ESBS嵌段共聚物的制备及反应机理研究

利用甲酸和过氧化氢原位生成的过氧甲酸对苯乙烯-丁二烯-苯乙烯（SBS）嵌段共聚物进行环氧化,制备了环氧化SBS（ESBS）。采用FT—IR、GPC、TGA和MFR对ESBS进行了表征,分析了环氧化反应机理。结果表明,在环氧化反应过程中,SBS分子链上聚丁二烯链段1,4-结构中C=C双键的反应活性要大于1,2-结构中C=C双键的反应活性。当反应时间较长时,ESBS会发生环氧基开环副反应。在SBS的环氧化反应初期,会有部分分子链发生断裂生成小分子产物,反应后期会发生环氧基或C=C双键引发的分子间偶联反应,容易形成交联不溶物。     

通过环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物与亚硫酸氢钠的开环反应制备磺化离聚体

用环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物（ESBS）在相转移催化剂、开环催化剂存在下与亚硫酸氢钠的水溶液进行开环反应制备了SBS磺化离聚体,用傅里叶变换红外光谱法对产物进行了表征。研究表明,当环氧基转化率达90％时,反应条件为ESBS的质量浓度0．12g／mL。NaHSO3／环氧基（摩尔比）1．8,促进剂／NaHSO3（质量比）0．36。四乙基澳化铵／ESBS（质量比）0．05,二甲基苯胺／ESBS（质量比）0．05,60℃,7h。     

相转移催化剂对苯乙烯-丁二烯-苯乙烯嵌段共聚物环氧化反应的影响(英文)

研究了三辛基甲基氯化铵(MTAC)、三十二烷基三甲基氯化铵(TMAC)、十六烷基三甲基溴化铵(HTAB)、十八烷基三甲基溴化铵(OTAB)以及聚乙二醇(PEG-400)等5种相转移催化剂对苯乙烯-丁二烯-苯乙烯嵌段共聚物环氧化反应的影响.结果表明,MTAC的环氧化效果最好,当其质量分数为1.0%时,可使环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物(ESBS)的环氧基质量分数从18.1%提高到20.1%;HTAB和PEG-400有利于ESBS的环氧基质量分数的提高;而OTAB和TMAC由于自身较大的分子体积反而使ESBS的环氧基质量分数下降.傅里叶变换红外光谱分析表明,MTAC可以有效抑制环氧基开环副反应的发生.     

SBS／ESBS共混体系力学性能及熔体流动速率的研究

研究了苯乙烯-丁二烯-苯乙烯（SBS）和环氧化苯乙烯-丁二烯-苯乙烯（ESBS）质量配比及ESBS环氧基质量分数对SBS／ESBS共混物的力学性能以及熔体流动速率的影响。结果表明,随着SBS与ESBS质量配比的减小,共混物的绍尔A硬度逐渐增大,拉伸强度和断裂伸长率先增大后减小,熔体流动速率先减小后增大。当SBS和ESBS质量配比为60：40时,共混物的邵尔A硬度为85,拉伸强度和断裂伸长率分别为26．86MPa和795．5％,综合性能最佳。随着ESBS环氧基质量分数的增大,SBS／ESBS共混物的硬度逐渐增大,拉伸强度和断裂伸长率降低,熔体流动速率变小。     

环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物的热性能

采用差示傅里叶变换红外光谱分析了环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物(ESBS)的热氧老化和热老化行为,通过热重分析和动态力学分析研究了ESBS的热性能.结果表明,ESBS在热氧老化及热老化过程中,其C=C的稳定性均优于环氧基,老化产物为醛、酮、醚、羧酸等;相对于热老化而言,热氧老化对ESBS分子结构的破坏程度更大;与苯乙烯-丁二烯-苯乙烯(SBS)相比,ESBS的耐热性稍有下降;ESBS具有-63.5,-33.4,103.8℃3个玻璃化转变温度,分别对应于聚丁二烯链段、环氧化聚丁二烯链段和聚苯乙烯链段.     

