酯化改性苯乙烯马来酸酐共聚物及其盐的制备与应用

采用聚醚对苯乙烯马来酸酐共聚物(SMA)进行酯化改性,再使用胺中和部分剩余羧酸得到苯乙烯马来酸酐酯化及中和产物(SMAE-N)。并对不同的催化剂种类及其用量、不同的溶剂种类以及不同的反应温度、时间等因素对酯化率的影响进行探究。考察了反应过程中酸值变化,对酯化产物使用核磁共振氢谱(H-NMR)与傅里叶红外光谱(FT-IR)进行结构表征。同时探索了不同种类的聚醚和胺对钛白粉、炭黑等颜料分散性能的影响。结果表明,当溶剂使用乙酸丁酯、固体酸催化剂DP91,且用量为反应物质量分数的1%,苯乙烯马来酸与聚醚1007投料物质的量比为1∶4,115℃情况下反应5 h,酯化率可达到62.84%,再用三乙胺中和剩余羧酸的70%。颜料分散应用结果表明,SMAE-N对钛白粉、炭黑等颜料具有显著的分散效果。     

桐油改性苯乙烯 -马来酸酐共聚物的制备及其对水性炭黑色浆的分散性研究

通过对桐油进行二次酯交换获取桐油基醇（ TOBA）然后以桐油基醇（ TOBA）、苯乙烯 -马来酸酐共聚物（ SMA）和甲氧基聚乙二醇（ MPEG）为主要原料，，合成了不同桐油含量的梳型聚合物分散剂（TOBA-SMA-MPEG），并将 TOBA-SMA-MPEG作为分散剂制备了水性炭黑色浆。采用 FT-IR和 ¹H NMR对 TOBA-SMA-MPEG的化学结构进行了表征；通过对水性炭黑色浆的微观形貌、黏度、展色性、粒径、离心稳定性及贮存稳定性进行分析，考察了桐油含量及分散剂用量对炭黑分散性能的影响。结果表明：成功制备了 TOBA、SMA和 MPEG物质的量比为 1∶1∶3的 TOBA-SMA-MPEG聚合物分散剂；当其添加量为 6%时，对水性炭黑色浆的分散性最好，色浆平均粒径可降至 181. 8 nm；经桐油改性后的梳型聚合物分散剂可以提高水性炭黑色浆的分散稳定性。     

低温合成苯乙烯-马来酸酐交替共聚物

苯乙烯(St)和马来酸酐(MA)自由基引发共聚反应,生成共聚物SMA,是典型的交替共聚。在过氧化苯甲酰(BPO)引发下,以丙酮为溶剂,采用溶液聚合法合成苯乙烯-马来酸酐共聚物,并用收率作为评价标准,对反应条件进行研究。结果表明,在温度为60℃,BPO的质量分数x(BPO)=0.3%,n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=30%,反应2 h的条件下,聚合物的收率可达到98.5%。利用化学滴定法测得聚合物中马来酸酐摩尔分数为49.91%,结合理论,证明了合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。一种低温合成苯乙烯-马来酸酐交替共聚物的工艺得到开发。     

可生物降解苯乙烯-马来酸酐共聚物的合成工艺研究

以苯乙烯与马来酸酐为聚合单体,在适宜的条件下合成得到可降解的苯乙烯-马来酸酐共聚物。考察了引发剂用量、反应温度、反应时间、物料比等因素对SMA共聚物中马来酸酐含量及特性粘数的影响。结果表明,BPO量为0.3%、n(St)/n(MA)=1.2∶1、聚合反应温度125℃、聚合反应时间3 h,可以得到相对分子质量Mn=27 303、分子量分布Mw/Mn=1.873 736的SMA共聚物。利用红外谱(IR)、凝胶渗透色谱(GPC)对产物进行了表征确认。     

可生物降解苯乙烯-马来酸酐共聚物的合成工艺研究

以苯乙烯与马来酸酐为聚合单体,在适宜的条件下合成得到可降解的苯乙烯-马来酸酐共聚物。考察了引发剂用量、反应温度、反应时间、物料比等因素对SMA共聚物中马来酸酐含量及特性粘数的影响。结果表明,BPO量为0.3%、n(St)/n(MA)=1.2∶1、聚合反应温度125℃、聚合反应时间3 h,可以得到相对分子质量Mn=27 303、分子量分布Mw/Mn=1.873 736的SMA共聚物。利用红外谱(IR)、凝胶渗透色谱(GPC)对产物进行了表征确认。     

