Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101

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Advanced Industrial and Engineering Polymer Research

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A brief discussion on advances in polyurethane applications

Abhijit Das*, Prakash Mahanwar
Department of Polymer and Surface Engineering, Institute of Chemical Technology, Mumbai, 400019, India

a r t i c l e i n f o a b s t r a c t

Article history: Polyurethane is a material that defines the word ‘versatile’. The structure property relationship of di-
Received 27 February 2020 isocyanates and polyols is such that it provides ample variety and customization to the manufacturer.
Received in revised form The properties of the polyurethane can range to extremes from soft touch coatings to rock hard rigid
15 July 2020
construction material. These mechanical, chemical and biological properties and the ease of tailoring has
Accepted 15 July 2020
produced a huge amount of interest in not only the scientific community but also in the concerned
industries as well. The enhancement of the material can be done by manipulating the raw materials as
Keywords:
well as adding different additives and nanomaterials as well. Proper modifications in the raw material
Polyurethane
Structure-property
can hence produce a polyurethane virtually suitable for every application. The study here throws light
Automobile upon the basic chemistry of the building blocks of polyurethane and its recent advancements in appli-
Marine industry cations in fields such as medical science, automobiles, coatings, adhesives, sealants, paints, textile, ma-
Isocyanates rine industry, wood composites and apparels.
Application © 2020 Kingfa SCI. & TECH. CO., LTD. Production and Hosting by Elsevier B.V. on behalf of KeAi
Advancements Communications Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://
Coatings creativecommons.org/licenses/by-nc-nd/4.0/).
Adhesives

1. Introduction focused on products obtained from the reaction of diamine and

In the pre-world war II era (1937) Dr. Otto Bayer and his team
made material which they called ‘Das Di-lsocganat-Poluaddi-
tionsverfahren’ or Polyurethane, and little did they know that this
invention at IG Farben in Leverkusen, Germany [1] would further
change the world of materials and engineering. Polyurethane in
many aspects is a very different and versatile as compared to its
contemporary polymers. The simplicity in the production and the
excellent properties that they provide has made polyurethane one
of the most sort after polymer. The reaction between diisocyanate
and polyester diol [2,3] led to the formation of the polyurethane
and also to the polyurethane industry in 1937. First developed as an
alternative for the elastic rubber that was used in the world war II
but due to its adaptability it quickly replaced other materials as well
like woven fibres and metals. For example, PU coatings were
explicitly utilized for impregnating paper and delivering articles of
clothing that were impervious to mustard gas [4] and corrosion.
They were additionally utilized as synthetically safe coatings for
wood, stone work, and metal, and as polished completions for
aeroplanes [5]. The preliminary works on polyurethane was largely
* Corresponding author.
E-mail address: dasabhijit.7898@gmail.com (A. Das).
aliphatic diisocyanates, which generated polyurea. Polyurea was
mainly the research area until the exciting properties of urethane
obtained from diisocyanates and diols, were appreciated. In the
year of 1952, (after World War II) Polyisocyanates became
commercially available, the commercial scale production of PU was
obtained from the reaction of toluene diisocyanate (TDI) and
polyester polyols. In the years that followed (1952e1954), different
polyester-poly-isocyanate systems were developed by Bayer [7,8].
At present PU holds one of the largest market shares in plastic in-
dustry and in CASE (coatings, adhesives, sealants and elastomers).
The division of share of PU in various applications is shown in Fig. 1
[9,10]. Polyurethane has almost touched every area of material
engineering, from shoes to aeronautical coatings because of its
multifaceted properties. Additionally, the development of cheap
polyether polyols led to the production of flexible foams and other
automotive and upholstery applications that are still relevant to
this date. Rigorous research and continuous improvement in for-
mulations, additives and processing techniques has given rise to a
wide range of polyurethane applications [11,12]. The main advan-
tage of polyurethane has been the durability, toughness and
excellent chemical resistance. The polymer can be as durable as a
metal while being elastic as a rubber, this has led to polyurethane
being the replacement for various metals, plastics and rubber based
engineering as well as commodity application [12,13]. PU has been

