加压下FeCl_3催化Friedel-Crafts酰化反应合成二苯甲酮

研究了在加压和催化量 Fe Cl3存在的条件下 ,苯甲酰氯和苯发生 Friedel- Crafts酰化反应合成二苯甲酮的工艺。 3 1 5 .2 g苯、1 43 .4g苯甲酰氯和 14.4g Fe Cl3混合于 2 L的高压釜中 ,在压力为 1 .6× 1 0 6～ 1 .8× 1 0 6Pa、温度为 1 80～ 2 0 0°C的条件下反应 8h,经纯化处理得到二甲苯酮 1 49.3 g,收率为 82 .1 %,纯度为 99.8%( GC分析 )     

一种简便的丁二酰亚胺的合成方法

以亚磷酸为催化剂对由丁二酸和氨水合成丁二酰亚胺的工艺进行了探讨 ,实验结果表明 ,反应物的摩尔比为 1∶ 1 .1 ,反应温度初期为 70°C,然后在 1 2 0°C保温 1 h;环合反应温度为 1 95°C,然后在此条件下保温 5 h是较好的工艺参数 ;能获得高产率的丁二酰亚胺。此工艺已在工厂进行了2 0 0 kg级的实际生产 ,结果良好     

由柠檬醛合成柠檬腈的工艺研究

从山苍子提取出的柠檬醛 ,与硫酸羟胺反应生成柠朦肟 ,脱水后可得到柠檬腈。通过正交实验确定了柠朦肟合成的最佳工艺条件是 :n(柠檬醛 )∶n(硫酸羟胺 ) =1∶ 1 .5 ,p H=6～ 7,反应温度为 45°C,反应时间 3 .5 h。柠朦腈合成的最佳工艺条件是 :n(柠檬肟 )∶ n(乙酸酐 ) =1∶ 5 ,反应温度为 1 2 5～ 1 3 0°C,反应时间 1 h。柠檬腈的产率约为 89.7%。     

对苯二酚二苄醚合成的新工艺

采用对苯二酚与氯化苄在适量还原剂 Na2 S2 O4存在下 ,用相转移催化剂催化合成对苯二酚二苄醚的新工艺 ,最佳工艺条件为 :对苯二酚 :氯化苄 :氢氧化钠 =1∶ 3∶ 2 ,还原剂用量为 5 % ,氢氧化钠浓度为 3 3 % ,反应温度 70～ 75°C,反应时间 3 h。此法革除了反应溶剂 ,改善了产品的色泽 ,缩短了反应时间 ,收率 96 .5 5 % ,mp1 2 4 .5～ 1 2 5°C。     

Sol-Gel法制备超细TiO_2粉体条件的研究

通过红外光谱图分析 ,研究了溶胶 -凝胶法制备超细 Ti O2 过程发生的化学物理变化 ,并确定了超细 Ti O2 的生成条件。实验结果表明 :乙醇及水与钛酸丁酯的摩尔比分别为 ( 3～ 9)∶ 1和 ( 2 4～ 2 5 )∶ 1时 ,才能生成稳定的湿凝胶 ;在 5 0～ 60°C,5 .3～ 8.0 k Pa条件下 ,真空干燥 2 4 h,湿凝胶可以转化为干凝胶 ;干凝胶在 5 1 0～ 90 0°C及大于 90 0°C下焙烧 ,分别能得到锐钛矿型和金红石型超细 Ti O2 粉体     

4,4'-双(氯甲基)联苯的合成

研究了 4,4′-双 (氯甲基 )联苯 ( BCMB)的合成方法及工艺条件。以多聚甲醛、联苯、氯化氢气体为原料 ,氯化锌为催化剂 ,经氯甲基化反应合成 BCMB,最佳工艺条件 :多聚甲醛∶联苯∶氯化锌 =2 .1～ 2 .3∶ 1∶ 1.68(摩尔比 ) ,氯化锌∶水 =2 .8(质量比 ) ,反应温度 5 6～ 60°C,反应时间 5 h。产品熔点 12 7-13 3°C,收率 (以联苯计 )达 48%。     

4,4'-双(氯甲基)联苯的合成

研究了 4,4′-双 (氯甲基 )联苯 ( BCMB)的合成方法及工艺条件。以多聚甲醛、联苯、氯化氢气体为原料 ,氯化锌为催化剂 ,经氯甲基化反应合成 BCMB,最佳工艺条件 :多聚甲醛∶联苯∶氯化锌 =2 .1～ 2 .3∶ 1∶ 1.68(摩尔比 ) ,氯化锌∶水 =2 .8(质量比 ) ,反应温度 5 6～ 60°C,反应时间 5 h。产品熔点 12 7-13 3°C,收率 (以联苯计 )达 48%。     

