Production of Polyurethane: exploring novel raw materials and processes

Phase 1: Production of Polyols

1. Introduction

Polyurethanes (PUs) are one of the most dynamic group of polymers which are mainly

used in foams, elastomers, coatings, adhesives and more. They are versatile in many

applications for their low thermal conductivity, flexibility and high mechanical strength

(Aydogmus & Kamisli, 2017). PU, whose structural unit is shown in Figure 1, is obtained from

the reaction of polyols (organic substances with multiple hydroxyl groups) with diisocyanates.

Figure 1. Structural unit of polyurethane

The –NHCOO is the urethane group which are esters of carbamic acid. Conventionally,

polyols and diisocyanates are obtained from petroleum sources. However, it was determined

that continuous use of the said source might lead to the depletion of natural fossil resources.

Further, as consumers have increasing concerns on environmental impacts, it is highly desired

to develop polyurethane from bio-renewable feedstock. With this, rigorous studies have been

done on synthesizing raw materials for PU production from other renewable sources

(Aydogmus & Kamisli, 2017; Pfister, Xia, & Larock, 2011; Tan, Macosko, & Hoye, 2010;

Veronese, Menger, Forte, & Petzhold, 2011). Of particular focus is on the production of

polyols from plant oils to produce bio-based polyurethanes.

 Polyols

As of the current, only polyols (POs) can be effectively made from bio-renewable materials

and replace petroleum-derived POs (Garrison, 2013). Polyols in polymer chemistry, are

organic compounds which contain more than one hydroxyl groups (-OH) capable of

polyaddition reaction (Pilla, 2011). Generally, there are two types of POs used for PU

production namely the polyester and polyether polyol (Tan, Macosko, & Hoye, 2010). The

former is conventionally synthesized from direct polyesterification of diacids and glycols such

as phthalic acid and diethylene glycol, respectively (Figure 2). The latter on the other hand is

generally obtained through anionic polymerization in which an initiator containing two or more

active hydrogen atoms is added to initiate ring opening and oxide addition. An example would

be the reaction of ethylene glycol with propylene oxide to produce a polyether diol (Figure 3).

Polyether POs are also the predominantly used polyols in the industry owing to its low cost,

low viscosity and high functionality (Ionescu, 2005).

Figure 2. Sample reaction for the production of polyester polyols (Tan, Macosko, & Hoye, 2010).
 Figure 3. Sample reaction for the production of polyether polyols (DOW, 2017).

The nature of POs, together with the isocyanates (physical and chemical properties) have

a great impact on the properties of the final polyurethane product. For POs in particular, the

molecular weight and hydroxyl (-OH) functionality further differentiates PUs in terms of

applicative purposes into two categories: rigid and flexible polyurethanes (Table 1).

Table 1. Properties of polyols for rigid and flexible polyurethanes (Ionescu, 2005; Tan,
Macosko, & Hoye, 2010).
Polyol property Flexible foams Rigid foams
Molecular Weight (Daltons) 2000 – 10000 300 – 1000
Functionality (fn) 2-3 3-8

Functionality (fn) is defined as the average number of hydroxyl groups in a molecule.

Mathematically, it is obtained by dividing the molecular weight of the polyol by its equivalent

weight as seen in Equation 1.

molecular weight
Functionality (fn ) = equivalent weight [1]

where,

56,100
Equivalent weight = OH number [2]

From Table 1, a polyol with a high molecular weight and low functionality yields flexible

PUs. This category is known for its applications as cushioning and packaging material. On the
contrary, POs with high functionality and relatively low molecular weight lead to rigid PUs

which is characterized for its application as insulation and flotation material (Ionescu, 2005).

Polyols from plant oils

Vegetable oils

As mentioned, the production of PUs is highly dependent on petroleum sources. In fact, a

study by Pfister et al (2011) indicated that the PU industry accounts for roughly 7% of the

worldwide oil and gas consumption. With the possibility of depleting the natural fossil

resources, several biorenewable feedstocks for the production of plastics have been looked

into. To mention some are cellulose, starch, proteins, natural oils and sugars (Pilla, 2011). For

polyurethane production in particular, vegetable oils are found to be a promising source of

polyols for PU synthesis.

Vegetable oils are triglycerides which are triesters of glycerol and different fatty acids.

