• Applied Chemistry for Engineering
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• v.20 no.3
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• pp.258-265
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• 2009

An anionic polyurethane dispersions (PUDs) were synthesized from the poly (tetramethylene glycol) (PTMG, Mw = 2000 g/mol), mixed isocyanate of dicyclohexylmethane-4,4'-diisocyanate $(H_{12}-MDI)$ and 4,4'-diphenylmethane diisocyanate (MDI), and dimethylol propionic acid (DMPA) as anionic site, following a prepolymer mixing process. Triethylamine (TEA) was used as a neutralization agent and the ethylenediamine (EDA) as the chain extender of the prepolymer. The effects of the DMPA molar ratio and aromatic diisocyanate content in the mixed isocyanate on the particle size and viscosity of PUD were studied. Also, the mechanical and thermal properties of the PUD cast films were discussed according to the molar ratio of DMPA and aromatic isocyanate content. It was found that the particle size and the viscosity of an anionic PUD decreased with increasing DMPA molar ratio but increased with increasing aromatic isocyanate (MDI) content in the mixed isocyanate at the constant DMPA content. Tensile strength of the PUD cast films increased and elongation at break decreased with increasing DMPA content at the constant mixed isocyanate molar ratios. In thermal degradation temperature of PUD cast films, the effect of DMPA contents was great but the effect of aromatic isocyanate contents at the low DMPA content was very slight respectively.

• Journal of the Korean Applied Science and Technology
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• v.27 no.4
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• pp.461-469
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• 2010

Polyurethane adhesive is used in various fields as flexible packaging materials including a food packaging field. Therefore, the purpose of this study is synthesis of polyurethane adhesive which uses aliphatic isocyanate, and compares with aromatic isocyanate. The isocyanates for this test are toluene-2,4-diisocyanate(TDI), hexamethylene diisocyanate(HDI), 4,4-dicyclohexyl ethane diisocyanate($H_{12}MDI$), and isophorone diisocyanate(IPDI). And, the effect of any other diisocyanate are evaluated by several methods as for curing rate test, accelerate weathering test, and peel strength test. The polyurethane adhesive using curing catalyst and HDI has adhesion strength of about 560 g/15 mm between aluminium foil and nylon, about 1,520 g/15 mm between nylon and CPP. Those parameters are similar to polyurethane adhesive with TDI. Also, in case of curing rate, those are similar to TDI type polyurethane adhesive. Moreover, data of ${\Delta}E$ as color variation by QUV tester is equal to 4.12, as 48% against those of TDI type.

• Macromolecular Research
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• v.13 no.5
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• pp.427-434
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• 2005

To improve the performance and reduce raw material costs, blocked isocyanates were prepared with mixture of blocking agents in many industries. Three blocked isocyanates (adducts) namely $\varepsilon$-caprolactam/benzotriazole-blocked 4,4'-diphenylmethane diisocyanate (MDI), toluene-2,4-diisocyanate (TDI) and 4,4'-dicyclohexyl-methane diisocyanate ($H_{12}$MDI) were synthesized. Six reference adducts were also prepared by blocking MDI, TDI, and $H_{12}$MDI with $\varepsilon$-caprolactam ($\varepsilon$-CL) or benzotriazole. The reactions were carried out in acetone medium and dibutyltin dilaurate (DBTDL) was used as a catalyst. The progress of the blocking reaction was monitored by IR spectroscopy. De-blocking temperatures (dissociation temperatures) of these adducts were studied using DSC and TGA and the results were correlated. As expected, the thermal analysis data showed that de-blocking temperature of blocked aromatic isocyanates was lower than that of the blocked aliphatic isocyanates. The low de-blocking temperature of blocked aromatic isocyanate could be due to electron withdrawing benzene ring present in the blocked isocyanates. It was also found that benzotriazole-blocked adducts de-blocked at higher temperature compared with $\varepsilon$-CL-blocked adducts.

• Journal of Adhesion and Interface
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• v.7 no.4
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• pp.53-59
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• 2006

The paper highlights technical advances and introduces recent innovations such as smart curing laminating adhesives for flexible packaging with low migration rates of aromatic isocyanates and amines. Latent reactive one-part systems on the basis of surface deactivated solid isocyanates open up new dimensions for heat setting adhesives and waterborne PU dispersions. The new generation of Purmelt Micro Emission adhesives contains less than 0.1% of MDI monomer, thereby drastically reducing the emission of hazardous isocyanate vapors during processing and setting a significantly improved technical standard in occupational safety. Once again, polyurethane adhesives have demonstrated their unique ability to adapt to new process, product, safety and environmental requirements.

• Journal of the Korean Chemical Society
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• v.20 no.1
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• pp.59-72
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• 1976

The addition of one mole of zinc chloride to 2.33 moles of sodium borohydride in tetrahydrofuran at room temperature gave a clear chloride-free supernatant solution of zinc borohydride after stirring three days and standing at room temperature.The approximate rates and stoichiometry of the reaction of zinc borohydride with 54 selected organic compounds were determined in order to test the utility of the reagent as a selective reducing agent. Aldehydes and ketones were reduced rapidly, aromatic ketones being somewhat slowly, and the double bond of cinnamaldehyde was not attacked. Acyl halides were reduced rapidly within one hour, but acid anhydrides were reduced at a moderate rate. Carboxylic acids, both aliphatic and aromatic, were slowly reduced to alcoholic stage. Esters were inert to this reagent but a cyclic ester, γ-butyrolactone, was slowly attacked. Primary amides were reduced slowly with partial evolution of hydrogen, whereas tertiary amides underwent neither reduction nor hydrogen evolution. Epoxides and nitriles were all inert, as well as nitro, azo, and azoxy compounds. Cyclohexanone oxime and phenyl isocyanate were reduced slowly but pyridine was inert. Disulfide, sulfoxide, sulfone and sulfonic acids were stable to this reagent.