https://doi.org/10.1016/j.aiepr.2020.07.002
2542-5048/© 2020 Kingfa SCI. & TECH. CO., LTD. Production and Hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
94 A. Das, P. Mahanwar / Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101
Fig. 1. United States PU production by end-use market (2012) as a percentage of total cost (5.5 billion pounds) of PU materials and additives (Source: CPI 2012 end-use market
survey on the polyurethane industry).
used in a variety applications such as biomedical applications,
automotive, building, construction, textiles and several other
because of the combination of elongation, hardness, strength and
modulus [14e16]. Although the exclusive merit of using poly-
urethane lies in the wide variety of high-performance plastics that
can be produced, polyurethanes may often compete with low cost
polymers, because the raw material costs are not only the consid-
erations in the total costs of a finished product. Factors of identical
importance are cycle time, cost of tooling, finishing and rejection
rates as well and the potential for recycling [17]. The making of
polyurethanes is a very different story. The fundamental difference
between the polyurethane and other polymers is most of the
thermoplastics, are polymerized in large chemical factories and
then it is sold to the user or consumer in the form of granules or
powder. These are then converted into useful articles of products by
different processing techniques. The properties of these products
depend solely upon the properties of the thermoplastic supplied or
purchased from the raw material manufacturer. However, in the
case of polyurethane most of the polymerization is carried out by
the converter and not by the chemical manufacturer. The latter sells
polyurethane parent or base materials. Specifically, blended poly-
urethane chemical components are also sold for a specific appli-
cation or service [18]. A urethane group is formed by the chemical
reaction between a diol and an isocyanate. Hence the main raw
materials in a polyurethane production are a diol and an isocyanate
that react to form urethane linkage [3,19,20]. The basic chemistry
behind the polyurethane synthesis is discussed later in this review.
Polyurethane can be manufactured in extremely wide range of
grades, in densities from 6 to 1220 kg/m3 and polymer stiffness
from flexible elastomers to rigid and very hard plastics for high-
performance applications. The industrial base for the poly-
urethanes that has evolved of the last 50 years is driven by two
important factors first is the economics of the raw material pro-
duction and second is the diversity of the market from hard plastics
to paint and adhesives [21]. Polyurethane also differs from most of
the other polymer present in the market because it allows the
processor or the fabricator to tailor the polymer as to his needs or to
match a unique end product property. This is possible because the
variables in polyurethane decide the property of the material thus
formed. For example, polyether polyols give much more flexibility
in the product whereas polyester polyols provide good hardness
and strength to the article. The same goes with the isocyanates as
well for different isocyanates (aliphatic and aromatic) impart
different properties to the polyurethane thus formed. Thus, the
potential market for polyurethane applications is virtually endless.
This review is concentrated upon the recent developments in the
application of the polyurethanes. The polyurethane material itself
has been a revelation since its inception in the industry, it has
grown into foams (flexible, rigid, fire retardant), elastomers,
binders, coatings, paints. It has been one of the best performing
material in automotive, furniture, construction, thermal insulation,
footwear etc. Polyurethane synthesis consists of different compo-
nents which adds to its properties, such components and their
reason for inclusion is discussed in Table 1 below.
2. Basic chemistry of polyurethane
Polyurethane are formed by the reaction of di/poly isocyanate
and a diol or polyol, forming repeating urethane linkage as shown
in Fig. 2 in the presence of chain extender and other additives.
The building blocks of the polyurethane can be trimmed down
to two mother components i.e. a polyol and an isocyanate. Both the
polyol and the isocyanate determine the final properties of the
product. Varying the polyol or the isocyanate may bring about
drastic change in the properties of the polyurethane, hence the
structure property relationship of polyol and isocyanate plays a
vital role in understanding and designing polyurethane products
[31]. The polyol and the isocyanate form different domains or re-
gions in the formed polyurethane. These domains are responsible
for imparting properties like softness, flexibility or hardness to the
final product. The soft segments and hard segments are illustrated
in Fig. 3. The polyols tend to have longer chain length which results
in better mobility and hence provide the flexibility to the poly-
urethane, diols of higher chain length provide more flexibility.
Meanwhile the hard segments are governed by the isocyanates and
the chain extender used. The isocyanates are generally very short
 A. Das, P. Mahanwar / Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101 95

Table 1
Various components of Polyurethane formulation.

Components Effect/Inclusion Ref.

