obtained by the double vacuum distillation of technical

CSNL under atmospheric and reduced pressure between 180–230◦ C, the yield

being 50% [79, 80]. Cardanol is a complex mixture of 3-n-pentadecylphenol, 3-

(n-pentadeca-8-enyl) phenol, 3-(n-pentadeca-8, 11-dienyl) phenol and 3-(n-

pentadeca-8, 11, 14-trienyl) phenol. Cardanol exists usually as mixture with

saturated component 5.4%, mono olefin 48.5%, diolefin 16.8% and triolefin

29.33% [81]. Cardanol monomers have the average value of unsaturation 1.7 and



molecular weight 300. It has been found that cardanol and its polymers have

interesting structural features for chemical modification and polymerization into

speciality polymers.

Typical applications of cardanol include brake linings, paints and

varnishes, foundry core oil, and distilled cardanol for epoxy resins and laminates.

The other minor uses of cardanol are, in chemically resistant cements, oil

tempered hardboard, and waterproofing compounds and resins [82,83].

1.4.1 Applications of Cardanol

Cardanol is a commonly available component which has been used in

many chemical applications such as paints and varnishes [84], polymer phenol-

formaldehyde resins [85, 86], polymers with surface activity [78] and others [87].

Because of their natural origin and structure, anacardic acids and cardanols are

likely candidates for preparing ‘‘green’’ surfactant species like cardanol

sulfonates, cardanol ethoxylates and cardanol-formaldehyde ethoxylates polymers

[88, 89]. They have been used in semi synthetic processes to prepare products

with biological and pharmaceutical applications.

1.4.1.1 Cardanol as Phenolic resins

Cardanol is used in the manufacture of special phenolic resins for

coatings, for lamination, and as friction material [51]. The polymers are

synthesized from cardanol either by poly-condensation with electrophilic

compounds such as formaldehyde, furfuraldehyde, or chain polymerization

through the unsaturation presents in the side chain using acid catalysts, or by



functionalization of the hydroxyl group and subsequent oligomerization to obtain

a functionalized prepolymer. Cardanol can be condensed with active hydrogen-

containing compounds such as formaldehyde at the ortho- and para positions of

the phenolic ring under acidic or alkaline conditions to yield a series of polymers

of novolac or resol types [90, 91]. Later on it has been used in the preparation of

many speciality materials, such as liquid crystalline polyesters [92], nanotubes

[93], cross-linkable polyphenols [94, 54], polyurethanes [95-97] and a range of

other speciality polymers and additives [98-105].

Interest has been shown on the formylation of cardanol in presence of acid

catalyst [106]. The use of certain metal salts like zinc, magnesium, calcium

acetate etc results in the formation of novalac resins with high concentration of

ortho-ortho repeat units. Novalac resin with mole ratios 1:0.6, 1:0.8 of cardanol to

formaldehyde were prepared by using adipic acid catalyst [106]. Novalac resin

with mol ratios 1:0.8 of cardanol to formaldehyde were prepared by using

succinic acid catalyst [107].These resins because of their stability, heat resistance,

electrical insulation, dimensional stability, chemical resistance etc find

widespread application as commodity materials, microelectronics and optical

lithography and matrix materials in FRP for wide industrial application

[108,109]. Phenolic resins are used as wood adhesives [110]. Phenyl ethynyl

functional addition curable phenolic resins were synthesized by reacting a

mixture of phenol and 3-(phenylethynyl) phenol (PEP) with formaldehyde in

presence of an acid catalyst and they have great potential for high performance

composite application [111].



An epoxy-cardanol resin was developed using epichlorohydrin, bisphenol-

A and cardanol by L.K.Aggarwal.et.al [112].A number of resins have been

synthesized by condensing cardanyl acrylate with furfural and selective organic

compounds in the presence of acid catalyst [106]. Cardanol functionalized with

methacrylate was found to have application in the synthesis of several heat-

resistant resins. Copolymers of MMA and cardanyl acrylate having a small

fraction of cardinyl acrylate showed better thermal stability than the PMMA

homopolymer [113].

