International Journal of Chemical &

Petrochemical Technology (IJCPT)

ISSN(P): 2277–4807; ISSN(E): 2319–4464
Vol. 11, Issue 1, Jun 2021, 1–12
© TJPRC Pvt. Ltd.

SYNTHESIS AND CHARACTERIZATION OF RIGID POLYURETHANE (PU) FOAM

WITH FLY ASH AS REINFORCING AGENT

GITA RANI1,* RAMAN SWAMY2 & VISHAL SAINI3

1,2
Department. of Chemistry, Ch. Devi Lal University, Sirsa, Haryana, India
3
Department of Chemistry, CRDAV Girls College, Ellenabad, Haryana, India
ABSTRACT

The global PU market cost was 65.5 US billion dollars in 2018, 95.13 US billion dollars in 2019 and its expected
projection growth to almost 150 US billion dollars by 2023 at 12% compound annual growth rate. In present study, Rigid
PU foam was synthesized by using castor oil, glycerol, 4,4-dimethyldiisocyanate, silicon as surfactant using cobalt
octoate and trimethylamine as catalyst. To study the effect of reinforcing agent on the structure of PU foam and its
mechanical strength, PU foams were again prepared by adding 5%, 10% and 15% fly ash and tested their structure
changes. Characterization was carried out with Scanning electron microscopy and Fourier transform infrared
spectroscopy. Shifting of some FTIR peaks and change in intensity of some peaks are the results of some interactions of
reinforcing agent with basic component of PU foam and also due to the change in the cell size and structure of cell.

Original Article
KEYWORDS : Castor Oil, Fly Ash, Polyurethane Foam & Reinforcing Agents

Received: Feb 14, 2021; Accepted: Mar 04, 2021; Published: Mar 19, 2021; Paper Id.: IJCPTJUN20211

1. INTRODUCTION

In the field of polyurethane foam, polyether polyols are commonly used to make that type of rigid polyurethane
foam which is mainly used in packaging materials, building insulation, construction materials and refrigeration. In
the case of mattresses and seats, flexible polyurethane foams formed by polyester polyols are widely used. Polyester
can also be used in adhesives, fibres, elastomers and coating but to prepare rigid polyurethane foams having flame
retardant properties, heat ageing, wear resistance, chemical resistance and high adhesion. polyester polyols
competes the polyether polyols due to its low costs and high thermal retardant properties. The main problem related
to polyols is its sensitive nature to oxidation during its transportation and storage. To make polyurethane foam more
effective toward flame retardant, aromatic polyester polyols are preferred but high viscosity and low functionality
caps on the use of polyester polyols in wide range.

2. LITERATURE

Credit of invention of polyurethane foam goes to Otto Bayer (1940) who prepared first PU foam by using polyols,
isocyanates, catalysts and curing agents[1]. That time, its adhesive property and wetting property were the center of
attraction over the wood substrates. Silvaet al.(2010)[2] worked on a solventless castor oil based PU with different
NCO/OH molar ratio. They found that the joints formed by the solventless castor oil based have 75% more peeling
strength and 20% more lap shear strength than the joints formed by solvent based commercial PU foam adhesives.
Somani et at.(2003)[3] worked on PU adhesive made from renewable sources to make cost effective and
biodegradable adhesives for wood-wood bonding. Patel et al. (2009)[4] worked on modifications of castor oil to

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2 Gita Rani,* Raman Swamy & Vishal Saini

utilize double bond of unsaturated fatty acid and carboxyl group to yield activated polyols, which can enhance the adhesive
property of PU foam. They explained the role of NCO/OH ratio for adhesive power of PU foam and found that 1.5
NCO/OH was optimized for adhesives and higher NCO/OH ratio than 1.5 increases cross-linkage and decreases adhesive
power. Lower NCO/OH ratio also decreases the adhesive power by lowering low cross-linking density. Cardoso et
al.(2012)[5-6] worked on PU foam for thermal insulation by applying dynamic climate conditions and found that rigid PU
foam can be used in roof systems. They studied thermal conductivity, thermo-gravimetric analysis and kinetic study of PU
foam which provided the lifespan and thermal insulation of PU foam. Moura (2010)[7] showed that in the field of roof
systems, packaging and ceilings, the study of heat insulation has been got more attention in the research of PU foam. More
researches in this field also have been reported in literature such as work of Teemusket al.(2009)[8], Fao(2010)[9],
Preigaukas (2011)[10], Cangemietal.(2010, 2008)[11-12]. Tan et al. (2011)[13] used soyabean oil-based polyol (SBOP) to
increase the density of PU foam which enhanced the glass transition temperature, compressive strength and lowered the
thermal conductivity. SBOP has been proved more eco-friendly, less toxic[14] and better modifications over many natural
oil based PU foam which don’t have hydroxyl groups[15-16]. Lyon (1974) worked on introduction of hydroxyl groups in
natural oils. They prepared rigid foams from sunflower oil by adding cross-linkers[17]. Many studies on palm oils and
rapeseed oil based PU foam have been reported to enhance the cross linkage and compressive strength [18]. In this field more
works have been reported by Guo et al. (2006, 2007)[19-20], Narineet al. (2007)[21], Tuet al. (2006)[22], Das et al.(2020)[23].

