三元乙丙橡胶/丁腈橡胶并用胶增容剂丙烯腈接枝三元乙丙橡胶共聚物的研制

采用溶液聚合法制备三元乙丙橡胶(EPDM)/丁腈橡胶(NBR)并用胶增容剂丙烯腈(AN)接枝EPDM(PANg-EPDM)共聚物,研究AN/EPDM用量比、引发剂BPO用量、溶剂种类、反应温度和反应时间对接枝率的影响。结果表明,在AN/EPDM用量比为5/6、引发剂BPO质量分数为0.005、溶剂为正庚烷、反应温度为70℃、反应时间为2.5 h的最佳溶液聚合反应条件下,PAN-g-EPDM共聚物的接枝率为26%,该接枝率的PAN-g-EPDM共聚物对EPDM/NBR并用胶增容性较好。     

EPDM-g-SAN接枝共聚反应的研究

探讨以正庚烷 /甲苯混合物为溶剂 ,采用共聚法制备EPDM接枝聚苯乙烯 丙烯腈 (EPDM g SAN)的反应条件。试验得出的优化反应条件为 :单体苯乙烯 /丙烯腈质量比　 3 /1,EPDM/单体质量比　 45 /5 5 ,引发剂BPO浓度　3 3 8× 10 - 3mol·L- 1 ,正庚烷 /甲苯体积比　 60 /4 0 ,反应温度　 80℃ ,反应时间　 2 0h。在此条件下 ,反应的单体转化率、接枝率和接枝效率分别为 75 % ,3 3 %和 3 6%。红外光谱分析证明 ,EPDM分子链上接枝了SAN支链     

AEMS的力学性能及热稳定性分析

用乙烯-丙烯-二烯烃三元共聚物(EPDM)与甲基丙烯酸甲酯-丙烯腈(简称MAN)进行溶液接枝共聚合,生成MAN接枝EPDM(EPDM-g-MAN)共聚物,用其与苯乙烯-丙烯腈共聚物(SAN)共混制备耐老化性能优异的熔融共混物(简称AEMS);研究了EPDM含量与AEMS力学性能的关系.随着EPDM含量的增加,AEMS的Izod缺口冲击强度先升后降,在w(EPDM)为25%时最大,达61.0 k/m2,拉伸强度和弯曲强度则逐渐下降.EPDM和SAN相具有良好的相容性,使AEMS具有剪切屈服的增韧机理和脆韧转变的性质,从而赋予AEMS高抗冲韧性.随着EPDM含量的增加,AEMS的热失重起始温度有所下降,但不影响其熔融加工的热稳定性.     

悬浮接枝共聚合成POE-g-MAS及其对SAN树脂的增韧作用

合成了乙烯-辛烯共聚物(POE)和甲基丙烯酸甲醋(MMA)-丙烯腈(SAN)-苯乙烯(St)的接枝共聚物(POE-g-MAS)。研究了单体比率、POE/单体比率和引发剂浓度等因素对接枝共聚合反应的影响。聚合产物用丙酮抽提得到接枝共聚物POE-g-MAS,傅里叶变换红外光谱分析证明MMA-AN-St已经接枝在POE分子链上。用POE-g-MAS与Stet树脂共混制备了具有高抗冲性能的POE-g-SAN/SAN共混物,并用扫描电镜观察共混物的冲击断面,探讨了其增韧机理。     

EPDM／St-AN相反转乳液接枝共聚合及AES的结构与性能

以过氧化二苯甲酰为引发剂,正庚烷为溶剂,用"相反转"乳液共聚合法合成了三元乙丙橡胶和苯乙烯-丙烯腈(St-AN)的接枝共聚物(EPDM-g-SAN),并与苯乙烯-丙烯腈共聚物(SAN)熔融共混(共混物简称 AES)。研究了丙烯腈 AN 在共单体中的含量和 EPDM/St-AN 的质量比对单体转化率、接枝率和接枝效率的影响。冲击实验表明,AN 含量为35%～40%时,接枝率约为35%,所制备的 EPDM-g-SAN 对 SAN 树脂有显著的增韧作用,增韧后所制得的工程塑料 AES 的悬臂梁缺口冲击强度最高可达50.7 kJ/m~2;差示扫描量热分析表明 AES 存在界面相;动态热力学分析表明 EPDM-g-SAN 与 SAN 树脂之间的相界面结合紧密;透射电镜和扫描电镜分析表明,AN 在共单体中的含量为35%时,EPDM-g-SAN 在 SAN 树脂基体中有良好的分散性,相界面模糊,因而两相结合紧密,其增韧机理以空穴化为主兼有剪切屈服。     

