新型含联萘基团的旋光聚氨酯的制备与性能表征

以旋光联萘二酚(BINOL)和甲苯-2,4-二异氰酸酯(TDI)为原料, 采用氢转移加成聚合法制备了含联萘基团的新型旋光聚氨酯(S-BPU和R-BPU), 并用FTIR, 1H NMR, UV-Vis, CD和DSC/TGA等手段对该聚氨酯进行了结构和性能表征. 结果表明, 当BINOL的光学纯度逐渐增加时, BPU的旋光度和特性粘度逐渐增大, S-BPU和R-BPU的旋光度最高可分别达到-78°和＋54.6°, 具有较高的旋光能力; S-BPU和R-BPU的玻璃化转变温度(Tg)分别达到258.4和286.6 ℃, 热分解温度(Td)分别为305.6和323.6 ℃, 热分解温度比通常的PU材料提高了100 ℃ 左右, 显示了较好的热稳定性; R-BPU和S-BPU的红外发射率分别为0.682和0.618, 显示了较低的红外发射率.     

Preparation and properties of optically active polyurethane/TiO2 nanocomposites derived from optically pure 1,1′-binaphthyl

In this study, optically active polyurethanes (PU) were prepared from chiral 1,1′-binaphthyl (BINOL) and 2,4-toluene diisocyanate (TDI) by the simple hydrogen transfer addition reaction and the high-intensity ultrasonic was applied to the preparation of polyurethane/TiO₂ nanocomposites. The (R)-BPU and (S)-BPU were analyzed by ¹H NMR, FT-IR spectroscopy, thermogravimetric analysis (TGA), UV-vis spectroscopy and circular dichroism (CD) spectra. The results indicated that the polymers exhibited stronger CD signals with positive and negative Cotton effect in their CD spectra. Meanwhile, the nanocomposites were characterized by IR, powder X-ray diffraction, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results manifested the improvement of heat stability of the nanocomposites with the presence of TiO₂ nanoparticles. As a result, the infrared emissivity (8-14 μm) study revealed that the nanocomposites possessed much lower infrared values compared with those of the neat polymers and nanoparticles, respectively.     

Preparation, characterization, and infrared emissivity property of optically active polyurethane/TiO2/SiO2 multilayered microspheres

Optically active polyurethane/titania/silica (LPU/TiO₂/SiO₂) multilayered core–shell composite microspheres were prepared by the combination of titania deposition on the surface of silica spheres and subsequent polymer grafting. LPU/TiO₂/SiO₂ was characterized by FT-IR, UV–vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), SEM and TEM, and the infrared emissivity value (8–14 μm) was investigated in addition. The results indicated that titania and polyurethane had been successfully coated onto the surfaces of silica microspheres. LPU/TiO₂/SiO₂ exhibited clearly multilayered core–shell construction. The infrared emissivity values reduced along with the increase of covering layers thus proved that the interfacial interactions had direct influence on the infrared emissivity. Besides, LPU/TiO₂/SiO₂ multilayered microspheres based on the optically active polyurethane took advantages of the orderly secondary structure and strengthened interfacial synergistic actions. Consequently, it possessed the lowest infrared emissivity value.     

Synthesis,Characterization and Physicomechanical Properties of Novel Water-based Biodegradable Polyurethane Dispersion

Novel water-based biodegradable polyurethane dispersions with an aim to develop environmentally friendly materials, including medicine, various industries, have been prepared in this study. Biodegradable ionic polyurethanes (IPU) were synthesized based on polyols from renewable resources, such as castor oil (CO), in the presence of a polyester polyol and polyethylene glycol (PEG) with hydrophilic property and 1,6-hexamethylene diisocyanate. 1,4-Butanediol and dibutyltin dilaurate, were used as a chain extender and catalyst, respectively. The comprehensive investigations of the structure and properties of five types of synthesized polyurethanes demonstrated biodegradability relationship of these polyurethanes with their structure and composition. In this research effects of different types and content of polyols on biodegradability and physico mechanical properties of prepared PUDs were investigated. The structure, properties and physico mechanical and application behavior of mentioned materials were characterized by ¹H NMR, FTIR spectroscopy, thermogravimetric analysis (TG/DTG) and dynamic mechanical thermal analysis (DMTA). The adhesion properties were measured by pull off test as well. Particle size was measured by dynamic light scattering (DLS) methods. The biodegradability of prepared polyurethane dispersions was confirmed by water uptake, hydrolytic and enzymatic degradation in phosphate buffer saline (PBS) with lipase enzyme in PBS. Results showed that by the incorporation of natural components into the polymer chain, adjusting of hydrophilic and hydrolytic liability properties of soft segments and especial relevant designs, useful polyurethane can be synthesized with desirable property of biodegradability and dispersion stability. Except for one sample, other samples were decomposed totally in enzymatic media.     

