同时测定工业双戊烯中对伞花烃、双戊烯和异松油烯含量的气相色谱方法

采用液体进样方式、毛细管色谱柱分离、火焰离子化检测器检测、外标法定量,建立了一种同时测定工业双戊烯中对伞花烃、双戊烯和异松油烯含量的气相色谱方法。该方法的精密度、重复性、加标回收率均符合要求,能够对工业双戊烯中对伞花烃、双戊烯和异松油烯的含量进行快速、准确定量,为工业双戊烯及其衍生产品的品质评价、利用研究提供技术支持。     

工业双戊烯脱氢裂解反应及其产物分析

通过GC／MS手段分析和鉴定了工业双戊烯原料及其脱氢产物和裂解产物的成分，工业双戊烯原料由7种相对含量超过1．00％的主要成分组成，大戊烯含量为79．08％，对伞花烃含量为10．51％。脱氢产物中有7种相对含量大于1．00％的化合物，裂解产物中有13种相对含量大于0．90％的化合物，分析结果显示主产物对伞花烃的相对含量为79．67％，裂解主产物甲苯的相对含量为58．10％。双戊衡脱氢反应质量损失率为3．45％，双戊烯连续脱氢和裂解反应质量损失率为23．92％。最后讨论了双戊烯脱氢和裂解反应过程。     

工业双戊烯催化脱氢制备对伞花烃放大试验统计

开展了20 t/a规模工业双戊烯连续气相催化脱氢反应放大试验装置的设计和测试统计。在温度280~300℃、氮气流速2.0 L/min、工业双戊烯进料速度4.0 L/h时,上述催化脱氢反应可连续进行,工业双戊烯原料与脱氢粗产物的平均质量比为1.11。经真空精馏装置处理,脱氢粗产物极易被提纯精制。工业双戊烯原料与对伞花烃成品的质量比(即工业双戊烯单耗)分别为1.81(纯度99.0%以上)、1.69(98.0%以上)、1.54(96.0%以上)和1.45(90.0%以上)。纯度99.5%对伞花烃成品的沸点、相对密度和折光指数分别为177.1℃、0.857 g/mL和1.490。该放大统计可为工业双戊烯生产对伞花烃的工程化或工业化开发提供服务。     

工业双戊烯气相催化脱氢制对伞花烃的研究

对工业双戊烯气相催化脱氢制备对伞花烃进行了研究并取得了理想结果。制备条件为：催化剂组成（ＰｄＯ－Ｓ／Ｃ）为ＰｄＯ５．５２％，Ｓ０．２５％，载气流量Ｎ２０．０２０ｍ３／ｈ，反应温度２８０℃，进样量１ｍｌ／ｍｉｎ，产品得率９６６％，对伞花烃含量８５７％。主要副产物为莰烷、异莰烷及对艹孟烷。     

工业双戊烯在精细化学品制备中的应用

介绍了工业双戊烯的来源、组成和物理化学性质。从双戊烯合成香料、催化加氢合成对艹孟烷、双戊烯合成萜烯马来酸酐加合物、双戊烯脱氢合成对伞花烃等4个方面综述了工业双戊烯在精细化学品制备中的应用情况;分析总结了国内外的研究进展、合成方法及反应条件;并提出了解决双戊烯工业化问题的有效途径。     

煤化工下游产品开发及技术进展

煤化工下游产品开发主要涉及4个方面:由合成气直接合成其他产品、甲醇下游产品、尿素下游产品和新型煤化工产品。介绍了这些产品的主要用途及技术进展,对于技术成熟度不高的产品,如甲基丙烯酸甲酯、碳酸二甲酯、聚甲氧基二甲醚等,综述了其技术进展情况,并列出相关科研单位及工业化推广情况。     

丙烯酸的市场及技术状况分析

正面对醋酸产能过剩的状况,大力研发醋酸下游产品,逐步形成以醋酸为基础原料制备大宗化工产品是较好的应对之策。醋酸下游产品的开发及下游产业链的延伸,已经成为国内醋酸企业十分关注并迫切需要解决的问题。但是传统的醋酸及其下游产业链,如醋酸乙烯、对苯二甲酸、醋酸酯、醋酐、氯乙酸、双乙烯酮等未来几年产能增速缓慢,需求的增速明显慢于醋酸产能的扩张速度。因而,寻找新的下游     

我国石化行业分析——炼油、乙烯、芳烃现状和展望

阐述了我国石化行业面临的产能过剩、资源约束、安全环保、节能减排等突出问题。重点分析了炼油行业进展、面临的主要问题和主要替代能源如燃料乙醇、甲醇汽油、煤制油的发展趋势;对乙烯发展现状、原料多元化等进行了分析,从市场需求、准入规模、技术可得性等方面对乙烯和丙烯下游主要产品提出了发展建议;分析了芳烃及下游产品市场情况和甲醇制芳烃、轻烃芳构化等技术进展情况,对PTA精细化下游产品提出了发展建议。     

对孟烷制备工艺改进

采用气质联用仪，微机图谱自动检索对不同来源的双戊烯的化学组成进行了分析。实施分阶段控制反应条件，用雷尼镍催化，使大多数组分均加氢成对孟烷，无需提纯，即达到工业级的要求。     

