PVC／PE交联共混体系的动态学力学研究

在ＰＶＣ／ＰＥ共混体系中加入交联剂和引发剂能产生ＰＶＣ－ＣＯ－ＰＥ共聚物，这种共聚物在共混物中可起到增容剂的作用，通过动态力学分析和扫描电镜研究了ＰＶＣ／ＰＥ交联混体系的相容性，发现引发剂，交联剂，稳定剂和增塑剂等对共混和的中的交联反应均有较大的影响。     

PVC／PE交联共混体系的动态力学研究

在ＰＶＣ／ＰＥ共混体系中加入交联剂和引发剂能产生ＰＶＣ－ＣＯ－ＰＥ共聚物，这种共聚物在共混物中可起到增容剂的作用。通过动态力学分析和扫描电镜研究了ＰＶＣ／ＰＥ交联共混体系的相容性。发现引发剂、交联剂、稳定剂和增塑剂等对共混物中的交联反应均有较大的影响。     

聚β—羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性与结晶行为

研究了制样过程聚β－羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性和结晶行为的影响。ＤＳＣ、ＳＡＸＳ、ＰＯＭ等实验结果表明，ＰＨＢ／ＰＶＡｃ共混物经溶液成膜后处于分相的状态，ＰＶＡｃ对ＰＨＢ的结晶能力影响不大；而经融处理后，ＰＨＢ／ＰＶＡｃ共混物则处于相容的均相状态，随ＰＶＡｃ的含量含量的增加。     

固相法氯化聚乙烯增韧聚氯乙烯的研究Ⅱ．CPE的氯含量及共混方式与PVC／CPE相容性的关系

研究了聚氯乙烯（ＰＶＣ）与固相法氯化聚乙烯（ＣＰＥ）的相容性与氯含量、共混方式以及ＣＰＥ链结构的关系。动态力学性能表明ＰＶＣ／ＣＰＥ为部分相容体系，ＣＰＥ中类似ＰＶＣ的链段与ＰＶＣ形成相间过渡层，共混方式影响共混体系的相容程度。透射电镜结果表明ＣＰＥ呈连续网络结构分布于ＰＶＣ粒子表面。共混条件一定时，共混物的抗张强度随相容性的改善而增加。     

固相法氯化聚乙烯增韧聚氯乙烯的研究

研究了聚氯乙烯与固相法氯化聚乙烯的相容性与氯含量、共混方式以及ＣＰＥ链结构的关系，动态力学性能表明ＰＶＣ／ＣＰＥ为部分相容体系，ＣＰＥ中类似ＰＶＣ的链段与ＰＶＣ形成相间过渡层，共混方式影响共混体系的相容程度，透射电镜结构表明ＣＰＥ呈连续网络结构分布于ＰＶＣ粒子表面，共混条件一定时，共混物的抗张强度随相容性的改改善而增加。     

氯乙烯/邻苯二甲酸二烯丙基酯悬浮共聚特征

对４５℃时的氯乙烯／邻苯二甲酸二烯丙基酯（ＶＣ／ＤＡＰ）的悬浮共聚进行了研究，得到表观竞聚率ｒＶＣ＝０７６９、ｒＤＡＰ＝０３７４．凝胶点对应的ＤＡＰ临界起始浓度在０４６６～０４９３ｍｍｏｌ／ｍｏｌＶＣ之间（聚合转化率为８０～８５％），当ＤＡＰ起始浓度小于临界浓度时，ＶＣ／ＤＡＰ共聚物均为溶胶，溶胶平均聚合度随ＤＡＰ起始浓度和聚合转化率的提高而增大；当ＤＡＰ起始浓度大于临界浓度时，共聚物由溶胶和凝胶组成，凝胶含量随ＤＡＰ浓度和聚合转化率的提高而增加，溶胶聚合度则随ＤＡＰ浓度的提高而减小．在凝胶点前，共聚物的分子量分布随ＤＡＰ浓度的增加而变宽；凝胶点以后，分子量分布随ＤＡＰ浓度的增加而变窄．     

