CHAPTER

Raw materials, properties,

and structure of polyurea

Khanisya Palaniandy1, Sheik Ambarine Banon Auckloo1, Eng-Seng Chan2,

3
Pooria Pasbakhsh3
1
Mechanical Engineering Discipline, School of Engineering, Monash University Malaysia, Subang
Jaya, Selangor, Malaysia; 2Chemical Engineering Discipline, School of Engineering, Monash
University Malaysia, Subang Jaya, Selangor, Malaysia; 3Advance Engineering Platform,
Mechanical Engineering Discipline, School of Engineering, Monash University Malaysia, Subang
Jaya, Selangor, Malaysia

3.1 Introduction
Polyurea formulation is divided into two parts; generally referred as the A-side or
part A and the B-side or part B like its counterparts; epoxy, polyurethanes, and sil-
icones. The typical synthesis route adapted to produce polyurea chains is illustrated
in Fig. 3.1. The A-side isocyanate may be a monomer, prepolymer, or quasi-
prepolymer (isocyanate-amine mixture). The B-side is a resin blend amine and/or
hydroxyl-terminated. In a two-step polymerization, diisocyanate reacts with water
to produce an intermediate polyamine and an end-product polyurea [1]. Polyure-
thane on the contrary is derived by replacing the amine-terminated B-side with a hy-
droxyl group terminated resin or polyol. The reaction between isocyanate and amine
group is fast setting due to the high nucleophilicity of amines thus, the catalyst is not
required for the production of pure polyurea [2]. However, hybrid polyurea/polyure-
thane may require a catalyst to speed up the reaction. There is insignificant foaming
in the synthesis of polyurea in absence of moisture due to high reactivity of isocy-
anates and amines which is about 1000 times more than diols with isocyanates to
form polyurethanes. However, when moisture is present, the formation of carbon di-
oxide is likely to be trapped in the polymer and cause bubbles or foams.
The hard segment, soft segment formation, and the dual-phase segregated struc-
ture of polyurea are shown in Fig. 3.2A and B, respectively. The mechanical prop-
erties of polyurea are strongly influenced by two factors; one, the nanoscale
segregation of hard segment (HS) (urea linkages) with high glass transition temper-
ature, Tg (190e210
C) [3,4] and soft segment (SS) (amine backbone) with low Tg
(75 to 50
C) [4,5], second, the percentage segregation of these two segments in
the chain [6]. The molecular segregation on the other hand arises due to the bidentate
hydrogen bonding between urea linkages for different HS in the polymer chain. This
strong hydrogen bonding leads to self-assembly of HS in the soft matrix. The HS
somehow acts as a reinforcing component for the soft matrix [7]. The two glass

Polyurea. https://doi.org/10.1016/B978-0-323-99450-7.00005-8 37
Copyright © 2023 Elsevier Inc. All rights reserved.
38 CHAPTER 3 Raw materials, properties, and structure of polyurea

FIGURE 3.1
Common synthesis routes of polyurea (A) reaction of diisocyanate with diamine leads to
urea linkage; (B) reaction of diisocyanate with water leads to two-step polymerization to
produce polyurea.

(a) (b)

So domain
Hard domain

FIGURE 3.2
(A) Reaction between diisocyanate and diamine producing polyurea consisting of hard
segment (HS), soft segment (SS) and urea bond, (B) microphase separation in polyurea
forming hard and soft domains.
 3.2 Raw materials 39

transitions are caused by the creation of cooperative motions of molecular segments