3. EXPERIMENTAL
3.1 Physiochemical Studies of Raw Materials

To enhance functionality of polyols, modifications in polyols are carried out by mixing castor oil with glycerol in suitable
proportion. Castor oil is the most promising one to make polyols due to its cost effectiveness volume stability. Second raw
material to prepare the rigid polyurethane foam for research work is the mixture of 4,4’-MDIwith 2,4’-MDI because it has
bi-functional nature with two NCO groups. The selection of blowing agent depends upon the range of desired property of
PU foam such as to form rigid PU foam with low thermal conductivity and high stability, water can be used as blowing
agent while carbon dioxide is used as blowing agent in making flexible PU foam. Blowing agent is major effective
component to form PU foam and to enhance cell size and density of foam because these properties influence the insulation
performance of PU foam. To prepare PU foam, 4,4’-Diphenylmethandiisocyanate (MDI) was selected as isocyanate
monomer, Castor oil (Easily accessible and cheap vegetable oil) as polyol monomer, Methyl chloride as blowing agent,
cobalt octoate as catalyst and silicon oil as hardening agent as well as surfactant. Selection of materials was based upon the
easily accessibility, cost effectiveness, eco-friendly nature and replacement of petroleum products in formation of foam
with vegetable oil.

Modification of Castor Oil

By the study of composition of Castor oil it was found that the major constituent of castor oil is Ricinoleic acid (85-95%)
which has a hydroxyl group on 12th carbon in its molecule. To enhance the hydroxyl group on both end of oil trans-
esterification of castor oil with glycerol was performed which produce sebacic acid in Figure 1 [24].

Characterization of Modified Vegetable Oil and MDI

Acid Value of Polyols

Acid value is indicator of oxidation of polyol which is essential for its lubrication and its corrosiveness property. For a

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Synthesis and Characterization of Rigid Polyurethane (Pu) Foam with Fly Ash as Reinforcing Agent 3

good lubricant, polyol acid should be very low because very high value represents its corrosiveness. Acid value of polyol
was determined by titration of a known volume of polyol sample with standard solution of KOH by volumetric titration
and then calculated the acid value of polyols by using the formula below and the results are given in Table 1.

Where, V(ml) is KOH solution used for titration, W(g) is weight of sample and N is Normality of KOH.

Hydroxyl Value of Polyols

Hydroxyl value is the number of hydroxyl end groups in one gram of sample. It is important factor for quality control in
production of polyurethane. It was determined by the titration of 3 ml polyol with 1 N KOH solution with the help of
phenolphthalein indicator and calculated the hydroxyl value by the formula below and the results are given in Table 2.

Where, V(ml) is NaOH solution used for titration, W(g) is weight of sample and N is Normality of KOH.

Percentage of NCO

Percentage of NCO is the measure of the isocyanate content of MDI which is the weight percentage of unreacted
isocyanate groups in the sample. It was determined by the titration of 1ml MDI with N/2 HCl solution with the help of
bromo-phenol blue indicator and calculated percent of NCO by following relation and the results are given in Table 3.

Where, V(ml) is net volume of used HCl, W(g) is weight of sample and N is Normality of HCl.

Synthesis of Vegetable Oil based Rigid Polyurethane Foam

After the Characterization of raw material, polyurethane foam was prepared from modified castor oil, MDI, 3% catalyst,
15% blowing agent and surfactant by heating at ambient temperature with constant and vigorous stirring by scheme
reported in literature5. To enhance the thermal properties, mechanical properties and durability of foam, foam was prepared
with fly ash as a reinforcing agent. Properties of PU foam can be studied by various test method. The several researchers
(You et al. (2017, 2018)[25-26]) provided various methods for the study of PU foam.

4. RESULTS AND DISCUSSIONS

Characterization of Rigid Polyurethane Foam

To characterize PU foam, chemical and morphological characteristics of foam was studied with the help of FTIR and SEM
(Scanning Electron Microscope).