They are inexpensive, annually renewable and are available in high purity and vast quantities

which makes them an attractive venture for the PU industries. The composition of vegetable

oils in terms of the fatty acid side chains that is, the number of carbons and carbon-carbon

double bonds generally depends on the source of the oil. Vegetable oils contain five (5) major

fatty acids namely palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2) and

linolenic acid (C18:3) (Petrovic, 2008). In general, these oils are obtained from palm, soybean,

rapeseed and sunflower seeds accounting for approximately 86% of the global production of

vegetable oils (USDA, 2017). Presented in Table 2 are the percentage fatty acids content of

the major sources of vegetable oils.

 Table 2. Percentage composition of fatty acids (wt%) for different sources of vegetable
oils (Li, Luo, & Hu, 2015; Gunstone, 1996; Jamieson & Baughman, 1922)
Fatty Acid profile (wt%)
Source
Palmitic Stearic Oleic Linoleic Linolenic
Palm 44 4 38 10 trace
Soybean 10.7 3.9 22.8 50.8 6.8
Rapeseed 4 2 56 26 10
Sunflower 3.5 2.9 33.4 57.5 2.5 (trace)

The availability of the unsaturated sites in the fatty acids (C = C) can be used to introduce

hydroxyl groups thus making it possible to synthesize polyols from vegetable oils. The

efficiency of using vegetable oils have already been proven by several studies and patents

(Maisonneuve, Chollet, Grau, & Cramail, 2016; Salleh, Tahir, & Mohamed, 2017; Narine,

Kong, & Bouzidi, 2007). Even bio-based polyurethane foams are already commercialized. One

of its breakthrough applications is on the automotive industry as seen in Table 3.

Table 3. Examples of commercial bio-based polyurethane foams for automotive

applications presented according to their bio-based raw materials (Pilla, 2011).
Raw Trade Name of Type Company for Automotive
Materials PUR/Polyols PUR/ Polyols Applications
Soybean Oil SoyOyl®-based Flexible foams  Baydure ®  Seat-cushion and
PUR foams, such PUR: Bayer seat-backs in Ford
as Baydur®  SoyOyl® Mustang, Ford
polyurethanes polyols: Expedition
Urethane Soy
System
BioFoamTM Flexible foams  BioFoamTM  Seat-cushion and
based on BiOHTM PUR: seat-backs in Ford
polyols Woodbridge Escape 2009
 BiOHTM
polyols:
Cargill
Castor oil Lupranol® Flexible and BASF  Automobile seats
BALANCE50- rigid foams arm and head rests
based PUR foams
Sunflower Bio-based PUR Flexible and Mitsui Chemicals  Automobile seats
and/ or foams rigid foams
rapeseed oil
 In the Philippine context, majority of these vegetable oils are not of usual commodity. Out

of the sources mentioned, only palm oil has been produced in the country at considerably large

quantities (RBOI, 2017). Production volumes though cannot ultimately meet the demand from

domestic consumers as seen in Figure 4 (Corpuz & Verzani, 2017). With this, it is necessary

to investigate other bio-renewable sources for the production of polyols.

1200

1000

800
1000 MT

600
Production
Consumption
400

200

0
2008 2010 2012 2014 2016 2018
Year

Figure 4. Production and consumption of palm oil in the Philippines

(Corpuz & Verzani, 2017).

Alternative sources of polyols

Coconut oil
One possible source that maybe looked into are coconut oils. Although majority of the fatty

acids in coconut oils are saturated in nature, a process known as the

transesterification/amidation can be used to produce polyols from the said source. Though

scarce information about this process are available, according to Yakushin et al (2013),
diethanolamides of some oils have already been synthesized (nahar and palm) which were able

to produce polyurethanes with good characteristics.

If harnessed successfully, this would be a sound economic venture for countries like the

Philippines which is considered as one of the top producers of coconut oils. Additionally, a

data from the Department of Agriculture (2017) indicated a total coconut oil production of 13

million MT/year which makes us second from Indonesia as the biggest producer of coconut

oils in the world.

Waste cooking oil

Aside from fresh vegetable oils, waste cooking oil can also be a source of POs (Salleh,

Tahir, & Mohamed, 2017; Aydogmus & Kamisli, 2017; Rus, Salim, & Sapiee, 2015). Waste

cooking oils result from cooking of foods by cooks, food manufacturers and catering

establishments such as fast food chains, restaurants and industrial kitchens. These oils contain

significant amounts of unsaturated fatty acids which can be synthesized further into POs. A

study by Salleh et al (2017) for example was able to produce PU from waste cooking oil in

which the properties are comparable to that of PUs from petroleum derive POs.

