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1.3 - Polyols
A great polyol variety is used in PU's. Among the most widely employed are polyether polyols, which are
obtained by the polymerization of propylene, ethylene and butylene oxides. Most commonly used are
poly (propylene oxide) glycol and copolymers of (propylene/ethylene oxides) glycols (PPG's) (Table 1.5).
Other polyether polyols, such as poly (tetramethylene oxide) glycol, are used in PU fibers and high
performance elastomers, while polymeric polyols are used in high resilience flexible foams. Besides, one
can cite the polyester polyols (Table 1.6), used in high performance applications, castor oil, hydroxyl-
terminated polybutadiene (HTPB), etc. Usually, polyols having molecular weight between 1,000 and
6,000 and functionality between 1.8 and 3.0 are used in flexible foams and elastomers. Short chain
(250<1,000), high functionality (3<12) polyols yield high cross-linked rigid chains and are used in rigid
foams and high performance coatings. The molecular weight distribution of polyether polyols follows the
Poisson probability equation, being narrower than the polyester distribution (thermodynamically
controlled in agreement with the Flory equation).

1.3.1 - Polypropylene glycols (PPG's)

PPG's are obtained through anionic polymerization of propylene oxide (PO) and propylene and ethylene
oxides (EO) copolymerization. The first stage of the PPG polymerization process is the reaction of an
alcohol with a strong base (usually potassium hydroxide), forming the corresponding alcoholate. Figure
1.22 shows the mechanism of secondary hydroxyl formation resulting from the nucleophilic attack to the
less hindered PO carbon atom.

Figure 1.22 - PPG preparation

PPG's narrow molecular weight distribution is due to the anionic polymerization process. The polyether
functionality corresponds to the functionality of hydroxyl or amine group-containing compounds used as
initiators (Tables 1.5 and 1.6). The PPG's viscosity is between 100 and 1,000 cP @ 25°C. PPG's diols of
MW between 400 and 4,000 and hydroxyl number from 265 to 28 mg of KOH/g are used in CASE
products, and the trifunctional ones, of molecular weight between 3,000 and 6,000, hydroxyl number
from 56 to 28 mg of KOH/g are used in flexible foams, those of higher MW being used in high resilience
foams (HR). High functionality polyols, of MW lower than 1,000, hydroxyl number between 300 to 800
and high viscosity (in some cases until 17,000 cP @ 25°C) yield highly crosslinked polyurethanes and
are used in rigid foams. A few examples of polyether polyols based on propylene and ethylene oxides,
used in different applications, are shown in Table 1.5.

Table 1.5 - Typical properties of polyether polyols

Applications CASE1 Flexible Foams Rigid Foams
Conventional Conventional HR
Polyol composition propylene glycol glicerine + amine + trimethylolpropane trimethylolpropane sucrose +
+ propylene propylene and propylene oxide + propylene and + propylene oxide propylene oxide
oxide ethylene oxides ethylene oxides
Average MW 2000 ± 100 3000 ± 200 3750 ± 200 4800 ± 300 440 ± 35 860 ± 60
OH number (mg KOH/g) 56 ± 3 56 ± 3 60 ± 3 35 ± 2 380 ± 25 380 ± 25
OH content (meq/g) 1.0 1.0 1.1 0.6 6.8 6.9
Average functionality2 2.0 3.0 4.0 3.0 3.0 5.8
Insaturation (meq/g) < 0.04 0.04 < 0.04 < 0.05 < 0.005 < 0.005
o
Viscosity at 25 C (mPa.s) 250 – 350 450 – 550 580 – 720 750 – 900 600 - 700 11000 – 15000
- 36 - 31 - 35 - 38 - 22 -2
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Pour point (oC)

pH 6.5 – 8.0 6.5 – 8.0 8.6 – 9.6 6.5 – 8.0 6.0 – 7.5 6.5 – 8.0
Density, 25oC (g/cm) 1.00 1.01 1.00 1.02 1.03 1.1
1 – coatings, adhesives, sealants e elastomers, 2 – Average functionality = PM x OH content (meq/g) / 1000

Usually, diols such as propylene glycol are used as initiators for the production of polyether diols; triols
such as glycerin and trimethylol propane to obtain polyether triols, and products of higher functionality
such as sorbitol and sucrose in the production of high functionality polyether polyols (Table 1.6).

