Polyol applications

The most important segments of polyester polyol applications are those of polyurethane elastomers (43% of global polyester polyols consumption), flexible foams (15-18%), coatings, adhesives, rigid foams, synthetic leather, and sealants. 

Giordano M, ladonisi A (2014) Tin-mediated regioselective benzylation and allylation of polyols applicability of a catalytic approach under solvtmt-fiee conditions. J Org Chem 79 (l) 213-222... 

Synthetic Applications. Oxazolines, which ate synthesized as indicated above, have been utilized in many different appHcations (25). When used in resin formulations, AMP, AEPD, and TRIS AMINO can incorporate the oxazoline stmeture into the polymer stmeture (26). Because they ate polyols, both AEPD and TRIS AMINO can be used in polyester resin modification. Oxazoline alkyd films ate characterized by improved performance, particularly salt-spray resistance and gloss (see Alkyd resins Coatings, special purpose, high performance). 

Miscellaneous Commercial Applications. Dimer acids are components of "downweU" corrosion inhibitors for oil-drilling equipment (see Petroleum Corrosion and corrosion inhibitors). This may account for 10% of current dimer acid use (71). The acids, alkyl esters, and polyoxyalkylene dimer esters are used commercially as components of metal-working lubricants (see Lubrication). Dimer esters have achieved some use in specialty lubricant appHcations such as gear oils and compressor lubricants. The dimer esters, compared to dibasic acid esters, polyol esters and poly(a-olefin)s, are higher in cost and of higher viscosity. The higher viscosity, however, is an advantage in some specialties, and the dimer esters are very stable thermally and can be made quite oxidatively stable by choice of proper additives. 

One unusual but nevertheless important application of SAN has been in the manufacture of polymer polyols used in the manufacture of flexible polyurethane foams. Proportions of up to 40% of the polyol may be used to increase stiffness as foam bulk densities are lowered (see Section 27.5.4). 

Interest in the RIM process appears to have abated somewhat in the 1990s. Nevertheless, nearly 100000 tonnes of polyol and polyisocyanate were consumed for this application in the USA alone in 1993. 

Many isocyanates have good adhesive properties and one of them, triphenyl-methane-pp /7"-triyl tri-isocyanate, has been successfully used for bonding of rubber. Isocyanates are, however, rather brittle and somewhat limited in application. Somewhat tougher products are obtained from adhesives involving both polyols and isocyanates, i.e. polyurethane-type materials. The major application of these materials to date is in the boot and shoe industry. 

The first urethane reaction in Fig. 1 is used in two major ways in adhesives. In one case, a two-component adhesive usually employs a polyol and polyisocyanate with catalyst. This can react at room temperature to form the polyurethane. The second use of this reaction is to make an isocyanate-terminated prepolymer. Reacting a stoichiometric excess of isocyanate with polyol can produce an isocyanate-terminated prepolymer. A prepolymer is often made with an NCO/OH ratio of 2.0, as shown below, but the isocyanate ratio can range from 1.4 to over 8.0, depending upon the application ... 

Most moisture-curing liquid adhesives utilize poly(oxypropylene) (PPG) polyols, as shown above. These raw materials produce among the lowest-viscosity prepolymers but may not have sufficient modulus at higher temperatures for some applications. A certain percentage of polyester polyols may also be utilized to boost performance, but these may cause a large increase in viscosity, and so they are more often used in conjunction with polyether polyols to provide a high-performance adhesive with workable viscosities. Poly(butadiene) polyols may be utilized for specific adhesion characteristics. 

Hie most representative member of this class of polyesters is the low-molar-mass (M 1000-3000) hydroxy-terminated aliphatic poly(2,2/-oxydiethylene adipate) obtained by esterification between adipic acid and diethylene glycol. This oligomer is used as a macromonomer in the synthesis of polyurethane elastomers and flexible foams by reaction with diisocyanates (see Chapter 5). Hydroxy-terminated poly(f -caprolactonc) and copolyesters of various diols or polyols and diacids, such as o-phthalic acid or hydroxy acids, broaden the range of properties and applications of polyester polyols. 

