亚氨基二乙腈生产草甘膦中间体双甘膦降低能耗工艺条件改进

N-膦酰基甲基亚氨基二乙酸（简称双甘膦）是合成草甘膦的关键中间体，其合成是将亚氨基二乙酸（或其一钠盐）与甲醛、亚磷酸（或三氟化磷）反应制得。亚氨基二乙酸其合成根据原料的不同，有二乙醇胺脱氢路线和亚氨基二乙腈碱解路线，目前国内有多家草甘膦生产企业采用了亚氨基二乙腈碱解路线。     

IDA路线草甘膦的清洁生产方法和绿色化学合成技术

以二乙醇胺为起始原料,在Cu/Zr催化剂存在下,与氢氧化钠脱氢(氧化)反应生成的亚氨基二乙酸(IDA)二钠盐收率达95%;采用固体IDA法生产双甘膦,反应收率高达97%;双甘膦氧化采用空气(含氧气体)氧化法制备草甘膦,反应收率达95%,草甘膦原药含量达97%以上。并通过采用膜分离技术提浓草甘膦母液、回收脱氢反应废气中的氢气制备双氧水、改进双甘膦制备过程废水和废渣的回收利用,使IDA路线草甘膦生产工艺基本实现了安全、节能、环保和资源充分利用的清洁生产和循环经济,并提高了产品质量,降低了生产成本。     

高浓度双甘膦催化氧化合成草甘膦新工艺

研究了一种新的催化氧化合成草甘膦工艺.以高质量浓度的双甘膦、氧气为原料,活性炭为催化剂,55℃反应,利用高效液相色谱法有效监控反应终点,最后得到草甘膦合成液.草甘膦的收率94.5%,选择性达96.1%.     

卡洛芬合成工艺研究

以环己烯酮和甲基丙二酸二乙酯为起始原料,经Fischer合成法与对氯苯肼盐酸盐环合,用氯酸钠氧化脱氢。水解得到兽用非甾体抗炎药卡洛芬,反应总收率为44．8％。该方法使用氯酸钠替代价格昂贵的DDQ、四氯苯醌等试剂氧化脱氢,使工艺更为简便、经济、绿色。     

亚氨基二乙腈：渐成投资热点产能扩大须谨慎

一、极具发展前景的草甘膦生产中间体作为一种重要的氰化物产品和有机合成中间体，亚氨基二乙腈主要用于合成草甘膦，与草甘膦的生产、发展有着密切的关联关系。用亚氨基二乙腈代替二乙醇胺合成亚氨基二乙酸，再氧化成双甘膦，进而生产草甘膦的工艺路线与传统方法相比可降低原料成本约3000元／t。草甘膦是一种高效、低毒、广谱、内吸传导型茎叶处理灭生性除草剂，由于其优异的除草性能，自1971年美国孟山都研制出来后，迅速在市场上得到推广，目前尚无替代产品。     

甘氨酸法合成草甘膦工艺研究

草甘膦是美国孟山都化学公司开发的一种高效、低毒除草剂。以甘氨酸为原料合成的草甘膦是目前应用最为广泛的除草剂品种。全国甘氨酸生产企业有20余家，2008年消耗量超过30万吨，我们课题组经过技术攻关取得了新的突破，成功的开发出了草甘膦制备方法，该技术可以降低污染物排放，节能降耗，已经规模化生产。实践证明：该技术科技含量高．经济效益好，可以帮助企业走资源节约型、环境友好型的工业化道路。草甘膦的合成方法，有很多专利报导，其合成方法之多，在农药中是少见的。国内外草甘膦的生产合成路线主要有以下几种．     

12-溴-13,14-脱氢松香酸甲酯氧化呋咱的合成与表征

以脱氢松香酸为起始原料合成了一种新型的12-溴-13,14-脱氢松香酸甲酯氧化呋咱。其结构经IR、NMR、MS、元素分析及其单晶结构确证。     

乙腈市场需求情况与技术分析

介绍了乙腈的用途及市场需求情况,综述了国内外合成乙腈的主要工艺方法,在与乙酸氨化路线、乙醇氨氧化路线对比分析的基础上,着重分析了乙醇脱氢氨化法合成乙腈技术,结果表明,用乙醇作为原料直接合成乙腈,原料相对易得、价格低廉,设备腐蚀性小,并且可以副产氢气。从长远来看,只要开发出高效的催化剂,乙醇脱氢氨化合成乙腈技术更有工业应用前景。     

催化合成咔唑的研究进展

综述了催化合成咔唑的研究进展。介绍了有关负载钯和雷尼镍催化剂在脱氢反应中的理论与实验研究,阐述了以1,2,3,4-四氢咔唑为原料,经催化脱氢反应得到咔唑的具体条件,脱氢的效率与催化剂的用量和种类、溶剂的种类以及反应条件等有关。以廉价原料二苯胺合成咔唑,反应由负载钯或铂催化剂催化;2-氨基联苯可经催化氧化反应或贵金属催化的偶联反应得到合成咔唑,这两条路线是制备咔唑的重要途径。     

一种草甘膦循环生产工艺介绍

氯气和黄磷反应生成三氯化磷,三氯化磷和甲醇生成亚磷酸二甲酯,以亚磷酸二甲酯作原料,利用烷基酯法生产草甘膦同时得到草甘膦母液,草甘膦母液分离出的三乙胺回用,分离三乙胺后得碱母液,碱母液通过湿式氧化后,分离磷酸氢二钠的氧化母液,经膜分离,淡液电解得氢氧化钠溶液、氯气和氢气,氢氧化钠用于三乙胺回收、中和稀甲醇,氯气重新用于三氯化磷合成,氢气与氯气制得盐酸用于草甘膦生产。做到钠、氯循环利用。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.