Nickel-Catalyzed Selective C(sp2)−F Bond Alkylation of Industrially Relevant Hydrofluoroolefin HFO-1234yf

The selective transition-metal catalyzed C−F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp²)−F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed selective C(sp²)−F bond alkylation of HFO-1234yf with alkylzinc reagents. The resulting 2-trifluoromethylalkenes can serve as a versatile synthon for diversified transformations, including the anti-Markovnikov type hydroalkylation and the synthesis of bioactive molecule analogues. Mechanistic studies reveal that lithium salt is essential to promote the oxidative addition of Ni⁰(L_n) to the C−F bond; the less electron-rich N-based ligands, such as bipyridine and pyridine-oxazoline, feature comparable or even higher oxidative addition rates than the electron-rich phosphine ligands; the strong σ-donating phosphine ligands, such as PMe₃, are detrimental to transmetallation, but the less electron-rich and bulky N-based ligands, such as pyridine-oxazoline, facilitate transmetallation and reductive elimination to form the final product.     

R1234yf/RE170混合工质用于汽车空调的可行性

目前汽车空调常用的制冷剂四氟乙烷(R134a)存在较高的温室效应指数(GWP=1 300),会对环境造成不利的影响。将R1234yf和RE170以质量配比为70:30组成新型混合制冷剂(代号NCUR04)应用于汽车空调中,通过热力学性质、环境特性、循环性能、安全特性、润滑特性方面综合考虑替代R134a的可行性,并与潜在替代制冷剂R1234yf进行对比。研究表明:NCUR04环境性能、热力学性质较R134a和R1234yf优异;单位质量制冷量分别比R134a和R1234yf高24.7%和66.2%;单位容积制冷量比R134a低4.5%,比R1234yf高5.9%;能效比(COP)分别比R134a和R1234yf高1.4%和8.8%;排气温度比R134a低2.4℃,比R1234yf高5.5℃;与POE润滑油互溶性良好。因此,NCUR04替代R134a用于汽车空调具有可行性。     

Influence of water on HFO-1234yf oxidation pyrolysis via ReaxFF molecular dynamics simulation

ABSTRACT

The effect of water molecules on HFO-1234yf oxidation pyrolysis was investigated by ReaxFF-molecular dynamics simulation from 1900 to 4200?K. The initial pyrolysis of HFO-1234yf starts around 2500?K and the water molecules participate in chemical reactions at 2800?K when the reactants pyrolysis reached the highest reaction rate. The primary products including HF, COF₂ and CO₂ are observed at 2600, 2700 and 2900?K, respectively. The influence of water molecules on products is mainly reflected in the promotion activity on the conversion from COF₂ to CO₂ and the generation of HF molecules. Four formation pathways are observed and calculated to further elucidate the procedure of pyrolysis. The main conversion process from H₂O to HF is the ?F?+?H₂O?=?HF+?OH reaction, and the paths from H₂O to ?OH radical and COF₂ to ?CFO radical which are promoted by ?F and ?H radical, respectively, have relatively low energy barriers of 10.44 and 40.29?kJ/mol, and both reaction processes released HF molecules.     

Defluorosilylation of Industrially Relevant Fluoroolefins Using Nucleophilic Silicon Reagents

A number of new magnesium and lithium silyl reagents were prepared and shown to be outstanding nucleophiles in reactions with industrially relevant fluoroolefins. These reactions result in a net transformation of either sp² or sp³ C?F bonds into C?Si bonds by two modes of nucleophilic attack (S_NV or S_N2′). The methods are mild, proceeding with high chemo‐ and regioselectivity. Mechanistic pathways are described that lead to new substitution patterns from HFO‐1234yf, HFO‐1234ze, and HFO‐1336mzz, previously inaccessible by transition metal catalyzed difluorosilylation routes.     

