Polymeric polyisocyanate

Polymeric polyisocyanate n. A generic term for a family of isocyanates derived from aniline-formaldehyde condensation products, used as reactants in the production of polyurethane foams. 

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. 

Processing of rigid foams from two part formulations involves combining measured quantities of the polyisocyanate with a polyhydroxyl such that there are no or limited reactive isocyanate functional groups. Moisture is not required to complete the cure. Once the reactants are combined the mixture is poured into a form where expansion and polymerization take place simultaneously. Cure times are usually very fast, on the order of minutes. 

The anionic polymerization of isocyanates using NaCN as an initiator was first reported in I960.998 The living coordinative polymerization of n-hexylisocyanate has been described using the titanium(IV) complexes (345) (348).999-1001 A trifunctional initiator has also been used to prepare star polyisocyanates.1002... 

It is important to be aware of the chemical effects of isocyanates. The polynre-thanes you will develop will be combinations of polyols and isocyanates. The ratio of the two compounds will in pait dictate both the physical and chemical properties of the product. As a general rule, the isocyanates are hard segments that impart rigidity to the polymer. The polyol is the so-called soft segment. The various molecular weights (more correctly equivalent weights available in the form of polymeric MDIs) provide certain advantages. Table 2.2 lists a few commercially available polyisocyanates and their physical properties. 

The significance of this study goes to the heart of our task. In our discussion of the extraction of pollutants, we suggested that polyglycols had utility as extracting solvents, but because of their physical nature (water solubility) they were not useful. We proposed to polymerize the glycols into water-insoluble polymers by reactions with polyisocyanates. We then presented data to support the notion that the polymers maintained the solvent properties, but they were translated into a water-insoluble matrix (a polyurethane). 

Reactions with Isocyanates, TYZOR TPT catalyzes the trimerization of isocyanates and polyisocyanates to isocyanurates and polyisocyanurates (38). Titanium alkoxides of the type Cl3TiOR initiate the living polymerization of isocyanates. Polyisocyanates possessing controlled molecular weights and narrow polydispersities can be synthesized using these catalysts (39) ... 

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. 

The use of SSL or lignosulphonates in other polymeric adhesive systems has also been examined [e.g., with polyacrylamide, proteins/aldehydes, polyethylene oxide, polyethylene imine, epoxides, melamine, styrene oxide, polyisocyanates (55)]. So far, these procedures, for different reasons, have not led to any major practical application (36). It would, however, be interesting to reexamine some of these processes using not crude spent sulphite liquors, but instead those purified by membrane filtration. 

A recent innovation in in-situ microencapsulation is the development of acid-triggered release of pesticide from the microcapsules [12]. Diols and aldehydes are reacted to form an acid labile acetal moiety. The acetal is then reacted with isocyanate to create a prepolymer. The prepolymer is a polyisocyanate cmitaining the acid labile moiety and suitable for in-situ shellwall polymerization. The prepolymer is dissolved into a pesticide, emulsified into water, and shellwall formed in-situ. Under alkaline or neutral pH conditions in a container, the insecticide is safely contained in the microcapsules. Acid could be added to the spray tank to rapidly release capsule contents prior to application. Alternate shellwall chemistry for in-situ microencapsulation utilizes etherified urea-formaldehyde prepolymers in the oil phase that are self-condensed with acid catalyst to produce encapsulating aminoplast shellwalls [13]. This process does not have the problem of continuing CO2 evolution. Water-soluble urea-formaldehyde and melamine-formaldehyde prepolymers can be selected to microencapsulate water or aqueous solutions [14]. 

Polyisocyanates are very reactive compounds and produce various polymers such as fibers, resins, elastomers, foams, coatings and adhesives by the reaction of polyaddition, polycondensation or stepwise polymerization. 

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. 

Example (1) Unsaturated monoalcohol (acryloesterol) and styrene monomer are reacted with a polyisocyanate in the presence of a urethane catalyst and a radical polymerization catalyst to form hybrid resins (52). Styrene monomer acts as a crosslinker and at the same time, acts also as a reactive diluent. The trade name of a commercial product of such systems is Arimax (Ashland Chemical) (107). 

The second factor important in obtaining highly flame-retardant isocyanurate foams is the NCO/OH equivalent ratio. Fire endurance, i.e., flame retardance) and temperature resistance, can be increased with increase of the NCO/OH equivalent ratio when polymeric isocyanate is used as the polyisocyanate component. 

The polyisocyanates used for preparing carbodiimide foams include TDl, TDl-based prepolymers, liquid-MDl oligomers and polymeric isocyanates. Many catalysts for producing carbodiimide foams have been disclosed in the patent literature. Some of these are shown in Table 13. 

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