Optically active poly(hydroxyurethane)s derived from cyclic carbonate and L-lysine derivatives

The polyaddition of L -lysine hydrochloride and bifunctional five-membered cyclic carbonate 1 was carried out in DMAc in the presence of 1 equiv of DBU or 2 equiv of sodium hydride for 24 h to afford optically active polyurethane 2 bearing hydroxy and carboxyl group. The polyaddition of L -lysinol and 1 was also carried out in NMP to afford higher molecular weight of optically active polyurethane 3 bearing hydroxy group in quantitative yield. These polyurethanes reacted with cupric acetate, sodium tetrahydroborate, and titanium tetraisopropoxide to afford the corresponding crosslinked gels immediately. © 1996 John Wiley & Sons, Inc.     

苯乙烯基噻吩单体及对应的聚脲烷的合成 及其非线性光学性能

一种新型的反式-7-［4-N,N-二(β-羟基乙基胺基苯)］-3,5-二硝基乙烯基-噻吩（HBDT）单体分子及对应的预聚物和聚脲烷被合成和表征.由于噻吩环的电子去局域化能量低于苯环,在受授有机共轭化合物中噻吩环比苯环表现出更有效的共轭和更高的非线性,同时也能使目标分子保持好的光、热稳定性.该单体分子及其对应的聚脲烷在普通有机溶剂中具有良好的可溶性,聚脲烷膜具有好的热稳定性.制备了高质量的聚脲烷膜并进行了电晕极化.单体在甲醇中的紫外可见吸收峰（530nm）与对应未经电晕极化聚脲烷膜的吸收峰基本上没有改变.通过溶剂变色法及简并四波混频（DFWM）法测试了单体的二阶和三阶非线性极化率,其β     

Effects of reaction temperature and acyl group for lipase-catalyzed chiral binaphthol synthesis

Candida antarctica lipase-catalyzed hydrolysis of O-butyryl-BINOL [(±)-3] or O-butyryl-6,6′-dibromo-BINOL [(±)-5] yielded optically active BINOL [(R)-1] or 6,6′-dibromo-BINOL [(R)-4] with high enantiomeric excess at 80 °C. Reaction temperature and acyl group of substrate had a great influence on the reactivity and enantioselectivity, respectively, of lipase-catalyzed hydrolysis for chiral binaphthol synthesis.     

Surface characteristics of chitin-based shape memory polyurethane elastomers

Shape memory polyurethanes (SMPUs) were prepared from polycaprolactone diol 4000 (PCL 4000), 1,4-butanediol (BDO), chitin, dimethylol propionic acid (DMPA), triethylamine (TEA) and 4,4′-diphenylmethane diisocyanate (MDI), and the structures of the synthesized materials were verified by infrared spectroscopy. The effects of chitin and DMPA contents in the polyurethane formulation on surface properties were investigated. DMPA provides function of making hydrophilic polyurethanes. The crystalline structure of chitin enhanced the hydrophobicity of the synthesized materials. Contact angle, water absorption, surface free energy, work of water adhesion and swelling behavior of the synthesized polyurethanes were affected by varying the DMPA and chitin contents. The interactions of the PU films with solvents on the surface were clearly related to the contents of DMPA and chitin in the final polyurethane formulation.     

Synthesis, spectroscopic, and thermal properties of polyurethanes containing zwitterionic sulfobetaine groups

A series of novel polyurethanes (PUs) containing zwitterionic sulfobetaine groups were synthesized from polycarbonatediol with alkyne groups and 3-((2-azidoethyl)dimethylammonio)propane-1-sulfonate using the copper-catalyzed 1,3-dipolar cycloaddition (click) reaction. All the polyurethanes were fully characterized by ¹H NMR, Fourier transform infrared spectrometer, gel permeation chromatography, and elemental analysis; the thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. It has been proved that the thermal stability of zwitterionic sulfobetaine functionalized polyurethanes were greater than the starting alkyne-containing polyurethane. Protein adsorption was measured and it was indicated that PUs with zwitterionic sulfobetain structure are a kind of biocompatible materials with a better anti-protein fouling property compared to the corresponding alkyne-containing polyurethanes.     

