聚碳酸酯Fries重排与流变行为的关联研究

系统考察了双酚A型聚碳酸酯(PC)的分子量、残留单体、端基种类和含量、Fries重排结构与毛细管流变行为的内在关联。研究发现,270℃下PC分子链没有明显的热氧降解,改变端羟基含量、封端基种类、残留单体含量也不会对降解产生显著影响,流变测试非常稳定。流变行为呈现典型的剪切变稀效应,但是在低剪切区没有看到牛顿流体特征,黏度总是随剪切速率降低而出现不同程度的升高。进一步研究表明,低剪切区的非牛顿流动指数n与PC分子量和测试温度没有关系,但是随Fries重排结构含量的增加而线性下降。酯交换法PC由于在聚合过程中经历了长时间的高温和真空环境,Fries重排结构含量较高,因此n值明显小于光气法PC,但前者具有较高的熔体强度和黏流活化能。     

振荡剪切对聚乳酸熔体分子链解缠结的研究

利用哈克旋转流变仪在一定的温度和压力条件下对聚乳酸(PLA)熔体施加应变为正弦变化的振荡剪切场,从而对PLA分子链进行高效的降黏解缠.结果表明,当温度为190°C、样品厚度为1.5 mm时,PLA熔体在振动频率和剪切应变分别为3.5 Hz和50%处呈现最佳的降黏效果,其黏度相比于未经处理的熔体黏度下降了3~4个数量级.同时,凝胶渗透色谱(GPC)测试结果表明经过振荡剪切处理的PLA其分子量基本不变,表明熔体黏度的大幅下降是由PLA分子链有效解缠结导致而非分子链降解.示差扫描量热仪(DSC)结果表明,解缠效果最佳的PLA样品相比于未经处理的样品呈现出更低的玻璃化转变温度和较高的结晶度,进一步验证了熔体解缠的效果.不仅如此,我们研究了不同退火时间(1~30 min)和温度(180~200°C)对PLA分子链重新恢复缠结的影响,发现随着退火温度和时间的增加,PLA在120°C下等温结晶的半结晶时间不断增加,并向未经解缠处理的PLA样品的半结晶时间不断靠近,表明振荡剪切导致的解缠能在低温度下保持较长时间,在高温下快速复缠.     

氢键作用对端羟基超支化聚酯熔体流变性能的影响

以三羟甲基丙烷(TMP)为核,二羟甲基丙酸(DMPA)为支化单体,通过熔融缩聚法合成了第一至五代端羟基脂肪族超支化聚酯,采用旋转流变仪系统地研究了氢键作用对端羟基超支化聚酯熔体流变性能的影响.结果表明,与高代数超支化聚酯相比,低代数超支化聚酯的线性黏弹区较窄,松弛时间更长.无论是稳态剪切测试还是振荡测试,第一、二代端羟基超支化聚酯熔体均表现出假塑性流体的剪切变稀行为,而第三至五代端羟基超支化聚酯熔体则表现为牛顿流体的流变行为.端羟基超支化聚酯的流变行为均不遵循Cox-Merz方程.温度谱的测定发现,低代数超支化聚酯相对于高代数的结晶度更高.流变测试中所出现的现象都与分子间的氢键作用密切相关.     

过冷等规聚丙烯熔体的流变学行为

采用毛细管流变仪研究低于表观熔点的过冷聚丙烯熔体的流变学行为.过冷聚丙烯熔体先经过一段诱导期后,熔体发生凝胶化,剪切黏度在短时间内大幅度升高,最终固化结晶.在诱导期中,过冷聚丙烯熔体的流变行为与高于聚丙烯熔点的常规熔体的流变行为相仿.诱导期的长度与温度有关.在160℃下,诱导期的长度足够长,于是使用过冷聚丙烯熔体进行纺丝加工成为可能.实验结果表明,由过冷熔体制备的初生纤维各项性能与由高温熔体制备的初生纤维亦相似,因此,通过降低喷丝头温度的方法发展一种节能降耗的聚丙烯纤维制造技术有潜在的可能性.     

