聚合条件对合成聚1-丁烯热塑性弹性体的影响

以1-丁烯(B t)为原料,负载钛(简称Ti)-三异丁基铝(简称Al)为催化体系,用本体聚合法合成了聚1-丁烯(PBt)热塑性弹性体(TPE)。考察了聚合条件对PBt TPE的影响,并用差示扫描量热法对聚合物进行了分析。结果表明,随着氢气压力的升高,单体转化率、催化效率呈下降趋势;随着Al/Ti(摩尔比)的增加,转化率和催化效率先升高后降低;随着Ti/Bt(摩尔比)的增加,转化率和催化效率逐渐升高;随着聚合温度的升高,转化率和催化效率先升高后降低;在氢气压力为0.2 MPa、Al/Ti为300、Ti/Bt为2×10-5、反应温度为30℃的聚合条件下,合成出转化率为80.0%的PBt TPE。随着氢气压力的升高,聚合物的特性黏数([η])和全同立构质量分数都呈下降趋势,氢气压力能较好地调节聚合物的相对分子质量;随着Al/Ti的增加,[η]逐渐下降,全同立构质量分数变化不明显;随着Ti/Bt的增加,[η]先升高后降低,最后趋于平稳,而全同立构质量分数略有降低后趋于平稳;随着聚合温度的升高,[η]和全同立构质量分数都呈下降趋势。反应温度为40℃时,PBt TPE的结晶度最高,为20.3%。     

负载钛催化1-己烯聚合

研究了负载钛催化1-己烯(He)聚合的规律,考察了聚合条件对转化率和聚合物性能的影响。结果表明:以MgCl2为载体的负载钛高效催化剂体系催化合成的聚1-己烯(PHe)为高相对分子质量、无定型、透明的弹性体;较适宜的合成条件是Ti/He(摩尔比)为(3～5)×10-5,Al/Ti(摩尔比)为250～300,温度为30℃;氢气压力是调节相对分子质量的有效手段,随着氢气压力的不断增加,聚合物的相对分子质量急剧下降。     

负载钛催化体系合成低相对分子质量反式聚丁二烯蜡

以高压氢气为相对分子质量调节荆,采用TiCl4／MgCl2负载型体系催化丁二烯本体沉淀聚合,合成了低相对分子质量反式-1,4-聚丁二烯蜡(LMTPBW),研究了聚合条件对催化活性和聚合物相对分子质量的影响。结果表明,氢气压力能有效调节聚合物的相对分子质量,随着氢气压力升高,聚合物相对分子质量下降;当氢气压力从1．0MPa升至4．5MPa时,聚合物的特性黏数从3．64dL／g降至1．43dL／g,相对分子质量分布变窄。在氢气压力为3．0～4．0MPa时,催化效率出现最大值;随着聚合温度的升高,LMTPBW的相对分子质量下降,相对分子质量分布也变窄,催化效率在30～60℃下一直增大;氢气压力不仅可调节本体聚合的相对分子质量,还可在一定范围内调节反式结构质量分数：在氢气压力1、0～4．5MPa,聚合温度30～60℃条件下,所得聚合物的数均相对分子质量为1000～4000。     

亚磷酸酯化合物对镍系催化剂催化丁二烯聚合活性及产物支化结构的影响

在丁二烯聚合的Ni（naph）2-Al（i-Bu）3-BF3·OEt2（简称Ni-Al-B）催化体系中引入第4组分三壬基苯基亚磷酸酯（简称P）,考察了P/B（摩尔比）、Al/B（摩尔比,含P体系）对丁二烯聚合活性和聚合产物结构的影响,并用傅里叶变换红外光谱、凝胶渗透色谱（GPC）和GPC-激光光散射仪-黏度计在线联用系统对聚合物的相对分子质量、微观结构及支化结构等进行了表征。结果表明,当P/B不大于0.03、Al/B为0.5~1.0时,单体转化率均达到85%以上;聚合物的相对分子质量可通过改变P/B或Al/B进行调节;P的引入对聚合产物的高顺式1,4-结构含量没有明显的影响,聚合产物中高相对分子质量级分支化程度较不加入P时明显提高,聚合物溶液的剪切黏度呈升高趋势。     

负载钛体系催化合成聚1-丁烯热塑性弹性体

研究了采用TiCl4/MgCl2 Al(i Bu)3负载钛催化体系合成聚1 丁烯(PBt)热塑性弹性体的规律。结果表明:最佳聚合条件是:Bt质量分数25%,n(Ti)∶n(Bt)=1×10-5∶1,n(Al)∶n(Ti)=(200～300)∶1,温度30℃。与聚合瓶小试条件相比,由于有良好的搅拌增加了传热传质效果,因此可获得更高的聚合速率和产率,且所合成的PBt的Mw和不溶物含量均较相同聚合条件下聚合瓶中的有所降低;氢气可有效调节PBt相对分子质量。     

