氧化石墨烯-水性环氧树脂固化剂的制备及性能

首先，将三乙烯四胺(TETA)和氧化石墨烯(GO)球磨，得到TETA改性GO分散液TGO；然后向其中依次滴加双酚A型环氧树脂E44、三羟甲基丙烷三缩水甘油醚(TPEG)、甲氧基聚氧乙烯-2,3-环氧丙烷(MEH)和γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(KH560)，采用原位聚合法合成了氧化石墨烯-水性环氧树脂固化剂(TGO-WPEA)；采用上述工艺，不添加GO的条件下制得水性环氧树脂固化剂(WPEA)。将WPEA和TGO-WPEA分别与环氧树脂乳液(Epikote-6520)复合制得水性环氧树脂(EP)和氧化石墨烯改性水性环氧树脂(TGO-EP)防腐涂料。通过FTIR、XPS和XRD对材料进行了结构表征，采用电化学测试和盐雾实验对TGO-EP的防腐性能进行了评价。结果表明，水性环氧树脂固化剂(WPEA)分子通过共价键连接到GO表面，改善了GO在EP中的分散稳定性和接枝率，提高了TGO-EP复合涂料对腐蚀介质的屏蔽性能。与纯EP涂层相比，TGO-EP涂层腐蚀电位从–0.267 V提高到–0.125 V，腐蚀电流密度从5.44×10^–8 A/cm²     

聚醚封端剂对自乳化环氧树脂固化剂性能的影响

通过高分子分子结构设计,以E44(双酚A型环氧树脂)、TETA(三乙烯四胺)、TPEG(三羟甲基丙烷三缩水甘油醚)和MEH(甲基聚氧乙烯环氧基醚)为原料,合成了一系列非离子型自乳化的WPEA(水性环氧树脂固化剂),并通过转相法制备得到WPEA-EP(固化剂-环氧树脂复合乳液)。研究结果表明:随MEH含量的增加,WPEA胺值下降,黏度呈现先下降后增加的趋势;当MEH含量为0.01 mol时,固化剂胺值为347.50 mg KOH/g,黏度最低达到8 235 mPa·s;复合乳液粒径随MEH含量的增加呈下降趋势。当MEH含量为0.03 mol时,漆膜的综合性能最佳,在水中浸泡7 d后吸水率最低为w(MEH)=1.81%(相对于单体总质量而言),浸泡40 d后的漆膜附着力最高为5.94 MPa。     

功能化氧化石墨烯在粉末涂料中的分散性及防腐性能的应用研究

表面经γ-(2,3-环氧丙氧)丙基三乙氧基硅烷(KH560)修饰的氧化石墨烯(GO)与没食子酸基环氧树脂(GEP)混合形成功能化氧化石墨烯(FGO),可有效提高GO的分散性,进而使其均匀地分散在粉末涂料中,通过静电喷涂法成功制备了防腐涂层。采用SEM、傅里叶红外光谱仪(FT-IR)、盐雾测试、耐冲击测试、接触角测试等对GO及涂层性能进行表征和测试。考察了KH560用量在四氢呋喃(THF)及粉末涂料中分散性的影响;同时也考察了KH-560修饰GO用量对涂层性能的影响。结果表明:以KH560功能化GO制备的涂层具有优异的防腐性能和机械性能。     

氨基化GO/磺化聚苯胺改性水性环氧防腐涂料的制备与性能

以氯磺酸、苯胺和过硫酸铵为主要原料合成磺化聚苯胺（SPANI）,利用聚乙烯亚胺（PEI）还原GO,合成PG复合材料。利用GO上活性位点,将SPANI与PG结合,制备了SPG复合材料。利用SPG与水性环氧树脂共混制备水性环氧防腐涂料。通过FT-IR、XRD对SPG复合材料结构表征,结果表明,PEI上的氨基成功与GO结合,SPANI成功增加了PG的层间距;通过盐雾、电化学等实验对水性环氧涂层的防腐性能进行测定,并分析了涂层的物理性能。结果表明,当添加2wt%SPG时（添加量以环氧树脂和固化剂总质量为基准,下同）的水性环氧防腐涂层具有最优异的耐腐蚀性,腐蚀效率可达到99.19%,与纯EP相比,腐蚀电流密度从1080 nA?cm-2减小至307 nA?cm-2,腐蚀电压从-0.840mV升高至-0.347mV。     

乳化型环氧固化剂的制备及其防腐性能研究

以不同环氧值的双酚A型环氧树脂、三乙烯四胺(TETA)、三羟甲基丙烷三缩水甘油醚(TPEG)和甲基聚氧乙烯环氧基醚(MEH)为原料,合成了一系列非离子型自乳化的水性环氧树脂固化剂(WPEA),并通过转相法制备得到固化剂-环氧树脂复合乳液(WPEA-EP)。通过FTIR及H1-NMR对WPEA的结构进行了表征,通过对固化剂粘度、胺值和分子质量的测定研究了环氧值对WPEA性能的影响,并讨论了环氧值对WPEA-EP粒径和涂层性能的影响。结果表明:随环氧值的增加,WPEA胺值上升,粘度下降,复合乳液粒径也随环氧值的增加变小。当环氧值为0.35 mol/100 g时,漆膜的综合性能最佳。在水中浸泡7 d后的吸水率为1.81%,浸泡40 d后的漆膜附着力为5.94 MPa。在3.5%氯化钠溶液中浸泡240 h后涂层低频(10 m Hz)阻抗可达6.01×106Ω·cm2,表现出长时效的屏蔽防腐性能。     

