低温非水环境中疏水缔合聚丙烯酸钠与两性离子表面活性剂的相互作用

疏水缔合聚合物和表面活性剂是构建黏弹性流体的重要物质, 二者的相互作用对流体性质具有显著影响, 一直是该领域的研究热点, 但此前的研究仅聚焦于水溶液中室温及以上温度范围, 而零下极端低温环境中的相互作用尚未涉及. 本文以疏水缔合聚丙烯酸钠(HMPA)为模型聚合物, 研究了低温(-20~20 ℃)环境中其与两性离子表面活性剂N-(顺-二十二碳-13-烯酸酰胺基丙基)-N,N-二甲基羧酸甜菜碱(EDAB)在乙二醇/水混合溶剂中的相互作用及混合体系的流变性质. 先后考察了HMPA溶解于纯水和乙二醇/水混合溶剂时的流变行为和HMPA-EDAB在乙二醇/水混合溶剂中的流变行为及自组装结构形貌. 研究发现, 加入50%(体积分数)的乙二醇会阻碍HMPA疏水支链形成缔合结构, 减弱其增黏性能, 但同时也会大幅降低体系的冰点. 在HMPA- EDAB混合体系中, HMPA疏水支链会进入EDAB胶束内核自组装形成混合胶束. 混合胶束的形貌取决于 HMPA和EDAB的浓度及环境温度, 进而影响体系的流变行为. 零下的低温有助于EDAB形成蠕虫状胶束, 因此HMPA与EDAB表现出更强的协同增效作用.     

聚乙烯-g-聚苯乙烯对线性低密度聚乙烯/聚苯乙烯共混物机械性能和发泡行为的影响

以通过开环易位聚合、加氢反应和原子转移自由基聚合技术结合制备的聚乙烯-g-聚苯乙烯(PE-g-PS)作为增容剂,研究了加入不同PS支链长度的PE-g-PS对于线性低密度聚乙烯/聚苯乙烯(LLDPE/PS)共混物的机械性能和发泡行为的影响。 以典型组成m(LLDPE):m(PS)=70:30共混物为例,考察了PE-g-PS对共混物拉伸性能的影响。 相对于二元共混物,增容剂的加入使得断裂伸长率、拉伸强度和屈服强度皆提高,且含长PS支链的增容体系提高更明显。 采用超临界CO₂釜式发泡工艺,考察了PE-g-PS中PS支链长度对共混物发泡行为的影响。 结果表明,相对于短PS支链体系,加入PE-g-PS_1.59k(PS相对分子质量为1590)后的泡孔结构更加均一,完全没有“缝隙”形貌的出现。 当发泡温度降至80 ℃时,即使存在LLDPE发泡空间限制作用(LLDPE无法发泡),加入支链长度更长的PE-g-PS_1.59k后泡孔分布也更加均一。     

PBT／PC共混体系流变性能与形态结构研究

采用毛细管流交仪测定了ＰＢＴ／ＰＣ共混物的表观粘度、剪切应力，观察了不同共混物组成和不同温度下共混物的流变行为，并借助扫描电镜对共混物和微观形态结构进行分析。结果表明：ＰＢＴ／ＰＣ熔体共混物的流变行为接近假塑性流体．温度对共混物的流变行为影响很大，共混物的熔体粘度在ＰＢＴ／ＰＣ为９０／１０和６０／４０时呈双极值．共混物为两相结构，ＰＣ含量为４－５０％时呈两互锁结构。     

