A new solid acid SO_4^(2-)/TiO_2 catalyst modified with tin to synthesize 1,6-hexanediol diacrylate

A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,infrared spectroscopy of adsorbed pyridine,temperature-programmed desorption of ammonia and thermal gravimetric analysis.The structure,acidity and thermal stability of the SO4^2-/TiO2-SnO2 catalyst were studied.Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO4^2-/TiO2 catalyst.The total acid sites of the modified catalyst increased and Bronsted acid strength remarkably increased with increasing tin content.The decomposition temperature of sulfate radical in the modified catalyst was 100 ℃ greater and its mass loss was more than twice that of the SO4^2-/TiO2 catalyst.The SO4^2-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid.The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions：crylic acid to 1,6-hexanediol molar ratio = 3.5,catalyst loading = 7%,reaction temperature = 130 ℃ and reaction time = 3 h.The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.

固体酸法合成1,6-己二醇二丙烯酸酯的工艺研究

文章研究开展了固体酸催化剂对1,6-己二醇二丙烯酸酯的合成工艺过程研究,在1,6-己二醇二丙烯酸酯的合成工艺研究中,以自制的XDP催化剂和SO2-4/Ti O2/γ-Al2O3复配型剂型为催化剂,以1,6-己二醇的转化率为评价指标,利用单因素实验,对1,6-己二醇转化率和1,6-己二醇二丙烯酸酯选择性进行分析。利用Box-Behnken响应面法对1,6-己二醇的转化率进行优化,得出最佳的合成工艺条件:酸醇摩尔比3.6∶1,催化剂加入量12.4%,反应时间4.7 h,反应温度133.2℃,在此条件下进行5次平行实验,得到1,6-己二醇转化率为97.8%。

Core-shell Cu@SiO_(2)/SiO_(2) catalyst for 1,6-hexanediol dehydrogenation toε-caprolactone:High activity and stability from core-shell nanostructure

The gas-phase dehydrogenation of 1,6-hexanediol(1,6-HDO)toε-caprolactone(ε-CL)over the high-performance Cu-based catalysts is highly desirable,but with grand challenges,because the Cu nanoparticles(NPs)are easy to be sintered with the low Hüttig temperature(<150℃ vs.>250℃ of reaction temperature).Herein,we report a highly efficient silica-encapsulated nano-Cu catalyst(Cu@SiO_(2)/SiO_(2))prepared via a complexation–impregnation method for the dehydrogenation of 1,6-HDO,exhibiting a 1,6-HDO conversion of 95.3%andε-CL selectivity of 80.0%at 270℃.The catalyst also has the outstanding thermal stability(without sintering up to 270℃ for 100 h on stream),which can be attributed to the effective encapsulation of the SiO_(2)shell.In addition,the reaction network of 1,6-HDO dehydrogenation is proved.Finally,the pyridine-diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and in-situ X-ray photoelectron spectroscopy(XPS)reveal that the Cu^(0) species favor the conversion of 1,6-HDO toε-CL.The synergistic effect of Cu+and Cu^(0) benefits the conversion ofε-CL to 2-methylcyclopentanone(2-MCPN).This study is beneficial for designing the high-performance Cu-based catalysts for 1,6-HDO toε-CL,understanding the reaction network of 1,6-HDO dehydrogenation over the Cu-based catalysts,and offering a strong foundation for the largescale production ofε-CL.

Reductive amination of 1,6-hexanediol with Ru/Al2O3 catalyst in supercritical ammonia

Hexamethylenediamine(HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol(HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al_2O_3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al_2O_3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature,time, H_2 and NH_3 pressure were examined, and the reaction processes were discussed in detail.

Surface Modification of Commercial Aromatic Polyamide Reverse Osmosis Membranes by Crosslinking Treatments

Crosslinking treatments for a commercially available aromatic polyamide reverse osmosis membrane were carried out to improve its chlorine resistance.The crosslinking agents including 1,6-hexanediol diglycidyl ether,adipoyl dichloride and hexamethylene diisocyanate ester with long flexible aliphatic chains and high reactivity with N-H groups were used in the experiments.Attenuated total reflective Fourier transform infrared spectra verified the successful preparation of highly crosslinked membranes by crosslinking treatments.It was suggested that the crosslinking agents were connected to membrane surface through the reactions with amine and amide Ⅱ groups,which is confirmed by surface charge measurements.Based on contact angle measurements,crosslinking treatments decreased membrane hydrophilicity by introducing methylene groups to membrane surface.With increasing amount of crosslinking agent molecules connected to membrane surface,the hydrolysis of unconnected functional groups of crosslinking agent produced polar groups and increased membrane hydrophilicity.The highly crosslinked membranes showed higher salt rejections and lower water fluxes as compared with the raw membrane.Since the active sites(N-H groups) vulnerable to free chlorine on membrane surface were eliminated by crosslinking treatments,the chlorine resistances of the highly crosslinked membranes were significantly improved by slighter changes in both water fluxes and salt rejections after chlorination.

丙烯酸酯增韧聚乳酸的制备与性能

采用1,6-己二醇二丙烯酸酯(HDDA)和聚乳酸(PLA)为原料,通过反应共混法制备了PLA/HDDA共混物,并利用拉力试验机、冲击试验机、扫描电子显微镜、差式扫描量热仪和偏光显微镜研究了HDDA含量对共混物力学性能、断面形貌、热性能和结晶性能的影响。结果表明,HDDA对PLA具有良好的增韧效果,随着HDDA含量的增加,共混物的断裂伸长率和冲击强度显著提高;当HDDA含量为20%时,冲击强度达到8. 2 kJ/m^2,断裂伸长率为62. 8%,而拉伸强度仍保持在较高水平(39. 8 MPa)。HDDA的加入使共混物的冲击断面变粗糙,断裂形态为韧性断裂;随着HDDA含量的增加,共混物中PLA相的玻璃化转变温度逐渐降低,冷结晶温度先升高后降低,结晶度则先减小后增大。