Montefrio and Obbard (2008) estimated that approximately 35, 000 liters of waste cooking

oil per month can be recovered from the household and commercial sectors of the cities in the

Philippines. Majority of these oils are illegally dumped into rives and landfills causing

environmental pollution hence, efforts have been extended on the recycle of waste cooking

oils for other purposes (Namoco et al 2017). To date, some waste cooking oils are made

feedstocks for biodiesel as well as on the production of animal feeds.

Processes involved for the Production of Polyols

There are five known paths for the synthesis of polyols from plant oils. These processes as well as the corresponding advantages and

disadvantages are presented in Table 4.

Table 4. Processes involved in the production of polyols from vegetable oils (Li et al, 2015; Pfister et al, 2011; Guo et al,
2002)
Processes Process Definition Advantages Disadvantages
Epoxidation and Epoxidation has been one of the most  Simple reaction steps and does  Produces secondary –OH
Oxirane Ring- commonly used methods for the not require the use of groups which are less
Opening Pathway functionalization of carbon-carbon hazardous chemicals and reactive than the primary
double bonds. Once the double bonds expensive catalysts. ones.
are epoxidized, they can be converted  Synthesis conditions are not  Presence of dangling chains
into –OH by oxirane ring-opening harsh. Maximum temperature in the polyol structure which
agents such as alcohols, acids and o
setting is at 80 C. may cause steric hindrances
hydrogen.  If reaction conditions are for crosslinking during the
properly optimized the polyurethane production.
conversion of fatty acids to  Polyurethane produced have
polyol can reach up to 90%. higher aging rates which
 High functionality of polyols means that its thermal
can be obtained. conductivity increases with
time due to N2 permeation.
 Polyol modification (e.g.
addition of halogens) is
sometimes necessary.
Hydroformylation In this process, the double bonds in  If properly optimized,  Expensive catalysts are
and Hydrogenation plant oil structures are first converted conversion of fatty acids to required for the synthesis
Pathway to aldehydes via catalyzed polyol can reach 95%.
 hydroformylation by syngas and then  The major advantage of the such as the rhodium and
to hydroxyl groups via hydrogenation process is the formation of raney nickel.
of aldehyde. primary hydroxyl groups,  The presence of
which are preferred to the heterogeneous hydroxyl
secondary hydroxyl groups functionality distribution
usually obtained from which has shown negative
epoxidation and oxirane ring- effect on the performance of
opening pathway. the PU obtained.
 Polyols produced are more
reactive thus requires less
catalyst and isocyanates in PU
synthesis.
Ozonolysis Pathway Polyol production from plant oils  Because of the cleavage of all  The functionality of the
involves two steps: (1) formation of double bonds during polyol produced can only be
ozonide at the unsaturation sites of ozonolysis, only primary at most three.
vegetable oils and simultaneous hydroxyl groups can be made  Use of potentially hazardous
decomposition of ozonide into which have high reactivity chemicals such as ozone.
aldehyde and carboxylic acids and (2) towards polyurethane  Expensive reagents and
reduction of aldehyde into alcohol formation. catalyst for the synthesis.
with a catalyst.  The dangling chains are
removed which may act as
plasticizers to weaken the PU
formed.
 Polyols produced are less
viscous which makes it easy to
handle.
 Polyurethanes produced
exhibit higher glass transition
temperatures and better
mechanical properties
compared to polyurethane
produced from other methods.
Thiol-ene Coupling Thiol-ene coupling reactions involve 
Pathway a free radical chain mechanism by
which thiols are grafted onto double 
bonds. They are not sensitive to
oxygen and can be carried out in the
absence of photoinitiators through a 
photoreaction.
Transesterfication/A Transesterification and amidation use 
midation Pathway a different approach that makes use of
the ester moieties in the structures of
plant oils to produce polyols
 Amidation-derived
 Polyols from this process are
High conversion yield and fast  Harsh reaction conditions
reaction rate. which involves UV
Polyols produced from this irradiation.
process have high  Expensive catalysts used for
functionality. the synthesis of polyols.
PUs derived from these two
polyols showed properties
such as thermal and
mechanical properties similar
to those from a commercial
polyol
The transesterification of  Since all hydroxyl groups in
vegetable oils with an excess polyols derived from
of glycerol leads to the transesterification of
formation of monoglycerides vegetable oils, all of the acid
in a single step and therefore side chains would act as
has advantages economically. dangling components when
polyols polyols are crosslinked with
from vegetable oils, such as
isocyanates.
linseed, soybean and coconut
oils have been used for the  Tendency of some
development of PU foams and diglycerides formed in the
coatings with satisfactory transesterification reaction
physical and mechanical to crystallize at room
properties. temperature.
found to be advantageous
because all the hydroxyl
groups are equivalent and,
therefore, equally reactive
Challenges encountered and Outlook

