CHAPTER TWO

BASIC RAW MATERIALS FOR THE PRODUCTION OF

LINEAR POLYURETHANES

The basic pool of feeds applicable in the manufacture of polyurethanes

is made up of: diisocyanates, polyether polyols or polyester polyols, diols,
diamines employed as low-molecular-weigh extenders of isocyanate pre-
polymer chains, catalysts for the polyaddition process of diisocyanates
and compounds with unstable hydrogen atoms (water, alcohols, amines),
and auxiliary substances selected for specific processes, e.g. blowing
agents for foamed polyurethanes, poly-functional amines or isocyanates
as cross-linking agents, or organophosphorus antipyrene compounds
which are widely used in foamed polyurethanes. The choice of those
materials was discussed in detail in numerous review papers intended
to present production processes of individual polyurethane products
[2, 22]. Basic isocyanate and polyol feedstocks were also mentioned in
this work, just for regularity, but what was more stressed here is their
structural characteristics and chemical reactivity resulting therefrom as
the key feature for the step-growth polyaddition processes.

2.1 Diisocyanates

The only technically reasonable method today for the production of

PU plastics is the polyaddition process of diisocyanates and polyols.
Hence, the manufacturing methods and properties of the isocyanate
feedstocks make the deciding factor for the production of polyurethanes.
The situation is so critical that the biggest polyurethane producers
have their captive production of isocyanate raw materials at the same
time.
Those compounds found their beginning in the synthesis of phenyl
isocyanate, developed by Hoffmann, and based on thermal dehydro-
genation of di(N-phenyl)oxamide (equation 5):
C 6 H5 N H CO CO NH C 6 H5 2 C 6 H5 NC O + H 2 (5)
8 chapter two

Diisocyanates can be obtained in a laboratory by rearrangement of

compounds with electron deficiency at the nitrogen atom (nitrenes).
The Curtius method can be used for that purpose (rearrangement of
acyl azides) or alternatively amides can be subjected to the Hoffmann
rearrangement. Commercially, however, only the Hetschel method has
so far been employed, i.e. phosgenation of amines with further modi-
fications (equation 6) [24]:
R N H2 + C OC l2 R NC O + HCl (6)
The above reaction is pretty simple. Yet, the synthesis process based
on it involves many steps in fact, it is troublesome and it has a bed
environmental reputation—all that because of extreme toxicity of
phosgene, toxicity of amine feeds and toxicity of diisocyanate products
themselves.
In order to minimise the environmental impact of COCl2, extensive
research has been directed toward the development of effective catalyst(s)
for oxidative carbonylation (equation 7):
R NH2 + R' OH + CO + 1/2 O2 RNHCOOR' + H2O (7)

and reductive carbonylation (equation 8):

R NO 2 + 3 CO + R' OH RNHCOOR' + CO 2 (8)

The synthesised carbamates would then be subjected to thermal decom-

position to yield isocyanates (equation 9) [25]:
R N HC OOR' R NC O + R' OH (9)

None the less, phosgene is still needed for the commercial production
of diisocyanate monomers with the vital importance for the polyure-
thane technology.
When analysing the changes which took place over the last decade in
the diisocyanate production processes, a clear qualitative revaluation can
be noticed. The group of regular products, like aliphatic diisocyanates
(e.g. 1,6-diisocyanatohexane, HDI), (formula 10),
OC N (C H2 )6 NC O (10)

and aromatic diisocyanates: toluene-2,4-diisocyanate and toluene-2,6-

diisocyanate (TDI), utilised as a mixture of isomers (formula 11),
 basic raw materials 9

CH3 CH3
NCO OCN NCO

(11)

NCO
2,4-TDI (80 %) 2,6-TDI (20 %)

and 4,4’-methylenebis(phenyl isocyanate) (MDI) (formula 12),

OCN CH2 NCO (12)

or 1,5-naphtylene diisocyanate (NDI) (formula 13), which is not so

frequently used,
NCO

(13)

NCO

was joined by new alicyclic diisocyanates, which can be converted into

polyurethane coatings more resistant to photo-degradation in direct
sunlight service:
isophorone diisocyanate [5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclo-
hexane] (IPDI) (formula 14),
H3C N=C=O

H3C (14)

CH 2 N = C = O
H3C
 10 chapter two

and 4,4’-methylenebis(cyclohexyl isocyanate) (HMDI) (formula 15):

O=C=N CH2 N=C=O (15)

