MDI的生产及市场

介绍了国内外MDI的生产、应用及市场情况 ,并对影响MDI市场的关键因素进行了分析     

H_(12)MDI型端硅烷基聚氨酯预聚物的合成

以H12MDI(4,4′-二环己基甲烷二异氰酸酯)和不同Mr(相对分子质量)的PPG(聚丙二醇醚)为原料、DBTDL(二月桂酸二丁基锡)为催化剂和A1170[双-(γ-三甲氧基硅丙基)胺]为封端剂,合成了SPU(端硅烷基聚氨酯)预聚物。研究结果表明:SPU预聚物的合成包括PU预聚物的合成和封端反应两个阶段;PU(聚氨酯)预聚物的合成反应速率随催化剂用量增加而加快,当催化剂用量约为50 mg/kg、反应温度为80℃和反应时间为4 h时,PU预聚物的合成反应可基本完成;封端反应的最佳温度为70℃,反应3 h后体系—NCO含量可降至0;通过调节R值[即n(—NCO)/n(—OH)]和PPG的Mr,可使SPU预聚物的黏度控制在56.70~229.92 Pa·s范围内。     

1,5-萘二异氰酸酯型聚氨酯弹性体的制备及性能

通过预聚法合成了以己二酸乙二醇丙二醇二酯、聚四氢呋喃二醚、1,5-萘二异氰酸酯(NDI)、甲苯二异氰酸酯(TDI)、1,4-丁二醇及4,4'-二氨基-3,3'-二氯二苯甲烷为主要原料的聚氨酯弹性体。通过水解后弹性体的拉伸、撕裂等力学性能保持率的比较,发现NDI型聚氨酯弹性体比TDI型具有更好的水解稳定性;通过不同温度下和热空气老化后弹性体力学性能保持率的对比,证明NDI型聚氨酯弹性体的耐热稳定性要优于TDI型。     

Formation of polyurethane networks based on poly(propylene glycol) and 4,4′-diphenylmethane diisocyanate

The formation of a polyurethane network from poly(propylene glycol) terminated with 4,4′-diphenylmethane diisocyanate and from 1,1,1-trimethylolpropane was investigated by light scattering and electron microscopy. The results indicate that the nonhomogeneities are formed in the system and that their size increases with increasing conversion up to gel point. The formation of nonhomogeneities is explained by strong intermolecular interactions with the participation of urethane groups; the existence of such interactions was confirmed on model systems by using inverse gas chromatography. An addition of dimethylformamide to the reaction mixture accelerates the reaction and suppresses nonhomogeneities.     

Some technological aspects of methane aromatization (direct and via oxidative coupling)

The investigations on transformation of methane to benzene and naphthalene have been carried out in aim to verify and supplement earlier reported data and on this basis to estimate real industrial perspectives of the CH₄ aromatization concept, the main challenges and barriers. Methane aromatization (direct and via oxidative coupling) has been studied over Mo/HZSM-5 catalyst used both for direct methane dehydroaromatization and for aromatization of methane oxidative coupling (OCM) products. The effects of Mo content in the catalyst, temperature, space velocity, the presence of CO₂, CO, H₂O, C₂H₄, C₂H₆ and their mixtures in the feed have been studied. The effectiveness of the catalyst regeneration in the air was also examined. All results were confronted with the literature data and analyzed from technological point of view. It was confirmed that direct CH₄ aromatization process was characterized by a low CH₄ single-pass conversion, low single-pass yields of the main products (benzene, hydrogen and naphthalene) and a low catalyst stability (rapid catalyst deactivation). Various possible technological schemes were analyzed. It was concluded that real industrial chances of direct methane aromatization or aromatization via OCM would depend largely on the advancement in the cost-effective separation techniques. The methane aromatization concept was also confronted with other methane conversion processes.     

