一种新型双子表面活性剂的合成与性能

以丙酮为溶剂的条件下,顺丁烯二酸酐、乙二醇、己醇酯化后经磺化合成新型的gemini型磺基琥珀酸盐表面活性剂。反应的较佳工艺条件为:催化剂用量为顺酐质量的1%,n(顺酐)∶n(乙二醇)=2.05∶1,于70℃下单酯化反应2.0 h,得到酯化率约94.6%的单酯化产物;n(己醇)∶n(顺酐)=1.15∶1,160℃下双酯化反应40 min,可得到酯化率约95%的双酯化产物;n(NaHSO3)∶n(顺酐)=1.05∶1,110℃下反应2.5 h,可得到磺化率99.5%的目标产物。合成的样品显示出优良的表面活性和较好的乳化、润湿、渗透、去污等应用性能,是一种较为理想的表面活性剂。     

碳基固体酸催化合成月桂醇聚氧乙烯醚(7)异辛基磺基琥珀酸混合双酯钠

采用碳基固体酸为酯化反应催化剂,合成了月桂醇聚氧乙烯醚(7)异辛基磺基琥珀酸混合双酯钠,对各步反应进行考察,得到最佳工艺条件为:单酯化反应:n(顺酐)∶n(聚醚7)=1.10∶1.00,ω(碳基固体酸)=1%(以顺酐质量计),反应温度130℃,反应时间2.5 h,在此条件下得到产率为98.16%的单酯化产物;双酯化反应:n(顺酐)∶n(异辛醇)=1.00∶2.00,反应温度200℃,反应时间5.0 h,在此条件下得到产率为93.94%的双酯化产物。测定了产物的表面性能和应用性能,并与对甲苯磺酸作催化剂进行了比较。结果表明:碳基固体酸做催化剂时异辛醇用量少了一半;产物性能一致。     

羧化不对称聚氧乙烯醚马来酸双酯表面活性剂的合成及性能

以壬基酚聚氧乙烯醚10(TX-10)、月桂醇聚氧乙烯醚9(LE9)、马来酸酐(MAH)和富马酸(FA)为原料经3步合成了羧化不对称聚氧乙烯醚改性Gemini表面活性剂。最佳工艺条件为:①n(TX-10)∶n(MAH)=1.00∶1.00,于120℃,2%(相对于MAH)对甲苯磺酸(TsOH)催化下反应4.5 h,得酯化率为100%的聚氧乙烯醚马来酸单酯;②n(LE9)∶n(MAH)=1.00∶1.00,于210℃,3%(相对于MAH)TsOH催化下反应5.0 h,得酯化率为88.3%的双酯化产物;③n(FA)∶n(MAH)=2.00∶1.00,130℃反应5 h,得最终产物羧化不对称聚氧乙烯醚马来酸双酯,并测定了产物的性能。     

乙二醇双子琥珀酸2-甲基戊基双酯磺酸钠的合成与性能研究

采用以碳基固体酸为双酯化反应催化剂,中间产物不需提纯分离等环境友好的合成工艺路线,在常压下合成了乙二醇双子琥珀酸2-甲基戊基双酯磺酸钠。对各步反应条件进行了考察,得到的最佳工艺条件为:单酯化反应:n(顺酐)∶n(2-甲基-1-戊醇)=1.05∶1.00,w(对甲苯磺酸)=1%,反应温度80℃,单酯化反应时间1 h,在该条件下得到产率为98.88%的单酯化产物;磺化反应:n(顺酐)∶n(亚硫酸氢钠)=1.00∶1.05,反应温度70℃,磺化反应时间2.0 h,在该条件下得到产率为98.71%的磺化产物;双酯化反应:n(顺酐)∶n(乙二醇)=1.00∶2.20,w(碳基固体酸)=3%,加热介质温度180℃,双酯化反应时间3.5 h,在该条件下得到产率为85.03%的双酯化产物。测定了目标产物的表面张力为27.79 mN/m;临界胶束浓度为2.5×10-3 mol/L。     

