疏水缔合两性聚丙烯酰胺的合成与性能研究

利用疏水单体苯乙烯能够提高分子链刚性,可以与丙烯酰胺进行共聚,并且苯乙烯与丙烯酰胺共聚物在水溶液中存在疏水缔合作用的特性,将苯乙烯、丙烯酰胺和3-[2-(N-甲基丙烯酰胺基)-乙基二甲基铵基]丙基磺酸盐采用反相乳液聚合的方式进行聚合反应得到一种疏水缔合的两性聚丙烯酰胺。聚合物结构经过核磁和红外验证,并对其耐盐性能进行验证,着重研究了其耐温性能,该种聚合物耐温性能有显著提高。该聚合物经100℃老化48h后剪切黏度保留率达到63%,而80℃老化48 h后剪切黏度保留率则高达87%。     

一种疏水缔合聚合物的合成及溶液性能

将十八烷基-二甲基甲代烯丙基氯化铵(C18DMMAAC)作为疏水单体,与丙烯酸(AA)、丙烯酰胺(AM)在水溶液中通过自由基聚合得到疏水缔合聚合物HAPAM-18,通过1HNMR和红外光谱对其结构进行了表征。最佳的聚合反应条件为:n(AM)∶n(AA)∶n(C18DMMAAC)=74.94∶25∶0.06,AA的摩尔中和度为95%,单体总质量分数为20%,引发剂质量分数为0.05%(以单体总质量计),温度45℃,反应时间12 h。研究表明,聚合物溶液的临界缔合质量浓度为2 g/L;聚合物溶液对温度较为敏感,80℃时黏度保留率为70.93%;聚合物溶液仍为剪切变稀的假塑性流体,但表现出良好的抗剪切性能,剪切1 h后黏度保留率达115%;由于设计为含较多阴离子的聚合物,该聚合物的抗盐性较差。     

耐高温低伤害清洁水性稠化剂的制备及性能

针对高温储层压裂需求,以丙烯酰胺（AM）、丙烯酸（AA）、十八烷基二甲基烯丙基氯化铵（ODAAC）和十八烷基甲基丙烯酸酯（SMA）为原料制备了一种疏水缔合聚合物（AAOS）,再使用低分子醇（乙二醇、丙三醇、正丙醇）、表面活性剂（椰子油脂肪酸二乙醇酰胺和十二烷基硫酸钠）和AAOS配制开发一种“自交联”耐高温清洁水性稠化剂（FPM-1）。SEM结果表明,质量分数为0.30 %的FPM-1水溶液能显著增强AAOS聚合物分子间的疏水缔合交联作用,增大聚合物的流体力学体积。通过对FPM-1的溶解性、表观黏度、耐盐性、流变学测试表明,FPM-1溶液为高黏弹性流体,悬砂性能好;质量分数为0.27 %的AAOS在水中的溶解时间为7 min,最终黏度为90 mPa·s,质量分数为0.60 %的FPM-1（具有等效聚合物含量）在水中的溶解时间仅需3 min,且最终黏度为165 mPa·s,表明FPM-1体系能显著提高聚合物的黏度和溶解速度。在90℃,170 s-1条件下剪切1 h后,质量分数为0.27 %的AAOS水溶液的黏度为51 mPa·s,质量分数为0.60 %的FPM-1水溶液黏度为77 mPa·s;质量分数为1.40 %的FPM-1水溶液在180℃,170 s-1条件下剪切1 h,最终黏度为53 mPa·s;质量分数为0.60 %的FPM-1在5×104 mg/L矿化度盐水中黏度保持率为60 %,因此,FPM-1水溶液具有优异的耐盐、耐高温、耐剪切性能。通过对破胶液的表/界面张力测试表明,FPM-1体系破胶液具有低的表/界面张力,有利于破胶液的返排和回收再利用。     

