Diisocyanates activity

Although Synhydride (resp. Dilactamate) is not considered to be a normal initiator, it is today being used in industrial polymerization casting to some extent (private confidential communication). Recently, Synhydride has been applied, in combination with diisocyanate activators, for the preparation of powder polyamides (see Section 7.10). 

The hydroxyl groups can be esterified normally the interesting diacrylate monomer (80) and the biologicaky active haloacetates (81) have been prepared in this manner. Reactions with dibasic acids have given polymers capable of being cross-linked (82) or suitable for use as soft segments in polyurethanes (83). Polycarbamic esters are obtained by treatment with a diisocyanate (84) or via the bischloroformate (85). 

Developments in aliphatic isocyanates include the synthesis of polymeric aliphatic isocyanates and masked or blocked diisocyanates for appflcafions in which volatility or reactivity ate of concern. Polymeric aliphatic isocyanates ate made by copolymerizing methacrylic acid derivatives, such as 2-isocyanatoethyl methacrylate, and styrene [100-42-5] (100). Blocked isocyanates ate prepared via the reaction of the isocyanate with an active hydrogen compound, such as S-caprolactam, phenol [108-95-2] or acetone oxime. 

Other Preparative Reactions. Polyamidation has been an active area of research for many years, and numerous methods have been developed for polyamide formation. The synthesis of polyamides has been extensively reviewed (54). In addition, many of the methods used to prepare simple amides are appHcable to polyamides (55,56). Polyamides of aromatic diamines and aUphatic diacids can also be made by the reaction of the corresponding aromatic diisocyanate and diacids (57). 

Blocked isocyanate, for our purposes, will refer to the reaction product of a diisocyanate or isocyanate-terminated prepolymer in which the isocyanate functionality has been reacted with a blocking agent . Once blocked , the diisocyanate can be added to polyols or certain chain extenders, and these materials will not react at room temperature. The concept is shown in the sixth item of Fig. 1. An adhesive formulated with a blocked isocyanate is basically a two-component adhesive that does not react until heated to the activation temperature. When an adhesive is made with a blocked isocyanate together with hydroxyl-containing curatives, the adhesive has a good long shelf life at room temperature. However, once heated... 

Methylene dianiline is normally a very reactive diamine in the presence of diisocyanates. However, a sodium chloride complex that is relatively unreactive at room temperature is commercially available. When the complex is heated to 21°C, it activates to quickly cure the urethane [76]. 

To incorporate a labile azo group as the essential active site to MAI, a series of azo compounds such as 2,2 azobisisobutyronitrile (AIBN), 4,4 -azobis(4-cyanopen-tanoyl chloride) (ACPC), 2,2 azobis (2-cyanopropanol) (ACPO), 2,2 azobis [2-methyl-N-(2-hydroxyethyl)prop-ionamide] (AHPA), etc., were used as starting materials for polycondensation with various diols, diamines, diacids, or diisocyanates. 

A special situation is created in a polymerization of isolated dienes or similar compounds like diisocyanates. Addition of such a monomer to a growing polymeric chain leaves its second reactive unit in the vicinity of the active center. Consequently, the addition of this unit is favored to the addition of any other unit, and in fact it is governed by a unimolecular and not bimolecular kinetic law. Its addition leads to the formation of a ring, and if ring closure is... 

Methyl methacrylate can also be polymerized by radiation using either a cobalt-60 source or accelerated electrons at dose rates up to 3 megarads/sec. The activation energy for the electron beam polymerization is about 7.0kcal/ mole (Ref 12). Radical polymerization can also occur using diisocyanates or hydroperoxides as the initiating species (Ref 15)... 

These results have been fit to experimental data obtained for the reaction between a diisocyanate and a trifunctional polyester polyol, catalyzed by dibutyltindilaurate, in our laboratory RIM machine (Figure 2). No phase separation occurs during this reaction. Reaction order, n, activation energy, Ea, and the preexponential factor. A, were taken as adjustable parameters to fit adiabatic temperature rise data. Typical comparison between the experimental and numerical results are shown in Figure 7. The fit is quite satisfactory and gives reasonable values for the fit parameters. Figure 8 shows how fractional conversion of diisocyanate is predicted to vary as a function of time at the centerline and at the mold wall (remember that molecular diffusion has been assumed to be negligible). 

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... 

Polyurethanes (13) have been prepared with optically active diols and various diisocyanates.69 Chiral recognition depends on the diisocyanate... 

Polyurethanes are frequently used in anticorrosion coatings. The R D drive of most coatings and resin producers is the reduction of the solvent content of the paint and resin systems. One method of achieving the environmental aims demanded by legislation in the PU coatings industry is to use oxazolidines which are suitable as latent hardeners to enable production of single-pack moisture activated PUs. The isocyanate chosen for this research is tetramethylxylene diisocyanate, which has been available commercially only since 1988. 19 refs. 

Dextran hydrogels, cross-linked by diisocyanate, released drug only in the distal part of the colon, where the conditions for absorption are not as conducive as in the proximal part [96], The pH-sensitive dextran hydrogels were prepared by activation... 

A study in mice examined immune responses following topical exposure to three allergenic diisocyanates diphenylmethane-4,4 -diisocyanate (MDI), dicyclohexyl-methane-4,4 -diisocyanate (HMDI), and isophorone diisocyanate (IPDI). Contact and respiratory sensitizers induce differential immune responses in mice characteristic of Thl and Th2 T helper cell activation, respectively. All three chemicals are contact allergens. MDI is, in addition, a known human respiratory allergen. HMDI and IPDI did not produce an immunologic response in the mouse similar to MDI. These findings suggest that HMDI has much less potential to cause respiratory sensitization in humans than does MDI ... 

Dieter MP, Boorman GA, Jameson GW, et al The carcinogenic activity of commercial grade toluene diisocyanate in rats and mice in relation to the metabolism of the 2,4-and 2,6-TDI isomers. Toxicol Ind Health 6 599-621, 1990... 

The Environmental Protection Agency (EPA) identifies the most serious hazardous waste sites in the nation. These sites make up the National Priorities List (NPL) and are the sites targeted for long-term federal clean-up activities. Hexamethylene diisocyanate has not been found in any of the 1,445 current or former NPL sites. However, the total number of NPL sites evaluated is not known. As more sites are evaluated, the number of sites at which HDI is found may increase. This is important because exposure to this substance may harm you and because these sites may be sources of exposure. 

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