一种氟硅表面活性剂的合成及其表面活性

研究了2-甲基-2-全氟-2'-甲基-3'-氧代己酰氧基乙氧基羰基乙基甲基二聚氧乙烯基硅烷(Ⅴ)的制备方法和表面活性。以甲基丙烯酸-2-全氟-2'-甲基-3'-氧代己酰氧基乙基酯(Ⅰ)和甲基二氯硅烷(Ⅱ)为原料,0.5%Karsted催化剂存在下(以Ⅰ的质量计),发生硅氢化反应,得到2-甲基-2-全氟-2'-甲基-3'-氧代己酰氧基乙氧基羰基乙基甲基二氯硅烷(Ⅲ)。Ⅲ与聚乙二醇(Ⅳ)缩合反应得到非离子表面活性剂Ⅴ。用FTIR和MS对其结构进行了表征,优化了硅氢化反应工艺条件,测试了Ⅴ溶液的表面张力、临界胶束浓度(CMC)和处理玻璃后的疏水性能。以四氢呋喃为溶剂,中间体Ⅲ的较优合成条件为:n(Ⅰ)∶n(Ⅱ)=1.2∶1,50℃下反应28 h,化合物Ⅱ的转化率可达到68.2%。表面活性剂Ⅴ水溶液的CMC为0.52 g/L,临界表面张力γ_(CMC)为22.8 m N/m,用V的THF溶液处理玻璃后,玻璃表面具有很好的疏水性和较好的疏油性。     

N-(p-全氟壬烯氧基苯磺酰基)肌氨酸钠的合成与表面活性

以全氟壬烯基苯基醚、氯磺酸和肌氨酸为主要原料,经氯磺化和酰胺化反应制备了含氟表面活性剂N-(p-全氟壬烯氧基苯磺酰基)肌氨酸钠,用红外光谱和19F-NMR,1H-NMR对中间体和产物分子结构进行了表征.正交实验法优化了各步反应条件,氯磺化反应较佳工艺条件:n(全氟壬烯基苯基醚): n(氯磺酸)＝1: 4,四氯化碳溶剂中70 ～75℃反应5 h;酰胺化反应较佳工艺条件:n(p-全氟壬烯氧基苯磺酰氯): n(肌氨酸钠): n(氢氧化钠)＝1.00 : 1.75 : 2.00,在四氢呋喃溶剂中,室温下搅拌反应3.0 h,得含氟表面活性剂N-(p-全氟壬烯氧基苯磺酰基)肌氨酸钠.以全氟壬烯基苯基醚计,反应总收率96.0%.表面活性测试结果表明,N-(p-全氟壬烯氧基苯磺酰基)肌氨酸钠表面活性剂的临界胶束浓度为5×10-4 mol·L-1,其水溶液的表面张力γcmc 为22.8 mN·m-1(25℃).     

一种含氟经皮渗透剂的合成

研究了2-甲基-2-(全氟-2-三氟甲基-3-氧代己酰氧基)乙氧基羰基乙基甲基二聚氧乙烯基硅烷(V)及其经皮吸收性能。甲基丙烯酸-2-全氟-2'-甲基-3'-氧代己酰氧基乙基酯与甲基二氯硅烷,经硅氢化反应后,直接用聚乙二醇醇解反应得到V,产物经红外光谱(IR)和质谱(MS)表征确认。采用改良的Franz扩散装置,以离体鼠皮为屏障,研究2%薄荷醇、0.5%V、2%薄荷醇+0.5%V、2%氮酮对双氯芬酸钠经皮吸收的影响,增渗倍数分别为3.11、1.19、5.46和6.21。V经皮促渗透效果:单独使用时效果不佳,与薄荷醇混合使用时效果好。     

对全氟壬烯氧基苯磺酸钠的合成与表面活性

以全氟壬烯、苯酚和氯磺酸为主要原料,经醚化、磺化和中和反应制备对全氟壬烯氧基苯磺酸表面活性剂,用红外光谱和19FNMR,1HNMR对分子结构进行了表征。研究了醚化反应投料方式对全氟壬烯基苯酚醚收率的影响,氯磺酸和全氟壬烯基苯酚醚的配比以及反应时间对磺化反应收率的影响。结果显示,向苯酚、三乙胺和二甲基甲酰胺(DMF)的混合物中滴加全氟壬烯,比向全氟壬烯、苯酚和二甲基甲酰胺的混合物中滴加三乙胺,醚化反应收率高17%。氯磺酸和全氟壬烯基苯酚醚的摩尔比为3∶1,40℃反应2h,磺化反应收率67.6%。表面活性的测定结果表明,对全氟壬烯氧基苯磺酸钠表面活性剂的临界胶束浓度为1.28×10-3mol/L,γcmc为19.23mN/m(20℃)。对全氟壬烯氧基苯磺酸钠表面活性剂性能优良。     

氟硅阳离子表面活性剂的制备及性能

以含氢硅油(PMHS)、N-甲基-N-烯丙基-2-全氟-2-甲基-3-氧代己酰胺(NF2)、N,N-二甲基烯丙胺(DAEMA)为原料,在Karstedt催化剂作用下,经硅氢化反应后,再与CH3I进行季铵化反应,制备了氟硅阳离子表面活性剂(PF2DI);考察了温度、催化剂、反应物比例对硅氢化反应的影响;采用IR和19FNMR对产物结构进行了表征,并测定了产物分子量、阳离子活性物含量、溶解度、表面张力和润湿性能。得到较优硅氢化反应条件:n(Si—H)∶n(NF2)∶n(DAEMA)=10∶1∶9,2.5 g含氢硅油,120μL Karstedt催化剂(16.123 g Pt/L),80℃反应6 h,在该条件下转化率为58%。当n(Si—H)∶n(NF2)∶n(DAEMA)从10∶0.5∶9.5到10∶2∶8变化时,PF2DI的重均分子量Mw和数均分子量Mn、阳离子活性物含量、在水和乙醇中溶解度、临界胶束浓度(CMC)均逐渐减小;PF2DI水溶液的γCMC和在有机玻璃板及石蜡表面的接触角都先减小再增大;当n(Si—H)∶n(NF2)∶n(DAEMA)=10∶1∶9时,三者均达到最小值,此时PF2DI水溶液润湿性能最佳。     

