Structure
Structure
PUs molecular structure can vary from rigid polymeric (crosslinked), to linear, elastomeric flexible
chains (Figure 1.35). Flexible foams and TPU elastomers have segmented structures, made up of
long flexible chains (polyols) linked by polyurethane and polyurea aromatic hard segments. Their
character depend largely on hydrogen bonds between polar groups of the polymeric chain, mainly
among N-H groups (electron acceptors) and carbonyl groups (electron donors) of urea and
urethane groups. Hydrogen bonds can also be formed among N-H groups and polyester carbonyl
groups and, more difficultly, with polyether oxygen atoms (weak bonds). Hard segments of flexible
PUs, especially of polyurea, form strong secondary chemical bonds (hydrogen bonds) with a
tendency to form hard segment domains. On the other hand, as a result of the polyfunctional
reagents used, rigid PU foams are highly crosslinked, and they don't show the segmented
structures present in flexible PUs. Besides urethane bonds, the PUs macromolecular chain
possesses a multiplicity of other groups that contribute to the cohesive macromolecular forces
(Table 1.12).
a - urethane linkage
b - polyol chain
b) Polymers with a segregated domain structure (high modulus elastomers and flexible foams)
- = diurethane linkage
T= triurethane linkage
+ = tetraurethane linkage
* = polyurethane linkage
Properties of PUs produced from 1,6-hexane diisocyanate and 1,4-butane diol are like those of
polyamides of similar structures. Amorphous PUs (prepared with TDI and diethylene glycol) are
rigid and transparent, but they show low dimensional stability at high temperatures. On the other
hand, there are PUs formed exclusively by soft segments, obtained by the stoichiometric reaction
of a difunctional polyol with diisocyanate, resulting in amorphous products with elastomeric
properties. Here, intermolecular forces are essentially between the polyol soft segments so that
properties such as hardness and mechanical resistance are poor. All these products have a single
phase and they don't present segmented structures. The only non-segmented PUs of commercial
importance are the highly cross-linked PUs such as rigid foams and non-textile coatings.
Segmented PUs is formed by the reaction of a polyol, diisocyanate and a chain extender, which
can be a glycol, diamine or water. These PUs represent a class of products, characterized by a
segmented structure (polymeric blocks) made up of two or more different polymeric phases. These
segmented structures are responsible for the excellent PUs properties.
A PU prepared with one mole of long chain linear polyol [poly(1,4-butane diol adipate)], two moles
diisocyanate (MDI) and one mole chain extender (1,4-butane diol) presents the structure shown in
Figure 1.36. Soft segments, which are quite mobile and are normally present in a coiled shape,
and hard segment units, alternate.
Usually, Pus' soft segments are incompatible with the hard and polar ones. As a consequence a
phase separation (segregation) occurs and covalently linked microphases are formed. The
coherent matrix, which consists of flexible soft segments, results in high deformability of the
resulting material. In contrast, within the hard segment domains, molecules are fixed by physical
interaction. Because of covalent coupling to the soft segments, they inhibit plastic flow of the
chains, thus creating elastomeric resiliency. Hard segmented domains can be looked at as
multifunctional spacious crosslinked areas. The larger the phase segregation, the lower the polarity
of the flexible segments. Therefore, segregation is less pronounced in polyester urethanes
compared to polyether urethanes and is most pronounced in polybutadiene urethanes (Figure
1.37).
The melting range of the hard segment domains determines the dimensional thermal stability of
linear segmented PUs. Above the melting range the material is thermoplastic. With the increasing
length of the hard segment the melting range also rises and with the use of different chain
extenders and isocyanates the melting range can be intentionally modified (Chapter 6.3). Above
the melting range of the hard segments, linear PU's form a viscous homogeneous liquid that can
be processed as a thermoplastic material. Whenever the melting range is above 250oC (which
means higher than the PU decomposition temperature), even linear PUs will not exhibit
thermoplastic properties. Upon increasing the amount of hard segment, PU shows an increase in
hardness and modulus, and above 60% by weight there is a change in behavior from elastomeric
to a brittle, high-modulus plastic.
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Other studies show that, for polyester-based PU elastomers, the formation of hydrogen bonds
depends on the size of the polyester soft segment. In polymers with high urethane concentration,
hydrogen bridges between N-H groups and urethane -CO- groups are more frequent. Though,
when urethane concentration is reduced, connections between N-H urethane groups and polyester
-CO- groups become more important. Spectroscopic infrared analyses of polyester and polyether
systems indicate that in polyester systems hydrogen bonds are formed mainly with polyester -CO-
groups, while in polyether systems, such bonds are formed with urethane -CO- groups.
The effect of crosslinking density on physical properties of PUs elastomers is shown by data (Table
1.13) obtained by the substitution of 1,4-butane-diol for trimethylol propane for, as chain extender
of PU based-polyester produced with MDI and ethylene glycol polyadipate. These data show the
molecular weight increase of crosslinking units (Mc) (or decrease in crosslinking density) with the
triol amount in the reagents. The initial decrease in modulus with the increase in crosslinking
degree is opposite to the results observed in conventional polyhydrocarbon elastomers, where an
increase in the reticulation corresponds to a modulus increase. With PUs, it happens that a larger
crosslinking number reduces the chain orientation and formation of hydrogen bonds or other
intermolecular interactions. This phenomenon prevails until the crosslinking density is sufficiently
strong to exert its own effect towards increasing PU modulus.
2.1 - Catalysts
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