沉淀相转化法磁性聚砜超滤膜的性能研究

以聚砜为基材、聚乙烯吡咯烷酮为致孔剂、二甲基乙酰胺为溶剂,四氧化三铁为填料,采用浸没沉淀相转化法分别在水平磁场和无磁场的条件下制备聚砜-Fe_3O_4超滤膜,并采用死端超滤装置测试了的膜的渗透性,截留率,耐污染性等性能。实验结果表明:超滤膜通量、截留率随Fe_3O_4含量增加而增加;Fe_3O_4含量高于40%(质量分数)时,未磁化膜性能有明显的提高,Fe_3O_4含量高于60%(质量分数)时,磁化膜性能有明显的提高;相同Fe_3O_4含量下,Fe_3O_4高于60%(质量分数)时,磁化膜通量更大,截留率略低,绝对耐污染性更强,相对耐污染性更弱。     

高通量反渗透膜基膜的制取研究

以聚砜(PSF)为溶质,N-甲基吡咯烷酮(NMP)为溶剂,聚乙二醇(PEG)为添加剂制备铸膜液。一定温度下,通过调节PSF含量、PEG的相对分子质量和添加量,研究不同的铸膜液组成对基膜水通量、截留率、水接触角、耐压密性和膜截面结构的影响。结果表明,基膜的水通量随PSF含量的增加而降低,截留率升高但幅度较小,耐压密性增强。同一相对分子质量的PEG随着PEG含量的增加,通量先增加后减小,截留率变化不大,耐压密性先减小后增大但最终耐压密性低于初始耐压密性。同一含量的PEG随着其相对分子质量的增加,通量呈先增加后减小趋势,截留率变化不大,耐压密性呈减小趋势。综合考虑,选择PSF、NMP的质量分数分别为21%、71%,质量分数8%的PEG-2000作添加剂改性PSF基膜为好。     

共混制备抗菌聚醚砜中空纤维超滤膜及其表征

辣素衍生物N-(4-羟基-3-甲氧基-苄基)丙烯酰胺HMBA和乙烯基单体(丙烯酸乙酯和丙烯酰胺)通过溶液聚合方法合成的共聚物HAE,将这种共聚物做为抗菌材料与聚醚砜共混均匀形成铸膜液,通过干-湿相转化法制备改性中空纤维超滤膜。铸膜液中共聚物的质量分数为0~3%,通过傅里叶红外全反射FTIR-AIR、水静态接触角(CA)、扫描电子显微镜(SEM)、错流过滤评价仪、抗菌实验、长期抗耐污染性实验对纤维膜进行表征及分析。结果表明,共混改性之后中空纤维超滤膜表面含有亲水基团,膜表面的接触角显著降低;当HAE在铸膜液中的质量分数为1%时,膜的纯水通量能达到193.7 L/(m2·h),膜对牛血清蛋白的截留率为95%,相对基膜分别提高90.5%和5.5%,通过去离子水清洗之后膜的通量恢复率能达到90.82%;抗菌性随着共聚物含量的增加而增强,当HAE的质量分数为3%时,超滤膜的抗菌率达到90%。由长期的耐污染测试发现改性膜对微生物具有很好的抵抗能力。     

表面化学改性法制备抑菌性聚醚砜超滤膜

以辣素衍生物N-(5-甲基-3-异丁基-2羟基-苄基)-丙烯酰胺(HMBA)为改性材料,利用表面化学接枝法在聚醚砜(PES)超滤膜表面接枝辣素单体,提高膜的抑菌性。分别研究了单体含量、不同引发剂以及反应时间对接枝反应的影响;并采用全反射红外光谱(ATR-FTIR)对接枝前后聚砜膜进行表征,用原子力显微镜(AFM)观察接枝前后聚砜膜的形貌变化。结果表明,在单体的质量分数为1%,引发剂为过硫酸钾(K2S2O8)、焦亚硫酸钾(K2S2O5),处理时间60 min,接枝反应温度为40℃时,获得最佳接枝效果。接枝改性后的聚砜膜抑菌率达到80%,高于改性前的18%;表面水静态接触角能够降低到60°左右。     

光照溴化诱导接枝聚合两步法对PAN/PSU共混膜的表面改性

采用表面光接枝改性方法对聚丙烯情/聚砜(PAN/PSU)共混膜进行改性,对PAN/PSU共混膜进行光照溴化和紫外诱导接枝聚合丙烯酸,测定了膜的红外光谱、水通量和牛血清蛋白(BAS)截留率.结果表明:紫外光照溴化3 b后,PAN/PSU膜的结构即破坏,膜表面产生了C-Br键;随溴化程度增加,膜的水通量从67 L/(m2·h)下降到48 L/(m2·h),膜的BAS截留率从85%上升到92%;紫外诱导接枝聚合丙烯酸过程中,仅有少量溴参与改性.处理时间小于1 h,膜的分离特性未有明显改变;延长改性时间,膜的水通量降低,截留率升高.     

