镍系充油顺丁橡胶的工业化应用

通过中试及工业化试验,对环烷酸镍-三异丁基铝-三氟化硼乙醚络合物-含氧化合物的催化丁二烯聚合体系进行了催化特性、生产工艺、胶液与高芳烃油混合工艺、物料消耗和能量消耗分析。结果表明,该体系催化活性高,稳定性好,能灵敏地调节顺丁橡胶的门尼黏度;加入含氧化合物不会影响顺丁橡胶的微观结构;高芳烃油与高门尼黏度顺丁橡胶胶液的相溶性较好;工业化试验中,丁二烯质量浓度较低,聚合反应偏弱,挂胶较重。     

催化剂配比对镍系顺丁橡胶支化结构的影响

以环烷酸镍(Ni(naph)_2)-三异丁基铝(Al(i-Bu)_3)-三氟化硼乙醚络合物(BF_3·OEt_2)(Ni-Al-B)三组分组成的镍系催化剂催化丁二烯(Bd)配位聚合,在反应初期加入含不饱和双键的低相对分子质量聚合物,研究催化剂组分对此顺丁橡胶的支化度和相对分子质量的变化规律及由此带来的溶液黏度的变化。结果表明,聚合产物的相对分子质量分布随着n(Al)/n(Ni)的增大而变宽,胶液黏度随着n(Al)/n(B)的增大逐渐上升,但是n(Ni)/n(Bd)对胶液的黏度影响不大。在n(Al)/n(Ni)为6、n(Al)/n(B)为0.6、n(Ni)/n(Bd)为3×10~(-5)时,丁二烯聚合支化程度最高。     

镍催化剂存在下丁二烯的聚合——Ⅰ、催化剂组分用量变化对聚合的影响

对环烷酸镍—三异丁基铝—三氟化硼乙醚络合物催化剂存在下丁二烯的聚合作了研究。在Al/丁(克分子比)=5×10~(-5)时,考察了Ni和B的不同用量对聚合转化率、聚合速度和分子量的影响。实验结果表明催化剂组分之间的最适比例与催化剂用量有关。     

镍催化体系合成顺式聚丁二烯的研究——Ⅲ.催化剂加料方式的评选

引言 用环烷酸镍—三异丁基铝—三氟化硼乙醚络合物(以下分别简称为Ni、Al、B)为催化剂,以抽余油为溶剂,可使丁二烯聚合为高顺式聚丁二烯,並已工业化。 众所周知,定向聚合催化剂的加料方式对催化聚合活性关系很大。目前,国内有几     

齐鲁石化橡胶厂两研发项目通过鉴定

近日,由齐鲁石化橡胶厂承担的中国石化低凝胶含量顺丁橡胶的开发和低门尼丁苯橡胶SBR1507技术开发两个项目通过鉴定。 低凝胶含量顺丁橡胶采用环烷酸镍、三异丁基铝、BF3·D络合物的新型镍系三元催化体系,可以合成出凝胶含量较低的不同门尼粘度的聚丁二烯橡胶,目前该技术已获得中国发明专利授权。     

ESBR1712基础胶乳门尼黏度的影响因素研究

通过乳聚法合成了充油乳聚丁苯橡胶SBR1712基础胶乳,研究了引发剂加入量、聚合转化率、相对分子质量调节剂加入量及加入方式对SBR1712基础胶乳门尼黏度的影响。结果表明,在相同转化率条件下,随着引发剂用量的增大,基础胶乳的门尼黏度逐渐降低;随着聚合转化率的提高,胶乳的门尼黏度上升;随着相对分子质量调节剂用量的增加,基础胶乳门尼黏度逐渐降低;相对分子质量调节剂一次加入的胶乳门尼黏度随转化率升高波动较大,而分批加入相对分子质量调节剂胶乳的门尼黏度较稳定。     