Table 1.6 - Common initiators for polyether polyols

INITIATORS STRUCTURE FUNCTIONALITY
Water HOH 2
Ethylene glycol HOCH2CH2OH 2
1,2-Propylene glycol HOCH2CH(CH3)OH 2
Glicerine 3

Trimethylolpropane 3

Triethanol amine N-(-CH2-CH2OH)3 3

Pentaerythritol C-(-CH2OH)4 4
Ethylene diamine H2NCH2CH2NH2 4
2,4-toluene diamine or 4
(2,6-toluene diamine)

4’.4’-diphenyl methane 4
diamine
Diethylene triamine H2NCH2CH2NHCH2CH2NH2 5
Sorbitol 6

Sucrose 8

Primary amines can also be used as initiators to obtain polyether polyols. Due to the stronger
nucleophilic character of the amines as compared to hydroxylated compounds, the use of KOH as
catalyst may be dispensed with. Ethylene and toluene diamines are initiators for obtaining tetra functional
polyether polyols. The higher basicity of the resulting polyols having tertiary amine groups makes them
more reactive towards isocyanates.

1.3.1.1 - Copolymers with ethylene oxide

Reactive PPG's are used in cold molded PU foam systems, and their reactivity depends on the degree of
primary hydroxyl groups (Figure 1.23). PPG's produced only with PO possess less reactive secondary
hydroxyl groups. For obtaining more reactive primary hydroxyls, reaction with EO is carried out in the
final stage of the polymerization. Usually the EO block is less than 20% of the polymer chain and it
improves the polyol solubility in water. PO/EO copolymers increase the water solubility and decrease the
heterogeneous phases, where the reaction of water with isocyanate occurs and forms rigid polyurea
macrophases, resulting in softer flexible foams (Chapter 3).
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Figure 1.23 - PPG's reactivity

1.3.1.2 - Low monol degree PPG's

The conventional propylene oxide based polyether polyols (PPG) are produced commercially through the
base catalyzed, using an alkali metal salt such potassium hydroxide (KOH), propoxylation of so-called
starters, which have two or more hydroxyl groups. Typically, propylene glycol is used to produce diols
and glycerin to produce triols. However, their functionality is slightly lower than that of the initiator
compound, this sometimes being due to small amounts of remaining water in reagents. It is well known
that base catalyzes not only the addition of propylene oxide to the growing polyol molecule, but also a
side reaction in which propylene oxide isomerizes to allyl alcohol (Figure 1.24).

Figure 1.24 - PPG monol formation

Allyl alcohol acts as a monofunctional starter resulting in propoxylated allyl alcohol referred to as monol.
These monofunctional products act as chain terminators during the PU formation, resulting in a decrease
in mechanical properties. As PPG monol is double bond- terminated, the monol degree can be quantified
by the insaturation (in meq/g). The PPG's insaturation level or monol content increases with the
molecular weight (Table 1.7). For example, a 2000 MW conventional PPG diol has a monol content of
about 0,03 meq/g, which correspond to a functionality of 1,92, whereas, a 4000 MW PPG diol has a
monol content of about 0.085 meq/g and functionality of only 1.7. Syntheses of low insaturation degree
(<0.02 meq/g) polyether polyols have been carried out by using double metal cyanide (DMC) catalysts
based on Zn3[Co(CN)6]2 (zinc hexacyanocobaltate). The new generation of ultra low monol content
polyols has a typical monol (insaturation) content of 0.005 meq/g or less, which correspond to a
functionality of 1.98 for a 4000 MW diol.

Table 1.7 - Characteristics of commercial PPG's

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Molecular Weight OH number Viscosity at Insaturation Monol % Average

Conventional Low monol (mg de KOH/g) (25OC) (meq/g) (mol) Functionality*
1000 111 145 0.01 1 1.99
1000 111 145 0.005 0,5 1.995
2000 56 335 0.03 6 1.94
2000 56 335 0.005 1 1.99
3000 37 570 0.05 14 1.86
3000 37 580 0.004 1 1.99
4000 28 980 0.09 31 1.69
4200 28 860 0.005 2 1.98
8000 14 - - -
8200 14 3000 0.05 4 1.96
* calculated using Carothers equation.

