双丙烯海松酸酯多元醇的合成研究

研究了丙烯海松酸在一定条件下与乙二醇、二甘醇和三甘醇的酯化反应，生成双丙烯海松酸酯多元醇。测试了酯化产物的分子量、聚合度、粘度、羟值和官能度等理化参数，并对各产物的耐热性和红外光谱进行了讨论。结果表明，所有酯化产物均可作为耐热的多元醇原料使用。     

丙烯海松酸的合成研究

通过松香与丙烯酸的Diels-Alder加成反应制备了丙烯海松酸,考察了原料摩尔比对反应的影响。实验结果表明,随着丙烯酸用量的增加,产物的酸值和软化点逐步升高至不变;紫外光谱研究发现,随着丙烯酸用量的增长,枞酸型树脂酸相对含量下降,而海松酸型树脂酸的含量未见显著变化;气相色谱-质谱联用分析显示,在松香树脂酸与丙烯酸的加成反应中,树脂酸中的海松酸、异海松酸、脱氢枞酸等不参与反应,而长叶松酸、枞酸和新枞酸异构化为左旋海松酸,与丙烯酸发生加成反应;即使丙烯酸过量,长叶松酸和枞酸转化率最高也只可以达到91%和86%;研究还发现,加成产物丙烯海松酸有二种构造异构体,分别占丙烯海松酸量的20%和80%。     

微波辐射条件下丙烯海松酸的合成

以松香和丙烯酸为原料，在微波辐射条件下合成丙烯海松酸，探讨了反应时间、反应温度、微波功率、物料配比等因素对丙烯海松酸含量的影响。确定了微波辐射条件下丙烯海松酸最佳的合成工艺条件：反应时间为1 h，反应温度为180℃，丙烯酸和精制松香的摩尔比为1.2∶1，微波辐射功率为110W。实验结果表明微波辐射能够显著地加速丙烯酸和...     

丙烯海松酸聚乙二醇酯的合成及聚集行为

以松香和丙烯酸为单体合成了丙烯海松酸,利用气相色谱-质谱联用技术（GC-MS）对合成的丙烯海松酸进行了表征。以丙烯海松酸和聚乙二醇2000为单体采用条件温和的steglich酯化法合成了两亲性的丙烯海松酸聚乙二醇酯,并应用红外（FT-IR）、凝胶渗透色谱（GPC）和热重（TG）研究了该物质的结构和性能。结果表明：丙烯海松酸聚乙二醇酯数均相对分子质量为4 700,多分散系数为1.2,分解温度在308~410℃范围内。采用表面张力和芘稳态荧光法测定了该物质的临界胶束质量浓度（CMC）,其CMC为1 g/L。用共振光散射（RLS）、动态光散射（DLS）和扫描电镜（SEM）法研究了丙烯海松酸聚乙二醇酯水溶液的聚集行为,结果表明：1 g/L的丙烯海松酸聚乙二醇酯水溶液在高于聚集温度74℃时胶束聚集,随着溶液的质量浓度由1 g/L增加到1.5 g/L时,聚集温度由74℃降低到65℃;1 g/L丙烯海松酸聚乙二醇酯水溶液的温度由25℃升高到85℃时,水合粒子平均直径（D_h）由295 nm增加到1 056 nm。     

丙烯海松酸甘油酯聚氧乙烯醚的合成及性能

合成了新的非离子表面活性剂丙烯海松酸甘油酯聚氧乙烯醚,研究丙烯海松酸与甘油的部分酯化及甘油酯与环氧乙烷的加成反应。适宜的反应条件为:丙烯海松酸与甘油反应温度260-270℃,用料摩尔比为1:3,反应时间5 h,催化剂ZnO用量为酸质量的0.08％;甘油酯与环氧乙烷的加成反应催化剂为KOH,用量为酯质量的0.7％-0.8％,温度150℃。测定了产物的表面物理化学性能,研究了环氧乙烷聚合度对产物表面物理化学性能的影响。     

丙烯海松双酰基硫脲衍生物的合成

松香与丙烯酸通过Diels-Alder双烯加成反应得到16-异丙基-5,9-二甲基四环[10.2.2.01,10.04,9]十六烷基-15-烯基-5,14-二酸(即丙烯海松酸),丙烯海松酸再经酰氯化、酯化,最后与芳胺反应生成标题化合物,通过IR、NMR、MS和元素分析等对产物进行了表征,并对反应条件进行了优化,产品收率...     

UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及应用

以2,4-甲苯二异氰酸酯(TDI)、丙烯海松酸二甘醇聚酯二元醇和丙烯酸羟丙酯(HPA)为主要原料合成了可紫外光固化的涂料用丙烯海松酸聚氨酯丙烯酸酯(APAPUA)低聚物。对产物进行了红外表征,并考察了其光固化行为。测试了APAPUA固化膜的硬度、柔韧性及其他力学性能,同时考察了其热稳定性。结果表明,该低聚物固化膜铅笔硬度达到4H,附着力1级,耐冲击性55 cm,初始分解温度245℃,具有固化速度快,力学性能及耐热性优良等特点,可以作为价格低廉的耐热性低聚物应用于光固化涂料。     

丙烯海松酸基双酰胺类化合物的合成及生物活性研究

经松香与丙烯酸的D-A加成反应制备丙烯酸改性松香,从中分离提纯得到丙烯海松酸。将丙烯海松酸转化为双酰氯,再与苯胺类化合物发生N-酰化反应,合成得到一系列新型丙烯海松酸基双酰胺类化合物,利用IR、1HNMR和13 CNMR表征了目标化合物的结构。初步生物活性测试表明,所合成的目标化合物在50μg/mL浓度下都对苹果轮纹病菌有一定的抑制活性,化合物丙烯海松酸基双对甲氧基苯酰胺在100μg/mL浓度下对油菜的胚根生长显示良好的抑制活性(达到A级活性水平)。     

丙烯海松酸基双酰腙类化合物的合成及生物活性研究

通过松香与丙烯酸的Diels-Alder环加成反应制备丙烯海松酸,经酰化后再与水合肼反应得到丙烯海松酸双酰肼.其在冰醋酸催化下与取代芳香醛反应,合成得到11个新型丙烯海松酸基双酰腙类化合物.初步探索了合成条件,并利用1HNMR、13CNMR、FT-IR和MS表征了目标化合物的结构.初步生物活性测试表明,目标化合物具有一定的杀菌活性(尤其对苹果轮纹病菌)和一定的植物生长调节活性;丙烯海松酸基双邻氯基苯酰腙对黄瓜枯萎病菌的抑制活性达65.5％.     

UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及其涂膜性能

以2,4-甲苯二异氰酸酯(TDI)、丙烯海松酸二甘醇聚酯二元醇和丙烯酸羟丙酯(HPA)为主要原料合成了UV固化涂料用丙烯海松酸聚氨酯丙烯酸酯(APAPUA)低聚物.对产物进行了红外表征,并考察了其光固化行为.测试了APAPUA固化膜的硬度、柔韧性及其他机械性能,同时考察了其热稳定性.结果表明该低聚物固化膜具有优良的力学性能及耐热性.     

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.