Page No.:70

2.12.12.12.1 Introduction Introduction Introduction Introduction

Today, the high price of petroleum raw materials, scarcity

of petroleum products and stringent environmental rules and

regulations oblige synthetic polymer scientists to utilize natural

renewable resources as their feed stocks for the development of

polymers. These feed stocks are well accepted by chemists

because of social, economical and environmental reasons.

Fortunately, many researchers are now using renewable natural

resources as their feed stocks in the development of many

polymers.[1-2]

Petrochemical resources (crude oil, natural gases and so

on), used intensively in the worldwide chemical industry, are in

fact limited resources and in a certain period of time will be

depleted. The chemical industry is making big efforts to find

alternatives to the petrochemical raw materials.

One alternative represents the renewable resources which

already play an important role in the development of the

chemical industry. These renewable resources are relatively

inexpensive, accessible, produced in large quantities

(regeneratable every year and practically unlimited). [3-7]

Owing to the increase in the cost and limited availability of

petroleum sources recent trends of research is towards

development of alternative polyols from renewable resources. The

contribution of polyunsaturated vegetable oil and natural polyol

based polyurethane are reported by several authors. [8-9]

Vegetable oils and fats are very important resources for

polyols. The vegetable oils such as soybean oil, castor oil,

sunflower oil, palm oil, rapeseed oil, olive oil, linseed oil and so

on, with a worldwide production of around 110 millions t/year

(in 2000) [10-12] are used mainly in human food applications

(76%), in technical applications (19.5% only 7.5% is converted

into soaps, and 10.5% is used in oleochemical industry) and

1.5% in other applications. Soybean oil is the most important

Page No.:71

vegetable oil produced worldwide, representing 25% from the

total oils and fats, the second place being occupied by palm oil

(18%) [13-14].

In the polyurethane (PU) industry the development of

polyols based on renewable resources always played an

important role. One can say that all the history of PU was

strongly linked to the renewable resources.

The commercial use of isocyanate for polyurethane requires

not only appropriate co-reactants but also their ease of

availability at a reasonable price. So far these requirements have

been fulfilled almost completely by polyols, such as higher

molecular weight hydroxyl terminated polyether and polyester

polyols. [15]

Polyols are reactive substances, usually liquids containing

at-least two Hydroxyl groups attached to a single molecule. The

structure of polyol has a profound effect on the performance

properties of the finished polyurethane. Molecular weight,

functionality and molecular structure of polyol chain are equally

important. The Polyol compounds used for polyurethane

production have in general an average molecular weight between

200 to 1000 and functionality between 2 to 6. Nowadays

Polyether [16], Polyester [17], Polylactone [18], Polyacrylic resins

[19], Polycarbonate [20] etc are used for polyurethane

production. Among which compounds that have received most

attention are polyester and polyether based polyol. [20]

2.1.12.1.12.1.12.1.1 Polyols used for Renewable resourcesPolyols used for Renewable resourcesPolyols used for Renewable resourcesPolyols used for Renewable resources

In 1992, the total world’s production of vegetable oils

amounted to approximately 63 million metric tons (MMT), of

which 11.8 MMT found its way to industrial applications, mainly

to applications such as soaps and oleo chemicals. About 0.5

MMT was used in lubricants and coatings. [21] It was anticipated

that the total world’s production of oils and fats will rise to

Page No.:72

about 105 MMT per annum around the year 2010. [22] It is

expected that the use of vegetable oils, particularly in

lubricants, surfactants, coatings, genetic engineering and Bio-

degradable plastic [23] and bio-degradable binders for coatings

[24-25] will increase substantially.

The transformation of vegetable oils and other natural

products in polyols has opened up and is a very promising area

for new developments, such as genetic engineering to create new

triglycerides containing hydroxyl groups, synthesis of new

polyols by selective oxidation of vegetable oils (for example

microbial oxidation), new reactions for the transformation of

double bonds in polyols such as ozonolysis-reduction,

oxygenation reactions with molecular oxygen using special

complex catalysts (nickel complexes such as nickel

acetylacetonates), enzymic reactions, direct hydroxylation

reactions with heterogeneous catalysts (titanium silicalite) and

so on.[26]

For non-food applications, oleo chemical as well as fine-

chemical industries have expressed their interest in new fatty

acids with unusual properties and functionalities, since current

sources contain no more than approximately 10 different types

of fatty acid. Such usual fatty acids (Table: 1&2) could, on the

one hand, replace raw materials from petrochemical origin with

renewable resources and on the other hand, expand the existing

range of raw materials available and potentially lead to novel

products. Moreover, consumer products made from renewable

resources may also carry an appealing Environment-friendly or

“Green” label. Table: 1&2 gives an overview of a number of major

plant oils and their fatty acids that find use in coating

formulations together with some of their characteristics. The

major reactions of unsaturated triglyceride oils and derivatives

are depicted in Figure: 1.

Page No.:73

Table:Table:Table:Table:---- 1 1 1 1 Chemical Structures of fatty acids.Chemical Structures of fatty acids.Chemical Structures of fatty acids.Chemical Structures of fatty acids.

Page No.:74

FigureFigureFigureFigure:::: 1 1 1 1 Unsaturated Triglyceride ReactionsUnsaturated Triglyceride ReactionsUnsaturated Triglyceride ReactionsUnsaturated Triglyceride Reactions

Page No.:75

Table:Table:Table:Table:----2 2 2 2 Component fatty acids of Plant oils Component fatty acids of Plant oils Component fatty acids of Plant oils Component fatty acids of Plant oils

currently used in Coacurrently used in Coacurrently used in Coacurrently used in Coatings Industriestings Industriestings Industriestings Industries

Page No.:76

Dehydrated Castor oil:Dehydrated Castor oil:Dehydrated Castor oil:Dehydrated Castor oil:----

Castor oil is pale amber viscous liquid derived from the

seeds of the plant Ricinus Communis, sometimes known as

Ricinus oil. [27] Castor oil is one of the few naturally occurring

glycerides that approach being a pure compound, since the fatty

acid portion is nearly nine-tenths ricinoleic.

A crude Castor oil is a pale straw colour [27-28] but turns

colorless or slightly yellowish after refining and bleaching. The

crude oil has distinct odour, but it can easily be deodorized in

the refining process. Like any other vegetable oils and animal

fats, it is a triglyceride, which chemically is a glycerol molecule

with each of its three hydroxyl group esterified with a long clown

fatty acid. Its major fatty acid is the unsaturated, hydroxylated

12-hydroxy, 9-octadecenoic acid, known familiarly as Ricinoleic

acid. The fatty acid composition of a typical castor oil contains

about 87% of ricinoleic acid.

Castor plant (Recinus Communis) from which castor beans

and oil are subsequently derived grows naturally over a wide

range of geographical regions and may be activating under a

variety of physical and climatic regimes. The plant is however

essentially a tropical species, although it may grow in temperate

regions.[28] Literature revealed that Castor beans contains

about 30-35 percent oil [27-28] which can be extracted by

variety of processes or combination of processes, such as

hydrate presses, continuous screw presses and solvent

extraction. However the most satisfactory approach is hot

pressing using a hydraulic press, followed by solvent extraction.

[27-29]

However, castor oil and its derivatives are used in the

production of paints, varnishes, lacquers, and other protective

coatings, lubricants and grease, hydraulic fluids, soaps, printing

inks, linoleum, oil cloth and as a raw material in the

manufacturing of various chemicals sebacic acid and

undecylenic acid, used in the production of plasticizer and

Nylon. [30]

Page No.:77

The castor plant grows widely in the tropical and near-

tropical regions of the world as a perennial and is cultivated in

the tenlperate zones as an annual. About one billion pounds of

beans per year are processed, which yield about 500 million

pounds of oil. The principal producing-areas are in Brazil and

India. About 125 million pounds of castor oil were used in the

United States during 1958.

One hundred years ago castor oil was obtained from castor

beans grown in the United States. At the beginning of the 20 th

century increasing quantities of beans were imported until,

shortly after World War I, all oil used in this country was

obtained from imported beans. Beginning in 1950, oil began to

be imported as well as beans. The dependence on foreign sources

has resulted in shortages and wide fluctuations in price. It had

been recognized for some time that domestic production of the

bean was desirable to assure a supply of this critical commodity

in case of a natural emergency as well as a stable price to foster

development of new products and uses from castor oil as the raw

material. While previous studies had been conducted; in 1948 a

concentrated effort by the government and private industry

started to reestablish castor as a domestic crop. The current

success of this program is indicated by noting that 1,800,000

lbs. of castor oil were obtained from domestic seed grown in

1956, 10,000,000 in 1957, 22,000,000 will be produced from

seed grown this past year. While this is still only 15% of our

current consumption, the trend is significant. It is already

having a stabilizing influence on the price of castor oil, which is

reflected in the supply and price of dehydrated castor oil. While

there is still work to be done, the agronomists and engineers

have done a fine job in breeding new castor varieties to reduce

the size, decrease seed shattering, and develop appropriate

harvesting machinery. In 1958 the average yield of seed,

expressed as castor-oil equivalent, from one acre of land was

about 1,000 lbs. While most of the crop was on irrigated land, it

is of interest to note that this is about five times as much oil as

from an average acre of flax or soybeans. Castor oil occupies a

unique position in the field of natural fats and oils. While, like

Page No.:78

other common vegetable oils, it is a triglyceride, it is unusual in

that the acid components are predominantly a hydroxy

compound, also called ricinoleic acid. There is still some minor

disagreement among authorities as to the exact fatty acid

composition of the oil.

In the preparation of dehydrated castor oil, we shall be

concerned only with the chemistry of the ricinoleate portion. The

other acid components remain essentially unaltered.

Castor oil and its chemical derivatives are used by many

industries and in a large number of products. A recent U.S.I) .A.

circular states the total apparent disappearance of castor oil in

the United States in 1958 to be 120 million pounds. It breaks

down the consumption as soap less than 1/2 million pounds,

drying oil products 47 million, miscellaneous products 33

million, and unreported, including government stockpiling, as 39

million. [31-32]

Dehydrated castor oil is prepared by the removal of the

hydroxyl group and an adjacent hydrogen atom from ricinoleic

acid chain as water to form octadecadienoic acid chain, with the

double bonds at the 9,12-positions or at the 9,11-positions. The

conversion results in 2-3 parts of nonconjugated groups to each

one part of conjugated group.