聚β-羟基丁酸酯/聚醋酸乙稀酯共混物结晶行为的研究

以ＤＳＣ，ＰＯＭ，ＷＡＸＤ实验方法研究了聚β－羟基丁酸酯／聚醋酸乙稀酯（ＰＨＢ／ＰＶＡｃ）共混体系的结晶行为。结果表明：随共混物中非晶组份ＰＶＡｃ含量的增加，ＰＨＢ结晶的活化能增大。用Ａｖｒａｍｉ方程处理实验数据，结果表明ＰＶＡｃ的加入对ＰＨＢ结晶的生长方式影响不大，但结晶速率却明显下降。ＷＡＸＤ实验表明，ＰＶＡｃ的加入不影响ＰＨＢ的结晶结构，但微晶尺寸和结晶度却明显变小。偏光显微镜观察结果与ＤＳＣ实验结果基本一致。     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的相容性研究（Ⅰ）

用ＤＳＣ，ＤＭＴＡ研究了醋酸纤维素（ＣＤＡ），聚乙烯基吮咯烷酮（ＰＶＰ）及ＣＤＡ／ＰＶＰ共混体系的玻璃化转变行为．用精密量热法测定了该体系的混合热焓．结果表明：共混体系只存在一个玻璃化转变温度（Ｔｇ），其值随共混组成的变化而改变；共混体系的混合热焓为负值，其绝对值随组成中ＰＶＰ含量的增加而减少．力学性能研究表明，共混体系具有协同效应．上述试验结果证明，ＣＤＡ和ＰＶＰ是一对相容性高聚物．     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的相容性研究（Ⅰ）

 用ＤＳＣ，ＤＭＴＡ研究了醋酸纤维素（ＣＤＡ），聚乙烯基吮咯烷酮（ＰＶＰ）及ＣＤＡ／ＰＶＰ共混体系的玻璃化转变行为．用精密量热法测定了该体系的混合热焓．结果表明：共混体系只存在一个玻璃化转变温度（Ｔｇ），其值随共混组成的变化而改变；共混体系的混合热焓为负值，其绝对值随组成中ＰＶＰ含量的增加而减少．力学性能研究表明，共混体系具有协同效应．上述试验结果证明，ＣＤＡ和ＰＶＰ是一对相容性高聚物．     

聚β－羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性与结晶行为

研究了制样过程对聚β－羟基丁酸酯（ＰＨＢ）／聚醋酸乙烯酯（ＰＶＡｃ）共混体系的相容性和结晶行为的影响，ＤＳＣ、ＳＡＸＳ、ＰＯＭ等实验结果表明，ＰＨＢ／ＰＶＡｃ共混物经溶液成膜后处于分相的状态，ＰＶＡｃ对ＰＨＢ的结晶能力影响不大，而经熔融处理后，ＰＨＢ／ＰＶＡｃ共混物则处于相容的均相状态，随ＰＶＡｃ在共混物中含量的增加，ＰＨＢ的冷结晶温度升高，球晶增长速率下降，织态结构变得不规整。当ＰＶＡｃ的含量高于８０％时，ＰＨＢ失去结晶能力。     

EFFECT OF PLASTICIZER ON THE MICROSTRUCTURE OF PS/PVC BLENDS

In this work, controlling of the particle size of PVC in PS/PVC blends was studied. Itis shown that viscosity ratio and particle size can be changed by adding a third composition,such as plasticizers, and the distribution of the third composition in two phases plays avery important role in controlling viscosity ratio and particle size. When DOP was used asthe plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduceddue to the transference of DOP into PS phase. When polycaprolactone (PCL) was usedas the plasticizer of PVC in the same blends, the particle size of PVC could be descreasedobviously because PCL does not migrate to PS phase.     

