Diols polyurethane elastomers

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. 

Polyester and polyether diols are used with MDI in the manufacture of thermoplastic polyurethane elastomers (TPU). The polyester diols are obtained from adipic acid and diols, such as ethylene glycol, 1,4-butanediol, or 1,6-hexanediol. The preferred molecular weights are 1,000 to 2,000, and low acid numbers are essential to ensure optimal hydrolytic stabihty. Also, caprolactone-derived diols and polycarbonate diols are used. Polyether diols are... 

Fatty acids, both saturated and unsaturated, have found a variety of applications. Brassilic acid (1,11-un-decanedicarboxylic acid [BA]), an important monomer used in many polymer applications, is prepared from erucic acid (Scheme 2), obtained from rapeseed and crambe abyssinica oils by ozonolysis and oxidative cleavage [127]. For example, an oligomer of BA with 1,3-butane diol-lauric acid system is an effective plasticizer for polyvinylchloride. Polyester-based polyurethane elastomers are prepared from BA by condensing with ethylene glycol-propylene glycol. Polyamides based on BA are known to impart moisture resistance. 

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. 

Studies have been made of the elastic (time-independent) properties of single-phase polyurethane elastomers, including those prepared from a diisocyanate, a triol, and a diol, such as dihydroxy-terminated poly (propylene oxide) (1,2), and also from dihydroxy-terminated polymers and a triisocyanate (3,4,5). In this paper, equilibrium stress-strain data for three polyurethane elastomers, carefully prepared and studied some years ago (6), are presented along with their shear moduli. For two of these elastomers, primarily, consideration is given to the contributions to the modulus of elastically active chains and topological interactions between such chains. Toward this end, the concentration of active chains, vc, is calculated from the sol fraction and the initial formulation which consisted of a diisocyanate, a triol, a dihydroxy-terminated polyether, and a small amount of monohydroxy polyether. As all active junctions are trifunctional, their concentration always... 

Despite the improvements, a more durable elastomer was clearly needed. A battery of polyurethane elastomers including Pellethane were prepared and implanted subcutaneously in rats. Before implantation, the polymers were extruded into tubes and elongated over mandrels to 400%. The implants were left in place for 6 months and examined under a scanning electron microscope. One of the better performing polyurethanes was based on poly(l,6-hexyl 1,2-ethyl carbonate) diol. Polyesters typically are considered less durable due to the presence of esterase enzymes in vivo. From the data recovered during the implant period, it was determined... 

In a recent patent, Reuter (110) describes a polyurethane prepared from PTHF (mol. wt. 1000 to 3000), 1,4-butanediol, and OCN(CH2)6CN0. In another case Murbach and Adicoff (67) interrupted the regularity of PTHF by copolymerization with ethylene oxide before chain extension with diphenyl-methane-4,4 -disiocyanate. Dickinson (99) prepared a series of polyurethane elastomers from THF-PO copolymer diols and 2,4-tolylene diisocyanate. He found that the use of copolymers with approximately 75 wt.-% THF led to polyurethanes with very good properties relative to the use of propylene oxide homopolymer. 

The shorter the linear diol chains, the better the compression set and the higher the melt temperature of the polyurethane elastomer. The hysteresis curve shows the least retained energy, thus giving a lower heat buildup under load. These desirable properties can be achieved more readily by the diols ranked in the following series ... 

However, one of the main points to be considered in the making of a polyurethane elastomer (apart from the reactivities of the isocyanate and curative) is the water absorption. Special precautions must be taken to keep a diol curative (such as butanediol) sufficiently dry for use. Diols have to be kept dry with molecular sieves and dry nitrogen blanketing. 

Harris, R.F., M.D. Joseph, C. Davidson, C.D. Deporter, and V.A. Dais. Polyurethane Elastomers Based on Molecular Weight Advanced Poly(Ethylene Ether Carbonate) Diols. Comparison to Commercial Diols. Journal of Applied Polymer Science 41 (1990) 487-507. 

Soft blocks are composed of linear, dihydroxy poly ethers or polyesters with molecular weights between 600 and 3000. In a typical polymerization of a thermoplastic polyurethane elastomer, the macroglycol is end capped with the full amount of aromatic diisocyanate required in the final composition. Subsequently, the end-capped prepolymer and excess diisocyanate mixture reacts further with the required stoichiometric amount of monomeric diol to complete the reaction. The diol links the prepolymer segments together while excess diol and diisocyanate form short hard-block sements, leading to the (AB)n structure illustrated in Figure 1. Block lengths in (AB)n polymers are frequently much shorter than those in anionically synthesized ABA block copolymers. 

The most important telechelic polymer obtained by cationic polymerization is a,w-diol used in manufacture of polyurethane elastomers. The scheme of the process used on industrial scale is outlined below ... 

If the diol chain extender is used in exact molar proportion to the unreacted isocyanate, then a linear polyurethane elastomer is obtained. The resulting thermoplastic elastomer may be extruded or injection-moulded, and the properties arise from the ability of the hard and soft segments to form semi-crystalline domains that act as virtual crosslinks in the polymer and give it elastomeric properties, as shown in Figure 1.17. 

The Structure of the Hard Segments in MDI/ diol/PTMA Polyurethane Elastomers... 

Polyurethane elastomers derive their elastomeric properties from phase separation of the hard and soft copolymer segments, such that the hard (urethane) segment domains serve as crosslinks between the amorphous soft segment domains, which are usually polyesters or polyethers. We are interested in the systems in which the hard segments are prepared from diphenyl-methane 4,4 -diisocyanate (MDI) with a linear diol as the chain extender ... 

Polybutadiene diols and hydrogenated polybutadiene diols are used for producing thermoplastic polyurethane elastomers, hydrolytically stable PU elastomers, adhesives, sealants, coatings, encapsulation and electrical insulation polyurethanic products. 

The polyurethane elastomers based on these polysiloxane diols conserve their high elasticity at very low temperatures and have exceptional oxidative stability and electrical insulation properties [1,9]. 

Thus, from high MW diols (MW = 1000-4000 daltons) polyethers (polyalkyleneoxides, polytetrahydrofuran (PTHF)), polyesters, polycarbonates (PC), polybutadienes, etc., by the reaction with diisocyanates [toluene diisocyanate (TDI), or pure diphenyl methane diisocyanate (MDI)], high MW linear polyurethanes are obtained (no crosslinking), with high elasticity (polyurethane elastomers, spandex fibres, some adhesives and sealants, etc). 

Polyurethanes are used in four principal types of products foams, elastomers, fibers, and coatings. The majority of polyurethane is used as rigid or flexible foams. However, about 15% is used for elastomer applications. Production of polyurethane elastomers involves a number of steps. As indicated above, an intermediate hydroxyl-terminated low-molecular-weight polyester or polyether is prepared. This intermediate is reacted with an isocyanate to form a prepolymer (macrodiisocyanate). The prepolymers are coupled or vulcanized by adding a diol or diamine ... 

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