工业双戊烯——有待开发利用的化工资源

综述了工业双戊烯在合成精细化工产品中的应用研究及利用途径。     

Reactions of unsaturated fatty alcohols. XV. Styrentation of fatty vinyl ether polymers in terpene solvents

Styrenation of fatty vinyl ether polymers in dipentene at 145–165C gives products containing from 20 to 67% styrene by weight but little or no unreacted monomeric styrene remained. After 27 mounths no gelation occurred in these products. Apparently dipentene serves as an effective chain transfer agent during styrenation, keeps the growing polymer chains short, and reduces crosslinking reactions. The amount and type of unsaturation needed in the fatty side chains of the polymer to produce homogeneous products were studied. Ultraviolet and infrared analyses were useful in determining the function of unsaturation in these reactions. Tests on baked films from these products showed that as the amount of styrene was increased, both hardness and alkali resistance were significantly increased. Films prepared from products containing 34 and 67% styrene had Sward hardness values of 10 and 60, and alkali resistance of 33 days and over 65 days, respectively. Films from products prepared in aromatic solventsversus dipentene at the same styrene level showed no difference in hardness, but the alkali resistance of the “dipentene film” was greater. Presented at the AOCS meeting in St. Louis, Mo., 1961. A laboratory of the No. Utiliz. Res. & Dev. Div. ARS, USDA.     

The degradation of guayule rubber and the effect of resin components on degradation at high temperature

Degradation of pure guayule rubber and rubber in the presence of stearic, oleic, linoleic, and linolenic acid, has been studied at high temperatures (from 150°C to 600°C) using thermogravimetric analysis (TGA). On-line mass spectrometric analysis of the products of decomposition has also been done to understand the mechanism of degradation. Degradation of rubber starts around 230°C in air and 330°C in nitrogen. Presence of acids changes the onset of degradation, because of low decomposition temperature of the acids. In the derivative curve, there is one T_max for degradation in nitrogen; two for rubber; and three for rubber containing acids are observed for degradation in air. The activation energy of degradation, as observed by isothermal kinetics, in the 1–10% weight loss region, is 225 kJ/mol in nitrogen and 167 kJ/mol in air. In the 10–100% region, however, the activation energy of degradation measured by the Freeman and Carroll method using dynamic thermogravimetry, is 239 kJ/mol in both nitrogen and air atmosphere. The main products of pyrolysis in inert atmosphere are propylene, propane, isobutylene, methyl butene, isoprene, 2,3-dimethyl cyclopentene, octene, 2,4-dimethylcyclohexene, dipentene, etc. Isoprene is found to be the most abundant. Fragments having m/e values of 136, 121, 107, 93, 79, and 53 are also produced in large quantities. The ratio of concentration of dipentene to isoprene increases marginally with temperature. The concentration of other fragments however increases drastically with temperature. The additives have no effect on the nature of products obtained. The conversion to different fragments depends upon the temperature of degradation and the stability of intermediate products. All smaller molecules are obtained from either dipentene or isoprene. A mechanism of formation of these products has been suggested.     

用工业双戊烯合成萜烯酚醛树脂增粘剂

]本文比较了莰烯、β-蒎烯、α-烯、松节油和工业双戊烯作原料对萜烯酚醛树脂性能的影响，发现用工业双戊烯合成的树脂具有色泽浅、油溶性好、用量少、得丰高、价廉等优点，同时探索了苯酚与甲醛配比及双烯用量对树脂软化点以及在甲苯中溶解性能的影响。     

环氧氯丙烷下游产品生产现状及市场前景

论述了环氧氯丙烷的主要下游产品环氧树脂、合成甘油、氯醇橡胶等的生产现状、市场前景等,指出:我国氯碱行业应该重视这些环氧氯丙烷下游精细化工产品的开发,以促进我国环氧氯丙烷的发展。     

三氟单体系列产品发展现状浅析

三氟单体系列产品在高端氟材料领域具有重要的应用,对三氟单体系列产品中的主要产品三氟氯乙烯（CTFE）、三氟乙烯（Tr FE）、三氟溴乙烯（BTFE）,以及三氟溴乙烯主要下游产品如氟溴油、六氟-1,3-丁二烯、三氟苯乙烯的发展现状进行综述和分析,包括制备工艺、主要应用领域以及当前生产和市场现状等。     

Synthesis and properties of a novel (main‐chain)– (side‐chain) polymeric peroxide

A novel (main‐chain)‐(side‐chain) vinyl polyperoxide, poly(dipentene peroxide) (PDP), an alternating copolymer of dipentene (DP) and oxygen, has been synthesized by thermal oxidative polymerization of DP. The PDP was characterized by ¹H NMR, ¹³C NMR, FTIR, DSC, TGA, and EI‐MS studies. The overall activation energies of the degradation from Kissinger's method were 28 and 33 kcal/mol, respectively, for the endocyclic and acyclic peroxide units. The side‐chain peroxy groups were found to be thermally more stable than the main chain. Above 45°C the rate of polymerization increases sharply at a particular instant showing an “autoacceleration” with the formation of knee point. The kinetics of autoacceleration has been studied at various temperatures (45–70°C) and pressures (50–250 psi). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1549–1555, 2001