Sixty years ago it was known that drying properties could

be developed in castor oil by heating. However the principal

interest in castor oil was then in its use as a lubricant. Thus

development work on dehydration was directed towards making

castor oil soluble in mineral oils. In 1913 Rassow [33] showed

that the product obtained from heating castor oil in the presence

of acid catalysts had increased unsaturation. Fokin [34-35]

identified the products as conjugated and nonconjugated fatty

acids similar to those obtained from linseed and tung.

Apparently the practical aspects of these observations were not

realized.

Until Scheiber [36] in 1928 announced his "discovery" of

his method for making a drying oil from castor oil. Seheiber's

process started with the castor oil fatty acids, technical

Page No.:79

ricinoleic acids, which were obtained from the oil by hydrolysis.

These acids were destructively distilled to give the linoleic acids.

By re-esterification with glycerol, dehydrated castor oil was

formed, known as "Seheiber Oil." While his process would be

considered impractical under current conditions, it was of

interest in Germany at that time because of the acute shortage

of tung oil. Furthermore it served to call attention to the

desirable properties of dehydrated castor oil for protective

coatings. Shortly after Scheiber's disclosures, methods for

catalytically processing the oil were developed. Ufer [37] is

usually given credit for the first practical process. Dehydrated

castor oil became a commercial product in this country in 1936.

Since the pioneering work of scheiber (1930) introducing

castor oil, after dehydration, as a substitute for tung oil,

extensive work has been carried out to find a suitable

dehydration catalyst. During dehydration of castor oil ricinoleic

acid is transformed in to 9, 11- and 9, 12-linoleic acid.

Commercial varieties of dehydrated castor oil contain

appreciable amount of this 9,11 isomer and so approach tung oil

in drying properties tung oil, however contains a conjugated

triene acid, viz. elaeo-stearic acid, which is absent in D.C.oil.

The absence of triple unsaturated fatty acids in dehydrated

castor oil imparts to it an outstanding non-yellowing

characteristic. The properties of tung oil have been compared

with various natural drying oils by Priest and von Mikusch

(1941). The drying time, rate of heat polymerization and water

and alkali resistance of the varnish film of dehydrated castor oil

is intermediate between that of linseed oil and tung oil. The

films produced by it are soften than those obtained from linseed,

perilla or tung oil but possess superior elasticity.

In the paints and varnish industry, dehydrated castor oil

has been achieved a place of its own along with the natural

drying oils. Terrill (1950) has reported that the conjugated

isomers in unbodied dehydrated castor oil generally amount to

30% Priest and von Mikusch (1940) have shown that the

conjugated isomers do not appreciably increase during bodying

of the dehydrated oil. A high proportion of non-conjugated

Page No.:80

octadecadienoic acid is found to be present in dehydrated castor

oil. The chemistry of the process dehydration of castor oil is still

ambiguous as a unanimous conclusion has not yet been reached

regarding the mechanism of some of the essential steps involved.

The primary object of the previous investigators had been

to obtain the maximum dehydration possible and with this object

in view, many empirical reaction conditions have been

suggested. In most of the investigations claiming complete

dehydration, the extent of dehydration has been ascertained by

determining the hydroxy value of the dehydrated oil. It has

however been shown by Kappeleimer et. al. (1948) that reactions

other than the conversion of ricinoleic acid to linoleic acid take

place during dehydration and so the procedure of using the

observed hydroxyl value as a measure of dehydration should be

denounced. The exact extent to which the various possible side

reactions occur depends on the conditions employed and its

absolute determination offers a rather difficult analytical

proposition. The influence of the constituent fatty acids in

castor oil, other than ricinoleic acid, on the course of

dehydration has not been studied. [38]

� Structure of Dehydrated castor oilStructure of Dehydrated castor oilStructure of Dehydrated castor oilStructure of Dehydrated castor oil

Page No.:81

� Jathropha oilJathropha oilJathropha oilJathropha oil

JATROPHA (Jatropha curcas L. ) Locally known as tuba-

tuba is one of the most promising sources of bio-fuel today.

About 30 percent of the tuba-tuba nut is composed of oil. This

oil can be easily processed into fuel that can replace or mixed

with petroleum based diesel to save on imported oil and most

importantly increase local employment and help the economy to

grow. The tuba-tuba has been planted for quite sometime but it

was mainly as fencing. It is also known in the Tagalog region as

“tubing bakod” and”sambo” while the Ilocanos call it “tawa-

tawa” while it is called “tagumbao” in Nueva Ecija and

Pangasinan. In the Cagayan Valley, it is known as “kalunay” and

“kasla” among the Ilonggos. In the Lanao region, it is known as

“tangantangan”.

Jatropha is a drought-resistant perennial shrub with an

economic life of up to 35 years and can even extend up to 50

years. The shrub has a smooth, gray bark which exudes a

whitish color, Watery latex when cut. The size of the leaves

ranges from 6-15 cm in length and width. It sheds Leaves in the

dry season and rejuvenates during the rainy season.

The flowers of Jatropha are formed terminally with the

female flowers usually slightly larger. It has two flowering peaks

which occur during the wet season. It is pollinated by insects

and each inflorescence yields fruits. Jatropha starts producing

seeds within 14 months from planting but reaches its maximum

productivity level after 4 to 5 years.

The seed matures when the capsules changes from green to

yellow about 2-3 months after flowering.

Jatropha is a potential source of biodiesel for local

production to replace a portion of the country’s dependence on

imported oil. The extracted oil from Jatropha can be used in

diesel engines (in lover blends with diesel fuel). Blending of fuel

Page No.:82

can be done up to 20 percent (B20) without engine modification.

Using Jatropha as biodiesel reduces greenhouse gas emissions.

Jatropha can be grown on marginal and degraded land, thus,

leaving prime agricultural lands for Food crops, and at the same

time restoring the fertility of these marginal lands.

Aside from using the seed oil as biodiesel, the extracted oil

can also be used in making soap. The leaves can be used for

fumigating houses to expel bugs. The root extract can be used as

yellow dye while the bark extract as blue dye. The seeds when

pounded can be used for tanning while the roots, flowers and

latex of the tuba-tuba plant are said to have medicinal

properties.

With the ever increasing interest in biodiesel fuels, we may

be one day getting used to the idea that fuel for our vehicles was

harvested from local plantations instead of using imported oil.

[39-40]

Jatropha seed oil is extracted from the plant Jatropha

Curcas. The plant grows almost anywhere even on gravelly,

sandy and saline soils easily, which would otherwise lie waste. It

is a perennial plant which does not require much care and is

productive for 30-40 years. [41] Plantation of Jatropha is done in

the Tamilnadu, Andhra Pradesh, Bihar, Gujarat and certain

other plants of India.

The plant of Jatropha is a medium sized woody plant with

simple palmate or lobed leaves and umbel inflorescence. The

plant has brightly colored flower which makes it an ornamental

plant. The fruit tends to be capsular green when tender, yellow

when strong and dark brown when dry.

The oil content is 25-30% in seeds and 50-60% in the

kernel. [42] It contains 30-40% oleic acid and 35-40% linoleic

acid which the amount of linolenic acid is only 1-2.0%. There are

some chemicals elements in the seed, cursin, which are

Page No.:83

poisonous and render the oil not suitable human consumption.

Various methods for recovering of oil from seeds, including

extraction with organic solvents and water have been

investigated. The enzyme supported aqueous extraction offers a

nontoxic alternative to common extraction methods using

organic solvents with reasonable yields. [43]

The oil has a very high Saponification value and is being

extensively used for soap making in some countries. Also, the oil

is used as an illuminant in lamps as it burns without emitting

smoke. The latex of Jatropha curcus contains an alkaloid known

as Jatrophine which is belived to have anti – cancerous

properties. It is also used for skin diseases as an external

application. Jathropha curcus is also used for the preparation of

dye and alternative to diesel. [44] The oil is used as a thermal

stabilizer. [45] and as a biofuel. [46] staumann R, G.Foidl et al

produced biogas from Jatropha curcas press cake. [47]

� Structure of Jathropha oil:Structure of Jathropha oil:Structure of Jathropha oil:Structure of Jathropha oil: ----

Page No.:84

� Sesame Oil:Sesame Oil:Sesame Oil:Sesame Oil:

Sesame, Sesamum indicum L., is an ancient oil crop

supplying seeds for Confectionery purposes, edible oil, paste

(tahini), cake and flour. It is typically a crop of small farmers in

the developing countries. In 1993, all but 1000 half of the about

7 million has of sesame grown were in developing countries.

Sesame has important agricultural attributes: it is adapted to

tropical and temperate conditions, grows well on stored soil

moisture with minimal irrigation or rainfall can produce good

yields under high temperatures, and its grain has a high value

($Al000/t).

Sesame seed is believed to be one of the oldest seeds to

have been used as a condiment, as well as for the home-based

production of oil. Sesame oil is traditional cooking oil with a

long history, which is mainly cultivated in India and china but

also in Sudan and neighboring countries and in parts of Central

America (e.g. Mexico).It is derived from the seeds of the sesame

plant which is mainly cultivated in tropical and sub-tropical

areas with a dry and a rainy season. It requires a lot of water in

order to grow and ripen and a dry season during the harvesting.

It is an annual plant, growing on average between 50 to 250cm

high and is rich in flowers. Ideal growing temperatures lie

between 27 and 30°C. Harvesting is done by hand, with the

plants being cut manually and dried in the field. They are then

shaken so that the seeds fall out of the open pods. The

harvesting period in the Northern Hemisphere is between

October and December and, in the Southern Hemisphere, March.

The largest producers in Asia are China and India; in Africa it is

Sudan followed by Nigeria while, in Central America, it is Mexico

and Guatemala. [49]

Page No.:85

Sesame world production areas have remained generally

stable over the years, but in some countries the crop is being

marginalized. Competition from more remunerative crops and a

shortage of labour have pushed sesame to the less fertile fields

and to areas of higher risk. Left unchecked, sesame production

may decrease in the foreseeable future. This provides an

opportunity for Australia to produce larger quantities of high

quality sesame seed to replace ‘lost’ world production.