Other diisocyanates, in particular 1,3-phenylene diisocyanate and 1,1-

biphenylene diisocyanate, gained much less importance and they are
employed in very specific applications only [26]. The fundamental prob-
lem to be considered when using diisocyanates is the need to provide
adequate reactivity of their functional groups towards the compounds
with unstable hydrogen atoms in their molecules. The isocyanate group,
–N=C=O, is generally very active due to its two cumulated double
bonds. However, depending on its location within the chain (primary
group, secondary group), depending on possible steric hindrance(s), and
depending on the so-called substitution effect which is frequently the
case in some diisocyanates or urethaneisocyanates, considerable differ-
ences in reactivity can be observed. Such differences can be important
for commercial processes and they should be controlled by the use of
suitable catalysts. Those problems made subjects of many theoretical
analyses in the past [27]. A more detailed analysis will be presented
below for reactivity of isocyanate groups in the most popular mono-
mers: 2,4- and 2,6-TDI.

2.2 Polyols

2.2.1 Aliphatic linear polyethers

The basic polyether polyols applicable for the production of linear
PUs can be obtained by the addition reaction (following the anionic
mechanism principle) of ethylene or propylene oxide to suitable glycols,
produced beforehand in the water addition process to corresponding
oxiranes in the catalytic presence of NaOH. What is especially wor-
thy of notice here is block polyethers which go under the name of
PLURONIC (formula 16):
H (O CH2 C H2 )n (O CH C H2 O) k (C H2 C H2 )n OH
(16)
C H3

and which offer only primary hydroxyl groups—more reactive towards

isocyanates. Similar performance is available from poly(tetramethylene
 basic raw materials 11

oxide)glycol (formula 17), which is produced by cationic polymerisation

of tetrahydrofuran, and which is much more expensive.
H (O C H2 C H2 C H2 C H2 )n OH (17)

Polyether polyols are produced in Poland, their trade name is

ROKOPOLs, and their molecular weights fall within a pretty wide
range of 400–3,000 g/mol. The properties which are important from
the viewpoint of application are: viscosity and water content; the latter
should not exceed 0.05 wt %. Polyethers impart softness and flexibility
to polyurethanes.
It would be advisable to make a secondary comment in this place:
the grafting process of oxiranes on multi-functional polyols (glycerol or
pentaerythritol) [28, 29], on amines (triethanolamine), on hydrocarbons
or on phenol-formaldehyde resins, and on hydroxymethyl derivatives of
compounds having imine group(s) in their structures (formula 18):
N CH2 CH2 (O CH2 CH2 O) n H (18)

(urea, melamine, uric acid or barbituric acid) can yield very interesting
poly-functional polyethers applicable in the production of thermally
stable, cross-linked foams [30–31]. The use of dihydroxyl derivatives
of parabanic acid (formula 19) can also be of some importance for the
production of linear polyurethanes;
O C C O

HO CH C H2 N N C H2 CH OH (19)

R O R

they can be obtained from the reaction of parabanic acid with formal-
dehyde, oxiranes or ethylene carbonate [32, 33].

2.2.2 Aromatic polyethers

Within the group of aromatic polyethers which are important for
the polyurethane processes, dianoles are worthy of notice. They are
polyethers (e.g. Dianole 24) obtained in the reaction of 2,2-bis(4-
hydroxyphenyl)propane (bisphenol-A) with oxiranes (formula 20) [34,
35]:
 12 chapter two

C H3

HO C H2 C H2 n O C O C H2 C H2 O H (20)
1 n2
C H3

or bisphenol-S polysulfone with oxiranes (formula 21) [36]:

O
HO C H2 C H2 O S O C H2 C H2 O H (21)
n1 n2
O

Dianoles can be additionally subjected to esterification with glycolic

acid, phosphoric acid or acrylic acid, which yields linear polyester
polyols—also applicable in the production of PUs [37, 38].

2.2.3 Aliphatic saturated polyesters

The polycondensation process of dicarboxylic acids and glycols makes
the most frequently used method for the synthesis of linear polyestrols.
Polyadipates of ethylene glycol, diethylene glycol or propylene glycol
(formula 22) are usually utilised as linear polyesters in the polyurethane
elastomers production processes.
H[ O CH2 CH2 O OC (CH2)4 CO O CH2 CH2 )]n OH (22)

Since more and more attention is paid to the need of biodegradability

(in part at least) of polyurethanes, polycaprolactone diol started gain-
ing popularity as a polyol-type feed useful for the manufacture of such
polymers. It is obtained by grafting ε-caprolactone on glycol. The initial
monomer, on the other hand, is obtained by oxidation of cyclohexanone
(equations 23 and 24):
O
C
[O] C O (23)
O

O
C
2n + HO CH2 CH2 O CH2 CH2 OH
O

(24)
O O
H O (CH2)5 C nO CH2 CH2 O CH2 CH2 O C (CH2)5 O n H
 basic raw materials 13