Synthesis and properties of highly hydrophilic polyurethane based on diisocyanate with ether group

Highly hydrophilic polyurethane elastomers (PUEs) were synthesized from 1,2-bis(isocyanate) ethoxyethane (TEGDI), poly(ethylene oxide-co-propylene oxide) copolyol (EOPO) and 1,4-butane diol/1,1,1-trimethylol propane (75/25) (wt/wt) by a prepolymer method. 4,4′-Diphenylmethane diisocyanate (MDI)-based PUEs were synthesized as a control as well. Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) measurements revealed that the degree of microphase separation of the TEGDI-based PUEs was much weaker than for the MDI-based PUEs. Young's modulus and elongation at break of the TEGDI-based PUEs were quite lower and larger than for the MDI-based PUEs, respectively. This is due to quite weak cohesion force of the hard segment chains in the TEGDI-based PUEs. The degree of swelling of the TEGDI-based PUEs was five times larger than for the MDI-based one. This is associated with the hydrophilic nature of TEGDI and weak cohesion force in the TEGDI-based PUEs.     

The effect of irradiation on morphology and properties of the PET/HDPE blends with trimethylol propane trimethacrylate (TMPTA)

The mechanical properties of poly(ethylene terephthalate)/high-density poly(ethylene) (PET/HDPE) blends were improved by γ-ray irradiation combined with using a cross-linking agent—trimethylol propane trimethacrylate (TMPTA). The effect of the weight ratio of PET/HDPE, the content of TMPTA and the absorbed dose on the phase morphology and the mechanical properties of the PET/HDPE blends were investigated through scanning electron microscopy (SEM), gel fraction, Fourier transform infrared spectroscopy (FTIR), tensile and impact tests. SEM images showed that the phase structure changed significantly as TMPTA coexistence. The results of tensile and impact tests indicated that their mechanical properties depended on their structures. FTIR spectra suggested that a new structure of HDPE-g-PET was generated. When the weight ratio of PET/HDPE blend was 80/20, the content of TMPTA was 1 wt% and the absorbed dose was 30 kGy, the tensile strength, elongation at break and impact strength of irradiated blends were improved greatly compared with non-irradiated blends.     

Cure and properties of unfoamed polyurethanes based on uretonimine modified methylene–diphenyl diisocyanate

The curing behaviour of a series of polyurethanes based on modified methylene–diphenyl diisocyanate (MDI) and poly(propylene oxide) polyols was studied using isothermal Fourier‐transform infrared spectroscopy (FTIR), temperature‐ramped differential scanning calorimetry (DSC) and adiabatic exotherm experiments. The effects of catalyst type and content, and of polyol molecular weight and functionality on the curing behaviour of the material were investigated. Increasing catalyst concentration or decreasing the polyol molecular weight raised the rate of reaction and shifted the DSC peak exotherm temperature to lower temperatures, but the heat of reaction was effectively constant. A marked increase in reaction rate was observed when a 1 °‐alcohol‐based polyol (from ethylene oxide end‐capping) was used in place of the standard poly(propylene oxide) end‐capped 2 °‐polyols. FTIR isocyanate conversion during polyurethane formation for a range of dibutyltin dilaurate (DBTDL) concentrations was satisfactorily fitted to second‐order kinetics. An approximately linear relationship between DBTDL catalyst concentration and reaction rate constant was found, but increasing the concentration of DBTDL was found to have no significant effect on the magnitude of the activation energy. The activation energy for polymerization was found to be independent of the molecular weight of the diol or triol systems. Dynamic mechanical thermal analysis revealed a linear increase of the glass transition temperature with decreasing triol weight fraction, and was in good agreement with a theoretical model based on copolymer and crosslinking effects. © 2000 Society of Chemical Industry     

The effect of diisocyanate isomer composition on properties and morphology of polyurethanes based on 4,4′-dicyclohexyl methane diisocyanate and mixed macrodiols (PDMS–PHMO)

