Aliphatic polyurethanes

Toluene diisocyanate (TDI) and the various forms of methylene 4,4 -bis(phenylisocyanate) (MDI) are the most common isocyanate compounds in commercial polyurethanes. Aliphatic isocyanates (hexamethylene diisocyanate) are not generally used in foams, but... 

It is extremely important to assure the durability of the strengthening applied by the use of a protection layer on the external surface of the support. For instance, the external surface can be varnished with a two-pack polyurethane aliphatic resin, yielding excellent resistance to UV rays, to weathering agents, chemical attacks, chlorine, wear and tear, and high temperatures. 

Aliphatic isocyanates have a small but growing market application in thermoplastic polyurethanes (TPU). Medical appflcafions include wound dressings, catheters, implant devices, and blood bags. A security glass system using light-stable TPU as an inner layer is under evaluation for shatterproof automotive windshield appflcafions. 

The tendency of aliphatic ethers toward oxidation requires the use of antioxidants such as hindered phenoHcs (eg, BHT), secondary aromatic amines, and phosphites. This is especially tme in polyether polyols used in making polyurethanes (PUR) because they may become discolored and the increase in acid number affects PUR production. The antioxidants also reduce oxidation during PUR production where the temperature could reach 230°C. A number of new antioxidant products and combinations have become available (115,120,124—139) (see Antioxidants). 

Multiblock systems. A somewhat similar approach is involved in the production of thermoplastic polyurethane elastomers. In this case the chain contains soft segments that are largely aliphatic polyether in nature and also hard segments that are primarily polyurea (see Chapter 27). 

Whilst the aliphatic nylons are generally classified as being impact resistant, they are affected by stress concentrators like sharp comers which may lead to brittle failures. Incorporation of mbbers which are not soluble in the nylons and hence form dispersions of rubber droplets in the polyamide matrix but which nevertheless can have some interaction between mbber and polyamide can be most effective. Materials described in the literature include the ethylene-propylene rubbers, ionomers (q.v.), polyurethanes, acrylates and methacrylates, ABS polymers and polyamides from dimer acid. 

This tri-isocyanate is reported to impart good light stability and weather resistanee in polyurethane eoatings and is probably the most widely used aliphatic isocyanate. A number of other aliphatic polyisocyanates have been introduced recently in attempts to produce polyurethanes with improved light stability. Amine derivatives of diphenylmethane are made by reacting aniline of toluidines with formaldehyde. These can lead to a mixture of di-isoeyanates, the diphenylmethane di-isocyanates (MDIs) of commerce. Triphenylmethane-pp p"-tny tri-isocyanate is produced from leucorosaniline. 

As previously mentioned the initial research on polyurethanes was directed towards the preparation of fibre-forming polymers. Many poly hydroxy compounds and many di-isocyanates were used and the melting points of some of the more linear aliphatic polyurethanes produced cU"e given in Table 27.1. 

Polyurethane dispersions (PUD s) are usually high-performance adhesives based on crystalline, hydrophobic polyester polyols, such as hexamethylene adipate, and aliphatic diisocyanates, such as methylene bis(cyclohexyl isocyanate) (H12MDI) or isophorone diisocyanate (IPDI). These PUD s are at the more expensive end of the waterborne adhesive market but provide excellent performance. 

Nearly all of the polymers produced by step-growth polymerization contain heteroatoms and/or aromatic rings in the backbone. One exception is polymers produced from acyclic diene metathesis (ADMET) polymerization.22 Hydrocarbon polymers with carbon-carbon double bonds are readily produced using ADMET polymerization techniques. Polyesters, polycarbonates, polyamides, and polyurethanes can be produced from aliphatic monomers with appropriate functional groups (Fig. 1.1). In these aliphatic polymers, the concentration of the linking groups (ester, carbonate, amide, or urethane) in the backbone greatly influences the physical properties. 

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. 

Due to low hydrolytic and chemical resistance and to low melting point, aliphatic polyesters have long been considered to be limited to applications such as plasticizers or macromonomers for the preparation of polyurethane foams, coatings, or... 

Example 5. Glycolysis of Polyurethanes with Propylene Oxide after Pretreatment with Ethanolamine.55 A rigid polyurethane foam (ca. 100 g) was dissolved in 30 g ethanolamine by heating. Excess ethanolamine was stripped, leaving a clear solution. Infrared and GPC analysis indicated that the clear solution obtained contained some residual polyurethane, aromatic polyurea, aliphatic polyols, aromatic amines, and N,N -bis(f -hydroxyethyljurea. Next the mixture was dissolved in 45 g propylene oxide and heated at 120°C in an autoclave for 2 h. The pressure increased to 40 psi and then fell to 30 psi at the end of the 2-h heating period. The product was a brown oil with a hydroxyl number of485. 

Mechanical properties. See also Dynamic mechanical analysis (DMA) of polyamides, 138 of polyester LCPs, 52 of polyurethanes, 242-244 of semicrystalline aromatic-aliphatic polyesters, 45 Mechanical recycling, 208 Medical applications, for polyurethanes, 207... 

Other reports on the morphology and mechanical behavior of organosiloxane containing copolymeric systems include polyurethanes 201 202), aliphatic 185, 86) and aromatic117,195> polyesters, polycarbonates 233 236>, polyhydroxyethers69,311, siloxane zwitterionomers 294 295) and epoxy networks 115>. All of these systems display two phase morphologies and composition dependent mechanical properties, as expected. 

The potential of using extrinsic (fluorescent) probes for monitoring the initial stages of oxidation was explored for the photo-oxidation of a UV-cured aliphatic polyurethane-acrylate-based adhesive [68]. The two probes investigated were p-dimethylamino salicylic acid (p-DASA) and 2, 7 -difluorescein (Oregon Green... 

Telechelic polymers rank among the oldest designed precursors. The position of reactive groups at the ends of a sequence of repeating units makes it possible to incorporate various chemical structures into the network (polyether, polyester, polyamide, aliphatic, cycloaliphatic or aromatic hydrocarbon, etc.). The cross-linking density can be controlled by the length of precursor chain and functionality of the crosslinker, by molar ratio of functional groups, or by addition of a monofunctional component. Formation of elastically inactive loops is usually weak. Typical polyurethane systems composed of a macromolecular triol and a diisocyanate are statistically simple and when different theories listed above are... 

We report here that polyethylene adipate (PEA) and polycaprolactone (PCL) were degraded by Penicillium spp., and aliphatic and alicyclic polyesters,ester type polyurethanes, copolyesters composed of aliphatic and aromatic polyester (CPE) and copolyamide-esters (CPAE) were hydrolyzed by several lipases and an esterase. Concerning these water-insoluble condensation polymers, we noted that the melting points (Tm) had a effect on biodegradability. 

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