溶液聚合法合成苯乙烯-马来酸酐交替共聚物

在过氧化苯甲酰(BPO)引发下,以丁酮为溶剂,采用溶液聚合法合成了苯乙烯-马来酸酐共聚物,并详细研究了温度、引发剂用量、苯乙烯与马来酸酐配比、单体(苯乙烯与马来酸酐)质量分数及聚合时间对聚合反应的影响。研究表明,在温度80℃,x(BPO)=0.6%(相对于苯乙烯与马来酸酐),n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=15%(相对于混合溶液),反应时间4 h的条件下,聚合物收率可达99%。采用13CNMR、IR、GPC、元素分析对共聚物结构进行了表征。利用TG测定了其热稳定性。结合共聚物的元素分析与13CNMR的分析结果,表明合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。     

高马来酸酐SMA及梳型表面活性剂SMA-g-MPEG的制备

分别采用均相聚合及非均相沉淀聚合法,制备了苯乙烯马来酸酐共聚物(SMA)。考察了引发剂种类和浓度、单体摩尔比、反应温度和反应时间等因素对SMA中马来酸酐(MA)摩尔分数的影响。优化的反应条件为:采用非均相聚合法,以过氧化二苯甲酰(BPO)为引发剂,聚合时间8 h,温度80℃,引发剂浓度0.01 mol/L,单体摩尔比n(St)∶n(MA)=1∶1.5,在该条件下,所合成SMA中马来酸酐的摩尔分数为37.43%,黏均相对分子质量约为89 000,交替性好。将得到的SMA与聚乙二醇单甲醚(MPEG)进行接枝反应,可以制得临界胶束质量浓度为1.03 g/L、表面张力为35.29 mN/m的梳型表面活性剂(SMA-g-MPEG)。     

垃圾焚烧发电厂喷淋石灰浆用阻垢剂的制备及性能

以过硫酸铵为引发剂,马来酸酐、丙烯酸、丙烯酰胺、苯乙烯磺酸钠为单体,采用水溶液聚合法制备了四元共聚物P(MA-AA-AM-SSS)。使用红外光谱法和核磁共振氢谱法对聚合物进行表征。研究了单体比例及引发剂用量对共聚物阻垢效果的影响,结果表明,马来酸酐、丙烯酸、丙烯酰胺、苯乙烯磺酸钠的物质的量比为2.5∶1.0∶1.0∶1.5时,引发剂质量分数为44%,共聚物阻垢效果最好,阻垢率为90.8%。     

苯乙烯-马来酸酐共聚物阳离子化改性及其在颜料分散中的应用

采用环氧丙基三甲基氯化铵(ETA),通过界面反应对苯乙烯-马来酸酐共聚物(SMA)进行改性,制备高分子分散剂(SMG)。红外光谱测试结果表明,ETA和SMA中酸酐发生反应,生成了酯键,当ETA对SMA摩尔比为1.3、对甲苯磺酸占SMA总质量的14%、反应时间6 h、反应温度78℃时,SMG阳离子化度为30.96%。应用实验表明,SMG对炭黑的分散效果明显优于SMA,当SMG阳离子度大于14%、pH=9、SMG对颜料的质量分数为7%时,制备炭黑分散体粒径为170 nm,炭黑分散体热稳定性较佳,60℃处理24 h,粒径变化率仅为3.6%。所制备分散体在pH=3时,炭黑Zeta电位为+28.61 mV,当pH>6.5后,Zeta电位变为负值,表现出两性特征。     

苯乙烯-马来酸酐共聚物的酯化改性及其对炭黑的分散性能

采用异丁醇对苯乙烯-马来酸酐共聚物(SMA)进行酯化改性,研究了反应温度、时间、催化剂用量、异丁醇用量等因素对共聚物酸值的影响。红外光谱测试表明,SMA中酸酐与异丁醇发生了酯化反应。在以丁酮为反应溶剂,SMA质量占反应体系总质量的5%,异丁醇质量占反应体系总质量的12%,对甲苯磺酸质量占SMA质量的1%,反应温度80℃,反应时间4 h的条件下,SMA部分酯化物(SME)的酸值降低到了271.6 mg KOH/g。炭黑分散研究结果表明,SME对炭黑分散效率优于SMA,当SME酸值低于355.1 mg KOH/g,其用量为炭黑质量的20%,pH=9时,制备炭黑分散体平均粒径为154 nm,制备的炭黑分散体表现出良好的离心稳定性。     

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.     

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.