Liquid viscosity of low-GWP refrigerant mixtures (R32 + R1234yf) and (R125 + R1234yf)

In this work, the viscosity of R1234yf, (R32 + R1234yf), and (R125 + R1234yf) in one-phase liquid was measured. The combined expanded uncertainty of viscosity measurement apparatus of confidence of 0.95 (k = 2) is about 2.0%. The measurements of mixtures containing (30.0, 50.0, and 70.0) wt% R32 or R125 were carried out between T = (283.0 and 323.0) K (at intervals of T = 5 K) and P = (1.58 and 2.74) MPa, with a moving piston viscometer (VISCOpro 1600, accuracy ±1.0%) and a Coriolis flowmeter (Ultramass MKII, accuracy ±0.001 g/ml). The measured data were correlated with a hard-sphere (RSH) method and the Grunberg and Nissan method. The average absolute deviations are (2.2 and 3.3)% for the (R32 + R1234yf) and (R125 + R1234yf) mixtures by RSH method, (2.8 and 1.3)% for the (R32 + R1234yf) and (R125 + R1234yf) mixtures by Grunberg and Nissan method, while (3.5 and 2.4)% for the (R32 + R1234yf) and (R125 + R1234yf) mixtures by RefProp V9.1, respectively.     

Theoretical and experimental studies on the thermal decomposition and fire-extinguishing performance of cis-1,1,1,4,4,4-hexafluoro-2-butene

Due to the environmental problems caused by the existing Halon substitutes, it is essential to explore new extinguishants with better environmental friendliness. In this study, in order to evaluate the practicability of cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)) as a potential Halon substitution product, the thermal decomposition mechanism and fire-extinguishing performance of HFO-1336mzz(Z) were studied by using density functional theory calculation and experimental analysis. The computational results show that thermal decomposition of HFO-1336mzz(Z) would result in some products that can further react with active OH˙ and H˙ radicals, which are indispensable reactants in the flame and combustion. Moreover, during the interaction between HFO-1336mzz(Z) and flame, the fire-extinguishing radical CF₃˙ would be produced, indicating the chemical-extinguishing mechanism and the pronounced fire-extinguishing performance of HFO-1336mzz(Z). To explore its actual fire-extinguishing effect, the fire-extinguishing concentration (FEC) of HFO-1336mzz(Z) on methane-air flame was measured in cup-burner. The FEC value of HFO-1336mzz(Z) is 6.84% in volume, which is lower than those of HFC-125 and HFC-116, and is slightly higher than that of HFC-236fa. Both the experimental and theoretical results suggest that HFO-1336mzz(Z) can be a promising candidate for Halon substitute.     

HFO-1234yf与HFC-134a比较分析

总结了HFO-1234yf的最新研究成果,对比分析了HFO-1234yf和HFC-134a的热物性参数及实验表现,结果表明两者的热物性参数及实验表现非常相似,HFO-1234yf是较好的替代制冷剂之一。为了更好的评价该制冷剂,还需要进行全面的热物性测试。     

低GWP的HCFCs替代制冷剂的可行性研究

阐述了目前HCFCs替代的形势、替代制冷剂和替代技术路线。从各个方面介绍了几种有潜力的单一替代制冷剂R32、R161、R1234yf和R1234ze等。并对将来替代制冷剂的发展进行分析,认为混合制冷剂是大势所趋。     

Experimental study on condensation heat transfer in vertical minichannels for new refrigerant R1234ze(E) versus R134a and R236fa

Experimental condensation heat transfer data for the new refrigerant R1234ze(E), trans-1,3,3,3-tetrafluoropropene, are presented and compared with refrigerants R134a and R236fa for a vertically aligned, aluminum multi-port tube. Local condensation heat transfer measurements with such a multi-microchannel test section are very challenging due to the large uncertainties related to the heat flux estimation. Presently, a new experimental test facility was designed with a test section to directly measure the wall temperature along a vertically aligned aluminum multi-port tube with rectangular channels of 1.45 mm hydraulic diameter. Then, a new data reduction process was developed to compute the local condensation heat transfer coefficients accounting for the non-uniform distribution of the local heat flux along the channels. The condensation heat transfer coefficients showed the expected decrease as the vapor quality decreased (1.0-0.0) during the condensation process, as the mass velocity decreased (260-50 kg m⁻² s⁻¹) and as the saturation temperature increased (25-70 °C). However, the heat transfer coefficients were not affected by the condensing heat flux (1-62 kW m⁻²) or by the entrance conditions within the tested range. It was found that the heat transfer performance of R1234ze(E) was about 15-25% lower than for R134a but relatively similar to R236fa. The experimental data were then compared with leading prediction methods from the literature for horizontal channels. In general, the agreement was poor, over-predicting the high Nusselt number data and under-predicting the low Nusselt number data, but capturing the mid-range quite well. A modified correlation was developed and yielded a good agreement with the current database for all three fluids over a wide range of operating conditions.