in soft domains and regions near the hard nanodomains. The regions and interactions
near the nanodomains in hard segments are stiffer and stronger and therefore making
the polymer chains less mobile which leads to higher Tg for hard domains [4].
Polyurea technology is so unique that various formulations of the resin blend and
isocyanate are able to provide desired curing time, pigmentation, resistance to mois-
ture, corrosion-free, high heat capacity, self-healing behavior, etc. While the use of
isocyanate component in the synthesis of polyurea is popular in the industry, it draws
an environmental and health concern for its toxic nature. Peters et al. reportedly
observed severe changes in the ventilatory capacity of workers upon exposure to
toluene diisocyanate (TDI) [8]. The famous Bhopal hazardous incident took thou-
sands of lives due to leakage of methyl isocyanate which opened the eyes of not
only the local authority, but also researchers to develop a nonisocyanate route for
the production of polyurea. Alternatively, more studies are being conducted to pro-
duce isocyanate-free polyurea [9e11]. Studies showed that polyurea could be syn-
thesized using dicarbamates and diamines as it allows a more controlled
polymerization even in an aqueous environment as dicarbamates are less reactive
in water than isocyanates [11]. Although the production of isocyanate-free polyurea
could result in high tensile strengths (up to 49 MPa) and biodegradability that re-
leases ammonia gas for plant uptake, the extremely low elongation of 146% to fail-
ure shows that there is no enough room for strain hardening to occur which leads to a
compromise in the mechanical properties [12]. Though the synthesis of polyurea
without the use of solvents and isocyanates would result in a greener material which
is biodegradable, the availability of biological feedstocks and the cost of production
of this polyurea is a great concern [13].
This chapter comprises only basic raw materials to produce linear polyurea.
Basic isocyanate and polyamine feedstocks are also mentioned in this work, but
what was more emphasized here is their structural characteristics and chemical reac-
tivity resulting as the key feature for the step-growth polymerization.

3.2 Raw materials

3.2.1 Part A: isocyanate
Isocyanate is a functional group with the formula N ¼ C ¼ O. They are produced
from amines via phosgenation reaction whereby the reaction is treated by phosgene
ðCOCl2 Þ, releasing hydrochloric acid as a byproduct [14]. The isocyanate compo-
nent forms the HS which gives strength to the polymer and can be an aromatic or
aliphatic, such as toluene diisocyanate (TDI) and diphenylmethane diisocyanate
(MDI) for aromatic systems, isophorene diisocyanate (IPDI) and hexamethylene dii-
socyanate (HDI) for the aliphatic systems.
The NCO % in the prepolymer will affect the hardness, stiffness, strength prop-
erties as well as speed of reactivity. On the other hand, the number of reactive sites
described as the functionality of isocyanate polymer will affect the temperature
stability, hardness, stiffness, impact resistance, and elongation or strain [15].
40 CHAPTER 3 Raw materials, properties, and structure of polyurea

Holzworth et al. [16] reported that the increasing stoichiometry ratio of isocyanate
and the amine resin (known as index) increases the glass transition temperature (Tg)
but decreases the increment on heat capacity at Tg. The increase in isocyanate con-
tent also means an increase in crosslinking density which leads to high storage
modulus [16]. Theoretically, the 1:1 volume ratio, i.e., the number of
N ¼ C ¼ O groups equivalent to the number of NH2 groups will yield the high-
est degree of polymerization as summarized by Carothers equation [17]. However,
an index of 1.05 is always recommended for the isocyanate as the 5% excess of iso-
cyanate component account for the loss of isocyanate with residual moisture during
storage and final applications [18].
According to the formulation manual prepared by Polyurea Development Asso-
ciation (PDA) Europe in 2014, prepolymers with lower NCO% are limited by the
resulting increase in viscosity that causes a worsening of the miscibility of the
two components. Prepolymers with a higher NCO% in the chain have a lower vis-
cosity, which aids the miscibility of the two components, making the system more
reactive, giving an increased surface hardness [18,19]. To promote stability, careful
selection of reactants, including the type of isocyanate must be performed such that
it reduces the decomposition reaction, which will lead to chain rupture in the final
mixture [20].
Table 3.1 lists commonly used aromatic and aliphatic diisocyanates with their
properties. Increasing NCO% in the isocyanate prepolymer results in decrease in
its viscosity. Typically, the isocyanate prepolymer is polymeric isocyanates which
is a blend of the isomers or oligomers of the specific components. 100% pure iso-
cyanates typically exist as solid which is not favorable for polyurea they require
even mixing with component B. Hence, isocyanates are synthesized in a liquid state
and are comprised of different levels of isomers of the component, for example, MDI
and TDI are usually used as a mixture of 2,4- and 2,6- isomers with a ratio of 80:20
[36]. The structure of diisocyanate influences the extent of hydrogen bonding
behavior, the microphase morphology, and overall molecular dynamics of polyurea
[37]. He et al. [38] reported that symmetric 2,6-TDI exhibited more continuous hard
domains than the asymmetric 2,4-TDI. Hence, 2,6-TDI led to a greater degree of HS/
SS demixing or segregation. They have also reported that the high phase mixing in
polyurea derived from 2,4-TDI variant resulted in a broader segment relaxation pro-
cess resulting in higher strength. This shows that asymmetric diisocyanates incur in
high-phase mixing polyurea which gives more clarity to the molecular segregation.
Various adhesives, sealants, and thermoplastic polymers can be produced using
modified MDI where they are combined with long-chain polyethers, polyesters, or
other polyols, including short-chain diols or triols [39]. Isonate 143L and Wannate
1635 having 29 wt% NCO are polycarbodimide-modified MDI which is claimed to
have high stability at low temperatures [26,30]. Similarly, Rubinate 9447 and 9495
are urethonomine-modified MDI containing propylene carbonate as a diluent claim
to have improved physical properties on the resulting system it is applied into [23].
A number of guides on isocyanate particularly used for polyurea and polyure-
thane systems, mentioned that the use of most reactive prepolymers increases the
Table 3.1 Types of isocyanates used for polyurea production and their properties of products available in the market and
used by most researchers and users.
Dynamic
viscosity
Commercial % at 258C,
Isocyanate products Company NCO Functionality Pa.s Application References

