Methylene Bisphenyl Diisocyanate Research Articles

Spectroscopic Characterization of Model Urea, Urethane Compound, and Diamine Extender for Polyurethane−Urea

During the reaction injecting molding process of polyurethane−urea (PUU) based on 4,4‘-methylenebisphenyl diisocyanate (MDI), urethane as well as urea linkages are produced when a highly fluorescent aromatic diamine is used as a chain extender. To explore intrinsic fluorescence as a cure characterization technique, model urethane and urea compounds with similar chemical structures to MDI-based PUU were synthesized. Their fluorescence behavior were compared with that of diethyltoluenediamine (DETDA), which is often employed as a chain extender. The emission maxima for DETDA in polypropylene oxide (PPO) polyol occurred at 336 nm, while the urea (diphenylurea) and the urethane (ethyl N-phenylcarbamate) model compounds showed emission maxima at 301 and 303 nm, respectively. The relative quantum yield for DETDA was determined to be 57 times greater than the urea compound, while the urethane compound possessed a relative quantum yield 11 times greater than the urea compound. The viscosity effect increased DETDA...

Exposure to chemical agents in Swedish aluminum foundries and aluminum remelting plants--a comprehensive survey.

Secondary aluminum melting is mainly performed in sand, die, and static die-casting foundries and remelting plants. In seven Swedish foundries and two remelting plants, the exposure and area concentrations of total dust, metals, organic gases, and vapors were determined mainly as daily, time-weighted averages (TWAs). For most combinations of jobs and agents, the exposure levels were well below the current threshold limits suggested by the American Conference of Governmental Industrial Hygienists (ACGIH). However, high exposure levels of mineral oil mist (geometric mean [GM] = 0.6 mg/m3) were observed in the die-casting process, with a maximum of 4 mg/m3. The findings were similar for total dust (GM = 5.1 mg/m3) and crystalline quartz (GM = 0.05 mg/m3) during molding operations in the sand foundries, maximum air concentrations being 31 mg/m3 and 0.22 mg/m3, respectively. Other agents which occasionally reached high exposure levels included furfuryl alcohol (up to 23 mg/m3 during furan binder use in sand foundries), aniline (up to 2.6 mg/m3 during thermal degradation of cold-box binders), and dimethylethylamine (up to 9 mg/m3) in the cold-box process used in static die-casting and sand foundries. The average aluminum exposure levels (GM = 0.043 mg/m3) were low in all foundries, individual values not exceeding 0.94 mg/m3. The exposures to metals were below 10 percent of their threshold limits. Similarly low levels were detected of polyaromatic hydrocarbons, phenol, formaldehyde, methylenebisphenyl diisocyanate, and phenylisocyanate. In the aluminum remelting plants, a few high exposure levels of total dust (GM = 1.4 mg/m3) up to 8 mg/m3 were detected in furnace workers. Aluminum and other metals were well below 10 percent of their threshold limits, with the exception of a few high concentrations of manganese, up to 0.14 mg/m3. The between-worker variability (GSDB) in the foundries for total dust, aluminum, and oil mist were on the order of 3-4. The heterogenicity of secondary aluminum melting requires assessment of a wide variety of chemical agents. For certain exposures, technical and medical monitoring programs are still needed.

Mechanical and viscoelastic properties of semi‐interpenetrating polymer networks of poly(vinyl chloride)/thermosetting resin blends

AbstractSemi‐interpenetrating polymer networks (SIPNs) of PVC/thermoset were prepared by premixing porous, 150 μm diameter particles of PVC and a small quantity (from 5 to 15% by weight) of a single thermosetting liquid preresin from one of five types (e.g. methylene bis‐phenyl diisocyanate (MDI), oligomeric MDI isocyanates (PAPI), toluene diisocyanate (TDI) prepolymer, epoxy, and vinyl ester resins, respectively). Two roll milling of these mixtures was followed by hot‐press curing. Mechanical testing indicated that most of these blends exhibited increased tensile, impact, and flexural strengths. The strength increments were greater when going from 0 to 5% thermoset content than when going from 5 to 10% or 10 to 15% thermoset. In many cases, increasing thermoset content from 10 to 15% gave slightly decreased or unchanged tensile, impact, and flexural strengths. This behavior is in accord with a “thermoset dilution effect” in PVC. Most of these SIPN blends exhibited a tan δ peak temperature lower than that for pure PVC in the glass transition region. The tan δ peak temperatures were progressively lowered as the amounts of thermoset increased. Also, a single distinct peak existed in the E″ curves for most of the blends. Only the PVC/epoxy (90/10) blend showed two peak maxima in E″ vs. temperature curves. All blends exhibited peak E″ values at a lower temperature than those of PVC which had been exposed to the same processing temperatures. These observations seem to rule out the presence of large domains of PVC, which are phase‐separated from PVC/thermoset SIPN, and pure thermoset domains. A substantial amount of the added thermoset appears to exist in SIPN type phases in these five blend types.

Effect of crosslinking on mechanical and viscoelastic properties of semiinterpenetrating polymer networks composed of poly(vinyl chloride) and isocyanate crosslinked networks

Semiinterpenetrating polymer networks (SIPNs) of PVC/isocyanate/poly-triol were prepared by premixing small (150 μm dia.) porous (30% voids) unplasticized PVC particles, 10% by weight of isocyanate, and a triol at different OH/NCO mol ratios. Three types of isocyanates (methylene bis-phenyl diisocyanate (MDI), oligomeric MDI isocyanates (PAPI), and toluene diisocyanate (TDI) prepolymer/polytriol) were used. Two-roll milling was followed by hot-press curing. The tensile, flexural, and impact strengths increased when small amounts of crosslinked isocyanate networks were created in PVC. The isocyanate/polyol hydroxyl stoichiometry was varied, and the effects of crosslinking on the tensile, impact, and flexural strengths of PVC/isocyanate/triol SIPNs were examined. The strength increments were greater when the OH/NCO mole ratio went from 0 to 0.25, than when it went from 0.25 to 1.0. In many cases, increasing OH/NCO mol ratio from 0.5 to 1.0 decreased tensile, impact, and flexural strengths. Both PAPI and MDI (30% NCO content) gave bigger improvements in the these mechanical strengths than the TDI (only 9.7% NCO). These SIPN blends exhibited lower tan δ peak temperatures and a single distinct loss modulus, E″, peak values at lower temperatures than those of PVC that had been exposed to the same processing temperatures. Substantial amounts of isocyanate networks exist in SIPN phases according to DMTA studies. The OH/NCO ratio did not generally correlate with the decreases in the glass transition temperatures in these three sets of blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1402–1411, 2000

An approach to area sampling and analysis for total isocyanates in workplace air.

An approach to sampling and analysis for total isocyanates (monomer plus any associated oligomers of a given isocyanate) in workplace air has been developed and evaluated. Based on a method developed by the Occupational Health Laboratory, Ontario Ministry of Labour, Ontario, Canada, isocyanates present in air are derivatized with a fluorescent reagent, tryptamine, in an impinger and subsequently analyzed via high-performance liquid chromatography (HPLC) with fluorescence detection. Excitation and emission wavelengths are set at 275 and 320 nm, respectively. A modification to the Ontario method was made in the replacement of the recommended impinger solvents (acetonitrile and 2,2,4-trimethylpentane) with dimethyl sulfoxide (DMSO). DMSO has the advantages of being compatible with reversedphase HPLC and not evaporating during sampling, as do the more volatile solvents used in the Ontario method. DMSO also may dissolve aerosol particles more efficiently during sampling than relatively nonpolar solvents. Several formulations containing diisocyanate prepolymers have been tested with this method in the laboratory. This method has been issued as National Institute for Occupational Safety and Health (NIOSH) Method 5522 in the first supplement to the fourth edition of the NIOSH Manual of Analytical Methods. This method is recommended for area sampling only due to possible hazards from contact with DMSO solutions containing isocyanate derivatives. The limits of detection are 0.1 microgram/sample for 2,4-toluene diisocyanate, 0.2 microgram/sample for 2,6-toluene diisocyanate, 0.3 microgram/sample for methylene bisphenyl diisocyanate, and 0.2 microgram/sample for 1,6-hexamethylene diisocyanate.

Critical Review of Methods of Sampling, Analysis, and Monitoring for TDI and MDI

This article is a critical review of certain methods that have been used for the sampling, analysis, and monitoring of toluene diisocyanate (TDI) and methylene bisphenyl diisocyanate (MDI). Only those methods that have received relatively widespread application are addressed. The review includes a “tutorial style” discussion of basic definitions, and basic principles and procedures of quality control and metrology for sampling, analysis, and monitoring. Recommendations are given for future work in this area. Proper exposure assessment is critical in the risk analysis process, since both exposure and effect measurements are required.

Case studies: Workplace Exposure to Methylene Bisphenyl Diisocyanate

Case studies: Workplace Exposure to Methylene Bisphenyl Diisocyanate

Contact sensitivity induced in mice by methylene bisphenyl diisocyanate

An experimental model of contact sensitivity has been developed in C57BL/6 mice using methylene bisphenyl diisocyanate (MDI), a raw material of polyurethane resins. Sensitization through a single epidermal application of 1% MDI solution in ethyl acetate to the backs of the mice resulted in marked ear swelling. The time course of the swelling was characteristic of delayed-type hypersensitivity and the increment of the ear thickness was compatible with that induced by toluene diisocyanate (TDI). Passive transfer of the MDI-induced contact sensitivity was successfully achieved using lymphocytes from the lymph nodes of MDI-sensitized syngeneic mice, and the effector cells were found to be T cells. Cross reaction between MDI and TDI has shown that MDI is not only a potent contact sensitizer but also can form a contact sensitizer group together with TDI.