共聚酯PEIT-PEG结晶性能的研究

通过偏光显微镜、广角X衍射与FTIR三种测试手段对共聚酯PEIT-PEG的结晶性能进行了系统的研究，重点分析了间苯二甲酸(IPA)、聚乙二醇(PEG)分子量和含量对共聚酯结晶性的影响。研究表明，PEIT与PEG之间发生了共聚反应，IPA的引入使PET结晶性能下降，晶粒尺寸减少，结晶度降低。引入PEG后，当PEG分子量和含量较低时，共聚酯结晶性能提高；当PEG含量较高时，在PEG分子量不变的情况下，随着PEG含量的增加，结晶性能下降；若PEG重量含量相同，PEG分子量越高，结晶性能越好。     

N,N-二甲基甲酰胺中铀(V)吸收光谱的研究

以中压汞灯为光源，采用吸收光谱法，观察了UO2（NO3）2•6H2O在DMF（N，N－二甲基甲酰胺）溶剂中光化还原时的吸收光谱随照射时间、铀浓度及溶液酸度的变化．经短时间光照后，在UO2（NO3）2－DMF溶液中有铀（Ⅴ）形成，其吸收峰在755和635nm处．结果表明，它们分别是UO2+－DMF和UOOH2＋－DMF的特征吸收，溶液中铀（Ⅴ）的岐化反应与H＋浓度密切相关，UOOH2＋是岐化反应的中间体．     

Migration of Additives from Poly(vinyl chloride) (PVC) Tubes into Aqueous Media

The stability and migration product of medical PVC tubes plasticized with polyadipates were investigated by ageing in phosphate buffer at pH 1.679 and water at different temperatures. Changes in the PVC tubes were studied by water absorption, weight loss, Fourier infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The low molecular weight migration product that was released was extracted and silylanized before gas chromatography/mass spectroscopy (GC/MS) identification and quantification. After 70 days, the weight loss was less than 0.5% and only a small amount of adipic acid migrated when a tube was aged at 37°C in water and phosphate buffer (pH 1.679), and at 70°C in water after 56 days. However, when aged at 70 and 110°C, gradual deactivation of heat stabilizer after 21 days of ageing in buffer solution and separation of plasticizer from PVC matrix occurred. When the tube was aged at 110°C, significant degradation of both polyadipates and PVC were observed. Adipic acid and 1,4-butanediol monomers and oligomers of polyadipate were the major migration products from polyadipates in the water ageing solution, while only a relatively high amount of adipic acid was identified as the main product in the buffer ageing solution.     

A study of wet PVC gels by raman spectroscopy

Raman spectroscopy has been used to study PVC gels made in cyclohexanone in the wet state at concentrations from 21 to 93% by weight of PVC. Parallel and perpendicular spectra were obtained in the C-Cl stretching region, and after subtraction of the solvent spectrum they were analyzed into a set of overlapping peaks due to various structural components. The positions of the peaks found were in good agreement with those found earlier for PVC samples in the solid state. The fractional contribution of the areas of peaks assigned to crystalline material to the total area under the C-Cl stretching region was used to estimate the crystallinity of the gels, and changes in their depolarization ratios and relative intensities were interpretated as providing further evidence for the presence of two types of crystallites in PVC gels. From a determination of the crystallinity at the gel transition point and reasonable assumptions, the contributions of the two types of crystallites to the total crystallinity were estimated.     

EFFECT OF STRESS-INDUCED REACTIONS ON MORPHOLOGICAL STRUCTURE AND PROCESSABILITY OF PVC DURING PAN-MILLING

The effect of pan-milling on morphological structure, processability and properties of PVC was studied through SEM, FTIR, granulometer, GPC and mechanical properties test in the hope of gaining ease in operation, needless of plasticizers, a clean and efficient route for improving the processability of PVC through stress-induced reactions,fulfilling the idea of “plasticizing PVC by itself”. The experimental results show that during pan-milling at ambient temperature, within 2-3 min, the microcrystalline structure of PVC becomes indistinct, the grain size of PVC is reducedfrom 130-160 μm to 1-50 μm the molecular weight of PVC is slightly decreased, the variation of molecular weight distribution is indistinct, the plasticizing time and torque at balance drop a great deal from 71-132 s to 31-33 s and from 18.2-22.1 Nm to 14.7-18.4 Nm, respectively, the processability of PVC is markedly improved, and the mechanical properties get enhanced too.     