氧化石墨烯在水性防火防腐一体化涂料中的作用机理研究

将氧化石墨烯（GO）和不含卤素的磷 -氮阻燃剂均匀地分散到水性环氧树脂体系中,利用凝聚相阻燃和气相阻燃混合阻燃技术制备了防火防腐一体化涂层,研究了氧化石墨烯对涂层的耐火性能、生烟速率以及耐腐蚀性能的影响,并结合微观形貌观察、热分析、腐蚀产物分析等研究了氧化石墨烯在防火防腐一体化涂层中的作用机理。结果表明： GO表面丰富的含氧官能团中羟基与环氧树脂侧链上的羧基间相互作用使得 GO在水性环氧体系中具有优异的分散性; GO的加入能将耐火性能试验时间较纯试样提升 73. 0%,同时延长外界气体和腐蚀性介质的渗透路径,有效增强涂层抗渗透性,在增加涂层耐火性能和减少生烟速率的同时,提升了涂层耐腐蚀性能。     

ATO/GO纳米复合材料的制备及性能

以氧化石墨烯(GO)为前体,通过氨丙基三乙氧基硅烷(KH550)将氧化锡锑(ATO)锚定到氧化石墨烯片层上,制备得到氧化锡锑-氧化石墨烯纳米复合材料(ATO/GO)。通过高速分散法与水性环氧树脂乳液(AE)共混,制备得到氧化锡锑-氧化石墨烯/水性环氧树脂复合乳液(ATO/GO-AE)。通过XRD,XPS和SEM对其结构进行了表征。考察了ATO/GO含量对水性环氧涂料防腐及抗静电性能的影响。结果表明:随ATO/GO含量的增加,复合涂料表面电阻降低,ATO/GO质量分数等于3.0%时,表面电阻降低至1.0×10~9?以下,达到了抗静电的使用要求,漆膜水蒸汽透过率降低至62.13 g/(m~2·h),具有最低的腐蚀电流(Icorr=3.73×10~(-9) A/cm~2)和最高的腐蚀电压(Ecorr=–0.1993 V),ATO/GO的防腐效率与AE相比提高了99.95%。     

石墨烯掺杂水性环氧树脂的隔水和防护性能

通过物理混合将自制的石墨烯分散液与双组分水性环氧树脂制备成石墨烯环氧树脂。用扫描电镜(SEM)考察了石墨烯在水溶液中的分散情况。通过极化曲线、交流阻抗谱和中性盐雾试验探讨了含0.5%石墨烯的E44水性环氧涂层(0.5%G-E44)在模拟海水溶液中的隔水和耐腐蚀性能并与纯环氧涂层E44进行比较。结果表明:石墨烯在水溶液中分散良好,其在水性环氧树脂中层层叠加,形成了致密的物理隔绝层,减缓了水分子在涂层中的扩散速率,拥有较好的隔水性能。E44和0.5%G-E44涂层在浸泡初期的Fick扩散系数分别为5.56×10-9 cm2/s和1.61×10-11 cm2/s。添加石墨烯明显提高了水性环氧树脂涂层的防护效果,自腐蚀电流密度减小,涂层电阻和电荷转移电阻增大,200 h中性盐雾试验后涂膜平整,无明显腐蚀。     

三聚磷酸铝/氧化石墨烯复合材料在水性防腐涂料中的应用

采用球磨分散法制备得到三聚磷酸铝/氧化石墨烯水性复合防腐浆料(AlTP/GO),并与水性环氧树脂复配制得纳米复合防腐涂料(EP-AlTP/GO)。通过场发射扫描电镜(FE-SEM)观测到AlTP/GO可均匀分散到EP树脂内部。吸水率测试结果表明,氧化石墨烯的引入提高了涂层的耐水性和屏蔽性能;附着强度测试结果表明,三聚磷酸铝可提高涂层在金属基材上的附着强度;电化学测试(Bode)和环境扫描电镜测试(E-SEM)结果表明,AlTP/GO可有效增强水性环氧涂层对腐蚀介质的屏蔽作用,限制了腐蚀反应的扩散,在3.5%NaCl水溶液中浸泡40 d后其低频阻抗达到7.02×10~7Ω·cm~2,盐雾测试400 h后金属表面平滑,金属腐蚀未发生明显扩散,EP-AlTP/GO人工破损处周边含氧量低至15.66%,遏制了氧化铁的形成。     

多巴胺改性氧化石墨烯-TiO_2纳米复合材料在水性环树脂中物理性能和腐蚀动力学研究

利用多巴胺(DA)改性氧化石墨烯(GO),并将纳米TiO_2负载在氧化石墨烯GO表面,制备了纳米PDA@GO-TiO_2复合材料。通过FT-IR、XRD、Raman光谱、XPS和TEM等表征手段对纳米PDA@GO-TiO_2复合材料的结构、微观形貌等进行表征分析。采用超声分散与机械搅拌相结合的方法将改性纳米PDA@GO-TiO_2复合材料分散到水性环氧树脂中,制备了纳米PDA@GO-TiO_2复合水性环氧树脂涂层(PGT/WEP)。测试了PGT/WEP涂层的硬度、耐冲击性、附着力等物理性能,并对其电化学性能进行了评价。结果表明:在水性环氧树脂中添加纳米PDA@GO-TiO_2复合材料比在相同百分比下使用GO或纳米TiO_2的涂层具有更好的物理性能。涂层性能和腐蚀动力学分析表明,PDA改性GO-TiO_2作为水性环氧涂料的添加剂具有潜在的应用前景。     

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.