双子表面活性剂——二元醇双琥珀酸双酯磺酸钠(GMI-01)的合成与性能研究

采用1,4 丁二醇、马来酸酐、十二烷基聚氧乙烯醚(AEO2)为主要原料和环境友好的工艺路线,合成了一种易降解的双子(Gemini)表面活性剂———二元醇双琥珀酸双酯磺酸钠(GMI-01)。对各步合成条件采用正交实验或均匀设计进行优化,得出各步反应的最优工艺条件如下:酯化反应Ⅰ,配比为n(马来酸酐)∶n(1,4 丁二醇)=2 15∶1 00,反应时间1h,催化剂w(乙酸钠)=1 0%,以丙酮作溶剂,回流操作。酯化反应Ⅱ,配比为n(1,4 丁二醇双马来酸单酯)∶n(AEO2)=1 00∶2 15,反应温度150℃,反应时间14h,催化剂w(PW12/C)=1 5%。磺化反应,配比为n(1,4 丁二醇双马来酸AEO2双酯)∶n(NaHSO3)=1 00∶3 00,反应时间4h,反应温度80℃,相转移催化剂w(CTAB)=1 5%。对每步合成产物均用IR和1HNMR进行了表征,终产物GMI-01的平衡表面张力γCMC=38 4mN/m,CMC为0 049mmol/L。     

二元醇双琥珀酸双酯磺酸钠(GMI-02)的合成

采用1,4-丁二醇、马来酸酐、月桂醇为主要原料和环境友好的工艺路线,合成了一种易降解的双子(Gemini)表面活性剂--二元醇双琥珀酸双酯磺酸钠(GMI-02)。对各步合成条件采用正交实验进行优化,得出各步反应的优化工艺条件:酯化反应I,配比为n(1,4-丁二醇)∶n(马来酸酐)=1∶2.15,反应时间2h,催化剂w(乙酸钠)=1.0%,反应温度95℃,以丙酮作溶剂,回流操作;酯化反应Ⅱ,甲苯为溶剂,反应时间6h,反应温度145℃,催化剂w(对甲苯磺酸)=1.0%,n(1,4-丁二醇双马来酸单酯)∶n(月桂醇)=1∶2.20。磺化反应,石蜡加热,石蜡温度(加热温度)控制在115℃,时间为6h,原料配比为n(1,4-丁二醇双马来酸双酯)∶n(亚硫酸氢钠)=1∶2.50。对每步合成产物均用IR进行了表征。     

TiO_2负载磷钨酸催化合成1,4-丁二醇双琥珀酸十八醇双酯磺酸钠

采用1,4-丁二醇、马来酸酐、十八醇为主要原料,合成出一种双子表面活性剂1,4-丁二醇双琥珀酸十八醇双酯磺酸钠.此化合物的合成由两步酯化以及一步磺化反应组成,双酯化反应采用TiO_2负载磷钨酸(PW_)12)/TiO_2)为催化剂.通过正交实验确定了1,4-丁二醇双马来酸十八醇双酯合成的优化反应条件为:n(1,4-丁二醇双马来酸单酯)∶n(十八醇)=1.00∶2.20,催化剂用量ω(PW_(12)/TiO_2)=1.5%,反应温度150 ℃,反应8 h,酯化率达到95.8%,产率为82.4%.通过正交实验确定了磺化反应的优化条件为:双酯与NaHSO_3物质的量比1.00∶3.00;反应4 h;反应温度90 ℃;催化剂(CTAB)用量1.5%,磺化率达到92.7%,产率为74.9%.     

SiO_2负载磷钨酸催化合成1,4-丁二醇双琥珀酸十八醇双酯磺酸钠

采用1,4-丁二醇、马来酸酐、十八醇为主要原料,合成出一种双子表面活性剂1,4-丁二醇双琥珀酸十八醇双酯磺酸钠。此化合物的合成由两步酯化以及一步磺化反应组成,双酯化反应采用SiO2负载磷钨酸(PW12/SiO2)为催化剂。通过正交实验确定了1,4-丁二醇双马来酸十八醇双酯合成的优化反应条件为:n(1,4-丁二醇双马来酸单酯):n(十八醇)=1.00:2.20,催化剂用量1.5%,反应温度150℃,反应8h,酯化率达到97.2%,产率为84.9%。磺化反应的条件为:n(1,4-丁二醇双马来酸双酯):n(NaHSO3)=1.00:3.00;反应4h;反应温度90℃;催化剂(CTAB)用量1.5%,磺化率达到92.7%,产率为74.9%。在25℃水溶液中测得该表面活性剂的表面张力γcmc为41.9mN/m,CMC为7.2×10-5mol/L。表明该表面活性剂具有很低的临界胶束浓度。     