Three series of polyurethanes were prepared having 42 wt % hard segments based on 4,4′-dicyclohexyl methane diisocyanate (H₁₂MDI) with trans,trans isomer contents in the 13 to 95 mol % range and 1,4-butanediol chain extender. The soft segments were based on macrodiols poly(hexamethylene oxide) (PHMO, MW 696), α,ω-bishydroxyethoxypropyl polydimethylsiloxane (PDMS, MW 940), and two mixed macrodiol compositions consisting of 80 and 20% (w/w) PDMS. H₁₂MDI with 35, 85, and 95% trans,trans isomer contents were obtained from commercial H₁₂MDI (13% trans, trans) by fractional crystallization, and all polyurethanes were prepared by a one-step bulk polymerization procedure. The polyurethanes based on the commercial diisocyanate-produced materials soluble in DMF with molecular weights in the 53,655–75,300 range and generally yielded clear and transparent materials. The polyurethanes based on H₁₂MDI with trans,trans contents of 35% or higher yielded materials insoluble in N,N-dimethylformamide (DMF) and were generally opaque. Mechanical properties, such as tensile strength and elongation at break, decreased with increasing trans,trans content, while the Young's modulus and Shore hardness increased. The polyurethanes based on mixed macrodiols yielded higher tensile properties than those of materials based on individual macrodiols. The best mechanical properties were observed for a polyurethane consisting of a soft segment based on PDMS–PHMO (80/20) and a hard segment based on commercial H₁₂MDI and BDO. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were employed to characterize the polyurethane morphology. DSC results confirmed that the polyurethanes based on H₁₂MDI with high trans,trans isomer were very highly phase separated, exhibiting characteristic hard segment melting endotherms as high as 255°C. The other materials were generally phase mixed. FTIR spectroscopy results corroborated DSC results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 573–582, 1999     

Preparation and properties of polyurethane coatings based on acrylic polyols and trimer of isophorone diisocyanate

This paper presents a study on the effect of NCO/OH ratio and an increase in hydroxyl content of acrylic polyols on the properties of polyurethane (PU) coatings. Coating properties studied are gloss, scratch resistance, flexibility and adhesion, mechanical properties include tensile strength, modulus, percent elongation and Shore hardness, while physicochemical properties include chemical resistance and solvent absorption of coated PU samples. A series of acrylic polyols (copolymers) based on butyl acrylate (BA), methyl methacrylate (MMA), styrene and 2-hydroxy ethylacrylate (HEA) were prepared by selecting different percentage of hydroxyl content. Trimer of isophorone diisocyanate (IPDI) was also synthesized in the laboratory. This trimer has trifunctionality. Isocyanurate ring of trimer increases thermal properties of PU. Polyurethanes from these acrylic polyols (containing different percent hydroxyl) and trimer of IPDI were prepared with two different NCO/OH ratios viz, 1.1:1 and 1.2:1. Polyurethanes were coated on substrates for measuring coating properties. Mechanical properties were measured on cast films of the PUs. The experimental results revealed that all polyurethane coatings based on acrylic polyols and IPDI trimer showed good gloss, scratch resistance and excellent adhesion. Thermal stability of these PU samples was found to be better. Physicochemical properties reflected that these PU have excellent chemical and solvent resistance.     

Studies on chain extension of a novel bio‐based engineering elastomer using 4,4‐diphenyl methane diisocyanate as a chain extender

A novel hydroxyl‐terminated bio‐based engineering elastomer (BEE) was synthesized from four bio‐based monomers by adding excess diol. Then the BEE was chain extended in Haake torque rheometer with 4,4‐diphenyl methane diisocyanate (MDI) as chain extender. The molar ratio of NCO/OH, reaction temperature and reaction time of the chain‐extension reaction were studied, and the optimum condition was determined by the gel permeation chromatography (GPC), soxhlet extraction, and fourier transform infrared spectroscopy (FTIR) results. After chain extension, (i) the number‐average molecular weight of BEE became about 3.5 times of the original BEE, (ii) the thermal stability was improved and the crystallization rate was lower, (iii) and the mechanical properties were significantly improved with nano‐SiO₂ as reinforcing filler. The chain‐extended BEE would have potential wide applications in engineering field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40756.     