Novel blends were prepared from elastomeric materials and thermosetting

resins, for example natural rubber and cardanol-formaldehyde resins, in order to

improve mechanical properties (such as toughness) and thermal properties (such

as high-temp. resistance) [114]. Cardanol-formaldehyde resin (CF) and cardanol

glycidyl ether (CGE) were synthesized for reinforcing natural rubber (NR), blend

of NR and styrene-butadiene rubber (SBR), and nitrilebutadiene rubber (NBR)

[115]. The novolac CF resin reinforced NR, SBR, and NBR and the resol CF

were found to be a hardener for NBR. The CGE could be used as a reinforcing

agent for NR and for crosslinking maleated NR.

1.4.1.2 Cardanol as Raw Material for Polyurethanes, Polyimides

Rigid polyurethanes have been synthesized using 4,4/-

dicyclohexylmethane diisocyanate by sathiyalekshmi et.al [59]. Cardanol was

used in the synthesis of thermoplastic polyurethanes [116]. Bhunia et al. [96]

investigated the synthesis of novel polyurethanes by solution polycondensation



reaction of 1,6-diisocyanatohexane with 4-[(4-hydroxy-2-pentadecenylphenyl)

azo]phenol (HPPDP) and 1,4-butanediol.

There are many reports on the synthesis of polyethers from cardanol

[113]. A novel polyether was synthesized by cationic polymerization of glycidyl

3-pentadecenylphenyl ether (GPPE) in the presence of a latent thermal initiator,

N-(benzyl) N, N-di-Meanilinium hexafluoroantimonate. Nguyen et al. [117]

reported the modification of unsaturated polyester with maleated cardanol-epoxy

resin.

Maldar [118] reported the synthesis of some polyimides from substituted

p-phenylene diamines based on cardanol. Vernekar et al. [119,120] reported the

synthesis of novel polyimides and polyamides from a cardanol based diamine 4,

4’-sulfonyl bis(phenyleneoxy)]-3-pentadecylbis(benzeneamine). A novel liquid

crystalline polymer containing azophenyl group was synthesised by performing a

diazotisation reaction between cardanol or pentadecyl phenol and p-

aminobenzoic acid and polymerization of the resulting monomer to get poly 4-[4-

hydroxy-2-pentadecyl phenyl) azo] benzoic acid .The cardanol based novolac-

type phenolic resins may be further modified by epoxidation with

epichlorohydrin to duplicate the performance of such phenolic-type novolacs.

These epoxy resins are comparable to conventional epoxy resins.

Synthesis of new polyphenols with attractive properties from natural

phenolic compounds such as cardanol by oxidative polymerization using enzymes

has been reviewed by Uyama et al. [121-123]. Enzymic homo and



copolymerization of alkylphenols derived from cashew nut shell gave

homopolymers that are soluble in organic solvents, but the copolymers were

crosslinked, with negligible solubility [124]. The enzymic polymerization was

found to be dependent on the solvent mixture used. Polymerization in a dioxane-

water solvent mixture resulted in spherical particles in the case of

homopolymerization while structures without distinctive morphologies were

obtained in the case of copolymerization.

1.4.1.3 Cardanol as interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) are new type of polymer blends

in network form in which at least one of the components is polymerized and

crosslinked in immediate presence of the other [125,126].The synthesis of

interpenetrating polymer networks (IPNs) is a useful technique for designing

materials with a wide variety of properties. IPNs generally possess enhanced

physico-mechanical properties against the normal poly blends of their

components. IPNs could also be called polymer alloys and they are considered to

be one of the fastest growing areas of polymer blends during the last two decades

[127].

IPNs typically consist of a flexible elastomer and one or more rigid, high

modulus component. IPNs could be classified as sequential or simultaneous,

depending on the way that the polymerisation is carried out. They could be also

defined as a latex IPNs, when the polymers are synthesised by emulsion

polymerisation; a gradient IPN, when each surface of the film is predominately of



one type of polymer and there is a gradient inside the film; a thermoplastic IPN,

when there is physical crosslink rather than chemical crosslink in the polymers,

and a semi-IPN (SIPN) when just one of the polymers is a network [128].

