聚四甲撑二醇热塑性聚氨酯弹性体的合成研究

七十年代初期,以聚四甲撑二醇(PTMG)为主要原料的聚醚型热塑性聚氨酯弹性体开始有商品生产。我们用PTMG和4,4′-二苯基甲烷二异氰酸酯(MDI)合成了具有较好物理机械性能和加工工艺性能的聚四甲撑二醇热塑性聚氨酯(PTMG-TPU)弹性体。     

扩链剂对TODI型聚氨酯弹性体性能的影响研究

以3,3′-二甲基-4,4′-联苯二异氰酸酯(TODI)和聚四氢呋喃均聚醚(PTMG)合成聚氨酯预聚体,分别以1,4-丁二醇(BDO)和二胺类的3,5-二甲硫基甲苯二胺(E-300)、3,3′-二氯4,4′-二氨基二苯甲烷(MOCA)和4,4′-亚甲基双(3-氯-2,6-二乙基苯胺)(M-CDEA)为扩链剂,研究了扩链剂对聚氨酯弹性体力学性能和耐热性能的影响。结果表明:以M-CDEA为扩链剂的TODI弹性体综合力学性能最为优异;在耐热性能方面,以4种扩链剂制备的TODI型聚氨酯弹性体的顺序为MCDEA>MOCA>BDO>E-300。     

高性能聚氨酯密封材料的微相结构和热性能(Ⅱ)

采用聚碳酸酯二醇(PCDL)、聚四亚甲基醚二醇(PTMG)和4,4′-二苯基甲烷二异氰酸酯通过预聚体法和半预聚体法合成了一系列聚氨酯(PU)弹性体。采用示差热扫描量热,热失重和动态力学性能分析对PU弹性体的性能及多元醇结构和组成,合成方法对PU弹性体微相结构形态的影响进行了研究。结果表明,由预聚体法合成的弹性体的微相分离程度高于半预聚体法,二胺扩链的弹性体的硬段结晶性优于二醇扩链的弹性体,单一二醇合成弹性体的硬段的结晶性优于混合二醇合成的弹性体,几种弹性体的的硬段结晶性依次为PU-LF-950APU-PCDL≈PUPTMGPU-PCDL+PTMG。几种弹性体的热稳定性依次为PU-PCDLPU-PCDL+PTMG≈PU-PTMGPU-LF-950A。PU-LF-950A和PU-PTMG的低温性能优于PU-PCDL和PU-PCDL+PTMG。PU-LF-950A还具有较好的高温动态性能和微相分离程度。     

HTBN/PTMG双软段聚氨酯弹性体的制备及力学性能研究

以甲苯二异氰酸酯(TDI)、端羟基聚丁二烯-丙烯腈共聚物(HTBN)、聚四氢呋喃醚二醇(PTMG)为主要原料,3,5-二甲硫基甲苯二胺(DMTDA)为扩连剂,采用浇铸法制备了聚氨酯弹性体。研究了聚氨酯预聚体中NCO含量、HTBN/PTMG质量比、PTMG相对分子质量和改变扩链剂用量以及热处理时间对聚氨酯弹性体力学性能的影响。结果表明,低相对分子质量PTMG和高热处理温度有利于提高聚氨酯弹性体的力学性能,当聚氨酯预聚体中HTBN/PTMG的质量比为50∶50、NCO质量分数为5.98%、NCO/NH2摩尔比为1.20、115℃下热处理2 h时,聚氨酯弹性体的力学性能最佳。     

软段组成对MDI型聚氨酯弹性体性能的影响

采用半预聚体法,分别以聚四氢呋喃二醇(PTMG)、聚己内酯二醇(PCL)和聚己二酸新戊二醇酯二醇(PNA)为软段,液化MDI、1,4-丁二醇(BDO)为硬段制备具有不同软段组成的聚氨酯弹性体,研究了软段组成对聚氨酯弹性体性能的影响。结果表明,PCL型和PNA型聚氨酯弹性体力学性能较好,玻璃化转变温度较高,接触角较大,吸水率较低;浸水7 d后,PTMG型聚氨酯弹性体强度保持率较高。     