Structural Analysis of PU Foam by FTIR

To study the polymerization reaction of PU foam and the presence of free isocyanate groups, IR spectrum study was
carried out by using 400 FTIR spectrometer. FTIR was used to analyze the characteristic bonds of the synthesized
polyurethane FTIR analysis of the PU foam is given in Figure 2 and the analysis of characterization of the PU foam is

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4 Gita Rani,* Raman Swamy & Vishal Saini

given in Table 4. Analysis of the characterization of FTIR of PU foam through the Table 4 and Figure 2 clearly indicate the
formation of urethane linkage and the mechanism of the formation of PU foam as discussed in the preparation of PU foam.

Effect of Reinforcing Agents on Structure of PU Foam

To study the effect of reinforcing agent on the structure of PU foam and its mechanical strength, PU foams were again
prepared by adding 5%, 10% and 15% fly ash as reinforcing agent with respect to the amount of polyol in the PU foam and
tested their structure changes with the help of changes in their FTIR spectrum. By analysis of the FTIR spectrum of 5% Fly
ash (Figure 3), it is found that the basic pattern of FTIR is similar which indicates that the mechanism of formation of PU
foam and the basic structural arrangements are similar with PU foam given in Figure 4 but the shifting of some FTIR peaks
and change in intensity of some peaks are the results of some interactions of reinforcing agent with the basic component of
PU foam and also due to the change in the cell size and structure of cell.

By deep analysis of effect of concentration of fly ash in the foam structure, it was found that the N-H stretching
strength is increased by increase in concentration of fly ash but the stretching of C-H of methylene group, stretching of O-
Si-H of silicon oil, N-H bending and stretching of O-H of sebacic acid are decreased by increase in concentration of fly
ash.

The shifting of N-H stretching peak and N-H bending peak towards higher wave number with the rise in
concentration of reinforcing agent provide the evidence in favour in increase of strength of PU foam but the shifting of O-
Si-H linkage peak toward the lower wavelength with increase in concentration of fly ash provide the evidence of ionic
interaction of components of fly ash with silicon oil surfactant. Similar results are also shown by other peaks of FTIR
spectrum of PU foam with 15% concentration of reinforcing agents (Figure 4 and Figure 5).

Morphological Analysis by SEM

The Cross-sectional surfaces of the dry Polyurethane rigid foam were investigated using a JSM 6100 Scanning Electron
Microscope manufactured by JEOL Japan working at an accelerating voltage of 0.3-30 kV with resolution of 4.0 nm at
8mm working distance.

Characterization of Blank PU Foam without reinforcing agents

Microstructures of the polyurethane foam have proven to exhibit some relations with the behaviour of cellular solids. By
the analysis of the SEM images of PU foam without any reinforcing agents, it is found that the most of cell geometry in PU
foam are as honeycomb-like or polyhedral geometry. Closed type cell model was found in which two adjoining cells share
a wall and three cell edges meet a curved triangular plateau border at most of sites. Most of cells are pentagonal and
hexagonal arrangement but in a closed manner as shown in Figure 6. There are some ruptured cell structures and irregular
cell shape and there is large cell space which provides the evidence of less compactness and less strength of PU foam
without any reinforcing agents (Figure 7).

Characterization of Blank PU Foam with Fly ash as reinforcing agent

Presence of fly ash as the reinforcing agent decreases the cell size of PU foam as compared to blank samples of PU foam
(Figure 8). More cell size and layer formation of the cell were found with high resolution as shown in Figure 9.The data of
FTIR shows the hardness and high strength of the PU foam with fly ash as reinforcing agent which is evident by the SEM
images of very high resolution (x200 and x1000) of foam with fly ash (Figure 10 and 11) in which cell space is filled by

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Synthesis and Characterization of Rigid Polyurethane (Pu) Foam with Fly Ash as Reinforcing Agent 5

the filler (reinforcing agent fly ash) and the interaction of the Si with the components of the fly ash.

5. CONCLUSIONS

Presence of IR peaks at 1708.4 cm-1, 3406.4 cm-1, 1534.9cm-1and 1313.3 cm-1 represents the basic structure of
polyurethane foam with νC=Ostretching, νN-H amide stretching, νN-H amide bending and νN-C amide stretching respectively.
PU foam has honeycomb like or polyhedral geometry with closed type cell structure but some ruptures in cell wall of large
space weakness the compactness of strength of PU foam. Addition of fly ash as reinforcing agent decreases the cell size
and increases the hardness and strength of PU foam by interaction of silicon with fly ash. Increase in concentration of fly
ash enhance the stretching strength of N-H and decreases stretching of C-H of methylene group and stretching of O-Si-H of
silicon oil which provide the evidence in favor of increase in strength of PU foam.