活性正离子聚合及原位制备聚醋酸乙烯酯-g-聚四氢呋喃共聚物/纳米银复合材料

通过将烯丙基溴/高氯酸银引发体系引发四氢呋喃活性正离子开环聚合与"grafting onto"合成方法相结合,原位制备了不同接枝密度和接枝链长度的新型聚醋酸乙烯酯-g-聚四氢呋喃接枝共聚物(PVAc-g-PTHF)及其与纳米银(Ag)的复合材料.采用傅里叶变换红外光谱(FTIR)、核磁共振波谱(1H-NMR)和多角度激光光散射-黏度-凝胶渗透色谱仪(MALLS-VIS-GPC)分别表征了该接枝共聚物的化学结构、共聚组成、分子量、分子量分布、接枝支链数目及支化度,采用原子力显微镜(AFM)、示差扫描量热分析(DSC)、偏光显微镜(POM)研究了接枝共聚物中接枝支链数目及支链长度对其微观形态、单端受限链段结晶行为的影响,并探讨了该纳米复合材料的抗菌性能.结果表明:所制备的不同支链数目和支链长度的PVAc-g-PTHF/Ag纳米复合材料,均表现出良好的抗菌性能;接枝共聚物PVAc-g-PTHF的重均分子量可达4.52×10~5,分子分子量较窄(M_w/M_n~1.8),支化因子可达0.19.接枝共聚物PVAc-g-PTHF可形成明显的相分离结构,其微观形态与接枝支链数目有关;相比相同分子量的双端不受限的PTHF链,PVAc-g-PTHF接枝共聚物中单端受限PTHF支链的结晶速率明显降低;在确定接枝支链数目的情况下,随着支链中PTHF链段长度增加,其结晶逐渐增强,结晶熔融温度及熔融焓均稍有增加.     

胶质液体泡沫的流变性

应用RV-30旋转粘度计和锥板式RS300应力控制流变仪, 采用稳态剪切方法和小振幅振荡剪切对胶质液体泡沫(CLA)体系的流变特性进行了系统分析, 讨论了温度、 相体积比(油相与水相体积比, PVR)和剪切速率对体系流变性质的影响. 稳态剪切实验结果表明, CLA体系表现出非牛顿流体特征, 其流变行为符合Herschel-Bulkley流变模式. 同时, CLA体系表现出剪切稀释特性, 不具有触变性. 粘弹性实验结果表明, 在低PVR(PVR=2~4)条件下, CLA无线性粘弹性区; 当PVR=8时, 表现出一定程度的粘弹性; 温度对体系的流变行为和粘弹性的影响不显著. 通过与高内相乳状液(HIPRE)体系比较, 发现CLA与HIPRE具有相似的流变特性, 这也说明两者在微观结构上具有一定的相似性.     

单色化X射线对薄膜表面高分子降解行为的影响

采用聚甲基丙烯酸甲酯(PMMA)和苯乙烯-丙烯腈无规共聚物(SAN)薄膜体系, 在不同的实验温度下, 研究了单色化的X射线对其中一个组分(PMMA)降解行为的影响.     

高分子材料支化结构与流变性的联系串讲北大核心CSCD

高分子链结构为直链型或支化型以及高分子支链的形态、多寡和长度对材料的剪切黏度、黏流活化能、熔体破裂现象等流变性能有显著影响,且与高分子材料成型加工行为密不可分。本文以串讲方式讨论了高分子材料支化结构与流变性能之间的联系。理解、串并、归纳和总结高分子支化结构与流变性之间的联系有利于使学生更加深刻领会《聚合物流变学》课程中高分子材料结构与性能间的关系,串联高分子物理、聚合物流变学、高分子材料成型加工系列专业课程知识。     

高分子材料支化结构与流变性的联系串讲

高分子链结构为直链型或支化型以及高分子支链的形态、多寡和长度对材料的剪切黏度、黏流活化能、熔体破裂现象等流变性能有显著影响,且与高分子材料成型加工行为密不可分。本文以串讲方式讨论了高分子材料支化结构与流变性能之间的联系。理解、串并、归纳和总结高分子支化结构与流变性之间的联系有利于使学生更加深刻领会《聚合物流变学》课程中高分子材料结构与性能间的关系,串联高分子物理、聚合物流变学、高分子材料成型加工系列专业课程知识。     

聚甲基丙烯酸甲酯/聚(苯乙烯-丙烯腈)共混体系相分离的特征动态流变响应

采用动态流变学方法,结合小角激光光散射(SALLS)测定,对聚甲基丙烯酸甲酯(PMMA)/聚(苯乙烯－丙烯腈)(SAN)共混体系的动态流变行为与相分离的关系进行了研究.发现在低频区域,时温叠加失效与共混物体系发生相分离有关,时温叠加失效温度T_b与用SALLS测定的浊点温度T_c一致,用低频区域动态储能模量G'与频率的关系[1gG'～lg(α_T)]偏离线性粘弹模型或时温叠加失效温度表征PMMA/SAN共混体系的相分离是有效的.     