抗氧剂Irganox1010对聚氨酯弹性体老化性能的影响

通过傅里叶红外变换光谱、热分析与力学性能测试,研究了抗氧剂四(3,5-二叔丁基-4-羟基苯丙酸)季戊四醇酯(Irganox1010)对聚氨酯弹性体老化性能的影响。力学测试结果表明,150℃下老化48h后,未加抗氧剂的聚氨酯弹性体的拉伸强度与老化前相比较下降11.6%,而添加抗氧剂的聚氨酯弹性体的拉伸强度与老化前相比较没有下降。热重分析、差示扫描量热分析和红外光谱分析结果表明,抗氧剂Irganox1010能阻碍聚氨酯分子链的断裂,减缓材料的老化,因此能促进聚氨酯弹性体的抗老化性能。     

M-CDEA在聚氨酯弹性体中的应用研究

分别以聚ε-己内酯多元醇(PCL)、聚四氢呋喃醚二元醇(55PTMG)和甲苯二异氰酸酯(TDI)为原料合成聚氨酯预聚体,分别用M-CDEA[4,4′-亚甲基-双-(3-氯-2,6-二乙二基苯胺)]和3,3’-二氯-4,4’-二氨基二苯基甲烷(MOCA)作为扩链剂合成聚氨酯弹性体,比较了两种不同扩链剂对聚氨酯弹性体的力学性能和耐热性能的影响。实验结果表明:与MOCA相比,由M-CDEA扩链的聚氨酯弹性体的硬度、撕裂强度、回弹和耐磨性较高。DSC和TG测试结果表明:经M-CDEA扩链的聚氨酯弹性体的耐热性能优于MOCA。     

聚氨酯弹性体的合成与耐热性能研究

分别以聚己内酯二醇(PCL)、聚四亚甲基醚二醇(PTMG)为低聚物二醇原料,以对苯二异氰酸酯(PPDI)、二苯基甲烷二异氰酸酯(MDI)或2,4-甲苯二异氰酸酯(TDI)为异氰酸酯原料,以1,4-丁二醇(BDO)或3,3'-二氯-4,4'-二氨基二苯基甲烷(MOCA)为扩链剂,采用预聚体法合成了结构不同的聚氨酯(PU)弹性体,并对其进行了物理机械性能测试、热重分析(TG)和动态力学分析(DMA)。结果表明,PCL/PPDI/BDO聚氨酯弹性体的力学性能和耐热性能最好; PPDI/BDO/PCL聚氨酯弹性体的储能模量优于TDI/MOCA/PCL弹性体;当硬段结构为PPDI/BDO时,较低温度下,PCL体系的储能模量优于PTMG体系,较高温度下,PTMG体系优于PCL体系。     

软段结构对脂肪族聚氨酯弹性体的结构与性能影响

分别采用聚丙二醇(PPG)、聚四氢呋喃二元醇(PTMG)、聚己二酸一缩二乙二醇三羟甲基丙烷酯多元醇(726)和聚己二酸新戊二醇酯二元醇(756)4种不同软段制备了基于异佛二酮二异氰酸酯(IPDI)的脂肪族聚氨酯弹性体(PUE),并通过FT-IR、DSC和TGA等表征了软段结构对PUE结构与性能的影响。结果表明,在相同硬段含量的条件下,PTMG制备的PUE具有最高的交联密度和最低的氨酯羰基氢键化程度。聚酯型PUE的耐热性和热氧老化性能均优于聚醚型PUE,由756合成的PUE具有最好的老化性能和热稳定性。     

PTMG/PPG基CPU的相分离及力学性能研究

分别以聚四氢呋喃二醇(PTMG)、聚氧化丙烯二醇(PPG)及两者共混物(PTMG/PPG)作为软段,以2,4-甲苯二异氰酸酯(TDI)和扩链剂3,3'-二氯-4,4'-二氨基二苯甲烷(MOCA)作为硬段,采用预聚体法,制备了5种不同PTMG/PPG配比的浇注型聚氨酯弹性体(CPU)。研究了PTMG/PPG不同的配比对CPU的力学性能和微观相分离的影响。结果表明,纯PTMG型聚氨酯力学性能优于纯PPG型聚氨酯性能,随着PPG在混合聚醚多元醇的比例增加,所形成的CPU的力学性能出现一定程度的下降。纯PTMG型聚氨酯的玻璃化转变温度(Tg)低于纯PPG型聚氨酯的Tg,随着PPG在混合聚醚中的配比增加,所合成相应的聚氨酯弹性体的Tg移向高温区,微观相分离程度减小。     

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.