A number of semi-interpenetrating polymer networks (semi-IPNs) have

been synthesized by condensing cardanol-formaldehyde hydroxyacetophenone or

furfural novolac resins with polyurethanes prepared from castor oil and

diisocyanates [129]. Thermal properties of the semi- interpenetrating polymer

networks composed of castor oil polyurethanes and cardanol- furfural resin have

been studied [130,131]. Semi-interpenetrating polymer networks of various

compositions based on crosslinked poly (urethane) and linear poly (methyl

methacrylate) were prepared by L. F. Kosyanchuk et.al [132].

Semi-interpenetrating polymer networks (semi-IPNs) have been

synthesized using polyurethane and cardanol derivatives like acetylated cardanol

and phosphorylated cardanol [133]. Both novalac and resol resins of cardanol-

formaldehyde and cardanol formaldehyde-poly (methylmethacrylate) semi-

interpenetrating polymer networks were synthesized. The thermal characteristics

of poly (methylmethacrylate) (PMMA) interpenetrated with cardanol-

formaldehyde resin was studied by Manjula et al. [134]. The interpenetrating

polymer networks showed only 15% weight loss at 3500

C whereas PMMA

showed around 50% weight loss at this temperature. There are several other

reports on the synthesis of semi-interpenetrating polymer networks from cardanol

[135]. The novel interpenetrating polymer networks (IPNs) based on cyclo



aliphatic epoxy resin containing cyclohexene oxide groups and tri-functional

acrylate, trimethylol-1, 1, 1-propane trimethacryllate were synthesized by

Jingkuan Duan et.al. [136].

1.5 Castor oil

Natural oils and their derivatives are being researched for plastic and

polymer applications due to their availability, renewability and biodegradability.

Edible oils such as castor oil, ground nut oil, sunflower oil and coconut oil are an

excellent source of naturally occurring hydrocarbons which are biologically

degradable (bio hydrocarbons). Castor oil is one of the most naturally and

abundantly occurring plant oil [137].It is obtained from the extraction of the seed

of a plant which has the botanical name Ricinus communis of the family

Eurphorbiacae [138]. The oil is not only a naturally occurring resource, but it is

inexpensive and environmental friendly. Castor oil is viscous, pale yellow non-

volatile and non-drying oil with a bland taste and is sometimes used as a

purgative. It has a slight characteristic odour while the crude oil tastes slightly

acrid with a nauseating after taste. Chemically castor oil is a triglyceride (ester) of

fatty acids (7). Approximately 90% of the fatty acid content is ricinoleic acid, an

18-carbon acid having a double bond in the 9-10 position and a hydroxyl group

on the 12th carbon. This combination of hydroxyl group and unsaturation occurs

only in castor oil. Other fatty acids (8) present are linoleic (4.2%), oleic (3.0%),

stearic(1%), palmitic(1%), dihydroxy stearic acid(0.7%), linolenic acid (0.3%)

and eicosanoic acid(0.3%).



(7)

OH

HO

O

89.5 % Ricinoleic Acid

4.2. % Linoleic Acid

3.0% Oleic Acid

1.0 % Stearic A cid

1.0% Palmtic A cid

0.7% Dihydroxystearic Acid

0.3% Linolenic Acid

0.3% Eicosanoic A cid

H O

O

H O

O

H O

O

HO

O

H O

O OH

O H

HO

O

HO

O

(8)

Because of its highly polar hydroxyl groups, castor oil is not only

compatible but will plasticize a wide variety of natural and synthetic resins,



waxes, polymers and elastomers. It has excellent emollient and lubricating

properties as well as a marked ability to wet and disperse dyes, pigments and

fillers. The characteristics of castor oil are given in Table 1.2.