苯乙烯基噻吩单体及对应的聚脲烷的合成及其非线性光学性能

一种新型的反式-7-[4-N,N-二(β-羟基乙基胺基苯)]-3,5-二硝基乙烯基-噻吩(HBDT)单体分子及对应的预聚物和聚脲烷被合成和表征.由于噻吩环的电子去局域化能量低于苯环,在受授有机共轭化合物中噻吩环比苯环表现出更有效的共轭和更高的非线性,同时也能使目标分子保持好的光、热稳定性.该单体分子及其对应的聚脲烷在普通有机溶剂中具有良好的可溶性,聚脲烷膜具有好的热稳定性.制备了高质量的聚脲烷膜并进行了电晕极化.单体在甲醇中的紫外可见吸收峰(530nm)与对应未经电晕极化聚脲烷膜的吸收峰基本上没有改变.通过溶剂变色法及简并四波混频(DFWM)法测试了单体的二阶和三阶非线性极化率,其β_μ,χ⁽³⁾和γ值分别为8.443×10^-45esu,1.016×10^-12esu(c=3.96×10^-3mol/L),3.93×10^-32esu.     

The crystallographic structure of a Lewis acid-assisted chiral Brønsted acid as an enantioselective protonation reagent for silyl enol ethers

It is difficult to control the enantioselectivity in the protonation of silyl enol ethers with simple chiral Br?nsted acids, mainly due to bond flexibility between the proton and its chiral counterion, the orientational flexibility of the proton, and the fact that the proton sources available are limited to acidic compounds such as chiral carboxylic acids. To overcome these difficulties, we have developed a Lewis acid-assisted chiral Br?nsted acid (LBA) system. The coordination of Lewis acids with Br?nsted acids restricts the orientation of protons and increases their acidity. Optically active binaphthol (BINOL) derivative.SnCl4 complexes are very effective as enantioselective protonation reagents for silyl enol ethers. However, their exact structures have not yet been determined. We describe here optically active 1,2-diarylethane-1,2-diol derivative.SnCl4 as a new type of LBA for the enantioselective protonation as well as its crystallographic structure. A variety of optically active 1,2-diarylethane-1,2-diols could be readily prepared by asymmetric syn-dihydroxylation. This is a great advantage over BINOL for the flexible design of a new LBA. The most significant finding is that we were able to specify the conformational direction of the H-O bond of LBA, which has some asymmetric inductivity, by X-ray diffraction analysis. The stereochemical course in the enantioselective protonation of silyl enol ethers using LBA would be controlled by a linear OH/pi interaction with an initial step. The absolute stereopreference in enantioselective reactions using BINOL.SnCl4 can also be explained in terms of this uniformly mechanistic interpretation.     

Flame-Retarded Rigid Polyurethane Foam Composites with the Incorporation of Steel Slag/Dimelamine Pyrophosphate System: A New Strategy for Utilizing Metallurgical Solid Waste

Rigid polyurethane (RPUF) was widely used in external wall insulation materials due to its good thermal insulation performance. In this study, a series of RPUF and RPUF-R composites were prepared using steel slag (SS) and dimelamine pyrophosphate (DMPY) as flame retardants. The RPUF composites were characterized by thermogravimetric (TG), limiting oxygen index (LOI), cone calorimetry (CCT), and thermogravimetric infrared coupling (TG-FTIR). The results showed that the LOI of the RPUF-R composites with DMPY/SS loading all reached the combustible material level (22.0 vol%~27.0 vol%) and passed UL-94 V0. RPUF-3 with DMPY/SS system loading exhibited the lowest pHRR and THR values of 134.9 kW/m² and 16.16 MJ/m², which were 54.5% and 42.7% lower than those of unmodified RPUF, respectively. Additionally, PO· and PO₂· free radicals produced by pyrolysis of DMPY could capture high energy free radicals, such as H·, O·, and OH·, produced by degradation of RPUF matrix, effectively blocking the free radical chain reaction of composite materials. The metal oxides in SS reacted with the polymetaphosphoric acid produced by the pyrolysis of DMPY in combustion. It covered the surface of the carbon layer, significantly insulating heat and mass transport in the combustion area, endowing RPUF composites with excellent fire performance. This work not only provides a novel strategy for the fabrication of high-performance RPUF composites, but also elucidates a method of utilizing metallurgical solid waste.     

