新型孪尾疏水改性聚合物／表面活性剂的溶液性能研究

采用前加碱胶束共聚-共水解法制备了丙烯酰胺、丙烯酸钠和新型孪尾疏水单体N,N-二正辛基丙烯酰胺的三元共聚物P(AM/NaAA/DiC8AM),利用FTIR和1H-NMR确定了共聚物的结构,测定了共聚物/表面活性剂复合体系水溶液的表观粘度,研究了表面活性剂种类、温度、电解质、剪切速率等因素对复合体系溶液表观粘度的影响。P(AM/NaAA/DiC8AM)/SDS和P(AM/NaAA/DiC8AM)/CTAB复合体系的溶液表观粘度与HPAM共聚物溶液相比有明显的提高,疏水单体含量越大,复合体系的溶液表观粘度越大,且其溶液具有一定的耐温、耐盐和抗剪切性。     

ABS/PMMA合金流变行为的研究

对丙烯腈 丁二烯 苯乙烯共聚物(ABS)和聚甲基丙烯酸甲酯(PMMA)合金的流变行为进行了较详细的研究。内容包括:不同配比ABS PMMA混合物的熔体表观粘度随温度的变化;不同配比ABS PMMA混合物的熔体表观粘度随剪切速率的变化;相同配比ABS PMMA(70 30)混合物的熔体表观粘度随温度及剪切速率的变化。研究结果表明,ABS PMMA混合物熔体表观粘度随着体系中PMMA含量的增加而逐渐升高;高PMMA含量的ABS PM MA混合物的熔体表观粘度对温度更敏感。     

PC／SMA合金流变性能的研究

用XLY-Ⅱ型毛细管流变仪研究了聚碳酸酯/苯乙烯-马来酸酐共聚物(PC/SMA)合金的流变性能。实验结果表明:当温度升高、剪切速率加大时,合金表观粘度(η_a)明显降低;合金中η_a随着SMA的含量增加而下降。还研究了PC/SMA合金制造方法和SMA中MA含量对合金表观粘度的影响。     

PP/PET共混熔体的流变性能研究

以PP-g-AA作增容剂,研究了PP/PET共混熔体的流变行为。讨论了温度、剪切速率以及PET和增容剂含量对熔体表观粘度、非牛顿指数等方面的影响。结果表明,PP/PET共混物熔体表观粘度随剪切速率的增大而降低,随PET及增容剂含量的增加而下降,随温度的升高而下降。PET和增容剂的加入,在共混熔体中起到了增塑剂的作用。     

微乳液聚合法AM-SMA疏水缔合聚合物的研究

通过甲基丙烯酸十八酯(SMA)与丙烯酰胺(AM)微乳液聚合合成了疏水缔合聚合物,采用红外光谱(FTIR)表征了疏水缔合聚合物的结构,考察了SMA含量、AM含量、聚合物浓度、NaCl浓度以及剪切速率对疏水缔合聚合物溶液表观粘度的影响。结果表明聚合物水溶液临界缔合浓度为0.6g/dL,疏水缔合聚合物表现出较强的盐增粘效应和抗盐性;12%SMA的疏水缔合聚合物水溶液表现出剪切增粘和假塑性流体行为,FTIR谱图初步证实疏水缔合聚合物的结构。     

AM/AN/ANPE共聚物溶液性质研究

采用自由基胶束聚合法合成了丙烯酰胺(AM)/丙烯腈(AN)/烯丙基(对-壬基)苯基醚(ANPE)疏水缔合型水溶性共聚物,考察了温度、盐度和剪切时间对聚合物溶液表观粘度的影响。结果表明,所合成的AM/AN/ANPE三元共聚物的临界缔合质量浓度为4.39g/L,具有较好的抗盐、抗温及抗剪切性。     

甲壳胺/乙酸溶液表观粘度的影响因素

在低剪切速率下,研究了甲壳胺的浓度、溶液静置时间、溶液温度及溶剂乙酸浓度对甲壳胺/乙酸溶液表观粘度的影响。结果表明:甲壳胺/乙酸溶液的表观粘度随甲壳胺浓度的增加而上升,随溶液温度的上升而降低,随乙酸浓度的增加有所降低。配制甲壳胺/乙酸纺丝原液时,需现用现配,甲壳胺质量分数4.5%,乙酸质量分数2.0%,溶液温度20℃为宜。     

