聚乙烯醇/聚乙烯基吡咯烷酮共混体系相容性研究

用DSC、FTIR、SAXS和测定Flory-Huggins相互作用参数等方法对聚乙二醇(PVA1)/聚乙烯基吡咯烷酮(PVP)共混体系的研究。结果表明,该体系具有完全互容的性质。共混物只有一个玻璃化转变温度。用DMSO作溶剂浇铸的膜光学透明。PVA1的长周期和片晶厚度均随PVP含量增加而增大,但后者增大的幅度比前者小得多,表明PVP和PVA1的非晶部分形成均相并夹入到球晶内部。共混物中PVP羰基吸收峰和PVA1的羟基吸收峰与相应均聚物相比,在红外光谱图中皆向低频方向迁移,迁移波数随第二组分含量的增加而增大。表明二者间有氢键生成。用平衡熔点计算的Flory-Huggins相互作用参数为-0.88。     

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．     

PVA/PVP共混物的SAXS研究

聚乙烯醇(PVA)/聚吡咯烷酮(PVP)共混物的小角X-射线散射(SAXS)研究表明,PVA/PVP共混物的结构参数与共混物组分比及热历史密切相关。按Vonk一维电子密度相关函数法,得到PVA/PVP共混物的长周期,过渡层厚随PVP组分含量增加而增加;结晶片层厚和比内表面积却随PVP含量增加而降低。热处理可提高共混物的结晶性。     

聚乙烯醇/聚乙烯基吡咯烷酮共混体系的结晶行为

用DSC、WAXD和SAXS研究了聚乙烯醇(PVAl)/聚乙烯基吡咯烷酮(PVP)共混体系的结晶行为.PVAl的结晶度随PVP含量增加而减少,并存在结晶度为零的组成(PVAl)的重量分数约为50％.与纯PVAl相比,共混物的温度区间T_m-T_g减小,表明PVP对PVAl的结晶起抑制作用.共混物中PVAl的结晶速度下降,具体表现为PVAl过冷区随PVP含量增加而扩大,动力学速度常数减小,球晶增长速度下降.纯PVAl和共混体系的等温结晶速率均遵循Avrami方程.退火样品的长周期、片晶厚度和过渡层厚度大于相同组成未退火样品.两者长周期随PVP含量增长加显著增大,片晶厚度增长次之,过渡层厚度变化不大.     

STUDIES OF THE CRYSTALLIZATION BEHAVIOR IN THE CRYSTALLINE/AMORPHOUS POLYMER BLENDS: POLY(ETHYLENE OXIDE)/POLY(METHYL METHACRYLATE) AND POLY(ETHYLENE OXIDE)/POLY(VINYL ACETATE)

The crystallization process of poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)and PEO/poly(vinyl acetate) (PVAc) blends has been characterized by Fourier Transform Infrared(FTIR) spectra in conjunction with Differential Scanning Calorimeter (DSC) measurements. Thecrystallinity of PEO varies consistently with PEO content in PEO/PVAc blends and the PEO/PMMAblends containing 50 wt% or less PMMA. For the PEO/PMMA blends containing 60 wt% ormore PMMA, the crystallinity of PEO decreases more than PEO content but develops with crystal-lization time. These results can be explained in terms of difference between the crystallization tem-perature (T_c) and glass transition temperature (T_g) of the blends as a function of content of amorphouscomponent.     

Dynamic and Isothermal Thermogravimetric Degradation of Poly(vinyl Chloride)/Chlorinated Poly(ethylene) Blends

The thermal degradation of poly(vinyl chloride)/chlorinated poly(ethylene) (PVC/CPE) blends of different compositions was investigated by means of dynamic and isothermal thermogravimetric analysis in flowing atmosphere of nitrogen. Kinetic parameters (the apparent activation energy E, and pre-exponential factor Z) were calculated after Flynn-Wall-Ozawa method for the first stage of dynamic degradation of PVC/CPE blends, and after Flynn method for the isothermal degradation. In both cases, there is the compensation dependence between the values E and logZ. The values of compensation ratios as well as the characteristics of TG and DTG curves, confirm the stabilizing effect of CPE on PVC dehydrochlorination. This revised version was published online in July 2006 with corrections to the Cover Date.     