Isocyanate Responsible for the PU reactivity and curing properties [22]

Polyols Contributes flexible long segments, produce elastic polymers [23]
Catalysts speeds up the reaction at lower temperatures [24]
Plasticizers Reduces material hardness [25]
Pigments Aesthetics to the material (colour) [21]
Crosslinkers/Chain extenders For structural modification of PU, providing mechanical support to enhance tensile strength and hardness [26,27]
Blowing agents and surfactants To aid to the production of PU foams and control the foam cell structure [28]
Fillers To improve stiffness and tensile strength and reduce cost [29]
Flame Retardants To reduce material flammability [30]

Fig. 2. Urethane formation.

Fig. 3. Representation of soft and hard segments.

chain molecules and hence exhibit higher crystallization and thus
giving rise to compact and packed segments which are very hard
and non-flexible in nature [32]. This combination of hard and soft
segments gives the polyurethane its characteristic of being highly
versatile and effective for very large range of applications as well.
2.1. Polyols
Polyols are substances bearing more than one functional hy-
droxyl group. They may also contain ester, ether, amide, acrylic,
metal, metalloid, and other functional groups as well [14]. Polyols
are largely classified into either polyether polyols or polyester
polyols. Polyether polyols are made from reaction between an
epoxide and an active hydrogen-containing compound. They are
produced by the addition of either ethylene oxide or propylene
oxide to a polyhydroxy pre-cursor molecule in the presence of
catalysts. Typical mother molecules include glycerol, ethylene gly-
col, propylene glycol and trimethylol propane (TMP). Polyethers
can also be prepared by ring opening reaction or polymerization of
epoxy monomers [33,34]. An extensive variability of branched and
crosslinked polymers can be prepared as the functionalities of
parent moieties that is the hydroxyl terminated compounds or the
isocyanate can be changed or altered according to the need of the
reaction or application. Some of the simplest polyols are gylcols,
likewise ethylene glycol, 1,4- butane diol (BDO) and 1,6- hexane
diol. Technically the low molecular weight polyols result in the
formation of hard and rigid polyurethane because of the higher
concentration urethane linkage, and the shorter chain react more
vigorously with the eNCO to produce a higher molecular weight
polymer/pre-polymer. However, when higher molecular weight
polyols are used as the key reactants, since they contain chains with
fewer urethane groups or lower concentration of the urethane
links, and it results in more flexible alkyl chains. Soft elastomeric PU
are formed by long chain polyols with lower functionality (2) while
short chain polyols of high functionality (greater than 3) give more
rigid, cross-linked product [35,36]. Polyester polyols are derived
from virgin raw materials and are often produced through poly-
esterification of very diacids and glycols. Usually polyester polyols
are more viscous [37] more expensive compared to polyether pol-
yols. Polyester have a good amount of hydrogen bonding that helps
in creating strong bonds, which in-turn results in higher tensile
strength and hardness. However, they are of much importance as
PUs generated from them exhibit better abrasion, solvent and cut
resistance. Another group of polyester polyols are derived from
reclaimed raw materials. They are produced through trans-
esterification otherwise known as glycolysis of recycled poly-
ethylene terephthalate (PET). These aromatic polyols have low
weight and are often preferred for the production of rigid foams
96 A. Das, P. Mahanwar / Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101

