聚氨酯胶粘剂无溶剂化技术

出于环保上的考虑,溶剂型聚氨酯胶粘剂的趋势是转换为非溶剂型胶粘剂,转换的技术有三种,即不使用溶剂、使用水作溶剂或采用热熔技术。

连续化无溶剂法亚磷酸二甲酯工艺改造

针对目前亚磷酸二甲酯工业生产中存在的问题 ,通过对其合成工艺条件的研究 ,分析了该工艺的优缺点 ,提出了改进思路 ,设计了符合该合成路线的流程 ,并对连续化无溶剂法合成路线进行了改进。建立了中试装置并进行现场调试 ,集中优化了影响无溶剂法亚磷酸二甲酯收率的工艺操作参数 ,取得了满意的结果。

绿色化学与防腐蚀技术的发展方向

以绿色化学为基础 ,探讨了绿色防腐蚀技术研究开发的思路和方法 ,包括腐蚀设计的绿色化、防腐蚀材料合成与制备用原料的绿色化、采用无毒无害溶剂、采用无溶剂化反应以及发泡剂和喷雾剂的绿色化等 .

用铝镁锌系列合金颜料制备阳极型强屏蔽环氧重防腐涂料的研究

对采用铝锌、铝镁和铝镁锌合金粉体为颜料制备的阳极型强屏蔽环氧重防腐涂料涂层性能和防护机理进行了研究,同时还开展了对涂料的无溶剂化研究。通过对固化剂与助剂的优选,制得了融良好的施工性能和优异的防腐性能于一体的无溶剂铝镁锌阳极型强屏蔽涂料,其与有溶剂铝镁锌涂料的最佳颜料体积浓度相同,但电阻更高,屏蔽隔离能力更强。

环保防腐涂料开发的技术难点与实施对策

随着国家对环境整治力度的加大,涂料生产企业迫于政策形势的压力,纷纷开始通过调整产品结构朝向绿色方向转型升级。防腐涂料向环保产品转型有3个发展方向:一是高固含化,二是无溶剂化,三是水性化。然而,在转型研发过程中遇到诸多难题,该如何突破这些技术瓶颈,本文通过研发实践进行了总结,将经验分享给业界同仁。

胶粘剂的环保问题与对策

本文论述了胶粘剂中存在的环保问题，简要分析了主要污染物及其危害，提出了胶粘剂符合环保要求的发展方向是水性化、无溶剂化、固体化、低毒化。采用先进的清洁生产工艺，生产环保型绿色胶粘剂是当代可持续发展的迫切需要。

Influences of process parameters on solvent-free toluene oxidation over Au /γ-MnO_2 catalyst

γ-MnO2 nanorobs and Au/γ-MnO2 catalysts were synthesized and characterized by the X-ray powder diffraction XRD the scanning electron microscope SEM and transmission electron microscope TEM . The characterizations show that Au particles are well dispersed on the surface of γ-MnO2 nanorobs with a particle size of about 10 nm.The catalytic performance is evaluated in solvent-free toluene oxidation with oxygen. The influences of several process parameters such as reaction time reaction temperature initial oxygen pressure and catalyst amounts on the catalytic performance are studied.Catalytic results reveal that Au/γ-MnO2 catalyst has a unique selectivity to benzaldehyde and all these factors greatly influence the conversion of toluene and selectivity of bezaldehyde benzoic acid and benzyl benzoate.However these factors have slight influence on the selectivity of benzyl alcohol.

Selective suppression of toluene formation in solvent-free benzyl alcohol oxidation using supported Pd-Ni bimetallic nanoparticles

The solvent‐free oxidation of benzyl alcohol was studied using supported Pd‐Ni bimetallic nanoparticles.Compared with monometallic Pd,the addition of Ni to Pd was found to be effective in suppressing the nondesired product toluene,thereby enhancing the selectivity towards benzaldehyde.This result was attributed to a dual effect of Ni addition:the weakening of dissociative adsorption of benzyl alcohol and the promotion of oxygen species involved in the oxidation pathway.

Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides:Effect of the calcination temperature

The effects of calcination temperature on the physicochemical properties of manganese oxide catalysts prepared by a precipitation method were assessed by X-ray diffraction,N2 adsorption-desorption,X-ray photoelectron spectroscopy,H2 temperature-programmed reduction,O2 temperature-programmed desorption,and thermogravimetry-differential analysis.The catalytic performance of each of these materials during the selective oxidation of cyclohexane with oxygen in a solvent-free system was subsequently examined.It was found that the MnOx-500 catalyst,calcined at 500 °C,consisted of a Mn2O3 phase in addition to Mn5O8 and Mn3O4 phases and possessed a low surface area.Unlike MnOx-500,the MnOx-400 catalyst prepared at 400 °C was composed solely of Mn3O4 and Mn5O8 and had a higher surface area.The pronounced catalytic activity of this latter material for the oxidation of cyclohexene was determined to result from numerous factors,including a higher concentration of surface adsorbed oxygen,greater quantities of the surface Mn4＋ ions that promote oxygen mobility and the extent of O2 adsorption and reducibility on the catalyst.The effects of various reaction conditions on the activity of the MnOx-400 during the oxidation of cyclohexane were also evaluated,such as the reaction temperature,reaction time,and initial oxygen pressure.Following a 4 h reaction at an initial O2 pressure of 0.5 MPa and 140 °C,an 8.0% cyclohexane conversion and 5.0% yield of cyclohexanol and cyclohexanone were achieved over the MnOx-400 catalyst.In contrast,employing MnOx-500 resulted in a 6.1% conversion of cyclohexane and 75% selectivity for cyclohexanol and cyclohexanone.After being recycled through 10 replicate uses,the catalytic activity of the MnOx-400 catalyst was unchanged,demonstrating its good stability.

Solvent-free crystallization of ZSM-5 zeolite on SiC foam as a monolith catalyst for biofuel upgrading

Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy.Here,we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a honeycomb structure(ZSM-5/SiC).Characterizations of the ZSM-5/SiC by scanning electron microscopy,N2 sorption,and X-ray diffraction indicate that the zeolite sheath has been ideally coated on the surface of the SiC foam with high purity and crystallinity.Fixing Pd nanoparticles within the ZSM-5 zeolite crystals delivers a bifunctional Pd@ZSM-5/SiC catalyst,which exhibits high activity and selectivity toward diesel range paraffins in the hydrodeoxygenation of methyl oleate,a model molecule for biofuel.In comparison to the powder Pd@ZSM-5,the Pd@ZSM-5/SiC monolith catalyst shows more efficiency,which is attributed to the fast mass transfer and high heat conductivity on the honeycomb SiC structure.The durability test indicates that the Pd@ZSM-5/SiC catalyst is stable under the reaction and high-temperature regeneration conditions.

Efficient Solvent-free Synthesis of Chloropropene Carbonate from the Coupling Reaction of CO_2 and Epichlorohydrin Catalyzed by Magnesium Porphyrins as Chlorophyll-like Catalysts

Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlorophyll-like catalyst,MgTPP showed excellent activity for the coupling reaction of CO2 and epichlorohydrin to chloropropene carbonate,in which the turnover number could reach up to 9200.Moreover,different factors including the amount of catalyst,reaction temperature,pressure and time were systematically investigated and the optimal reaction conditions were obtained(epichlorohydrin 50 mmol,MgTPP 5.0×10- 3mmol,triethylamine 6.25×10-3 mmol,140°C,1.5 MPa,8 h).A plausible two-pathway mechanism for the coupling reaction of CO 2and epichlorohydrin is proposed to propound the catalysis of MgTPP.

A facile solvent-free synthesis strategy for Co-imbedded zeolite-based Fischer-Tropsch catalysts for direct gasoline production

A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.

Scalable synthesis of ultra‐small Ru_(2)P@Ru/CNT for efficient seawater splitting

In this study,an ultra‐fast and simple solvent‐free microwave method was successfully demonstrated using a series of ultra‐small(~2.5 nm)surfactant‐free Ru_(2)P@Ru/CNT heterostructures for the first time.The structure has a high‐density Ru component and Ru_(2)P component interface,which accelerates the hydrogen evolution reaction(HER).The prepared Ru_(2)P@Ru/CNT demonstrated excellent catalytic effects for the HER in alkaline media and real seawater.The experimental results indicate that ratio‐optimized Ru_(2)P@Ru/CNT(Ru_(2)P:Ru=66:34)requires only 23 and 29 mV to reach 10 mA cm^(-2)in 1.0 mol/L KOH and real seawater,respectively.These values are 10 and 24 mV lower than those of commercial Pt/C in 1.0 mol/L KOH(33 mV)and real seawater(53 mV),respectively,making it among the best non‐Pt HER reported in the literature.Additionally,the TOF of Ru_(2)P@Ru/CNT in alkaline freshwater and seawater were 13.1 and 8.5 s^(-1),respectively.These exceed the corresponding values for Pt/C,indicating that the catalyst has excellent intrinsic activity.The high current activity of Ru_(2)P@Ru/CNT in 1.0 mol/L KOH was explored,and only 77 and 104 mV were required to reach 500 and 1000 mA cm^(-2),respectively.After 100 h of durability testing,the catalyst retained excellent catalytic and structural stability in low current density,high current density,and seawater.

