钛系聚酯催化剂催化活性的影响因素研究

以二氧化钛(TiO2)为消光剂,采用钛系催化剂STiC-01或锑系催化剂乙二醇锑,在2 L间歇式聚合反应釜中制备半消光PET切片。根据PET切片的特性黏数和色度(L值及b值),比较了催化剂的催化活性,并研究了催化活性的影响因素。结果表明:在相同的聚合工艺条件下,STiC-01的钛用量为5μg/g(相对于PET质量)时的催化活性与乙二醇锑的锑用量为250μg/g(相对于PET质量)时的相当,PET切片的特性黏数达0.676 dL/g,钛系PET切片的L值高于锑系PET的,b值相当;磷化合物和镁化合物的用量应适当控制;催化剂在酯化前加入,TiO2在酯化后加入,STiC-01的催化活性不受TiO2的影响;相比乙二醇锑,STiC-01的催化活性受原料质量的影响小。     

无重金属膜级聚酯的合成及性能研究

使用自制的钛系催化剂TY-2合成了无重金属膜级聚酯切片,对照乙二醇锑催化剂,考察了催化剂对酯化、缩聚反应过程以及切片性能的影响,探讨了添加剂、稳定剂在合成过程中对催化剂的影响,并且考察了两种切片的热性能、结晶行为、流变性能。结果表明:钛系催化剂TY-2用量为210~230μg/g时,得到的无重金属聚酯切片的各项性能合格,色相b值比锑系聚酯仅上升0.5个单位,热性能、结晶行为、流变性能与锑系聚酯差别也不大,可采用锑系聚酯的工艺参数进行拉膜。     

钛系瓶级PET切片的合成及其固相增黏工艺研究

使用自制钛催化剂在2L聚合反应釜中合成钛系聚酯(PET)基础切片,探讨了调色剂、稳定剂、助剂对反应过程及切片性能的影响;然后在50 L聚合反应釜中进行了放大试验,并将基础切片在真空转鼓中进行固相增黏,得到瓶级PET切片。结果表明:在相同的聚合反应条件下,钛催化剂用量(以钛离子计,相对于精对苯二甲酸(PTA))为7μg/g时,合成的钛系基础切片的色相、乙醛含量与乙二醇锑用量(以锑离子计,相对于PTA)为220μg/g时得到的锑系基础切片相当;在钛系基础切片合成中添加助剂,在固相增黏时合理控制升温过程,可有效解决钛系基础切片在固相缩聚反应中存在的固相增黏速率、切片色相与乙醛含量之间相互制约的矛盾,增黏后的钛系瓶级PET切片的色相、乙醛含量等指标优于锑系瓶级PET切片。     

高稳定性钛系聚酯催化剂TiOC@SiO2的制备及应用

钛系聚酯催化剂因催化活性高、环境友好等优点,是传统锑系聚酯催化剂的理想替代品。为了制备出耐水解性好、分散性好、催化性能稳定的钛系聚酯催化剂,采用反相微乳液法,制备得到核壳结构催化剂TiOC@SiO₂。在钛有机化合物的表面包覆一层硅氧烷,以此稳定钛有机化合物的催化活性。利用多种现代表征方法对TiOC@SiO₂的形貌、结构和性能进行了表征分析,并探究其在合成聚对苯二甲酸乙二醇酯(PET)中的催化性能。研究结果表明,TiOC@SiO₂催化剂为粒径约200nm的核壳球形结构,无Ti—O—Si键,钛含量为6.95%。TiOC@SiO₂催化剂在90℃下水浴2h后,其结构和催化活性保持不变,复合结构显著提高了钛有机化合物的耐水解性和分散性。在聚酯合成实验中,仅添加5μg/g TiOC@SiO₂,在270℃下缩聚反应92min,即可制备出特性黏度为0.677dL/g、端羧基含量为14.4mol/t、b值为2.16的PET。     

新型钛系催化剂合成瓶用聚酯切片的研究

采用均一的液相新型钛系催化剂STi C-B1,在2 L间歇式聚合反应釜中制备钛系瓶用聚对苯二甲酸乙二醇酯(PET)切片;考察了催化剂中主要成分对PET切片色相及乙醛含量的影响,以及不同催化体系的PET切片的结晶性能及热性能;并进行了工业化应用评价。结果表明:在相同的聚合工艺条件下,STi C-B1钛用量为5μg/g(相对于PET)时的催化活性及其所得PET切片乙醛含量与乙二醇锑锑用量为180μg/g时相当;钛系PET切片结晶速度较锑系PET切片的慢,较慢的结晶速度可避免PET切片降温时出现结晶过快,从而有利于吹瓶;工业化应用表明钛系PET瓶片质量指标基本达到锑系PET瓶片的水平,其瓶坯乙醛含量低于锑系PET瓶坯的乙醛含量。     