力化学降解对聚氯乙烯加工流变行为的影响

采用Brabender塑化仪和毛细管流变仪研究了经力化学降解制得的聚氯乙烯(PVC)的加工流变行为。结果表明,降解的PVC塑化时间比未降解的PVC明显缩短,塑化速度和熔化效率也明显加快,熔体粘度及玻璃比温度降低。     

Effect of structural stress on the intercalation rate of kaolinite

Particle size in kaolinite intercalation showed an inverse reactivity trend compared with most chemical reactions: finer particles had lower reactivity and some of the fine particles cannot be intercalated. Although this phenomenon was noted in the early 1960s and several hypotheses have been reported, there is no widely accepted theory about the unusual particle size response in the intercalation. We propose that structural stress is a controlling factor in the intercalation and the stress contributes to the higher reactivity of the coarser particles. In this study, we checked the structural deformation spectroscopically and indirectly proved the structural stress hypothesis. A Georgia kaolinite was separated into nine size fractions and their intercalations by hydrazine monohydrate and potassium acetate were investigated with X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) analyses. The apical Si-O band of kaolinite at 1115 cm(-1) shifted to 1124 cm(-1) when the mineral was intercalated to 1.03 nm by hydrazine monohydrate, and its strong pleochroic properties became much weaker. Similar reduction in pleochroism was observed on the surface OH bands of kaolinite after intercalation. Both the bending vibrations of the inner OH group at 914 cm(-1) and of the surface OH group at 937 cm(-1) shifted to 903 cm(-1) after intercalation by hydrazine. A new band for the inner OH group appeared at 3611 cm(-1) during the deintercalation of the 1.03 nm hydrazine kaolinite complex. Pleochroism change in the apical Si-O band suggested the tetrahedra had increased tilt with respect to the (001) plane. The tilt of the Si-O apical bond could occur only if the octahedra had also undergone structural rearrangement during intercalation. These changes in the octahedral and tetrahedral sheets represent some change in the manner of compensation for the structural misfit of the tetrahedral sheet and octahedral sheet. As the lateral dimensions of a kaolinite particle increases, the cumulative degree of misfit increases. Intercalation breaks the hydrogen bonds between layers and allows for the structure to reduce the accumulated stress in some other manner. The reversed size effect on intercalation probably was not caused by crystallinity differences as reported in the literature, because the Hinckley and Lietard crystallinity indices of the four clay fractions were very close to each other. Impurities, such as dickite- or nacrite-like phases are not significant in the studied sample as suggested by the XRD and IR results, they are not the main reasons for the lower reactivity of the finer particles.     

Mechanical and dielectric absorption of poly(vinyl chloride) and some related polymers

The mechanical and dielectric low temperature absorptions of poly(vinyl chloride) (PVC) and several modified PVC's have been studied over the temperature range from ?60 to +60°C. with some tests extending to ?150°C. and others to +170°C. The results indicate that the low-temperature absorption near ?50°C (β₂ absorption) decreases in intensity with chlorination, while the absorption at a higher temperature near 0°C (β₁ absorption) decreases in intensity with hydrogenation. The apparent activation energies of the β₁ and β₂ absorptions were calculated to be 16 kcal/mole and 10.7 kcal/mole, respectively. Besides, the β₂ absorption markedly decreases in intensity with addition of plasticizer, while the intensity of β₁ absorption is not much affected by increasing plasticizer content. From these results, the β₁ and β₂ processes are concluded to be the results of molecular motion in crystalline and amorphous region in PVC, respectively. For samples of reduced Cl content, another low-temperature absorption was located near ?120°C (γ absorption) and attributed to the presence of short sequences of ethylene units. It has also been observed that the temperature location of the high temperature absorption near 100°C (α absorption) shifts linearly to higher temperature with increasing chlorine content and to lower temperature with increasing hydrogen content.     

The nature of singlet excitons in oligoacene molecular crystals

A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32 cm(-1), far smaller than the measured value of 631 cm(-1) and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601 cm(-1) and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport.