Isocyanates cellulose

In-situ intercalative polymerization of layered silicates is perhaps the best example of reactive molding of nanocomposites today. In-situ interactive polymerization of layered silicates, which was discussed above, can be achieved either with thermosetting matrices, such as polyurethane and epoxy, or with thermoplastic systems, such as nylon-6 [4, 23]. A general requirement for reactive molding of nanocomposites is that the particulate phase of a PNC is compatible with the monomer phase of the reactive molding system, which acts as a polymerizable solvent This makes it possible to achieve and maintain a fine dispersion of the particulate phase in the monomer during matrix consolidation, resulting in excellent particle distribution in the final PNC. Above, it was noted that the hydroxylated surface of cellulose makes it reactive to isocyanate. Cellulose whiskers may therefore represent the ideal particulate phase for a nano-RIM process. For this to be achieved, the whisker-polyurethane system needs to be better characterized, so that the RIM process can be adapted to fabrication of cellulose whisker PNCs. 

The acetyl content of cellulose acetate may be calculated by difference from the hydroxyl content, which is usually determined by carbanilation of the ester hydroxy groups in pyridine solvent with phenyl isocyanate [103-71-9J, followed by measurement of uv absorption of the combined carbanilate. Methods for determining cellulose ester hydroxyl content by near-infrared spectroscopy (111) and acid content by nmr spectroscopy (112) and pyrolysis gas chromatography (113) have been reported. 

The mechanical properties of composites reinforced with wood fibers and PVC or PS as resin can be improved by an isocyanate treatment of those cellulose fibers [41,50] or the polymer matrix [50]. Polymethylene-polyphenyl-isocianate (PMPPIC) in pure state or solution in plasticizer can be used. PMPPIC is chemically linked to the cellulose matrix through strong covalent bonds (Fig. 8). 

By the treatment of oat spelt xylan with phenyl or tolyl isocyanate in pyridine the fully fimctionahzed corresponding carbamates were prepared [416]. Xylan 3,5-dimethylphenylcarbamate showed higher recognition abihty for chiral drugs compared to that of the same cellulose derivative [417]. 

A similar procedure was adopted for synthesis of nanoparticles of cellulose (CelNPs). The polysaccharide nanoparticles were derivatised under ambient conditions to obtain nanosized hydrophobic derivatives. The challenge here is to maintain the nanosize even after derivatisation due to which less vigorous conditions are preferred. A schematic synthesis of acetyl and isocyanate modified derivatives of starch nanoparticles (SNPs) is shown in scheme 3. The organic modification was confirmed from X-ray diffraction (XRD) pattern which revealed that A- style crystallinity of starch nanoparticles (SNPs) was destroyed and new peaks emerged on derivatisation. FT-IR spectra of acetylated derivatives however showed the presence of peak at 3400 cm- due to -OH stretching indicating that the substitution is not complete. 

Carbamate derivatives (Table 1) of cellulose, chitin, amylose, amylopectin, and dextran were prepared using the isocyanates described in Part A of the Experimental Section. Amylose, amylopectin, dextran, and cellulose were obtained from Polysciences, Inc. and used without further purification. Chitin, obtained from Eastman Kodak, was decalcified and deproteinated by the method reported by Haye r prior to use. 

In a typical experiment the isocyanate (0.006 moles) was reacted with 1.5 g of the polysaccharide in 150 ml of a 5% LiCl/ N,N-dimethylacetamide solution at 90°C under nitrogen for two hours. The appearance of a strong infrared absorbance at 1705 cm l was an indication of carbamate formation. The derivatized polymer was isolated as a white powder by precipitation of the reaction solution into a nonsolvent such as methanol. Alternatively thin films were cast directly from solution the lithium salt could be removed by rinsing with acetone. Figure 1 illustrates the reaction of cellulose with phenyl isocyanate. 

Reactive organic chemicals can be bonded to cell wall hydroxyl groups on cellulose, hemicelluloses, and lignin. Much of our research has involved simple epoxides (1 3) and isocyanates (4), but most of our recent effort has focused on acetylation. Acetylation studies have been done using fiberboards (5f6), hardboards (7 11) particleboards (12-20), and flakeboards (21-23), using vapor phase acetylation (8,2 257, liquid phase acetylation (, ), or reaction with ketene (28). 

Fig. 7. Comparison of experimental phase boundary concentrations between the isotropic and biphasic regions for various liquid-crystalline polymer solutions with the scaled particle theory for wormlike hard spherocylinders. ( ) schizophyllan water [65] (A) poly y-benzyl L-glutamate) (PBLG)-dimethylformamide (DMF) [66-69] (A) PBLG-m-cresoI [70] ( ) PBLG-dioxane [71] (O) PBLG-methylene chloride [71] (o) po y(n-hexyl isocyanate) (PHICH°Iuene at 10,25,30,40 °C [64] (O) PHIC-dichloromethane (DCM) at 20 °C [64] (5) a po y(yne)-platinum polymer (PYPt)-tuchIoroethane (TCE) [33] ( ) (hydroxypropyl)-cellulose (HPC)-water [34] ( ) HPC-dimethylacetamide (DMAc) [34] (N) (acetoxypropyl) cellulose (APC)-dibutylphthalate (DBP) [35] ( ) cellulose triacetate (CTA)-trifluoroacetic acid [72]...