However, before sesame can realise its potential, extensive

research is needed to adapt the crop to mechanical agricultural

systems. Furthermore, as Australia is becoming more involved

with Asian regional activities, where much of the world’s sesame

is grown, Australia’s own agricultural self interest could be

combined with its international extension and aid programs by

taking the lead in a regional sesame research and development

project.

Sesame grows best on well drained soils of moderate

fertility. The optimum pH for growth ranges from 5.4 to 6.7.

Good drainage is crucial, as sesame is very susceptible to short

periods of water logging. Sesame is intolerant of very acidic or

saline soils. [49]

The response of sesame to both temperature and day

length indicates that it is well adapted to wet season production

in the tropics, or summer production in the warmer temperate

areas. While there is some variation between cultivars, the base

temperature for germination is about 16°C. In temperate areas,

soil temperatures determine the earliest date of sowing. The

Optimum temperature for growth varies with cultivar in the

range 27–35°C. Periods of high temperature above 40°C during

Flowering reduce capsule and seed development. Because sesame

is short day plant, with flowering initiated as day length declines

to a critical level, cultivars are developed for particular

latitudes.

Page No.:86

Sesame oil has an unsaponifiable fraction with a unique

composition. Sesamolin and sesamin may be found in

concentrations up to 1–1.5 %. They are reported to give a high

oxidation stability, especially at elevated temperatures.

Concentrates of these or straight sesame oil have been used as

an additive to increase the oxidation stability in frying oils.

Sesame oil is also mainly used for human consumption but

a small percentage is used in the soap, cosmetic and skin care

industries. The market for sesame oil is mainly located in Asia

and the Middle East where the use of domestically produced

sesame oil has been a tradition for centuries. Oriental sesame oil

has a dark Colour and characteristic, nutty odour, which is

developed by roasting the seeds before extracting the oil. [50]

M.Bhattacharjee, et. al. was study to evaluate the

performance of sesame oil as an alternative of soybean and

linseed oil in the formulation of offset printing ink. Three sets of

rosin modified phenolic resin based varnish were made for offset

ink applications (sheet fed ink) using linseed, Soya, and sesame

oil as vegetable sources. Three offset cyan inks were made with

these three varnishes and were critically evaluated the

performance of the inks. Sesame oil showed significant

advantages on the controlled rheological properties with good

print and post print properties in comparison with other

conventional oils like Soya and linseed. Sesame oil produced a

superior quality of printed specimen with less hazards in the

runnability in the machine. So sesame oil can be successfully as

an alternative vegetable oil printing ink formulation. [51]

Page No.:87

2.22.22.22.2 Literature ReviewLiterature ReviewLiterature ReviewLiterature Review

Since the present study aimed for the synthesis and

characterization of renewable resources based Modified polyol

the literature survey on various aspects of their synthesis,

characterization and applications pertaining to surface coatings

are discussed in the following section.

2.2.12.2.12.2.12.2.1 Synthesis of Polyol base on renewable Synthesis of Polyol base on renewable Synthesis of Polyol base on renewable Synthesis of Polyol base on renewable

resourcesresourcesresourcesresources

V. C. Patel, et. al. synthesized Alkyd resin based on

Jathropha and rapeseed oils using glycerol, phthalic, and maleic

anhydride to obtain the resins suitable for electrical

applications. These resins were characterized for the physical

and electrical properties. Varnishes were prepared using these

resins and characterized as per standard methods. [52]

D.A.Raval, et. al. synthesized HEKFA ( N,N-bis [ 2-

hydroxyethyl] karanja fatty amide) by reacting karanja oil and

diethanolamine amine and the resulting HEKFA was used to

formulate thermosetting compositions and was used as cross-

linking agent for acrylic resins. The coating performance of the

various compositions were tested by measurement of properties

like Scratch hardness, Impact strength and Chemical resistance

and it was found better than equivalent butylated MF based

compositions.[53]

Madhu Bajpai et. al. used Tobacooseed oil fatty acids to

esterify novalac based epoxy resins. The novalac epoxy resins

were prepared by using three different ratios of phenol to

formaldehyde. The films of prepared epoxy esters with different

oil lengths were evaluated for various performance tests and

were compared with those of bisphenol-A based epoxy resin and

found better scratch hardness than those with lower phenol to

formaldehyde ratio, and also with shortest oil length. Alkali

resistance, Acid resistance and water resistance were found

excellent. [54]

Page No.:88

A.I. Aigbodian et. al studied the technical and economic

benefits of modifying Rubberseed oil (RSO) based alkyd with

cardanol-formadehyde (CF) resin. RSO and CNSL are by-products

of rubber (Hevea Brasiliensics) and Cashew (Anacardium

Occidentals) respectively. Raw RSO and its alkyds of different oil

lengths were blended with CF resin in a ratio of 9:1 and the

products obtained were tested for drying time and chemical

resistance. RSO modified with CF resins greatly improves its

drying ability and its chemical resistance. [55]

A.S.Trevino. et. al. converted the hydroxyl functionalities

of castor oil to β-Ketoester by reaction with t-butyl acetoacetate.

The resulting acetoacetate ester were used to formulate

thermosetting coating compositions .the pencil hardness and

flexibility was good. [56]

Andrew Guo. et. al. prepared two types of soy Polyols. One

with secondary OH groups resulted from epoxidation of soybean

oil followed by methanolysis and other with primary OH group

created from hydroformylation of soybean oil followed by

hydrogenation. Cast polyurethane has been prepared. [57]

L.E. Gast. et. al described the preparation from linseed oil

of some new polyester amide protective coating vehicles. N, N -

bis (2-hydroxyethyl) linseed amide was prepared by the base

catalyzed aminolysis of linseed oil with diethanolamine. The

cured film gave good drying properties, hardness and Xylene

resistance. [58]

M. Mosiewicki. et. al. prepared a polyester resin from

linseed oil and used as a matrix for composite material and

ultimate properties of composites revealed its utilization in

practical applications. [59-60]

Ivan Javni. et .al. synthesized Soya based polyols through

ring opening reaction of epoxidised soyabean oil with series of

alcohol and carboxylic acid was reported. He reported polyols

typically having a hydroxyl number of 180-200 mg KOH/ gm and

viscosity of 5-7 Pas, and thus suitable for the preparation of

range of polyurethane materials. [61]

Page No.:89

F.H. Otey et. al. extensively studied tranesterification

reaction between starch derived glycosides and castor oil at

different temperatures and found that the maximum yield is

derived under optimized reaction condition. They also reported

series of surface coating compositions containing vegetable fatty

acid and cellulosic material. [62-63-64]

Angela Kockritz. et. al. reported review the current

literature of the last 10 years on selective oxidation reactions of

fatty acid derivatives and vegetable oils. The work is structured

in divisions including epoxidation, radical oxidations, Wacker-

type oxidation, dihydroxylation and C=C double bond cleavage.

[66]

H.P. Bhunia. et. al. prepared Novel polyurethanes by

solution polycondensation reaction of 1,6-diisocyanatohexane

with 4-[(4- hydroxy-2-pentadecenylphenyl) diazenyl] phenol

(HPPDP) and 1,4-butane diol. The monomer (HPPDP) was

synthesized from cardanol, a renewable resource and the by-

product of the cashew industry. It was characterized by CHN

analysis, UV, IR and 1HNMR spectroscopy techniques.

Polyurethane characterization included elemental analysis.

1HNMR, IR, UV spectral analysis, dilute solution viscometry,

differential scanning calorimetry (DSC), thermogravimetric

analysis (TGA) and X-ray diffraction studies. TGA of the

polyurethanes indicated a higher thermal stability of 2450C in

nitrogen atmosphere at 30% decomposition. [67]

A. R. Fornof. et. al. studied the effect of time and

temperature on the air oxidation of soybean oil in the absence of

catalysts or added initiators was investigated. It was possible to

divide the air oxidation of soybean oil into three regimes. The

first regime of air oxidation resulted in insignificant change in

the hydroxyl number. During this regime, it was proposed that

natural antioxidants, which are present in raw soybean oil, were

consumed and peroxide formation occurred. A drastic increase in

hydroxyl number due to the formation and subsequent

decomposition of peroxides marked the second regime of air

Page No.:90

oxidation. In the third regime of air oxidation, free radical

crosslinking of the soybean oil occurred, and an insoluble gel

was formed. [68]

Dunlap. et. al. investigated the condensation reaction

between polycarboxylic acid based oil and diols was studied and

various parameters affecting this reaction such as type and

concentration of catalyst, reaction temperature and mole ratio of

the reactants. The authors also investigated the preparation and

reaction kinetics of fatty acid polyol from linseed oil and usage

of metal acetate as catalyst. [69]

Eef. A. Oostveen. et. al. developed durable and sustainable

coatings and additives for thermoset and thermoplastic materials

based on renewable resources. Authors presented Phthalate free,

high solid alkyd resins based on inventive combination of

sucrose, fatty acids, and renewable cross-linkers. They prepared

reactive diluents, water –borne alkyd emulsion and plasticizers.

[70]

P. K. Arndt. et. al. reported a new degradation method

(pivaloylysis) and prepared cellulose oligomers and reported

series of structural modifications of cellulose oligomer.[71]

Bustos G. et. al. hydrolysed sugar cane bagasse under

different concentration of Hydrochloric acid (2% - 6%), Reaction

time (0-300 min) and Temperature (100-128 oC) and rationalized

the products and suggested optimal condition as 128 oC, 2 %

HCl and 51.1 min.[72]

Gladys Sanchez. et. al. hydrolysed the hemicellulose and

cellulose parts in the straw material Paja Brava (Sturdy grass)

by using dilute sulfuric acid at 0.5 to 1 Wt % at 170 and 230 oC.

[73]

Since the days of Cross and Bevan, Many other methods of

treatments of wood and plants have been developed. Two of these

methods are by W.G. Van Beckum [74] (Chlorination followed by

ethanol amine extraction) and G. Jayme [75] (Treatment with

acidify Sodium Chloride at pH 3-4)

Page No.:91

Frenny. et. al. treated wood successively with chlorine and

then with aqueous potassium hydroxide and prepared a crude

cellulose. They found that the crude cellulose actually contain

large amount of non cellulosic polysaccharides termed β and γ-

cellulose, which are now included under the general terms hemi

cellulose. [76]

Jurgen Metzer. et. al focused on the conservation and

management of resources for the newer developments, to which

the scientists will make considerable contribution and encourage

the environmentally sound use of renewable natural resources.