回收溶剂对EPDM/St-An接枝反应行为及AES性能的影响

以甲苯/正庚烷为溶剂,用溶液聚合法合成三元乙丙橡胶(EPDM)-苯乙烯(St)-丙烯腈(An)接枝共聚物(EPDM-g-SAN),用常压蒸馏法回收并提纯溶剂。以回收溶剂与新溶剂按比例混合,用于EPDM-g-SAN的合成。研究了EPDM/St-An的接枝共聚合反应行为以及EPDM-g-SAN与SAN树脂共混制备的AES。用气相色谱质谱分析了回收溶剂的组成,用FTIR及TG分析了回收溶剂的用量分别对接枝产物的结构和AES的热稳定性的影响。结果表明,回收溶剂有乙苯生成,并存在残留单体;回收溶剂中的甲苯、丙烯腈、甲基环己烷和3-甲基己烷的相对含量随回收次数的增加而提高,正庚烷和苯乙烯含量则有减少趋势;回收溶剂的用量对接枝共聚合反应行为和接枝产物的结构,以及对AES的冲击强度、拉伸性能、弯曲性能、熔体流动速率和热稳定性的影响甚微。     

三元乙丙橡胶-g-2-丙烯酰胺-2-甲基丙磺酸的制备与表征

采用反相乳液聚合法制备了三元乙丙橡胶-g-2-丙烯酰胺-2-甲基丙磺酸(EPDM-g-AMPS),考察了反应条件对接枝共聚物接枝率的影响,并用傅里叶变换红外光谱对EPDM-g-AMPS进行了表征。结果表明,在反应温度为55℃、反应时间为4 h、引发剂质量分数为0.8%、EPDM/AMPS(质量比)为1以及AMPS中和度为110%的条件下,所得共聚物为EPDM-g-AMPS,其接枝率最大为19%,且乳液的综合性能较好。     

EPDM与EA接枝共聚反应

以BPO为引发剂,二甲苯为溶剂,在EPDM上接枝丙烯酸乙酯(EA)红外光谱分析与溶解实验证明了接枝物的存在;接触角实验证明,接枝后EPDM的极性加大;皂化水解接枝物后,用化学滴定法测定了接枝物的接枝率。讨论了单体浓度、引发剂浓度及反应温度对接枝率的影响,也研究了氧对此反应体系的影响,并计算了此接枝反应体系的接枝反应活化能。     

影响苯乙烯丙烯腈在聚丁二烯乳胶粒上接枝共聚反应的因素

采用种子乳液聚合技术在聚丁二烯 ( PB)乳胶粒上接枝共聚苯乙烯 ( St)和丙烯腈 ( AN) ,合成了一系列 PB-g-SAN共聚物 ( ABS)。将这些共聚物用丙酮溶解并在超速离心机上将 PB-g-SAN和未接枝在 PB上的游离 SAN分离 ,计算出 SAN在 PB上的接枝率和接枝效率。通过改变共聚单体的组成和加料时间 ,研究了接枝率和接枝效率的变化。结果表明 SAN的接枝率随着 PB含量的增加而降低 ,在共聚单体中增加引发剂 ( CHP)和分子量调节剂 ( TD-DM)的含量 ,SAN在 PB上的接枝率和接枝效率表现出了下降的趋势 ,而共聚单体的配比 St/ AN和加料时间对接枝率和接枝效率的影响不大。     

EPDM-g-MAN的合成及AEMS的冲击性能研究

用(乙烯/丙烯/二烯)共聚物(EPDM)与甲基丙烯酸甲酯(MMA)、丙烯腈(AN)进行溶液接枝共聚合成了(EPDM/MMA/AN)接枝共聚物(EPDM-g-MAN),并将其与(苯乙烯/丙烯腈)共聚物(SAN)共混制得高抗冲耐老化黄变性能优异的EPDM-g-MAN/SAN共混物(AEMS).研究了AN用量对不同EPDM-g-MAN接枝体系单体转化率(CR)、接枝率(GR)、接枝效率(GE)及AEMS缺口冲击强度的影响.结果发现,随着AN用量的增加,EPDM-g-MAN的CR逐渐下降;GR、GE在AN质量分数为5%时出现最大值;AEMS的缺口冲击强度均在AN质量分数为10%时出现最大值,为61.0 kJ/m2;EPDM相以条状形态构成的近连续相结构存在,径向尺寸较小的EPDM条形结构能诱发SAN基体剪切屈服,径向尺寸较大的EPDM条形结构仅能诱发基体空穴化.     

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.