Polymeric isocyanate

Commonly used isocyanates are toluene dhsocyanate, methylene diphenyl isocyanate, and polymeric isocyanates. Polyols used are macroglycols based on either polyester or polyether. The former [poly(ethylene phthalate) or poly(ethylene 1,6-hexanedioate)] have hydroxyl groups that are free to react with the isocyanate. Most flexible foam is made from 80/20 toluene dhsocyanate (which refers to the ratio of 2,4-toluene dhsocyanate to 2,6-toluene dhsocyanate). High-resilience foam contains about 80% 80/20 toluene dhsocyanate and 20% poly(methylene diphenyl isocyanate), while semi-flexible foam is almost always 100% poly(methylene diphenyl isocyanate). Much of the latter reacts by trimerization to form isocyanurate rings. 

The isocyanates used with rigid foam systems are either polymeric MDI or specialty types of TDI. Both contain various levels of polymerized isocyanate groups which contribute to molecular weight per cross-link and also may affect reactivity due to steric hindrance of some isocyanate positions. 

The late 1950s also witnessed the emergence of a new polymeric isocyanate (PMDI) based on the condensation of aniline with formaldehyde. This... 

Isocyanates. The commodity isocyanates TDI and PMDI ate most widely used in the manufacture of urethane polymers (see also Isocyanates, organic). The former is an 80 20 mixture of 2,4- and 2,6-isomers, respectively the latter a polymeric isocyanate obtained by phosgenation of aniline—formaldehyde-derived polyamines. A coproduct in the manufacture of PMDI is 4,4 -methylenebis(phenyHsocyanate) (MDI). A 65 35 mixture of 2,4- and 2,6-TDI, pure 2,4-TDI and MDI enriched in the 2,4 -isomer are also available. The manufacture of TDI involves the dinitration of toluene, catalytic hydrogenation to the diamines, and phosgenation. Separation of the undesired 2,3-isomer is necessary because its presence interferes with polymerization (13). 

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. 

Low viscosity urethane polymers have been prepared from castor od and polymeric isocyanates (82). These low mix viscosity systems are extremely usehd for potting electrical components where fast penetration without air voids, and fast dispensing cycles are desirable. Very low viscosity urethane systems containing castor polyols have been prepared for use in reclaiming water-logged buried telephone cable and for encapsulating telephone cable sphces (83—86). 

PMDA, 20 266. See also Polymeric methylenedianiline (PMDA) PMDA-ODA, gel casting of, 20 271-272 PMDA-ODA structures, 10 214 PMDI polymeric isocyanate, 25 456, 457, 462. See also Polymeric methylene diisocyanate resins (PMDI) rigid polyurethanes from, 25 471-472 PMF/PMUF resins, 15 779 PMF resins, hardening of, 15 781 PMMA ionomer, 4DA and, 14 479 PM optimization (PMO), 15 466 PM process, 21 50 Pneumatic classification, 22 288 health and safety factors related to,... 

The aromatic polyols resulting from the reaction can be mixed with commercial polyols, blowing agents, surfactants, catalysts, and polymeric isocyanates to produce a rigid polyurethane foam. n compared w control foams produced from commercially available polyester polyols, the foams produced from reclaimed materials were found to have essentially the same properties. 

Weyel DA, Rodney BS, Alarie Y. 1982. Sensory irritation, pulmonary irritation, and acute lethahty of a polymeric isocyanate and sensory irritation of 2,6-toluene diisoeyanate. Toxicol Appl Pharmacol 64(3) 423-430. 

Title Metal Carbonate Initiator and Method for Polymerizing Isocyanates Using the Same... 

REGULATORYAGENCIES - PHARMACEUTICALS AND COSMETICS] (Vol21) PMDI. See Polymeric isocyanate. 

Polymeric isocyanates - [AMINES - AMINES,AROMATIC - METHYLENEDIANILINE] (Vol 2)... 

Rigid foams are based primarily on polyfunctional, low molecular weight alcohols and amines. Most global applications conventionally use polymeric isocyanates, TDI, or an undistilled grade of mixed TDI isomers. TDI prepolymers which have hydroxyl and isocyanate groups have been marketed as a low vapor pressure alternative to undistilled TDI. Density reduction is effected via the addition of chlorofluorocarbons, low molecular weight alkanes, or via the in situ generation of carbon dioxide. The resultant closed cell foams find applications as insulators in construction, appliance, transportation, pipeline, and tank end uses. 

The polyisocyanates which can be used for preparing isocyanate-based foams are mainly aromatic compounds and some aliphatic or aralkyl polyisocyanates. TDI (toluene diisocyanate) is widely used for flexible foams. Pure MDI (diphenylmethane diisocyanate) is used for elastomers and coatings. Modified TDI and modified MDI are used for high-resilience flexible foams. Polymeric isocyanates (polymeric MDI or oligomeric MDI) are mostly used for preparing rigid urethane and isocyanurate foams, and in part, for preparing flexible and semi-flexible foams. 

Cellular poly(carbodiimides) derived from polymeric isocyanate (PMDI) can be continuously produced using a phospholene oxide catalyst. As the component temperature is increased from 25 °C to 80 °C at a constant catalyst level, foam densities decrease with increasing component temperatures, with an expected corresponding decrease in compressive strength. The foam friability also decreases with increasing component temperature. 

The method of preparation involves mixii of polymeric isocyanate ( crude MDI) with the polyol, surfactant, catalyst and blowing agent, trichlorofluoromethane (fluorocarbon F-1 IB). The amounts of the latter and of the catalyst were chosen so that the apparent density was... 

In a study concerned with the decay resistance provided by isocyanate bonding to wood, the distribution of the methyl isocyanate reaction in southern pine showed that 60% of the lignin hydroxyls and 12% of the holocellulose hydroxyls are substituted at the point where resistance to biological attack occurs. Therefore, it can be surmised that the chemical bonding of wood by isocyanates through the urethane link can contribute significantly to the excellent performance of diphenylmethane-diisocyanate X or polymeric isocyanates XI as adhesive binder in particle boards (24, 25). 

The wetting and permeation of polymeric isocyanates mixed with a small amount of dye were observed in optical and scanning electron micrographs (27). The ready formation of an interphase by the permeation of polymeric isocyanates has important consequences for mechanical anchorage of adhesive as well as for the fracture behavior of the bonded wood composite. 

Isocyanates. The influence of various manufacturing parameters on the properties (IB, MOE, MOR, boiled MOR) of waferboard bonded by polymeric isocyanates was examined. The amount of adhesive used was 1.5-2.25%, the press time was 1-3 min, the temperature was 177-204 °C, and the density of the boards was 0.679 g/cm. The experiments indicated that under the conditions used the National Bureau of Standards (NBS) 2-B-2 standards can be achieved (J93). 

Manufacturing Process. Both prepolymer and one-shot processes are available, but the polymeric isocyanate-based one-shot process is used in preference because of the easy processing due to the low viscosity of the system, relatively low toxicity of polymeric isocyanates, and fewer environmental problems. However, a disadvantage of the one-shot process is a possible risk of shrunken-foam formation due to its higher closed-cell content. In contrast, the TDI-based prepolymer process has advantages including better in-mold flowability and higher open-cell content. 

One-Shot Process. Monomeric TDI (80/20 and 65/35 isomer ratios) was used as the polyisocyanate component in the early stages of the urethane-foam industry. But due to the toxicity problems of TDI at the present time, most of the isocyanates used for producing semi-rigid foams have been replaced by polymeric isocyanates, and the use of TDI is somewhat limited. 

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