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Structure

This document discusses the relationship between polyurethane structure and properties. It describes how polyurethanes can have rigid, crosslinked structures or flexible, segmented structures. Segmented polyurethanes have alternating soft and hard segments that provide different properties. The soft segments provide flexibility while the hard segments, through hydrogen bonding and crystallization, provide strength and thermal properties. Variations in soft and hard segment chemistry and length can be used to tailor polyurethane properties.

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0% found this document useful (0 votes)
64 views

Structure

This document discusses the relationship between polyurethane structure and properties. It describes how polyurethanes can have rigid, crosslinked structures or flexible, segmented structures. Segmented polyurethanes have alternating soft and hard segments that provide different properties. The soft segments provide flexibility while the hard segments, through hydrogen bonding and crystallization, provide strength and thermal properties. Variations in soft and hard segment chemistry and length can be used to tailor polyurethane properties.

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2017/6/29 Capítulo 1

1.6 - Correlations between structure and properties

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).

Table 1.12 - Cohesive molar energy of organic groups


Organic group Choesive molar enrgy (kcal/ml)
-CH2- (hydrocarbon) 0,68
-O- (ether) 1,00
-COO- (ester) 2,90
-C6H4- (aromatic ring) 3,90
-CONH- (amide) 8,50
-OCONH- (urethane) 8,74

a) Soft, high elongation elastomers

a - urethane linkage

b - polyol chain

b) Polymers with a segregated domain structure (high modulus elastomers and flexible foams)

a - hard block domain

b - soft block domain

c) Rigid, highly cross-linked polymers

- = diurethane linkage
T= triurethane linkage
+ = tetraurethane linkage
* = polyurethane linkage

Figure 1.35 - Polyurethane structures

1.6.1 - Segmented polyurethanes


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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.

Hard and soft segments

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.

a) sof segments, b) hard segments

Figure 1.36 - Representation of a segmented PU chain

Morphology of the segregated domains

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).

a - soft block domain

b - hard block domain

Figure 1.37 - TPU structures


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Hard domain morphology


Depending on the nature and length of the hard segments and the degree of segregation, three-
dimensional organized proximity areas are formed with structures of predominantly paracrystalline
nature. In case of very low cooling and sufficient length of the hard segments, even
microcrystallites can be formed (Figure 1.38). The secondary structure depends on the proximity
zone interaction between hard segments. This structure is mainly characterized by hydrogen
bonding between adjacent aromatic rings of symmetrical isocyanates. Another important
interaction is that existing between p electrons of the isocyanate aromatic rings.

a) sof segments, b) hard segments

Figure 1.38 - Interchain interaction between hard segments

1.6.2 - Effect of hard segments


Interactions between chains, mainly hydrogen bonds between hard segments, contribute to the
distinguishing properties of PUs. Thermo-mechanical properties of linear segmented PUs are
substantially different from those of chemically crosslinked products. Whenever mechanical forces
are applied, changes in the orientation and mobility of structures within hard segment domains,
which depend on temperature, can occur. In this process initial hydrogen bridges are broken and
other, energetically more favorable, are formed. A change in structure occurs, causing alignment in
the direction of the applied tension (Figure 1.39). As a consequence, applied tension is better
distributed and as a result, the resistance of the material against further stress is increased. This
effect contributes to the high tensile strain, elongation, tear strength, and permanent set values.

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.

Schematic representations of PU linear segmented structures


I -Relaxed structure II - Structure with 200% III - Structure with 500%
(without stress) elongation elongation

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a) soft segment, b) hard segment, c) reorientation after stress