In this contribution, author highlighted the chemical uses of fats

and oils as renewable stocks. [77]

2.2.22.2.22.2.22.2.2 Characterization of Polyol base on renewable Characterization of Polyol base on renewable Characterization of Polyol base on renewable Characterization of Polyol base on renewable

resourcesresourcesresourcesresources

N. Dutta et. al. synthesized three different polyester resins

from a purified Vegetable oil (Nahar Seed oil). The various

physical properties of the oil like iodine value, Saponification

value, specific gravity, moisture content, have been determined.

The monoglyceride have been obtained from the oil by

alcoholysis method. The synthesized resins have been

characterized by physico-chemical properties. [78]

S. Dutta. et. al. synthesized series of polyurethane resins

with varying NCO/OH resins from the monoglycerides of Mesua

Ferra L. seed oil, poly(ethylene glycol) and toluene diisocyanate

in the presence of dibutyltindilaurate as the catalyst. And

characterized the physical properties such as hydroxyl value,

acid value, Saponification value, iodine value, specific gravities

and isocynate value has been studied. [79]

B. Lin. et. al. synthesized Soybean oil based polyols (5-OH

polyol, 10-OH polyol and 15-OH polyol) from Epoxidized soybean

oil. The melting peak of polyols and the relationship between

melting peak and the number-average functionality of hydroxyl

Page No.:92

in polyols were investigated by differential scanning calorimetry

(DSC). The thermal decomposition of polyols and some of their

thermal properties by thermogravimetric (TG) and derivative

Thermogravimetric (DTG) were also studied. The thermal

stability of polyols in a nitrogen atmosphere was very close

hence they had a same base plate of triglyceride for polyols. [80]

Suresh S. Narine. et. al. prepared rigid polyurethane (PU)

foams using three North American seed oil as starting materials.

Polyol with terminal primary hydroxyl groups synthesized from

canola oil by ozonolysis and hydrogenation based technology,

commercial commercially available soybean based polyol and

crude castor oil were reacted with aromatic diphenylmethane

diisocyanate to prepare the foams. Their physical and thermal

properties were studied and compared using dynamic mechanical

analysis and thermogravimetric analysis techniques, and their

cellular structures were investigated by scanning electron

microscope. [81]

Azam Mukhtar. et. al. studied the fatty acid composition of

tobacco seed oil revealed that the oil is rich in unsaturated fatty

acids, having linoleic acid (71.63%), oleic acid (13.46%) and

Palmitic acid (8.72%) as the most abundant unsaturated and

saturated fatty acids respectively. So the tobacco oil was

characterized as semi-drying type on the basis of fatty acid

composition. The synthesis of alkyd resin was carried out by

alcoholysis or monoglyceride process using an alkali refined

tobacco seed oil, pentaerythritol, cis-1,2,3,6-tetrahydrophthalic

anhydride along with lithium hydroxide as catalyst. [82]

Sudhir. M. Malik et. al. selected alkyd resin prepared from

Neem oil (a non-traditional oil source) as one part and was

mixed with amino resin prepared with urea and thiourea in

various proportions. The properties of various mixtures of Neem

oil alkyd and amino resin determined to evaluate their

performance. [83]

Page No.:93

R.J.Parmar. et. al. utilized dimer fatty acids, obtained from

liquid fatty acids of Argemone and Rubberseed (the two non-

traditional oils) for making polyamide resins to be used as

curing agents for epoxy resins. Certain compositions were found

to have satisfactory performance when compared with that of

equivalent composition based on epoxy resin and polyamide

resin made from commercial dimer fatty acids. [84]

Kevin J Edgar. et. al. reviewed the performance of cellulose

derivatives in modern coating, control release activities, plastics,

composites and laminates, optical films, and membrane. [85]

Sun J. X. et. al. proposed three different procedures for the

isolation of cellulose from sugar cane bagasse. He compared and

characterized six samples of isolated cellulose by degradation

methods e.g. acid hydrolysis and thermal analysis. [86]

Mosier N.S. et. al. concluded that the acid catalyzed

hydrolysis of cellulose is proportional to H+ concentration after

systematically characterization of the acids with respect to

hydrolysis of cellobiose, cellulose in biomass, degradation of

glucose and compared the three kinetics data to dilute sulfuric

acid. [87]

William S. York. et. al. prepared a wide range of β-

glycosides (allyl alcohol, glycerol, ethanol, ethylene glycol, and

methanol) from cellulose and hemicellulose by using

Trichoderma reesei Cellulose enzymes as a catalyst. They also

reported a structural characterization of β-glycosides by MS and

NMR Spectroscopy. [ 88 ]

Sharif Ahmad. et. al. attempted to synthesize polyurethane

(PU) from linseed oil epoxy and developed from it an

anticorrosive coating. Physico-chemical characterization of the

synthesized resin was carried out as per standard methods and

he found that the resin showed good performance in various

corrosion tests and these studies showed that the material hold

promise for use as an effective anticorrosive coating compound.

[89]

Page No.:94

A.I. Aigbodion. et. al. evaluated Rubberseed oil (RSO) and

its derivatives, heated rubber seed oil (HRSO) and alkyd resins.

And they used as binders in air drying and waterborne coatings.

GPC analysis revealed that RSO consists of a rather high

molecular weight fraction that is rarely found in commonly

known vegetable oil and the average molecular weight of RSO

was higher than that of HRSO with later narrower in molecular

weight distribution. Low molecular weight species constitute

greater proportion of the alkyds and their number average

molecular weight range between 1379 and 3304 which are

comparable to those of commercial alkyds. All the alkyd samples

and HRSO were fairly resistant to water and alkali while they

were virtually unaffected by acid and salt solution. However,

samples of waterborne alkyds were more resistant than their

solvent borne counterparts but exhibited lower scratch / gauge

pencil hardness. [90]

Keyur Somani. et. al. synthesized Novel reactive polyols via

modification of castor oil, a renewable agricultural raw material

with epoxy resin and triethylamine as a catalyst. This polyol was

used for synthesis of polyurethane coatings. All coating

compositions showed good scratch resistance, better mechanical

and chemical properties. [91]

S.Singha. et. al. characterized and prepared three

Polyester amide resin were prepared from purified Nahar Oil

(Mesua Ferra) with phthalic anhydride, maleic anhydride and

adipic acid, separately. The polesteramide resins were

synthesized from N, N, bis (2-hydroxy ethyl) M ferra fatty amide

obtained from methyl ester of the oil by treatment of

diethanolamine amine. And the coating performance of the resins

was tested for gloss, pencil hardness, adhesion and chemical

resistance. The result showed better performance compared to

polyester resins of the oil. [92-93]

N.Dutta. et. al. Synthesized polyester resins from Nahar

seed oil and its Physico-chemical properties like acid value,

Page No.:95

Iodine value, drying time, volatile matter and viscosity were

measured according to the standard methods and the pencil

hardness and chemical resistance behavior of the cured resins

were also studied. [94]

D.A.Raval. et. al. synthesized polyesteramides from

Jathropha seed oil and physical, mechanical and chemical

properties of its coatings on mild steel panels have been

evaluated and the properties were compared with those of

pilufat based polyesteramides. [95]

Deewan Akram. et. al. studied polyols obtained from seed

oils have established themselves as excellent building blocks of

polymers, viz. polyurethanes. In this work, a novel attempt has

been made to incorporate boron in the backbone of polyol [LPO]

derived from linseed oil. Furthermore, LPO was treated with

phthalic anhydride [PA] and boric acid [BA] (in different molar

ratios) to obtain boron incorporated linseed polyester polyols

[BPPEs] through solvent less synthesis process. BPPEs were

characterized by spectroscopic techniques (IR, 1H NMR and 13C

NMR) to confirm the incorporation of boron and also to elucidate

their structures. Physico-chemical characterization and

antibacterial behavior of BPPEs was also investigated. It is

speculated that these resins may serve as excellent raw

materials for adhesives, coatings and as antibacterial agents.

[96]

Suresh S. synthesized Polyols by ozonolysis and

hydrogenation from canola oil were reacted with Aliphatic 1,6-

hexamethylene diisocyanates (HDI) to produce polyurethane (PU)

elastomers. The properties of the materials were examined by

dynamic mechanical analysis (DMA), thermo mechanical analysis

(TMA), modulated differential scanning calorimetry (MDSC), and

thermogravimetric analysis (TGA), and measurements were taken

of tensile properties. The effect of dangling chains on network

properties was assessed. The formation of hydrogen bonds was

observed by FTIR. [97]

Page No.:96

2.2.32.2.32.2.32.2.3 Applications of RenewaApplications of RenewaApplications of RenewaApplications of Renewable Resources based ble Resources based ble Resources based ble Resources based

MaterialsMaterialsMaterialsMaterials

Sandip D. et. al. synthesized Polyester polyols using

vegetable oil fatty acids having different characteristics (mainly

in terms of hydroxyl functionality) and epoxy resin, using

triethylamine as a catalyst. Polyols were characterized by the

FTIR spectroscopy. Polyurethane adhesives were synthesized

from it and used in bonding rubber. Treatment of sulphuric acid

on the non-polar styrene butadiene rubber (SBR) surface was

studied for the bond strength improvement via an increase in

wettability of the rubber surface. Wettability was found by

measuring the contact angle using Goniometer. Bond strength

was evaluated by 1800C T-peel test. The surface modification

and mode of bond failure were studied by Scanning Electron

Microscopy (SEM). The synthesized polyurethane adhesives were

compared with the commercial adhesive. [98]

A.I. Aigbodion, et. al. prepared Rubber seed oil (RSO) and

its derivatives, heated rubber seed oil (HRSO) and alkyd resins

were evaluated as binders in air drying solvent and waterborne

coatings. HRSO was obtained by heating RSO at 3000C until the

desired viscosity. Acid value of RSO (53) is somewhat high. The

major saturated fatty acids are Palmitic (10.2%) and Stearic

(8.7%) while the main unsaturated fatty acids are oleic (24.6%),

linoleic (39.6%) and linolenic (16.3%). Naturally, RSO is semi-

drying and heating enhances its drying ability. GPC analysis

reveals that RSO consists of a rather high molecular weight

fraction that is rarely found in commonly known vegetable oils.