PEG浓度对锂藻土分散液的再凝胶化及屈服行为的影响

通过离子电导率和pH考察了锂藻土自身释放的Na+浓度,说明未经透析或离子交换处理的cw=30mg/mL的锂藻土分散液静置老化后形成的软固体是反应置限团簇聚集(RLCA)的胶体凝胶.通过剪切流变方法研究了聚乙二醇(PEG)浓度cp对锂藻土/PEG分散液体系的线性和非线性黏弹性的影响.小幅振荡剪切(SAOS)频率扫描结果表明,随着cp增加,锂藻土发生"RLCA凝胶-黏弹性液体-排空(Depletion)凝胶"转变,可观察到该体系的再凝胶化行为.稳态剪切和大振幅剪切实验结果表明,锂藻土/PEG分散体系的再凝胶化的非线性流变学行为也有体现.     

耐温抗盐驱油聚合物溶液黏弹性

对3种不同结构类型的耐温抗盐驱油聚合物〔高分子量聚丙烯酰胺(HPAM)、磺化聚丙烯酰胺(S-HPAM)和疏水缔合聚丙烯酰胺(A-HPAM)〕的溶液黏弹性能进行了研究。在温度85℃下,通过稳态剪切和动态剪切试验,考察了质量浓度和矿化度对聚合物溶液黏弹性的影响。结果表明,随剪切速率增加,溶液表观黏度逐渐降低。质量浓度越高,溶液的储能模量(G')和损耗模量(G″)越大。由动态剪切实验数据,计算得到第一法向应力差(N1)。随质量浓度增加,聚合物溶液的N1逐渐增大;随矿化度增加,聚合物溶液的N1出现不同盐敏感区域,说明不同结构类型的驱油聚合物溶液对矿化度的弹性响应不同。研究结果为高温高盐油藏聚合物驱剂的选择及开发提供了理论参考。     

TiO(acac)2催化碳酸二甲酯和苯基乙酸酯合成碳酸二苯酯

碳酸二苯酯(DPC)是非光气法生产聚碳酸酯(PCs)的重要原料,具有多种酯交换法合成路线,如碳酸二甲酯(DMC)与苯酚酯交换法、DMC与苯基乙酸酯(PA)酯交换法、草酸二甲酯(DMO)与苯酚酯交换法等.本文对比测定了几种金属乙酰丙酮配合物和有机钛化合物对碳酸二甲酯(DMC)与苯基乙酸酯(PA)酯交换合成DPC反应的催化性能,结果表明,乙酰丙酮氧钛[TiO(acac)2]是一种良好的酯交换催化剂,具有优良的催化性能.在反应条件θ=180℃,n(PA)=0.8 mol,n(DMC)/n(PA)=1/2,n(TiO(acac)2)/n(PA)=0.006,t=4 h下,DMC转化率可达74.9%,甲基苯基碳酸酯(MPC)和DPC的选择性分别可达56.9%和38.9%.探索并提出了TiO(acac)2催化DMC与PA酯交换合成DPC反应的机理.     

TiO(acac)_2催化碳酸二甲酯和乙酸苯酯合成碳酸二苯酯(英文)

碳酸二苯酯(DPC)是非光气法生产聚碳酸酯(PCs)的重要原料,具有多种酯交换法合成路线,如碳酸二甲酯(DMC)与苯酚酯交换法、DMC与苯基乙酸酯(PA)酯交换法、草酸二甲酯(DMO)与苯酚酯交换法等.本文对比测定了几种金属乙酰丙酮配合物和有机钛化合物对碳酸二甲酯(DMC)与苯基乙酸酯(PA)酯交换合成DPC反应的催化性能,结果表明,乙酰丙酮氧钛[TiO(acac)2]是一种良好的酯交换催化剂,具有优良的催化性能.在反应条件θ=180℃,n(PA)=0.8 mol,n(DMC)/n(PA)=1/2,n(TiO(acac)2)/n(PA)=0.006,t=4 h下,DMC转化率可达74.9%,甲基苯基碳酸酯(MPC)和DPC的选择性分别可达56.9%和38.9%.探索并提出了TiO(acac)2催化DMC与PA酯交换合成DPC反应的机理.     

