氮官能化多锂引发合成星形苯乙烯-戊二烯-二烯共聚物的微观结构和玻璃化转变温度

以六亚甲基亚胺锂（LHMI）与二乙烯基苯（DVB）合成的氮官能化多锂（简称Li）为引发剂，N，N，N’，N’-四甲基乙二胺（TMEDA）为极性调节剂，环己烷为溶剂，制备了带有氮官能化基团的星形无规苯乙烯-异戊二烯-丁二烯共聚物（SIBR），用核磁共振法进行了表征，并分析了TMEDA用量、聚合温度、引发剂浓度及DVB/Li（摩尔比）对SIBR微观结构和玻璃化转变温度（Tg）的影响。结果表明，在DVB/LHMI（摩尔比）为0．8的条件下，SIBR中有C-N存在，并且为臂数不等的星形聚合物；随着TMEDA用量的增加和聚合温度的降低，SIBR中非l，4-结构含量增加，Tg提高；在实验范围内引发剂浓度和DVB/Li对SIBR中非1，4-结构含量和其，Tg影响不大。     

氮官能化多锂引发丁二烯/异戊二烯/苯乙烯聚合动力学

以自制氮官能化多锂(以下简称Li)为引发剂,N,N,N′,N′-四甲基乙二胺(TMEDA)为极性调节剂,环己烷为溶剂,对苯乙烯(St)、异戊二烯(Ip)、丁二烯(Bd)进行负离子聚合,合成了星形集成橡胶丁二烯-异戊二烯-苯乙烯三元共聚物(SIBR),研究了不同TMEDA/Li(摩尔比)下SIBR的聚合反应动力学。结果表明,在三元共聚合反应中,3种单体的反应速率与其各自浓度均符合一级动力学关系;在SIBR的合成体系中,随着TMEDA/Li的增大,Bd的反应速率常数先升高后降低,St的反应速率常数逐渐增加,Ip的反应速率常数逐渐降低;当TMEDA/Li为1·0、二乙烯基苯(DVB)/Li(摩尔比)为0·8、引发剂浓度为7·69×10-4mol/L时,单体Bd,Ip,St的表观增长反应活化能分别为31·59,47·64,31·76kJ/mol,链增长频率因子分别为1·02×104,1·09×106,5·27×103min-1。     

含氮有机锂引发剂制备溶聚丁苯橡胶

用正丁基锂(n-BuLi)和六亚甲基亚胺合成含氮有机锂引发剂六亚甲基亚氨基锂(LHMI),用于引发负离子聚合。用核磁共振的方法验证了LHMI是有效的引发剂。研究了TMEDA对LHMI引发的丁苯共聚表观反应速率常数(Kp')的影响,发现当TMEDA/LHMI质量比小于1.0时,Kp'随着TMEDA用量的增加而增加。与n-BuLi体系相比,用LHMI合成的溶聚丁苯橡胶,在不损失其他物理机械性能的基础上,滚动阻力降低。     

用氮锂引发剂合成端基官能化苯乙烯-丁二烯-苯乙烯三嵌段共聚物

研究了六亚甲基亚胺基锂、氮锂和正丁基锂引发剂引发苯乙烯的聚合速率,合成了端基官能化苯乙烯-丁二烯-苯乙烯三嵌段聚合物（SBS）。结果表明,在设计相对分子质量相同的情况下。随着四氢呋喃加入量的增加,端基官能化SBS的1,2-结构质量分数增加,顺式-1,4-结构和反式-1,4-结构质量分数下降,但两者比值基本不变。相同条件下,用氮锂引发剂制备的端基官能化SBS的1,2-结构质量分数要略高于用正丁基锂引发剂制备的SBS。     

Synthesis of end group functionalized styrene-butadiene-styrene three block copolymer using lithumamide as initiator

用氮锂引发剂合成端基官能化苯乙烯-丁二烯-苯乙烯三嵌段共聚物王强,廖明义,王玉荣,张雪涛,张春庆(大连理工大学化工学院,辽宁大连116012)研究了六亚甲基亚胺基锂、氮锂和正丁基锂引发剂引发苯乙烯的聚合速率,合成了端基官能化苯乙烯-丁二烯-苯乙烯三嵌段聚合物(SBS)。结果表明,在设计相对分子质量相同的情况下,随着四氢呋喃加入量的增加,端基官能化SBS的1,2-结构质量分数增加,顺式-1,4-结构和反式-1,4-结构质量分数下降,但两者比值基本不变。相同条件下,用氮锂引发剂制备的端基官能化SBS的1,2-结构质量分数要略高于用正丁基锂引发剂制备的SBS。     

