负离子封端法合成端基官能化SBS及其动态力学性能分析

采用自制的1,5-二氮二环[3．1．0]己烷为负离子聚合封端试剂,制备了不同相对分子质量的聚苯乙烯模型聚合物。结果表明,该封端试剂能定量地与聚苯乙烯活性种反应。末端氨基官能化苯乙烯-丁二烯-苯乙烯三嵌段共聚物末端接上极性基团后,产物的储存模量和损耗模量均上升;聚苯乙烯微区的损耗因子增加,而聚丁二烯微区的损耗因子下降。     

聚苯乙烯为规整侧链的支化SIS的设计及合成

以苯乙烯和对乙烯基苄氯(VBC)为原料,采用负离子聚合法合成含苯乙烯基末端的聚苯乙烯大分子单体,并以正丁基锂(BuLi)为引发剂,四氢呋喃(THF)为调节剂,环己烷为溶剂进行异戊二烯与大分子单体的负离子共聚合,用一锅法制备出侧链规整的支化结构苯乙烯-异戊二烯-苯乙烯(SIS)嵌段聚合物。通过核磁共振和凝胶渗透色谱等对聚苯乙烯大分子单体和支化SIS结构进行了表征,利用旋转流变仪对支化SIS进行了流变性能表征。结果表明,利用上述聚合方法成功合成了相对分子质量3000～5000的聚苯乙烯大分子单体;使用聚苯乙烯大分子单体制备出相对分子质量为10万～14万,分子量分布为1.1～1.2的支化结构SIS,并且其流体黏度明显低于相同相对分子质量及结合苯乙烯线型结构的SIS。     

用负离子原位聚合法合成链端氨基官能化集成橡胶

采用负离子原位聚合法,以N,N-二甲氨基苯甲醛缩苯胺为封端剂合成了链端氨基官能化集成橡胶,考察了封端剂用量、聚合物相对分子质量及大分子链活性端种类对分子官能化封端率的影响,并对聚合物进行了表征和性能测试.结果表明,该封端剂可以与大分子活性种等摩尔反应,聚合物相对分子质量及分子链末端种类对分子官能化封端率的影响不大;以N...     

烯丙基三甲氧基硅烷封端溶聚丁苯橡胶的合成

以丁二烯和苯乙烯为单体、正丁基锂为引发剂、双四氢糠丙烷为结构调节剂、1,1-二苯基乙烯为“盖帽剂”、烯丙基三甲氧基硅烷（TIOS）为封端剂,采用负离子聚合法合成了TIOS封端的溶聚丁苯橡胶（SSBR）。采用凝胶渗透色谱和核磁共振波谱表征了封端前后SSBR的结构和分子量及其分布,考察了封端反应时间、反应温度、TIOS用量及SSBR分子量对封端效率的影响。结果表明,封端反应时间为30 min、反应温度为60 ℃、TIOS与正丁基锂摩尔比为2.0及SSBR相对分子质量约为60 000时封端效率较高。     

双键单封端聚氨酯丙烯酸酯大分子单体的合成及表征

以异佛尔二酮异氰酸酯(IPDI)和聚醚二元醇(PEG)为单体、(甲基)丙烯酸羟乙酯和正丁醇为共封端剂,合成了以双键单封端为主的聚氨酯丙烯酸酯大分子单体.考察了反应条件的影响,对聚氨酯大分子单体进行了表征.结果表明反应温度越高、催化剂用皱越大、封端剂的羟基活性越强,预聚反应和封端反应所需时间越短;聚氨酯人分子单体中双键含量随IPDI与PEG摩尔比的增加而增加.     

以西弗碱为封端剂原位合成官能化苯乙烯-丁二烯-苯乙烯嵌段共聚物

合成了西弗碱(N,N一二甲氨基苯甲醛缩苯胺,DMABA),用负离子原位聚合法合成了末端官能化苯乙烯-丁二烯-笨乙烯嵌段共聚物(SBS),用模型聚合物的方法研究了DMABA与聚苯乙烯(PS)活性种的定量反应关系,以及反应温度、PS数均相对分子质量(M.)对官能度的影响,并对官能化聚合物进行了分析表征.结果表明,DMABA能和Ps活性种等摩尔进行反应,反应温度以及PS活性种的M.对聚合物的官能度影响不大;以DMABA为封端剂,n-BuLi或六亚甲基亚胺锂为引发剂,可以制得高官能度的w-SBS或a,w-双端官能化SBS,在提高SBS极性的同时,对SBS的相对分子质量分布及微观结构影响不大.     

