P（POSS-IA）纳米复合材料的制备及其鞣制性能

以八乙烯基笼型倍半硅氧烷（POSS-Vi）和衣康酸（IA）为原料，通过自由基聚合制得聚（笼型倍半硅氧烷-衣康酸）〔P（POSS-IA）〕纳米复合材料。通过FT-IR、1H-NMR、XRD、TEM对其结构进行了表征，POSS-Vi均匀分散在聚合物基体中，直径在50nm左右。将P（POSS-IA）应用于坯革鞣制工序中，与聚（衣康酸）〔P（IA）〕、聚（丙烯酸）〔P（AA）〕、聚（笼型倍半硅氧烷-丙烯酸）〔P（POSS-AA）〕、聚（甲基丙烯酸）〔P（MAA）〕、聚（笼型倍半硅氧烷-甲基丙烯酸）〔P（POSS-MAA）〕鞣制坯革进行了性能对比。结果表明，P（POSS-IA）鞣制坯革具有较高的收缩温度，达到68.2 ℃；P（POSS-MAA）鞣制坯革增厚率最大，可达到53.3%；P（POSS-AA）鞣制坯革的抗张强度和撕裂强度最高，分别达到31.6 MPa、59.3 N/mm。坯革的SEM和EDS结果表明，P（POSS-IA）纳米复合材料在鞣制坯革中分散更均匀。     

锌铝水滑石的制备及其在制革少铬鞣中的应用

通过共沉淀法制备了锌铝水滑石(ZnAl-LDH),采用XRD、FTIR、SEM对其结构进行了表征.将其配合用量为皮质量2％的铬粉(记为2％铬粉)应用于制革鞣制工艺中.考察了ZnAl-LDH制备时的金属源物质的量比、陈化时间对鞣制坯革收缩温度、鞣后废液中的Cr2O3质量浓度的影响.结果表明,ZnAl-LDH是尺寸在100～400 nm之间的片状材料.当n〔(Zn(NO3)2?6H2O)〕:n〔Al(NO3)3?9H2O〕=2.0:1.0,陈化时间为6 h时,制备的ZnAl-LDH-4具有优异的性能.与单独使用2％铬粉鞣制坯革相比,ZnAl-LDH-4(用量为皮质量的4％)配合2％铬粉鞣制坯革收缩温度由75℃提高到94℃,废液中的Cr2O3质量浓度由99.58 mg/L降低至46.98 mg/L,且加入ZnAl-LDH-4鞣制后,鞣后废液化学需氧量和生物需氧量均降低.     

含羧基水性环氧树脂的制备及其性能

以烯丙基缩水甘油醚(AGE)和甲基丙烯酸(MAA)为原料,采用"一步法",即基于自由基共聚理论,合成具有良好稳定性的含羧基水性环氧树脂。探讨了加料方式、引发剂种类及用量等因素对聚合物性能的影响,对含羧基水性环氧树脂的结构进行了红外、核磁表征,并将其应用于山羊酸皮的鞣制工序中。结果表明,采用氧化还原引发体系—过硫酸铵和亚硫酸氢钠,过硫酸铵用量为单体总质量的11%,单体全部滴加的方式制得聚合物稳定性良好,转化率为98%。应用结果表明,聚合物单独鞣制后坯革的收缩温度可达71℃,增厚率达46%;配合酸皮质量3%的铬粉鞣制后坯革的收缩温度为114.1℃,增厚率为104%;与传统铬鞣法相比,该工艺方法有效降低了废液中的Cr2O3含量,减少了环境污染。     

含氨基和羧基POSS/聚合物复合材料鞣制性能

以笼型八乙烯基倍半硅氧烷(POSS-Vi)、丙烯酰胺(AM)和甲基丙烯酸(MAA)为原料,通过自由基聚合法制备含氨基、羧基的POSS/聚合物复合材料P(POSS-AM-MAA)。采用FTIR、XRD、TEM等对P(POSS-AM-MAA)的结构和形貌进行表征。结果表明：复合材料P(POSS-AM-MAA)是具有立方笼型结构的POSS外围被聚合物链段包覆的材料。将复合材料P(POSS-AM-MAA)配合占酸皮重的4%戊二醛应用于山羊酸皮鞣制工艺中,考察了氨基含量、相对分子质量(简称分子量)大小、复合材料用量等对坯革性能的影响。结果表明：当复合材料P(POSS-AM-MAA)中氨基含量为433 μmol/g、数均分子量为27237,其用量为酸皮重的8%,结合pH为8.5时,结合鞣坯革收缩温度为83.7 ℃,增厚率为107.3%,相较于单独戊二醛鞣制坯革均有所提高;结合鞣坯革中的游离甲醛含量为28.3 mg/kg;结合鞣坯革的抗张强度为16.5 MPa,断裂伸长率为109.5%,撕裂强度为58.8N/mm,与戊二醛鞣制坯革相当。     

含羧基水性环氧树脂的制备及其性能研究

以烯丙基缩水甘油醚（AGE）和甲基丙烯酸（MAA）为原料,采用“一步法”,即基于自由基共聚理论,合成具有良好稳定性的含羧基水性环氧树脂。探讨了加料方式、引发剂种类及用量等因素对聚合物性能的影响,对含羧基水性环氧树脂的结构进行了红外、核磁表征,并将其应用于山羊酸皮的鞣制工序中。实验结果表明：采用氧化还原引发体系过硫酸铵和亚硫酸氢钠,过硫酸铵用量为11%,单体全部滴加的方式制得聚合物稳定性良好,转化率为98%。应用结果表明：聚合物单独鞣制后坯革的收缩温度可达71℃,增厚率达46%;配合3%铬粉鞣制后坯革的收缩温度为114.1℃,增厚率为104%;同时,与传统铬鞣法相比,此工艺方法有效降低了废液中的Cr2O3含量,减少了环境污染。     

