Study of slabstock flexible polyurethane foams based on varied toluene diisocyanate isomer ratios

The morphological features of three flexible slabstock polyurethane foams based on varied contents of 2,4 and 2,6 toluene diisocyanate (TDI) isomers are investigated. The three commercially available TDI mixtures, that is, 65:35 2,4/2,6 TDI, 80:20 2,4/2,6 TDI, and 100:0 2,4/2,6 TDI were used. The foams were characterized at different length scales with several techniques. Differences in the cellular structure of the foams were noted with scanning electron microscopy. Small‐angle X‐ray scattering was used to demonstrate that all three foams were microphase‐separated and possessed similar interdomain spacings. Transmission electron microscopy revealed that the aggregation of the urea phase into large urea‐rich regions decreased systematically on increasing the asymmetric TDI isomer content. Fourier transform infrared spectroscopy showed that the level of bidentate hydrogen bonding of the hard segments increased with the 2,6 TDI isomer content. Differential scanning calorimetry and dynamic mechanical analysis (DMA) were used to note changes in the soft‐segment glass‐transition temperature of the foams on varying the diisocyanate ratios and suggested that the perfection of microphase separation was enhanced on increasing the 2,6 TDI isomer content. The preceding observations were used to explain why the foam containing the highest content of the symmetric 2,6 TDI isomer exhibited the highest rubbery storage modulus, as measured by DMA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 258–268, 2003     

Slightly Cross‐Linked Polyrotaxanes Made by Linking α‐Cyclodextrins Entrapped in Polyrotaxanes Using Hexamethylene Diisocyanate

In this study polyrotaxane (PR)‐based triblock copolymers were first synthesized via the atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide initiated with the self‐assembly of a distal 2‐bromoisobutyryl end‐capped Pluronic 17R4 with a varying amount of α‐cyclodextrins (α‐CDs) in the presence of CuCl/PMDETA at 25°C in aqueous solution. The α‐CDs entrapped on the copolymer chain were then linked with hexamethylene diisocyanate to give rise to novel slightly cross‐linked polyrotaxanes (SCPRs) in DMF at 45°C. The structures of the PR‐based triblock copolymers and SCPRs were characterized by ¹H NMR, ¹³C CP/MAS, GPC and TGA analyses. The number‐average molecular weight of the resulting SCPRs was nearly three and five times of their precursor after linking with a low polydispersity index range of 1.08–1.28. The thermo‐responsive transition of both PR‐based supramolecular polymers in aqueous solution was demonstrated by turbidity measurements and the self‐aggregated morphologies were also evidenced by TEM observations.     

A Coated Piezoelectric Crystal Sensor for the Determination of 2, 4-Toluene Diisocyanate in Air

Abstract

2, 4-toluene diisocyanate (TDI) in air was detected and determined by a piezoelectric quartz crystal sensor coated with tetrakis(hydroxyethyl)ethylenediamine (THEED)/dithizone(diphenylthiocarbazone) solution (l:3v/v in acetone). The response curve is linear over the concentration range 3–24 ppb of TDI. The sensor can be used for more than 2 months without loss in sensitivity and presented good reversibility and reproducibility. Of the different possible interferents tested, only SO₂ caused a frequency change.     

双亲性氧化石墨烯的合成及生物相容性

以六亚甲基二异氰酸酯(HMDI)为偶联剂, 通过与氧化石墨烯(GO)中的羧基或羟基反应, 形成酰胺键或氨基甲酸酯键活化GO, 然后与TWEEN 80中的羟基反应, 将双亲性TWEEN分子偶联于GO表面, 制备了双亲性GO. 所制备的TWEEN 80接枝GO在水、 氯仿和己烷等溶剂中均可稳定分散. 以PC12及HeLa细胞为细胞模型, 考察TWEEN 80接枝GO所制薄膜的细胞毒性, 形态学观察及细胞活性检测(Calcein AM & EthD-1荧光染色及MTT检测)结果表明其具有良好的生物相容性.     

Synthesis of polyether‐based polyurethane‐silica nanocomposites with high elongation property

The NCO‐terminated prepolymers, prepared by reacting a mixture of poly(tetramethylene glycol) and fumed nanosilica with 4,4′‐diphenylmethane diisocyanate, were chain‐extended with 1,4‐ butanediol to yield polyurethane‐silica nanocomposites. The nanosilica particles were well dispersed in the polyurethane matrix up to 3 wt%. The polyurethane chains in the interfaces were covalently linked to the nanosilica surfaces through urethane bonds. Introduction of the nanosilica into the polyurethane enhanced both tensile strength and elongation of the resulting nanocomposite films. Especially, the elongation at break of the nanocomposite films containing 1 wt% nanosilica was 3.5 times greater than that of the pure polyurethane films. Copyright © 2005 John Wiley & Sons, Ltd.     