Table 1. 2

Specification for Castor oil

Sl.No Characteristics Castor oil

1 Appearance Light yellow

2 Odour Odourless

3 Specific gravity(g/cc at 300C) 0.964

4 Viscosity 1.965 ps

5 Moisture content 0.91

6 Hydroxyl value 2.1

7 Acid value 6.8

8 Iodine value (Wij's method) 84.54

9 Saponification value 91

Castor oil, like all other plant oils has different physical and chemical

properties that vary with the method of extraction. Cold-pressed oil has low acid

value, low iodine value and a slightly higher saponification value. The chemistry

of castor oil is centered on its high content of ricinoleic acid and the three points

of functionality existing in the molecule. These are the carboxyl group which can

provide a wide range of esterifications, the single point of unsaturation which can



be altered by hydrogenation or epoxidation or vulcanization and the hydroxyl

group which can be acytylated or alkoxylated or may be removed by dehydration

to increase unsaturation of the compound to give a semi drying oil. The oil is

characterized by high viscosity although this is unusual for plant oil. This

behaviour is due largely to hydrogen bonding of its hydroxyl groups. The

presence of hydroxyl group on castor oil adds extra stability to the oil and its

derivatives by preventing the formation of hydroperoxides. The presence of

hydroxyl groups and double bonds makes the oil suitable for many chemical

reactions and modifications.

1.5.1 Applications of Castor Oil

Castor oil is used to prepare polymers such as polyurethanes, polyesters,

epoxy polymers etc. Polyurethane is a versatile polymer with unique chemistry,

excellent mechanical and optical properties and has good solvent and oil

resistance, but lacks low temperature stability [127]. Castor oil is directly used as

a polyol to react with isocyanate groups in the preparation of polyurethanes

without any chemical modification [66, 139, 140-147]. Several researchers have

developed polyurethane materials using castor oil [148-150]. Castor oil based

polyurethanes are used as adhesives in wood industry [149].Castor oil based

polyurethane elastomers are a special type of synthetic rubbers [151].Novel

polyurethane insulating coatings are prepared from glycolyzed polyethylene

terephthalate and castor oil [152].Polyurethane nano particles are prepared by

mini emulsion polymerization from castor oil polyol [153].



Polyurethane-polyester non woven fabric composites are prepared from

castor oil [66]. Polyurethane biocomposites are prepared by reinforcing castor oil

polyurethane with hemp fiber. Polyurethane resin prepared from castor oil was

used to obtain graphite composite as an electrode material [154]. A new material

was prepared from castor oil based polyurethane resin and sisal and coconut

fibers [155].Castor oil based polyurethanes are also used as biodegradable

polymers [156].

Castor oil was used in the synthesis of low cost polyurethane coating

ingredient [157]. Kansara and co-workers [148] also studied castor oil based

polyurethane adhesives for wood. Yeganeh and Mehdizadeh [139] investigated

millable PU elastomers from castor oil-based polyols. Millable PU elastomers

(MPE) are a special type of synthetic rubber. Novel PU insulating coatings from

glycolyzed PET (GPET) and castor oil were also investigated by Yeganeh and

Shamekhi [151]. Yeganeh and Hojati-Talemi [143] also studied biodegradable

PU networks obtained from the PHCs of castor oil and PEG. Preparation of PU

nanoparticles by miniemulsion polymerization from castor oil polyol was

reported by Zanetti-Ramos et al. [152]. Ogunniyi et al. [29] reported the

preparation of PU foams using TDI and mixture of castor oil polyol and polyether

polyol.

1.6 Interpenetrating Polymer Networks

The synthesis of interpenetrating polymer networks (IPNs) is a useful

technique for designing materials with a wide variety of properties. IPNs



generally possess enhanced physico-mechanical properties against the normal

poly blends of their components. IPNs could also be called polymer alloys and

they are considered to be one of the fastest growing areas of polymer blends

during the last two decades. An interpenetrating polymer networks is any material

containing two polymers, each in network form [158]. Though, the term

interpenetrating polymer networks implies some kind of interpenetration of two

polymer networks, molecular interpenetration occurs in the case of mutual

solubility only [159]. In most cases, the molecular interpenetration may be

restricted and a super molecular level of penetration is observed .The

interpenetrating polymer networks can be characterised by studying the

morphology, mechanical properties, thermal behaviour, transport phenomena, etc.

Interpenetrating polymer networks are relatively, a novel type of multiphase

systems, where compatibility and certain degree of phase mixing is induced by

crosslinking and interpenetration of component polymer chains [159]. IPNs

constitute a group of polymer composite materials possessing unique properties

which are related to their method of synthesis. IPNs typically consist of a flexible

elastomer and one or more rigid, high modulus component [160]. Polyurethanes,

polystyrene, poly (methylmethacrylate) and poly (ethyl acrylate) are the most

common polymers that can be used in the preparation of IPNs.