The average molecular weight of RSO is higher than that of

HRSO with the latter narrower in molecular weight distribution.

Low molecular weight species constitute greater proportion of

the alkyds and their number average molecular weights range

between 1379 and 3304 which are comparable to those of

commercial alkyds. The narrower the size distribution the better

the quality of these alkyds as binders. Physico-chemical

Page No.:97

properties of solvent-borne alkyds vary with oil length (OL) and

they are optimum at 50% OL. Water-borne alkyds investigated

show that the sample with lower oil content contains lower

volatile organic content. All the alkyd samples and HRSO are

fairly resistant to water and alkali while they are virtually

unaffected by acid and salt solutions. However, samples IV and

V (water-borne alkyds) are more resistant than their solvent-

borne counterparts (samples I–III) but exhibited lower

scratch/gouge pencil hardness. [99]

John Argyropoulos, et. al.synthesized the hydroformylation

of seed oil based fatty acid methyl esters leads to aldehyde

intermediates that can be hydrogenated to give novel seed oil

based monomers. In this study, the seed oil based monomers

were polymerized with low molecular weight diols to produce

novel aliphatic polyester polyols with very low viscosities. The

seed oil polyester polyols provide environmentally friendly

(green) coating formulations with low volatile organic compound

emissions which lead to coatings with superior physical

properties, such as exceptional hydrolytic resistance and

flexibility. From these polyester polyols, waterborne

polyurethane dispersions were also developed with excellent

stability resulting in coatings with superior physical properties

(i.e., good toughness and abrasion resistance), and exceptional

hydrolytic and acid resistance. [100]

J. van Haveren, et. al. studied Due to limited fossil

resources and an increased need for environmentally friendly,

sustainable technologies, the importance of using renewable feed

stocks in the paint and coatings area will increase in the

decades to come. This paper highlights some of the perspectives

in this area. Alkyd resins for high-solid paints and reactive

diluents, completely based on commercially available renewable

resources, were prepared and characterized. Alkyd resins based

on sucrose and unsaturated fatty acids or oils showed a low

intrinsic viscosity, making them suitable to be used in high-solid

alkyd paints. Reactive diluents based on similar starting

Page No.:98

materials showed excellent properties with regard to thinning

behavior and effect on drying characteristics. Powder coating

polyester resins were synthesized, starting from isosorbide and

diacids. Polyester resins with glass transition temperatures up

to 700C were obtained. Incorporation of small amounts of other

diols and trifunctional components was found to improve color

and coating properties. In order to create completely renewable

resin systems, the development of renewable drying agents for

alkyds and crosslinkers for powder coatings is in progress. [101]

Esa Uosukainen, et. al. synthesized biodegradable

trimethylolpropane [2-ethyl-2- (hydroxymethyl)-1,3-propanediol]

esters of rapeseed oil fatty acids by transesterification with

rapeseed oil methyl ester both by enzymatic and chemical

means, both in bench and pilot scales. Nearly complete

conversions were obtained with both techniques. A reduced

pressure of about 2 to 5 kPa, to remove the methanol formed

during transesterification, was critical for a high product yield.

The quantity of added water was also critical in the biocatalysis.

Candida rugosa l ipase was used as biocatalyst and an alkaline

catalyst in chemical transesterifications. In biocatalysis the

maximum total conversion to trimethylolpropane esters of up to

98% was obtained at 42°C, 5.3 kPa, and 15% added water. The

maximum conversion of about 70% to the tri-ester was obtained

at the slightly higher temperature of 47°C. The reaction time was

longer in the biocatalysis, but considerably higher temperatures

were required in chemical synthesis. In the chemical synthesis

tri-ester yields increased when the temperature was first held at

85 to 110°C for 2.5 h and subsequently increased to up to 120°C

for 8 h. The trimethylolpropane esters obtained were tested as

biodegradable hydraulic fluids and compared to commercially

available hydraulic oils. The hydraulic fluids based on

trimethylolpropane esters of rapeseed oil had good cold stability,

friction and wear characteristics, and resistance against

oxidation at elevated temperatures. [102]

Page No.:99

Vikkasit Atimuttigul, et. al. prepared Short-oil alkyd resins

by using five different oil types: corn oil, rice bran oil, sunflower

oil, Soya bean oil and dehydrated castor oil (DCO). Among these,

Soya bean oil gave alkyd resin with the darkest color because

oxidation occurred. Auto air-dried coating films were developed

and it was shown that film prepared from rice bran oil-based

alkyd exhibited the longest drying time due to the low number of

double bonds compared to other and the extra natural

antioxidant in rice bran oil. DCO alkyd-based film revealed the

shortest drying time, the greatest hardness but the poorest

alkali and sea-water resistance. This is caused by the differences

in the type of fatty acid and double bonds, the high amount of

double bonds being in DCO. In addition, an increase in the

reaction temperature only had an influence on darkening the

alkyd color and decreasing the drying time of coating films. In

terms of technical properties and cost competitiveness, Soya

bean oil-based film is the best. Coating films derived from all

oil-based alkyds, except DCO, look promising for use in

surfboard manufacturing. [103]

Fengkui Li. et. al. prepared a variety of novel polymeric

materials ranging from elastomers to tough, rigid plastics by the

cationic copolymerization of regular soybean oil, low-saturation

soybean oil, or conjugated low-saturation soybean oil with

various alkene co-monomers. Using appropriate compositions

and reaction conditions, 70–100% of the soybean oil is

covalently incorporated into the cross-linked polymer networks,

contributing significantly to cross-linking during

copolymerization. The resulting thermosets exhibit

thermophysical and mechanical properties that are competitive

with those of their petroleum-based counterparts. In addition,

good damping and shape memory properties have been obtained

by controlling the degree of cross-linking and the rigidity of the

polymer backbone. New materials with similar characteristics

Page No.:100

have also been produced from other biological oils, including

Tung, and fish oils using the same technique. The new, more

valuable properties of these bioplastics suggest numerous

promising applications of these novel polymeric materials. [104]

Ogunleye O. et. al. studied on the effects of castor oil on

the properties of polyether based polyurethane foam such as

rising time ,density, hardness tensile strength, compression

,elongation and heat ageing. The castor oil was introduced into

the polyurethane foam by partially substituting it for silicone oil

through seven experimental set up based on the laboratory mix

formulation on 500g polyether based polyol with 0%, 20%, 40%,

50%, 60%, 80% and 100% castor oil substitutions .Incorporating

castor oil significantly increased density from 21kg/m3 for foam

without castor oil up to 25.73kg/m3 for 80% castor substitution

and hardness index from 119kN up to 125kN. Improved

compression set from 7.14% to 3.45 % was also noticed why

tensile strength and elongation decreased with increased castor

oil. Also heat ageing did not significantly affect the properties of

the foam samples. The rising time of foam also increased with

the increased castor oil. Clear cut conclusions on 100%

substitution of castor oil could not be made as the experimental

sample collapsed totally. [105]

James W Pollock. et. al. compared the environmental

impact of two Soya polyol materials with a conventional

petroleum derived polyol for Polyurethane products for variety of

applications. The Soya based Polyol feed stocks showed only

about one quarter of total environmental impact. [106]

V.C. Malshe. et. al. reviewed developments of newer

materials from renewable resources. The review also highlight

on the various modification and application of renewable

resources in coatings and industrial applications. [107]

Page No.:101

Bajpai. M, Seth. S. et. al. prepared the alkyd resin of short

oil length with low acid value was modified with novolac- based

epoxy esters, prepared by using tobacco seed oil fatty acids. The

prepared blends were cured using an aliphatic amine as curing

agent. The films of cured resins were applied over various panels

and their film characterized was studied. It was found that the

scratch hardness and corrosion resistance increased with the

increased of epoxy esters in the blend. The chemical resistance

was also studied and found to be better with increasing epoxy

esters in the blends. [108]

Johannes T. P. Derksen. et. al. discussed advancement in

renewable resources in formulating various types of coatings.

These reviews also included recent developments in the

application of vegetable oils and plant proteins in coating

systems. [109]

Bouyanzer. A, et. al. studied the effects of natural

Artemisia oil on the corrosion of steel in molar hydrochloric acid

were studied by the measurements of weight loss,

electrochemical and EIS polarization. The results obtained

revealed that Artemisia oil reduced the rate of corrosion. The

corrosion inhibition efficiency increased with the increase with

the inhibitor increase concentration. Potentiodynamic

polarization studies clearly revealed that the presence of the

natural Artemisia oil did not alter the mechanism of the

hydrogen evolution reaction and acted essentially as a cathodic

inhibitor. Good agreement between gravimetric and

electrochemical polarization results was noted. The effects of

temperature on the temperature range of 308-353 indicated that

inhibition that efficiency increased with temperature. The

adsorption of Artemise oil on the steel is followed by Frumkin

adsorption isotherm. [110]

J.M.E. Rodrigues, et. al. studied the Differential scanning

calorimetry (DSC) has been used to monitor the reaction between

Page No.:102

castor oil and isophorone diisocyanate (IPDI), using a non-

isothermal method, at different heating rates. The NCO/OH ratio

in these systems was 1, so that the concentration of NCO and

OH groups could be considered equivalent during all the

experiments. Despite the complexity of the system, in which

different order kinetics are possible, as well as physically

controlled diffusion processes, data were fitted to a simple

kinetic model, of apparent order n , apparent activation energy

EA, and apparent frequency factor A0. The dependency of these

parameters on heating rate was used to analyze kinetics of

polymerization of these systems. [111]

Saowaroj Chuayjuljit et. al. prepared rigid polyurethane

(PU) foam from palm oil-derived polyol. The polyol was

synthesized by transesterification reaction of palm oil and

pentaerythritol using calcium oxide as a catalyst. The obtained

palm oil-based polyol was reacted with commercial polymeric

diphenylmethane diisocyanate in the presence of water (blowing

agent), N,N dimethylcyclohexylamine (catalyst) and

polydimethylsiloxane (surfactant) to produce rigid PU foam. The

effects of the amount of the catalyst and surfactant on foam

properties (i.e. density, compressive strength and thermal

behaviors) were studied. [112]

Manawwer Alam, et. al. made to develop the room

temperature cured polyesteramide resin by condensation

polymerization reaction between fatty amide diol (N, N-bis 2-

hydroxy ethyl linseed oil fatty amide) obtained from oil of linseed

(Linum Ussitatissimum seeds) and pyridine dicarboxylic acid

(PyA) to develop pyridine polyesteramide (Py-PEA), which was

further treated with toluene-2,4-diisocyanate (TDI), in different

weight percentages to develop a series of pyridine poly(urethane

esteramide) resins (Py-UPEA). The structural elucidation of Py-

PEA and Py-UPEA were carried out by FT-IR, 1H-NMR and C-NMR

spectroscopic techniques. Physico-chemical characterizations of

Page No.:103

these resins were performed by standard laboratory methods.

