磷酸乙基新戊二醇酯的合成及阻燃性能测试

以新戊二醇、三氯氧磷、乙醇为原料,合成了一种阻燃剂磷酸乙基新戊二醇酯(Ⅱ),采用FTIR、~1HNMR、~(13)CNMR、~(31)PNMR、ESI-MS表征了其化学结构。考察了物质的量比〔n(新戊二醇磷酰氯)∶n(乙醇)〕、反应温度和反应时间等因素对反应的影响,得到最佳反应条件为∶n(新戊二醇磷酰氯)∶n(乙醇)=1∶5,反应温度50℃,反应时间8 h,产率达80.8%。将合成的阻燃剂磷酸乙基新戊二醇酯添加到硬质聚氨酯泡沫(RPUF)中,通过极限氧指数(LOI)、垂直燃烧(UL-94)实验测定了RPUF的阻燃性能,以及利用TGA表征了阻燃剂和RPUF的热稳定性。结果表明:磷酸乙基新戊二醇酯的添加,在一定程度上降低了RPUF的热稳定性,但是RPUF的阻燃性能有所提高。添加量为30%(质量分数,以材料总质量计)时可使RPUF的LOI值从17.1%提高到22.5%,通过垂直燃烧V-2级,以及在800℃时,残炭量由15.8%增加到18.9%。     

脱水磷酰氯法合成磷酸二异辛酯

研究了脱水磷酰氯法合成磷酸二异辛酯的新方法。先以五氧化二磷和二氯亚砜反应制备了脱水磷酰氯,脱水磷酰氯再与异辛醇反应制得目标产物磷酸二异辛酯。考察了磷酰氯与异辛醇物质的量比、异辛醇的滴加温度、反应时间、反应温度和真空度等关键因素对反应的影响。实验结果表明,n(脱水磷酰氯)∶n(异辛醇)=1.0∶2.1、15℃下滴加异辛醇、60℃下反应3 h、真空度为0.08 MPa的条件下,磷酸二异辛酯的收率达96.2%,含量达97.9%。利用FT-IR和NMR对产物磷酸二异辛酯进行表征。     

新型磷系阻燃剂1,2,3-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯的合成研究

以1,2,3-三羟基苯、新戊二醇、三氯氧磷等为主要原料,三乙胺为缚酸剂,采用简洁、高效的合成路线制备出标题化合物.制取目标化合物的最佳反应条件:n(1,2,3-三羟基苯)∶n(新戊二醇磷酰氯)∶n(三乙胺)=1∶4.5∶5.0,反应温度 50 ℃,反应时间6 h,产率75%.通过红外光谱、核磁共振氢谱、质谱及元素分析等表征了目标化合物结构.热失重分析表明,该阻燃剂具有较高的热稳定性和良好的成炭性,起始分解温度为287.47 ℃,500 ℃时炭残余量高达44.21%.     

一种环状磷酸酯的合成及其阻燃性能测定

以新戊二醇、三氯氧磷和1,1,1-三(4-羟基苯基)乙烷(THPE)为原料合成了一种环状磷酸酯阻燃剂1,1,1-三[4-(5,5-二甲基-1,3-二氧杂环己内磷酸酯基)苯基]乙烷(简称DOPC-THPE),采用红外光谱、氢谱、碳谱、磷谱表征了其化学结构。将合成阻燃剂添加到聚丙烯(PP)中,通过极限氧指数(LOI)、垂直燃烧(UL-94)实验测定了材料的阻燃性能,同时利用热重分析(TGA)表征了阻燃剂和材料的热稳定性。结果表明,DOPC-THPE具有较好的热稳定性和成炭性,700℃残炭量达35.9%,添加量为30%(质量分数,以材料总质量计)时可使PP的LOI值从17.5%提高到25.0%,通过垂直燃烧V-1级。     

双酚A双磷酰三聚氰胺的合成工艺研究

以双酚A和三氯氧磷、三聚氰胺为原料合成了双酚A双磷酰三聚氰胺氮-磷复合型阻燃剂。考察了反应温度、反应时间、反应物原料配比对产品收率的影响。结果表明,当第一步反应的反应温度为80℃、反应时间为7h、n(双酚A)∶n(三氯氧磷)为1∶2,第二步反应的反应温度为60℃、反应时间为5h、n(双酚A双磷酰氯)∶n(三聚氰胺)为1∶2时,产品双酚A双磷酰三聚氰胺的平均收率为61.78%,并通过红外光谱和热重分析,表征了产物的结构与性质。     

