Isocyanate Grafting

The isocyanate-coated MFC in dry THF could be immediately coated with bisamino-propyl amine or 3-ethylenamino-l-propylamine, thus introducing positive charges to the microfibril surfaces. 

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Isocyanate Grafting. Weakly O2 plasma-treated and diborane reduced polypropylene foils with about 7 OH/100 C were reacted with diisocyanates (hexamethylene diisocyanate (HDI), methylene-di-p-phenylene isocyanate (MDI) and toluylene-2,4-diisocyanate (TDI)) as schematically shown in Fig. 7. Subsequently, different fluorescence... 

RigidPoly(vinylchloride) Foam. The techniques that have been used to produce rigid vinyl foams are similar to those for the manufacture of flexible PVC foams. The two processes that have reached commercial importance for the manufacture of rigid vinyl foams (246) are the Dynamit-Nobel extmsion process and the Kleber-Colombes Polyplastique process for producing cross-linked grafted PVC foams from isocyanate-modified PVC in a two-stage mol ding process. 

Poly(phenylene oxide)s undergo many substitution reactions (25). Reactions involving the aromatic rings and the methyl groups of DMPPO include bromination (26), displacement of the resultant bromine with phosphoms or amines (27), lithiation (28), and maleic anhydride grafting (29). Additional reactions at the open 3-position on the ring include nitration, alkylation (30), and amidation with isocyanates (31). 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

Type AD-G is used in an entirely different sort of formulation. The polymer is designed for graft polymerisation with methyl methacrylate. Typically, equal amounts of AD-G and methyl methacrylate are dissolved together in toluene, and the reaction driven to completion with a free-radical catalyst, such as bensoyl peroxide. The graft polymer is usually mixed with an isocyanate just prior to use. It is not normally compounded with resin. The resulting adhesive has very good adhesion to plasticised vinyl, EVA sponge, thermoplastic mbber, and other difficult to bond substrates, and is of particular importance to the shoe industry (42,43). 

Isocyanates can be added to solvent-borne CR adhesive solutions as a two-part adhesive system. This two-part adhesive system is less effective with rubber substrates containing high styrene resin and for butadiene-styrene block (thermoplastic rubber) copolymers. To improve the specific adhesion to those materials, addition of a poly-alpha-methylstyrene resin to solvent-borne CR adhesives is quite effective [76]. An alternative technique is to graft a methacrylate monomer into the polychloroprene [2]. 

Scheme 8.4 Grafting of isocyanate-telchelic poly(l, 3-di(l -mesityl)-4- [(bicyclo[2.2.1 ]hept-5-en-2-ylcarbonyl)oxy]methyl -4,5-dihydro-l H-imidazol-3-ium tetrafluoroborate) on silica and generation of the immobilized second generation Grubbs catalyst.

The functionalization of silica with PPM and the subsequent immobilization of [Rh(COD)2]BF4 has been achieved by Pugin and Blaser [49]. The PPM ligand was immobilized by grafting the linker, 3-trimethoxysilylpropyl isocyanate, to the silica surface (the silicas used include Grace 332, Merck 100, Merck 60, Merck 40). The isocyanate moiety then reacts with the amine functionality of the PPM ligand to afford an amide linkage (35, Figure 5.17). Introduction of a solution of [Rh(COD)2]... 

The reaction of hydroxyl group on inorganic particles with reactive polymers having isocyanate (27.28), alkoxysilane (29,30), and chlorosilane (29) groups efficiently gave the polymer-grafted particles [Reactions (9) and (10)]. 

The big question is whether the seemingly ideal properties of a reticulated foam will be maintained when we start to change the chemistry (for cell adhesion, extraction, etc.). Changes in the polyol or isocyanate will inevitably affect its physical properties. A balance of chemical activity would have to be established. In many cases, this balance will degrade the desirable properties. An answer is the recent development of a composite of a chemistry designed according to desirable chemical features grafted to a reticulated scaffold. " Such a composite was developed and patented and it will be cited as an example for several applications. 

In automotive applications, e.g., automotive seats, molded HR foam is the major process used. HR foam is produced by using four kinds of technologies (a) crosslinker technology, b) graft-polyol technology, (c) PHD polyol technology, and (d) specialty isocyanate technology. 

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