CHAPTER 2

REVIEW OF RELATED LITERATURE

2.1. Economics of and Outlook on PU and RPUF

In 2021, the global PU market size was estimated to be more than Php 3.6 trillion (see

Figure 2.1) and is expected to expand at a compound annual growth rate (CAGR) of 4.3% from

2022 to 2030. In light of sustainability concerns worldwide, there is increasing investments in

smart, energy-efficient commercial and residential buildings or “Green Buildings” across all

sectors. In this regard, the demand for efficient insulating materials to regulate heating,

ventilation and air conditioning (HVAC) and to optimize energy savings increased, whereby PU

foams come as a prime choice. Aside from the construction industry, there is also rising demand

of PU foams from the automotive and packaging sectors worldwide. Moreover, with the PU

foam market concurrent with the growth of the construction sector, this demand is expected to

grow in the Philippines over its massive infrastructural projects by virtue of its continuing

“Build, build, build” program, its large and growing population needing the material for

residential and commercial use, and its national thrust for industry, innovation and especially

sustainability. [19-26]

According to a recent market report, [19]

in terms of PU product, rigid PU foams used in a

variety of sectors such as automotives, appliances, packaging and industrial insulations

accounted for more than a 30.0% of the global revenue in 2021. Owing to their structural and

thermal stability, RPUFs are a prime choice in manufacturing thermally insulating products.

They also possess sound insulation properties which rendered them more popularity.

Flexible PU foams used for cushioning in a variety of consumer and commercial products

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such as furniture, bedding, carpet cushion, fibers, and textiles, so far, is of timeless demand. In

terms of application (see Figure 2.1), the biggest segment for PU is the construction industry.

Accordingly, this market segment for PU held more than 25.0% of the global revenue in 2021. In

this sector RPUFs are applied as an insulation material or segments of load-bearing components

in insulating walls, windows, etc. In terms of region, Asia-Pacific dominate the PU demand and

accounted for more than 40.0% of the global revenue in 2021. Accordingly, this is due to their

growing urbanization and industrialization. Countries or regions with emerging economies such

as China, India and Indonesia, and the rising infrastructure development activities more

especially in regions experiencing extremities such the Middle East, North & South America and

Europe fuels the demand for PU foam and insulation.

The continuous expansion of the construction industry, automotive & equipment

manufacturers, and electronics, appliances, furniture and packaging sectors are expected to drive

the growth of the PU market. Furthermore, the government support to meet transitioning

standards for green buildings is anticipated to also drive the development of the PU industry by

virtue of the increased demand in insulation applications. Countries or regions with growing

urbanization and/or industrialization such as China, India and Indonesia, and the rising

infrastructure development activities more especially in regions experiencing extremities such

the Middle East, North & South America and Europe fuels the demand for PU foam and

insulation. The country (Philippines), itself, is home to expanding industries such as the

construction, automotive, electronics, manufacturing, furniture and packaging industries that that

provide opportunities for the PU industry. Moreover, with international thrust towards

sustainability—constructing “green buildings” and building smart cities, many countries across

the globe have changed landscape and resulted in increased investments in PU products. For

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example, stringent regulatory framework in Europe have shifted increased PU demand,

especially of RPUF. In the country, the Philippine Development Plan (PDP) and its international

commitment to the global Sustainable Development Goals (SDGs) ensures the growth of the PU

industry and future continuation. Lastly, PU products are expected to gain more significance and

market size on the account of rising consumer awareness regarding their sustainability and

versatility which include but not limited to its excellent thermo-physical properties, high

mechanical strength, lightness, strong chemical resistance or inertness. [19-26]

Figure 2.1. PU Market 2021 [19]