淀粉与丙烯酸接枝共聚的研究

采用过硫酸盐氧化方法将丙烯酸接枝到木薯淀粉上。研究了反应温度、反应时间、引发剂浓度和丙烯酸用量对接核反应的影响。反应温度升高,过硫酸盐分解速率加快,淀粉游离基增多,能提高接枝量和接枝效率。延长反应时间,可提高单体转化率,但对接枝量和接枝效率影响不大。引发剂用量以3.0×10~(-3)mol/L为宜。丙烯酸用量以2.5～5.0mol/L为宜。增加丙烯酸用量,均聚反应加快,对淀粉接枝不利。红外吸收光谱证明,淀粉-聚丙烯酸接枝共聚物出现淀粉和支链聚丙烯酸的特征吸收峰。电子扫描电镜图片表明,原淀粉表面光滑,呈球形颗粒结构。接枝淀粉表面沉积着聚合物,形貌上发生了很大的变化。由表观粘度随剪切速率升高而急剧下降可以看出,接枝共聚物的水溶液呈假塑性流体。高接枝量的接技物表观粘度较大,有较高的剪切稳定性。     

PC／PA1010共混物的流变性能

本文用XLY-Ⅱ型毛细管流变仪研究了PC/PA1010共混物的流变特性,讨论了剪切速率、温度和配比对共混物表观粘度的影响。结果表明:当温度升高和PA1010含量增大时,共混物表观粘度明显降低,剪切速率对共混物表观粘度的影响较小。     

聚丙烯/丙烯-乙烯共聚物共混体系的流变行为研究

采用毛细管流变仪和旋转流变仪研究了聚丙烯(PP)纤维专用料/丙烯-乙烯共聚物(PEC)共混体系的流变行为,探究了剪切速率、温度、共混物组成对熔体流变行为的影响。结果表明,随着剪切速率的增加,PP、PP/PEC和PEC均表现出"剪切变稀"行为;随着温度的升高,聚合物的表观黏度逐渐降低,特别是在低剪切速率下的这种现象更明显;随着PEC含量的增加,体系的非牛顿指数增加,黏流活化能降低,黏度对温度的敏感性降低,熔体剪切模量增加,熔体弹性增加。     

瓶级聚酯质量对流变及加工性能的影响研究

研究和分析了加工温度、特性黏数、摩尔质量及其分布、间苯二甲酸含量(IPA)、二甘醇(DEG)含量等因素对瓶级聚酯流变性及加工性能的影响。结果表明,在低剪切速率下,温度的升高使熔体的切力变稀现象逐渐减弱,当剪切速率达到8 000 s-1以上时,温度及剪切速率都几乎对熔体的表观黏度没有影响;摩尔质量越高,熔体黏度的切变速率依赖性越大,摩尔质量分布宽有利于成型加工条件的控制;在相同剪切速率下,熔体的剪切黏度随着IPA含量的增大而逐渐降低;DEG含量低的聚合物熔体在低剪切速率下出现非牛顿性流动的现象比DEG含量高的要明显得多。     

Viscosity behavior and surface and interfacial activities of hydrophobically modified water‐soluble acrylamide/N‐phenyl acrylamide block copolymers

In this study, the viscosity behavior and surface and interfacial activities of associative water‐soluble polymers, which were prepared by an aqueous micellar copolymerization technique from acrylamide and small amounts of N‐phenyl acrylamide (1.5 and 5 mol %), were investigated under various conditions, including the polymer concentration, shear rate, temperature, and salinity. The copolymer solutions exhibited increased viscosity due to intermolecular hydrophobic associations, as the solution viscosity of the copolymers increased sharply with increasing polymer concentration, especially above a critical overlap concentration. An almost shear‐rate‐independent viscosity (Newtonian plateau) was also displayed at high shear rates, and typical non‐Newtonian shear‐thinning behavior was exhibited at low shear rates and high temperatures. Furthermore, the copolymers exhibited high air–water and oil–water interfacial activities, as the surface and interfacial tensions decreased with increasing polymer concentration and salinity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2290–2300, 2003     

