Polyester type polyols

The polyester type polyols used in polyurethane laminating adhesives are produced by the direct esterification of polyfunctional carboxylic acids and glycols. Polyester polyols provide the soft segment in polyurethane products giving the adhesive flexibility. Ester groups of the polyol also contribute to adhesion. Polyester polyols provide limited wetting and adhesion of olefinic surfaces with amide slip additives (in contrast to polyether polyols). Typical examples include adipic acid, caprolactone, maleic acid and isophthalic based polyester polyols. 

Castor oil is a natural triol with a typical OH number 160 mg KOH/g (functionality = 2.7). Although it has three ester groups, it is not considered a polyester type polyol. 

TDI is also commonly used as a fast-reacting isocyanate that is reacted with the polyol. It Is very common for polyester-type polyols to be prereacted with TDI by the manufacturer and sold to fabricators as TDI-terminated prepolymers. 

Polyesters are another important class of polyols. There are many polyester types used, so a generic structure is shown in Scheme 4.4. They are often based on adipic acid and either ethylene glycol (ethylene adipates) or 1,4-butanediol (butylene adipates). Polyesters, because of the polar carbonyl groups, contribute more to intermolecular forces, and physical properties such as tear and impact resistance are often improved by using them. They are also utilized for their solvent and acid resistance and light stability. Relatively poor hydrolytic stability is... 

The diisocyanates and polyols are reacted to form a high molecular weight hydroxyl terminated millable gum. These millable gums are compounded and processed as conventional elastomers, both sulphur and peroxides being used to cure the polymers. Here again, polyether and polyester types are available, and the differences between these two types referred to above also apply here. 

Both types of TPUs dissolve in cyclohexanone, tetrahydrofuran, and pyridine. The polyether type burns with yellow flame with strong acrid odor and gray smoke. The material burns fast and completely and eventually chars. The polyester type burns slowly with yellow-orange flame. For positive identification, FTIR is most commonly used. FTIR as well as differential scanning calorimetry can differentiate between the two types of TPUs. NMR has been proven to be useful in determining types of polyols. 

Plasticizers. About 2.5% of U.S. adipic acid consumed in 1988 was used in two basic types of adipic ester based plasticizers (195). Simple adipate esters prepared from Cg—alcohols are used especially as PVC plasticizers (qv). Eor special appHcations requiring low volatility or extraction resistance, polyester derivatives of diols or polyols are preferred. 

Polyurethane foams may be rigid, semi-rigid or flexible. They may be made from polyesters, polyethers or natural polyols such as castor oil (which contains approximately three hydroxyl groups in each molecule). Three general processes are available known as one-shot, prepolymer or quasi-prepolymer processes. These variations lead to 27 basic types of product or process, all of which have been used commercially. This section deals only with flexible foams (which are made only from polyesters and polyethers). Since prepolymers and... 

Products intermediate to the flexible and rigid foams may be obtained from castor oil (a trihydroxyl molecule), synthetic triols of moderate molecular weight and polyesters with a moderate amount of trifunctional hydroxyl compound in the strueture. Current practice, however, is to use tipped polyols of the type used for flexible foams with MDI. Semi-rigid foams are used for such purposes as crash pads, car steering wheels and packaging equipment. 

The polyols used are of three types polyether, polyester, and polybutadiene. The polyether diols range from 400 to about 10,000 g/mol. The most common polyethers are based on ethylene oxide, propylene oxide, and tetrahydrofuran or their copolymers. The ether link provides low temperature flexibility and low viscosity. Ethylene oxide is the most hydrophilic and thus can increase the rate of ingress of water and consequently the cure rate. However, it will crystallize slowly above about 600 g/mol. Propylene oxide is hydrophobic due to hindered access to the ether link, but still provides high permeability to small molecules like water. Tetrahydrofuran is between these two in hydrophobicity, but somewhat more expensive. Propylene oxide based diols are the most common. 

The basic RIM process is illustrated in Fig. 4.47. A range of plastics lend themselves to the type of fast polymerisation reaction which is required in this process - polyesters, epoxies, nylons and vinyl monomers. However, by far the most commonly used material is polyurethane. The components A and B are an isocyanate and a polyol and these are kept circulating in their separate systems until an injection shot is required. At this point the two reactants are brought together in the mixing head and injected into the mould. 

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. 

Unsaturated polyester resins (UPRs) Uralkyd resins, 202 Urea-methylol reaction, 410 Urethane alkyds, 241 Urethane coatings, 202 Urethane elastomers, implanted, 207 Urethane foams, tests for, 244 Urethane gels, 205 Urethane-grade ATPEs, 223 Urethane-grade polyol types, 212 Urethane-grade raw materials, 246 Urethane hydrogel, preparation of, 250-251... 

Glycidyl ethers of aliphatic polyols based on polyglycol, glycerin, and other polyols are flexible epoxy resins. They are used as reactive diluents and flexibihzers for solvent-free epoxy resin formulations. Epoxy-polyglycol resins that are produced from the reaction of epichlorohydrin and polyester polyols based on ethylene or propylene oxide are the most common of these types of flexible epoxy resins. Examples of typical commercial aliphatic epoxy resins are shown in App. C. 

---