2.2. PU Chemistry and RPUF Production

PU is a polymer consisting of organic units of isocyanates (typically, diisocyanate;

functional group: –N=C=O) and polyols (functional group: –OH) origins joined by carbamate or

urethane linkages (–O–(C=O)–(NH)–; see Figure 2.2) formed by the reaction of the functional

groups involved. Moreover, because of the presence of polyfunctional groups available for

reaction, cross-links can be formed (see Figure 2.3). Depending on the application, the

isocyanate and polyol used for PU synthesis are varied to obtain a wide variety of material

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properties to satisfy requirements. For example, PU elastomers are produced by reacting a

diisocyanate with a combination of high molecular and low molecular weight diols, PU foams

are produced by reacting diisocyanate with a combination of high molecular weight triol and

water, and PU adhesives are produced by reacting a diisocyanate in stoichiometric excess with a

combination of two poly-(di)ol types—crystalline and amorphous. [15-18] Additionally,

catalysts, surfactants, blowing agents, cross linkers, flame retardants, light stabilizers, and fillers

are introduced in the PU formulation to control reactions and achieve certain product

characteristics. [14]

Figure 2.2. Generalized PU Reaction [37]

(Functional Groups of the Reactants & Carbamate/Urethane Linkage in Pink)

Figure 2.3. Cross-linking in PU Polymers [38]

In the case of producing PU foams, a blowing reaction can happen simultaneously with the

polymer cross-linking. While the cross–linking happens by virtue of the reaction between

available isocyanate and polyol, a blowing reaction happens by virtue of the reaction between

available isocyanate and water or by the evaporation of a physical blowing agent. [38]
Water is

conventionally used in producing PU foams. In water-blown foaming process, the reaction

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between an isocyanate group and water produce gaseous carbon dioxide (CO 2) responsible for

the foam expansion.

Figure 2.4. Generalized Blowing Agent Reaction [38]

Aside from the PU-forming and blowing reactions, other reactions can also take place

during the foam production. For example, available isocyanate can react with the amine formed

from water-blown reactions and produce a disubstituted urea. The disubstituted urea,

furthermore, can react with a free isocyanate group and create a biuret product. Also, available

isocyanate groups can react with the urethane product and produce allophanate (see Figure 2.5).

Moreover, the presence of other functional groups in the ingredients involved and impurities can

lead to several side reactions.

Figure 2.5. Other Reactions in PU Foam Production when water is used as a blowing agent [38]

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2.3. Gaps in the PU Manufacturing Industry, Current Alternatives, and Coconut Oil as a

Polyol Source for RPUF Production

Currently, however, PU industries rely heavily on the petroleum industry, having both

isocyanates and polyols for PU production largely derived from petroleum. With increasing

concerns regarding the rapid depletion of fossil fuels, the utilization of bio-based polyols as a

renewable alternative became of prime interest in the sustainable growth of the PU industry.

Depending on the geographical location, some common raw materials used for the production of

bio-based polyols include rapeseed and sunflower oils in Europe, soybean oil in America, and

palm and coconut oils in Asia. [1,2,3,2,5] In the Philippines, coconut is one of the major crops,

contributing 3.6% of the country's gross value-added (GVA) in agriculture through coco-based

products including oleochemicals such as coconut oil. The country’s annual coconut production

is estimated at an average of 14.5 metric tons from 2011 to 2020 on nearly 30% of the country’s

total farmlands. [2] With this abundance of the coconut supply, the opportunity for value

addition in its supply chain and the coconut industry, and the sustainability they offer to PU

process industries, research on coconut oil as a raw material for RPUF production comes very

significant. Recent studies have reported the feasibility of using polyols synthesized from

coconut oil in the development of bio-based PU foams with high performance. Leng, et al. made

PU foams from CO-based polyols synthesized by a one-step process through the purification of

industrial coconut fatty acid diethanolamide. [1] Dingcong, et al. made PU foams from CO-

based polyols synthesized through sequential glycerolysis and amidation reactions. [2] Both

authors highlight that the intrinsic tertiary amine moiety in the CO-based polyol by virtue of its

synthesis/functionalization endowed an auto-catalytic effect in the foaming process by

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accelerating the blowing reaction with water. Ultimately, foaming processes with shorter cream

time and gel time resulted compared to those utilizing commercial petroleum-based polyols.