Highly efficient and stable blue‐light‐emitting binaphthol‐fluorene copolymers: A joint experimental and theoretical study of the main‐chain chirality

In a quest for the main‐chain chiral and highly stable blue‐light‐emitting π‐conjugated polymers, a novel series of soluble conjugated random and alternating copolymers (PF‐BN) derived from fluorene and axially chiral 1,1′‐binaphthol (BINOL) were successfully synthesized by Suzuki coupling polymerization. The polymer structures, optical properties, and their electrochemical properties were investigated by ¹H NMR, TGA/DSC, UV‐Vis absorption, photoluminescence, cyclic voltammetry, circular dichroism spectroscopy, and DFT calculations. The blue‐light‐emitting BINOL‐containing copolymers with proper content of BINOL show highly efficient photoluminescence and ultra highly stable light‐emission with almost unchanged fluorescent spectra after annealing at 200 °C in air for 10 h. The joint experimental and theoretical study of the main‐chain chirality reveals that (1) the chirality of BINOL can be transferred to the polymer backbone, (2) the effective conjugation length is about one BINOL and three fluorenes, (3) the main active chiral block in the copolymers is probably composed by one BINOL with the other two or three fluorenes, and (4) the dihedral angle in the PF‐BN copolymers should be larger than 105°. The incorporation of BINOL into the polyfluorene backbone is an effective way to produce highly efficient and stable blue‐light‐emitting main‐chain chiral conjugated polymer with interesting optoelectronic properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3868–3879, 2010     

Pyrolysis Kinetics and Flammability Evaluation of Rigid Polyurethane with Different Isocyanate Content

Polyurethane (PU) is a typical product of the reaction between isocyanate and polyol, whose ratio would greatly influence material properties. In this paper, to investigate the influence of isocyanate on PU thermal stability and flammability, three kinds of rigid polyurethanes (RPUs) with different isocyanate ratio (1.05, 1.1, and 2.0) were manufactured in a laboratory and employed to have a series of TG (thermogravimetry), DSC (differential scanning calorimetry), and cone calorimetry tests. Kissinger’s method was used to calculate the activation energy and judge their stabilities. However, for such a complex degradation which consists of five reactions, it does not make sense by Kissinger method to obtain only two peak active energies. Considering complexity of PU degradation in air, genetic algorithm (GA) was employed to calculate kinetic triplets of five sub-reactions. The effects of isocyanate contents on each sub-reaction stability were obtained and then analyzed. By cone calorimeter testing, we found that great differences in heat release rate data. However, DSC analysis showed a complete opposite changed trend. Such difference is caused by DSC and calorimeter’s sample morphology, the former using grinded polyurethane powders but the latter polyurethane foam block.     

聚氨酯弹性体的热分解动力学研究

聚氨酯弹性体的热分解动力学研究;聚醚型聚氨酯;聚酯型聚氨酯;热分解;动力学;模型拟合法     

多代超支化水性聚氨酯的合成及表征

以甲苯-2,4-二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)和二乙醇胺(DEOA)为原料通过偶合单体反应法合成了一系列不同代数的超支化水性聚氨酯(HPU),通过红外光谱(FT-IR)和核磁共振波谱（NMR）对其结构进行了表征,利用三检测器的凝胶渗透色谱(GPC3)测定各代产品分子量,采用热重分析仪(TG)和示差扫描量热仪(DSC)对各代HPU及类似化学组成的线性水性聚氨酯(LPU)的热性能进行测试分析对比,结果表明,合成各代HPU产率最高可达91%;TG分析表明各代数HPU与LPU具有相近的初始分解温度,大约在200℃左右,但各代HPU与LPU的分解历程明显不同;DSC结果表明各代HPU产品的玻璃化温度(Tg)明显高于LPU,同时随着代数增高,Tg逐步由115.2℃升高到150.3℃;对比各代HPU掺杂涂膜发现,随代数的增加,光泽度和硬度明显提高。     

Thermal properties of polyurethanes synthesized using waste polyurethane foam glycolysates