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。     

Gemini表面活性剂——乙二醇双琥珀酸正辛醇双酯磺酸钠的合成与性能研究

采用马来酸酐、正辛醇、乙二醇和亚硫酸氢钠为主要原料合成了一种新颖的双子表面活性剂——乙二醇双琥珀酸正辛酸双酯磺酸钠(GMI-03)。对各步合成条件采用正交实验进行优化,得出各步反应的最优工艺条件如下:正辛醇与马来酸酐的单酯化反应(酯化反应Ⅰ),反应时间为3 h,反应温度为70°C,正辛醇和马来酸酐摩尔比为1.00∶1.05;磺化反应,反应温度为90°C,反应时间为4 h,马来酸酐与NaHSO3摩尔比为1.00∶1.05;中间体正辛醇琥珀酸单酯磺酸钠与乙二醇的双酯化反应(酯化反应Ⅱ):反应温度为150°C,反应时间为6 h,催化剂用量为物料总量的1.0%(质量分数),中间体正辛醇琥珀酸单酯磺酸钠与乙二醇的摩尔比为2.50∶1.00。对终产物GMI-03的性能进行测定,表面张力σ(γCMC)为:32.8 mM/m,CMC为:5.8×104mol/L。     

1,4-丁二醇双琥珀酸十八醇双酯磺酸钠的合成与性能研究

采用1,4-丁二醇、马来酸酐及十八醇为主要原料,合成出一种双子表面活性剂1,4-丁二醇双琥珀酸十八醇双酯磺酸钠。通过正交实验确定了1,4-丁二醇双马来酸十八醇双酯合成的优化反应条件为:1,4-丁二醇双马来酸单酯∶十八醇(摩尔比)=1∶2.15,对甲苯磺酸为催化剂,加入量占总质量的1.5%,在80℃条件下反应6 h。通过红外光谱和表面张力对产物进行了结构表征和性能测定,γcm c=41.5 mN/m,临界胶束浓度为0.065 mmol/L。     

石油环烷酸单乙醇酰胺双酯磺酸钠的合成

以石油环烷酸为主要原料合成出石油环烷酸双酯磺酸钠的新型双子表面活性剂。通过正交实验确定了酯化的优化反应条件为:n(1,4-丁二醇双马来酸单酯)∶n(石油环烷酸单乙醇胺)=1∶2.10,催化剂的加入量占总质量的百分数为:w(硼酸)=1.5%,在100℃条件下反应5 h。通过红外光谱和表面张力对产物进行了结构表征和性能测定,γCMC=39.8 mN/m,CMC=0.057 mmol/L。     

异辛基正丁基琥珀酸双酯磺酸钠的合成

以异辛醇、马来酸酐、正丁醇和亚硫酸氢钠为原料,通过单酯化、双酯化和磺化反应合成了标题化合物,通过FT-IR表征了产物的结构。对各步反应的条件进行了考察。异辛醇与马来酸酐单酯化反应的适宜条件为:n(马来酸酐)∶n(异辛醇)=1.05,反应温度80℃,反应时间90 min;异辛醇马来酸单酯与正丁醇双酯化反应的适宜条件为:n(正丁醇)∶n(异辛醇马来酸单酯)=1.5,催化剂对甲苯磺酸的用量(基于总反应物的质量)为0.20%,反应温度130℃,反应时间150 min;异辛基正丁基马来酸双酯与亚硫酸氢钠磺化反应的适宜条件为:n(亚硫酸氢钠)∶n(异辛基正丁基马来酸双酯)=1.1,反应时间150 min,反应温度95℃。在此优化反应条件下,异辛基正丁基琥珀酸双酯磺酸钠盐的总收率为91.38%。     

HBSS型琥珀酸(混合)双酯磺酸钠盐加脂剂的合成

以十六醇、正丁醇、马来酸酐为主要原料,合成了十六烷基正丁基琥珀酸(混合)双酯磺酸钠盐皮革加脂剂,对合成反应条件进行了优化。优化的十六醇与马来酸酐的单酯化反应条件为:n(十六醇):n(马来酸酐)=1:1.05,反应温度90℃,反应时间2.5h;十六烷基马来酸单酯与正丁醇双酯化反应条件为:n(十六烷基马来酸单酯):n(正丁醇)=1:1.5,反应温度130℃,反应时间90min,w(对甲苯磺酸)=0.5(基于总反应物的质量);十六烷基正丁基马来酸(混合)双酯与亚硫酸氢钠的磺化反应条件为:n〔十六烷基正丁基马来酸(混合)双酯〕:n(NaHSO3)=1:1.1,反应温度100℃,反应时间4h。该加脂剂具有较好的乳化能力,可以乳化自身质量33的鱼油。用IR表征了目标产物结构。     

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。