紫外辐照接枝甲基丙烯酸对无纺布性能影响的研究

以二苯甲酮作为光引发剂,利用紫外辐照法引发单体接枝聚合反应,将亲水性单体甲基丙烯酸接枝在无纺布表面对其进行改性。通过测定接枝率,评价聚合物在无纺布表面的接枝程度;通过测定未改性及改性无纺布的膜通量,考察了改性无纺布表面的透水性;通过ATR-FTIR红外光谱和扫描电镜(SEM)对改性前后无纺布进行结构表征。实验结果表明:单体体积分数20%,辐照距离20cm,辐照时间40min,光引发剂二苯甲酮浓度0.1mol/L时,接枝率和膜通量达到最大值,分别为20%和1387L/m2·h。ATR-FTIR红外光谱分析表明无纺布表面负载了亲水性-COOH。     

2,2'-氧代双乙胺改性复合纳滤膜的亲水性研究

使用聚砜超滤膜为基膜,以亲水二胺单体(2,2'-氧代双乙胺)为添加剂,与哌嗪以不同比例混合作为水相溶液,通过界面聚合反应制备出高亲水性的聚酰胺/聚砜纳滤复合膜。通过红外表征膜的表面化学结构;静态水接触角测试表征膜的表面亲水性能;渗透性能测试表征了原膜及改性膜的水通量和盐截留性能。结果显示,随着2,2'-氧代双乙胺单体含量增加,膜的亲水性能越好,改性膜的水接触角最低可达到32°;在氧代双乙胺质量分数0.67%,测试压力为0.7 MPa,温度为25℃条件下,改性膜对2 g/L的MgSO_4水溶液水通量为35.6 L/(m~2·h),盐截留率达到90%。     

低温水等离子体活化和表面接枝DMAE聚氯乙烯中空纤维膜研究

采用低温水等离子体技术,在三通道聚氯乙烯(PVC)膜表面接枝了甲基丙烯氧基苄基二甲基氯化铵(DMAE)单体,增强了膜亲水和抗菌性能。通过红外分析,表明DMAE成功接枝到了PVC膜上,水通量提高两倍,PVC-ir-H₂O膜(通过水等离子体处理的膜)对牛血清蛋白(BSA)的吸附能力下降67%,对BSA溶液的通量从7.7提高至40 kg?m^-2?h^-1,并且对BSA的截留能力不变。通过静态及动态抗菌实验,接枝后的PVC膜（PVC-g-PMAE膜）抗菌率达到100%,膜组件运行中的抗菌率也达到82%以上。在保证细菌截留率100%的同时,其渗透通量提高三倍。该膜表面修饰工程技术能实现膜表面的均一化改性,且绿色环保、操作简便、成本低,改性膜在饮用水处理领域,尤其是家用净水器中展现了很好的应用前景。     

二苯甲酮引发丙烯酸在聚氨酯表面接枝的研究

首次将光敏引发剂二苯甲酮(BP)用于聚氨酯表面的紫外光引发丙烯酸(AA)和丙烯酰胺(AAm)的接枝聚合,用ATR-FTIR、光电子能谱、接触角及接枝率对接枝的PU膜表面进行表征。结果表明,利用BP能有效地在PU表面接枝聚丙烯酸(PAA)和聚丙烯酰胺(PAAm)。研究了引发剂浓度、紫外灯与PU膜表面距离等条件对接枝的影响。     

聚砜超滤膜表面辐照改性研究

以聚砜为膜材料,聚乙二醇(PEG)为添加剂,采用浸入沉淀相转化法制备聚砜平板超滤膜,然后对实验制备的聚砜膜进行紫外辐照改性,考察了辐照对聚砜膜结构和性能的影响,研究了膜辐照前后断裂强度的变化,通过表面接触角测定仪、红外分析仪(FTIR)、扫描电镜(SEM)、改性膜的纯水通量和截留性能等方法来表征膜辐照前后的结构和性能变化.研究表明:聚砜膜断裂强度经辐照后变小,但降低幅度不大;在乙醇溶液中紫外辐照后,开始纯水通量提高而截留率降低,但降低幅度不大,时间增加到一定时通量又降低,截留率变化也不大;表面接触角随辐照时间的增长而减小,表明改性后膜表面的亲水性得到明显改善;通过FTIR分析证实在聚砜膜表面产生了新的官能团;SEM实验证实反应只发生在聚砜膜的表面而非膜内部.聚砜超滤膜经紫外辐照改性取得了良好的效果.     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

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.