DSC study of the polyurethane formation from poly(ethylene adipate) and toluene diisocyanate

The reaction of poly(ethylen adipate) (PEA) and toluene diisocyanate (TDI) is studied by means of isothermal DSC. The reaction has the stoichiometry of PEA/TDI = 0.5 and a reaction enthalpy of ΔH = ?65.0 kJ/mol hydroxyl group. The kinetic order is unity over a wide range of temperature and composition of the reaction mixture. The temperature dependence of the first-order rate constant yields an apparent activation energy of 61.1 kJ/mol. The kinetic data are accommodated by the following rate law: A mechanism involving a mobile preequilibrium to accommodate the experimental results is proposed.     

Dielectric and mechanical behaviour of polyurethane networks from poly(oxypropylene)diols or-triols and diisocyanate

Summary Thermally stimulated depolarization currents and dielectric and dynamic mechanical behaviour of polyurethane networks prepared from poly(oxypropylene)diols or-triols and 4,4-diphenylmethane diisocyanate were studied. While the frequency and temperature positions of mechanical and dielectric functions are predominantly determined by the concentration of polar urethane groups in the network chain, the equilibrium modulus correlates with network chain length. The effect of the chain polarity on the shape of loss permittivity vs. frequency curves is more pronounced in the low frequency region than in the high frequency one and is practically the same for stoichiometric and off-stoichiometric networks measured earlier.     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

Structural investigations of polypropylene glycol (PPG) and isophorone diisocyanate (IPDI) based polyurethane prepolymer by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF)-mass spectrometry

The wide application of polyurethane (PU) prepolymers in the reactive hot melt adhesives, sealant and coating sector has made it necessary to understand the changes occurring during polymerization. NCO terminated PU of polypropylene glycol (PPG-2000) and isophorone diisocyanate (IPDI) with NCO/OH ratio 2:1 were prepared. The reaction was continued up to 111 h and the prepolymer obtained at different reaction times were partly removed from the reaction kettle and end-capped with methanol. The end-capped samples were subjected to MALDI-TOF-mass spectral investigation. The peaks at different reaction times in the MALDI-TOF-mass spectra were identified as different PPG homologues. These results suggest that initially the reaction produces monourethane, which subsequently convert to diurethane during the course of reaction.     

Mechanical and dynamic mechanical properties of polyurethane and polyurethane/polyurea elastomers based on 4,4′-diisocyanatodicyclohexyl methane

The physical and thermal properties of hand-cast polyurethane and polyurethane/polyurea elastomers prepared from prepolymers of 20 and 97% trans,trans-4,4′-diisocyanatodicyclohexyl methane (t,t-rMDI) and C₃- and C₄-polyethers chain extended with either 1,4-butanediol (XB) or a commercial mixture of diethyl toluenediamine isomers (DETDA) were determined. The influence of the distribution of geometric isomers of the diisocyanate and of the chain-extender building blocks on these properties is significant. Urethane/ureas are harder and have higher modulus than polyurethanes formed from the same prepolymer. The polyurethane/polyurea elastomers all have somewhat high compression set. Dynamic Mechanical Analysis (DMA) suggests that DETDA extended systems based on 20% t,t-rMDI are phase separated, as illustrated by extended rubbery plateau regions and significantly higher softening points than the corresponding XB extended ones. Uniquely, these elastomers are transparent rather than opaque as typical with most other phase-segregated elastomers. Polyurethanes based on 97% t,t-rMDI are harder and have higher modulus than those based on 20% t,t-rMDI (Desmodur™ W). They have good phase separation and high softening points but they are opaque. Surprisingly, there is not much difference between the physical or thermal properties of polyurethane/polyureas and polyurethanes based on 97% t,t-rMDI. Replacing XB with DETDA gives only moderate improvement in properties, but it does make the elastomers optically clear. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 957–970, 1997     

