Polyester Polyols
Polyester Polyols
Polyester Polyols
Difunctional monomers are used to obtain a linear polymer; and monomers with functionality larger
than two as trimethylol propane and glycerin create ramified chains. The most used acids are
adipic and phthalics. Adipic acid based polyester polyols are used in applications where flexibility is
wanted, as in flexible foams and elastomers. Phthalic acids (or phthalic anhydride) based polyols,
have rigid chains and are used in rigid foams and in high performance coatings (Table 1.8).
In polyester polyols production process, the diol, triol, etc is first heated to a temperature of 60-
90°C. Then the dicarboxilic acid is added and removal of the reaction water begins. For obtaining
the targeted molecular weight the excess diol is calculated by means of Flory Equation. Diol can be
lost during removal of the water form the condensation reaction and through side reactions
(formation of ethers and aldehydes). The amount of diol lost is dependent upon the processing
conditions and upon type of diol. The amount of diol lost must be empirically determined. Usually
the reaction is completed at temperatures up to 200°C. Nitrogen, carbon dioxide, or vacuum is
used to remove the water and to reach the wanted conversion of 99.9%, and the resulting
polyester should have an acid number less than two. This conversion is necessary to minimize the
presence of residual carboxylic end groups that can reduce the reactivity. The polyesters are
composed of all possible oligomers raging from the monomers to high molecular weight species:
the molecular weight distribution follows a Frory probability. The properties of the PU based
polyester elastomers are governed mainly by the overall molecular weight of the polyester and only
to a minor degree by the molecular weight distribution.
Acids, bases and compounds of the transition metals can catalyze the esterification reaction. The
dicarboxylic acids also exert a limited catalytic effect. In practice catalysts are used reluctantly
because they cannot be removed and can have an undesirable effect on the following PU reaction,
since inorganic substances even in the smallest quantities favor or retard de PU processing
reaction. The p-toluenesulphonic acid can be used as an accelerator and left in the polyester. In
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cases where small amounts of catalysts do not later cause problems, compounds of tin, antimony,
titanium, lead and other metals, have proved especially effective. The amounts added lie in the
ppm range. Solid impurities are removed by hot filtration of the finished polyester.
Lightly branched poly(diethyleneglycol adipates), which are used mainly to make flexible foams,
and a wide range of adipates made with more than one aliphatic diol. These are used to make
solid and microcellular elastomers, flexible coatings and adhesives. Relatively low cost polyester
polyols, based on recovery materials are also available. Mixed adipic, glutaric and succinic acid
polyesters are made using purified nylon waste acids (AGS acids). AGS acids are also
hydrogenated to make a mixture of 1,4-butanediol, 1,5-pentanediol and 1,6-hexane diol, which is
used to make polyadipates having a low melting point. Mixed polyadipates from hydrogenated
AGS acids are used to make microcellular elastomers with good hydrolytic stability.
In comparison with PU based polyether polyols, the PU based polyesters are more resistant to oil,
grease, solvents and oxidation. They possess better properties related to: tension and tear
strength, flex fatigue, abrasion, adhesion and dimensional stability. On the other hand PU based
esters are more sensitive to hydrolysis and microbiological attack. The high mechanical properties
of PU based polyester can be explained by the greater compatibility between polar polyester
flexible segments and polar rigid segments, causing a slower phase separation resulting in better
distributed small crystalline rigid blocks (Chapter 1.7).
The hydrolysis stability of the ester linkage is inferior to that of the ether linkage in the polyethers,
and residual esterification catalysts accelerate the hydrolysis. The hydrolysis resistance of the
polyol polyester based PU increases with long chain glycols (1,6-hexane diol) or long chain diacids
(dodecanoic acid), as a result of the largest hydrophobic portion and small amounts of ester
groups. The hydrolysis stability can be improved with additives that react with carboxylic and
alcoholic groups, formed during hydrolysis. These additives may be: oxazolines, epoxy
compounds, aromatic polycarbodiimides and aliphatic monocarbodiimides. TPU's based polyester
polyols are stabilized by addition of 1 to 2% in weight of aromatic hindered carbodiimides, that
react with the acid generated by ester hydrolysis, which would act as catalyst of hydrolysis
reactions (Figure 1.29).
Polymeric polyester polyols are dispersions of vinyl polymers in polyadipate based polyol polyester
stabilized by a dispersant. Polymeric polyester polyols, containing 10 to 20% of vinyl polymers are
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used in shoe soles and flexible PU foams with greater hydrolysis stability, higher hardness for
same densities, more uniform cellular structures, and better dimensional stability.
The polyisophthalates glycols are obtained by anhydride phthalic polymerization with glycols as
diethylene glycol. The poly(diethylene isophthalate) glycol with average equivalent weight of 178
and 234, OH number of 230 to 330 mg KOH/g, viscosities from 2,000 to 4,500 cP at 25°C are used
in PUR and PIR foams. The ones with equivalent weight of 288, OH number of 195 mg KOH/g,
viscosity of 25,000 cP at 25°C can be used in resins and prepolymers for coatings, adhesives,
sealants and elastomers, and also as additive in polyol polyether flexible foams to improve fire
resistance and adhesion characteristics. The poly(neopentyl isophthalate) glycols with average
equivalent weight of 510, OH number of 110 mg KOH/g are used in adhesives, coatings and
elastomers with excellent hydrolysis resistance.
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PTMEG's are solid, white, waxy at room temperature, soluble in alcohols, esters, ketones and aromatic and
chlorinated hydrocarbons, and insoluble in aliphatic hydrocarbons and water. They have variable solubilities
for glycols: poly(oxypropylene) glycols and 1,6 hexanediol are completely miscible whereas only 20% of 1,4
butanediol can be dissolved in PTMEG 1000 and less than 10% in PTMEG 2000. PTMEG polyols are
hygroscopic and can absorb 2% moisture in an unprotected environment. Gross amounts of water are
removed by azeotropic distillation with toluene, and further reduction can be achieved by heating for several
hours at 120-150oC under reduced pressure (less than 20mm Hg). PTMEG's are stabilized with
antioxidants to prevent degradation during storage and normal handling. However, prolonged heating in the
presence of air at 50-60°C will result in partial oxidation and degradation, and thermal decomposition will
occur, in absence of air conditions at 210-220°C.
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Due to the free radicals process it has ramifications in polymeric chain, and functionality slightly higher than
two (2.1<2.3). HTPB possesses reactive allylic primary hydroxyl end groups, molecular weight of 2,800 and
hydroxyl number of 46 mg KOH/g. HTPB's hydrophobic polymeric chains form Pus with exceptional
hydrolysis stability, and its low humidity degree (<300 ppm), minimize or eliminate the previous drying. Due
to its very low glass transition temperature the PUs formed have excellent elastomeric properties at
extremely low temperatures. They possess great capacity to accept fillers as asphalt, aromatic and
paraffinic oils, pentanes, plasticizers, carbon black, etc. HTPB microstructure is 60% of 1,4-trans, 20% of
1,4-cis and 20% of 1,2-vinyl insaturations (Figure 1.33) that turn possible further vulcanization and chemical
modifications.
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