Polyether triols

Some of the simplest polyols are produced from reaction of propylene oxide and propylene glycol and glycerol initiators. Polyether diols and polyether triols are produced, respectively (27) (see Glycols). 

Tuz Golu (lake), 5 784 Tversky similarity, 6 8 T vessicant agent, 5 816 physical properties, 5 817t Twaron fiber, 13 373 Tween surfactants, 24 150 12-membered ring macrolides, 15 272, 275t 2,6-TDI, reaction with a polyether triol, 25 459. See also Toluene diisocyanate (TDI)... 

This reaction is truly tempting because it potentially satisfies the need in the search for a way to reclaim the chemical value of a polyurethane recycle foam project [12, 13]. When a polyurethane foam is hydrolyzed, it gives aromatic diamine and polyether polyol, both in very crude forms. The diamine can be purified by regular means, but the crude polyether polyol cannot be easily cleaned up due to its polymeric nature. If this Ganem reaction can work well, the polyether polyol stream can be converted to a low-molecular-weight chemical, which can then be purified by conventional process such as distillation. Indeed, when this reaction was tried on a polyether triol of 3000 molecular weight as a model, the diacetate of propylene glycol was isolated by distillation. Unfortunately, the yield was too low to be of practical interest. 

We observed in a previous investigation of PU s derived from a kraft lignin (KL)-polyether triol-diphenylmetane diisocyanate (MDI) system (Yoshida, H. Morck, R. Kringstad, K. P. Hatakeyama, H., submitted to J. Appl Polym. Set.) that KL fractions of low molecular weight yielded more flexible and less crosslinked PU s than the medium and high molecular weight KL fractions. This was attributed to the lower functionality of the low molecular weight KL fractions. 

For the reaction of TDI with a polyether triol, bismuth or lead compounds can also be used. However, tin catalysts are preferred mainly because of their slight odor and the low amounts required to achieve high reaction rates. Carboxylic acid salts of calcium, cobalt, lead, manganese, zinc, and zirconium are employed as cocatalysts with tertiary amines, tin compounds, and tin—amine combinations. Carboxylic acid salts reduce cure time of rigid foam products. Organic mercury compounds are used in cast elastomers and in RIM systems to extend cream time, ie, the time between mixing of all ingredients and the onset of creamy appearance. 

Yoshida H, Morck R, Kringstad KP, Hatakeyama H (1990) Kraft lignin in polyurethanes. II. Effects of the molecular weight of kraft lignin on the properties of polyurethanes from a kraft lignin-polyether triol-polymeric MDI system. J Appl Sci 40 1819-1932... 

This method has been applied to polyether triol-diisocyanate as well as polyether diol-trimethylolpropane-diisocyanate systems 142). The application of the branching theory enables to deal with systems involving groups of unequal and dependent reactivities. Determination of the substitution effect within amino groups in the epoxide-amine reactions is explained in a recent review143>). 

An ingeniously simple screening method was used by Britain and Gemeinhardt [146] to evaluate catalysts for the isocyanate/hydroxyl reaction. To approximate as closely as possible actual polymerization conditions, the 80 20 ratio of 2,4- and 2,6-tolylene diisocyanate (80 20 TDI) isomers and a polyether triol of 3000 molecular weight were mixed at NCO OH ratio of 1.0. A 10% solution of catalyst in dry dioxane was added, the final catalyst concentration being 1% of the weight of polyether. The time for the mixture to gel at 70°C was noted as an indication of catalytic strength. This technique used the same reactants employed in one-shot flexible polyether-based foam systems, almost completely eliminated solvent, and was used to screen quickly hundreds of possible catalysts. 

The catalyst makes it possible to product outstandingly high-equivalent-weight polyether polyols, e.g., about 10,000. In other words, polyether diols of 20,000 molecular weight and polyether triols of 30,000 molecular weight can be produced. 

Normally a 70/30 to 50/50 blend of a 4500-6500 EO-capped polyether triol with a polymer polyol is used, together with an 80 20 blend of TDI (80/20 isomer ratio) and polymeric MDI. Recently, higher-solids-content graft polyols, e.g., 30-50% solid polyols, have become available in the market. 

Figure 27. Relationship between Aliphaticity Index and equivalent ratio at different molecular weights of polyether triol (65).

All the oligo-polyols are used to build the polyurethane high MW structure in a reactive process, as a consequence of the oligo-polyols terminal hydroxyl group reaction with polyisocyanates. The reactivity of oligo-polyols in polyurethane fabrication is a very important practical characteristic. Reactivity is a measure of the reaction rate of an oligo-polyol with an isocyanate in order to make the final polyurethane polymer. One practical method is the measurement of viscosity, in time, by Brookfield Viscosity Test (BVT), especially used to determine the reactivity of ethylene oxide capped polyether polyols. Figure 3.12 shows the effect of the primary hydroxyl content upon the reactivity of ethylene-oxide capped polyether triols of MW of 5,000 daltons. 

If trifunctional initiators such as glycerol or trimethylolpropane are used as starters for the alkylene oxides polymerisation, star-like polyether triols are formed [1-13, 15-17, 54, 60, 69, 75] ... 

Figure 4.5 shows some structural possibilities for polyether diols and polyether triols [1-13]. 

The polyether triols are the most important class of polyether polyols and they are used in flexible PU foam fabrication. The majority of polyether triols used in flexible foams are copolymers of PO-EO. Random copolymers are used in continuous slabstock flexible foams and block copolymers (PO-EO), with terminal poly[EO] block, are used in moulded foams (hot moulding and cold cure moulding processes). 

The high MW polyether triols, copolymers of PO-EO are the most important oligo-polyols for PU, having the biggest volume of industrial production. This is the reason why the synthesis of polyether triols, by polymerisation of PO and/or EO and initiated by glycerol, will be presented in detail. 

Polyether triols with poly[EO] block linked to the starter (MW = 3000-3600)... 

Synthesis of Polyether Triols Based on Glycerol Homopolymers of PO... 

The PO homopolymers (MW of 3000) initiated by glycerol are some of the most popular polyols for flexible PO slabstock. This structure is one of the oldest structures of a polyether used for flexible PU foams. In essence these polyether triols are obtained by the anionic polymerisation of PO initiated by glycerol and catalysed by KOH. 

Both KOH and water present in glycerol are sources of polyether diols which decrease the functionality of the polyether triol [2-13] ... 

Polyether diols present in the mixture with polyether triols lead to an improvement of elongation and tensile strength, with a little sacrifice of the compression strength. 

We can conclude that the polyether triols obtained by anionic polymerisation of PO initiated by glycerol consist of four polymeric species ... 

The polyethers obtained by the anionic polymerisation of PO initiated by glycerol are not trifunctional, having a lower functionality than 3, but usually in the range 2 < f < 3. The diols and monols decrease the functionality. The functionality is lower for high MW polyethers and for the polyethers obtained at higher polymerisation temperatures. In Figure 4.6, one observes the strong polyether triol functionality decrease as the polyether MW increases. 

The polyether triol functionality as function of unsaturation and of diol content can be calculated using the following formula ... 

Figure 4.6 The real functionality of polyether triols, PO homopolymers, as function of...

In a polyether triol composition the following are present nj = mols of monols, of functionality = 1 n2 = mols of diols, of functionality f2 = 2 n3 = mols of triols, of functionality f3 = 3... 

---