Figure 1.39 - Effect of applied stress on PU segmented structure

1.6.3 - Soft segments effect


Chain mobility largely depends on the chemical nature and size of soft segments. Soft segments
control properties such as cold flexibility, as well as PU chemical behavior, such as resistance to
solvents, water, acids, bases and weather. In order to obtain suitable elastomeric properties,
especially impact resistance, the soft segment should be amorphous and possess a low enough
glass transition temperature. To prepare PUs with typical rubber elasticity an average molecular
weight of 1,000 to 4,000 is desirable, corresponding to a chain length of 120 to 300 A. Whereas the
elastomers freezing temperature TE (lower end of the glass transition) is about 20 to 30oC above
that of the polyol used, T* (the upper end of the glass transition) is dependent on the degree of
phase separation between the hard and soft segments. In products with large amounts of hard
segment (>50%), the mobility of the soft segment is considerably reduced. As a result, cold
flexibility properties are impaired. Tensile strength, 300% modulus and tear strength are
substantially affected by the melting point (TM) of the soft segment. Increasing chain length of the
soft segment and decreasing amounts of hard segments, as well as high linearity of the PU favor
crystallization.

1.6.4 - Molecular structures


The viscous-elastic behavior of segmented linear PU elastomers was investigated through
modulus/temperature experiments. Similar properties to those observed for block elastomers (e.g.,
a butadiene/styrene block copolymer) such as an extensive plateau in the high modulus area were
also found for segmented linear PU elastomers. The absence of hydrogen bonds in hydrocarbon
elastomers leads to the conclusion that hydrogen bridges are not the sole responsible for the
observed properties in PU elastomers. In the two systems, physical interactions reinforce the
structure until the melting temperature of high modulus blocks is reached. Through selective
solvation of aromatic PUs and segmented polyester with different solvents, it was possible to
demonstrate that an association of hard segments in the solid state (hard segment domains) is a
prerequisite for the existence of a high transition temperature.

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As previously mentioned, in segmented PU elastomers hydrogen bridges are formed between


active hydrogen atoms of -NH- urethane groups and -CO- urethane groups, with polyols polyester -
CO- groups, and more difficultly with the oxygen atom of polyol polyethers. Infrared investigations
of N-H stretching-related adsorptions indicate that more than 90% of the N-H urethane group
hydrogen forms hydrogen bonds. On the other hand, a study related to urethane -CO- groups
shows that only about 60% of these groups are linked or associated. This indicates that a
substantial portion of hydrogen bonds occurs between -NH- urethane groups and -CO- groups of
the polyester soft blocks.

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.

1.6.5. - Crosslinked PUs


Drastic modifications in PUs properties can be introduced by varying the crosslinking degree.
Reticulations may be formed by reaction of the isocyanate excess with urea or urethane groups
yielding biuret or allophanate cross-linking, or by using tri or poly-functional alcohols or amines as
chain extenders. Whereas elongation and permanent set decrease with increasing crosslinking
density, tension strength initially increases, but later on decreases. When a predominantly linear
segmented PU is reticulated, physical and chemical crosslinking effects overlap. However, if the
polyaddition reaction is carried out directly in presence of tri- or higher functional polyisocyanate or
polyols, which lead to an early network of primary valences, the formation of physically crosslinked
areas (domains) can be prevented. Hence at low chemical crosslinking, modulus of elasticity
decreases. Under extreme conditions, due to the fact that chains are already fixed, segregation will
not occur, and even temperature treatment (annealing) will not result in an improved property level.

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.

Table 1.13 - Effect of crosslinking density (Mc) on PU physical properties


MC Tensile strenght Elongation at Stress at 100% Tear resistence Hardness Tensile set Compression set
(MPa) break (%) strain (MPa) (kN/m) (Shore B) (%) (%)
2100 12,4 170 3,9 5,4 57 0 1,5
3100 12,0 200 3,0 4,5 53 0 16
4300 10,0 280 2,1 5,4 49 0 10
5300 19,3 350 1,9 5,4 46 0 0
7100 31,0 410 2,3 7,1 51 0 25
10900 38,6 490 3,2 10,8 55 5 40
21000 38,0 510 3,5 15,0 56 10 45
infinite 46,5 640 4,3 54,0 61 15 55
Mc - average molecular weight between cross-linking

2.1 - Catalysts
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