Methyldiphenyl Suprasec 2004 Huntsman 32.9 2 13 Low reactive Gurke et al. [22]
diisocyanate [21] systems and
(MDI) prepolymers
Rubinate 9433 [23] Huntsman 31.8 2 15 For high dynamic Pazhanikumar
elastomeric et al. [24]
properties
Suprasec 5025 Huntsman 31 2.7 21 One and two- Haddadi et al.
[21] component [25]
polyurea and
polyurethane
systems
Wannate 8312 [26] WANHUA 15.5 e 0.7 Waterproof system Zhou et al. [27]
chemical
Toluene Voranate T-80 [28] Dow 48.2 2 0.305 High resilience Li et al. [29]
diisocyanate chemical molding, flexible
(TDI) slab stock,
automotive seating,

3.2 Raw materials

specialty foams
Modified MDI Isonate 143LP Dow 29.2 e 33 Adhesives, Choi et al. [31]
(polycarbodimide chemical sealants,
modified) [30] automotive
bumpers, tires, etc
Continued

41
 42
Table 3.1 Types of isocyanates used for polyurea production and their properties of products available in the market and used by most

CHAPTER 3 Raw materials, properties, and structure of polyurea

researchers and users.dcont’d
Dynamic
viscosity
Commercial % at 258C,
Isocyanate products Company NCO Functionality Pa.s Application References
Hexamethylene Desmodur N3600 Covestro 22.5 e 1.5 Air and force drying Huynh et al. [33]
diisocyanate [32] e23.5 coatings for
(HDI) automotive
refinishing and
transportation.
Industrial finishing
and plastics.
Isophorene Vestanat IPDI [34] Evonik 37.8 e 14 Light stable Toader et al.
diisocyanate elastomer and resin. [35]
(IPDI) Clear coating
 3.2 Raw materials 43

level of stress within the polyurea system, making it more fragile during the first 24 h
following the application which then requires a longer curing time. Deriving a faster
gel time for polyurea systems may on the other hand lead to lower the quality of their
surface morphology. Thus, an optimal amount of isocyanate which is application-
specific required to produce a rigid and the right polyurea product [18,40].