含氨基和羧基POSS/聚合物复合材料鞣制性能

以笼型八乙烯基倍半硅氧烷(POSS-Vi)、丙烯酰胺(AM)和甲基丙烯酸(MAA)为原料,通过自由基聚合制备了含氨基、羧基的POSS/聚合物复合材料[P(POSS-AM-MAA)]。采用FTIR、XRD、TEM对P(POSS-AM-MAA)的结构和形貌进行表征。结果表明:P(POSS-AM-MAA)是具有立方笼型结构的POSS外围被聚合物链段包覆的材料。将复合材料P(POSS-AM-MAA)配合占酸皮质量4%的戊二醛应用于山羊酸皮鞣制工艺中,考察了氨基含量、相对分子质量、复合材料用量等对坯革性能的影响。当P(POSS-AM-MAA)中氨基含量为433μmol/g、数均相对分子质量(简称数均分子量)为27237,其用量为酸皮质量的8%,结合pH为8.5时,结合鞣坯革收缩温度为83.7℃,增厚率为107.3%,相较于单独戊二醛鞣制坯革均有所提高;结合鞣坯革中的游离甲醛含量为28.3 mg/kg;结合鞣坯革的抗张强度为16.5 MPa,断裂伸长率为109.5%,撕裂强度为58.8 N/mm,与戊二醛鞣制坯革相当。     

基于一步法制备含羧基环氧树脂/纳米二氧化锆复合材料

选用乙烯基三乙氧基硅烷改性纳米二氧化锆,与烯丙基缩水甘油醚、甲基丙烯酸通过自由基共聚法制备了含羧基环氧树脂/纳米二氧化锆复合材料。采用傅里叶红外光谱、X射线衍射分别对改性纳米二氧化锆和含羧基环氧树脂/纳米二氧化锆复合材料进行了表征。结果表明:纳米二氧化锆表面引入了双键;纳米二氧化锆较为均匀地分散在聚合物基体中,其表面灰色部分可能是聚合物形成的包裹。将含羧基环氧树脂/纳米二氧化锆复合材料应用于制革鞣制工艺中,应用结果表明:含羧基环氧树脂/纳米二氧化锆复合材料配合酸皮质量3%的铬粉鞣制坯革收缩温度为102.6℃,增厚率为67.26%,与酸皮质量8%的铬粉鞣制坯革相比,柔软度明显提高,鞣制后废液中的Cr_2O_3含量降低了73.2%。     

铁基金属有机骨架材料MIL-53-Fe的合成及鞣制性能

以六水合三氯化铁(FeCl_3·6H_2O)与对苯二甲酸(H_2BDC)为原料,通过溶剂热法制备了以H_2BDC为配体的铁基有机骨架化合物(MIL-53-Fe)。当以皮质量3%铬粉(以Cr_2O_3质量计为皮质量的0.75%)与皮质量2%超声后的MIL-53-Fe对酸皮进行结合鞣制时,鞣制后皮革收缩温度(T_s)达到101.8℃,与实验中纯铬鞣制皮革相比减少了铬鞣剂用量40%,鞣制后的皮革增厚率达到18.1%,抗张强度为29.56 MPa,断裂伸长率为89.77%,耐水洗性好,铬鞣剂的吸收率较高。将MIL-53-Fe进行单独鞣革,鞣制后皮革收缩温度为72.5℃,T_s相比于酸皮有所提高,表现出鞣性。结果表明,MIL-53-Fe可与铬鞣剂进行结合鞣制,能够促进铬鞣剂的吸收,提高成革耐水洗性。     

铁基金属有机骨架材料MIL-53（Fe）合成及鞣制性能

通过溶剂热法制备了以对苯二甲酸（H2BDC）为配体的铁基MOFs（MIL-53）材料。当以3%皮重铬鞣剂（以Cr2O3计为0.75%）与2%皮重超声后的MIL-53-Fe对酸皮进行结合鞣后，收缩温度达到101.8℃，减少了铬鞣剂用量40%，鞣制后的皮革增厚率达到18.1%，抗张强度为29.56MPa，断裂伸长率为89.77%，耐水洗性好，铬鞣剂的吸收率较高。将MIL-53-Fe进行单独鞣革，收缩温度为72.5 ℃。相比于酸皮有一定提高，表现出一定鞣性。实验表明MIL-53-Fe可与铬鞣剂进行结合鞣制，能够促进铬鞣剂的吸收，提高成革耐水洗性，少量未被吸收的MIL-53-Fe可以吸附废液中的有机废物，在减少铬用量的同时减少了废水中有害物质的含量，对于实现少铬鞣制与解决鞣制废水的污染问题有积极意义。     

醛酸共聚物/蒙脱土纳米复合材料的制备及性能研究

用水溶性聚合单体甲基丙烯酸和丙烯醛在钠基蒙脱土层间直接原位插层聚合,制备了水溶性醛酸共聚物/蒙脱土纳米复合材料。考察了引发剂用量及蒙脱土用量对纳米复合材料结构及应用性能的影响,并用X射线衍射和傅立叶变换红外光谱对纳米复合材料的结构进行了表征。研究结果表明:用坯革质量6%的纳米复合材料结合质量分数2%铬粉鞣制,可使坯革的收缩温度达90℃以上,增厚率达到70%以上,与常规铬鞣相比,可减少75%的铬粉用量。FTIR和XRD结果表明,所制备的纳米复合材料属于剥离型纳米复合材料,甲基丙烯酸与丙烯醛在蒙脱土层间发生了原位聚合。     

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。