阻燃剂V6的合成研究

以三氯化磷、季戊四醇、氯气及环氧乙烷为原料,四氯化钛为催化剂,通过三步反应合成了阻燃剂V6——四(2-氯乙基)-2,2-二(氯甲基)-1,3-亚丙基二磷酸酯。用IR、元素分析对合成的阻燃剂V6进行了表征,并且对各步的反应条件进行了优化,最佳反应条件为:反应物配比n(季戊四醇)∶n(三氯化磷)∶n(氯气)∶n(环氧乙烷)为1∶2.5∶2.2∶4.2;各步的最佳反应时间依次是2h,3h,4h;适宜的反应温度分别为80°C,23～25°C,80°C。产率达93.5%。     

N-乙酰-L-谷氨酸的制备

以 L-谷氨酸为原料 ,在碱性条件下用乙酸酐作为乙酰化试剂一步合成 N -乙酰 -L-谷氨酸的新工艺。获得最佳反应条件为 :L-谷氨酸与乙酸酐的摩尔比为 1 .0∶ 1 .3 ,酰化试剂分 3次加入 ;反应 p H值为 8～ 1 0之间 ;反应温度控制在 0～ 5°C;酸化结晶 p H值为 1 .0～ 2 .0 ;反应时间 1～ 3h。产品收率为 72 .0 %。     

氯化-3-氰-2-羟丙基三甲胺的合成

研究了氯化 3-氯 - 2 -羟丙基三甲胺 ( CHPTMA)氰化反应生成氯化 3-氰 - 2 -羟丙基三甲胺的工艺 ,得到了最佳工艺条件 :反应温度 40～ 45°C,反应时间 1 .5 h,物料配比 n( CHPTMA) ∶ n( Na CN) 为 1∶1 .0 5。在此条件下 ,产率为 78.8%。     

The influence of thermal treatment on color response of wood materials

In this study, the influence of thermal treatment on color changes of six different wood materials was investigated. Test specimens were subjected to three different temperatures (160, 180, and 200°C) and durations (3, 5, and 7 h). The data obtained were analyzed using variance analysis, and then the statistical analysis of Tukey's test was conducted. After this treatment, the results showed that the color values of the six wood materials changed significantly. It was determined that L* (lightness) values decreased; the minimum change in L* was ～4% for Juniper wood, and the maximum change in L* was ～64% for Beech wood. The values of a* (red coordinate) and b* (yellow coordinate) showed varying levels of increase when the heat treatment conditions were 160°C for 3 to 7 h (not including Cherry wood), but the values began to decrease slowly after treatment at 160°C for 5 h. The ratios of the minimum and maximum color change in a* and b* were determined at 180°C for 3 h in Plane wood, 200°C for 5 h in Hazelnut wood, and 160°C for 3 h and 200°C for 7 h in Beech wood. As temperature and duration were increased, the minimum total color change (ΔE) was ～3.5% for 160°C at 3 h in Cypress wood, and the maximum total color change (ΔE) was ～50% for 200°C at 7 h in Cypress wood. © 2010 Wiley Periodicals, Inc. Col Res Appl, 2010     

Brazing ZTA ceramic and Ti6Al4V alloy directly in air: Excellent oxidation resistance at 800 °C

The Ag-2mol.% CuO braze is adopted to successfully join the zirconia toughened alumina ceramic to the surface aluminized Ti6Al4V directly in air. Fine interfaces are formed between the reactive air brazing braze and the matrix on both sides. Nano-scale diffusion layers are observed at the Ag/ZTA interface. Too low brazing temperatures (≤970 °C) result in the insufficient wettability of Ag–CuO on ceramic, while excessively high temperatures (1030–1090 °C) lead to the over-oxidation of coated Ti6Al4V. A balance is achieved at 1000 °C, at which joints reach the highest shear strength (～56.8 MPa). The oxidation tests at 800 °C for 120 h prove that joints possess excellent oxidation resistance.     