Most vegetable oils are functionalized to polyols before they can be used in PU

manufacturing. It is due to their geopolitical advantage and abundance, the sustainability they

offer, and the simplicity of their preparation process that material scientists (and of the like) use

them for the purpose. Leng, et al. further adds that PU foams made from such materials are

recyclable. Their functionalization, however, exists as a critical concern for the PU foam

production due to the possibility of producing polyols of autocatalytic foaming effect. Though

faster curing of PU foams may be desired for increased product throughput, very fast cream

times or accelerated blowing reactions coupling with reactions of relatively slower gel time or

cross linking/length propagation can also in products of reduced mechanical properties. For

example, because the blowing reactions of the CO-based RPUFs become accelerated as a result

of their prior polyol functionalization, the mechanical properties of the resulting foam, at some

formulations, can be sacrificed as cross-links from CO-based polyols have less resistance to the

expansion force because they are short-chained. Thus, foresight of the cream time and gel time is

an invaluable resource in designing PU formulations made from bio-based polyols. However,

experimental foaming can be resource- and time-intensive for each run, reflect large errors, and

yield a myriad of wastes. Thus, a fast, reliable, non-waste generating method with minimal

resource utilization that can give good foresight on a foaming process’ cream time and gel time

is a sought-out asset in composing PU formulations and predicting product properties.

2.4. PU Simulations

While studies involving computational simulations exist, they have focused on simulation

of final foam properties, and numerical/computational studies that highlight the cream time and

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gel time of the RPUF production, especially of new bio-based systems, are less common.

Abdessalam, et al. predicted PU foam acoustic properties through macroscopic numerical

simulation of foaming process. The foams were made from commercial ingredients. Krol, et al.

developed a software for PU systems that are able to obtain two-dimensional diagrams of

changes of the following quantities versus reaction time: (a) concentrations of monomer, dimer,

trimer, and further fractions etc. specified as mole fraction or mass fraction, (b) conversion

levels, e.g. for –OH groups or –NCO, (c) number average molecular weight (MWn) for linear PU

through the simulation. The simulations allowed drawing conclusions about the impact of the

polymerization process parameters (time, temperature, ratio of monomers) on the structure of PU

produced (polymerization degree, distribution of molecular weights, concentrations of unreacted

monomers). The entry data required by their software are: (a) the initial concentration of

monomer A [mol/dm3], the initial molar ratio of monomers B and A, the reaction rate constant

[dm3 mol-1 s-1], a constant representing kinetic effect of substitution, molecular weights of parent

substances A and B [g/mol], and step for numerical integration of their model differential

equations [85] representing the differential changes during the PU production process as

assumed for the classical Euler’s method (h) [s]; and the limitations of their model included

negligence of side reactions such as biuretization, dimerization, and trimerizations. [1]

More specifically, existing numerical/computational kinetic studies have been concentrated

on commercial polyols, and kinetic simulations using coconut-based polyols have been scarce.

[8-13]. [20-22]
Lastly, kinetic models used in existing kinetic-based computational simulations

assumed that the reactivities of hydroxyl groups depend upon the polyol of origin. [17-19]

Imperative to this study is to generate a Temperature (T) versus time (t) profile of a PU

foam production made from coconut oil-based polyol. In the case where the coconut oil-based

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polyol is mixed with other polyols, and having water as the only blowing agent, the profile can

be modeled through an energy balance summarized as a linear differential equation (see