压裂用耐温乳液稠化剂的制备及性能

为发展耐温疏水聚合物压裂液体系,本文在丙烯酰胺、丙烯酸、2-丙烯酰胺-2-甲基丙磺酸（AMPS）中引入了疏水单体甲基丙烯酸十八烷基酯来提高稠化剂的耐温性,合成了聚合物稠化剂PAS。实验结果表明,制备改性聚合物的条件为：单体占总质量的30%,乳化剂占油相的10%,亲水亲油平衡值（HLB）为6,引发剂占单体质量的0.2%,油水相比为1∶2。其黏均分子量为450×104g/mol。测试了该聚合物1.5%的浓度在120℃、170s-1下剪切1.5h后黏度保持在80mPa·s,具有较好的耐温性,并具有剪切回复性能;其粒径分布为500～1200nm;在破胶剂过硫酸钾的用量为0.03%时,在90℃下,其黏度可以下降到5mPa·s,完成破胶。     

壳聚糖改性疏水缔合聚丙烯酰胺的制备及表征

为了改善疏水缔合聚丙烯酰胺的溶解性以及溶液稳定性，本文采用巯基壳聚糖对疏水缔合聚丙烯酰胺进行改性，红外表征结果说明巯基壳聚糖连接到了聚丙烯酰胺分子链上。对影响壳聚糖改性实验的因素进行分析，实验结果说明，壳聚糖中巯基含量增大、壳聚糖加入量增大以及改性反应温度升高都会造成聚合物分子量降低，当改性反应的反应温度不高于35℃、添加壳聚糖质量不高于单体质量的3%时，得到的改性聚合物分子量满足现场使用要求。对改性聚合物的溶解性及溶液稳定性进行了评价，结果表明，壳聚糖中巯基含量增大及壳聚糖加入量增大对聚合物溶解性及溶液稳定性有明显的改善，聚合物的溶解时间由改性前的150min最多缩短至20min，聚合物溶液黏度保留率由改性前的60%最多提高到90%以上，壳聚糖改性有望弥补疏水缔合聚合物现场使用中的一些不足。     

反相乳液制备缔合型耐盐聚合物及流变性能评价

摘要：以丙烯酰胺（AM）、2-丙烯酰胺-十二烷基磺酸钠（AMC12S）、疏水单体GTE-10为原料,通过反相乳液聚合法制备了一种缔合型耐盐聚合物p(AM/AMC12S/GTE-10)。通过FTIR、1HNMR、SEM、TEM及激光粒度分析仪对其结构和形貌进行表征,并对其流变性能进行评价。结果表明,疏水单体GTE-10成功引入聚合物中,聚合完成后的乳液粒径分布集中且均一,盐的加入使得p(AM/AMC12S/GTE-10)分子聚集态更紧密,形成的空间网络结构更稳定。质量分数为0.7%的p(AM/AMC12S/GTE-10)聚合物水溶液在140 ℃时表现出较好的耐温性能;在120 ℃,170 s-1条件下剪切1 h,在质量浓度为20000 mg/L的NaCl和CaCl2水溶液中分别配制质量分数0.7%的聚合物溶液,其黏度分别为64.7和54.2 mPa·s;触变性能测试表明,聚合物具有较好的剪切恢复性能;黏弹性测试结果表明,盐水条件下储能模量（G′）>损耗模量（G″）,金属离子与苯氧乙烯基发生络合反应,使分子间作用力增强,形成的空间结构更稳定且难被破坏,黏弹性更高。     

