辐照改性制备长支链型高熔体强度聚丙烯流变性能(Ⅱ)拉伸流变

通过辐照法制备了长支链型高熔体强度聚丙烯(LCB-HMSPP),采用Rheotens熔体拉伸流变仪研究了辐照改性PP的熔体强度和拉伸流变行为,讨论了敏化剂含量、辐照剂量、高分子量物质和温度对PP拉伸流变行为的影响。研究结果表明：PP的熔体强度、拉伸应力、拉伸黏度等拉伸流变物理量随敏化剂增加而显著增强,并随辐照剂量呈先上升后下降的趋势,辐照剂量为5kGy时,熔体强度和拉伸黏度到达最大。添加极少量高分子量物质(UHMWPE)也能有效提高PP的熔体强度。LCB-HMSPP的熔体强度活化能显著降低,熔体强度温度敏感性下降,可在较宽的温度范围内表现出较高的熔体强度。     

HDPE/石墨导热复合材料流变行为研究

制备了高密度聚乙烯(HDPE)/石墨导热复合材料,研究了该复合材料在毛细管流变仪中的流变行为。结果表明:该HDPE/石墨复合材料熔体在毛细管流变仪中的流动为非牛顿型流动,遵从假塑性流体的流动规律。随着石墨用量的增加,复合材料熔体的真实黏度、黏流活化能增大,非牛顿指数呈减小的趋势;随着剪切速率的增加,复合材料熔体的真实黏度和黏流活化能则均有所减小;而随着温度的升高,复合材料熔体的非牛顿指数呈增大的趋势。     

不同梳形支化结构聚苯乙烯熔体的流变行为

以主链长度相当、支链数目和支链长度变化的一系列梳形支化聚苯乙烯为对象,采用旋转流变仪测定其流变参数,研究了梳形支化结构对聚合物熔体流变行为的影响。结果表明,梳形支化聚苯乙烯的零剪切黏度随支化数目或支链长度的增加而增大。在支链长度低于链缠结临界分子量Me时,随支链数目增加,梳形支化聚苯乙烯的零剪切黏度与重均分子量对数曲线的斜率为2.8~2.9。在支链数目一定时,当支链长度增加到链缠结临界分子量Me之前,梳形支化聚苯乙烯的零剪切黏度与重均分子量对数曲线的斜率为3.2左右。梳形支化聚苯乙烯呈假塑性流动行为,其非牛顿指数小于1,且随支链数目或支链长度的增加有小幅下降。由于支链减轻了链缠结程度,导致梳形支化聚苯乙烯的黏流活化能低于线形聚苯乙烯,随支链数目增加,对链缠结的抑制作用增大,黏流活化能进一步下降。     

反应降解聚丙烯熔体的流变行为

采用双管毛细筒流变仪研究反应降解聚丙烯(PP)的非线性流变性能及其与分子结构参数的关系。结果表明:降解PP熔体为假塑性流体,降解程度越大,剪切黏度越低,而非牛顿流动指数增大,表明低相对分子质量PP的黏-切敏感性降低;不同相对分子质量PP试样的黏度随温度升高而下降,相对而言,低相对分子质量PP的黏-温依赖性略大,可能与分子链变短后构象熵减小有关;降解PP熔体的毛细管入口压力降(熔体弹性)随相对分子质量减小而降低;低相对分子质量PP的入口压力降~剪切速率曲线规律性差,说明降解PP熔体在毛细管入口区的流动稳定性较差。     

全氟磺酸树脂的流变特性

制备了一系列离子交换容量不同的全氟磺酸树脂（PFSR）,采用熔融流延工艺将其制备成膜。通过对不同的PF-SR进行红外光谱表征发现在1147,984cm^-1处谱峰相对强度的差异反映了聚合物离子交换容量的不同。采用毛细管流变仪测试了PFSR的表观黏度、非牛顿指数、黏流活化能等流变参数,讨论了剪切速率、温度、离子交换容量对PFSR熔体的表观黏度及非牛顿指数的影响和黏流活化能随剪切速率的变化规律。结果表明,PFSR熔体的表现黏度随剪切速率、温度、离子交换容量的升高而降低;在试验温度范围内,熔体的非牛顿指数小于1,属于假塑性流体;黏流活化能随剪切速率及离子交换容量的增大而明显减小。     

