KH570改性纳米SiO2的制备及应用

以硅烷偶联剂KH570为改性剂、乳化剂十二烷基硫酸钠(SDS)为助剂,对纳米SiO2进行表面改性。研究了改性剂和乳化剂用量对纳米SiO2亲油化度和平均粒径以及SiO2水溶液外观和稳定性的影响,获得了较佳的用量:KH570占纳米SiO2质量分数的9%,SDS则为3%。通过红外光谱、扫描电镜对改性纳米SiO2及其丙烯酸–聚氨酯(SPUA)复合膜进行了表征,与工业品丙烯酸–聚氨酯乳液(PUA)进行对比,测试了涂膜性能。结果表明,纳米SiO2与KH570发生了化学接枝键合;改性后的纳米SiO2粒径更小,分布更窄,在乳液中的分散性更好;SPUA涂膜的附着力、冲击强度和柔韧性与工业PUA产品相当,但硬度更高,吸水率降低。     

水性丙烯酸酯聚氨酯乳液的合成及性能

以异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇(N210)、甲基丙烯酸甲酯(MMA)等为原料,采用种子乳液聚合法制备了水性丙烯酸酯聚氨酯(PUA)乳液。探讨了异氰酸根指数R,二羟甲基丙酸(DMPA)、三羟甲基丙烷(TMP)和甲基丙烯酸甲酯(MMA)等用量以及中和度对PUA乳液及其漆膜性能的影响,获得了PUA乳液的最佳合成条件:R=1.3,DMPA添加量为PU质量的6%,TMP和MMA的添加量分别为PUA质量的1%和30%,中和度为90%~100%。红外光谱分析表明,成功合成了PUA乳液。在优化条件下制备的乳液外观呈蓝色半透明状,平均粒径71.89 nm,黏度为66.13 mPa·s,具有较好的稳定性。以该乳液制备的漆膜附着力1级,硬度H,吸水率13.84%,具有较好的耐醇性。     

改性纳米氧化锌对水性聚氨酯乳液性能的影响

以无水乙醇为溶剂、正硅酸乙酯(TEOS)为包覆剂对纳米Zn O表面进行无机包覆,然后用硅烷偶联剂(KH-550)对其表面进行改性,将改性后的纳米Zn O(即Zn O/Si O2/KH550)对水性聚氨酯乳液进行改性,研究了改性纳米Zn O的用量对水性聚氨酯(WPU)乳液涂膜的吸水率、吸甲苯率和拉伸性能的影响,通过傅里叶变换红外光谱(FT-IR)、扫描电镜(SEM)和水接触角测试对纳米Zn O和WPU改性前后的结构及疏水性进行了表征。结果表明,改性后的纳米Zn O粒子团聚减少,疏水性提高。当改性纳米Zn O的添加量为聚氨酯中有机物质量的0.6%时,所制备的用改性纳米Zn O改性的WPU乳液涂膜性能较好,吸水率、吸甲苯率分别为20.35%和30.50%,低于未改性的WPU;拉伸强度达到13.45 MPa,水接触角较未改性WPU涂膜提高了25°。     

含氟乳液的合成及其水性涂料性能 第一部分——水性涂料用含氟乳液的制备

以过硫酸铵(APS)为引发剂,通过乳液聚合法合成了甲基丙烯酸十二氟庚酯(FMA)–丙烯酸羟丙酯(HPA)–甲基丙烯酸月桂酯(LMA)–3氯2羟基甲基丙烯酸丙酯(CHMA)四元共聚乳液(FHLC),测定了乳液的物化性能,探讨了FHLC乳液性能的影响因素,确定了最佳工艺,并对其进行了红外光谱、透射电镜、粒径分布测量及Zeta电位测定。结果表明,当m(FMA)∶m(HPA)∶m(LMA)∶m(CHMA)为12∶3∶13∶2,APS质量分数为1.2%,反应温度为80°C时,所制备的乳液平均粒径为134.8nm,Zeta电位23.7mV,单体转化率95.1%,凝胶率3.6%,涂层的水接触角达到128°,吸水率为3.2%。     

硅溶胶改性水性聚氨酯丙烯酸酯复合乳液的性能研究

采用异氰酸酯基团封端的聚氨酯预聚体与硅溶胶混合的方法,制备出了水性聚氨酯丙烯酸酯 /硅溶胶纳米复合乳液,探究了分散在聚氨酯预聚体中的硅溶胶颗粒的粒径和复合漆膜中硅溶胶的含量对漆膜性能的影响。研究发现,分散在聚氨酯预聚体中的 19 nm小粒径硅溶胶颗粒容易团聚,漆膜性能较差;相比之下, 91 nm的硅溶胶无机粒子在乳液中具有良好的分散稳定性。复合漆膜中硅溶胶的含量对漆膜的吸水率和力学性能有明显影响,但对漆膜硬度、附着力和光泽的影响较小。结果表明,硅溶胶粒子粒径为 91 nm,加入量为复合乳液质量的 30%时漆膜性能最佳,吸水率为2. 67%,铅笔硬度为 3H,拉伸强度为 5. 77 MPa,断裂伸长率为 564. 58%,硅溶胶与树脂基质相容性最好。并且与未改性的聚氨酯丙烯酸酯漆膜相比,复合漆膜的耐水性和热稳定性显著提高。     