because of their low cost and better flame resistance than their
counterpart i.e. polyisocyanurate board stock foam. There is also a
group of polyols apart from ethers and ester which are used for
high-performance applications, ‘speciality polyols’ are required in
the manufacturing of sealants, elastomers and adhesives that need
ultimate or superior properties to withstand harsh chemical and
environmental factors. And different polyols may be obtained from
natural and renewable sources such as vegetable oils. These
renewable materials can either be fatty acids or dimer fatty acids
[38,39]. The vegetables from which these diols can be obtained
include castor, soyabean, pongamia glabra, neem and cotton seeds
[40]. The advantages and disadvantages of different polyols based
on their chemical moiety is discussed in Table 2.
2.2. Isocyanates
Isocyanates are essential building blocks for polyurethane syn-
thesis. These are di-or polyfunctional isocyanates containing two or
more eNCO groups per molecules. These can be aliphatic, cycloal-
iphatic and aromatic in nature. Isocyanates are incorporated into
the polyurethane back bone via reaction with hydroxyl containing
compounds like different polyols due to their high reactivity with,
although the reactivity is slow at room temperature and is
dependent upon various other factors as well [41]. Structures of the
frequently used isocyanates are given in Fig. 4.
Catalysts are generally used to increase the rate of the reaction
through the polarization of either the isocyanate or hydroxyl
compound through polar interactions. The isocyanate group bears
the cumulated double bond or unsaturation sequence as ReN]C]
O, where in the reactivity of the isocyanate is governed by the
positive character of the carbon atom, which is susceptible to attack
from nucleophiles, oxygen, nitrogen by electrophiles. Aromatic
isocyanates, like TDI (Toluene diisocyanate) and MDI (diphenyl
methane diisocyanate) are usually more reactive than their
contemporary aliphatic part such as IPDI (Isophorone diisocyanate)
and HDI (Hexamethylene diisocyanate). The main difference in the
reactivity is due to the change resonance stabilization of the aro-
matic rings which affects the carbon atom on the NCO as a result. In
case of aromatic isocyanates, the nature of the substituent also
determines the reactivity, i.e., electron attracting substituents in
ortho or para position increase the reactivity and electron donating
substituents lower the reactivity of isocyanate group. In diisocya-
nates, the presence of the electron attracting second isocyanate
increases the reactivity of the first isocyanate; para substituted
aromatic diisocyanates are more reactive that their ortho analogs
primarily attributed to the steric hindrance conferred by the second
eNCO functionality. The reactivities of the two-NCO groups in
isocyanates also differ with respect to each other, based on the
position of eNCO groups. For example, the two-NCO groups in IPDI
differ in their reactivity due to the difference in the point of location
of eNCO groups [8,17]. The effect of resonance on the eNCO group
due to the benzene is visualized in Fig. 4 (see Fig. 5) [6].
Most of the isocyanates are di-functional in nature but some-
times it varies such as in the case of MDI, which compromises of
mixture of two or more isocyanate groups. Industrial grade iso-
cyanates such as MDI and TDI are generally present as isomeric
mixtures. They are used for flexible foams for example in car seats
or slabstock for mattress [2]. The other group of isocyanates i.e. the
aliphatic and cycloaliphatic ones find application in other sectors
such as coatings, where transparency and clarity are highly desired.
Aliphatic isocyanates are preferred over the aromatic when it
comes to clear coatings for outdoor use, as aromatic isocyanate
based polyurethane coatings shows discolouration or photo-
reactivity when exposed to sunlight for longer periods [21,42].
Examples of aliphatic isocyanates are IPDI, 4,40 -diisocyanato dicy-
clohexylmethane or hydrogenated MDI (H12MDI), 1,6-hexam-
ethylene diisocyanate (HDI). Polyisocyanates such as triisocyanates
derived as TDI, HDI, IPDI adducts with trimethylolpropane (TMP),
dimerized isocyanates termed as uretdiones, polymeric MDI,
blocked isocyanates (where alcohols, phenols, oximes, lactams,
hydroxylamines are blocking agents) are also used in PU produc-
tion. Lately, fatty acid derived isocyanates are also prepared via
Curtius rearrangement with view to produce entirely biobased PU.
Lately Oligomeric polybutadiene diisocyanate was also being used
for preparing lignin-based polyurethane153.
3. Advances in polyurethane applications
The physical and chemical properties of PU are heavily depen-
dent over the polyol and the isocyanate that has been used. Mostly
60e70% of the properties of polyurethane is decided by the type of
polyurethane that has been used. The properties of the polymer can
be heavily altered by changing the chain length, molecular wright,
functionality and functionalization of the polyol chain with ele-
ments such as fluorine, acrylics or rubbers. This degree of cus-
tomization has given polyurethane an upper hand in many
industrial applications.
3.1. Coatings, adhesives, sealants and elastomers (CASE) industry
Polyurethane has quite rightly taken over the CASE industry in
the last few decades. This is because PU is the only material that
showcases excellent variety in physical and chemical properties
which can be manipulated and tailored according to the need of the
end application or the product [43]. Adhesives based on PU offers
very good bonding strength and at the same time polyurethane
based sealants provides remarkable tight seals. For polyurethane to
be used in suitable coating applications it needs have good adhe-
sion, high chemical resistivity, excellent drying, low temperature
flexibility and very good abrasion resistance [44]. Over the past two
decades there has been numerous research on appropriate material
for coating applications and polyurethane has always come out as a
great paint and surface coating material [45,46]. Recent research in
the coating zone has resulted in the development of non-linear,

Table 2
Advantages and disadvantages of polyols based on the moiety.