煤加氢液化残渣的流变特性研究

采用从煤直接液化实验装置取得的液化残渣，研究了它的流变性及温度和油、沥青质、固体含量对其流变性的影响。液化残渣是剪切变稀的非牛顿型假塑性流体，非牛顿指数随温度升高而不断减小，温度越高越接近牛顿流体行为。液化残渣对温度非常敏感，在升温过程中其表观黏度下降很快，且没有出现黏度峰。在液化残渣中加入少量的循环油后其表观黏度大幅下降；而在加入少量沥青质后则表现出低温下黏度变大，高温下黏度变小的现象；固体含量则始终是黏度增大的因素，表明其黏度与油、沥青质和固体含量关系密切。液化残渣的黏度－温度关系符合Arrhenius关系式，但在升温过程中出现了拐点，低温段的黏流活化能比高温段的要大。     

超高分子量聚苯乙烯的流变性能

以毛细管流变仪和Hakke转矩流变仪对稀土催化合成的超高分子量聚苯乙烯 (UHMWPS)的流变与加工性能进行了研究 .结果表明 ,UHMWPS最显著的流变特征为超高的熔体粘度和低剪切速率下出现不稳定流动 .不稳定流动与超高分子量聚合物长的松弛时间有关 ,并提出了临界剪切速率与分子量和温度的定量关系式 .较低的分子量和较高的温度有利于提高临界剪切速率 ,改善挤出物外观质量和降低熔体粘度 .分子链极度缠结不仅导致超高的熔体粘度 ,也使UHMWPS链解缠加快 ,导致更高的剪切速率敏感性 .UHMWPS塑化时熔体粘度高 ,转矩大 ,加工性能劣于通用聚苯乙烯 (GPPS)     

Branching by reactive end groups. II. Synthesis,branching, and melt rheology of (meth)acrylate/p‐t‐butylphenol‐coterminated bisphenol a polycarbonates

(Meth)acrylate/p‐t‐butylphenol (PTBP)‐coterminated bisphenol A polycarbonates (PCs) were prepared by interfacial processes and subsequently were reacted at high temperatures (≥200 °C) to form new branched polymers. Two interfacial methods were used to prepare the precursor linear PCs, one with (meth)acryloyl chloride [(M)AC] and the other with (meth)acrylic acid [(M)AA]. Both processes involve phosgenation in the presence of catalytic amounts of triethylamine. The process that used (M)AC formed disproportionately large amounts of bisphenol A di(meth)acrylate, whereas the process using (M)AA required about 50% more phosgene to achieve high (M)AA conversions than typical interfacial PC processes. The branching of the acrylate/PTBP PCs occurred with heating at temperatures greater than or equal to 250 °C. The molecular weight and degree of branching depended on the mole ratio of the thermally reactive and nonreactive coterminators, the total amount of coterminators, and the reaction conditions. The functionality of the branch points formed appeared to be dependent on the acrylate concentration. The branching of the methacrylate/PTBP PCs required the presence of a free‐radical initiator and temperatures up to about 200 °C. The methacrylate end group was less effective than the acrylate on a molar basis in increasing the branched polymer molecular weight and degree of branching. The melt rheology of the branched acrylate/PTBP PCs showed the expected increase in low shear viscosity and shear rate sensitivity with increasing weight‐average molecular weight and acrylate‐end‐group concentration. Small changes in the total terminator concentration and, therefore, the linear precursor polymer molecular weight produced large effects in the low shear rate melt viscosity. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2340–2351, 2000     

Improving the impact property and heat‐resistance of PLA/PC blends through coupling molecular chains at the interface