1.6.1. Polyurethane IPNs Based On Plant Oil Raw Materials

The research work involving interpenetrating polymer networks (IPNs)

using naturally occurring triglyceride oils was initiated by Sperling and co-

workers [161-164]. They have shown that relatively low levels of grafting can



cause significant changes in morphology and behaviour of the final product. The

oils which have attracted attention for preparation of IPNs and semi-IPNs are

castor, vernonia and lesquerella, palmitic etc.Castor oil is widely used for the

preparation of polyurethane for semi-IPNs (9) [165]. IPNs (10) from castor oil

polyurethanes and poly (2-ethyl hexyl acrylate) in different proportions were

prepared [166]. IPN was synthesized from castor oil by Yenwo et al. [167,168]

using toluene diisocyanate to form polyurethane, followed by polymerization of

styrene and divinyl benzene.

(9) (10)

A Large number of IPNs based on castor oil and toluene diisocyanate with

vinyl components such as styrene, divinyl benzene, n-butyl methacrylate, methyl

methacrylate etc are synthesized [154,169-180]. Similarly, a number of semi-

interpenetrating polymer networks (semi-IPNs) were synthesized by reacting

polyurethanes (prepared from castor oil and various diisocyanates) and a phenolic

resin (prepared from cardanol and furfural) [133]. IPNs from crosslinked



polystyrene and castor oil elastomers have also been reported [181,182]. Suthar

and co-workers [183-186] prepared IPNs from polyurethanes-based on castor oil

with other vinyl monomers. They prepared polyurethane IPNs from castor oil,

TDI/MDI, poly (ethyl acrylate)/ poly (methyl acrylate)/ poly (n-butyl

methacrylate). and ethylene glycol dimethacrylate crosslinker. The glass

transition temperature of these IPNs ranged from 38 to 41◦ C.

Sperling and co-workers [187] reported the preparation of interpenetrating

polymer networks from castor oil-based polyurethanes and styrene monomer.

Prashantha et al. [188] studied IPNs-based on polyol modified castor oil

polyurethane and poly (2-hydroxyethylmethacrylate). Sanmathi et al. [179]

synthesized IPNs from modified castor oil-based polyurethane and poly (2-

ethoxyethyl methacrylate). Kansara et al. [189,190] also studied the sorption and

diffusion behaviour of IPNs-based on PU and unsaturated polyester (UPE). The

PU was prepared from castor oil polyol. Xie and co-workers [191] studied the

damping behaviour of grafted interpenetrating polymer networks. They prepared

IPNs from castor oil, toluene di isocyanate, mono hydroxy terminated acrylic pre

polymer and acrylic monomer in the presence of dibutyl tin dilaurate and redox

initiators. The dynamic mechanical properties of the IPNs were observed to

exhibit high damping properties over a wide range of temperature. Xie and Guo

[192] studied adhesives made from IPNs for bonding with rusted iron without pre



treatment. They prepared two types of room-temperature curable IPNs: one from

castor oil-based PU and vinyl or acrylic polymer and the other from castor oil PU,

unsaturated polyester and vinyl or acrylic polymer. The lap shear strength of

joints between rusted iron plates and IPNs (adhesives) ranged from 1.51 to 8

MPa. Cunha et al. [193] employed a statistical method to accurately evaluate the

properties of castor oil-based semi interpenetrating polymer networks (sIPN). The

semi-interpenetrating polymer networks (sIPNs) were prepared from castor oil

polyol, toluene diisocyanate and methyl methacrylate.

A number of semi-interpenetrating polymer networks (semi-IPNs) have

been synthesized using polyurethane and cardanol derivatives like acetylated

cardanol and phosphorylated cardanol and also by condensing cardanol-

formaldehyde hydroxyacetophenone or furfural novolac resins with

polyurethanes prepared from castor oil and diisocyanates [131]. Thermal

properties of the semi- interpenetrating polymer networks composed of castor oil

polyurethanes and cardanol- furfural resin have been studied [130, 133,194].