1.3.1.3 - Copolymer Polyols

Polyether polyols can be "filled" with grafted organic polymers. The successful preparation of stable,
colloidal dispersions requires that the particles have some type of steric stabilization to prevent
flocculation of the suspension. These white and viscous modified polyol dispersions are useful in making
high hardness foams. Polymeric polyols are usually formed trough a free radical or step addition process
by in situ monomer grafting to PPG. There are two types of modified polyether polyols.

Copolymer Polyols - Copolymer polyols are obtained through free radical grafting of styrene and
acrylonitrile (SAN copolymer) to PPG. The product contains a mixture of PPG, SAN copolymer and graft
copolymer polyols that act as a stabilizer (Figure 1.25).

Figure 1.25 - Copolymer polyol reactions

The first commercial copolymer polyols were based on acrylonitrile as the sole monomer. This dispersion
contained 20% poly(acrylonitrile) and had viscosities of 3,000-5,000 mPa.s. These products were used
for the production of cold molded, high resilience flexible foams (HR), with improved hardness, strength,
foam processing, and cell opening. As the 100% acrylonitrile copolymer polyols cause discoloration
problems in slabstock flexible foams, styrene/acrylonitrile (SAN) copolymer polyols were developed.
These copolymer polyols require the use of a more efficient stabilizer molecule to form the grafted
portion of the polymer. This is because the styrene and acrylonitrile copolymerization is quite favorable,
and the tendency for free radicals to be generated on the polyol is reduced. The so-called macromer
stabilizers are PPG's which have been functionalized with a vinyl moiety (for the PPG's reaction with
maleic anhydride, ethylisocyanate methacrylate, methacryloyl chloride, etc), which will undergo
copolymerization with SAN monomers (Figure 1.26).

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Figure 1.26 - Copolymer polyol particle synthesis

a) graft macromer; b) "comb polymer"; c) phase separation; d) 0.01-0.05 microns particles; e) inside particle polymerization; f) 0.3-0.5 microns final particle.

Polymerization starts with the addition of base polyol and macromer, followed by initiator and monomer
feed. In the beginning the reaction mixture is homogeneous and the grafted polyol is formed. At some
point (corresponding to 1-3% of total added monomer) the polymeric "comb" associates into a spherical
structure, in which the insoluble copolymer is located in the center of the sphere, and the macromer
chains are in the surface, where they can interact with the continuous polyol phase. Polymerization
continues inside the particles that grow from 0.01-0.05 to 0.3-0.5 microns, yielding a narrow distribution
and monodisperse size particles. In molded and slabstock HR flexible foams copolymer polyols are used
with 25-40% solids and viscosity 2,500-7,000 mPa.s, and for conventional flexible foams, with 40-43%
solids and 4,000-6,000 mPa.s.

PHD Polyol (urea/urethane polyol) - PHD polyols (polyurea modified) are dispersions of polyurea
particles, formed by the reaction between TDI and diamines (hydrazine, ethylene diamine, etc) in a
conventional polyol. In the reaction of diamines and isocyanates, the low molecular weight polyurea
formed separates from the continuous phase. Since the reaction of a polyol and diisocyanate is slower
than that of a diamine and diisocyanate, their tendency to form small particles is less probable than that
of the SAN copolymer polyols. This leads to lower incorporation of polyol grafts and broader distribution
of particle sizes. The diamine quickly reacts with an excess diisocyanate and the formed polyurea-
modified isocyanate reacts with the polyol, forming poly(urea/urethane) that acts as stabilizer for the
polyurea dispersion in the PHD polyol (Figure 1.27). These polyureas, present in 20-30%, react with
isocyanate during foam manufacture, eventually increasing the cross-linking degree.

Figure 1.27 - Formation of PHD polyol

1.3.2 - Polyester polyols

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