The structure and elasticity of polyurethane networks: 1. Model networks of poly(oxypropylene) triols and diisocyanate

The equilibrium mechanical and optical behaviour of networks prepared from poly(oxypropylene) triols (PPT) and 4,4′-diphenylmethane diisocyanate (MDI) at various initial molar ratios of reactive groups, $\text{r}{}_{\mathrm{<mtext>H</mtext>}}\text{=}\text{[}\text{OH}\text{]}\text{[}\text{NCO}\text{]}$, in the range 0.6 < r_H < 1.75 have been investigated. The reaction proceeded at 80°C and in the presence of an organotin catalyst to a high conversion of minotirty groups (0.96–1.0). A comparison between experimental and theoretical (based on the theory of branching processes) dependences of the equilibrium modulus, G_e, on r_H or on the sol content, w_s, led to the following conclusions: (1) In the range r_H ? 1 the theory adequately describes experimental dependences, while in the range r_H < 1 excess crosslinking takes place, obviously due to the formation of allophanate groups. (2) In PPT networks with a higher molecular weight (M_n = 2630), G_e is about twice the theoretical value for the front factor A = 1, which is interpreted as a contribution due to permanent interchain interactions. (3) In networks of lower PPT (M_n = 708), experimental G_e values lie between the theoretical ones calculated for A = 1 (affine deformation crosslinks) and $\text{A =}\text{1}\text{3}$ (phantom network). (4) The difference between the eperimental and theoretical moduli for $\text{A =}\text{1}\text{3}$ may be adequately described by using Langley's concept of trapped entanglement contribution (for networks of the longer triol quite satisfactorily, for those of shorter PPT with some systematic deviation) with the same proportionality constant. (5) For correlations between the experiment and theory a generalized plot of the reduced modulus of the weight fraction of the gel proved to be useful.     

The effect of trimethylol propane tetraacrylate (TMPTA) and organoclay loading on the properties of electron beam irradiated ethylene vinyl acetate (EVA)/natural rubber (SMR L)/organoclay nanocomposites

Ethylene vinyl acetate (EVA)/natural rubber (SMR L)/organoclay nanocomposites were prepared by melt blending technique with 0–10 phr organoclay loading and 3 phr TMPTA. Electron beam initiated crosslinking on these samples was carried out using a 3.0 MeV electron beam machine with doses ranging from 50 to 200 kGy. XRD results proved that dispersion of organoclay in the nanocomposites was slightly improved by irradiation with TMPTA. This was further supported by transmission electron microscopy images, where the nanoscale dispersion of organoclay was more homogenous throughout the irradiated polymer matrix compared to nonirradiated samples. TMPTA also increased the gel fraction yield, tensile properties and thermal stability of the irradiated neat EVA/SMR L and its nanocomposites. TMPTA was found to act as a crosslink initiator, which promotes crosslink bridges via free radical mechanism in EVA/SMR L matrix. SEM observation shows that the fracture behavior of the irradiated neat EVA/SMR L and its nanocomposites with TMPTA is significantly different compared to the fracture behavior of the nonirradiated neat EVA/SMR L. The distinct failure surface structure formed in the irradiated samples with TMPTA explains the overall higher value of tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

三羟基丙烷交联聚氨酯/有机硅固相微萃取涂层的研制和应用

通过三羟基丙烷交联聚氨酯/有机硅合成了有机硅/聚氨酯共聚物,将其涂渍于纤维丝上制成了固相微萃取(SPME)探头并安装于SPME装置上,与气相色谱联用测定了水中氯苯等芳香化合物。考察了该共聚物制成的萃取头热稳定性及使用寿命、影响萃取效率的因素。结果表明:有机硅/聚氨酯共聚物涂层具有使用寿命长(100次以上)、成本低、耐高温(270℃)等特点,对样品中氯苯等芳香化合物的萃取效果优于其它探头。本方法检出限低(0.05～0.5μg/L),重现性好(RSD4.8%～5.9%)。