磷酸酯配体对镍系催化剂催化丁二烯聚合的影响

研究了在环烷酸镍-三异丁基铝(简称Al)-三氟化硼乙醚络合物(简称B)体系中添加磷酸二(2-乙基己基)酯(简称P)对丁二烯聚合活性的影响,并通过傅里叶变换红外光谱、凝胶渗透色谱、凝胶渗透色谱-激光光散射仪-黏度计在线联用系统等对聚合物结构进行了表征。结果表明,采用P-B预混的陈化方式,取P与B的摩尔比为0.020,在Al与B的摩尔比为0.7~2.0时单体转化率都达了90%以上。聚合物的相对分子质量可通过改变P/B或Al/B进行调节。P的引入对聚合产物的顺式结构含量几乎没有影响,产物仍为高顺式聚丁二烯;在高相对分子质量级分的支化度较高,所得聚合物溶液的剪切黏度下降。     

低AI/B值镍系顺丁橡胶的性能及分子结构

对于镍系顺丁橡胶(简称顺丁胶)工业聚合过程,当催化剂配方中三异丁基铝/三氟化硼乙醚络合物(以下简称Al/B)值降低到一定程度时,顺丁胶的性能将明显变坏,且影响该胶的生产和加工应用。本工作对不同Al/B值顺丁胶的辊筒工艺性能、流变性能、物理机械性能进行了研究,并对可能影     

氢气对钼系催化剂合成1,2-聚丁二烯的影响

在氢气存在下,以辛醇取代的五氯化钼及间甲酚取代的三异丁基铝为催化剂引发丁二烯配位聚合,研究了氢气加入量及加入方式对1,2-聚丁二烯相对分子质量及其分布、微观结构、剪切黏度、门尼黏度以及硫化胶物理机械性能的影响.结果表明,随着氢气加入量的增加,聚合物相对分子质量降低,分布变宽.当氢气压力大于0.40 MPa时,随着氢气加入量的增加,聚合物相对分子质量及其分布的变化趋缓,其中连续加入氢气的方式对聚合物相对分子质量及其分布的调节作用较一次性加入方式要好.加入氢气后所得聚合物的1,2-结构含量有所降低,聚合物溶液的剪切黏度下降明显,生胶门尼黏度略有增加.当氢气压力小于0.80 MPa时,聚合物硫化胶的扯断伸长率和永久变形降低,其他物理机械性能基本不受影响.     

乙丙共聚物相对分子质量分布的研究

以三氯氧钒-混合烷基铝、改性三氯氧钒-倍半烷基铝、三氯氧钒-倍半烷基铝、三乙酰丙酮钒-三异丁基铝为催化体系,以己烷为溶剂、氢气为相对分子质量调节剂,研究了不同催化体系对聚合物相对分子质量分布的影响。对主催化剂的加入量、助催化剂与主催化剂的比例、氢气的体积分数对聚合物相对分子质量分布的影响进行了较详细的研究。结果表明,采用不同的催化体系,得到的聚合物相对分子质量分布不同,n(Al)/n(V)对聚合物相对分子质量分布无影响。     

Sapindaceae,cyanolipids, and bugs

Scentless plant bugs (Heteroptera: Rhopalidae) are so named because adults of the Serinethinae have vestigial metathoracic scent glands. Serinethines are seed predators of Sapindales, especially Sapindaceae that produce toxic cyanolipids. In two serinethine species whose ranges extend into the southern United States,Jadera haematoloma andJ. sanguinolenta, sequestration of host cyanolipids as glucosides renders these gregarious, aposematic insects unpalatable to a variety of predators. The blood glucoside profile and cyanogenesis ofJadera varies depending on the cyanolipid chemistry of hosts, and adults and larvae fed golden rain tree seeds (Koelreuteria paniculata) excrete the volatile lactone, 4-methyl-2(5H)-furanone, to which they are attracted.Jadera fed balloon vine seeds (Cardiospermum spp.) do not excrete the attractive lactone. Loss of the usual heteropteran defensive glands in serinethines may have coevolved with host specificity on toxic plants, and the orientation ofJadera to a volatile excretory product could be an adaptive response to save time.Mention of a commercial product does not consititute an endorsement by the USDA.     

2008～2009年世界塑料工业进展

收集了2008年7月～2009年6月世界塑料工业的相关资料,介绍了2008～2009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、环氧树脂、不饱和聚酯树脂)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。     

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.     

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.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

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.