Elastomers polyurethanes

The concentrations of the allophanate links varies with the time of cure. Also, if the crosslinking reactions are conducted in inert nitrogen atmospheres, veiy little scission of crosslinks takes place and a network structure forms during the cure. In open air, however, the scissions of crosslinks are extensive and the products have poorer physical properties. 

A drawback to the cast elastomers is limited shelf-life and a need to store them in the absence of moisture. As a result, millable elastomers were developed. These are produced by first forming hydroxy-terminated linear polyurethanes through reactions of linear aliphatic polyesters or polyethers with diisocyanates. The prepolymers are rubber-like gums that can be compounded on rubber mills with other ingredients and crosslinked. Crosslinking is accomplished by adding either more diisocyanates, or sulfur, or peroxides. Diisocyanates dimers that dissociate at about 150 °C are often used  

Unsaturated prepolymers crosslink with peroxides or sulfur. This unsaturation can be present in the backbone or in the pendant groups. Vulcanization or crosslinking of elastomers with sulfur or peroxides is discussed in Chapter 8. 

Thermoplastic elastomers exhibit physical properties that are similar to those of cast and millable elastomers at ambient temperatures. These materials, however, are not crosslinked and flow at elevated temperatures. They are fabricated like other thermoplastic polymers, are high in molecular weight, and are hydroxy-terminated. Such polymers form from linear hydroxy-terminated polyester or polyethers that are condensed with diisocyanates and glycols. Strict stoichiometry must be maintained to achieve high molecular weights. 

7 Step-Growth Polymerization and Step-Growth Polymers 

As in neoprene, except that exposure should be for only 5—10 min, since this is not an acid-resistant rubber. Some workers suggest much shorter periods (10-45 s). 

This type of rubber, once called GR-S, is one of the most important synthetic rubbers. It is a copolymer of styrene and butadiene.Treatments are as follows  

A number of primers can be used, such as Chemlok primers AP-134, and AP-131 (LORD Corporation), or a chlorosilane supplied by GE Sealants, Rohm Haas (www.rohmhaas.com) or Dow Coming Corp. Methanol can be used as a degreasing agent prior to priming. 

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Butanediol. 1,4-Butanediol [110-63-4] made from formaldehyde and acetylene, is a significant market for formaldehyde representing 11% of its demand (115). It is used to produce tetrahydrofuran (THF), which is used for polyurethane elastomers y-butyrolactone, which is used to make various pyrroHdinone derivatives poly(butylene terephthalate) (PBT), which is an engineering plastic and polyurethanes. Formaldehyde growth in the acetylenic chemicals market is threatened by alternative processes to produce 1,4-butanediol not requiring formaldehyde as a raw material (140) (see Acetylene-derived chemicals). 

Trimethyl-l,3-pentanediol (7) is a white, crystalline soHd. It is used in surface coating and unsaturated polyester resins. It also appears promising as an intermediate for synthetic lubricants and polyurethane elastomers and foams. 

A. T. Chen, and co-workers, "Comparison of the Dynamic Properties of Polyurethane Elastomers Based on Low Unsaturation Polyoxypropylene Glycols and Poly(tetramethylene oxide) Glycols," Polyurethanes World Congress 1993, Vancouver, B.C., Canada, Oct. 10—13,1993. 

C. Hepburn, Polyurethane Elastomers, AppHed Science Ltd, London, U.K., 1982. 

The late 1950s saw the emergence of cast elastomers, which led to the development of reaction injection mol ding (RIM) at Bayer AG in Leverkusen, Germany, in 1964 (see Plastics processing). Also, thermoplastic polyurethane elastomers (TPUs) and Spandex fibers (see Fibers, elastomeric) were introduced during this time. In addition, urethane-based synthetic leather (see Leather-LIKEmaterials) was introduced by Du Pont under the trade name Corfam in 1963. 

The Hquid monomers are suitable for bulk polymerization processes. The reaction can be conducted in a mold (casting, reaction injection mol ding), continuously on a conveyor (block and panel foam production), or in an extmder (thermoplastic polyurethane elastomers and engineering thermoplastics). Also, spraying of the monomers onto the surface of suitable substrates provides insulation barriers or cross-linked coatings. 

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

Polymeric isocyanates or PMDI ate cmde products that vary in exact composition. The main constituents are 40—60% 4,4 -MDI the remainder is the other isomers of MDI, trimeric species, and higher molecular weight oligomers. Important product variables are functionaHty and acidity. Rigid polyurethane foams are mainly manufactured from PMDI. The so-called pure MDI is a low melting soHd that is used for high performance polyurethane elastomers and spandex fibers. Liquid MDI products are used in RIM 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. 