Polyol Type Advantages Disadvantages

Polyether polyol based on propylene oxide and Hydrolytic stability, cost, viscosity, flexibility Oxidative stability, modulus/strength, thermal stability,
ethylene oxide flammability
Aliphatic polyester polyol Oxidative stability, modulus/strength Viscosity, hydrolytic stability
Aromatic polyester polyol Flame retardance and modulus/stiffness Viscosity, low flexibility
Polyether polyols based on tetrahydrofuran Hydrolytic stability, modulus/strength Oxidative stability, viscosity, cost
Polycarbonate polyols Hydrolytic stability, Oxidative stability, modulus/ Viscosity, cost
strength
Acrylic polyols Hydrolytic/oxidative stability, hardness Viscosity, cost, low flexibility
Polybutadiene polyols Low temperature flexibility, solvent resistance Viscosity, thermal oxidizable (unless hydrogenated), cost
 A. Das, P. Mahanwar / Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101
Fig. 4. Common isocyanates.
Fig. 5. Resonance in aromatic isocyanate.
hyperbranched polymers which have high gloss and flexibility
properties [47]. However, reports in the literature have also sug-
gested that these hyperbranched PUs are generally non-flame
retardant or catch fire easily. To overcome this demerit the hyper-
branched PU was treated with compounds such as nitrogen, halo-
gens or phosphorus [48]. For creating a highly flame retardant
hyperbranched PU, tris (Bisphenol-A) mono phosphate was reacted
with polypropylene glycol and castor oil and using different dii-
socyanates such as TDI, HMDI and TDI. And the product was used
for nano-coatings [30]. In a different research, an one pot pre-
polymerization method was used to develop a castor oil based
hyperbranched PU, for a potential advanced surface coating mate-
rial [49]. A different approach for creating a marine anti-fouling
coating was produced from polyester based polyol. Poly-
condensation was done with e-caprolactum and HMDI trimer was
used as a cross-linker, whereas pentaerythritol and trimethylol-
propane were used as initiators [50]. Researchers have also tried
other sources recently for PU synthesis such as [51] soybean and
lignin, fatty acids [39,52], isocyanate trimers and polyester polyols
for better properties [53]. Liu et al. investigated protection of
asphalt pavements with a novel modified PU coatings [54]. The
approach was to prepare conductive PU based powder clear
97
coatings modified with Multi wall carbon nanotubes (MWCNT). The
obtained results indicated that the water contact angle, electrical
conductivity and the corrosion resistance of the PU coating were
increased by the MWCNTs addition [55]. Recently, a study was
conducted in order to make a hybrid PU for the application of solar
wafer. The hybrid PU exhibited the capability in undermining the
UV attack while maintaining the electrical conductivity of the
polymer from damaged sites and thus, extending the lifespan of
these polymeric materials [56].
3.2. Automotive industry
Automotive industry has been one of the key application areas
for polyurethane, may it be for comfort of a car seat or impact
resistance of the front bumpers and body of the car. Polyurethanes
can also be found in the car doors, windows and ceiling sections.
The biggest advantages of using polyurethane over metal or other
materials is that apart from comfort it reduces the weight of the car
drastically and hence increases the fuel economy, making the car
more efficient in its performance. It is also being used for insulation
and acoustic damping purposes [57]. Polyurethane seats and
cushions provide high comfort for the passengers [58]. Deng R. and
his team has been working on to increase the quasi-static features
of the PU foam by controlling the dynamic comfort for the driver
and the passenger. Polyurethane foams holds the highest market
share for polymeric foams [57]. Due to their low density, they can
be manufactured as both rigid and light components which can be
used as structural shapes, bumpers, interior panels in aircrafts,
stringers, transform cores in plastic boats which are reinforced.
These foams are also used in several high-end sports cars as
sandwich structures or materials. It is because PU provides
outstanding heat insulation combined with increased impact
resistance. Aluminum laminates use PU adhesive as their major
bonding agent. The adhesion property is influenced by the struc-
ture of the polyol and isocyanate used. These adhesives are pre-
pared from polycaptrolactone polyols and a micture of aromatic
98 A. Das, P. Mahanwar / Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101
and cyclo-aliphatic di-isocyannates. Polyurethane based coatings
or paint is not a new technology, but recently with the develop-
ment of nano-fillers and nanoparticles have opened a new field of
special property enhancement. Verma et al. studied the relation-
ship between the hard segments and the fillers. He showed that
intercalated and exfoliated clay platelets have preferential rela-
tionship over hard segments of the polyurethane resin [59]. An