Bio-based polyurethane are being investigated because of their potential to reduce waste

and environmental problems as well as the consumption of petroleum resources. However, several

challenges are accompanied with the production of such material.

In terms of the feedstock, the triglycerides contained within the oils are naturally

heterogeneous in which the variations are not only affected by the source but on the geographic

location as well (Pfister et al, 2011). This makes the production of consistent polyols a challenge.

Additionally, although natural oils are abundant in vast quantities, the processing cost for the

synthesis of polyols obviously adds cost. Hence, economic studies are important to enable

competitive price levels. Storz and Vorlop (2013) also indicated several challenges that must be

addressed in the feedstock selection. Emphasis was given on the lower overall yield of bio-based

plastics and the competition of the production to food and other bio-based chemicals.

In terms of the polyurethane produced, these foams are known to be water soluble and

sensitive to humidity which means bio-based PUs are possible to decompose by prolonged contact

with water. Additionally, bio-based foams are also limited in making foams that have micellar

structure which means they will be hard to make into thin sheets (Siversten, 2007).

However, the production of bio-based foams are important in reducing the amount of CO2

emissions. Advances in technology are also being developed to engineer oils with homogenous

functionalities leading to more uniform polyols. Further, it has been proven also by several studies

that these foams have efficient properties comparable to that of petroleum derive PUs. As of the

present, efforts are still continued so that these materials will continue to find more application in

various industries.
2. Objective

The goal of the study to produce polyol from locally available plant oils for bio-based

polyurethane production. Specifically, this study will

1. Determine the effect of using different feedstocks such as coconut oil and waste

cooking oils on polyol production yield and quality, and

2. Determine the production route (epoxidation/oxirane ring opening, ozonolysis and

transesterfication/amidation pathway) that will give the highest polyol yield and

suitable polyol quality.

3. Materials and Methods

3.1. Materials

Coconut oils (CO) and waste cooking oils (WCOs) will be obtained from the locality of Cebu.

Once received, the CO will be stored at ambient conditions while the WCOs will be undergo

pre-treatment before storage. Necessary reagents and chemicals will be purchased from local

chemical suppliers as well.

3.2. Methods

a. Polyol Synthesis

For WCOs, two process routes will be considered namely the epoxidation/oxirane ring opening

pathway and the ozonolysis pathway. For CO on the other hand, the transesterification/

amidation pathway will be used.

 List of chemicals/reagents Price

Hydrogen peroxide Php 4, 780 per 100 mL

Methanol Php 2,000 per 2 L

Raney nickel catalyst Php 3,700 per 100 g

Diethanol amine Php 2, 750 per 1 kg

Ozone (Machine required)

b. Analytical Methods

i. Fatty acid profiles of WCOs and CO will be determined using the Gas Chromatography –

Mass Spectrophotometer (GC-MS).

Equipment Price

Gas chromatography – mass

Php 4,365.00 per sample
spectrophotometer (GC-MS)

List of chemicals/reagents Price

Boron trifluoride – methanol solution Php 2, 000 per 30 mL

Hexane Php 4, 000 per 4 L

Sodium hydroxide pellets Php 2, 900 per 100 g

Anhydrous sodium sulfate Php 4200 per 500 g

ii. Functional groups of WCOs and CO as well as the polyols produced will be analzyed using

the Fourier Transform Infrared Spectroscopy (FTIR).

 Equipment Price

FTIR Spectrophotometer Php 1,500 per sample

iii. The percent fatty acids (%FFA), iodine value and hydroxyl value (–OH number) of the

WCOs and CO as well as the polyols produced will be analyzed according to the standardized

methods in AOAC.

List of chemicals/reagents Price

Ethanol Php 4,000 per 4 L

Carbon tetrachloride Php 5, 050 per L

Wijs solution Php 5, 490 per 500 mL

Potassium iodide Php 5, 500 per 500 g

Sodium thiosulfate Php 6, 100 per 500 g

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