Polyurethane elastomers diisocyanates

Thermoplastic polyurethane elastomers are produced from prepolymers by polycondensation (12,13). A relatively high molecular-weight polyester or polyether with terminal hydroxy groups (a polyglycol) first reacts with an excess of a diisocyanate. 

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. 

Singer S.M. and Allot M.T., Thermoplastic polyurethane elastomer based on a saturated hydroxyl terminated polyol, difunctional aromatic chain extender and 1,5-naphthalene diisocyanate, US Patent 5 599 874, 1997. 

In a polyurethane elastomer analysed by isobutane CI-MS and CI-MS/MS in TD/Py-CIMS (TD, 20-200°C Py, 200-300 °C) mode MDI (diisocyanate), BDO (chain extender), Stabaxol P (stabiliser), AA/ BDO/HDO (cyclic adipate) and residual cyclic ester oligomers were identified [65]. 

The equilibrium shear modulus of two similar polyurethane elastomers is shown to depend on both the concentration of elastically active chains, vc, and topological interactions between such chains (trapped entanglements). The elastomers were carefully prepared in different ways from the same amounts of toluene-2,4-diisocyanate, a polypropylene oxide) (PPO) triol, a dihydroxy-terminated PPO, and a monohydroxy PPO in small amount. Provided the network junctions do not fluctuate significantly, the modulus of both elastomers can be expressed as c( 1 + ve/vc)RT, the average value of vth>c being 0.61. The quantity vc equals TeG ax/RT, where TeG ax is the contribution of the topological interactions to the modulus. Both vc and Te were calculated from the sol fraction and the initial formulation. Discussed briefly is the dependence of the ultimate tensile properties on extension rate. 

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... 

Toluene diisocyanate is commonly produced as a mixture of the 2,4- and 2,6-iso-niers, that is used as a monomer in the preparation of polyurethane foams, elastomers and coatings, as a cross-linking agent for nylon-6, and as a hardener in polyurethane adhesives and finishes. Polyurethane elastomers made from toluene diisocyanates are used in coated fabrics and clay-pipe seals. Polyurethane coatings made from toluene diisocyanates are used in floor finishes, wood finishes and sealers, and in coatings for aircraft, tank trucks, truck trailers and truck fleets (United States National Library of Medicine, 1997). 

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. 

In the production of polyurethane elastomers, only diisocyanates are of any important use. The major diisocyanates manufactured and used are the 2,4 and 2,6-toluene diisocyanates (TDI) and 4,4 -diphenylmethane diisocyanates (MDI). See Figure 2.15. 

MDI MEK MOCA (MBOCA) Therefore, a two-part mold would have two master patterns. An abbreviation for diphenylmethane-4,4 -diisocyanate. Methyl Ethyl Ketone Trade name for methylene bischloroaniline, which is a widely used curing agent for hot cure polyurethane elastomers. There are... 

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. 

Table 4.5. Physical properties of polyurethane elastomers prepared from HTPB and 2,4-toluene diisocyanate (TDI) 205)...

Aud.nopropyl triethoxysilane, 140 Amorphous systems, polyurethane elastomers, 33 Anionic polymerization, caprolactams, 136-38 initiation, 138 thermal initiation, 137f termination reaction, 136 Annular cone and plate, 100-102 Annular vs. truncated cones, 101f Aromatic diisocyanate(s), RIM elastomers, 81... 

In this work, we describe an automated differential scanning calorimetric (DSC) technique that can be used to measure polymerization kinetics for formation of urethane block polymers. The same technique is also used to measure phase separation during formation of polyurethane elastomers and the effect that separation has on the polymerization. The elastomer formulations consisted of modified liquid p,p -diphenyImethyl diisocyanate (MDI), 1,4-butanediol and an (oxypropylene-oxyethylene) macroglycol for the soft segment. 

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 ... 

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). 

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