新型含氟季铵盐表面活性剂的合成与表面性能

以N-甲基二乙醇胺(MDEA)和全氟己基乙基碘为主要原料,合成了一种新型的含氟季铵盐表面活性剂。通过单因素和正交实验,考察了溶剂、反应温度、反应物摩尔比、溶剂体积和反应时间对MDEA转化率的影响,探讨优化出最佳工艺条件:溶剂为正丁醇,反应温度90℃,n(全氟己基乙基碘)∶n(MDEA)=2.5∶1,溶剂体积为8 mL,反应时间为42 h,转化率达到93.75%。通过傅里叶红外吸收光谱、质谱和核磁共振谱对目标产物进行表征,并通过测定其水溶液的表面张力研究了产物的表面活性。其临界胶束浓度(CMC)为1.518 mmol/L,临界胶束浓度下的表面张力(γCMC)为9.3 mN/m;单分子饱和吸附量、单分子饱和吸附面积和胶束化标准自由能分别为0.354×10-10 mol/cm2、4.69 nm2和-26.03 kJ/mol。与同类产品相比较,产物具有优异的表面性能。     

一种枝杈型含氟季铵盐型阳离子表面活性剂的合成及其性能

以枝杈型含氟醚(4-全氟-[(1,3-二甲基-2-异丙基)-1-丁烯]氧基苯基醚)为原料,通过磺酰化、胺解和季铵化,得到枝杈型含氟季铵盐型阳离子表面活性剂[N-[4-[全氟-(1,3-二甲基-2-异丙基)-1-丁烯]氧基苯磺酰胺基]乙基二乙基甲基碘化铵,其结构经IR、1H-NMR、MS得到确认;其水溶液的临界胶束浓度(CMC)为2.5×10?5 mol?L?1,此时的表面张力为21.0 mN?m?1通过对温度、电解质以及与碳氢表面活性剂的复配研究发现:随着温度的升高其水溶液的CMC和表面张力呈下降趋势;盐度对其影响不大且具有较好的复配性能。     

含全氟壬烯基的阳离子氟表面活性剂的合成

以p-全氟壬烯氧基苯甲酸为原料,经酰氯化、酰胺化和季铵化三步反应,制备了N-[3-(p-全氟壬烯氧基苯甲酰氨基)丙基]-N,N,N-三甲基碘化铵(Ⅰ),用IR、1HNMR、19FNMR对其结构进行了表征,并测试了其水溶液的表面张力。p-C9F17OC6H4COOH(Ⅱ)与过量SOCl2在40℃反应3 h后,与N,N-二甲基丙二胺反应,n(Ⅱ)∶n(N,N-二甲基丙二胺)=1∶2,乙腈作溶剂,70℃反应1 h,N-[3-(p-全氟壬烯氧基苯甲酰氨基)丙基]-N,N-二甲基胺(Ⅲ)收率89.3%。Ⅰ的较佳合成工艺条件为:n(Ⅲ)∶n(碘甲烷)=1∶1.2,乙腈作溶剂,回流1.5 h,收率88.3%。Ⅰ的水溶液CMC为9.67×10-4mol/L,γ为20.4 mN/m。     

氟硅非离子表面活性剂的制备及性能

以含氢硅油(PMHS)、N-甲基-N-烯丙基-2-全氟-2-甲基-3-氧代己酰胺(NF2)和烯丙基聚醚(F6)为原料,在Karstedt催化剂作用下,通过硅氢加成反应制备了氟硅非离子表面活性剂PF2F6;采用FT-IR、1H NMR和19F NMR对产物结构进行了表征,并测定了产物的溶解度、浊点、表面张力和润湿性。结果表明,PF2F6在弱极性溶剂中具有良好的溶解度,在水中的溶解度随着F6物质的量的增大而增大;当n(Si-H)∶n(NF2)∶n(F6)=2∶0.7∶1.3时,临界胶束浓度(cmc)和平衡表面张力(γcmc)最小,其值分别为0.13 g/L和22.8 mN/m;随着反应体系中F6物质的量的增加,PF2F6的浊点增加,而在有机玻璃(PMMA)表面的接触角减小。     

由六氟丙烯二聚体合成阳离子表面活性剂及其性能

以六氟丙烯二聚体和,N,N-二甲基丙二胺为主要原料,合成了N,N-二甲基N′-(2-三氟甲基-1-五氟乙基)全氟烯丙基丙二胺(Ⅰ),然后通过季铵化反应制得溴化[N,N-二甲基-N-乙基-N′-(2-三氟甲基-1-五氟乙基)全氟烯丙基氨丙基]铵(Ⅱ)阳离子表面活性剂。利用碱性溴酚蓝方法对季铵盐阳离子进行了定性测定,并通过红外光谱和19FNMR、1HNMR对其分子结构进行了表征。性能测试结果表明,该阳离子表面活性剂的表面张力为24．5 mN／m(20℃),其临界胶束浓度为2．04×10-3mol/L,克拉夫特点低于0℃,具有良好的水溶稳定性。     

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.     

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。