3.2.2 Part A: reactive diluent

The viscosity of isocyanate component may be varied at times; therefore, diluents
are required to lower the viscosity of the final product. Reactive diluents contain
small molecules which have acrylate behavior. Speckhard et al. [41] investigated
the effect of reactive diluent content and the type of diluent used on the properties
of UV-curable polyurethane acrylates. They reported that increasing the amount of
reactive diluent into isocyanate promotes the development of high Tg phase of the
material resulting in high strength and modulus [41]. They employed different types
of reactive diluents such as di-, tri-, and tetraethylene glycol diacrylate and N-vinyl
pyrrolidone in TDI from BASF Wyandotte [41]. Different types of diluents resulted
in differences in softening point (Tg) and the compatibility between the diluent and
final product is also different [41]. The addition of N-vinylpyrrolidone showed more
significant results in terms of higher modulus and tensile strength however lower
elongation in the polyurethane acrylates [41].
Propylene carbonate (PC) is another common reactive diluent typically used for
the aromatic-based MDI-prepolymers such as Isonate 143L. It has a high flash point,
low toxicity, and most importantly a nonvolatile organic compound (VOC). PC acts
as a compatibilizer and diluent in polyurea systems. It improves the shelf life of the
isocyanate-prepolymer, reduces the viscosity during mixing, and gives improved
leveling to the applied film [42]. Reducing viscosity is essential to allow ease in pro-
cessing and casting or application of the polyurea mixture. Usually, polyurea sys-
tems have a very fast curing time as short as just a few seconds [43]. Highly
viscous systems will only cause insufficient time for even dispersion of the mixture
and thus failing the purpose of the system to provide a strong and hard coating.
For coating systems in environments with high moisture such as construction
sites and water treatment systems, Brenntag Specialties developed the Arnox LV
diluent made from carbonate bridged bis-oxazolidine resinous material as coreac-
tants. This material is claimed to reduce VOC in polyurea and polyurethane systems
as it reacts directly with the raw materials [44]. Similarly, as an effort to reduce the
VOC release from coating systems, Incorez Limited developed Incozol LV to pro-
mote a formulation of higher solid content (lower VOC) polyurethane coatings
which can be used for polyurea coatings as well [45].

3.2.3 Part B: polyetheramines

Component B constitute of a resin blend that differs from the component B of poly-
urethane systems. The main component of the resin blend is a mixture of amine-
44 CHAPTER 3 Raw materials, properties, and structure of polyurea

terminated ethylene oxide and/or propylene oxide polyether with molecular weights
varying from 200 to 5000 g/mol. For maximum elongation and flexibility in resisting
chemicals and moisture, high-molecular weight ( > 1000 g/mol) polyamines are
recommended [46]. Polyamines containing primary amine groups (NH2-R) are
more advantageous than other types of amines providing speedy and solid reaction
with the NCO groups of the isocyanate component [47]. In some polyurea systems
especially the conventional ones, the use of polyaspartic ester instead of polyether-
amines is common. Polyaspartic esters are used when a slower reaction between the
A-side and B-side is preferred whereby the curing time is longer. Various applica-
tions such as painting and molding require slightly longer “open time” to allow uni-
form distribution of the coating dispersions and strong adhesion of the particles on
the coating surface [48].
Table 3.2 summarizes the properties of commonly used polyetheramines oligo-
mers in the synthesis of polyurea. Polyetheramines consist of primary and secondary
amines which are sometimes combined in the formulation of polyurea of the B-side
component [19,54]. The amine component which is used as the coreactant of isocy-
anates provides the SS with low Tg which gives flexibility and elongation when
stretched as it has a long backbone chain of polymer. Amine equivalent is a measure
of reactive NH2 groups in the particular resin to calculate the reaction stoichiometry.
High amine equivalent polyamine indicates a greater number of reactive amine sites
that are available to bond with isocyanate groups.
Substantial work [6,51,55,56] has been done to investigate the effect of SS length
and variation of molecular weight of polyamine on the mechanical properties and
behavior of polyurea at the molecular level. At the molecular level, Grujicic et al.
[57] found that the extent of nanophase segregation decreases with a decrease in
SS length. In Fig. 3.3, the hard domains are displayed as large spheres and soft do-
mains are displayed as smaller spheres, the backbone chains are not shown for better
clarity [57]. Fig. 3.3 (a) and (b), (c) and (d), (e) and (f) are polyurea compounds
derived from Versalink P1000, P650, and P250, respectively. As the molecular
weight decreases from 1000 to 650 to 250 g/mol, the morphology of segments be-
comes more rigid, resulting in the increased formation of hard domains. On the other
hand, Iqbal et al. [51] found an interesting observation which clearly supports the
computational results of Grujicic et al. The former reported that, while all the SS
lengths showed an elastomeric response, there was a significant increase in ductility
but a decrease in tensile strength with increasing SS length. This is because mechan-
ical properties of polyurea are strongly influenced by the two-phase-separated
microstructure comprising HS and SS. They added that, with increasing chain
length, the Tg and the frequency required to undergo phase-separated microstructure
formation increased as well. This indicates that by tuning the SS length of polyurea,
desired mechanical and thermal properties can be well established.