热稳定剂对PVC紫外光老化过程中微观结构及宏观性能演变的影响

通过UV-Vis、FTIR、DSC、以及色差、力学性能的测试表征,实时追踪分析了在紫外光老化过程中,含Pb、Sn以及Ca-Zn热稳定剂的PVC体系微观结构和宏观性能的演变过程.结果表明,在相同光老化条件下,PVC/Pb、PVC/Sn和PVC/Ca-Zn体系的微观结构变化规律基本一致,过程中主要的化学反应是,大分子吸收光能后,发生脱HCl生成共轭双键的反应、生成羰基的氧化反应、交联反应和降解反应;不同热稳定剂的作用,主要表现在对于微观结构变化的幅度和动力学过程的影响不同.相应地,3种体系的外观色差和力学性能的变化规律也相似,但色差的变化程度和速度以及老化后力学性能的保持率因所含热稳定剂的不同而不同,其中含Sn体系的颜色稳定性最好,含Pb体系的力学性能保持率最高。     

ENVIRONMENTAL STABILITY OF THE POLYENE PREPARED BY DEHYDROCHLORINATION OF POLY(VINYL CHLORIDE)

A high-quality polyene can be obtained by exensive dehydrochlorination of poly(vinyl chloride) (PVC) in aliquid/solid two-phase system. The liquid phase is a tetrahydrofuran solution of PVC containing a small amount ofpoly(ethylene glycol) with molar mass of 400 g as a phase transfer catalys. The solid phase is potassium hydroxide particles.The structure of the polyene is polyacetylene-like and has a long conjugated C=C sequence and a narrow dispersity ofpolyene sequences according to its FT-infrared and Raman spectra. The environmental stability of the polyene was alsostudied by IR, Raman spectra and elemental analysis. Experimental results demonstrated that the polyene was susceptible toair and could be changed into a material containing high concentrations of hydroxyl and carbonyl groups. The polyenesequences were shortened and its dispersity became broader due to the effect of dioxygen.     

Thermal degradation of poly(vinyl chloride)/poly(ethylene oxide) blends: Thermogravimetric analysis

Thermal stability of poly(vinyl chloride)/poly(ethylene oxide) (PVC/PEO) blends has been investigated by thermogravimetric analysis (TGA) in dynamic and isothermal heating regime. PVC/PEO blends were prepared by hot-melt extrusion (HME). According to TG analysis, PEO decomposes in one stage, while PVC and PVC/PEO blends in two degradation stages. In order to evaluate the effect of PEO content on the thermal stability of PVC/PEO blends, different criteria were used. It was found that thermal stability of PVC/PEO blends depends on the blend composition. The interactions of blends components with their degradation products were confirmed. By using multiple heating rate kinetics the activation energies of the PVC/PEO blends thermal degradation were calculated by isoconversional integral Flynn–Wall–Ozawa and differential Friedman method. According to dependence of activation energy on degree of conversion the complexity of degradation processes was determined.     

Thermal degradation studies in poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility, morphology, and thermal properties of poly(vinyl chloride) (PVC) blends with different concentrations of poly(methyl methacylate) (PMMA) have been studied. The interaction between the phases was studied by FTIR and by measuring the glass transition temperature (T_g) of the blends using differential scanning calorimetry. Distribution of the phases at different compositions was studied through scanning electron microscopy. The FTIR and SEM results show little interaction and gross phase separation. The thermogravimetric studies on these blends were carried out under inert atmosphere from ambient to 800 °C at different heating rates varying from 2.5 to 20 °C/min. The thermal decomposition temperatures of the first and second stage of degradation in PVC in the presence of PMMA were higher than the pure. The stabilization effect on PVC was found most significant with 10 wt% PMMA content in the PVC matrix. These results agree with the isothermal degradation studies using dehydrochlorination and UV-vis spectroscopic results carried out on these blends. Using multiple heating rate kinetics the activation energies of the degradation process in PVC and its blends have been reported.     