Thermal analyses of these resins were accomplished by

thermogravimetric analysis (TGA) and differential scanning

calorimetry (DSC) techniques. Coatings of Py-UPEA were

prepared on mild steel strips to evaluate their physico-

mechanical and chemical/ corrosion resistance performances

under various corrosive environments. It was found that among

all these systems, the sample having 14 wt% loading of TDI

showed the best physico-mechanical and corrosion resistance

performances. Thermal stability performance suggests that the

system could be safely used up to 200°C. [113]

2.32.32.32.3 Synthesis of Modified Polyols from Synthesis of Modified Polyols from Synthesis of Modified Polyols from Synthesis of Modified Polyols from

Renewable resourcesRenewable resourcesRenewable resourcesRenewable resources

Having understood the synthesis of various Modified

polyols from renewable resources like Dehydrated Castor oil,

Jathropha oil and Sesame oil and their applications in diverse

range of industrial products, it was thought to derive the polyols

from other sources to be used for surface coatings. Thus in the

present study, the Modified polyols are derived by reacting non-

traditional oils like Dehydrated castor Oil (DCO), Jathropha Oil

(JO), Sesame oil (SO) with hydroxyl compounds viz. Ethylene

Glycol (EG), Dipropylene Glycol (DPG), Glycerine and Trimethylol

Propane (TMP). The synthesis involved the alcoholysis reaction

between the above moieties. Thus the series of Modified polyols

are prepared by varying the type and amount of each ingredient.

The resulting Modified polyols are characterized for various

physico-chemical characteristics essentially significant in

context to their utilization in surface coatings. The instrumental

techniques like IR and GC were also employed.

Page No.:104

2.42.42.42.4 Experimental workExperimental workExperimental workExperimental work

2.4.1 2.4.1 2.4.1 2.4.1 Synthesis of Modified PolyolsSynthesis of Modified PolyolsSynthesis of Modified PolyolsSynthesis of Modified Polyols

2.4.1.12.4.1.12.4.1.12.4.1.1 Materials and MethodsMaterials and MethodsMaterials and MethodsMaterials and Methods

In the present study, Dehydrated Castor Oil was obtained

from Usha Coating, Vitthal Udhyognagar, Vallabh Vidyanagar,

and Gujarat. Sesame Oil was procured form local market and

Jathropha oil was obtained from Bio-diesel Research Centre,

Agriculture University, Anand (Gujarat). The Fatty acid

composition and its Characterization of oils (physical properties)

are shown in Table: 3-8.

Trimethylolpropane (TMP), Glycerol, was obtained from

Himalaya Resins, Halol. Gujarat. And Ethylene glycol and

Dipropylene glycol were obtained from Samir-Tech. Chem. Pvt.

Ltd. Baroda, Gujarat, India. Lithium hydroxide (LiOH) and

Methyl ethyl ketone was procured from Chitichem Corporation,

Baroda.

Reactive diluents like Trimethylol propane trimethacrylate

(TMPTMA) and Photointiator like Benzophenone was procured

from Merck, USA. Dimethylethnolamine was obtained from

S.D.fine chemical, Baroda.

2.4.1.2 Synthesis of Modified Polyols based on 2.4.1.2 Synthesis of Modified Polyols based on 2.4.1.2 Synthesis of Modified Polyols based on 2.4.1.2 Synthesis of Modified Polyols based on

renewable resourcesrenewable resourcesrenewable resourcesrenewable resources

Polyols were prepared via alcoholysis of triglyceride oil by

proprietary method [114-116].

Alcoholysis of Dehydrated castor oil, Jathropha oil and

Sesame oil with Ethylene Glycol, DiPropyleneGlycol, Glycerin,

Trimethylol propane was carried out separately in the presence

of powdered LiOH (catalyst) with the mole ratio of 1:0.75, 1:1,

1:2 (Oil:Polyol) by following process. The reaction was carried

out under nitrogen atmosphere in a 500 ml four-necked flask

Page No.:105

equipped with a thermometer, a mechanical stirrer, heating

arrangement, Dean and Stark assembly and condenser. The oil

and polyol in stoichiometric ratio along with the catalyst (LiOH)

were charged in the flask and heated to a temperature of 250-

260oC. The progress of alcoholysis was checked at regular time

intervals, and practically the endpoint was taken as the point at

which solubility in alcohol was reached. At this stage heating

was stopped and the reaction mixture allowed to cool to room

temperature. The reaction scheme explaining the above reaction

is depicted as Scheme: 1. The compositions tried in preparing

the series of modified polyols are as described in Table: 9-11.The

resulting polyols were characterized as per the standard

methods.

2.52.52.52.5 CharacCharacCharacCharactttteeeerization of Modified Polyols based rization of Modified Polyols based rization of Modified Polyols based rization of Modified Polyols based

on renewable resourceson renewable resourceson renewable resourceson renewable resources

All the above prepared Modified polyols based on renewable

resources were free flowing liquids. The Characterization was

emphasized particularly on the properties, which have direct

relevance to their application in polyurethane synthesis.

2.5.12.5.12.5.12.5.1 Colour and Clarity (Visual)Colour and Clarity (Visual)Colour and Clarity (Visual)Colour and Clarity (Visual)

The polyols were taken in 100 ml glass cylinder. The visual

appearance of the liquid was checked as a clear (transparent), or

translucent or opaque and accordingly reported. The colour of

polyols was reported in the Gardner 1933 tube colour standard

scale in the range of numbers 1-18. The results are given in

Table: 9-11.

2.5.22.5.22.5.22.5.2 ViViViViscosityscosityscosityscosity

In this test, a liquid (polyol) stream is allowed to flow

downward in the ring shaped zone between the glass wall of a

sealed tube and the rate of rise of air bubble is noted. The rate

at which bubble rises is direct measure of kinematic viscosity.

The rate of bubble rise is compared with a set of calibrated

bubble tubes containing silicon oils of known viscosities. The

results are given in Table: 9-11. [117]

Page No.:106

2.5.32.5.32.5.32.5.3 Hydroxyl Value Hydroxyl Value Hydroxyl Value Hydroxyl Value

Hydroxyl value can be defined as “Number of milligram of

KOH equivalent to the acetic acid which combines with one gram

of the hydroxyl containing sample.” It was performed according

to ASTM Standard [114] Detail procedure is as under…

About 1 gm of the sample (W) was weighed accurately in

glass capsule and charged in the flat bottom flask. 15-20 ml of

predistilled n-butanol was added as diluent. Exact amount of

acetylating mixture (pyridine: acetic anhydride; 3:1) was added

to the flask containing the above mixture. It was stirred

vigorously. Flask was then equipped with condenser and the

mixture was refluxed gently for 1-1.5 hours. It was slowly cooled

down and 15 ml of water was added from the top of the

condenser, so that unreacted acetic anhydride gets converted

into acetic acid. Excess of acetic acid was back titrated using

standardized alcoholic KOH (S). [118]

Blank (B) was performed following the same procedure

without sample.

Hydroxyl value of the polyol was calculated by using

following equation:

56.11 (B-S) x NKOH

W

Where, B = Blank Reading, ml of standard KOH soln.

S = Sample Reading, ml of standard KOH soln

W = Weight of the sample in gm

And N = Normality of KOH Solution

With the help of hydroxy value, the average molecular

weight of sample calculated by the fol lowing formula,

2 X 56.1 X 1000Mol.wt. = ---------------------

Hydroxy value

H y d r ox y l V a l u e =

Page No.:107

2.5.42.5.42.5.42.5.4 Iodine ValueIodine ValueIodine ValueIodine Value

Iodine value is defined as “The weight of Iodine in grams

absorbed per 100 gms of sample under specified conditions”. It

is the measure of proportion of unsaturated constituents present

in the sample.”

It was performed according to IS method [119]. Detail

procedure is as given below…

1 gm of resin (W) was weighed in the glass capsule and

carefully introduced in the Iodine flask (250 ml). CCl4 (25 ml)

was added to dissolve the sample. Exactly 25 ml of Wij ’s solution

was pipetted using Propipetter and added to the Iodine flask.

The flask was stoppered and set aside for the one hour in the

dark. After this 15 ml of 10% KI solution along with 100 ml of

distilled water added to the flask. The liberated Iodine was

titrated against 0.1 N Na2S2O4 solution (Standardize) using

starch solution as an indicator. Burette reading was noted when

colour changes from blue to colourless (S ml). A blank

determination was carried out at the same time (B ml) without

addition of sample.

Iodine value of the polyol is calculated using following

equation:

IV W

NSBx )(69.12 −=

Where, B = Blank Reading, ml of standard Na2S2O4 solution

S = Sample Reading, ml of standard Na2S2O4 solution

W = Weight of the sample in gm

And N = Normality of Na2S2O4 solution.

Page No.:108

2.5.52.5.52.5.52.5.5 Preparation of Fatty Acid Methyl EsterPreparation of Fatty Acid Methyl EsterPreparation of Fatty Acid Methyl EsterPreparation of Fatty Acid Methyl Ester

Approximately 1 gm of oil sample was taken in a 100 ml of

standard joint round bottom flask and to it 10 ml of 0.5%

methanolic KOH solution was added. Water condenser was

attached and refluxed for 2 hrs at 70oC-80oC on water bath. The

content of the flask was than neutralized with 0.1 N HCl

solutions. The material was then transferred to a separating

funnel and the methyl ester extracted by using hexane as

solvent. The hexane layer was washed twice with distilled water

to remove the inorganic materials. The hexane distilled out

under vacuum and the methyl ester thus prepared was checked

for its purity on TLC plate. To check the purity of methyl ester,

glass plate having dimension 10 cm × 20 cm coated with silica

gel G (Mesh size:350) was used. After spotting of the sample

(Prepared methyl ester) and the standard methyl ester the plate

was developed with the following solvent system: Hexane-

diethylether, 99:1(v/v). After development, the plate was dried

and visualized under Iodine vapour. One single spot of same R f

value for prepared and standard fatty acid methyl ester indicates

that the methyl ester thus prepared were pure.

