钛氟聚丙烯酸酯乳液的性能及应用

以纳米TiO_2(nano-TiO_2)、γ-甲基丙烯酰氧乙基三甲氧基硅烷(KH570)、全氟辛基乙基丙烯酸酯(FM)为主要原料,通过KH570改性纳米TiO_2后,与丙烯基单体共聚制得活性纳米TiO_2改性含氟聚丙烯酸酯复合乳液。通过FTIR、AFM及接触角测量仪表征共聚物的结构,测定了其性能。结果表明:改性纳米TiO_2、含氟单体均成功引入到聚丙烯酸酯共聚物中;乳胶粒呈球形分布,表面光滑且呈单分散状态,平均粒径为184 nm;与丙烯酸酯聚合物相比,改性后涂膜的粗糙度提高,有利于防水防油性能的提升。氟硅单体的加入使涂膜的接触角增大,对水和二碘甲烷的接触角分别为125°及110°,复合乳液用作表面施胶剂对纸张进行测试后,纸张对水接触角为147°,对二碘甲烷接触角为133°,纸张防水防油性随着氟单体的引入而显著增加。     

含氟丙烯酸酯共聚物的制备及性能

自制含氟丙烯酸酯单体与其他丙烯酸酯分别以溶液聚合和乳液聚合制得含氟丙烯酸酯溶液共聚物(Ⅰ)和乳液共聚物(Ⅱ),并与不含氟的丙烯酸酯共聚物(Ⅲ)性能进行了对比:Ⅰ在水中浸泡96h后涂膜完好,Ⅲ剥离;Ⅱ在水中浸泡24h后吸水率为12 01%～13 65%,Ⅲ为24 87%;Ⅰ、Ⅱ分别在丙酮和w(NaOH)=5%的水溶液中浸泡24h,涂膜基本完好,Ⅲ则剥离、破裂或溶解;w(氟单体)=5%时以KH-570改性Ⅰ并按上述方法测试性能,涂膜完好,硬度由HB提高到H;Ⅰ与水的平均接触角为62 1°～68 4°,Ⅱ为53 9°～61 0°,Ⅲ为29 1°～30 5°,KH-570改性Ⅰ后为63 4°～67 3°。上述结果表明:含氟共聚物涂膜的耐水性、耐碱性、耐溶剂性和自洁性均优于不含氟的共聚物,且含氟单体与KH-570具有良好的协同作用。     

含氟丙烯酸酯乳液高疏水性与低氟含量的平衡探索

为了研究含氟丙烯酸酯乳液涂膜的疏水性与氟含量的平衡关系,以甲基丙烯酸十二氟庚酯(DFHM)为含氟单体,双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)为交联单体,采用半连续核壳乳液聚合的方法合成了一系列自交联含氟丙烯酸酯共聚物乳液。研究表明:含氟单体含量为12%(即氟含量为6.84%,均以聚合单体的总质量计,下同)时,含氟基团在涂膜表面可以达到饱和,乳液固含量可达38.2%;再添加4%交联单体,涂膜的水接触角为116.6°。当含氟单体含量降为4%(氟含量2.28%)时,通过提高成膜温度或添加成膜助剂,也可使涂膜表面的水接触角达到104.2°,具有较好的疏水性能。     

氟代聚丙烯酸酯改性聚氨酯复合乳液的制备及其疏水性

为了提高聚氨酯-丙烯酸酯复合乳液的耐水性和耐溶剂性,将聚氨酯溶液作为反应介质,以丙烯酸十二氟庚酯(FA)和丙烯酸羟丙酯为单体,偶氮二异丁腈为引发剂,在溶液中进行聚丙烯酸酯自由基聚合,然后用N-甲基二乙醇胺进行亲水基扩链,通过溶液聚合相转化法制得新型阳离子氟代聚丙烯酸酯改性聚氨酯复合乳液。通过红外光谱、透射电镜、光电子能谱仪和接触角测定仪分别对复合乳液的结构、乳胶粒形态、膜表面的化学元素组成及疏水性进行了研究。结果表明,含氟链段成功接入了大分子链中,乳液形成稳定的核-壳结构,在膜材料表面形成了主要由含氟丙烯酸酯链段组成的界面,FA的引入可使复合乳液胶膜与水的接触角(PUA膜与水的接触角)由65°提高至98°。     

