Polyester polyols structures

By using the raw materials presented diols, triols and dicarboxylic acids, it is possible to obtain a large variety of polyester polyol structures. For example to use one type of glycol and one type of dicarboxylic acid, but many other combinations are possible, such as using one dicarboxylic acid and two types of glycol or to use a glycol together with a small quantity of triol, to obtain a branched polyester polyol. 

By using similar chemistry, aromatic polyester polyol structures are obtained by alkoxylation of the phthalic anhydride reaction product with glycerol (reaction 16.10). By the propoxylation of the reaction product of pyromellitic anhydride with DEG, tetrafunctional, highly viscous aromatic polyester polyols (16.11) are obtained. 

Isocyanates react with carboxylic acids to form amides, ureas, anhydrides, and carbon dioxide, depending on reaction conditions and the structure of the starting materials (Scheme 4.13). Aliphatic isocyanates more readily give amides. Aromatic isocyanates tend to react with carboxylic acids to first generate anhydrides and ureas, which at elevated temperatures (ca. 160°C) may further react to give amides. In practice, the isocyanate reaction with carboxylic acid is rarely utilized deliberately but can be an unwanted side reaction resulting from residual C02H functionality in polyester polyols. 

Carbodiimides, 81 Carbodiimidization, 226-227 Carbon-13 NMR spectroscopy. See 13C NMR spectroscopy Carbon-carbon structure, 4 Carbonyl-containing polyester polyols,... 

When reacting either ethylene carbonate or propylene carbonate with an aliphatic diamine, a polyurethane can be produced (Figure 2.14). Polyethylene ether carbonate) diols (Harris et al., 1990), when fabricated into polyurethanes using MDI and BDO, produce elastomers that have polyester polyol features. This was shown using 13C NMR. The structure gives rise to potential for a very high virtual cross-linking density. These carbonate-derived polyesters have superior hydrolysis resistance compared to the traditional materials. 

The superior characteristics of polyester polyol based polyurethanes are explained by a better crystalline structure [1, 7] in the urethane segment, compared to the majority of poly ether polyols which are amorphous [except polytetrahydrofuran (PTHF)], due to the superior secondary forces between the polyester chains [8] and also due to a superior thermal and fire resistance, compared to polyether polyol based polyurethanes. Polyester-based polyurethanes (flexible foams, coatings), have a superior solvent resistance compared to the polyether-based polyurethanes [8]. 

Figure 8.1 The structure of some representative polyester polyols used in polyurethane...

Chapter 12.5). Polyester polyols in reality, have the theoretical functionality, which is a great advantage for many polyurethane applications. For polyester diols the functionality is 2 OH groups/mol. This structural aspect results in the polyester diols giving PU elastomers with excellent physico-mechanical properties, superior to all polypropylene glycols obtained by anionic PO polymerisation. 

The composition and structure of the polyester polyols lead to polyurethanes with distinct properties. These polyester-based polyurethanes have specific applications, as shown in Table 8.5. 

Table 8.5 Specific applications of polyester polyol composition and structure ...

Representative PCL are the diols of MW of 2000-4000 daltons, used in hydrolytically stable PU elastomers. The diols used as starters are DEG, 1,4 butanediol and NPG. The melting point of PCL, of MW of 2000 daltons, is in the range of 40-60 °C and of MW of 1000 daltons in the range of 30-40 °C. If a polyfunctional polyol is used as a starter, polyfunctional PCL polyols are obtained. Thus, by polymerisation of CPL initiated by trimethylolpropane (reaction 8.32) a polyester triol is obtained and initiated by pentaerythritol, a polyester tetraol is formed. It is interesting that some low MW PCL triols with a MW of 300-900 daltons are liquid at room temperature (melting points in the range of 6-16 °C). The viscosities of PCL polyols, at 60 °C, are 40-1600 mPa-s, depending on the polyol structure. 

It is very interesting that acrylic polyols can be used as precursors to synthesise hybrid structures, such as acrylic - polyester polyols, by the polymerisation of some cyclic monomers such as e-caprolactone, initiated by hydroxyl groups of acrylic polyols (reaction 10.2). 

Mannich polyols, aromatic polyester polyols, novolak-based polyols) lead, by the reaction with crude MDI, to very rigid polyurethane structures [2] (see Chapter 15). 

The development of highly crosslinked rigid polyisocyanurate foams opens an excellent area of applications for polyester polyols [4-8]. The required polyols do not need high functionality and the plasticising effect of polyester structures is extremely beneficial for these highly crosslinked systems [6]. The first polyester polyols used for these applications were low viscosity polycondensation products of AA with ethyleneglycol (EG) or diethyleneglycol modified with phthalic anhydride or triols. 

The highly crosslinked structure is not derived from polyester polyol, which has a low functionality (f = 2-3 OH groups/mol), but is derived from the isocyanurate rings generated by the trimerisation of the excess of -NCO groups. 

Of course the thermal stability and char yield depend on the polyol structure too and the aromatic polyols are superior to aliphatic polyols from this point of view. This is the reason for the extremely rapid growth of aromatic polyester polyols, of low functionality, low viscosity and low cost. 

The bottom residues from DMT fabrication are benzyl and methyl esters of dicarboxylic and tricarboxylic acids with biphenyl or triphenyl structures together with DMT [4, 6. By the transesterification reactions of these complex ester residues with diethyleneglycol (DEG), aromatic polyester polyols with a functionality in the range 22-23 OH groups/mol are obtained. 

Of course during the polycondensation reaction superior oligomers are formed, such as the structure shown in reaction 16.7 and in the composition of the resulting polyester polyol, free DEG is present. 

In this section, several methods for rigid polyester polyols synthesis, of minor industrial importance at this moment, but which present a real potential for developing new polyol structures will be presented. 

Practically all the polyester polyols based on DEG or DPG are in fact ether-ester polyols, because they have in the same structure ether and ester groups. 

The most important structures of rigid polyester polyols presented in this chapter (Chapter 4.4) are the low functionality aromatic polyester polyols with terephthalic or phthalic structures, used for PU/PIR rigid foams. 

Figure 19.6 shows the structure of a third generation of a dendritic polyester polyol, based on dimethylolpropionic acid, initiated by pentaerythritol. 

Through the synthesis of poly(urethane-imide) films and their carbonization, carbon films were obtained whose macropore structure could be controlled by changing the molecular structure of polyurethane prepolymer [164-166]. Poly(urethane-imide) films were prepared by blending poly(amide acid), which was synthesized from pyromellitic dianhydride (PMDA) and 4,4 -oxydianiline (ODA), and phenol-terminated polyurethane pjrejwlymers, which were synthesized through the reaction of polyester polyol with either hexamethylene diisocyanate (HDI), tolylene-2,4-diisocyanate (TDI) or 4,4 -diphenyknethane-diisocyanate (MDI). The reaction schemes of two components, poly(imide) (PI) and poly(urethane) (PU), are shown in Fig. 46a). 

Polyester acrylates are synthesized by esterification of OH groups of polyester polyols with acrylic acid or its derivatives. The typical structure of polyester acrylate oligomers is presented in... 

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