Polyols of that type offer lower viscosity figures than oligoesters derived
from dicarboxylic acids and glycols. They are more expensive than tra-
ditional polyestrols, but product polyurethanes have superior mechanical
properties. However, PUs obtained from polyesterdiols are less resistant
to hydrolysis in relation to polyether polyurethanes [39–41].
General attention is attracted recently by one more type of polyes-
terdiols applicable in the production of PU elastomers, i.e. by aliphatic
polycarbonates obtained from cyclic alkylene carbonates (equation 25)
[42, 43]:
R R
R O R
n H OCH2 CCH2 OC OCH2 CCH2 OH
O O n-1
(25)
R R
O
R = H, CH3

2.3 Difunctional Chain Extenders

Diols make the group of difunctional chain extenders for urethane-iso-

cyanate prepolymers, which is most widely employed in the production
of PU elastomers. That group comprises ethylene glycol, diethylene
glycol, 1,4-butanediol and 1,6-hexanediol [44, 45]. Diamines, like 1,2-
ethylenediamine and 1,6-hexamethylenediamine, can also be used as
chain extenders, but in this case urethane chains are extended through
urea groups. Aliphatic amines are used frequently to extend chains of
urethane ionomers [46, 47].
A solid position in the PU anionomers production processes was
earned by the carboxylic-containing chain extender (formula 26)
[48]:
H2 C OH

H3 C C C OOH
(26)
H2 C OH
2,2-bis(hydroxymethyl)propionic acid (DMPA)
 14 chapter two

There also is a group of some more specific and interesting extenders,

like that shown by formula 27 [49]:
HO C H2 C H2 N C H2 C H2 OH
C O

(27)

N
N,N’-bis(2-hydroxyethyl)isonicotinamide

which is utilised in the production of PU cationomers for special

outlets [40], or like Dianoles as already mentioned above—these are
applicable for the conversion of PU elastomers with a higher number
of aromatic rings in the production of chemically resistant coatings
[35, 50] (formula 28):
CH3
HO CH2 CH2 O C O CH2 C H2 OH
(28)
CH3
bis[4-(β-hydroxyethoxy)]bisphenol A (Dianole-22)

Moreover, there is a pretty numerous group of low-molecular-weight

and difunctional diols and/or amines, which form rigid mesogens
utilised in liquid crystal linear PUs (formulas 29–31) [51–53]:

HO C H2 C H2 O O C H2 C H2 OH
(29)

4,4’-bis(2-hydroxyethoxy)biphenyl (BHBP)

H 2N NH2
(30)

4,4’-diaminobiphenyle (DABP)
 basic raw materials 15

CO O C H2 C H2 OH

(31)

CO O C H2 C H2 OH

bis-(p-hydroxymethyl-phenyl)terephthalate

2.4 Catalysts

The catalytic activity in the reaction of isocyanates and compounds

with unstable hydrogen atom(s) (i.e. alcohols, amines, water, carboxylic
acids, malonates, etc.) is shown by tertiary amines and organometallic
compounds, and among the latter the most important compounds are
those of Sn, Pb and Fe.
The most popular amine catalyst is 1,4-diazabicyclo-[2,2,2]-octane
(DABCO), and the most widely used tin catalysts are: dibutyltindilaurate
(DBTDL) and dibutyltindioctanate. And just these two types of com-
pounds make the basis for very specific catalytic systems, which have
been developed and which offer a high selectivity with respect to polyol
components with different molecular weights and with primary, second-
ary or tertiary hydroxyl groups, and also with respect to small amounts
of water possibly present in polyol feeds (or added for some specific
purpose). These catalysts are used in the liquid form in most cases, as
solutions in glycol(s) or polyol(s) which are employed for the so-called
polyol masterbatches. Catalytic salts of Bi, Fe, Ti, Co, Cd and Zn are
used less frequently. Iron(II) acetoacetate, trialkylphosphines, and such
compounds as N-methyl morpholine and piperidine, have also won some
significance. The problems of catalysis in the polyurethane technology
have been discussed in details in every monographic volume on PUs
presented so far [2, 54–56]. Moreover, there are many review papers
published on that subject [57–61]. It seems more important for the
materials engineering to understand the basic elements of PU chemistry
and the mechanism for step-growth polyaddition of diisocyanates and
polyols. The role of catalysts and the consequent kinetic questions can
16 chapter two

be presented on that background. Those issues are important not only

for the commercial production of linear polyurethanes by big produc-
ers, but they can also be critical for local processing in the automotive
industry, in civil engineering, in repair or renovation of power supply
systems, etc.