The influences of both the molecular structure and the melt viscosity differences between Poly(lactic acid) (PLA) and polycarbonate (PC) on the interpenetration of molecular chains at the interface were investigated by comparing the dynamic mechanical properties and morphologies of the as‐prepared PLA/PC solution‐casting blends with those of their corresponding annealed (180°C, 8 h) samples or PLA/PC melt blends. Additionally, two chain extenders containing epoxy groups (ADR and TGDDM) were used to improve the interfacial strength. Subsequently, the interpenetration of PLA and PC molecular chains at the interface was also surveyed. Finally, the effects of the morphology formed by after adding ADR or TGDDM on the impact property, and heat resistance were discussed. The results showed that there was no interpenetration of molecular chains at the interface in PLA/PC melt blends because of the serious hindrance of the molecular structure and the melt viscosity differences. Although the interfacial strength achieved significant increase after adding ADR or TGDDM, the increase of the interfacial strength should be caused by the connection of ADR or TGDDM molecules with PLA and PC molecules at the interface through chemical bonds rather than the entanglements of PLA and PC molecular chains because of no interpenetration of PLA and PC molecular chains at the interface. Thus, the morphology formed after adding ADR or TGDDM is still the type of complete phase separation, which may be the most suitable morphology for achieving high impact and heat resistance PLA/PC blends because these two properties strongly depend on the crystallinity of PLA phase. Copyright © 2015 John Wiley & Sons, Ltd.     

Melt rheology of polypropylene containing small amounts of high molecular weight chain. I. Shear flow

Large enhancements of the melt strength of polypropylene (PP) were achieved by the introduction of high molecular weight polyethylene (PE) into PP. The viscoelastic properties of the high‐melt‐strength PP melts under shear flow were investigated. It was found that the rheological properties of the high‐melt‐strength PP were distinctly different from those of conventional PP. The elastic response at low frequencies was significantly enhanced in comparison with the conventional PP, implying a presence of a long relaxation time mode that was not revealed in conventional PP. In step‐shear measurements, the fast and slow relaxation processes that characterized the linear viscoelastic properties were observed also for nonlinear relaxation moduli. The dependence of the damping for the slow process of the high‐melt‐strength PP on shear strain was much weaker than that of the fast process. These rheological behaviors characterizing the long relaxation time mode were further enhanced with the increasing concentration of high molecular mass PE. The unusual shear rheological behaviors were discussed in view of the role of high molecular weight PE as a long relaxation time mode within PP. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2692–2704, 2001     

线型聚乙烯及其共聚物的挤出畸变与熔体粘弹性的关系

采用恒速型双筒毛细管流变仪研究了一类线型聚乙烯熔体的挤出畸变与熔体非线性粘弹性的关系。实验研究了发生畸变时挤出压力的振荡规律,发现线型大分子或带小侧基的大分子熔体,容易发生壁滑和挤出压力振荡;而有较大侧基、或分子量分布宽、或带大量短支链的熔体,挤出畸变现象较轻。挤出畸变与熔体的弹性及熔体．壁面吸附状态紧密相关。容易发生壁滑和挤出压力振荡的熔体,弹性较大(入口压力降大);在壁面的吸附作用强(壁面临界剪切应力大)。稳态剪切粘度大小与挤出畸变和压力振荡的关系不大;而拉伸应力和拉伸粘度大的熔体较易发生壁滑和挤出压力振荡。     

Sonocrystallization of polycarbonate melts

In this paper, we showed the simplified continuous process to crystallize the polycarbonate (PC) melts using sonocrystallization which is based on ultrasonic cavitation and ‘hot spot’ theory. High power ultrasonic wave was introduced to crystallize the PC prepolymers which is generally used for solid‐state polymerization (SSP) to obtain the ultra‐high molecular weight PCs. The structure and properties of PC treated with ultrasonic wave such as torque changes and crystallinities were studied. The experimental results showed that ultrasonic wave could improve the crystallinities of PCs and sonication time was proportional to their crystallinity. This is attributed to the decrease of the specific volume and the resulting shrinkage is compensated by a flux of a polymer melt toward the crystallization front. Torque data were collected directly from the Haake internal mixer and crystallinities were evaluated from differential scanning calorimeter (DSC). This process is an environmentally benign process so that no additional solvents or treatments are needed and will be very useful in the conventional solid‐state process which is used industrially. Copyright © 2007 John Wiley & Sons, Ltd.     