叔丁基二苯基氯硅烷封端溶聚丁苯橡胶的制备与性能

首先以双官能团有机锂为引发剂、环己烷为溶剂、四氢呋喃为调节剂,采用负离子聚合法制备了具有双端活性的溶聚丁苯橡胶(SSBR),然后以叔丁基二苯基氯硅烷为封端剂,对SSBR进行封端改性,考察了封端比、反应时间、反应温度、SSBR的数均分子量、链端基结构对封端率的影响,并研究了封端改性SSBR的性能。结果表明,在SSBR数均分子量为5×104、封端比为2.0、封端温度为60℃、封端反应时间为70 min的条件下,叔丁基二苯基氯硅烷对SSBR的封端率可达77.2%;大分子链端基由苯乙烯转换为丁二烯后可显著提高封端率;用叔丁基二苯基氯硅烷封端显著提高了SSBR的拉伸强度和扯断伸长率,降低了SSBR的动态压缩温升和滚动阻力。     

含双官能团封端剂的合成及在负离子法制备端基官能化聚苯乙烯中的应用

设计合成了一种含有胺基和烷氧基硅烷基双官能团的封端剂——N-对二甲氨基苯亚甲基-3-三乙氧基硅烷基-1-丙胺(DTEOS),并将其用于通过活性负离子聚合技术制备端基官能化聚苯乙烯(PS-DTEOS)中。采用傅里叶变换红外光谱和核磁共振波谱对DTEOS和PS-DTEOS的微观结构进行了表征,并用凝胶渗透色谱法测定了它们的相对分子质量及其分布。研究了DTEOS与聚苯乙烯基锂的定量反应关系,以及DTEOS加入量、封端反应温度、封端反应时间和聚苯乙烯的相对分子质量对封端效率的影响。结果表明,封端反应在10~20 min内快速完成,且没有副反应发生;封端反应温度在50~80℃和聚苯乙烯的数均分子量在5 000~50 000内变化时对封端效率的影响不大;封端剂可与聚苯乙烯基锂进行等摩尔封端反应,封端效率在80%以上,实现了用封端反应制备官能化聚苯乙烯的预期设想。     

一种新型封端剂的合成、表征和应用（英文）

设计并合成了一种新型含硅氧烷基和氨基的封端剂N-苯亚甲基-3三乙氧基硅烷基-1-丙胺(Imine-TEOS);研究了在以苯乙烯为聚合单体、环己烷为溶剂、四氢呋喃为结构调节剂、正丁基锂为引发剂,采用活性负离子聚合技术合成聚苯乙烯(PS)时,ImineTEOS对PS的封端反应;通过傅里叶变换红外光谱和核磁共振对封端剂和端基PS的分子结构进行了表征。结果表明,Imine-TEOS顺利地进行了PS端基的封端反应,封端反应后PS的分子量分布略加宽,并且随ImineTEOS的加入在整个封端反应过程中未引发偶联等副反应。     

苯乙烯-对氯甲基苯乙烯共聚物胶乳微球的制备及表征

以苯乙烯（St）和对氯甲基苯乙烯（VBC）为共聚单体,过硫酸钾（KPS）为引发剂,十二烷基苯磺酸钠（SDBS）为乳化剂,采用乳液聚合法制备了富含氯甲基的苯乙烯-对氯甲基苯乙烯共聚物功能微球。采用红外光谱（FT-IR）、扫描电镜（SEM）、激光粒度仪和X射线光电子能谱（XPS）对样品进行表征,研究了乳化剂用量、单体用量、引发剂用量、反应时间、反应温度等因素对微球粒径、乳液转化率的影响。结果表明,产物微球粒径均一,表面光滑、富含氯甲基功能基团,采用此方法可以制备粒径在100～250 nm的功能高分子微球。     

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。