A dielectric study of poly(ethylene-co-vinylacetate)–poly(vinyl chloride) blends. I. Miscibility and phase behavior

Measurements of the complex permittivity were used to study miscibility and phase behavior in blends of poly(vinyl chloride) (PVC) with two random ethylene—vinyl acetate (EVA) copolymers containing 45 and 70 wt % of vinyl acetate. The dielectric β relaxation of the pure polymers and blends was followed as a function of temperature and frequency for different blend compositions and thermal treatments. Blends of EVA 70/PVC were found to be miscible for compositions of about 25% EVA 70 and higher. Blends of lower EVA 70 content showed evidence of two-phase behavior. EVA 45/PVC blends were found to be miscible only at the composition extremes; at intermediate compositions these blends were two-phase, partially miscible. Both blend systems showed lower critical solution temperature behavior. Phase separation studies revealed that in the EVA 45/PVC blends, PVC was capable of diffusing into the higher T_g phase at temperatures below the T_g of the upper phase. In the blends, ion transport losses were significant above the loss peak temperatures, and in the two-phase systems, often obscured the upper temperature loss process. It was shown possible, however, to correct the loss curves for this transport contribution.     

Electrical conductivity of thermally degraded poly(vinyl chloride)–polyacrylonitrile blends

Finely powdered blends of poly(vinyl chloride) (PVC) and polyacrylonitrile (PAN) have been thermally degraded at 275°C for 24 h in an inert atmosphere to effect complete de-hydrochlorination of PVC to a conjugated polyene structure and simultaneous internal polymerization of nitrile groups in PAN to a conjugated polyimine sequence. The room temperature d.c. conductivity of the degraded blends showed clear synergistic behavior. A maximum conductivity has been observed with a blend of 60 PAN/40 PVC which is about 4 orders of magnitude over the linearly weighted average conductivity of the individual degraded homopolymers. The results have been interpreted in terms of a possible donor-acceptor interaction between the degraded homopolymers leading to mutual doping and, hence, an enhanced electrical conductivity. © 1995 John Wiley & Sons, Inc.     

Kinetics of thermal degradation of poly(vinyl chloride)

Extensively studied thermal degradation of polyvinyl chloride (PVC) occurs with formation of free hydrogen chloride and conjugated double bonds absorbing light in visible region. Thermogravimetric monitoring of PVC blends degradation kinetics by the loss of HCl is often complicated by evaporation and degradation of plasticizers and additives. Spectroscopic PVC degradation kinetics monitoring by absorbance of forming conjugated polyenes is specific and should not be affected by plasticizers loss. The kinetics of isothermal degradation monitored by thermal gravimetric analysis in real time was compared with batch data obtained by UV/Visible absorption spectroscopy. Effects of plasticizer on kinetics of polyene formation were examined. Thermal degradation of PVC films plasticized with di-(2-ethylhexyl) phthalate (DEHP) and 1,2,4-benzenedicarboxylic acid, tri-(3-ethylhexyl) ester (TOTM) was monitored by conjugated double bonds light absorption at 350 nm at 160, 180, and 200 °C. Plasticizer-free PVC powder degradation kinetics and that of plasticized films were also obtained thermogravimetrically at temperatures ranging from 160 to 220 °C. Plasticizer-free PVC powder degradation and spectroscopically monitored degradation of plasticized PVC films occurred with the same apparent activation energy of ≈150 kJ mol⁻¹. No difference in degradation kinetics of films plasticized with DEHP and TOTM was detected.     