Nayak and co-workers reported the characterisation of some IPNs from

castor oil and cashewnut shell liquid [195] . This work is an attempt to synthesize

and characterize modified semi-IPNs from cardanol–formaldehyde–substituted

benzoic acid copolymerized resins. They [150] also synthesized using castor oil-

based interpenetrating polymer networks. First, they prepared polyurethanes from



castor oil and hexamethylene diisocyanate by varying the NCO/OH ratio and then

prepared IPNs by reacting polyurethanes with various acrylates such as

hydroxyethyl methacrylate and cardanyl methacrylate by using benzoylperoxide

as initiator and ethylene glycol dimethacrylate as crosslinker. Infra-red IR

spectroscopy, NMR spectroscopy, TGA, etc. were employed to study the

properties of resulting IPNs.

1.7. Addition Curable Polyester Resins and their IPNs

Polymers with hydrolysable backbones are susceptible to biodegradation

under particular conditions. Polymers that have been developed with these

properties include polyesters, polyamides, polyurethanes and polyureas, poly

(amide-enamines), polyanhydrides [11]. The aliphatic polyesters are almost the

only high molecular weight biodegradable compounds [13] and thus have been

extensively investigated. Aliphatic polyesters can be classified into two types

according to the bonding of the constituent monomers. The first class consists of

the poly hydroxyl alkanoates. These are polymers synthesized from hydroxyl

acids, HO-R-COOH. Poly (alkene dicarboxylates) represents the second class.

They are prepared by poly condensation of diols and dicarboxylic acids. Aliphatic

polyesters are the most extensively studied class of biodegradable polymers,

because of their important diversity and its synthetic versatility.



Unsaturated polyesters are low-molecular-weight maleate or fumarate

esters containing various chemical structures designed for their specific cost and

performance purposes [180,196,197]. In the chemistry of condensation polymers,

the maleation of natural oils, esterification of hydroxyl groups of ricinolic and

eleostearic acids and cis and trans isomerization generally occurs during the

polycondensation process. In polyester chain maleic anhydride is incorporated

mostly as fumarate groups. This is desirable phenomenon, as fumarate forms are

more reactive in copolymerization process with vinyl monomer. It has a favorable

effect on thermal and mechanical properties of obtained materials [197,198]. In

the unsaturated polyester chemistry the number and position of double bonds is

an important factor responsible for their properties. They act as a spacer to reduce

the number of double bonds and thus the cross-linking density [199].

Biodegradable hydroxyl terminated-poly (castor oil fumarate) (HT-PCF)

and poly(propylene fumarate) (HT-PPF) resins were synthesized as in situ-cross

linkable polyester resins for orthopedic applications [200].Unsaturated polyester

poly(propylene fumarate) (PPF) has been considered as one of the potential

biodegradable polymers for bone cement. Jayabalan et al. has prepared poly

(propylene fumarate-co-ethylene glycol) and evaluated for the use as scaffold for

correcting the bone defects [201-204].

Polycondensation of difunctional monomers preferentially yields low

molecular weight polyesters. Ring opening polymerization is preferred when high



molecular polyesters are desired. Most biodegradable polyesters are prepared via

ring opening polymerization of six or seven membered lactones [205,206].

Unsaturated polyesters were synthesized by the condensation of saturated and

unsaturated anhydrides (maleic anhydride and phthalic anhydride) with glycols

(propylene glycol and ethylene glycol, and diethylene glycol); the condensate

obtained is mixed with styrene monomer to get conventional crosslinked

polyester [207]. Lipase-catalyzed polyester synthesis has been attempted to avoid

condensation reaction at higher temperature [208]. However the polyesters

prepared by condensation polymerization lead to generation of water/methanol

and consequent formation of voids. Therefore addition polymerization and cross

linking is alternate process to generate void-free polyester materials.

With the emergence of novel polymer systems and technologies, which

enhance performance characteristics of the end products and replace conventional

polymer processing methods, the science on addition-curable resins have

occupied major importance in recent years. Therefore, it is relevant and important

to investigate plant oil-based addition-curable polyester resin, bio polyesters and

IPNs through environmentally safe processing methods towards the development

of value-added products.



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