The product was thus ready for injection in Gas

Chromatography.

2.5.62.5.62.5.62.5.6 GGGGas Chromatography of prepared fatty acid as Chromatography of prepared fatty acid as Chromatography of prepared fatty acid as Chromatography of prepared fatty acid

methyl estermethyl estermethyl estermethyl ester

Gas chromatography of the methyl ester was carried out in

Perkin-Elmer gas chromatograph (Model: Auto system XL) using

BP 225 capillary column (Length: 25 meter, Inner Diameter:

0.250mm, Thickness: 0.25 micron) where fused silica was the

stationary phase. The mobile phase was hydrogen gas (Flow rate:

9 psi). Injection port and detector temperature were 250oC and

300oC respectively. The Gas Chromatograph was run in non-

Page No.:109

isothermal condition where the Initial Temperature was 65oC and

it was held for 5 minutes, then the temperature was raised to

220oC (Final Temperature) at 10oC/min and it was held for 20

minutes. Each time the sample (0.2 µL, dissolved in Chloroform)

was injected through micro syringe and the peaks obtained were

identified by comparing the relative retention time of these peaks

with those of standard fatty acid methyl esters. The fatty acid

compositions and Gas Chromatography Spectra were reported in

Table: 3-8 and Figure: 2-4.

2.5.72.5.72.5.72.5.7 IR IR IR IR ––––SpecSpecSpecSpectroscopytroscopytroscopytroscopy

IR spectrum of polyols is considered to be one of the useful

methods of characterization. In principle, it provides qualitative

and quantitative information about the structural details of the

polyols under examination. IR spectra are measured either by

making pallet with KBr or in the form of solution with suitable

solvent or by putting a drop of a sample between two KBr prisms

if sample is liquid. One of the most popular applications of IR

spectra is detection of functional group in the polymer chain.

In recent years, with the introduction of commercial

Fourier Transformation Infra Red (FTIR) spectrometer, that are

operatable over the entire IR frequency range, many application

of IR analysis that were impossible or at least difficult using

conventional dispersive instruments are now readily

accomplished [120].

The IR-Spectra [121] were scanned on Nicholet FTIR-

spectrophotometer in the range of 4000–400cm -1. The liquid

sample was taken on KBr- cell (The crystal of potassium

bromide). The representative spectra of oil and polyol are shown

in Figure: 5-16.

Page No.:110

2.62.62.62.6 Result and DiscussionResult and DiscussionResult and DiscussionResult and Discussion

2.6.12.6.12.6.12.6.1 Colour and ClarityColour and ClarityColour and ClarityColour and Clarity

The colour of liquid Modified polyols (Table: 9-11) derived

from (Dehydrated Castor oil, Jathropha oil, and Sesame oil) are

little darker then their parent oils. This may be due to partial

oxidation of fatty acid components during the hydrolysis

reaction [122].

2.6.22.6.22.6.22.6.2 ViscosityViscosityViscosityViscosity

The viscosity of liquid Modified polyols derived (Table: 9-

11) from Dehydrated Castor oil, Jathropha oil, and Sesame oil

can be compared and visualized on the bases of hydrogen

bonding and number of free hydroxyl groups. The hydroxyl

values of DCE-3, DCD-3, DCG-3, DCT-3, JE-3, JD-3 JG-3, JT-3

and SE-3, SD-3, SG-3, ST-3 are higher than those of other

description codes and that is mainly due to their tendency to

form intermolecular hydrogen bonding compared to the

corresponding ones. At the same time since TMP & Glycerine is

slightly more bulkier then Ethylene Glycol and

Dipropyleneglycol. It also affects the tendency of hydrogen

bonding of these said compounds.

2.6.32.6.32.6.32.6.3 Hydroxy ValueHydroxy ValueHydroxy ValueHydroxy Value

Hydroxyl values of the entire range of Modified polyols

prepared have been experimentally determined and the results

are reported in Table: 9-11. The renewable resources like

Dehydrated Castor oil, Jathropha oil, and Sesame oil based

Modified polyols, with increase in hydroxyl group content,

showed an increase in hydroxyl value of the polyols. At the same

time in almost all the polyols synthesized, the experimental

hydroxyl values are found to be slightly lower than the

theoretically calculated values. This can be attributing to the

following reasons.

Page No.:111

a) There may be a possibility of a side reaction such as

etherification of polyol under the conditions of

processing [123].

b) Polyol may have undergone an addition reaction with

carbon – carbon double bond to give a hydroxyl acid

[124].

The above side reactions would consume hydroxyl groups

without loss of carboxyl groups. This might result in the

reduction in experimental hydroxyl values.

2.6.42.6.42.6.42.6.4 IodineIodineIodineIodine Value Value Value Value

Iodine Value of all liquid Modified polyol is represented in

Table: 9-11. From the results it appears that the degree of

unsaturation of fatty acid chain is not significantly altered.

Based on the iodine values of the corresponding oil, it has been

found to be very close to the experimentally determined value.

These results are consistent with the proposed mechanism for

polymerization for alkyd [125], where, unsaturation of fatty acid

is not believed to be taking part in the reactions. The

unsaturated fatty acid system might have undergone

polymerization to form dimer by mechanism as suggested by

Harrision et al [126]. However, such reaction would not occur

due to the lower processing temperature and in the absence of

any catalyst and in the inert atmosphere.

2.6.52.6.52.6.52.6.5 Gas ChromatographyGas ChromatographyGas ChromatographyGas Chromatography

The oils used for the present work were characterized for

their fatty acid composition using gas chromatography. The

chromatograms of Dehydrated Castor oil, Jathropha oil and

Sesame oil are shown in Figure: 2-4. The fatty acid compositions

of each of the oil used in the present work are shown in Table:

3,5&7.

Page No.:112

2.6.62.6.62.6.62.6.6 Infrared spectral studyInfrared spectral studyInfrared spectral studyInfrared spectral study

Figure: 5-16 represents the IR–Spectra of Renewable

resources like oil (Dehydrated castor oil, Jathropha oil and

Sesame oil) and Modified polyol, derived from it.

The peak at 3400 cm -1 is more sharp and longer in polyol

than in parent oil which confirms the presence of free hydroxyl

groups upon alcoholysis of oil with polyhydroxy compound. The

peak at 1750 cm -1 also becomes sharp and longer in polyol than

for oil which also confirms the alcoholysis (Tran-esterification)

reaction of oil with polyhydroxy compound

Strong and sharp band at 1150 cm -1 can well be assigned

to C-O stretching of secondary -C-OH group along with the band

at 1350 cm -1 due to bending of C-OH group in the polyol.

Similarly strong band at 1050 cm -1 and at 1350 cm -1 can be

assigned to O-H bending vibrations and C-O stretching

vibrations of primary alcohol groups –CH2OH present in polyols.

The absorption bands at 1580-1600 cm -1 can be attributed

to diene type of unsaturation present in oil as well as polyols

and the strong bands at 1700 cm -1 of course to carbonyl group of

esters.

The unsaturation is also confirmed by the presence of -C-H

bending vibrations due to -CH=CH- group at 1420 cm -1 both in

oil and polyol.

2.72.72.72.7 SummarySummarySummarySummary

The Modified polyols were prepared successfully from

Renewable resources like (Dehydrated castor oil, Jathropha oil

and Sesame oil) by reacting with EG, DPG, Glycerin and TMP

and are all in liquid form having enough number of hydroxyl

groups required for further reaction with diisocyanates for the

synthesis of urethane acrylate oligomers. The instrumental and

physico-chemical characterization of these polyols revealed their

excellent suitability for utilization in synthesis of urethane

acrylate oilgomers to be used for UV-curable coating

compositions.

Page No.:113

Page No.:114

Figure: 2 Figure: 2 Figure: 2 Figure: 2 Gas Chromatography of Dehydrated Gas Chromatography of Dehydrated Gas Chromatography of Dehydrated Gas Chromatography of Dehydrated

Castor oilCastor oilCastor oilCastor oil

Page No.:115

Figure: 3 Figure: 3 Figure: 3 Figure: 3 Gas Chromatography of Jathropha oilGas Chromatography of Jathropha oilGas Chromatography of Jathropha oilGas Chromatography of Jathropha oil

Page No.:116

Figure: 4 Figure: 4 Figure: 4 Figure: 4 GGGGas Chromatography of Sesame oilas Chromatography of Sesame oilas Chromatography of Sesame oilas Chromatography of Sesame oil

Page No.:117

Table:Table:Table:Table:----3333 Fatty acid composition of Dehydrated Fatty acid composition of Dehydrated Fatty acid composition of Dehydrated Fatty acid composition of Dehydrated

Castor oilCastor oilCastor oilCastor oil

Dehydrated Castor oil Sr No. Name C-Group

Theoretical GC

1 Palmitic Acid C16 (1-3) % 1.6

2 Stearic Acid C18 (1-3)% 1.5

3 Oleic Acid C18:1 (3-5) 3.8

4 Linoleic Acid C18:2 (45-49)% 48

5 Linolenic Acid C18:3 (3-6)% 5.01

6 Arachidic Acid C20 (0.4-1) 0.9

Table:Table:Table:Table:----4 4 4 4 Physical Properties of Dehydrated Physical Properties of Dehydrated Physical Properties of Dehydrated Physical Properties of Dehydrated

Castor OilCastor OilCastor OilCastor Oil

Sr No.