新型复合材料-纳米TiO2/聚丙烯酸酯复合乳液的研究

实验以乳液聚合法制备了纳米TiO2／聚丙烯酸酯复合乳液,发现将未经任何改性处理的纳米TiO2与单体共同发生聚合发应,当添加量在一定范围之内时,可以得到稳定的无机一有机纳米复合乳液,且涂膜性能优良。     

核壳型短链含氟丙烯酸酯乳液的合成及表征

该文研究了核壳型短链含氟丙烯酸酯乳液的合成与表征。以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)的共聚体为核,短氟碳链2-(全氟己基)乙基甲基丙烯酸酯(FMA6)和非氟烷基丙烯酸酯的共聚体为壳,采用多步乳液聚合法,合成系列具有核壳结构的含氟丙烯酸酯乳液,研究了壳相中氟单体用量和非氟烷基丙烯酸酯的烷基链长度n(链长n=4、8、12、16、18)对产物疏水疏油性能的影响,并对产物进行表征。结果表明:当采用氟单体用量为总单体质量的8.5%,甲基丙烯酸十六酯(CMA)的共聚体为壳层时,由合成乳液制得的乳胶膜的疏水疏油性最佳,对水接触角为124.67°,对二碘甲烷接触角为112.76°。FTIR、TEM和DSC/TGA表征表明,原料单体均参加了反应;乳液颗粒具有明显的核壳结构;聚合物存在两个玻璃化温度(-18.87℃和32.08℃),热分解温度比不含氟的聚合物提高了近20℃。由此说明,用合成的核壳型短链含氟丙烯酸酯乳液制得的涂膜具有优异的疏水疏油性和耐热性能。     

含氟丙烯酸酯乳液合成及其内墙涂料防涂鸦性的研究

以烯丙氧基羟丙基磺酸钠(COPS-1)、壬基酚聚氧乙烯醚硫酸铵(CO-436)和NP-10为复合乳化剂,过硫酸铵为引发剂进行了含氟丙烯酸酯乳液聚合研究,测定不同含氟单体含量制备的乳液干膜及漆膜与水、油的接触角,比较含氟单体含量、不同交联单体及含量对涂膜耐污性能的影响。研究结果表明:随含氟单体含量增加,乳液干膜及涂膜与水、油接触角增大;由12%甲基丙烯酸十二氟庚酯、5%双丙酮丙烯酰胺所合成的含氟丙烯酸酯乳液,稳定性高,耐沾污性好;当乳液含量为涂料配方总量的36%时,涂膜对水彩污迹的耐污性能明显改善,且遮盖力好。     

核壳型纳米SiO2/含氟聚丙烯酸酯复合乳液的合成与表征

采用原位乳液聚合法,在可聚合阴离子乳化剂/非离子乳化剂复配体系下,以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)改性的纳米SiO2、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)等为核相组成,以MMA、BA及甲基丙烯酸十二氟庚酯(DFMA)为壳相单体,合成纳米SiO2/含氟聚丙烯酸酯复合乳液.考察了纳...     

改性纳米SiO_2/聚丙烯酸酯复合乳液的制备及应用研究

用A-151和KH-570对纳米SiO2进行改性,并与丙烯酸酯单体反应制备得到复合乳液。用傅里叶红外光谱仪对改性硅溶胶进行了检测,测定了复合乳液的密度和黏度。加固过的土块耐水能力和抗压能力提高了2倍,并且抗盐碱和抗冻融能力有明显的提高。改性纳米SiO2/聚丙烯酸酯复合乳液可以应用于土遗址保护。     

氟硅改性水性丙烯酸酯乳液的合成及其对胶膜的影响

以甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸为主要原料,1,3,5-三(甲基三氟丙基)环三硅氧烷(D3F)和硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)分别为含氟及含硅改性单体,采用酮肼交联体系,通过溶液聚合合成了改性水性聚丙烯酸酯乳液。考察了改性单体用量对乳液稳定性、粒径及浇铸膜吸水率的影响,并对乳液浇铸膜进行了表面水接触角的测定,热重分析及红外表征。结果表明,D_3F与KH-570接入丙烯酸酯链段中,改性单体的加入使丙烯酸酯膜的吸水率降低,表面性能提升,热稳定性提高。当D_3F∶KH-570质量比约为4∶1时,胶膜吸水率低,表面接触角超过90°,热稳定性高,综合性能更好。     

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。