疏水缔合聚丙烯酰胺溶液性质研究

用粘度法和核孔膜过滤法研究了实验室自制相对分子质量约1000万的疏水缔合聚丙烯酰胺(HAP)溶液的缔合效应,用粘度计考察了电解质浓度、温度和剪切速率对HAP溶液表观粘度的影响,并与相同测试条件下相对分子质量为1770万的部分水解聚丙烯酰胺3530进行对比。结果表明:HAP溶液在70℃的高温和矿化度为5727的高盐条件下,在1000mg/kg附近存在一临界缔合浓度,在临界缔合浓度以上,HAP溶液粘度迅速增加;而3530不存在临界缔合浓度,粘度增加缓慢。浓度为1250mg/kg的HAP溶液通过核孔膜20mL的过滤时间是347.3min,而相同浓度下3530的过滤时间仅为2.1min。浓度为1000mg/kg的HAP溶液即使在矿化度为30000、70℃的高温、30r/min转速的条件下,粘度仍达到32.8mPa·s,而聚合物3530的粘度仅有4.11mPa·s;当剪切速率增加到140r/min、温度为70℃,用矿化度为5727的模拟采出水配制的HAP溶液的粘度为9.21mPa·s,而3530溶液的粘度仅5.18mPa·s。HAP具有良好的耐温抗盐抗剪切能力。     

聚酰胺酸纺丝溶液的流变性能研究

由均苯四酸二酐(PMDA)和4,4'-二氨基二苯醚(ODA)在N,N-二甲基乙酰胺(DMAc)中共聚合制得聚酰亚胺前驱体——聚酰胺酸的纺丝溶液,采用哈克流变仪研究了溶液的流变性能。结果表明:聚酰胺酸溶液属于切力变稀的非牛顿流体;溶液的表观黏度随溶液温度的升高而降低,随溶液浓度的升高或聚合物特性黏度的增大而增大。溶液温度的升高、浓度的降低或聚合物特性黏度的减小均使得聚酰胺酸溶液呈现切力变稀行为的临界剪切速率变大,使得溶液的非牛顿指数增大,同时使得溶液的结构黏度指数减小。溶液的黏流活化能随剪切速率的增加或随溶液浓度的增高而下降。     

丙烯腈溶液共聚过程体系黏度变化的动态测定与理论分析

通过BrookField DV-Ⅲ Ultra可编程旋转流变仪实时测定了以偶氮二异丁腈为引发剂,二甲基亚砜为溶剂,丙烯腈-衣康酸二元溶液共聚合体系的零剪切黏度变化。同时设计相同条件的封管实验测定转化率,并利用Arrhenius-Frenkel-Eyring方程导出了适合描述丙烯腈溶液共聚合体系的零剪切黏度随固含量、温度及黏均分子量变化的经验关联式。结果表明,各工艺条件对体系黏度都有显著影响,原料配比细微的差别将导致最终原液黏度相差数百帕秒以上,调控黏度时需综合考虑。值得注意的是,所有实验条件下反应2～3 h后,体系黏度激增1000倍以上,即从约2 mPa·s的初始黏度迅速增加至2～3 Pa·s;而当总单体含量达到28%时体系产生凝胶效应,反应一定时间后黏度急剧增长。另外发现,当体系达到某一临界固含量时,溶液中大分子发生链缠结,固含量微小的增量就会导致体系黏度剧增。     

碳添加剂对聚丙烯腈溶液流变性影响的研究

以碳纳米管(MCNT)和碳黑(CB)为添加剂,采用溶液共混的方法,讨论了添加剂浓度、放置时间、温度、剪切速率对聚丙烯腈溶液的表观黏度及黏流活化能(ΔΕη)的影响。结果表明:随着MCNT含量的增加,聚丙烯腈溶液的黏度先增大后减小,添加1.0%MCNT时,聚丙烯腈溶液的黏度最大,活化能也同时达到最大;随着碳黑含量的增加,黏度与活化能都随之增加,但增加幅度不大。两种PAN溶液都属于明显的切力变稀的非牛顿流体,随着剪切速率的增加,黏度下降;但在高切变速率(>800s-1)时,黏度几乎不变。     

Influence of styrene-butadiene-styrene polymer modification on bitumen viscosity

Effects of polymer content/structure and bitumen type on viscosity characteristics of styrene-butadiene-styrene (SBS) polymer modified bitumens were investigated. The study indicated that SBS polymers were not inert additives and increases in kinematic and dynamic viscosities of the modified bitumens were not directly proportional to polymer content; a marked viscosity increase was observed when the polymer content increased from 3 to 6% by weight of the blend. Modification with a sufficiently high polymer content also increased the degree of non-Newtonian behaviour of the bitumens. The base bitumens and modified bitumens containing 3% SBS were observed to be essentially shear rate independent, while those containing 6 or 9% SBS displayed shear-thinning behaviour. Compared to the modified bitumens with linear SBS, the modified bitumens with branched SBS demonstrated a higher degree of shear-thinning behaviour. These effects were dependent on ranges of shear rate and temperature. The increased degree of non-Newtonian behaviour was observed to influence the correlations between kinematic and dynamic viscosities.     