不同聚丙烯发泡体系的流变性能研究

采用ARES流变仪和毛细管流变仪，对线形聚丙烯（LPP）、长链支化聚丙烯（LCBPP）、LPP/LCBPP共混体系分别与纳米黏土的复合发泡体系的动态剪切和稳态剪切流变性能进行了研究。考察了复合体系制备过程中螺杆转速、相容剂含量对复合体系熔体弹性的影响，研究了不同温度下复合体系的剪切黏度、剪切应力与剪切速率之间的关系。结果表明：将纳米黏土引入PP发泡体系中可有效改进PP树脂的可发性。复合体系制备过程中，螺杆转速并未对LPP、LCBPP与纳米黏土复合体系的熔体弹性产生影响；随相容剂马来酸酐接枝聚丙烯用量的增加，LPP、LCBPP／纳米黏土复合体系的熔体弹性有小幅降低，但幅度并不显著；LCBPP／纳米黏土复合体系的剪切黏度具有较高的温度敏感性，随温度升高，表观剪切黏度下降显著。在低剪切速率区，LCBPP／纳米黏土复合体系的表观剪切黏度低于LPP、（LCBPP／LPP）／纳米黏土复合体系，但在高剪切区，三者的剪切黏度趋于接近。     

聚丙烯/丙烯-乙烯共聚物共混体系的流变行为研究

采用毛细管流变仪和旋转流变仪研究了聚丙烯(PP)纤维专用料/丙烯-乙烯共聚物(PEC)共混体系的流变行为,探究了剪切速率、温度、共混物组成对熔体流变行为的影响。结果表明,随着剪切速率的增加,PP、PP/PEC和PEC均表现出"剪切变稀"行为;随着温度的升高,聚合物的表观黏度逐渐降低,特别是在低剪切速率下的这种现象更明显;随着PEC含量的增加,体系的非牛顿指数增加,黏流活化能降低,黏度对温度的敏感性降低,熔体剪切模量增加,熔体弹性增加。     

聚丙烯/纳米羟基磷灰石复合材料流变性能研究

采用毛细管流变仪对聚丙烯/纳米羟基磷灰石(PP/n HA)复合材料的流变性能进行了研究,并讨论了复合材料的表观黏度、非牛顿指数、黏流活化能与温度、剪切速率、n HA用量之间的关系。结果表明:PP/n HA熔体为假塑性流体,其表观黏度随着n HA用量的增加总体呈上升趋势,但在其用量为1%时达到极小值;非牛顿指数随着温度的提高而增大,随着n HA用量的增加而逐渐减小;黏流活化能则随着剪切速率的增加逐渐降低,随着n HA用量的增加呈上升趋势。     

辐照诱导长支链聚乳酸的流变性能

采用电子束辐照诱导法改性线形大分子结构的聚乳酸(PLA),使其发生断链和支化。采用动态剪切流变方法研究了辐照改性PLA的剪切流变行为。辐照改性制备的支化PLA具有较好的熔体黏弹性,在低频端剪切储能模量U‘明显提高,内耗正切tan变小。讨论了PLA大分子旋光性、丙烯酸酷类双官能度单体(BDDA)用量和辐照剂量对PLA剪切流变行为的影响。实验发现,左旋聚乳酸(PLLA)比消旋聚乳酸对电子束更为敏感,更容易支化,并且在辐照剂量为l kGy时,其熔体弹性随BDDA用量的增加而增加;BDDA用量为J份的PLLA时,熔体弹性随辐照剂量增加而增加。     

氢氧化镁阻燃EVAC的流变性能研究

采用熔融共混法制备了Mg(OH)2阻燃乙烯-乙酸乙烯酯塑料(EVAC),并采用毛细管流变仪对其流变性能进行了研究。讨论了温度、剪切速率和剪切应力对熔体表观黏度的影响;研究了黏流活化能与剪切速率的变化规律。结果表明,熔体的表观黏度随温度的升高而降低,随剪切速率和剪切应力的增大而减小;黏流活化能随剪切速率的增大而降低。其非牛顿指数小于1,说明Mg(OH)2阻燃EVAC为假塑性流体。当剪切应力无限小时,由Spencer-Dillon公式外推得到阻燃EVAC的零切黏度。     

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.