气相色谱-质谱法测试胶粘剂中甲苯二异氰酸酯

利用气相色谱-质谱法（GC-MS）测定胶粘剂中甲苯二异氰酸酯含量,研究了进样口温度、初始柱温和柱子极性的影响.试验表明,应选择弱极性柱或非极性柱进行分析,进样口温度设置为200℃,初始柱温为100℃.同时考察了溶剂中的水分含量对于测试的影响,表明试剂除水的重要性.由于标准中多数采用FID检测器,故将GC-MS的结果与GC-FID的结果进行了比较,发现FID的定量结果与MS基本一致.因此,实际的检测过程可以利用GC-MS进行定性定量分析.     

气相质谱法对小鼠体内甲苯二异氰酸酯代谢产物的鉴定分析

应用气相质谱测定小鼠体内甲苯二异氰酸酯(TDI)的代谢产物,并鉴别了其在机体中的代谢途径。TDI色谱条件为Supelco PTETM-5色谱柱(30 mm×0.25 mm×0.25 μm),起始柱温90 ℃保持30 min,以40 ℃·min-1升至280 ℃,保持5.25 min;汽化室温度250 ℃;载气为氦气,流速为1.0μL·min-1。TDI体内代谢产物色谱条件为30+2mX0.25+0.02mm 94%甲基、4%乙烯基键合相弹性石英毛细柱,起始温度30 ℃保持5 min,以8 ℃·min-1升至280 ℃,保持5 min。汽化室温度250 ℃;载气为氦气,流速1.0μL·min-1。质谱条件为电离方式EI,电离能量70eV,连接管温度280 ℃,扫描范围35～350μ;进样量1.0μL。结果表明2,4甲苯二异氰酸酯在血液、尿液、粪便中都被代谢成为2,4甲苯二胺。GC-MS法可有效分离并鉴定TDI体内代谢产物。     

Novel type of SO3H–functionalized nano‐titanium dioxide as a highly efficient and recyclable heterogeneous nanocatalyst for the synthesis of tetrahydrobenzo[b]pyrans

n ‐Butylsulfonated nano‐titania (n‐TiO₂‐NH‐(CH₂)₄‐SO₃H) as a highly efficient and reusable nanocatalyst was prepared by grafting 2,4‐toluene diisocyanate as a bi‐functional covalent linker onto a nano‐titania support, followed by reduction and then ring opening‐reaction of the synthesized amine with 1,4‐butanesultone. Fourier transform infrared spectroscopy, X‐ray diffraction, field‐emission scanning electron microscopy and thermogravimetric analysis were used to characterize the catalyst. The catalytic activity of n‐TiO₂‐NH‐(CH₂)₄‐SO₃H was evaluated in the synthesis of tetrahydrobenzo[b ]pyrans, which affords high yields. Statistical experimental design was applied as an efficient and powerful method to achieve the optimal conditions for this catalytic reaction leading to high yield. Moreover, the catalyst was recovered and reused at least six times without a significant decrease in catalytic activity.     

生物酶催化合成甲苯二氨基甲酸甲酯反应的研究

甲苯二氨基甲酸甲酯(TDC),是碳酸酯法制备甲苯二异氰酸酯(TDI)的中间产物.碳酸二甲酯(DMC)代替光气与2,4-二氨基甲苯(TDA)反应合成TDC,TDC经催化或热分解制得TDI,这是一条没有污染物产生的绿色合成路线.……     

13C-NMR Study of Anomalous Linkages in Polyurethane

Several kinds of model compounds for anomalous linkages in polyurethanes (branching or crosslinking; allophanate and biuret) were prepared. The phenylisocyanate (PHI) based models were identified by IR and NMR. The ¹³C-NMR chemical shifts effects due to the anomalous linkages were determined. The 4,4′-diphenylmethane diisocyanate (MDI) based models were purified incompletely but the characteristic signals of the aromatic carbons were nevertheless found in their spectra. Two types of segmented polyurethane (SPU) were prepared and the anomalous linkages were investigated by ¹³C-NMR. The signals due to the allophanate (Al) and the triphenylbiuret (TB) linkages were observed in the spectra of the SPU prepared at high temperature (>80°C) or prepolymer gels yielded by abnormal reaction. A small signal due to a phenyl carbon of biuret (Bi) linkage was observed even in a normally prepared SPU (polyetherurethane-urea). Employing the phenyl carbon signals was advantageous for the determination of anomalous linkages because of their larger intensities.