水性封闭异氰酸酯乳液的合成及稳定性研究

采用甲苯二异氰酸酯(TDI)、三羟甲基丙烷(TMP)、二羟甲基丙酸(DMPA)为原料,2-甲基咪唑为封闭剂,三乙胺为中和剂制备了水分散封闭异氰酸酯(WBI)乳液,考察了中和剂和Zeta电位(ζ-电位)对WBI乳液稳定性的影响,探讨了乳液耐电解质能力及其温敏特性对其解封温度及双组分聚氨酯漆膜性能的影响。实验结果表明:用三乙胺作为中和剂时,乳液粒径较小,稳定性及贮存稳定性均较好,最佳中和度为100%。随DMPA用量的增加,乳液的ζ电位绝对值增大,乳液粒径减小、耐电解质能力增强,乳液的稳定性提高。乳液的Zeta电位及粒径受温度影响较小,说明乳液较为稳定。DMPA用量为20%～25%(摩尔分数)较适宜。差示扫描量热法(DSC)分析表征其解封温度为125.6～138.1℃,应用表明此类WBI作为固化剂可以赋予涂料较好的耐水性、耐醇性、硬度及耐冲击性。     

改性纳米硅溶胶–丙烯酸树脂复合乳液的制备及性能研究

以丙烯酸及丙烯酸酯类单体为原料,在预聚过程中加入自制的改性纳米硅溶胶,采用溶液聚合法制备了改性纳米硅溶胶–丙烯酸树脂复合乳液,研究了反应时间、m(引发剂)/m(单体)和m(SiO_2)/m(单体)对复合乳液稳定性及其漆膜性能的影响。结果表明,反应时间为4 h、m(引发剂)/m(单体)为3%、m(SiO_2)/m(单体)为5%时,复合乳液的综合性能最优。与市售产品相比,所制备的改性纳米硅溶胶–丙烯酸树脂复合乳液涂膜性能更优,其硬度为4H,附着力0级,冲击强度50 kg·cm,柔韧性2 mm。     

双重改性聚氨酯丙烯酸酯的制备及应用性能

以聚氨酯乳液为种子乳液,引入功能性单体十六烷基烯丙基琥珀酸双酯磺酸钠(SCASD)和环氧树脂(E-44)制备了双重改性聚氨酯丙烯酸酯复合乳液(SEPUA)。采用X-光电子能谱、粒径分析仪、热重分析仪等探讨了不同SCASD及E-44用量对乳液及胶膜性能的影响。结果表明:SEPUA胶膜中含有C、O、N、S和Na元素;随着SCASD用量的增加,乳液的Zeta电位绝对值从38.9 mV增加到48.4 mV;当SCASD用量为4%时,乳液稳定性最佳,乳液粒径呈现单峰分布,SEPUA胶膜的热分解温度逐步提高。当E-44用量为6%时,胶膜的拉伸强度为10.58 MPa,吸水率降低至8.23%,而交联度升高到81.6%。将SEPUA乳液配制成水性清漆,漆膜柔韧性优良、附着力好,随着SCASD用量的增大,漆膜光泽逐渐增大。     

大分子乙烯基硅氧烷/丙烯酸酯单体核壳乳液聚合及表征

以甲基丙烯酸-2-羟乙酯(HEMA)和聚甲基氢硅氧烷(PMHS)为原料,合成了甲基丙烯酸乙氧基聚甲基氢硅氧烷醚(MEPMHSE)。以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主单体,加入合成的硅单体MEPMHSE作为聚丙烯酸酯改性剂进行核壳乳液共聚合,制得平均粒径为135.2 nm,粒径分布窄(PDI=0.045)的有机硅改性的具有核壳结构的聚丙烯酸酯乳液。采用FT-IR、1H NMR对MEPMHSE进行表征,并使用TEM、DSC以及Zeta电位及纳米激光粒径分析仪来表征乳胶粒子的结构与粒径。研究乳化剂的配比、含量以及MEPMHSE的加入量对乳液稳定性、吸水率、凝胶量以及乳液胶膜疏水性的影响。研究结果表明:用MEPMHSE改性的丙烯酸酯乳液胶膜的疏水性得到较大的提高,MEPMHSE添加量为6%时,所得丙烯酸酯乳液胶膜对水的接触角由空白对照样的65°提高到98°。     

亲水单体对聚氨酯丙烯酸复合乳液性能的影响

采用种子乳液聚合法,以甲苯二异氰酸酯(TDI)、聚醚二元醇(N210)、二羟甲基丙酸(DMPA)和甲基丙烯酸甲酯(MMA)为主要原料合成了聚氨酯丙烯酸(PUA)复合乳液。考察了DMPA对PUA乳液的制备和性能的影响;确定了DMPA的添加工艺及中和度。发现随DMPA添加量增加,PUA乳液的外观变好,乳液粒径变小,乳液黏度增大,乳液凝胶量降低,稳定性变好。随DMPA添加量增大,PUA乳液涂膜的吸水率增大,涂膜的耐水性越差。综合得到w(DMPA)=7 5%,采用后添加DMPA的工艺,且DMPA的中和度90%～100%,可得到性能优异的PUA复合乳液。     

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。