月桂醇聚氧乙烯醚(7)己基磺基琥珀酸混合双酯钠的合成与性能

采用控制酯化率和非外加相转移催化剂在常压进行反应的方法合成了月桂醇聚氧乙烯醚(7)己基磺基琥珀酸混合双酯钠。最佳工艺条件为:n〔月桂醇聚氧乙烯醚(7)〕∶n(顺酐)=1 00∶1 10,于130℃下单酯化反应2 5h,得到产率为99 6%的单酯化产物。n(己醇)∶n(顺酐)=4 0∶1 0,于170℃下双酯化反应2 0h,得到产率为95 8%的双酯化产物。n(亚硫酸氢钠)∶n(顺酐)=1 10∶1 00,加热介质温度为170℃下磺化反应2 5h。测得产物的表面张力、临界胶束浓度、乳化力、渗透力、分散力、耐硬水性能分别为30 7mN/m、3 548×10-5mol/L、3 5min、3 7s、59 5%和14min。与磺基琥珀酸双己酯钠盐(DHSS)和月桂醇聚氧乙烯醚(7)磺基琥珀酸单酯二钠盐(LESS)进行了性能对比。结果表明:分散力、乳化力和耐硬水性能较DHSS均得到了改善,渗透性能较LESS得到了较大的提高。     

1,4-丁二醇双子琥珀酸聚醚(3)异辛基混合双酯磺酸钠的合成与性能

采用自制的碳基固体酸为双酯化反应催化剂,反应过程无需溶剂、中间产物无需分离等对环境友好的工艺,在常压下合成了1,4-丁二醇双子琥珀酸聚醚(3)异辛基混合双酯磺酸钠(GSS4AEO3-62)。对各步反应条件进行了考察,得到的最佳工艺条件为:单酯化反应:n(顺酐)∶n(1,4-丁二醇)=2.15∶1.00,反应温度110℃,反应时间2.0 h,在该条件下得到产率为99.23%的单酯化产物;双酯化反应Ⅰ:n(顺酐)∶n〔聚醚(3)〕=1.00∶0.55,w(碳基固体酸)=1%(以顺酐质量计),反应温度170℃,反应时间2.0 h,双酯化反应Ⅱ:n(顺酐)∶n(异辛醇)=1.00∶0.60,反应温度220℃,反应时间4.5 h,在该条件下得到产率为94.36%的双酯化产物;磺化反应:n(顺酐)∶n(亚硫酸氢钠)=1.00∶1.05,反应温度140℃,反应时间5.5 h。产物经IR、GC/MS进行结构表征,测定了其表面性能、应用性能和毒理性,并与磺基琥珀酸聚醚(3)异辛基混合双酯钠(AEOSS3)、1,4-丁二醇双子琥珀酸二异辛酯磺酸钠(GSS462)进行了比较。结果表明,GSS4AEO3-62的临界胶束浓度比AEOSS3、GSS462低1²个数量级,而且毒性低。     

醇醚辛基磺基琥珀酸混合双酯钠的合成与性能研究

通过控制酯化率和不外加相转移催化剂在敞开体系中进行酯化、磺化的方法合成了月桂醇聚氧乙烯醚(5)辛基磺基琥珀酸混合双酯钠,最佳工艺条件为:n(月桂醇聚氧乙烯醚(5))∶n(顺酐)=1.00∶1.10,于110℃下单酯化反应2.5h,得到产率为99.7%的单酯化产物;n(二乙基辛醇)∶n(顺酐)=3.0∶1.0,于170℃下双酯化反应4h,得到产率为94.2%的双酯化产物;n(亚硫酸氢钠)∶n(顺酐)=1.10∶1.00,加热介质温度为160℃下磺化反应4h,可使双酯化产物完全磺化得到标题化合物。测定了产物的表面张力、临界胶束浓度、耐硬水能力、乳化力、渗透力、分散力、钙皂分散力和去油污力,并与磺基琥珀酸二辛酯钠盐(快T)和月桂醇聚氧乙烯醚(5)磺基琥珀酸单酯二钠盐(LESS5)进行了比较。结果表明:其耐硬水能力、分散力、乳化力、钙皂分散性能和去油污性能均较快T有所改善;与LESS5相比,渗透性能得到了较大提高。     