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20. C.K. Lyon, V.H Garrett and E.N. Franker, J. Am. Oil Chem. Soc., 51, 331 (1974).

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Table 1: Observations and Results of Titration to determine the acidic value of Polyols
Volume of Polyol Normality of KOH used for Volume of KOH used for Acid Value of
taken titration (N) titration (V) Polyol
2ml 0.1 N 0.4ml 1.163 mg

Table 2: Observations and Results of Titration to determine the hydroxyl value of polyols
Volume of Polyol Normality of NaOH used for Volume of NaOH used for Hydroxyl Value
taken titration (N) titration (V) of Polyol
3ml 1N 26.2ml 507.71 mg

Table 3: Observations and Results of Titration to determine Percentage of NCO

Volume of MDI Normality of HCl used for Volume of HCl used for %NCO
taken titration (N) titration (V) Value
1ml 0.5 N 19.2ml 33%

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Synthesis and Characterization of Rigid Polyurethane (Pu) Foam with Fly Ash as Reinforcing Agent 7

Table 4 Analysis of Characterization of PU Foam through FTIR

IR Peaks Functional Group Analysis Evidence of Structural part in PU
1708.4 νC=O : Stretching of carbonyl group Polyurethane Linkage
of amide linkage
3406.4 νN-H : Stretching of N-H of amide Polyurethane Linkage
linkage
1534.9 νN-H : Bending of N-H of amide Polyurethane Linkage
linkage
1313.3 νN-C : Stretching of C-N of amide Polyurethane Linkage
linkage
1233.3 νC-O : Stretching of C-O-C of Functional group in backbone of PU foam due
anhydride linkage due to alcoholic to Sebacic acid part of monomer
part of monomer
3031.0 ν=C-H : Stretching of C-H of Benzene ring in backbone of PU foam due to
benzene ring MDI part of monomer
2931.8 νC-H : Symmetric Stretching of C-H Presence of CH2 group of aliphatic chain in the
of methylene group backbone of PU foam due to the part of Sebacic
acid monomer
2975.9 νC-H : Assymmetric Stretching of Presence of CH2 group of aliphatic chain in the
C-H of methylene group backbone of PU foam due to the part of Sebacic
acid monomer
1376.6 νC-H : Symmetric Stretching of C-H Presence of CH2 in between two benzene rings
1413.7 of methylene group in backbone of PU foam due to MDI part of
monomer
1081.1 νC-O : Stretching of C-O of acid Presence of δ bonds between C-O atoms related
to polyol or presence of capryl alcohol
2591.3 νO-H : Stretching of O-H of acid Presence of sebacic acid as polyol monomer
2280.2 ν O-Si-H : Stretching of O-Si-H of Presence of silicon oil
Silicon
Peaks at lower values are associated with the Skelton vibrations of C-C bonds of sebacic acid produced
by castor oil and the presence of aromatic rings in MDI.

Figure 1: Mechanism of Modification of Castor Oil with Ricinoleic Acid

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8 Gita Rani,* Raman Swamy & Vishal Saini

Figure 2: FTIR Spectrum of PU Foam without any Reinforcement Agents.

Figure 3: FTIR Spectrum of PU Foam with 5% Fly Ash Reinforcing Agent.

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Synthesis and Characterization of Rigid Polyurethane (Pu) Foam with Fly Ash as Reinforcing Agent 9

Figure 4: FTIR Spectrum of PU Foam with 10% Fly Ash Reinforcing Agent.

Figure 5: FTIR Spectrum of PU Foam with 15% Fly Ash Reinforcing Agent.

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10 Gita Rani,* Raman Swamy & Vishal Saini

Figure 6: SEM Image of Simple Blank PU Foam (Resolution x 20)

Figure 7: SEM Image of Simple Blank PU Foam (Resolution x 50)

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Synthesis and Characterization of Rigid Polyurethane (Pu) Foam with Fly Ash as Reinforcing Agent 11

Figure 8: SEM Image of PU Foam with 5% Fly Ash at Resolution of x20.

Figure 9: SEM Image of PU Foam with 5% Fly Ash at Resolution of x140.

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12 Gita Rani,* Raman Swamy & Vishal Saini

Figure 10: SEM Image of PU Foam with 5% Fly at Resolution of x200.

Figure 11: SEM Image of PU Foam with 5% Fly Ash at Resolution of x1000.

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