疏水聚合物Mannich碱的合成及溶液性能

将增黏用碳五石油树脂(C_5)作为疏水单体,与丙烯酰胺(AM)聚合反应得到AM/C_5二元共聚物,通过胺甲基化反应制得疏水聚合物Mannich碱。考察了单体质量比、引发剂用量、反应温度以及pH对聚合反应的影响;讨论了反应时间、反应温度以及溶液pH对Mannich碱溶液表观黏度的影响。采用FTIR、~1HNMR对产品进行结构表征,并对产品性能进行分析。结果表明,最佳聚合条件为:反应温度40℃,pH=8,引发剂用量为0.5%(以单体质量计),丙烯酰胺与碳五石油树脂的质量比为15∶1。当反应时间为5 h,温度60~70℃,pH=9,丙烯酰胺、甲醛、二甲胺的物质的量比为1∶1.1∶1.5,Mannich碱溶液黏度达到最佳(418 m Pa·s)。温度为90℃时,Mannich碱的黏度保留率为43.3%;当加入的NaCl、CaCl_2的质量浓度均为2 000 mg/L时,其黏度保留率分别为32.8%、21.7%。该Mannich碱具有较好的增黏、耐温及耐盐性。     

耐盐型疏水缔合聚合物的制备及流变性能

采用丙烯酰胺(AM)、丙烯酸(AA)、2-丙烯酰胺-2-甲基丙烷磺酸(AMPS)和水溶性阴离子疏水单体S-18制备了新型耐盐疏水缔合聚合物S-18HPAM。聚合放热测试表明:疏水单体含量的增加导致放热时间的延长,更有利于疏水结构的形成。微观结构测试表明:聚合物具有复杂的网状结构,在NaCl溶液中网状结构更为明显。流变测试结果表明:聚合物在盐溶液中具有良好的耐温和抗剪切性能。聚合物质量分数为0.3%(基于溶液总质量),温度90℃,剪切速率170 s–1和NaCl质量浓度20000 mg/L条件下,剪切后表观黏度大于70 mPa·s。在总矿化度20000 mg/L模拟地下水条件下,S-18HPAM质量分数为0.3%,剪切后黏度为70 mPa·s,加入质量分数0.5%表面活性剂十二烷基硫酸钠(SDS)后,黏度增加到170m Pa·s。储能模量G'随着聚合物质量分数的增加而增大,体系弹性增强,同时疏水结构单元数量增加,形成致密的空间网络结构。     

一种具有表面活性的双尾疏水缔合丙烯酰胺共聚物

文章以自制双尾疏水丙烯酰胺单体丙烯酰胺(N-苄基-N-辛基丙烯酰胺,N-benzyl-N-octylacrylamide,BOAM)和表面活性单体(辛基酚聚氧乙烯醚丙烯酸酯,OP-10-AC)与丙烯酰胺(acrylamide,AM)水溶液共聚合成新型疏水缔合共聚物(AM-Na A-OP10AC-BOAM)。实验结果表明,当聚合物浓度大600mg/L时,表观黏度迅速增加,表现出明显的缔合行为;共聚合物溶液具有良好的黏弹性和表面活性,SEM扫描电镜照片显示共聚物溶液中存在网状的缔合微观形貌特征。     

表面活性剂对孪尾缔合聚合物水溶液表观黏度的影响

用黏度法研究了孪尾疏水缔合水溶性聚合物聚（丙烯酰胺／丙烯酸钠／N,N-二己基丙烯酰胺）[P（AM／NaAA／DiC6AM）]与十二烷基硫酸钠（SDS）、十六烷基三甲基溴化铵（CRAB）、OP-10的相互作用。结果表明,水溶液的表观黏度随SDS、CTAB质量浓度的增加急剧上升,超过一定浓度后水溶液黏度又急剧下降;黏度上升的幅度随疏水单体用量的增加、表面活性剂与疏水单体的摩尔比率（SMR值）的减小而增大;随水解度的增加,黏度上升的幅度较小。P（AM／NaAA／DiC6AM）的临界缔合浓度cac约为30g/mL,当加入SDS、CTAB时,能显著地降低。随OP-10质量浓度的增加,水溶液表观黏度几乎不变。表明P（AM／NaAA／DRAM）与SDS、CTAB的疏水缔合作用较强,而与OP-10的疏水缔合作用较弱。     

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。