In this work thermal transitions and thermal stability of polyurethane intermediates and polyurethanes were investigated. The intermediates were obtained by glycolysis of waste polyurethane (PUR) in the reaction with hexamethylene glycol (HDO). The excess of HDO was not separated from the product after the glycolysis process was finished. The effects of different mass ratio of HDO to PUR foam on selected physicochemical properties (hydroxyl number, Brookfield viscosity and density) were also determined. The polyurethanes were synthesized from the obtained intermediates by the prepolymer method using diisocyanate (MDI) and glycolysis product of molecular mass in range 700/1000 g mol^–1. Hexamethylene glycol, 1,4-butanediol and ethylene glycol were used as chain extender agents. Influence of NCO groups concentration in prepolymer on glass transition temperature (T _g) and storage and loss modulus (E’, E’’) of polyurethanes were investigated by the DMTA method. Thermal decomposition of obtained glycolysates and polyurethanes was followed by thermogravimetry coupled with Fourier transform infrared spectroscopy. Main products of thermal decomposition were identified.     

FTIR-ATR技术研究聚氨酯类文物保护材料的光降解

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.     

Synthesis and characterization of biodegradable poly(ϵ‐caprolactone urethane)s. I. Effect of the polyol molecular weight,catalyst, and chain extender on the molecular and physical characteristics

Biodegradable polyurethanes with potential for applications in medical implants were synthesized in bulk with aliphatic hexamethylene diisocyanate, isophorone diisocyanate, poly(?‐caprolactone) diols of various molecular weights, 1,4‐butane diol, 2‐amino‐1‐butanol, thiodiethylene diol, and 2‐mercaptoethyl ether chain extenders. The catalysts used were stannous octoate, dibutyltin dilaurate, ferric acetyl acetonate, magnesium methoxide, zinc octoate, and manganese 2‐ethyl hexanoate. The synthesis reactions were second‐order. All the materials had narrow, unimodal molecular weight distributions and polydispersity indices of 1.5–1.9. The chemical structures of the polyurethanes, as assessed from ¹H NMR and ¹³C NMR spectra, were in good agreement with the monomer stoichiometric ratios. The glass‐transition temperatures of the materials ranged from ?38 to ?57 °C and were higher for polymers based on isophorone diisocyanate and with higher hard‐segment contents. For polyurethanes with the same hard‐segment content, there was no effect of the material molecular weight on the thermal properties. The tensile strengths of the materials were 12–63 MPa, and the tensile moduli were 8–107 MPa. These increased with an increasing hard‐segment content. The least effective catalyst was magnesium methoxide, and the most effective was ferric acetyl acetonate. Stannous octoate and manganese 2‐ethyl hexanoate were less effective than dibutyltin dilaurate and zinc octoate. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 156–170, 2002     

Synthesis and characterization of fluorinated polyurethane containing carborane in the main chain: Thermal,mechanical and chemical resistance properties

In this study, two fluorinated polyurethanes(FPU) containing carborane groups in the main chains were firstly designed and synthesized via the reaction of hexamethylene diisocyanate trimer(HDI trimer) with fluorinated polyesters(CFPETs) having hydroxyl-terminated carborane groups at room temperature. The structures of carborane fluorinated polyesters(CFPETs) and polyurethanes(CFPUs) were characterized by gel permeation chromatography(GPC), Fourier transform infrared(FTIR) spectroscopy and nuclear magnetic resonance(NMR) measurements. The thermal stability, mechanical properties, Shore A hardness, solvent resistance and acid-alkali resistance of the carborane fluorinated polyurethane films were also studied. Thermogravimetric analysis(TGA) tests manifested that the introduction of carborane groups into the main chain of fluorinated polyurethane endowed the obtained fluorinated polyurethane with excellent thermal stability. The thermal decomposition temperature of carborane fluorinated polyurethane(CFPU) increased by 190 °C compared with that of the carborane-free fluorinated polyurethane(FPU). Even at 800 °C, CFPU showed the char yield of 66.5%, which was higher than that of FPU(34.3%). The carborane-containing fluorinated polyurethanes also showed excellent chemical resistance and prominent mechanical property even after the cured films being immersed into Jet aircraft oil or 37% HCl for 168 h or at high temperature(700 °C). It is found that the structural characteristics of carborane group and the compacted structure of CFPU effectively improve the thermal stability, mechanical property, solvent resistance and acid-alkali resistance of the carborane-free fluorinated polyurethane. These excellent properties make CFPU as the useful raw materials to prepare the high temperature resistant coatings or adhesives for automotive engines, engine or fuel tank of aircraft and other equipment working in high-temperature or high concentrations of acid-alkali environments.