interesting method was deployed to design a sound dampening PU
foam by inducing silicon-acrylic filler particles. The best sound
absorption performance was achieved at 2 wt% filler particles with
the smallest cavity size and the highest partial-open pore ratio,
with improved damping motions of polymer matrix [60]. Mean-
while, a detailed study was conducted on automotive structural
adhesives to know their variability of property with molecular
weight. It was noticed that time for crosslinking of an adhesive
effectively decreased with increasing PU molecular weight under
thermal curing conditions and the increase in the molecular weight
of PU has negative effects on its properties such as lap-shear and T-
peel strength [61].
3.3. Medical applications
Due to their availability, good mechanical properties and
biocompatibility, polyurethanes are used in the medical applica-
tions such as tubing, surgical drapes, catheters, hospital beddings,
wound dressing and several other applications [62e64]. However,
the most frequent application of polyurethane in the medical field
is for shot-period implants. Due to the cost effectiveness, toughness
and longevity PU has found usage in medical purposes [65]. The
former mentioned properties have helped polymer to beat other
materials such as metals, metal, alloys and ceramic. In 2012 the
market for bio-based polyurethane was 1554 tonnes [66]. The
market for bio-polyol in USA is currently worth around 5.03 billion
dollars according to the study conducted by Grand View Research,
Inc. In one study crystalline pre polymers very used or improving
the biodegradability of polyurethane in which water was used as a
chain extender. There was a palpable increase in mechanical and
degradation properties while comparing it with PU which are
extended with ethylene glycol as chain extender. Furthermore,
these properties were deemed suitable for application as joint
endoprostheses [37]. Due to the change in pH during sexual inter-
course, special drug delivery systems like vaginal pessaries and
microbicides which could help in hindering sexual transmitted
diseases including HIV-AIDS have been suggested [67,68]. For these
applications highly sensitive and smart PU for vaginal drug delivery
were also synthesized [69]. Polyurethane has also found applica-
tions in drug delivery system for the colon [70,71] and intra-vaginal
rings [72]. Other studies have hinted that carbohydrates are suit-
able components of biodegradable and biocompatible PUs. These
castor based biocompatible PU were synthesized using propylene
glycol as the main polyol and different carbohydrates serving as the
cross-linkers [73]. The study found that there was a considerable
change in the thermal, mechanical and degradation properties of
the polymer due to the incorporation various carbohydrates
structure. And hence can be used in bio-medical applications where
the biocompatibility property can be exploited. This report also
confirmed similar studies and reports by other authors that incor-
poration of starch and cellulose in the polyurethane backbone
could enhance properties such as biodegradability, biocompati-
bility and mechanical strength [74,75]. Recently researchers have
also developed low cost, biodegradable, aliphatic polyurethanes,
with high saline stability up to 37oC without significant loss in
mechanical properties [76]. Moreover, new medical application
based studies also include chitosan based PU for anti-bacterial [77]
and biodegradable electroactive PUs for cardiac tissue engineering
[78]. Recently a promising study was conducted by Bahrami et al.
comprising of electroconductive polyurethane with graphene
composite aiming at biomedical application. It showed good results
as there was a significant increase in electroconductivity after 2%
graphene concentration and biological evaluation demonstrated
that the inherently electroconductive substrates prepared support
cell adhesion and proliferation and are non-toxic [79]. Another
thought-provoking research work was conducted by Wang et al. to
coat the magnesium (Mg) with functionalised Polyurethane in or-
der to improve the corrosion resistance and anti-bacterial property.
The results shown significant improvement in corrosion resistance
of Mg as compared to uncoated ones. In addition to that, the
functionalised PU showed outstanding performance against
microorganism, preventing bacterial adhesion to the surface. One
of the promising result that was found out from this study, was the
increase in compatibility with human blood [80].
3.4. Textile and apparels
Since its inception PU was considered a good material for ap-
parels. Initially PU are converted into thin threads and then incor-
porated into Nylon to make light and stretchable garments. But
with the advancement in research more and more improved gar-
ments have surfaced in the industry. More improved spandex fibers
and thermoplastic elastomers have heavily influenced new-age PU
apparels. Due to the advancements in technology the manufac-