3.2.4 Part B: chain extenders

Polyurea is typically synthesized using low equivalent weight polyamine as chain
extender. Increasing the concentration of chain extender in polyurea formulation in-
creases the tensile strength and hardness of the material as it increases the length of
Table 3.2 Properties of commonly used polyetheramines in research studies and industry.
Molecular
a
Commercial weight Amine Viscosity
Polyetheramine products Manufacturer (g/mol) equivalent at 258C Application References

Oligomeric Versalink P-250 Evonik 250 220e250 Solid High temperature Runt et al. [6]
aromatic diamine Versalink P-650 Evonik 650 335e475 2500 mPa/s and heat Alizadeh et al.
resistance, [49]
Versalink P-1000 Evonik 1000 575e625 3000 mPa/s excellent adhesion Youssef et al.
but high viscosity [50]
Polyoxypropylene Jeffamine D-2000 Huntsman 2000 980e1050 247 mPa/s Exhibit enhanced Iqbal et al.
diamine peel strength and [51]
adhesive surface
Jeffamine T-3000 Huntsman 3000 900e980 36 mm2/s For moderate Sanchez-
reactivity and Ferrer et al.
adhesive surfaces [2]
used for
crosslinking
Jeffamine D-230 Huntsman 230 60 9.5 mm2/s Reacts quickly with Iqbal et al.
isocyanates, used [52]
as coreactant in
small amount
alongside other
polyamines for

3.2 Raw materials

clear coating
PTMEG/PPG Jeffamine THF- Huntsman 1000 1870e2060 121 mm2/s For improved Qian et al.
copolymer-based 100 amine anticorrosion and [53]
diamine mechanical
properties
a
The viscosity shown in the tables is expressed as kinematic viscosity with unit mm2/s and dynamic viscosity with unit mPa/s.

45
46 CHAPTER 3 Raw materials, properties, and structure of polyurea

FIGURE 3.3
Prototypical coarse-grained microstructures in fully mixed (left column) and nanophase
segregated (right column) states of three polyurea compositions [6]: (A, B) P1000; (C, D)
P650; and (E, F) P250.
Reprinted with permission from J. Runt, A. Pangon, A. Castagna, Y. He, M. Grujicic, 2 - Phase Separated
Microstructure and StructureeProperty Relationships of High Strain Rate Elastomeric Polyureas, in: R.G. Bar-
soum (Ed.), Elastomeric Polymer With High Rate Sensitivity, William Andrew Publishing, Oxford (2015) 5e16.
https://doi.org/10.1016/B978-0-323-35400-4.00002-7.
 3.2 Raw materials 47

polymer chain [54]. Additionally, increasing the amount of chain extender increases
the stiffness of the material, however, a very large amount may cause the elastomer
to become brittle. Chain extenders are typically added to the system which requires
high flexural modulus such as for structural applications; protective coatings for con-
cretes [58,59]. The addition of chain extenders elongates the polymer chain and in-
creases the HS content thus increases the tensile strength of polyurea. Fig. 3.4 is a
simple illustration of polyurea formation with the help of diamines and triamines;
DETDA is a dietyltoluenediamine that acts as a chain extender and T-5000 is a tri-
amine chain that acts as a crosslinker to bind two or more polyurea chains to form a
network [60]. This shows that DETDA reduced the distance between adjacent urea
groups and replaced the high molecular weight amine (D2000). Additionally, inclu-
sion of chain extender leads favors the formation of bidentate hydrogen bonding
increased formation of hard domains with high Tg.
Table 3.3 shows the different types of chain extenders used in polyurea synthesis.
Both aromatic and aliphatic chain extenders can be used in all kinds of polyurea