负载钛体系催化1-丁烯与1 - 己烯共聚合

以负载钛体系(简称Ti)为主催化剂,三异丁基铝(简称Al)为助催化剂,加氢汽油为溶剂,通过1-丁烯(Bt)与1-己烯(He)共聚合成了新型无规热塑性弹性体。研究了单体摩尔比、Ti/(He Bt)(摩尔比)、Al/Ti(摩尔比)、反应温度、反应时间对转化率、催化剂效率(CE)、聚合物的特性黏数([η])及其在CH2Cl2中不溶物含量的影响,并用傅里叶变换红外光谱、核磁共振对共聚物进行了表征。结果表明,Bt与He最佳共聚合条件为He/Bt0·25,Al/Ti400~500,Ti/(He Bt)3×10-5~4×10-5,反应温度40~50℃,反应时间4h。随着共聚单体中He初始含量、Ti/(He Bt)的增加,共聚物的[η]增大;随着Al/Ti的增加、反应温度的升高,共聚物的[η]减小;随着Al/Ti的增加及反应温度的升高,共聚物在CH2Cl2中的不溶物含量下降;随着Ti/(He Bt)的增加和反应时间的延长,共聚物在CH2Cl2中的不溶物含量增大;He的加入降低了聚1-丁烯(1-PBt)的立构规整性和1-PBt的结晶度。     

负载钛-三异丁基铝体系催化苯乙烯聚合Ⅰ.聚合条件对苯乙烯聚合的影响

考察了负载钛(简称Ti)-三异丁基铝(简称Al)催化体系聚合条件对苯乙烯(St)聚合的影响.实验表明随着n(Al)/n(Ti)的增加,催化剂效率先升高后降低,最高为12 kg/(mol·h).随着聚合温度升高,催化剂效率逐渐升高,但增幅逐渐减缓.最佳聚合条件St初始浓度为5 mol/L,Ti浓度为1.3 mmol/L,n(Al)/n(Ti)为30,聚合温度为60℃;同时,聚合物的相对分子质量和全同立构含量均随n(Al)/n(Ti)和聚合温度升高而降低,全同立构含量可通过调节n(Al)/n(Ti),使之在40.4%～90.0%.     

溶液聚合法合成低分子反式-1,4-聚异戊二烯蜡

以加氢汽油为溶剂，采用负载型TiCl4／MgCly-Al(i-Bu)，体系催化异戊二烯聚合，高压氢气调节相对分子质量，溶液聚合法合成出了低相对分子质量反式-1，4-聚异戊二烯蜡(LMTPIW)，并分别探讨了氢气压力和聚合温度对LMTPIW的相对分子质量、聚合物组成以催化效率的影响。结果表明：氢气压力由0．8MPa增加至4．0MPa，LMTPIW的特性粘数由0．391dL／g下降至0．1951dL／g，相应数均相对分子质量从1500降至1000以下，常温下汽油可溶物的质量分数由49．3％逐渐上升至77．6％，相对分子质量分布变窄。随聚合温度的升高，LMTPIW的相对分子质量有所增大，分布加宽。氢气压力及聚合温度的上升均使体系催化效率下降，但仍可保持在2500g／gTi以上。     

负载钛催化1-丁烯本体聚合动力学

采用TiCl4/MgCl2-Al(i-Bu)3催化体系在10 L聚合釜中研究了本体法1-丁烯的聚合动力学.结果表明,在反应温度为20 ℃的条件下,聚合的速率方程为Rp=157[Ti]1.1[Bt]PH20.4;在10～30 ℃时的聚合活化能为46 kJ/mol.提高催化剂浓度、聚合温度和氢气压力均能明显提高单体转化率,加快聚合速率.     

异丙氧基钕[Nd（Oi-Pr）3]/甲基铝氧烷（MAO）催化体系催化月桂烯聚合

以Nd（Oi-Pr）3/MAO为催化体系进行月桂烯聚合。结果表明,该催化体系具有高活性和高顺式-1,4选择性,所得聚合物顺式-1,4-结构摩尔分数可达95.6%。聚合温度的升高可显著提高聚合速率,在0℃下聚合24 h,聚合物收率仅为15.8%;而在70℃下聚合1 h,聚合物收率可达99.0%。随着聚合温度的升高,链转移反应增强,聚合物的相对分子质量下降;同时由于体系中所形成的对式Nd-η^3-烯丁基转变为热力学上更为稳定的同式异构体,使得顺式-1,4-结构含量下降。     

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.