turers have a whole new wide variety of PU based faux leather, bra
cups and man-made skins, which have applications in various
rigorous sports attire and in a large range of accessories. The textile
industry has highly benefited from water borne polyurethane of
WPUs or polyurethane dispersions (PUDs) [81]. Water borne
polyurethanes do not have harmful volatile organic compounds as
their solvent counter parts and hence are environmentally friendly
and worker friendly as well with low toxicity. They also showcase
excellent properties such as permeability, abrasion resistance,
softness (soft to touch surface). Also, crack fastness, fastness of
washing and soap fastness of reactive dyes, acid dyes and direct
dyes on dyed fabrics may be immensely improved by the use of
WPU as finishing agents [82,83]. To improve the washing fastness
and UV protection of the fabrics, UV quenchers or absorption
groups were added to the polyurethane dispersions. This was
achieved by using N,N-dimethyl allyl p-benzoyl benzyl ammonium
bromide as the UV absorber, which significantly increased the UV
dyeing protection of the cotton fabrics [81]. Researchers have also
studied, a low molecular weight chitosan which was used for chain
extension in polyurethane dispersion [84]. It was used and applied
on different quality of plain weave poly-cotton dyed and printed
fabrics pieces to improve the stiffness, pilling resistance and me-
chanical strength. Pure cotton and woolen fabrics can also benefit
from the same. Mazzon et al. tried to induce hydrophobicity to a
silicon fluid that is normally used as a fabric softener by making it
an emulsion, by the addition of aqueous dispersion of Poly-
carbonate diol with Isopropyl alcohol as a co solvent. The emulsion
was found out to be stable with particle size of 1.5m and an
exceptional water contact angle exceeding 143 [85]. Recently, an
excellent study was directed by Sultan et al. to corelate the soft
segment size of polyurethane dispersion with the physiochemical
and antimicrobial properties for textile applications [86].
3.5. Marine applications
Polyurethane has been a great addition in the marine technol-
ogy along with the epoxy. Polyurethane based epoxy is not only an
excellent building material but also excels at marine coatings too. It
protects from corrosion, water erosion and also manages the drag
 A. Das, P. Mahanwar / Advanced Industrial and Engineering Polymer Research 3 (2020) 93e101
flow of the boat's hull by not allowing aquatic life to settle or grow
on the ship [87]. This anti-fouling and algae protection have been
one of the best utilities of the PU marine coatings. PU foams are also
used in boats and ships because they provide outstanding insu-
lation with very effective noise controlling or damping properties.
Boat parts made up of PU are generally lighter in weight than its
metal counterpart hence increasing the efficiency of the boat en-
gine and it also highly resistant to corrosion than the metals.
Polyurethane also provides increased tear and abrasion resistance
and load bearing capacity even at lower temperatures. Exploiting
these properties, the marine industry has taken PU into various
products such as cables and wire coatings, drive belts, hydraulic
tubing as well as boat and ship construction. Recently polyurethane
is being used as a removal media, i.e. removing organic substances
from water [88]. Cyclodextrin PU has been reported for the removal
of paraben from aqueous bodies [53]. These types of PU can be
produced by microwave assisted synthesis, and they are usually
insoluble in water and hence is very highly effective in collection
and removal of unwanted organic substances from water bodies. It
has been reported that cyclodextrin PU are also very good at
removal of phenol as well as Nile red dye from water. According to a
recent study by Nasiri et al. cyclodextrin PU having magnetic nano-
conjugates are very efficient at the removal of crystals and methyl
violet dyes from aqueous solutions [89]. Researchers have further
studied this application of PU in removal of toxic waste from the
environment [90]. The above PU technology was reported for the
successful removal of dyes, such as crystal violet and aniline blue
from laundry water waste [91]. Marine applications demand
withstanding very harsh environment and high environmental
resistance. Extreme environment can lead to swelling, de-bonding
of fillers, hydrolysis, plasticization and loss of mechanical strength.
For combating these conditions and assessing the extent of damage,
accelerated weathering tests are very important in marine industry
for example ISO 11346. Davies et al. conducted long term studies of
2 and 5 years observing polyurethane made up of polyether under
influence of seawater and adverse conditions [92]. The finding of
the study throws light upon the excellent weather durability of
polyether-based PU. Even under harsh seawater conditions, the
sample retained all of its true tensile properties. Yesudass et al. tired
to formulate a novel Polyurethane having antibacterial property for
