Flexible foams from polymer polyols

The steric effects in isocyanates are best demonstrated by the formation of flexible foams from TDI. In the 2,4-isomer (4), the initial reaction occurs at the nonhindered isocyanate group in the 4-position. The unsymmetrically substituted ureas formed in the subsequent reaction with water are more soluble in the developing polymer matrix. Low density flexible foams are not readily produced from MDI or PMDI enrichment of PMDI with the 2,4 -isomer of MDI (5) affords a steric environment similar to the one in TDI, which allows the production of low density flexible foams that have good physical properties. The use of high performance polyols based on a copolymer polyol allows production of high resiHency (HR) slabstock foam from either TDI or MDI (2). 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

With amine initiators the so-called self-catalyzed polyols are obtained, which are used in the formulation of rigid spray foam systems. The rigidity or stiffness of a foam is increased by aromatic initiators, such as Mannich bases derived from phenol, phenolic resins, toluenediamine, or methylenedianiline (MDA). In the manufacture of highly resilient flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. 

Dow also developed polyurethane foams from polyols via hydroformylation of fatty acids. The foams have properties which are comparable to foams from petrochemicals in terms of density and flexibility. The advantages of using sustainable feedstocks in viscoelastic foams are increased load bearings and tensile and tear properties [39, 40]. The hydroformylation and consecutive hydrogenation of fatty acids derived from seed oil can also be used to form low viscosity polyester polyols. Therefore, fatty acid methyl esters are transesterified with diols, e.g., glycol (Scheme 12). The polymer contains chemically active hydroxy groups which can be used for polyurethanes in coating applications [41]. 

From high MW triols or low branched oligo-polyols (MW = 3000-6500 daltons) polyethers, polyesters, filled polyols (polymer polyols), are obtained elastic PU with a low degree of crosslinking (flexible and semiflexible foams, coatings etc). 

Hydroxy-terminated polyethers have now assumed a dominant role in the commercial production of polyurethanes. The most widely used polyethers are derivatives of propylene oxide and these polymers are described in Section 8.4.3.1. Linear, glycol-initiated propylene oxide polymers and propylene oxide-ethylene oxide block copolymers find some use in the preparation of elastomers. Polyether triols of relatively high molecular weight (about 3000) are extensively used for the production of flexible foams whilst polyols of low molecular weight (about 500) are used for rigid foams and surface coatings. Poly(oxytetramethylene) glycols prepared from tetrahydrofuran (Section 8.4.6) are used for the preparation of elastomers and spandex fibres. 

Thermal degradation of foams is not different from that of the solid polymer, except in that the foam structure imparts superior thermal insulation properties, so that the decomposition of the foam will be slower than that of the solid polymer. Almost every plastic can be produced with a foam structure, but only a few are commercially significant. Of these flexible and rigid polyurethane (PU) foams, those which have urethane links in the polymer chain are the most important. The thermal decomposition products of PU will depend on its composition that can be chemically complex due to the wide range of starting materials and combinations, which can be used to produce them and their required properties. Basically, these involve the reaction between isocyanates, such as toluene 2,4- and 2,6-diisocyanate (TDI) or diphenylmethane 4,3-diisocyanate (MDI), and polyols. If the requirement is for greater heat stability and reduced brittleness, then MDI is favored over TDI. 

Polyurethanes are very versatile polymers. They are used as flexible and rigid foams, elastomers, and coatings. Polyurethanes are available as both thermosets and thermoplastics. In addition, their hardnesses span the range from rigid material to elastomer. Thermoplastic polyurethanes will be the focus of this section. The term polyurethane is used to cover materials formed from the reaction of isocyanates and polyols. The general reaction for a polyurethane produced through the reaction of a diisocyanate with a diol is shown in Fig. 2.35. 

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