A new Li-based ceramic of Li4MgSn2O7: Synthesis,phase evolution and microwave dielectric properties

A pure-phase Li₄MgSn₂O₇ (L₄MS) was successfully synthesized through optimizing the calcination condition. Microwave dielectric properties of the L₄MS ceramic with the phase evolution were investigated together with its low-temperature sintering. The sample maintains a single L₄MS phase as sintered below 1200?°C, such that τ_f remains a constant value of ～12.4?ppm/°C. Accompanied by the appearance of impurity phases (Li₂SnO₃)_ss and especially (MgO)_ss at higher sintering temperatures, excellent microwave dielectric properties of ε_r?=?13.1–13.5, Q?×?f?=?106,800–126,810?GHz and τ_f ?=?0–?4.2?ppm/°C are obtained in samples sintered at 1215–1260?°C for 4?h. Reduction of sintering temperature using LiF sintering aid also helps achieve pure-phase dense L₄MS ceramic. The L₄MS?+?x wt.% LiF ceramic exhibits ε_r～13.7, Qxf～97,000?GHz (x?≤?3) and τ_f ～8–13?ppm/°C sintered at 850?°C for potential LTCC applications, and ε_r ～13.9, Qxf～146,000?GHz and τ_f ～1.5–6?ppm/°C (x?≥?4) as sintered 1000?°C, exhibiting large potentials for microwave dielectric candidates.     

Effects of temperature and temperature shift on docosahexaenoic acid production by the marine microalge Crypthecodinium cohnii

The effects of temperature and temperature shift on the fatty acid composition and docosahexaenoic acid (DHA, C22∶6n−3) content and productivity of the marine microalga Crypthecodinium cohnii ATCC 30556 were investigated. The microalga grew well over the entire range of temperatures (15–30°C) studied. High temperature favored the growth of the microalga with the highest specific growth rate of 0.092 h⁻¹ at 30°C. In contrast, low temperature favored the formation of polyunsaturated fatty acids. The highest DNA content was obtained at 15°C in the early stationary phase (i.e., 72h). In order to achieve high DHA productivity, a shift from high temperature to low temperature at a later stage of cultivation (i.e., 48h) was also attempted. A temperature shift from 25°C (for 48 h) to 15°C (for 24 h) resulted in an increase in cellular DHA content by 19.9% and productivity by 6.5% as compared to that maintained at 25°C (for 72 h).     

New titanium alloys for blended elemental powder processing

Six powder metallurgy titanium alloys based on commercial compositions were prepared using blended elemental titanium sponge and master alloy powders. The compositions were Ti-6Al-4V; Ti-6Al-4V + 0.5Fe; Ti-6Al-4V + 0.5Ni; Ti-6Al-6V-2Zr + 1Fe + 1Cu; Ti-6Al-6Zr-6Mo and Ti-10V-2Fe-3Al. The powders were cold isostatically pressed at 400 MPa and sintered at 1238 °C for 4 hours. The as-sintered samples had ～ 94% of the theoretical density, uniaxial yield strengths from 710 to 880 MPa and reductions in area from 0.5 to 8%. After a hot isostatic pressing cycle of 900 °C and 100 MPa for 2 h, the samples had ～ 99% of the theoretical density, yield strengths from 840 to 1035 MPa and reductions in area from 5 to 15%.     

Combined Urea Complexation and Argentated Silica Gel Column Chromatography for Concentration and Separation of PUFAs from Tuna Oil: Based on Improved DPA Level

Eicosapentaenoic acid (EPA, 20:5n‐3), docosapentaenoic acid (DPA) isomers (22:5n‐6 and 22:5n‐3) and docosahexaenoic acid (DHA, 22:6n‐3) derived from tuna oil were concentrated by three stages of urea fractionation at various crystallization temperatures and different fatty acid/urea ratios. Thereafter, polyunsaturated fatty acids concentrate containing comparatively enriched DPA levels was purified by argentated silica gel column chromatography. A product containing 22.2 ± 0.6 % EPA, 4.6 ± 0.0 % DPAn‐6, 5.9 ± 0.1 % DPAn‐3 and 42.3 ± 1.2 % DHA was obtained at 1:1.6 fatty acid/urea ratio (w/w) by crystallization at ?8 °C for 16 h, ?20 °C for 8 h, and ?8 °C for 16 h. A DPA isomer concentrate containing 26.1 ± 0.5 % DPAn‐6 and 22.3 ± 0.4 % DPAn‐3 was achieved by argentated silica gel chromatography in the 6 % acetone/n‐hexane solvent fraction (v/v), and the recovery of both fatty acids was 66.1 ± 3.2 and 70.7 ± 2.2 %, respectively. Furthermore, 91.9 ± 2.5 % EPA and 99.5 ± 2.1 % DHA with recoveries of 47.8 ± 2.0 and 56.7 ± 3.3 %, respectively, were obtained in various fractions.     