Equation 2.1). Here, ∆ H gel ,i represents the heat of the gelling reaction with respect to polyol i,

r gel ,i represents the gelling reaction rate of polyol i, ∆ H blow represents the heat of the blowing

reaction, r blow represents the reaction rate of the blowing reaction, U represents the overall heat

transfer coefficient from the surroundings (having the foam as the system), A represents the

surface area of the foam related to different foam height, T s represents the temperature of the

surroundings and ∑ ( n ×C p ) represents the summation of heat capacities of all chemicals used.
[14, 39-40]

dT
∑ ∆ Hgel,i r gel,i + ∆ H blow r blow + UA( Ts -T (t) )
i
= Eq. 2.1
dt ∑ ( n× Cp (T) )
The equation also assumes that the heat of reactions and heat capacities are constant with

respect to variables T and t. ∆ H gel ,i , ∆ H blow , U , and C p can be found from literature or

experimentation, while A and T s can be assumed as fixed, but not controlled, parameters and

can be determined with simple laboratory instruments. r gel ,i and r blow are represented by the

equations that follow (Eq. 2.2 to 2.3). There, k gel ,i represents the gelling reaction rate constant of

gel i, C cat , gel represents the concentration of the gelling catalyst, C iso represents the concentration

of the isocyanate groups, C OH , i represents the concentration of hydroxyl groups of polyol i, k blow

represents the blowing reaction rate constant, C cat , blow represents the concentration of the blowing

catalyst, C water represents the concentration of water.

r gel ,i= k gel ,i × C cat ,gel ×C iso ×C OH ,i Eq . 2.2

r blow = k blow × C cat ,blow ×C iso × C water Eq . 2.3

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 Equations 2.1 to 2.3 can be combined in a code in many programming platforms to

simulate a T vs. t PU foam profile. Depending on the programming platform, a graphical or

tabular profile may be generated. The code may need the input of pertinent information to run

the code. The information could be written within the code, or the code could be written to ask

for a user-input. Depending on available information and program features, codes can also be

written to determine certain parameters. [Insert intro about the hassles of brute force

computations/method, highlight other computer-aided features: resizable, pannable, etc. graph,

higher/larger data storage, possibility of solving complex matrix operations at shorter times

A previous study conducted by Zhao et. al. (2013) modeled the reaction kinetics during the

foaming process of rigid polyurethane foam. The process was comprised of gel and foaming

reactions between an isocyanate and three polyols separately, then with isocyanate and a mixture

of the three polyols. The gelling reactions were done to obtain the activation energy, the heat of

reaction, and reaction rate constant. On the other hand, the foaming reaction was also performed

to get the kinetic parameters of the blowing reaction.

The modeling focusses on the reaction kinetic parameters that were fitted with the

experimental temperature data as a function of time. In this manner, the temperature profile was

accurately modeled for a single – polyol polyurethane formulations. Using the component of a

pure polyurethane kinetic parameters, the temperature profile of a mixture of polyol was also

accurately predicted.

Even though there were errors that contributed to the experimental deviation, the results of

their research showed promising results in modeling the reaction kinetics of the polyurethane

formation. Their model will set as a precursor for future studies that will use bio – based polyol

as alternatives for the petroleum – based polyol.

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 Table 1. Theoretical reactions occurring for the PU foam production* [14]
No. Reaction No. Reaction

1a A + B → P 3d APX + BP → P
1b A + BP → P 4a A + W → N + CO2

1c AP + B → P 4b AP + W → N + C O2

1d AP + BP → P 5a A + N → P
2a A + BX → P 5b A + NP → P
2b A + BPX → P 5c AP + N → P
2c AP + BX → P 5d NP + AP → P
2d AP + BPX → P 6a A + Ur → Y
3a AX + B → P 6b A + UrP → Y
3b AX + BP → P 6c AP + Ur → Y
3c APX + B → P 6d AP + UrP → Y
*A = Isocyanate, B = Polyol, AP = A on Polymer, BP = B on Polymer, X = Catalyst, P = PU, W = Water,
N = Amine, CO2 = Carbon Dioxide, NP = N on Polymer, Ur = Disubstituted Urea/Urethane, UrP = Ur on Polymer,
Y = Biuret/Allophanate

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