Polyisocyanate

Polyurethanes. The hard portion of polyurethane consists of a chain extender and polyisocyanate. The soft component is composed of polyol segments. 

Polyurethanes. About 3% of the U.S. polyurethanes market in 1988 was derived from the condensation product of polyisocyanates with low molecular weight polyadipates having hydroxyl end groups (195). In 1986 this amounted to 29,000 t, or 4% of total adipic acid consumption. The percentage was similar in Western Europe. About 90% of these adipic acid containing polyurethanes are used in flexible or semirigid foams and elastomers, with the remainder used in adhesives, coatings, and spandex fibers. 

Tetraethylene glycol may be used direcdy as a plasticizer or modified by esterification with fatty acids to produce plasticizers (qv). Tetraethylene glycol is used directly to plasticize separation membranes, such as siHcone mbber, poly(vinyl acetate), and ceUulose triacetate. Ceramic materials utilize tetraethylene glycol as plasticizing agents in resistant refractory plastics and molded ceramics. It is also employed to improve the physical properties of cyanoacrylate and polyacrylonitrile adhesives, and is chemically modified to form polyisocyanate, polymethacrylate, and to contain siHcone compounds used for adhesives. 

Diisocyanates or Polyisocyanates. The thiol end groups of the hquid polysulfides are quite reactive with isocyanates (eq. 3). Typical chisocyanates, such as 1,3-toluene chisocyanate (m-TDl) and diphenylmethane-4,4 -diisocyanate (MDl), ate effective in curing hquid polysulfides. Using hquid polysulfides in-... 

HMD was originally produced by Du Pont as a coproduct in the manufacture of Qiana fiber. Du Pont subsequently sold the product to Bayer. In the 1990s MDA is hydrogenated by Air Products for Bayer (see Amines, aromatic-methylenedianiline). Commercial HMDI is a mixture of three stereoisomers. Semicommercial aUphatic diisocyanates include /n j -cyclohexane-l,4-diisocyanate (CHDI) and y -tetramethylxylylene diisocyanate (TMXDI). A coproduct in the production of TMXDI is y -isopropenyl-a,a-dimethylben2yl isocyanate (TMI), which can be copolymerized with other olefins to give aUphatic polyisocyanates. 

Cellular organic plastics. Elastomer, polystyrene, polyisocyanate, polyisocyanurate, and polyvinyl acetate. 

By the same reaction polyhydroxy materials will react with polyisocyanates to yield polyurethanes. For example, the reaction between 1,4-butanediol and hexamethylenedi-isocyanate is shown below ... 

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. 

Foam may be made from such polycaprolactones by reaction with polyisocyanates in the presence of tin catalysts. 

Interest in the RIM process appears to have abated somewhat in the 1990s. Nevertheless, nearly 100000 tonnes of polyol and polyisocyanate were consumed for this application in the USA alone in 1993. 

The polycarbamylsulphonates are water-soluble reactive bisulphite adducts of polyisocyanates and are being investigated as possible materials to render woollen fabrics crease-resistant. 

Nitrile rubber adhesives. The main application corresponds to laminating adhesives. PVC, polyvinyl acetate and other polymeric films can be laminated to several metals, including aluminium and brass, by using NBR adhesives. NBR adhesives can also be used to join medium-to-high polarity rubbers to polyamide substrates. The adhesive properties of NBR rubbers can be further improved by chemical modification using polyisocyanate or by grafting with methyl methacrylate. 

Terpene phenolic resins can also be added to solvent-borne CR adhesives to increase open tack time and to provide a softer glue line than /-butyl phenolic resins. To provide adequate hot bond strength, these resins are used in combination with a polyisocyanate curing agent. 

Effect of the addition of polyisocyanate to polychloroprene on ASTM softening point [2]... 

Shoe adhesives. CR adhesives are used for the permanent attachment of shoe soles. For difficult-to-bond sole materials (plasticized PVC, EVA foaming soles, thermoplastic rubber, SBR) graft polymer solutions of Neoprene AD-G combined with a polyisocyanate provide a good adhesion. Another major area for CR contact adhesives is the manufacture of leather goods, particularly leather shoe sole bonding and belt lamination. 

E.I. Du Pont de Nemours, Colloidal stable solvent cement compositions comprising chloro-prene polymers, phenolic resins and polyisocyanate, U.S. Patent 3,318,834, 9 May, 1967. 

R is an organic moiety, which can be aliphatic or aromatic. Most commonly used in adhesives are the aromatic isocyanates, e.g., methylene diphenylisocyanate (MDI) and toluene diisocyanate (TDI). These polyisocyanates and others will be discussed in Section 3. 

The first urethane reaction in Fig. 1 is used in two major ways in adhesives. In one case, a two-component adhesive usually employs a polyol and polyisocyanate with catalyst. This can react at room temperature to form the polyurethane. The second use of this reaction is to make an isocyanate-terminated prepolymer. Reacting a stoichiometric excess of isocyanate with polyol can produce an isocyanate-terminated prepolymer. A prepolymer is often made with an NCO/OH ratio of 2.0, as shown below, but the isocyanate ratio can range from 1.4 to over 8.0, depending upon the application ... 

In certain instances, for additional performance, polyisocyanates may be added to the solvent-borne adhesive or may be incorporated [55]. 

Two-component waterborne urethane dispersions are similar to the one-component PUD s in that a polyurethane dispersion comprises one of the two components. The second component is usually a crosslinker from the following classes of materials (a) polyisocyanates, (b) aziridines, (c) polycarbodiimides, and (d) epoxies. Many of the crosslinkers are not inherently water-soluble or water-dispersible. Therefore, they must be modified with surface active agents themselves, so as to become emulsifiable in water. 

There are two approaches to forming urethane-acrylic hybrids. First, an acrylate terminated urethane oligomer can be used [147]. Alternatively, polyisocyanate and benzoyl peroxide can be combined in one side of the adhesive, and methacrylate monomers and urethane curatives (especially polyols) in the other [148]. 

Like other adhesives, PMDI is a specific mixture of different molecules. The greater part of the functional groups of polyisocyanates are of low reactivity because of the different positions. The molecular weight distribution influences the reactivity, but also the typical properties of adhesives like viscosity, wetting and fluidity. In the monomer form (MDI) the functionality is 2 and the NCO-content is 33.5%, while PMDI has an average funetionality of 2.7 with a NCO-content of approximately 30.5%. The HCl-content is usually below 200 ppm. PMDI is used whenever the color of the finished adhesive is not of concern [138]. 

PMDI also contains isocyanates with higher molar masses (triisocyanates, tetraisocyanates, polyisocyanates), whereby the structure and the molar mass depend on the number of phenyl groups. This distribution influences, to a great extent, the reactivity, but also the usual properties like viscosity, flowing and wetting behavior as well as the penetration into the wood surface. 

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