3种星形苯乙烯-异戊二烯-丁二烯三元共聚物的结构与性能

以多官能度锂(简称Li)为引发剂,在不同条件下合成了3种星形苯乙烯(St)-异戊二烯(Ip)-丁二烯(Bd)三元共聚物,分析了共聚物的结构。结果表明,两次投料法的产物为两嵌段共聚物,低R[四氢呋喃(THF)与Li的摩尔比]值合成的聚异戊二烯(PI)链段的玻璃化转变温度(Tg)为-58.3℃,1,4-结构为83.8%;高R值合成的无规共聚段的Tg为-36.2℃。低R值一次投料法产物为多嵌段共聚物,-69℃为Bd-Ip无规共聚段的Tg,1,4-结构含量高;22.7℃为Ip-St共聚段的Tg,含摩尔分数为6.6%的PS嵌段。高R值一次投料法的产物为三元无规共聚物,1,4-结构含量低,只有1个Tg,为-28.9℃。     

二乙二醇单乙醚基钡/三异丁基铝/正丁基锂引发体系合成高反式苯乙烯-异戊二烯-丁二二烯三元共聚物

以二乙二醇单乙醚基钡(简称Ba)/三异丁基铝(简称Al)/正丁基锂(简称Li)为三元引发体系,采用负离子聚合法合成了高反式苯乙烯-异戊二烯(Ip)-丁二烯(Bd)三元共聚物(SIBR),考察了引发剂组分、单体配比和聚合温度对SIBR微观结构的影响,并研究了Al/Li(摩尔比)和Bd/Ip(质量比)对SIBR结晶行为的影...     

六亚甲基亚氨基锂引发的丁二烯负离子聚合动力学

研究了以六亚甲基亚氨基锂(LHMI)为引发剂、环己烷为溶剂、TMEDA为极性调节剂的丁二烯自聚。其中LHMI可以预先制备,也可以在聚合体系中原位合成。当TMEDA/LHMI质量比小于2时,速率常数(Kp')随着TMEDA/LHMI的增大而升高。与正丁基锂引发体系的Kp'相比,相同条件下LHMI引发体系的Kp'变化不大,说明LHMI不起调节剂的作用。     

Copolymerization of butadiene and isoprene with TMEDA as modifier

以正丁基锂(n-BuLi)为引发剂,N,N,N',N＇-四甲基乙二胺(TMEDA)为调节剂,环己烷为溶剂,通过负离子聚合制备了丁二烯和异戊二烯的共聚物.结果表明,随着TMEDA用量的增加,聚合速度加快,丁二烯单体竞聚率增加,异戊二烯单体竟聚率减少,二者差值逐渐增大,在TMEDA/n-BuLi(摩尔比)不小于0.8时,这种变化趋势变缓,表明共聚物分布不均匀程度增加.     

正丁基锂/乙基四氢糠基醚/十二烷基苯磺酸钠体系引发苯乙烯-异戊二烯-丁二烯三元共聚合

以n-BuLi为引发剂、乙基四氢糠基醚（ETE）和十二烷基苯磺酸钠（SDBS）二元复合调节体系为调节剂、己烷/环己烷为混合溶剂,在聚合温度为50 ℃时采用负离子聚合法进行苯乙烯-异戊二烯-丁二烯（SIBR）三元共聚合,考察了ETE/n-BuLi（摩尔比）和SDBS/n-BuLi（摩尔比）对SIBR微观结构含量和玻璃化转变温度（Tg）的影响。结果表明,当ETE/n-BuLi从0.5增加到2.0、SDBS/n-BuLi为0.1时,SIBR中聚丁二烯的1,2-结构质量分数和聚异戊二烯的3,4-结构质量分数分别增加了5.4和7.6个百分点,Tg上升了28.84 ℃左右;当SDBS/n-BuLi从0.1增加到0.8、ETE/n-BuLi为0.5时,SIBR中聚丁二烯的1,2-结构含量、聚异戊二烯的3,4-结构含量和Tg变化很小;ETE调节SIBR中聚丁二烯的1,2-结构和聚异戊二烯的3,4-结构的能力远远大于SDBS。     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

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.