Characteristics Specification Results

1 Refractive Index (1.4805-1.4825) 1.4820

2 Relative density@ 250C (0.925-1.115) 1.1171

3 Color ( Gardner) (5-15) (5-15)

4 Acid Value (mg KOH/gm),max (2-5) 1.8

5 Iodine Value (125-145) 142.2

6 Saponification Value (188-195) 182

Table:Table:Table:Table:----5 5 5 5 Fatty acid composition of Jathropha oilFatty acid composition of Jathropha oilFatty acid composition of Jathropha oilFatty acid composition of Jathropha oil

Jathropha oil Sr No. Name C-Group

Theoretical GC

1 Palmitic Acid C16 (14.1-15.3) % 15.2

2 Stearic Acid C18 (3.7-9.8)% 8.5

3 Oleic Acid C18:1 (34.3-45.8)% 43.20

4 Linoleic Acid C18:2 (29.0- 44.2)% 40.45

5 LinolenicAcid C18:3 (0-0.3)% 0.1

6 ArachidicAcid C20 (0- 0.3)% 0.2

Page No.:118

Table:Table:Table:Table:----6 6 6 6 Physical Properties of Jathropha oilPhysical Properties of Jathropha oilPhysical Properties of Jathropha oilPhysical Properties of Jathropha oil

Sr No. Characteristics Specification Results

1 Refractive Index (1.355-1.485) 1.422

2 Relative density@ 250C (0.925-1.00) 1.0171

3 Color ( Gardner) (9-15) 10

4 Acid Value (mg KOH/gm),max (5-9) 6.2

5 Iodine Value (135-145) 132

6 Saponification Value (180-195) 190.1

Table: Table: Table: Table: ---- 7 7 7 7 Fatty acid composition of Sesame oilFatty acid composition of Sesame oilFatty acid composition of Sesame oilFatty acid composition of Sesame oil

Sesame oil Sr No. Name C-Group

Theoretical GC

1 Palmitic Acid C16 (7-9)% 9.1

2 Stearic Acid C18 (4-5)% 4.3

3 Oleic Acid C18:1 (37-49)% 45.4

4 Linoleic Acid C18:2 (35-47)% 40.4

5 LinolenicAcid C18:3 (3-6)% 4.09

6 ArachidicAcid C20 (0.4-1) 0.8

Table:Table:Table:Table:----8 8 8 8 Physical Properties of Sesame OilPhysical Properties of Sesame OilPhysical Properties of Sesame OilPhysical Properties of Sesame Oil

Sr No. Characteristics Specification Results

1 Refractive Index (1.470-1.474) 1.472

2 Relative density@ 250C (0.925-0.990) 1.0171

3 Color ( Gardner) (12-15) 14

4 Acid Value (mg KOH/gm),max 2 1.8

5 Iodine Value (103-116) 112

6 Saponification Value (188-195) 192.5

Page No.:119

Table: Table: Table: Table: ---- 9 9 9 9 Characterization of Dehydrated Castor Characterization of Dehydrated Castor Characterization of Dehydrated Castor Characterization of Dehydrated Castor

oil based Modifiedoil based Modifiedoil based Modifiedoil based Modified Polyols Polyols Polyols Polyols

Sr. No.

Description Code

Polyol type Oil:

Polyol Ratio

OH Value

Viscosity @30oC

Color Specific Gravity

Iodine Value

%OH Group

1 DCE-1 Ethylene

glycol (1:0.75) 80.00 245 12 0.9245 136.2 2.85

2 DCE-2 Ethylene

glycol (1:1) 110.0 255 12 0.9856 132.2 4.85

3 DCE-3 Ethylene

glycol (1:2) 212.0 260 13 0.9977 128.6 6.72

4 DCD-1 Dipropylene

glycol (1:0.75) 80.00 235 10 0.9245 134.4 2.82

5 DCD-2 Dipropylene

glycol (1:1) 105.0 235 12 0.9618 132.2 4.62

6 DCD-3 Dipropylene

glycol (1:2) 183.09 255 12 0.9858 130.8 9.39

7 DCT-1 Trimethylol

propane (1:0.75) 120.00 245 12 0.9630 141.2 5.29

8 DCT-2 Trimethylol

propane (1:1) 155.10 245 13 0.9745 138.3 7.95

9 DCT-3 Trimethylol

propane (1:2) 282.0 260 13 0.9978 135.2 8.94

10 DCG-1 Glycerin (1:0.75) 125.00 235 12 0.9630 142.2 4.42

11 DCG-2 Glycerin (1:1) 160.00 245 13 0.9845 140.6 8.20

12 DCG-3 Glycerin (1:2) 302.00 255 13 0.9978 136.5 9.55

E - Ethylene Glycol

D - Dipropyleneglycol

T - Trimethylol propane

G - Glycerin

DCO - Dehydrated castor oil

Page No.:120

Table: Table: Table: Table: ---- 10 10 10 10 Characterization of Jathropha oil based Characterization of Jathropha oil based Characterization of Jathropha oil based Characterization of Jathropha oil based

Modified PolyolsModified PolyolsModified PolyolsModified Polyols

Sr. No.

Description code

Polyol type Oil:

Polyol Ratio

OH Value

Viscosity @30oC

Color Specific Gravity

Iodine Value

%OH Group

1 JE-1 Ethylene glycol (1:0.75) 80.00 200 10 0.9356 126.2 2.85

2 JE-2 Ethylene glycol (1:1) 115.1 225 11 0.9798 122.5 5.95

3 JE-3 Ethylene glycol (1:2) 220.0 230 12 0.9958 120.5 6.98

4 JD-1 Dipropylene

glycol (1:0.75) 80.18 210 10 0.9258 126.5 2.80

5 JD-2 Dipropylene

glycol (1:1) 108.8 215 12 0.9618 124.5 4.79

6 JD-3 Dipropylene

glycol (1:2) 193.70 225 12 0.9858 121.4 5.60

7 JT-1 Trimethylol

propane (1:0.75) 120.11 220 10 0.9230 134.5 4.48

8 JT-2 Trimethylol

propane (1:1) 160.00 235 12 0.9945 132.5 6.72

9 JT-3 Trimethylol

propane (1:2) 287.0 250 13 0.9978 128.5 7.68

10 JG-1 Glycerin (1:0.75)

130.0

220 10 0.9530 134.5 4.60

11 JG-2 Glycerin (1:1)

170.0

235 13 0.9845 132.5 8.72

12 JG-3 Glycerin (1:2)

310.0

250 13 0.9978 130.5 9.81

E - Ethylene Glycol

D - Dipropyleneglycol

T - Trimethylol propane

G - Glycerin

J - Jathropha seed oil

Page No.:121

Table: Table: Table: Table: ---- 11 11 11 11 Characterization of Sesame oil based Characterization of Sesame oil based Characterization of Sesame oil based Characterization of Sesame oil based

Modified PolyolsModified PolyolsModified PolyolsModified Polyols

Sr. No.

Description code

Polyol type Oil:

Polyol Ratio

OH Value

Viscosity @30oC

Color Specific Gravity

Iodine Value

%OH Group

1 SE-1 Ethylene

glycol (1:0.75) 90.10 200 10 0.9265 110.0 3.23

2 SE-2 Ethylene

glycol (1:1) 115.10 200 12 0.9898

109.2

5.95

3 SE-3 Ethylene

glycol (1:2) 220.00 250 12 0.9958 106.5 6.98

4 SD-1 Dipropylene

glycol (1:0.75) 80.00 200 10 0.9708 109.1 2.80

5 SD-2 Dipropylene

glycol (1:1) 110.00 200 12 0.9918 106.8 4.85

6 SD-3 Dipropylene

glycol (1:2) 195.22 225 12 0.9958 102.0 5.65

7 ST-1 Trimethylol

propane (1:0.75) 125.0 200 10 0.9950 106.0 4.67

8 ST-2 Trimethylol

propane (1:1) 160.0 250 13 0.9985 105.2 6.72

9 ST-3 Trimethylol

propane (1:2) 294.21 250 13 0.9998 100.0 7.88

10 SG-1 Glycerin (1:0.75)

130.0 220 10 0.9950 106.4 4.60

11 SG-2 Glycerin (1:1)

170.00 250 13 0.9985 102.2 8.72

12 SG-3 Glycerin (1:2)

310.00 250 13 0.9998 100.8 9.81

E - Ethylene Glycol

D - Dipropyleneglycol

T - Trimethylol propane

G - Glycerin

S - Sesame seed oil

Page No.:122

FigureFigureFigureFigure: : : : 5555 Dehydrated Castor oilDehydrated Castor oilDehydrated Castor oilDehydrated Castor oil

Page No.:123

FigureFigureFigureFigure: 6: 6: 6: 6 Dehydrated Castor oilDehydrated Castor oilDehydrated Castor oilDehydrated Castor oil (1:0.75) (1:0.75) (1:0.75) (1:0.75)

Page No.:124

FigureFigureFigureFigure: 7: 7: 7: 7 Dehydrated Castor oilDehydrated Castor oilDehydrated Castor oilDehydrated Castor oil (1: (1: (1: (1:1)1)1)1)

Page No.:125

FigureFigureFigureFigure: 8: 8: 8: 8 Dehydrated Castor oilDehydrated Castor oilDehydrated Castor oilDehydrated Castor oil (1: (1: (1: (1:2)2)2)2)

Page No.:126

FigureFigureFigureFigure: 9: 9: 9: 9 Jathropha oilJathropha oilJathropha oilJathropha oil

Page No.:127

FigureFigureFigureFigure: 10: 10: 10: 10 Jathropha oilJathropha oilJathropha oilJathropha oil (1:0.75) (1:0.75) (1:0.75) (1:0.75)

Page No.:128

FigureFigureFigureFigure: 11: 11: 11: 11 Jathropha oilJathropha oilJathropha oilJathropha oil (1: (1: (1: (1:1111))))

Page No.:129

FigureFigureFigureFigure: 12: 12: 12: 12 Jathropha oilJathropha oilJathropha oilJathropha oil (1: (1: (1: (1:2222))))

Page No.:130

FigureFigureFigureFigure: 13: 13: 13: 13 Sesame oilSesame oilSesame oilSesame oil

Page No.:131

FigureFigureFigureFigure: 14: 14: 14: 14 Sesame oilSesame oilSesame oilSesame oil (1:0.75) (1:0.75) (1:0.75) (1:0.75)

Page No.:132

FigureFigureFigureFigure: 15: 15: 15: 15 Sesame oilSesame oilSesame oilSesame oil (1: (1: (1: (1:1111))))

Page No.:133

FigureFigureFigureFigure: 16: 16: 16: 16 Sesame oilSesame oilSesame oilSesame oil (1: (1: (1: (1:2222))))

Page No.:134

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