• Journal of the Korean Applied Science and Technology
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• v.19 no.1
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• pp.25-32
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• 2002

Two PU flame-retardant coatings, 2,3-DBPO/N-l00 (DBPON) and 2,3-DBPO/IL (DBPOI), were prepared by curing 2,3-dibromo modified polyester (2,3-DBPO) with isocyanate curing agent Desmodur N-l00 (or Desmodur IL) at room temperature. The physical properties and flame-retardancy of the two coatings were tested and compared. As a result, the pot-life, yellowness index, lightness index difference, $60^{\circ}$ specular gloss, cross-hatch adhesion, viscosity, and accelerated weathering resistance of DBPON were better than those of DBPOI; the fineness of grind of the two coatings were the same; and the drying time, hardness, and abrasion resistance of DBPOI were better than those of DBPON. The flame retardancy of the flame-retardant coatings increased with the content of the flame retarding component, 2,3-dibromopropanoic acid (2,3-DBP); and the LOI values of the two coatings were in a range of $27{\sim}29%$ when the content of 2,3-DBP was 30wt%.

• Elastomers and Composites
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• v.58 no.3
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• pp.121-127
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• 2023

The effect of diisocyanate type on the decomposition temperature of polyurethane (PU) hydrolysis was investigated in a subcritical water medium up to 250℃. PU samples were prepared using different types of diisocyanate: two aromatic diisocyanates (4,4'-methylene diphenyl diisocyanate (MDI) and methyl phenylene diisocyanate (TDI)), one unbranched aliphatic diisocyanate (hexamethylene diisocyanate (HDI)), and two cyclic aliphatic diisocyanates (4,4'-methylene dicyclohexyl diisocyanate (H₁₂MDI) and isophorone diisocyanate (IPDI)). The pressure had no effect on hydrolysis in the range of 70-250 bar. The decomposition temperature of the PU samples increased in the following order: TDI-PU (199℃) < H₁₂MDI ≈ IPDI ≈ HDI (218-220℃) < MDI-PU (237℃). This order of increase in temperature is related to the electron-donating ability of the group to connected to the nitrogen of the urethane unit. When the temperature of the (PU + water) mixture reached the specific decomposition temperature, the PU samples hydrolyzed completely within 5 min into primary amine and 1,4-butanediol. The hydrolysis products from MDI-PU and H₁₂MDI-PU were separated into a liquid phase rich in (BD + water) and a solid low phase rich in amine, whereas the products from TDI-, IPDI-, and HDI-PU existed in a single aqueous phase.

• Journal of the Korean Chemical Society
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• v.21 no.2
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• pp.108-120
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• 1977

The approximate rates and stoichiometries of the reaction of lithium borohydride, with fifty two selected organic compounds containing representative functional groups under the standard condition (tetrahydrofuran, $0^{\circ}$), were studied.Among the active hydrogen compounds,primary alcohols and compounds containing an acidic proton liberated hydrogen relatively fast, but secondary and tertiary alcohols very sluggishly. All the carbonyl compounds examined were reduced rapidly within one hour. Especially, among the ${\alpha}{\beta}$-unsaturated carbonyl compounds tested, the aldehydes consumed one hydride cleanly, however the cyclic ketones consumed more than one hydride even at $-20^{\circ}$. Carboxylic acids were reduced very slowly, showing about 60% reduction in 6 days at $25^{\circ}$, however acyl chlorides reduced immediately within 30 minutes. On the other hand, the reductions of cyclic anhydrides proceeded moderately to the hydroxy acid stage, however the further reductions were very slow. Aromatic and aliphatic esters, with exception of the relatively moderate reduction of acetate, were reduced very slowly, however lactones were reduced at a moderate rate. Epoxides reacted slowly, but amides and nitriles as well as the nitro compounds were all inert to this reagent. And cyclohexanone oxime and phenyl isocyanate were reduced very sluggishly. Last of all, all sulfur compounds studied were inert to this hydride.

• Journal of the Korean Chemical Society
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• v.17 no.4
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• pp.275-285
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• 1973

The addition of one mole of aluminum chloride to three moles of sodium borohydride in tetrahydrofuran gives a turbid solution with enormously more powerful reducing properties than those of sodium borohydride itself. The reducing properties of this reagent were tested with 49 organic compounds which have representative functional groups. Alcohols liberated hydrogen immediately but showed no sign of hydrogenolysis of alkoxy group. Aldehydes and ketones were reduced rapidly within one hr. Acyl derivatives were reduced moderately, however, carboxylic acids were reduced much more slowly. Esters, lactones and epoxides were reduced readily than sodium borohydride or borane. Tertiary amide was reduced slowly, however, primary amide consumed one hydride for hydrogen evolution but reduction was sluggish. Aromatic nitrile was reduced much more readily than aliphatic nitrile. Nitro compounds were inert to this reagent but azo and azoxy groups were slowly attacked. Oxime was reduced slowly but isocyanate was only partially reduced. Disulfide and sulfoxide were attacked slowly but sulfide and sulfone were inert. Olefin was hydroborated rapidly.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.873-881
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• 1994

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.