Hydroxylated polyesters reactions

The preparation of hydroxylated polyesters involves reactions of various polyols and polyol combinations with polybasic acids to give a wide range of properties. In the design of these resins, the polyol source is generally determined by the amount of hydroxyl groups available for further reaction of the polyester chain with cross-linking polymers. The polyols most often used as sources of available hydroxyls are pentaerythritol V, trimethylolethane VI, and trimethylolpropane VII. 

Keywords Additives Aliphatic Aliphatic isocyanates Amine-isocyanate reaction Aromatic isocyanates Blocked isocyanates Chain extenders Construction (application in) Glass transition temperature Hydroxyl-isocyanate reactions Hot melt reactive PU Isocyanates MDl Moisture curing PU One-component PU Packaging (application in) Plastic and composites (application in) Polyester Polyether polyols Polyisocyanates Sealants Silane PU hybrids TDI Testing of PU adhesives testing of PU sealants Testing standards TPU thermoplastic PU Transportation (application in) Two-component PU Water-borne PU... 

The primary and secondary alcohol functionahties have different reactivities, as exemplified by the slower reaction rate for secondary hydroxyls in the formation of esters from acids and alcohols (8). 1,2-Propylene glycol undergoes most of the typical alcohol reactions, such as reaction with a free acid, acyl hahde, or acid anhydride to form an ester reaction with alkaU metal hydroxide to form metal salts and reaction with aldehydes or ketones to form acetals and ketals (9,10). The most important commercial appHcation of propylene glycol is in the manufacture of polyesters by reaction with a dibasic or polybasic acid. 

Chemical Properties. Trimethylpentanediol, with a primary and a secondary hydroxyl group, enters into reactions characteristic of other glycols. It reacts readily with various carboxyUc acids and diacids to form esters, diesters, and polyesters (40). Some organometaUic catalysts have proven satisfactory for these reactions, the most versatile being dibutyltin oxide. Several weak bases such as triethanolamine, potassium acetate, lithium acetate, and borax are effective as stabilizers for the glycol during synthesis (41). 

Chemical Properties. The chemistry of 1,4-cyclohexanedimethanol is characteristic of general glycol reactions however, its two primary hydroxyl groups give very rapid reaction rates, especially in polyester synthesis. 

Liquid crystal polyesters are made by a different route. Because they are phenoHc esters, they cannot be made by direct ester exchange between a diphenol and a lower dialkyl ester due to unfavorable reactivities. The usual method is the so-called reverse ester exchange or acidolysis reaction (96) where the phenoHc hydroxyl groups are acylated with a lower aHphatic acid anhydride, eg, acetic or propionic anhydride, and the acetate or propionate ester is heated with an aromatic dicarboxyHc acid, sometimes in the presence of a catalyst. The phenoHc polyester forms readily as the volatile lower acid distills from the reaction mixture. Many Hquid crystal polymers are derived formally from hydroxyacids (97,98) and thein acetates readily undergo self-condensation in the melt, stoichiometric balance being automatically obtained. 

The diisopropoxy-bis-(triethanolamine)-titanate, TYZORTE [36673-16-2] is an excellent cross-linker for aqueous solutions of hydroxyl-containing polymers. The reaction product of TYZORTPT with a mixture of trialkano1 amines and dialkanolarnines or monoalkano1 amines can be used to cure polyester-based powder coatings (109). Other ligands of this type iaclude triisopropano1 amine [122-20-3] ... 

This process is based on the very high reactivity of the isocyanate group toward hydrogen present ia hydroxyl groups, amines, water, etc, so that the chain extension reaction can proceed to 90% yield or better. Thus when a linear polymer is formed by chain extension of a polyester or polyether of molecular weight 1000—3000, the final polyurethane may have a molecular weight of 100,000 or higher (see Urethane polymers). 

Polyurethanes are essentially the reaction products of polyisocyanates and polyesters containing free hydroxyl groups. They are comparable with the... 

The isocyanate group is more reactive than the epoxy group in that it will react at room temperature with water and hydroxyl groups as well as with amine groups. However, the latter reaction is too fast to be practicable so the standard two-pack coatings are based on isocyanate and polyhydroxyl prepolymers such as hydroxyl terminated polyesters or polyethers as in the last example given in the section on epoxy resins. 

PUR are a broad class of highly cross-linked plastics prepared by multiple additions of poly-functional hydroxyl or amino compounds. Typical reactants are polyisocyanates [toluene diisocyanate (TDI)] and polyhydroxyl molecules such as polyols, glycols, polyesters, and polyethers. The cyanate group can also combine with water this reaction is the basis for hardening of the one-part foam formulations. 

Block copolymers with materials such as a polyester (PE) (qv) can be prepd by the reaction of diisocyanate-terminated polyesters with hydroxyl-terminated PMMA according to Wilkes and Grezlak (Ref 21). The basic structure was found to be PMMA-PE-FMMA, with a mw of from 7500 to 47000. The purpose of the work was to produce a stronger copolymer (in terms of stress-strain) by tailoring the amt of each monomer used to produce the copolymer Further information on polymerization can be found in Refs 2a 6a... 

Due to the high reaction temperatures required during the last stages of these syntheses, side reactions cannot be avoided. Acetaldehyde, carboxyl endgroups, and vinyl endgroups are formed during PET and PEN synthesis. The formation of 2,2/-oxydiethylene moieties in polymer chains by etherification of hydroxyl endgroups is also a well-known side reaction of EG polyester syntheses.264 These reactions should be carefully controlled since they can exert an important influence on polymer properties such as Ts, mechanical properties, hydrolytic stability, and discoloration. 

Unsaturated polyesters were obtained by reacting the glycolyzed product widi maleic anhydride at a hydroxy-to-carboxyl ratio of 1 1. The hydroxyl number was determined without separation of die free glycol. The polyesterification reaction was conducted in a 2-L round-bottom dask equipped with a condenser, a gas bubbler, a thermowell, and a stirrer. The reaction mixture was heated from room temperature to 180°C in about 1-1.5 h. The temperature was maintained at 180°C for about 3 h, dien raised to 200°C and maintained until die acid value reached 32 mg KOH/g. 

The susceptibility of polyesters and polyamides to interchange reactions, such as may occur in the former between a terminal hydroxyl of one molecule and an interunit ester group of another, was discussed in Chapter III. These interchange processes do not decrease the number of molecules, and hence do not affect Mnj but they might permit some molecular species to be formed in preference to others. In other words, they may conceivably bring about an alteration of the molecular size distribution. 

---