Optimization of conjugated linoleic acid triglycerides via enzymatic esterification in no-solvent system

We compared four esterifiable enzymes. The lipase Novozym 435 possessed the highest activity for the conjugated linoleic acid esterification during the synthesis of triglycerides. The triglycerides were synthesized by esterification of glycerol and conjugated linoleic acid （CLA） in a no-solvent system using lipase catalysis. We investigated the effects of temperature, enzyme concentration, water content, and time on esterification. Enzyme and water concentrations of up to 1% of the total reaction volume and a system temperature of 60℃ proved optimal for esterification. Similarly, when the esterification was carried out for 24 h, the reaction ratio improved to 94.11%. The esterification rate of the rotating screen basket remained high （87.28%） when the enzyme was re-used for the 5th time. We evaluated the substrate selectivity of lipase （NOVO 435） and determined that this lipase prefers the 10,12-octadacadienoic acid to the 9,11-octadecadienoic acid.

Surfactant-coated Candida rugosa Lipase as Catalyst for Hydrolysis of Olive Oil in Solvent-Free Two-Phase System

The surfactant-coated Candida rugosa lipase was used as catalyst for hydrolysis of olive oil in two-phase system consisting of olive oil and phosphate buffer without organic solvent. For both the coated and native lipases,the optimal buffer/oil volume ratio of 1.0, aqueous pH 6.8 and reaction temperature 30℃ were determined. The maximum activity of the coated lipase was ca 1.3 times than that of the native lipase. The half-life of the coated lipase in olive oil and the native lipase in phosphate buffer was ca 9 h and 12 h, and the final residual activity was 27% and 20% of their initial values, respectively. The final substrate conversion by the coated lipase was ca 20% higher than that of the native lipase.

Microwave Assisted One-Pot Preparation of Quinoline Derivatives without any Solvent According to Green Chemistry

The convenient and efficient procedure for one-pot preparation of quinaldine derivatives from multi component reaction of anilines, acetone and benzaldehyde without any solvent under microwave irradiation on the surface of alumina impregnated with hydrochloric acid is developed.

Mechanochemical Reaction of Aromatic Ketones and Aldehydes in the Presence of Zn-ZnCl_2

The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinacol coupling and reduction products in varying yields.

Iron catalyzed Michael addition: Chloroferrate ionic liquids as efficient catalysts under microwave conditions

The iron containing ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate （[C4mim]C1/FeCl3; Z = 0.5） proved to be an efficient catalyst for the solvent-free metal catalyzed Michael addition of β-keto esters and enones. Due to the ionic structure of the catalyst, a significant acceleration of the reaction rate was observed under microwave conditions. Furthermore, recycling of the ionic liquid catalyst could be performed after simply distilling off the products.

Solvent-free synthesis of zeolite catalysts

The most used method for preparation of zeolites is hydrothermal synthesis from silicate or aluminosilicate gels at temperatures in the range of 60-200 ℃. Excess water used in the industrial process results in several issues, including high autogeneous pressure, low efficiency, pollution, etc. To solve these problems, several strategies have been developed. This review describes the solvent-free synthesis of zeolites. The combination of solvent-free synthesis and organotemplate-free synthesis can open the pathway to a highly sustainable zeolite synthesis protocol in industry.

Green and efficient cycloaddition of CO2 toward epoxides over thiamine derivatives/GO aerogels under mild and solvent-free conditions

Thiamine derivatives that are cheap, readily available, non-toxic and green are used as heterogeneous catalyst for the generation of cyclic carbonates through cycloaddition of CO_2 to epoxides without the need of co-catalyst and solvent. The interaction between thiamine hydrochloride(VB_1-Cl) and substrates(CO_2 and propylene oxide) was proven by ultraviolet-visible spectroscopy and ~1H nuclear magnetic resonance analysis, and it is deduced that the synergistic action among multi-functional groups(hydroxyl, halide anion and amine) is a favorable factor for cycloaddition reaction. A series of VB_1/GO aerogels were facilely prepared through the addition of aqueous VB_1 derivatives to a suspension of GO in ethanol at room temperature. It was found that the aerogel generated through the interaction of VB_1-Cl with GO shows catalytic activity and stability higher than those of VB_1-Cl. It is because the electrostatic interaction between GO and VB_1-Cl enhances the nucleophilicity and leaving ability of anion. The effects of reaction temperature, catalyst loading, CO_2 pressure and reaction time on CO_2 cycloaddition to propylene oxide were thoroughly studied.