Rapid Crystallization of Silicalite Nanocrystals in a Capillary Microreactor

Silicalite nanocrystals were synthesized in a pressurized capillary microreactor at 150 °C within 11 min with synthesis solutions aged at 80 or 100 °C for 1–6 h. The effects of aging of the synthesis solution and the reaction pressure were examined. The resulting products were characterized by XRD, DLS, TEM, FT‐IR and TG‐DSC. Aging of the synthesis solution played an important role in shortening the crystallization time of the silicalites. The synthesis pressure should be higher than the saturation vapor pressure of water at 150 °C (～0.5 MPa) and silicalite nanocrystals with crystallinities of 70 % and 100 % could be produced from the synthesis solution aged at 100 °C for 2 h with residence times of 11 min at 0.7 MPa and 1 MPa, respectively. The mean particle sizes of these two samples were 102.2 nm and 166.4 nm, respectively. Thus, the crystallization time of the silicalite nanocrystals is shown to be significantly reduced in the capillary microreactor compared to a traditional batch system.     

Perkin反应合成肉桂酸工艺的改进

采用对苯二酚为阻聚剂 ,对苯甲醛与乙酐以 Perkin反应合成肉桂酸的工艺进行了改进。通过正交试验 ,选择了最佳工艺 ,从而降低了反应温度 ,缩短了反应时间。最佳条件为 n(苯甲醛 ) :n(乙酐 ) :n(碳酸钾 ) =1∶ 3∶ 1 .0 8,对苯二酚 2 % (摩尔分数 ) ,反应时间 1 h,反应温度为 1 80°C,肉桂酸产率可达 74.74% ,熔点 1 32～ 1 33°C。     

Evolution of phase morphology and ‘network‐like’ structure of multiwall carbon nanotubes in binary polymer blends during melt‐mixing

Polyamide6 (PA6)/acrylonitrile butadiene styrene copolymer (ABS) blends with unmodified multiwall carbon nanotubes (MWNTs) were prepared via melt‐blending in a conical twin‐screw micro‐compounder with varying melt‐mixing time. To improve the state of dispersion of MWNTs, non‐covalent organic modifiers for MWNTs have been utilized: sodium salt of 6‐amino hexanoic acid (Na‐AHA) and 1‐pyrene‐carboxaldehyde (PyCHO). PA6/ABS blends with MWNTs have shown a phase morphology transition from ‘matrix‐dispersed droplet’ type to ‘co‐continuous’ type as a function of melt‐mixing time with the exception of 40/60 PA6/ABS blend with PyCHO‐modified MWNTs. Non‐isothermal crystallization studies revealed the heterogeneous nucleating action of MWNTs through the presence of double crystallization exothermic peaks (at ～192^°C and >200^°C) while pure PA6 shows bulk crystallization peak at ～192°C. 40/60 and 60/40 (wt/wt) PA6/ABS blends with 5 wt% unmodified MWNTs exhibited electrical conductivity values of ～3.9 × 10^?11 S/cm and ～4.36 × 10^?6 S/cm, respectively. A significant enhancement in electrical conductivity was observed with Na‐AHA and PyCHO‐modified MWNTs (order of ～10^?6 and ～10^?4 S/cm, respectively). POLYM. ENG. SCI., 55:429–442, 2015. © 2014 Society of Plastics Engineers     

A fully bio-based monomer derived from undecylenic acid,glycerol, and CO2 useful for the synthesis of polyhydroxyurethanes

Undecylenic acid, glycerol, and CO₂ were used as building blocks for obtaining a fully bio-based carbonated monomer, useful for polyurethanes. The functionality of the monomer was close to 3 cyclic carbonates/mol, located in terminal positions. In a first stage, a synthetic triglyceride was obtained with 99% selectivity by esterification of glycerol and undecylenic acid at 160°C. The triglyceride was then epoxidized using H₂O₂ and Amberlyst 15 or Amberlite IR-120 acidic exchange resins at 57°C. The selectivity to epoxide was kept constant at 98% using Amberlite IR-120. Terminal cyclic carbonates were then inserted through epoxide moieties under mild conditions by the chemical fixation of CO₂ at 80°C and 6 MPa in 6 h. A complete conversion was obtained in 6 h reaction while the selectivity to carbonate groups was near to 99% during all the reaction time. An elastomeric polyhydroxyurethane was obtained by aminolysis of the carbonated monomer with ethylenediamine at 70°C, affording a Young's modulus of 22.6 MPa and T_g of −15.2°C. The material showed a good thermal stability below 240°C.