The largest segment of the CASE family of polyurethanes are elastomers. Cast polyurethane elastomers reached a new dimension when high pressure impingement mixing led to reaction injection molding (RIM). This technology is used widely in the automotive industry, and reinforced versions (RRIM) and stmctural molded parts (SRIM) have been added in more recent years. 

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... 

Metal salts of neodecanoic acid have also been used as catalysts in the preparation of polymers. For example, bismuth, calcium, barium, and 2kconium neodecanoates have been used as catalysts in the formation of polyurethane elastomers (91,92). Magnesium neodecanoate [57453-97-1] is one component of a catalyst system for the preparation of polyolefins (93) vanadium, cobalt, copper, or kon neodecanoates have been used as curing catalysts for conjugated-diene butyl elastomers (94). 

E. Linak, F. P. Kalt, and Y. Sakuma, Polyurethane Elastomers, CEH Marketing Kesearch Keport, Stanford Research Institute, Menlo Park, Calif., July 1990, p. 525.6600A. 

Properties. Polyurethane elastomers generally exhibit good resiHence and low temperature properties, excellent abrasion resistance, moderate solvent resistance, and poor hydrolytic stabiHty and poor high temperature resistance. As castable mbber, polyurethanes enjoy a variety of uses, eg, footwear, toys, soHd tires, and foam mbber. 

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. 

Table 6. Trade Names of Multiblock Thermoplastic Elastomers Based on Polyurethane/Elastomer, Polyether/Elastomer, and Polyamide/Elastomer Block Copolymers...

Table 11. Properties of Polyurethane/Elastomer Block Copolymers...

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). 

Blends or alloys of polyacetals with polyurethane elastomers were first introduced by Hoechst in 1982, who were then followed by other manufacturers. The key features of these materials are their improved toughness with little change in other important properties. There are two aspects with respect to the impact toughness ... 

One partieular form of thermoplastic polyurethane elastomers is the elastic fibre known as spandex fibre. Like the usual thermoplastic rubbers these materials consist of hard and soft segments but to qualify for the term spandex by the US Federal Trade Commission the polymer used should contain at least 85% of segmented polyurethane. The first commercial material of this type was introduced by Du Pont in 1958 (Lycra). Several other similar materials have since been introduced including Dorlastan (Bayer), Spanzelle (Courtaulds) and Vyrene (US Rubber). 

Polyester-based thermoplastic polyurethane elastomers (Section 27.4). 

Thermoplastic polyurethane elastomers have now been available for many years (and were described in the first edition of this book). The adipate polyester-based materials have outstanding abrasion and tear resistance as well as very good resistance to oils and oxidative degradation. The polyether-based materials are more noted for their resistance to hydrolysis and fungal attack. Rather specialised polymers based on polycaprolactone (Section 25.11) may be considered as premium grade materials with good all round properties. 

Whilst approximately twice the raw material cost of TPO- and S-B-S-type polymers, thermoplastic polyurethane elastomers find applications where abrasion resistance and toughness are particular requirements. Uses include gears, timing and drive belts, footwear (including ski boots) and tyre chains. Polyether-based materials have also achieved a number of significant medical applications. There is also some minor use as hot melt adhesives, particularly for the footwear industry. 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

Wright, P. and Cummings, A., Solid Polyurethane Elastomers. Gordon and Breach, 1969. Buist, J.M. and Gudgeon, H., Advances in Polyurethane Technology. Elsevier, Amsterdam, 1968, p. 72. 

Rosato, D.V. ed. Rosato, D.V. (ed.) Blow Moulding Handbook, Hanser, Munich (1989). Hepburn, C. Polyurethane Elastomers (ch 6-RIM) Applied Science Publishers, London (1982). Martin, L, Pultrusion Ch 3 in Plastics Product Design Handbook - B ed by E. Miller, Dekker Inc, New York (1983). 

Since it possesses good properties of both PVC plastics and polyurethane elastomers, it has been used in those areas where PVC and polyurethane have traditionally played dominant roles. For example, it is a very promising replacement for flexible PVC used for medical purposes and in the food industry [I6,l7], because it essentially eliminates the concern regarding plasticizer contamination. It has been used in combination with the copolymer of butadiene and acrylonitrile (NBR) to make the abrasion-resistant aprons and rolls used on textile machines [18]. A PVC/TPU/ABS blend serves as a substitute for leather [19]. This could have a tremendous impact on the shoe industry. It has also been found to have an application as a building coating [20,21]. This trend will certainly grow and more applications will be found. This in turn should bring new developments in the material itself. 

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. 

Another area of recent interest is covulcanization in block copolymers, thermoplastic rubbers, and elasto-plastic blends by developing an interpenetrating network (IPN). A classical example for IPN formation is in polyurethane elastomer blended acrylic copolymers [7]. 

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