Polyester polyols account for only ca. 10% of the total polyol market, which is dominated by polyether polyols such as hydroxy-terminated polyoxyethylene or polyoxypropylene. Polyester polyols are preferred for applications where better mechanical properties, wear resistance, and UV stability are required. The largest application of polyester polyols is flexible specialty polyurethane foam in the furniture, packaging, and automotive industries. Polyester polyols are also used for nonfoam applications such as coatings, paints, sealants, and adhesives 47... 

Urethane gels and ultrasoft elastomers are a more recent development.18 They are made primarily by reacting high-molecular-weight polyether polyols with a stoichiometric deficiency of isocyanate. The low NCO-to-OH ratio allows for a wide latitude in hardness adjustment. These low-hardness elastomers are used for seating applications (such as gel bicycle seats), shoe inserts, and soft padding for orthopedic devices. 

Polybutadienes, polycaprolactones, polycarbonates, and amine-terminated polyethers (ATPEs) are shown in Scheme 4.4 as examples of other commercially available polyols. They are all specialty materials, used in situations where specific property profiles are required. For example, ATPEs are utilized in spray-applied elastomers where fast-reacting, high-molecular-weight polyamines give quick gel times and rapid viscosity buildup. Polycarbonates are used for implantation devices because polyuredtanes based on them perform best in this very demanding environment. Polycaprolactones and polybutadienes may be chosen for applications which require exceptional light stability, hydrolysis resistance, and/or low-temperature flexibility. 

Another family of polyols is the filled polyols.llb There are several types, but die polymer polyols are die most common. These are standard polyether polyols in which have been polymerized styrene, acrylonitrile, or a copolymer thereof. The resultant colloidal dispersions of micrometer-size particles are phase stable and usually contain 20-50% solids by weight. The primary application for these polyols is in dexible foams where the polymer filler serves to increase foam hardness and load-bearing capacity. Other filled polyol types diat have been developed and used commercially (mainly to compete with die preeminent polymer polyols) include the polyurea-based PEID (polyhamstoff dispersion) polyols and the urethane-based PIPA (poly isocyanate polyaddition) polyols. 

Polyols and polyamines are the most important coreactants for isocyanates. As briefly outlined in Section 4.2.2, the two most common classes of urethane-grade polyols are the polyethers and polyesters. In this section their synthesis and structure are discussed. Other polyol types, such as acrylic resins and polycarbonates, are of more limited applicability and are not presented here. 

By depolymerizing PET waste with a polyol and subsequently condensing the oligomeric product with a polycarboxylic acid or anhydride, polyester resins are produced which have wide industrial applications. Depending on the polyol and polycarboxylic acid or anhydride used, saturated resins, alkyd resins, or unsaturated resins are obtained. PET wastes have been used for the production of alkyd resins in water thinnable paints. The materials obtained from the reaction of PET with a mixture of fatty acids high in linoleic acid content and trimethylolethane have been used in the preparation of water-dispersible coatings. Products of the depolymerization of PET with trimethylolpropane and pentaerythritol are used in the manufacture of high-solids paints. In the first step, PET is depolymerized with trimethylopropane and pentaerythritol at temperatures of 230-240°C. The final paint compositions contain 30-50% of PET depolymerization products.12... 

Over 4 billion PETP bottles will be available for colleetion across Europe in 1999. PUR Products has introduced technology into the UK which involves glycolysis of postconsumer PETP into materials for the manufacture of rigid urethane foams for building insulation. This application offers a substantial new market for aromatic polyester polyols derived from glycolised PETP recyclate. PUR(PRODUCTS)LTD. 

The application of a glycolysis process with simultaneous deamination to the recovery of polyols from rigid PU and polyisocyanurate foam waste is described. Properties and applications of the polyols obtained are examined. GETZNER CHEMIE GMBH... 

A split phase glycolysis process for the recovery of polyols from PU foam waste is described. Applications of the polyols in the manufacture of flexible and rigid PU foams are examined, and the economics of the process are analysed. 2 refs. 

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