乙二醇双子琥珀酸2-乙基丁基酯磺酸钠的合成及性能

采用碳基固体酸作酯化反应催化剂于常压下反应的方法合成了乙二醇双子琥珀酸2-乙基丁基酯磺酸钠,酯化反应无需有机溶剂,磺化反应不外加相转移催化剂。最佳工艺条件为:单酯化反应,n(乙二醇)∶n(顺酐)=1.00∶2.10,催化剂碳基固体酸用量为顺酐质量的2%,100℃反应4.7 h,酯化率99.21%(质量分数);双酯化反应,n(2-乙基-1-丁醇)∶n(顺酐)=1.30∶1.00,于210℃反应1 h,酯化率95.17%(质量分数);磺化反应,n(亚硫酸氢钠)∶n(顺酐)=1.05∶1.00,于120℃反应1 h,磺化率100.65%(质量分数)。对产物结构进行了IR和1HNMR光谱表征,对产物性能进行了测定:CMC为2.99×10-3mol/L,γCMC为27.96 mN/m,乳化力4.35 min,渗透力为11.6 s,耐硬水力为13.3 min。     

琥珀酸脂肪醇聚氧乙烯醚(9)已基磺酸钠的研究

采用不加相转移催化剂在敞开体系中进行反应的新方法合成脂肪醇聚氧乙烯醚(9)己基磺基琥珀酸混合双酯钠。最佳工艺条件为:n[脂肪醇聚氧乙烯醚(9)]∶n(顺酐)=1.00∶1.20,于140℃下单酯化反应2.0h,得到产率为100.0%的单酯化产物;n(己醇)∶n(顺酐)=5.0∶1.0,于170℃下双酯化反应2.5h,得到产率为95.4%的双酯化产物;n(亚硫酸氢钠)∶n(顺酐)=1.10∶1.00,加热介质温度为180℃下磺化反应2.75h。测定了所得产物的表面活性和应用性能。表面张力30.5×10-3N/m、临界胶束浓度7.943×10-5mol/L、乳化率3.0min、渗透率3.7s、分散力71.7%、耐硬水性能17min。与磺基琥珀酸双己酯钠盐(DHSS)和脂肪醇聚氧乙烯醚(7)磺基琥珀酸单酯二钠盐(AESS)进行性能对比。结果表明:通过在DHSS中引入乙氧基,分散力、乳化力和耐硬水性能均得到了改善,并较单酯钠盐AESS相比,渗透性能得到了较大的提高。     

月桂醇聚氧乙烯醚(9)辛基磺基琥珀酸混合双酯钠的合成与性能

采用控制酯化率和非外加相转移催化剂在敞开体系中进行反应的方法,合成了月桂醇聚氧乙烯醚(9)辛基磺基琥珀酸混合双酯钠。最佳工艺条件为:n〔月桂醇聚氧乙烯醚(9)〕∶n(顺酐)=1.00∶1.10,于140℃单酯化反应2.0 h,得到产率为99.8%的单酯化产物。n(2-乙基己醇)∶n(顺酐)=4.0∶1.0,于加热介质温度240℃条件下双酯化反应5.5 h,得到产率为94.4%的双酯化产物。n(亚硫酸氢钠)∶n(顺酐)=1.10∶1.00,加热介质温度210℃条件下,磺化反应6 h得终产物。测得产物的表面张力为32.5 mN/m、临界胶束浓度为1.1×10-4mol/L、耐硬水能力为24 m in、乳化力为3.3 m in、渗透力为3 s、分散力为90.5%、钙皂分散力为13%、去油污力为99.1%。与磺基琥珀酸二辛酯钠盐(快T)和月桂醇聚氧乙烯醚(9)磺基琥珀酸单酯二钠盐(LESS)进行性能对比,结果表明:耐硬水能力、分散力、钙皂分散性能和去油污性能较快T均得到了改善,渗透性较LESS得到了提高。     

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。