Static ultrasonic oscillations induced degradation and its effect on the linear rheological behavior of novel propylene based plastomer melts

The ultrasonic degradation of novel propylene based plastomer (DP) melts with different melt viscosities was conducted in a “static” ultrasonic device where the samples were taken from various distances from the tip of an ultrasonic probe. The effects of ultrasonic time, oscillation temperature, ultrasonic intensity and the distance from the ultrasonic probe tip on the degradation behavior of DP melts as well as the ultrasonic degradation effect on the linear rheological behavior of DP melts were studied. The results show that the increase of initial melt viscosity of DP (higher molecular weight) has greater impact on the ultrasonic degradation of DP melt. The molecular weight and intrinsic viscosity of DP decrease with the increase of ultrasonic oscillation time and they approach to a limiting value. The molecular weight distribution of DP increases after ultrasonic degradation. Decreasing oscillation temperature and distance from probe tip and increasing ultrasonic intensity lead to an increase in the degradation of DP melt. The linear rheological behavior measurements of the samples obtained near the ultrasonic probe tip show that ultrasonic oscillations decrease the complex viscosity, zero shear viscosity, viscoelastic moduli, cross modulus, relaxation time and the slope of log G′ − log G″ for DP melts.     

聚醚酯嵌段共聚物熔体的流变性能

采用毛细管流变仪测定了组成比、聚醚分子量、熔融时间和熔融温度对嵌段聚醚酯熔体表观粘度的影响．结果发现在所研究的温度和切变速率范围内,该结构聚醚酯熔体为假塑性非牛顿流体,其粘度随聚酯段含量的增加而增加,随熔融时间增加而降低,随聚醚分子量的增大而增大．聚醚酯的零切粘度可由Ｓｐｅｎｃｅｒ Ｄｉｌｌｏｎ 公式外推得到,零切粘度对温度的依赖关系服从Ａｎｄｒａｄｅ 公式．     

丁醛等离子体处理填料对填充聚烯烃熔体流变性的影响

用毛细管流变仪研究了经丁醛等离子体处理的云母粉填充高密度聚乙烯熔体(160℃)和聚丙烯熔体(180℃)的流变性。数据表明,处理削弱填充聚烯烃熔体流动的非牛顿性,熔体流动非牛顿指数随等离子体处理时间的延长而增大;处理降低填充聚烯烃熔体在低切变速率下的表观粘度,提高其在高切变速率下的表观粘度,发生转变的临界切变速率对填充聚乙烯和聚丙烯分别为150S~(-1)和50S~(-1)。扫描电镜观察熔体形态证实,处理对熔体粘度的复杂影响,是处理改善填料在熔体中的分散性和提高填料与基体界面结合力两者综合作用的结果。     

用辐射交联方法测定含氟聚合物分子量FEP分子量的测定

本文提出并研究了用辐射交联方法测定难溶高聚物的分子量问题。不同熔融指数FEP共聚物,辐射交联后,其凝胶化剂量随熔融指数增大而增高。由高温弹模测得FEP的交联G值为1.2。由交联G值和凝胶化剂量计算得FEP的,它与熔融指数的关系为log∞3.5log(1/Ml)·该结果与一般高聚物的本体粘度与分子量关系相一致。     

Influence of polydispersity and long chain branching on the melt viscosity of polycarbonate

The Newtonian and non-Newtonian melt viscosities of bisphenol A polycarbonate (PC) at 280°C were treated according to the generalized multivariable power function, where the average molecular weights, polydispersity degree and branching degree are considered as variables. The shear rate was also considered as a variable for non-Newtonian conditions. In the same way, the melt fluidity was treated as a multivariable power function. It has been found that the same melt flow properties of polymer can be obtained by an appropriate combination of Newtonian melt viscosity (being a function of molecular weight) and long chain branching. The experimental data on PC agree with the theoretical approach of Bucche and Graessley.