阴离子分散剂对酸化膨润土流变性的影响

研究了阴离子分散剂聚丙烯酸钠对质量分数为10%的酸化膨润土分散体系流变性的影响. 结果表明, 添加0.4%分散剂的分散体系的剪切应力、表观黏度和屈服应力最低. 其它体系流体均表现为从假塑型到胀流型流体的转变, 而含0.4%分散剂的体系始终表现为胀流型流体. 采用Herschel-Bulkley模型对各体系的流变曲线进行了拟合, 得到较好的拟合曲线, 同时探讨了酸化膨润土分散体系的流变机理.     

Rheology of the Melt of Acrylonitrile–Styrene Copolymer Modified with Montmorillonite

The rheological properties of the acrylonitrile–styrene copolymer modified with hydrophobized montmorillonite Cloisite 30B and composites are studied in a wide range of shear rates and shear frequencies at a temperature of 230°C. It is shown that the filler insignificantly affects the viscoelastic properties of the compositions, but the viscosity of composite melts considerably increases at low shear rates and monotonically grows with increasing concentration, whereas at high shear rates the effective viscosity declines appreciably in the concentration range of about 0.3 vol %.     

Modification of the rheological properties of polyurethanes by adding fumed silica: influence of the preparation procedure

The way of addition of fumed silica determined the rheological properties of polyurethane (PU) adhesives. The higher the shear rate during preparation of fumed silica containingPU adhesives, the higher viscosity and improved plasticity and thixotropy in the solutions. The improved properties of these adhesive solutions were ascribed to the creation of interactions between the silanol groups on the fumed silica, the polar groups in the soft segments of the polyurethane and/or the solvent. However, the way of incorporate the fumed silica in the polyurethane did not affect the rheological properties of fumed silica-PU composites (obtained by solvent removal from the solutions), indicating the key role of the solvent in the rheology of PU adhesive solutions.     

Rheological properties of polyurethane adhesives containing silica as filler: influence of the nature and surface chemistry of silica

Four silicas, two fumed silicas (one hydrophilic and one hydrophobic) and two precipitated silicas (one hydrophilic and one hydrophobic), were added as filler to solvent‐based polyurethane (PU) adhesive formulations. In general, the addition of silica increased the viscosity, the storage and loss moduli of the PU adhesives but only the hydrophilic fumed silica exhibited pseudoplasticity and thixotropy. The rheological properties imparted by adding filmed silicas to PU adhesive solutions were more noticeable than that of precipitated silicas. Interactions between the hydrophilic fumed silica, the polyurethane and/or the solvent seemed to be responsible for the improved rheological properties of filled PU adhesives.     

SC-CO2中聚氨酯吸附樟脑的研究

研究了在SC－CO2中不同聚合物对樟脑的吸附,发现聚氨酯、乙烯－醋酸乙烯酯共聚物等非晶型和高分子的吸附效果优于聚乙烯等结晶型高分子。继而以聚氨酯为对象,分别讨论了实验温度、压力、吸附时间和不同共溶剂分子对其吸附结果的影响,结果表明,实验温度越高,吸附时间越长,则聚氨酯对樟脑的吸附量越大。当吸附时间相同,吸附量随压力增先增后减,在临界压附近会出现一级大值,在共溶剂的使用中,醇类分子比酮类和胺类分子能更大地提高聚氨酯的对樟脑的吸附量。     

热塑性聚氨酯及其复合材料的界面形态与流变特性

以聚酯型热塑性聚氨酯(thermoplastic polyurethane,TPU)、玻璃纤维(glass fiber,GF)和玻璃微珠(glass bead,GB)为主要原料制备了TPU/GF、TPU/GB共混物,考察了复合体系的热性能、微观结构、动态流变特性.研究发现,TPU是温敏型聚合物,其温敏性与材料的硬段含量有关,在加工过程中,除考虑剪切速率的影响外,需重点考虑温度对其加工性能的影响;GF,GB填充TPU体系具有良好的分散形态和界面结合牢度,GF和GB的加入能够增加体系的黏度,降低TPU的温敏性,加宽TPU的加工温度窗口,从而改善其成型加工性,并能一定程度地提高其耐热性.研究还发现,复合体系黏度的增加程度不仅和填料的含量有关,而且与填料的形状有关,可用等效直径表征.另外,从比表面积的角度比较了玻璃纤维和玻璃微珠对体系热稳定性的影响.     