苯乙烯-异戊二烯-苯乙烯三嵌段共聚物的环氧化

以甲酸和过氧化氢反应生成的过氧甲酸为氧化剂、聚乙二醇(PEG-400)为相转移催化剂,对苯乙烯-异戊二烯-苯乙烯三嵌段共聚物(SIS)进行了环氧化,考察了SIS的环氧化反应影响因素,并探讨了环氧化反应机理。结果表明,在C=C/甲酸/过氧化氢(摩尔比)为1/2/6、反应时间为2 h、反应温度为50℃、SIS质量分数为20%时,SIS的环氧化效果最好,环氧度可达到39. 2%;加入相转移催化剂PEG-400可以大幅度提高环氧度,当PEG-400/SIS(质量比)为1. 0时,环氧度可达到59. 5%; SIS的环氧化反应主要发生在聚异戊二烯链节中1,4-结构的双键上,且反应活性由强到弱依次为顺式-1,4-结构、反式-1,4-结构、3,4-结构。     

SBS环氧化及其产物作为环氧固化体系增韧剂的研究

在相转移催化剂的存在下,将苯乙烯-丁二烯-苯乙烯(SBS)嵌段共聚物进行环氧化改性,并引入环氧极性基团,同时对该产物(ESBS)应用于双酚A型环氧树脂(E-44)/脂肪胺(DMDC)的固化体系进行增韧改性。结果表明,当SBS质量浓度为130 g/L、m(甲酸)/m(SBS)=10%、n(过氧化氢)/n(甲酸)=1、m(PEG-400)/m(SBS)=3%、反应温度为70℃和反应时间为150 min时,SBS环氧化反应较佳,可得到环氧基质量分数为8.2%的ESBS。进一步添加2%(质量分数)ESBS到E-44/DMDC环氧固化体系中,能有效提高该固化体系的力学性能,拉伸强度增加37.0%,弯曲强度增加17.4%。     

用相转移催化剂聚乙二醇环氧化苯乙烯-异戊二烯-苯乙烯三嵌段共聚物（英文）

利用甲酸和过氧化氢反应原位生成的过氧甲酸为氧化剂,以具有两亲性的聚乙二醇(PEG-400)为相转移催化剂,在甲苯溶剂中对苯乙烯-异戊二烯-苯乙烯三嵌段共聚物进行环氧化。结果表明,当PEG-400质量分数为1%时,产物环氧度由39.1%提高到59.5%,且环氧化反应主要发生在聚异戊二烯链段的1,4-结构双键上,1,4-结构的摩尔分数由50.70%下降到33.55%,特征峰位置没有明显变化。     

管道防腐用环氧化SBS热熔胶的研制

利用有机过氧化物对SBS(苯乙烯-丁二烯-苯乙烯三嵌段共聚物)进行环氧化改性,得到ESBS(环氧化SBS);然后以此为基体树脂,辅以适宜种类及用量的增黏树脂、增塑剂和抗氧化剂等,制备出一种油气管道防腐用ESBS基热熔胶。结果表明:制备ESBS基热熔胶的最佳配方(以质量分数计)为47%ESBS、47%增黏树脂、1%抗氧剂和5%增塑剂;经环氧化改性后,ESBS基热熔胶对极性材料的粘接强度明显提高,其剥离强度和(钢/钢)剪切强度均满足使用要求。     

两亲性硫酸钾基(苯乙烯-丁二烯-苯乙烯)嵌段共聚物离聚体的合成、表征及其性能

以四乙基溴化铵(TEAB)为相转移催化剂、N,N-二甲基苯胺(DMA)为开环催化剂,环氧化(苯乙烯-丁二烯-苯乙烯)嵌段共聚物(ESBS)甲苯溶液与硫酸氢钾(PBS)水溶液通过开环反应制备了硫酸钾基(苯乙烯-丁二烯-苯乙烯)嵌段共聚物离聚体(SSBS),考察了合成条件对ESBS开环反应的影响,用傅里叶变换红外光谱法表征了SSBS,研究了SSBS的耐溶剂性能、特性黏数[η]及乳化性能.结果表明,当TEAB/ESBS(质量比)为5%、DMA/ESBS(质量比)为5%、ESBS溶液质量浓度为0.12 g/mL、PBS与环氧基的摩尔比为1.8、反应温度为75 ℃、反应时间为7 h时,ESBS的开环率达到41.7%;开环反应过程中同时形成了硫酸盐基和羟基;随着离子基团含量及离子电位的增加,SSBS的吸水率和[η]增大,耐油性能增强;SSBS能乳化甲苯/水体系,其乳化体积随着离子含量、离聚体用量及离子电位的增加而增大.     

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.