2-氟-4-（4′-乙基）环己基苯硼酸的脱硼酸方法与表征

以2-氟-4-（4′-乙基）环己基苯硼酸化合物异构体的混合物为原料,在催化剂钯碳、相转移催化剂四丁基溴化胺的作用下,于碱性条件下,60～68℃反应6～8h,得到3-（4′-乙基）环己基氟苯芳香烃化合物,它是生产相应的2-氟-4-（4′-乙基）环己基苯硼酸的初始原料。开发出的硼酸化合物的脱硼酸基技术,收率75%,回收有用原材料、降低2-氟-4-（4′-乙基）环己基苯硼酸生产成本、减少硼酸生产中的废物排放量。     

2-氟-4-（4′-乙基）环己基苯硼酸的脱硼酸方法与表征

以2-氟-4-（4′-乙基）环己基苯硼酸化合物异构体的混合物为原料,在催化剂钯碳、相转移催化剂四丁基溴化胺的作用下,于碱性条件下,60～68℃反应6～8h,得到3-（4′-乙基）环己基氟苯芳香烃化合物,它是生产相应的2-氟-4-（4′-乙基）环己基苯硼酸的初始原料。开发出的硼酸化合物的脱硼酸基技术,收率75%,回收有用原材料、降低2-氟-4-（4′-乙基）环己基苯硼酸生产成本、减少硼酸生产中的废物排放量。     

食品级硅藻土脱除湿法磷酸中氟的实验研究

为降低湿法磷酸脱氟成本,以食品级硅藻土替代白炭黑作为脱氟剂对湿法磷酸进行脱氟。研究食品级硅藻土的脱氟效果,分析脱氟成本,并与白炭黑作脱氟剂进行比较。结果表明,利用食品级硅藻土作为脱氟剂,脱氟率为75.64%~82.05%,优于白炭黑的67.94%~76.92%,脱氟成本较白炭黑降低3.72~8.20元/t,除氟后磷酸满足饲料级磷酸盐生产的要求。     

气相色谱-质谱法测定酱油中3-氯-1,2-丙二醇

建立了气相色谱-质谱法测定酱油中3-氯-1,2-丙二醇(3-MCPD)的含量的分析方法。样品采用EXtrelut NT柱吸附,乙醚洗脱,洗脱液中的3-MCPD经苯硼酸衍生,GC-MS方法测定,内标法定量。当样品中3-MCPD添加量为0.025~0.100 mg/kg时,本方法相对标准偏差为1.3%~2.0%,回收率在84.5%~92.9%之间,方法检出限为0.005 mg/kg。     

2,3-二氟-4-羟基苯硼酸的合成

本文以邻二氟苯为原料,利用其定位效应,通过与丁基锂、硼酸三甲酯直接作用得到2,3-二氟苯硼酸,再通过与H2O2反应得到2,3-二氟苯酚。以所合成的2,3-二氟苯酚为原料,通过叔丁基二甲基氯硅烷保护酚羟基,再在低温下与丁基锂、硼酸三甲酯等作用得到2,3-二氟-4-羟基苯硼酸,5步反应总产率为83%。     

一氯五氟苯为原料合成五氟苯酚

以工业废物六氯苯制备六氟苯过程中副产物一氯五氟苯为原料,与镁反应制得五氟苯基氯化镁,反应温度45~50℃,反应时间2.5 h;选用硼酸三异丙酯为硼化剂,制得五氟苯硼酸二异丙酯,反应温度-10~-15℃,反应时间3 h;五氟苯硼酸二异丙酯在酸性条件下水解制得五氟苯硼酸;五氟苯硼酸与过氧化氢反应制得五氟苯酚,反应温度65℃,反应时间5 h。制得的产品纯度99.5%(GC)以上,3步合计收率60.25%。化合物结构经GC-MS、IR、1H-NMR确证。具有原料来源方便,反应条件温和,收率和产品纯度高、成本低的特点。     

3,4,5-三氟-2'-硝基联苯的工艺合成

3,4,5-三氟-2'-硝基联苯是合成杀菌剂氟唑菌酰胺的重要原料.本文考察了以3,4,5-三氟苯硼酸与邻氯硝基苯为原料,Ms-Pd(分子筛负载氯化钯)作为偶联反应催化剂,制备3,4,5-三氟-2'-硝基联苯.通过反应条件优化,实验确定的最佳反应条件是:以Ms-Pd为催化剂,碳酸钾为缚酸剂, DMF为反应溶剂,邻氯硝基苯和3,4,5-三氟苯硼酸进行反应,反应温度40℃,反应时间10h.产品收率92%,液相含量98.3%.催化剂Ms-Pd套用4次活性无降低.     

食品级磷酸氢钙中和剂的选择和优化

简要分析了以肌醇渣为原料制备食品级磷酸氢钙的重要性。对现有工艺中和剂的选择和提纯优化进行了具体分析,最终确定以氯化钙和氢氧化钠为复合中和剂。分别选取活性γ-氧化铝和碱改性活性炭对氯化钙和氢氧化钠进行吸附脱氟实验,探讨了不同吸附条件对其脱氟率的影响。用脱氟精制的复合中和剂中和精磷酸,得到符合GB 1889—2004《食品添加剂:磷酸氢钙》要求的食品级磷酸氢钙,氟质量分数为0.004 8%~0.005 0%。较适宜吸附参数:活性γ-氧化铝对氯化钙的脱氟过程,吸附温度为室温、活性γ-氧化铝用量为20 g、吸附时间为50 min、氯化钙溶液pH=6、氯化钙浓度为2.7 mol/L,最佳脱氟率为93.73%;碱改性活性炭对NaOH的脱氟过程,碱改性活性炭用量为1.0 g、吸附温度为35℃、吸附时间为60 min、氢氧化钠浓度为8.75 mol/L,最佳脱氟率为72.60%。     

Pd(PPh3)4催化Suzuki偶联反应合成4-溴-2-氟-联苯

以苯硼酸和2-氟-4-溴碘苯为起始原料,经Suzuki偶联反应合成了色谱纯度99.5%以上的医药和液晶中间体4-溴-2-氟-联苯,目标化合物进行了1HNMR、IR和GC-MS表征。结果表明,反应体系中氧气的存在是导致硼酸自偶副产物产生的主要原因;Pd(PPh3)4催化剂及过量的苯硼酸均会导致三联苯副产物的产生。     

废芳基硼酸类化合物的回收利用

为了提高芳基硼酸化合物的收率,减少芳基硼酸制备过程中含硼酸副产物对环境的污染,开发出了芳基硼酸化合物的脱硼酸技术,以4’-乙基-4-苯基-2-氟苯硼酸(Ⅰ)脱除硼酸基团为例,在碱性条件下,于60~68℃反应,得到了(Ⅰ)的初始原料4’-乙基-4-苯基-2-氟苯,收率87%。并对4’-乙基-4-苯基-2-氟苯的结构进行了质谱确认,对芳基硼酸化合物脱硼酸的机理给出了推测,利用此技术可以回收有用原材料,减少芳基硼酸生产中的废物排放量。     

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.     

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.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。