水性防腐涂料贮存稳定性的研究

由于水性树脂、颜料和填料等多方面的影响,水性防腐涂料在贮存中容易分层、沉淀,在不同体系中添加不同类型的触变剂可以有效地改善产品的贮存稳定性,使之在不同的环境温度下避免分层、沉淀等问题。     

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料，成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP），用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性，氮气气氛下的初始分解温度为191.9℃，700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%，最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²，总产烟量从10.5 m²下降到5.3 m²。     

Synthesis and properties of castor oil-based polyurethane containing short fluorinated segment

This study successfully incorporated a short-segment fluorine-containing chain extender (2,2,3,3-tetrafluoro-1,4-butanediol [TF]) into castor oil-based polyurethane (COPU) to synthesize TF/COPUs. The interactions between TF and COPU components were identified by Fourier transform infrared and X-ray photoelectron spectroscopies, the results revealed that the increase in the TF content increased the van der Waals forces in C F…CO and the hydrogen bonding force in C F…H N. Atomic force microscopy indicated that the addition of more TF contributed to a higher level of microphase separation in the TF/COPUs. Thermogravimetric analysis showed that the TF component can enhance the thermal resistance of TF/COPUs. Differential scanning calorimetry and dynamic mechanical analysis indicated that the glass transition temperature (T_g) of TF/COPUs increased with the TF content. The stress–strain testing showed that the tensile strength and elongation at break values decreased with the TF content. This tensile behavior may be due to the molecular weight of a TF/COPU decreased with the TF content as evidenced by the gel permeation chromatography results. The hydrolytic degradation tests of dipping TF/COPUs in 3 wt% NaOH solution indicated that TF could lower the surface free energy and enhance the degradation stability of TF/COPUs.     

线性富磷化阻燃剂在聚氨酯泡沫中的应用研究

通过界面聚合法合成了一种线性富磷化阻燃剂（LPRFR），将LPRFR与可膨胀石墨（EG）复配制备了阻燃聚氨酯泡沫（RPUF），使用红外光谱分析仪、核磁共振分析仪对阻燃剂LPRFR的化学结构进行了表征，并通过极限氧指数仪、锥形量热仪、扫描电子显微镜和红外光谱分析仪对RPUF的燃烧性能、微观形貌和化学结构进行了分析。结果表明，仅10 %（质量分数，下同）的LPRFR 与8 %EG复配后，RPUF的极限氧指数（LOI）便达到26.1 %；LPRFR和EG能大幅降低RPUF的热释放速率，并提高基体的成炭能力； LPRFR参与了燃烧过程中的成炭反应，形成了含P—O—C及P=O结构的高质量炭层，有效隔绝了氧气和热量；LPRFR是一种对于聚氨酯泡沫阻燃性能优异的新型阻燃剂。     

聚酯类增塑剂的合成与应用研究进展

综述了国内外聚酯增塑剂的合成及应用的最新研究进展，重点介绍了超支化、生物基、石油基聚酯增塑剂的合成与制备方法以及不同类型聚酯增塑剂在聚氯乙烯(PVC)、淀粉、聚乳酸、聚氨酯弹性体与橡胶制品中的最新应用研究进展；并对聚酯增塑剂未来发展方向做了展望。     

不同硬度PTMG型CPUE与硫化橡胶的性能对比研究

通过改变硬段含量、扩链系数等制备了几种不同硬度的四氢呋喃均聚醚(PTMG)浇注型聚氨酯弹性体(CPUE),讨论了PTMG型CPUE与硫化橡胶(VR)的物理机械性能、拉伸应力应变行为以及动态力学性能的区别。结果表明,随CPUE硬度的提高,材料的刚性增强,力学性能是低硬度VR的数倍。通过对CPUE硬度的调节,可以使之兼具聚氨酯和橡胶的优良性能。在玻璃态温度下CPUE的储能模量随硬度的减小而降低,但都高于VR,而且CPUE的硬度越大,二者相差越大,温度越低,相差也越大;在室温以上温度范围内,CPUE具有比VR更小的力学损耗。     

Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

Optimizing the lignin based synthesis of flexible polyurethane foams employing reactive liquefying agents

The present work is focused on the optimization of a green process based on the employment of by‐products obtained from wood treatments as raw materials for producing flexible polyurethane foams. More specifically, lignin was employed in flexible polyurethane foams in order to partially replace the usual fossil polyols; therefore glycerol (GLY) and glycerin polyglycidyl ether (EJ 300) were used as the polyol fraction for lignin liquefaction. Polypropylene glycol triol was used as a chain extender in different ratios with liquefaction solvents, and polymeric diphenylmethane diisocyanate as an isocyanate fraction. Liquefaction of lignin was performed by microwave irradiation, thus reducing the processing time and energy required compared to present industrial production processes. All the foams were produced in controlled expansion through the adoption of a ‘one‐shot’ approach, using water as a blowing agent and with an isocyanate index (NCO/OH) of less than 100 to improve the flexibility of the foam. This approach allowed for the substitution of up to 12% of common petro derived polyol with commercial soda lignin. Finally, the foams were characterized, presenting properties that could be modulated as a function of lignin content, GLY/EJ 300 ratio and isocyanate index. The qualities of the foams were compatible with existing materials used for furniture and for the interiors of car seats and couches. © 2015 Society of Chemical Industry     

Fire safety of thermoplastic polyurethane based on pyromellitic dianhydride

In this paper, pyromellitic dianhydride (PMDA) was firstly used as fire safety agent for thermoplastic polyurethane (TPU). And, the fire safety improvement of PMDA in TPU was intensively investigated by limiting oxygen index (LOI), smoke density test (SDT), cone calorimeter test, and thermogravimetric/infrared spectroscopy, respectively. It has been found that PMDA could significantly improve the ignition level, and the LOI value increase to 28.5% when 8.0 wt% PMDA was incorporated into TPU; PMDA also could effectively suppress the smoke production and heat release during the combustion process. The peak heat release rate and total smoke release of the sample with 8.0 wt% PMDA were decreased by 68% and 22% compared with pure TPU in cone calorimeter test. The thermogravimetric/infrared spectroscopy results showed that PMDA could improve the thermal stability of TPU composites at high temperature and increased the release of CO₂, H₂O, and so on. All results confirmed that PMDA would have a good prospect in reducing the fire hazard of TPU.     

Polyurethane/doxorubicin nanoparticles based on electrostatic interactions as pH‐sensitive drug delivery carriers

In order to obtain a pH‐sensitive delivery carrier for doxorubicin (DOX), DOX‐loaded polyurethane (PU·DOX) nanoparticles were readily prepared in water by electrostatic interactions between amphiphilic polyurethane with carboxyl pendent groups (PU‐COOH) and doxorubicin hydrochloride (DOX·HCl). The structures of the products obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy, gel permeation chromatography, UV–visible spectroscopy, dynamic light scattering and transmission electron microscopy. The average hydrodynamic size of the PU·DOX nanoparticles was around 182 nm with negative surface charge (?1.1 mV) and a spherical or rodlike shape. PU·DOX nanoparticles had a higher drug‐loading content of 14.1 wt%. The in vitro drug release properties of PU·DOX nanoparticles were investigated at pH 4.0, 5.0 and 7.4, respectively. PU·DOX nanoparticles exhibited a good pH‐sensitive drug release property, but there was almost no release of DOX from PU·DOX nanoparticles at pH 7.4. The in vitro cellular uptake assay and the Cell Counting Kit‐8 assay demonstrated that PU·DOX nanoparticles had a higher level of cellular internalization and higher inhibitory effects on the proliferation of human breast cancer (MCF‐7) cells than pure DOX. The enhancement of the inhibition effects resulted from increasing apoptosis‐inducing effects on MCF‐7 cells, which was related to the enhancement of Bax expression and the reduction of Bcl‐2 expression confirmed by terminal deoxynucleotidyl transferase mediated dUTP nick end labeling (TUNEL) assay, real‐time polymerase chain reaction (PCR) assay and western blot assay. © 2018 Society of Chemical Industry