聚氨酯相变储能微胶囊合成及其反应动力学

以异佛尔酮二异氰酸酯（IPDI）,聚丙二醇（PPG-500）和三乙醇胺（TEA）为原料,以二十烷为囊芯,采用界面聚合法制备一种微胶囊相变材料。采用红外光谱（FTIR）研究了聚氨酯/二十烷微胶囊的化学结构,采用扫描电子显微镜（SEM）和光学显微镜（OM）分析了乳化剂种类和用量、反应温度和搅拌速率等工艺条件对这种微胶囊的形成过程、表面形貌、粒径大小及分布和壁厚的影响。微胶囊形貌呈现规则球形,囊壁致密性好,热稳定性好。微胶囊呈正态分布,平均粒径为18.18μm,囊芯含量为58.46%,产率约91.00%。采用二正丁胺-丙酮滴定法,研究IPDI和PPG-500制备聚氨酯的反应动力学,得到反应速率常数k=327.08 L/(mol·min),活化能E=33.48 k J/mol,聚氨酯囊壁合成反应为二级反应,随着反应温度升高,反应速率迅速增大。采用DSC研究了复合相变材料的相变温度和相变焓值以及储能/释能的性能。     

微胶囊复合相变材料的制备及性能表征

以低熔点的相变材料为芯材,三聚氰胺脲醛树脂为囊壁材料,用原位聚合法制备了相变储能微胶囊。采用红外光谱、扫描电子显微镜、差示扫描量热分析和热重分析测试技术表征了制备的相变微胶囊的结构组成、形貌特征及热性能。实验结果表明,相变储能微胶囊复合相变材料热稳定性好,在160℃以下无质量损失,其相变温度和焓值分别为15.3℃,132.3 J/g。制备得到的微胶囊呈球形,平均粒径小于20μm,固化剂滴加速度为0.5 mL/m in时微胶囊形貌较佳,优化的芯/壁质量比为1∶1.5,且微胶囊的亲水性随芯材含量增加而降低。     

聚氨酯相变微胶囊的储能和热分解性能

以聚氨酯为囊壁,二十烷为囊芯通过界面聚合法制备微胶囊,采用光学显微镜（OM）、扫描电子显微镜（SEM）对该微胶囊材料进行表征,采用示差扫描量热仪测量分析微胶囊的热性能和储能性能及其相变机理,采用Kissinger法和Ozawa法研究该微胶囊材料的热分解动力学。结果表明,制得的微胶囊呈规则球形,表面形貌光滑致密,粘连少,平均粒径18μm,囊壁厚度为1.80μm,产率为91.00%,囊芯质量分数为58.46%。经过多次热循环得到微胶囊的DSC曲线,均表现为单一熔融峰和双重结晶峰,其相变过程中同时发生固-固和固-液相变,相变机理属于随机成核和随后生长,相变机理函数为G(a)=-ln(1-a),相变过程表现为一级反应。相变储能材料存在三个热失重阶段,聚氨酯囊壁的保护作用使得相变储能材料的起始分解温度提高23℃,储热能力较好。根据Kissinger和Ozawa方程计算该微胶囊的活化能分别为311.27 kJ/mol、293.16 kJ/mol,热分解过程为一级反应。     

复凝聚法制备明胶/阿拉伯胶含油微胶囊工艺过程的研究

研究了复凝聚法制备含油微胶囊的工艺过程。以大豆油为囊芯材料,阿拉伯胶与明胶为璧材,研究了溶液pH值,反应温度,反应时间,壁材浓度,搅拌条件等对微胶囊产品质量的影响。发现搅拌速度对微胶囊的粒径大小和分布影响很大。最佳工艺条件为:明胶与阿拉伯胶质量比为1,浓度都为2%,pH值为4.0~4.5,搅拌速度为1500 r/min,反应温度为55℃,凝聚时间为15~20min,固化温度为10℃,固化时间60 min。     