PM/PEPA协同阻燃硬质聚氨酯泡沫塑料的性能研究

将磷酸三聚氰胺盐(PM)和季戊四醇磷酸酯(PEPA)复配成一种新型的无卤阻燃剂,并对硬质聚氨酯泡沫(RPUF)塑料进行阻燃。利用极限氧指数(LOI)和热重分析(TGA)考察了阻燃RPUF的阻燃性能及热降解行为,采用残炭率和燃烧试验对阻燃RPUF进行测试分析。结果表明,PM和PEPA按质量比为1∶1复配而成的阻燃剂对RPUF塑料阻燃时效果优异,在阻燃剂添加量为16%时,RPUF氧指数达到24.3%左右,500℃时残炭率为37.4%。PM和PEPA复配能使RPUF高温燃烧时形成较稳定的炭层,对RPUF塑料具有阻燃协同作用。     

丙烯酸(2-氯乙基)酯的合成研究

采用强酸性阳离子交换树脂为催化剂,以丙烯酸、氯乙醇为原料合成了丙烯酸(2'-氯乙基)酯,分别研究了反应温度、反应时间、原料配比、催化剂用量和阻聚剂用量等条件对合成反应的影响。得到了合成丙烯酸(2'-氯乙基)酯最适宜的条件是:反应温度为85～95℃,反应时间3h,原料摩尔比n(丙烯酸)∶n(氯乙醇)为0.2∶0.25,丙烯酸为0.2mol的情况下,阻聚剂的用量为0.15g,催化剂的用量1g,丙烯酸(2'-氯乙基)酯的收率可达到91.59%以上。     

新型环状磷酸酯的合成及其阻燃性能研究

本文以新戊二醇、三氯氧磷和1,1,1-三（4-羟基苯基）乙烷（THPE）为原料合成了一种环状磷酸酯阻燃剂DOPC-THPE,采用红外光谱、核磁氢谱、核磁碳谱、核磁磷谱表征了其化学结构。将该阻燃剂添加到聚丙烯（PP）中,通过极限氧指数（LOI）、垂直燃烧（UL-94）实验研究了材料的阻燃性能,同时利用热重分析（TGA）表征了阻燃剂和材料的热稳定性。结果表明DOPC-THPE具有较好的热稳定性和成炭性,700 ℃残炭量达35.9%,30%添加量可使PP的LOI值从17.5%提高到25.0%,通过垂直燃烧V-1级。     

乙醇/水无卤发泡及木质素磷酸酯基阻燃硬质聚氨酯泡沫的制备及性能研究

首先用二苯氧基磷酰氯与碱木质素反应合成木质素磷酸酯反应型阻燃剂,再以乙醇、水协同作无卤发泡剂,木质素磷酸酯、可膨胀石墨协同作无卤阻燃剂,制备了无卤发泡及阻燃硬质聚氨酯泡沫。结果表明,使用乙醇作发泡剂可显著降低物料黏度,提高物料流动性,使发泡反应更完全。傅里叶变换红外光谱(FTIR)及核磁共振氢谱(¹H NMR)分析表明已成功制备木质素磷酸酯反应型阻燃剂,正交试验及统计产品与服务解决方案(SPSS)数据分析确定具有26.6%最高聚氨酯泡沫极限氧指数(LOI)的木质素改性工艺参数为：二苯氧基磷酰氯7 g、反应温度60℃、反应时间5 h。热重(TG/DTG)分析结果表明木质素苯环的环状结构,磷酸液膜、蠕虫状膨胀石墨炭层及聚氨酯降解后残渣炭层形成的致密联合体提高了炭层的热稳定性,添加木质素磷酸酯/可膨胀石墨(EG)前后无卤发泡硬质聚氨酯泡沫在800℃的残炭量分别为19.3%、27.4%。聚氨酯泡沫表观密度随着木质素磷酸酯添加量的增加而增加,压缩强度先上升后下降,压缩强度最高时可达485.2 kPa。     

1,3-二(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯合成方法的改进

以新戊二醇、三氯氧磷和间苯二酚为原料,三乙胺为缚酸剂从另外一条路线合成了1,3-二(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯,即新戊二醇先与三氯氧磷反应制得新戊二醇磷酰氯,再以该磷酰氯与间苯二酚反应制得目标产物。其适宜的反应条件为:n(新戊二醇磷酰氯)∶n(间苯二酚)∶n(三乙胺)=2∶1∶4,回流温度(~64℃)下反应时间为4 h,以间苯二酚计的目标产物收率为66.2%。产物结构通过IR、NMR分析进行了确认。与1998年的5 852 197号美国专利方法相比,该法降低了原料三氯氧磷的用量,省去了蒸馏过量三氯氧磷的操作,收率提高了20.9%。     

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.     

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.     

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。     

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.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.