FIGURE 3.4
Schematic of formation of crosslinked polyurea with the help of low molecular weight
amines [60].
Reprinted with permission from N. Iqbal, M. Tripathi, S. Parthasarathy, D. Kumar, P.K. Roy, Polyurea spray
coatings: Tailoring material properties through chemical crosslinking, Prog. Org. Coatings. (2018). https://doi.
org/10.1016/j.porgcoat.2018.07.005.
 48
CHAPTER 3 Raw materials, properties, and structure of polyurea
Table 3.3 Types of chain extenders and their key properties for polyurea formulation.
Industrial Kinematic viscosity Amine equivalent
Chain extender product Type (mm2/s) (g/eq) References

Diethyl toluenediamine (DETDA) Ethacure 100 Aromatic 15.5 at 25
C 89 Iqbal et al. [61]
Dimethylthio-toluene diamine Ethacure 300 Aromatic 69 at 25
C 107 Wang et al.
(DMTDA) [62]
Ethylenediamine e e 15.4 at 25
C e Jiang et al.
[63]
Cycloaliphatic secondary amine Jefflink 754 Aliphatic 0.8 at 40
C 127 Toader et al.
[35]
Clearlink 1000 11 at 25
C 161 David et al.
[64]
 3.3 Conclusion 49

systems. Qian et al. [65] synthesized aliphatic polyurea using 1 to 3.6 mass ratio of
IPDI to Jeffamine D2000 with an addition of 9.5 wt.% diethyltoluenediamine
(DETDA) aromatic chain extender of the total mixture. They reported that this
formulation resulted in 13.1 MPa and the elongation of 609%. On the other hand,
Cai et al. [66] reported only 2.2 MPa for aliphatic polyurea using IPDI and Jeffamine
D2000 without the addition of chain extenders. On the contrary, Posey et al. [54]
evaluated the aliphatic chain extender (Jefflink 754) on the aliphatic polyurea using
IPDI and Jeffamine D2000. They reported tensile strength of 18.1 MPa for an addi-
tion of 44 wt.% of Jefflink 754 diamine which is an aliphatic chain extender into the
B-side resin blend. American Plastics Council Staff [67] used almost 50 wt.% of
Clearlink 1000 in the B-side resin blend and reported 28 MPa for its tensile strength.
Iqbal et al. [61] investigated the effect of aromatic and aliphatic chain extenders in
polyurea formulation and found that an optimal ratio of the two forces growing
macromolecule to self-assemble in such a way that it results in optimal hydrogen
bonding. Aromatic chain extenders are more reactive than the aliphatic ones which
lead to shorter gel time which suggests that trial experiments need to be performed to
find the best ratio of aromatic and aliphatic chain extender in polyurea formulation
to provide better coatings.
Recently, Tripathi et al. [68] did a thorough study on the effect of increasing the
chain length of different types of chain extenders on the mechanical and perfor-
mance of MDI-based isocyanate prepolymer polyurea systems made through a reac-
tive spray processing technique. They have found a relationship between the ratio of
the aromatic and aliphatic chain extenders and optimal hydrogen bonding where
growing macromolecule can be aligned together and contribute to their improved
mechanical properties [68]. Aromatic chain extenders were reported to decrease
the distance between urea linkages more as compared to aliphatic chain extenders.
This is due to the linearity and unstable spatial orientation that is adapted in aliphatic
structure. Hypothetically, the closer the urea linkages, the more they are prone to
hydrogen bonding and the higher degree of hard domain formation. An optimum ra-
tio of aromatic and aliphatic chain extenders therefore forces the molecules to align
and form intermolecular hydrogen bonding [61,68]. Tripathi et al. [68] discovered
that a 63% contribution of aromatic chain extenders demonstrated the highest tensile
strength.

3.3 Conclusion
The above analysis considers the chemical structure of basic raw materials for the
production of linear polyurea. Moreover, the microstructure and selected physical-
mechanical and thermal properties of linear polyurea derived from commonly
used raw materials described in the literature reports are also presented and critically
analyzed. Despite that, there are still many potential raw materials available to syn-
thesize new polyurea systems and to fine-tune known chemical structures and phase
structures where polyurea is involved. It is critical to attain specialized knowledge
50 CHAPTER 3 Raw materials, properties, and structure of polyurea

on the kinetics of polymerization of polyurea in order to make a sensible choice of

the required raw materials. The use of computational simulation methods in
designing the microstructure of polyurea and yielding information on hard and
soft domain arrangement and interactions showed new potential for the synthesis
of polyurea in the future.

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