The advanced applications for nitrocellulose plastisol propellants require that they be integrally bonded to the motor case. Successful case bonding for the multiyear storage life of a rocket calls for special adhesives and liners which are completely compatible with these highly plasticized propellants. Best results have been obtained with a combination of an impervious rubber liner and a crosslinked adhesive system with a limited affinity for the plasticizers used in the propellants. Examples of effective liners are silica-filled butyl rubber and chlorinated synthetic rubber. Epoxy polyamides, isocyanate-crosslinked cellulose esters, and combinations of crosslinked phenol-formaldehyde and polyvinyl formal varnishes have proved to be effective adhesives between propellant and impervious liners. Pressure curing of the propellants helps... 

The final section addresses degradation and oxidation reactions in a commonly used derivatization system for cellulose, a mixture of DMSO and phenyl isocyanate to achieve cellulose carbanilation, e.g. for analytical purposes. Mechanistic studies were aimed at verifying the assumed oxidative action of this reaction system, and trapping methodology was employed to detect responsible intermediates. 

Cellulose tricarbanilate, obtained by reaction of cellulose with phenyl isocyanate - mostly in DMSO or pyridine as the solvents - has been used widely for the determination of analytical parameters of celluloses by gel permeation chromatography (GPC) in organic solvents, such as THE... 

The oxidative power of carbanilation mixtures containing DMSO and isocyanates was concluded from cellulose degradation in these mixtures. The mechanism of cellulose degradation was proposed to be a combination of oxidation and subsequent chain cleavage at the oxidized positions according to a /3-elimination mechanism triggered by auxiliary bases [ 106]. 

Scheme 24 Proving the oxidizing effect of DMSO/phenyl isocyanate mixtures under conditions used for carbanilation of cellulose by means of sterically hindered alcohol model compounds...

DMSO/isocyanate carbanilation medium on cellulose. It should be noted that the oxidation per se does not cause chain cleavage and cellulose degradation, but only the introduction of carbonyl functionalities along the cellulose chain. However, these groups constitute points of pronounced chemical instability where subsequent cleavage, mainly under basic conditions in /(-elimination processes, will readily occur. 

Polyurethane adhesives are known for excellent adhesion, flexibiUty, toughness, high cohesive strength, and fast cure rates. Polyurethane adhesives rely on the curing of multifunctional isocyanate-terminated prepolymers with moisture or on the reaction with the substrate, eg, wood and cellulosic fibers. Two-component adhesives consist of an isocyanate prepolymer, which is cured with low equivalent weight diols, polyols, diamines, or polyamines. Such systems can be used neat or as solution. The two components are kept separately before appUcation. Two-component polyurethane systems are also used as hot-melt adhesives. 

First, PDMS network was combined to a cellulose acetate butyrate (CAB) network into an IPN architecture in order to improve the thermomechanical properties of PDMS network (Scheme 1). The linear CAB can be cross-linked through its free OH groups with a Desmodur N3300 pluri-isocyanate. The alcohol/isocyanate reaction is catalyzed by DBTDL leading to urethane cross-links. Simultaneously, PDMS oligomers must be cross-linked independently in order to form the PDMS network. In order to carry out independent cross-linking reactions. 

Cellulose can be esterified by reacting with acids, acid chloride, anhydrides, or unsaturated agents [5,73] such as CS2, phenyl isocyanate [128,145] and urea. Model Glucosides. The esterification of simple glycoside in homogeneous system generally indicated [84,141] that the 6-OH group is more reactive... 

Cellulose reacts with isocyanates in anhydrous pyridine or with urea and substituted ureas at relatively high temperature to yield carbamates. The optimum carbamation reaction of microcrystalline cellulose with urea in a dry solid mixture has been studied [51]. In addition, a preferentially C6-modified cellulose carbamate derivative has been obtained [52]. Heating of cellulose with thiourea at 180°C yielded cellulose thiocarbamate [53]. Heat treatment of cellulose isocyanate products has been utilized for the production of urethanes [54]. When ceUuIose was treated with phenylisocyanate at 100 C in DMF in the presence of dibutyltin dilaurate and triethylenediamine, celiuiose bisphenylcarbamate was formed [55]. Treatment of cellulose with urea at temperatures at or above the latter s melting point (where urea decomposes into isocyanic acid and ammonia) has been employed for the production of cellulose carbamates fibers [56]. The advantages and disadvantages of using urea as an intermediate for production of fiber have been discussed [57]. 

Metal chelating amino acid derivatives of cellulose were recently obtained via modification of cellulose with 2,4-toluenediisocyanate, followed by treatment with amino acid ester derivatives [58,59]. Diisocyanates are able to crosslink cellulose chains and/or to yield reactive cellulose isocyanate, depending on the reaction conditions. Sato and his coworkers [60] examined the optimum conditions for the reaction between cellulose and 2,4-toluenediisocyanate and succeeded in introducing 0.30 mol of free isocyanate group per glucose unit. Cellulose isocyanate was further converted into isothiocyanate [61]. This derivative has also been synthesized by condensation of cellulose with 2,4-diisocyanototoluene, followed by hydrolysis and thiophosgene treatment [61]. 

Carboxyl-substituted aminodeoxycellulose (Cell-CH2NH-R-C02H) prepared by the reaction of amino acids with chlorodeoxycellulose adsorbed various heavy metal ions with high efficiency [131]. Cellulose isocyanate reacted with amino acids or their esters in DMSO at low temperature to yield cellulose derivatives containing amino acid residues [60]. These derivatives adsorbed various kinds of metal ions in their free acid state with relatively high... 

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