聚砜包覆双环戊二烯微胶囊的制备

采用简单易控的溶剂挥发法成功制备了聚砜包覆双环戊二烯微胶囊,讨论了反应温度、分散剂、芯壁比及搅拌速度对微胶囊性能的影响,并通过扫描电子显微镜、光学显微镜和热重分析仪对微胶囊的表面结构、形貌和热性能进行了研究。结果表明,选择明胶溶液作为分散剂,反应温度为30 ℃时,可制备出粒径和壁厚可控的具有规则球形的微胶囊;随着芯材比例的增大,微胶囊壁厚减小;粒径随着搅拌速度的加快而减小。     

采用悬浮聚合法批量制备相变储能材料微胶囊

采用悬浮聚合法,利用自己设计的相变材料微胶囊(Micro PCMs)批量制备的生产设备合成了以正十八烷为囊芯,以苯乙烯马来酸酐-甲基丙烯酸甲酯共聚物P(MMA-co-SMA)为囊壁的相变储能微胶囊,熔融热焓值最高可达到150.12 J/g,结晶热焓值可达151.05 J/g,并通过扫描电子显微镜,差示扫描量热仪等对其性能进行了分析。讨论了乳化速度和乳化时间对批量制备相变储能微胶囊的热焓值和产量的影响。     

制备工艺条件对固化剂微胶囊性能的影响

以改性胺1618固化剂为囊芯、以脲醛树脂为壁材单体,采用界面聚合技术,成功制备了一种新型聚脲改性胺微胶囊固化剂。考察了芯壁质量比、反应体系p H及搅拌速率对微胶囊包覆率、分散性及分布情况的影响,确定最佳制备工艺条件。采用傅里叶变换红外光谱、扫描电镜及热重分析仪对微胶囊的化学结构及性能进行表征。结果表明,当芯壁质量比为0.8、反应体系p H为2~3、搅拌速率为0.5 kr/min,该条件下制备的微胶囊包覆率为66.7%,分散性及表面致密性好,其热稳定温度达到216℃。     

石蜡-密胺树脂微胶囊相变材料制备与表征

研究中采用了正十八烷石蜡相变材料(PCM)芯材,密胺树脂作为囊壁材料,用原位聚合法制备成微胶囊材料。通过改变芯材和囊壁材料的质量比,探讨了微胶囊制备过程中O/W乳化液的相稳定性,并采用SEM,FT-IR,粒度分析仪和DSC对微胶囊的形态及性能进行表征。结果表明芯材增大O/W乳化液的相稳定性下降,微胶囊数量平均粒径和体积平均粒径均减小,当芯材和囊壁材料的质量比(Core/Shell)为1.5∶1时,微胶囊表面光滑致密,平均粒径为3.6μm,相变焓为98.6 MJ/mg。     

基于乙基纤维素构建缓释型NaCl微胶囊及性能研究

以氯化钠为囊芯材料,乙基纤维素(EC)为微胶囊壁材,通过乳化-溶剂挥发法制备缓释型融雪剂NaCl/EC微胶囊。利用扫描电子显微镜(SEM)、X射线能谱仪(EDS)、热分析仪(TG)和电导率仪对NaCl/EC微胶囊的微观形貌、包封效能和缓释性能进行表征,考察微胶囊形成参数(搅拌速度、溶剂挥发温度、NaCl掺量)对缓释性能的影响。结果表明,在搅拌速度400 r/min,溶剂挥发温度30℃,NaCl与EC质量比为2∶1的优化条件下,制得的NaCl/EC微胶囊产物呈规则球形,分散均匀,表面光滑,缓释效果较好。     

聚砜包覆环氧树脂微胶囊的制备

采用溶剂蒸发法制备了聚砜包覆双酚A型环氧树脂微胶囊,通过光学显微镜、激光粒度分布仪和微机差热天平对微胶囊的形貌、粒径分布及热性能进行了表征,讨论了分散剂种类及用量、搅拌速度、反应温度以及壁材与芯材投料质量比对微胶囊制备的影响。结果表明,反应温度过高时不能形成微胶囊;选择1.0 %（质量分数,下同）的聚乙烯醇分散剂、搅拌速度为750 r/min、反应温度为30 ℃、壁材与芯材投料质量比为2∶1时制得的微胶囊呈规则球形,产率较高,微胶囊分散较好,平均粒径在100 μm之内。     

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.     

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.     

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.     

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。