环保型钛系瓶级聚酯切片的研究

使用自制钛催化剂在2 L聚合反应釜中合成了环保型钛系瓶级聚酯切片。考察了钛催化剂对酯化反应、聚合反应、固相缩聚反应的影响;探讨了添加调色剂、稳定剂、助剂对反应过程及切片性能的影响;并在50 L酯化聚合反应釜中进行了放大试验。结果表明:在同样的聚合反应条件下,钛催化剂用量(钛离子计,相对于PTA)为7×10~(-6)时,合成产品色相、乙醛含量与乙二醇锑用量(锑离子计,相对于PTA)为220×10~(-6)相当,钛系聚酯的结晶速率稍慢于锑系聚酯切片,可避免聚酯切片降温时结晶过快,有利于吹瓶。放大试验证明钛系聚酯与锑系聚酯切片的固相缩聚速率相当,增黏切片的乙醛含量低于锑系聚酯切片的乙醛含量。     

钛系催化剂在PET合成中的催化性能研究

采用2 L不锈钢反应釜,考察了自制钛系催化剂对聚酯(PET)生产过程中酯化反应和缩聚反应以及产品色度的影响。结果表明:自制钛系催化剂对PET生产过程中的酯化反应具有催化作用,同三氧化二锑催化剂相比,自制钛系催化剂可缩短酯化反应时间33%;自制钛系催化剂在缩聚过程中的催化反应活性高于三氧化二锑催化剂,可缩短缩聚反应时间45%;随着反应体系中钛含量的增加,缩聚产物达到一定黏度所需的缩聚反应时间降低,但缩聚产物的色相b值升高;合理的自制钛系催化剂的起始添加量应控制在7μg/g以下。     

铝系催化剂催化合成聚酯的性能研究

以5种含铝化合物为催化剂,采用对苯二甲酸二甲酯（DMT）路线合成聚酯,对聚合产物进行特性黏度、色值和DSC分析。结果表明：5种铝系催化剂的催化活性均低于常规催化剂,其中,铝酸钠的催化活性最高;铝系催化剂所得的聚酯的色相b值高于Sb2O3催化的聚酯的b值,但低于钛酸正丁酯催化的聚酯的b值;铝酸钠和硅酸钠复合后作为催化剂,不改变PET切片的等温结晶规律,且催化所得聚酯的结晶青色力比常规Sb2O3催化的聚酯略有提高;选择溶解性好的含铝化合物和减少催化剂用量对增加催化活性和改善聚酯色相有利。     

钛系聚酯预结晶性能探索

主要通过 DSC 对钛催化剂合成 PET 聚酯的预结晶性能进行了研究,以探索钛催化剂对聚酯预结晶性能的影响,并将其与锑系聚酯进行对比。结果表明,相比较锑系聚酯,钛催化剂合成 PET 聚酯切片内部残留结晶度低,冷结晶速度慢,同样工艺条件下钛系聚酯预结晶过程更容易粘结。     

钛系催化剂在半消光聚酯生产中的应用

在300 t/d聚酯(PET)装置上通过减少锑系催化剂添加量,逐步将钛系催化剂添加比例由15%提高至100%,最终实现钛系催化剂生产环保型PET产品,分析了钛系催化剂替代量对PET切片质量、热性能以及过滤器切换周期的影响。结果表明:随着钛系催化剂替代比例的提高,PET切片色相b值大幅上升,将酯化Ⅰ釜温度由264℃下降至256℃,酯化Ⅱ釜温度由268℃下降至259℃,增大调色剂添加量控制在30μg/g以内,可保证色相L值不低于90;将预聚釜Ⅰ温度由271℃下降至265℃,预聚釜Ⅱ温度由276℃下降至274℃,终缩聚温度由278℃下降至276℃,可将端羧基含量控制在指标要求范围;将酯化Ⅰ釜压力由65k Pa提高至79 k Pa,工艺塔釜温由175℃提高至178℃,可缓解二甘醇含量下降幅度,但对二甘醇含量提高效果不明显;全钛系PET比全锑系PET降温峰值温度低13.66℃,降温峰值温度与冷结晶温度之差低20.29℃,有利于纺丝;全钛系PET生产中过滤器切换周期比全锑系PET的长。     

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。