Rheology of polyacrylonitrile‐based precursor polymers produced from controlled (RAFT) and conventional polymerization: Its role in solution spinning

Polymer solutions in dimethyl sulfoxide (DMSO) as a solvent, made from reversible addition fragmentation chain transfer (RAFT)‐mediated polyacrylonitrile (RAFT^¥ PAN) terpolymer with molecular weight (MW) of 260,000 g/mol and dispersity (Ð) of 1.29, behave differently under applied shear stress than polymer solutions made from conventional PAN (Control PAN) with similar MW (258,000 g/mol) but Ð of 2.05 in the same solvent. The unique rheology of RAFT PAN is because of the reduced amount of high MW polymer fractions. Specifically, a 25% (w/v) polymer solution of RAFT PAN had a viscosity of 198 Pas while the equivalent control PAN polymer solution had a viscosity of 968 Pas at a shear rate of 1 s^?1. Also, RAFT PAN polymer solutions had a longer Newtonian plateau than control PAN polymer solutions. This exhibits more liquid character in RAFT PAN polymer solutions than control PAN polymer solutions at same temperature and concentration. In dynamic tests, RAFT PAN polymer solutions gelled slower than their equivalent control PAN polymer solutions because of their longer polymer chain relaxation times. Slow gelling and higher liquid character in RAFT PAN polymer solutions can result in obtaining stronger and finer precursor fibers during wet spinning. Since RAFT PAN polymer solutions exhibit low viscosity and higher liquid character when compared to its equivalent control PAN at same concentration and temperature, these can allow a wider working window for wet spinning and can also allow higher solid content in the polymer solutions that remain easy to wet spin. This is expected to lead to compact and finer fibers with less voids and higher strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44273.     

PP/WSPET/ZnO三元共混合金的流变性研究

用CFT-500型毛细管流变仪研究了PP/WSPET/ZnO共混体系的流变性能。研究结果表明:PP/WSPET/ZnO共混合金为典型的假塑性流体,WSPET含量增加,流体产生不稳定流动的临界剪切速率增大。共混合金的表观黏度和零切黏度随WSPET含量和温度提高而减小。黏度对温度的依赖性随WSPET含量增加和剪切速率的增大而减小。     

Effect of composition on the solution rheology of stearyl methacrylate‐co‐styrene‐co‐vinyl pyrrolidinone in paraffinic base oil

The rheological behavior of dilute and semi‐dilute solutions of stearyl methacrylate‐co‐styrene‐co‐vinyl pyrrolidinone copolymers (SMA‐S‐VP) was investigated over a wide range of temperatures (20–140°C) under steady shear (0.1–5000 s^?1) and dynamic conditions (0.01–500 rad/s). The solvent used was polyalpha olefin, PAO4 (C20‐C40 fraction), a fully synthetic paraffinic oil normally used as base oil for lubricant oil formulations. The investigation focuses on the effect of the polar comonomer segment content, of the copolymer, on the viscosity‐temperature relationship of the solution. This information provides insight into the effect of polymer microstructure on the viscosity index (VI) behavior of the lubricant. Copolymers with different ratios of stearyl methacrylate, styrene and vinyl pyrrolidinone were synthesized by solution radical polymerization. The microstructure and molecular weight of the copolymers were evaluated by nuclear magnetic resonance spectroscopy (NMR). The molecular weight and polydispersity of the polymers were determined using GPC. The polymer solutions exhibit non‐Newtonian behavior, which is more evident at lower temperatures and higher concentrations. The temperature‐concentration superposition principle developed by Ferry (1) was applied to steady shear data and the resulting master curve was fitted to the Carreau model. A modified Fedors equation for intrinsic viscosity calculation, at low and moderate polymer solution concentrations, was used. The results confirm that the viscosity index improver properties (VII) of the copolymer are superior when the VP content is low. The polymer‐solvent interactions and solvency power of PAO4 were analyzed using an Arrhenius expression. The results show that at low VP content, PAO4 is a better solvent for the copolymer. Polym. Eng. Sci. 44:736–748, 2004. © 2004 Society of Plastics Engineers.