Investigation of properties of compatibilized TPU/SAN blends

The properties of compatibilized thermoplastic polyurethane/poly(styrene‐co‐acrylonitrile) (TPU/SAN) blends were investigated. Relaxation temperatures were studied by dynamic‐mechanical thermal analysis (DMTA). In comparison, thermal properties were determined by differential scanning calorimetry (DSC). The morphology of the samples was studied by transmission electron microscopy (TEM).     

Rheological properties of acrylonitrile—acrylamide—styrene copolymer solutions synthesized by classical and controlled radical polymerizations

Russian Chemical Bulletin - The results of a comparative study of the rheological properties of acrylonitrile copolymers solutions synthesized by classical and controlled radical polymerizations in...     

Effect of Na‐ionomer on dynamic rheological,dynamic mechanical and creep properties of acrylonitrile styrene acrylate (ASA)/Na+1 poly (ethylene‐co‐methacrylic acid) ionomer blend

A special class of engineered copolymers, called ionomers, comprising both electrically neutral repeating units and a fraction of ionized units was melt blended to weather resistant acrylonitrile/styrene/acrylate (ASA) terpolymer for improved electrical conductivity, heat sealing ability, direct adhesion to several polymers, glass and metals without affecting the aesthetics and colorability of ASA. The similar chemical nature of one of the components of each blended materials viz. acrylate rubber in ASA and acrylic acid of Na‐ionomer in addition to the presence of ionic crosslinking within Na‐ionomer, polar acrylonitrile group in ASA affects chain dynamics as compared to neat polymers. In this context, dynamic rheological properties, DMA properties, creep behavior and DSC of the newly developed ASA/Na‐ionomer blends were analyzed. Based on Na‐ionomer content, the blend system either forms “mushroom” or “brush” type conformation and formation of ionic crosslinking in “brush regime” leads to three tiers Caylay tree conformation. The different chain topology resulted into characteristic loss modulous (G″) curve during stress relaxation process. The chain conformation as well as ionic crosslinking and ion–dipole interaction between the blend components also affected DSC endotherm peak and glass transition temperature. The tan δ peak temperature from DMA also revealed the similar observation. The creep compliance of the blends was dependent on Na‐ionomer content and with temperature. The Findley model analysis of creep compliance suggested that the creep compliance was depended on Na‐ionomer content and ionic crosslinking controlled the creep. The findings can be utilized to design weather resistant smart polymer using suitable filler system. Copyright © 2014 John Wiley & Sons, Ltd.     

Polyurethane adhesive composition cured at room temperature

The influence of polyfunctional hydroxyl-containing oligomer on the rheological, physicomechanical, and adhesive properties of polyurethane composite based on multicomponent oligomer blend and polyisocyanate is investigated. The kinetics of curing is investigated by the viscometric method, and the composition lifetime is determined. It is shown that the polyurethanes under investigation can be used as fast-curing adhesive composites of cold curing operating in a temperature interval of up to +90°C.     

Anionic synthesis of poly[ethylene methylene bis(4-phenyl-carbamate)-g-acrylonitrile]

A relatively high-molecular-weight polyurethane based on MDI and ethylene glycol was prepared and characterized. This polymer was metalated with sodium hydride in N,N-dimethylformamide (DMF) at about 0°C. Metalation was confirmed principally by spectroscopic identification of the N-methyl derivative obtained by coupling the metalated polymer with methyl iodide. Under appropriate reaction conditions the metalated polyurethane was used for the anionic graft polymerization of the reactive monomers acrylonitrile and ethylene and propylene sulfides. Attempted anionic graft polymerizations with other monomers, including styrene and ethylene and propylene oxides, were unsuccessful. The polyurethane grafted with acrylonitrile was separated by fractionation from accompanying small amounts of polyacrylonitrile, a low-molecular-weight homopolymer. One sample of polyurethane grafted with acrylonitrile was identified by microanalysis, IR, NMR, and increase in weight and was also characterized by differential thermal analysis.