marine application. The novelty in the study was the nontoxic
nature of the coating and the zwitterion based blocked poly-
urethane polymer. The coating showed significant resistance
against marine anti fouling organisms and the hydrophobic nature
of the coating hinders the adhesion of fouling to the surface as well
[93]. Mishnaevsky et al. developed a simulation to calculate the life
cycle of PU coatings on wind blade turbine [94]. Polyurethane films
modified with a novel phytic acid doped PANI-ZnO nanocomposites
were presented as a significant solution against biofouling by
Mooss et al. The improved hydrophilicity, water permeability and
surface wetting properties acts as a barrier for bio adhesion [95].
3.6. Polyurethane wood composites
Polyurethane has stood out to be a very important material in
the wood composites field, their combined flexibility, lightweight
and strength provides for a suitable reinforcing material with
wood. Recently polyurethane based flat composites were produced
by inculcating activated carbon in order to tackle the interference
produced by electromagnetic waves or electromagnetic interfer-
ence shielding (EMI) [96]. Activated carbon loading was done into
PU for microwave adsorption and complex permittivity. The com-
posites made by this process performed better than polyethylene
and polyester which need metal additives for higher performance.
PU-wood composites are also generated from wood wastes [97]. In
99
a recent study the chemical modification of polyethylene tere-
phthalate (PET) was achieved through glycolysis. Although there
was an effective load transfer, there was no prominent improve-
ment in the thermal properties [98]. Using natural fibers with
polymer is not a new research topic. But the beauty of using natural
fibers is that they are rich in hydroxyl content and therefore can
react with di-isocyanates easily to form products with great variety
in properties. In one study cellulose nanocrystals (CNC) were used
in a very low quantity with polyurethane having high solid content.
The resulting product had a higher glass transition temperature
(Tg) of 76oC and very much improved Young's modulus of 1.52 GPa
[99]. The abrasion resistance was also improved by the addition of
cellulose nanocrystals. According to the report the increase in the
properties was due to the formation of covalent bonds between
polyurethane and the CNCs during the polymerization process.
Recently, Lu et al. conducted an extensive research on preparing a
bio-based polyurethane with Wood powder (pine wood, average
particle size: 65m) to function as a phase change material. From the
result, it was observed that the sample containing 3% wood powder
showed remarkable performance on phase change behaviors and
thermal stability [56]. Another recent research work by Zhang et al.
aimed at developing a composite involving polyurethane disper-
sion and sodium lignosulfonate to achieve UV absorption applica-
tion. The bio content of the composite is found out to be up to 70%
and was having excellent storage stability. In addition, the com-
posites were found to be having excellent UV resistance, which can
be incorporated for wide variety of applications [100].
4. Conclusion
Polyurethanes are virtually a wonder material when it comes to
material application world. They combine the hardness and rigidity
of metals and plastics with the flexibility of rubbers. This sweet spot
of material property and characteristics has made polyurethane as
the go-to material for many applications, even transcending metals
and plastics. They have been incorporated into many industries
from high performance sports cars to house-hold items. Poly-
urethane have been a major driving force behind coatings, adhe-
sives, sealants, elastomers, foams, textiles, automobiles and marine
industry. Recently polyurethane has also found its application in
the bio-medical field as well. Polyurethanes can be prepared from a
wide range of polyols and isocyanates; this helps in the fact that PU
can be made in large array of products having different properties.
The easy modification and property customization are the main
highlight of polyurethanes which enables the manufacturer to
produce polyurethanes for variety of application just by the
modification of the polyol or the isocyanate. The advancement in
the polyurethane applications has been growing leaps and bounds
in the last decade. Bio-based polyol is the main focus of the industry
in the recent past so as to make ‘green’ products. Solvent based
urethanes have given way to water-borne PUs for different appli-
cations. Researchers have also found ways to incorporate nano-
materials into the PU matrix for high performance products. Thus, it
can be said that with all these properties and advancements
polyurethane may be become one of the best materials we ever
seen in terms of performance and versatility.
Declaration of Competing Interest
The author declare no conflict of interest.
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