Polyester-polyols

Polyester film Polyester plasticizers Polyester polyol Polyester polyols Polyester resins... 

Miscellaneous chemicals are used to modify the final properties of rigid polyurethane foams. Eor example, halogenated materials are used for flammabihty reduction, diols may be added for toughness or flexibiUty, and terephthalate-based polyester polyols may be used for decreased flammabiUty and smoke generation. Measurements of flammabihty and smoke characteristics are made with laboratory tests and do not necessarily reflect the effects of foams in actual fire situations. 

The avadabihty of PMDI also led to the development of polyurethane-modified isocyanurate (PUIR) foams by 1967. The PUIR foams have superior thermal stabiUty and combustibiUty characteristics, which extend the use temperature of insulation foams well above 150°C. The PUIR foams are used in pipe, vessel, and solar panel insulation glass-fiber-reinforced PUIR roofing panels having superior dimensional stabiUty have also been developed. More recently, inexpensive polyester polyols based on residues obtained in the production of dimethyl terephthalate (DMT) have been used in the formulation of rigid polyurethane and PUIR foams. 

Polyester Polyols. Initially polyester polyols were the preferred raw materials for polyurethanes, but in the 1990s the less expensive polyether polyols dominate the polyurethane market. Inexpensive aromatic polyester polyols have been introduced for rigid foam appHcations. These are obtained from residues of terephthaHc acid production or by transesterification of dimethyl terephthalate (DMT) or poly(ethylene terephthalate) (PET) scrap with glycols. 

Polyester polyols are based on saturated aHphatic or aromatic carboxyHc acids and diols or mixtures of diols. The carboxyHc acid of choice is adipic acid (qv) because of its favorable cost/performance ratio. For elastomers, linear polyester polyols of ca 2000 mol wt are preferred. Branched polyester polyols, formulated from higher functional glycols, are used for foam and coatings appHcations. Phthalates and terephthalates are also used. 

In addition, polyester polyols are made by the reaction of caprolactone with diols. Poly(caprolactone diols) are used in the manufacture of thermoplastic polyurethane elastomers with improved hydrolytic stabiHty (22). The hydrolytic stabiHty of the poly(caprolactone diol)-derived TPUs is comparable to TPUs based on the more expensive long-chain diol adipates (23). Polyether/polyester polyol hybrids are synthesized from low molecular weight polyester diols, which are extended with propylene oxide. 

Most flexible foams produced are based on polyether polyols ca 8—10% (15—20% in Europe) of the total production is based on polyester polyols. Elexible polyether foams have excellent cushioning properties, are flexible over a wide range of temperatures, and can resist fatigue, aging, chemicals, and mold growth. Polyester-based foams are superior in resistance to dry cleaning and can be flame-bonded to textiles. 

Powder coatings are formulated from the reaction product of trimethylolpropane and IPDI, blocked with caprolactam, and polyester polyols. The saturated polyester polyols are based on aromatic acid diols, neopentyl glycol, and trimellitic anhydride for further branching. To avoid the release of caprolactam in the curing reaction, systems based on IPDI dimer diols are used. 

J. Low molecular weight symmetrical polyester polyols may be liquids as a result of many chain ends that disrupt crystalline packing entirely. 

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. 

Polyurethane dispersions (PUD s) are usually high-performance adhesives based on crystalline, hydrophobic polyester polyols, such as hexamethylene adipate, and aliphatic diisocyanates, such as methylene bis(cyclohexyl isocyanate) (H12MDI) or isophorone diisocyanate (IPDI). These PUD s are at the more expensive end of the waterborne adhesive market but provide excellent performance. 

The crystallization kinetics defines the open time of the bond. For automated industrial processes, a fast crystallizing backbone, such as hexamethylene adipate, is often highly desirable. Once the bond line cools, crystallization can occur in less than 2 min. Thus, minimal time is needed to hold or clamp the substrates until fixturing strength is achieved. For specialty or non-automated processes, the PUD backbone might be based on a polyester polyol with slow crystallization kinetics. This gives the adhesive end user additional open time, after the adhesive has been activated, in which to make the bond. The crystallization kinetics for various waterborne dispersions were determined by Dormish and Witowski by following the Shore hardness. Open times of up to 40 min were measured [60]. 

As previously mentioned, some urethanes can biodegrade easily by hydrolysis, while others are very resistant to hydrolysis. The purpose of this section is to provide some guidelines to aid the scientist in designing the desired hydrolytic stability of the urethane adhesive. For hydrolysis of a urethane to occur, water must diffuse into the bulk polymer, followed by hydrolysis of the weak link within the urethane adhesive. The two most common sites of attack are the urethane soft segment (polyol) and/or the urethane linkages. Urethanes made from PPG polyols, PTMEG, and poly(butadiene) polyols all have a backbone inherently resistant to hydrolysis. They are usually the first choice for adhesives that will be exposed to moisture. Polyester polyols and polycarbonates may be prone to hydrolytic attack, but this problem can be controlled to some degree by the proper choice of polyol. 

Synthesis MDI prepolymer with 1000 MW polyester polyol, NCO/OH = 2.0, chain-extended with 1,4-butandiol, acid number of polyester 0.6. 

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... 

H. Chinn, S. Cometta, and K. Sakota, Polyester Polyols, CEH Report, SRI Consulting, Menlo Park, CA, June 1999. 

Polyester polyols (Scheme 4.4) are prepared by condensation polymerization of dicarboxylic acids and diols. An excess of diol ensures OH functional product, minimizing die possibility of residual acid groups which react with isocyanates to generate C02 and act as inhibitors in catalyzed urethane reactions. The reactants are heated at 200-230°C under vacuum to remove the water by-product and drive the reaction to completion. The most common coreactants include adipic... 

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. 

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