Studies of polylactone/poly(vinyl chloride), polylactone/poly(vinyl fluoride), and polylactone/poly(vinylidene fluoride) blends

It is shown that polyvalerolactone/poly(vinyl chloride) (PVL/PVC) blends are miscible over all compositions since a single glass transition temperature T_g is observed, intermediate between those of pure PVL and pure PVC. Melting points, enthalpies of fusion and morphologies of PVL/PVC blends are also reported. It is also shown that polyvalerolactone, poly(α-methyl-α-n-propyl-β-propiolactone), poly(α-methyl-α-ethyl-β-propiolactone), and poly(caprolactone) are immiscible with poly(vinyl fluoride) and poly(vinylidene fluoride), despite the fact that all these polylactones are miscible with PVC. Differences in electronegativity, in atomic radius, and in molar attraction between the fluoride and the chlorine atoms are probably responsible for this difference in behavior.     

Miscibility and orientation behavior of poly(vinyl alcohol) / poly(vinyl pyrrolidone) blends

The miscibility of poly(viny1 alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) blends is investigated by differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD). The molecular orientation induced by uniaxial stretching of the blends is also examined by WAXD and birefringence measurements. It is shown by the DSC thermal analysis that the polymer pair is miscible, since a single glass transition temperature (T_g) is situated between the T_gs of the two homopolymers at every composition. The T_g versus composition curve does not follow a monotonic function but exhibits a cusp point at a PVP volume fraction of a little under 0.7, as in a case predicted by Kovacs' theory. The presence of a specific intermolecular interaction between the two polymers is suggested by an observed systematic depression in the melting point of the PVA component. A negative value of the polymer-polymer interaction parameter, χ₁₂ = 0.35 (at 513 K), is estimated from a thermodynamic approach via a control experiment using samples crystallized isothermally at various temperatures. The extent of optical birefringence (Δn) of the drawn blends decreases drastically with increasing PVP content up to 80 wt %, when compared at a given draw ratio, and ultimately Δn is found to change from positive to negative at a critical PVP concentration of a little over 80 wt %. Discussion of the molecular orientation behavior takes into consideration a birefringence compensation effect in the miscible amorphous phase due to positive and negative contributions of oriented PVA and PVP, respectively.     

聚己内酯和聚氧化乙烯共混体系中的两类片晶相间堆砌

对聚(ε-己内酯)(PCL)/聚氧化乙烯(PEO)共混物的相差显微镜、广角X-射线衍射(WAXD)、小角X-射线散射(SAXS)及示差扫描量热计(DSC)等的研究表明,只有当共混物中PCL(或PEO)的含量低于20％时,两组份是相容的.当PCL含量低于20％时,在共混物中形成了PEO片晶和PCL片晶相间堆砌的结晶形态,当PEO含量不超过20％时,PEO则完全以非晶形式混入PCL的非晶区,同时阻碍了PCL的结晶.可见在结晶过程中,相容的两组份对共混体系形态结构的影响却不尽相同.     

Development and characterization of reactive extruded PVC/polyacrylate blends

This paper describes a method to obtain polymer blends by the absorption of a liquid solution of monomer, initiator, and a crosslinking agent in suspension type porous poly(vinyl chloride) (PVC) particles, forming a dry blend. These PVC/monomer dry blends are reactively polymerized in a twin‐screw extruder to obtain the in situ polymerization in a melt state of various blends: PVC/poly(methyl methacrylate) (PVC/PMMA), PVC/poly(vinyl acetate) (PVC/PVAc), PVC/poly(butyl acrylate) (PVC/PBA) and PVC/poly(ethylhexyl acrylate) (PVC/PEHA). Physical PVC/PMMA blends were produced, and the properties of those blends are compared to reactive blends of similar compositions. Owing to the high polymerization temperature (180°C), the polymers formed in this reactive polymerization process have low molecular weight. These short polymer chains plasticize the PVC phase reducing the melt viscosity, glass transition and the static modulus. Reactive blends of PVC/PMMA and PVC/PVAc are more compatible than the reactive PVC/PBA and PVC/PEHA blends. Reactive PVC/PMMA and PVC/PVAc blends are transparent, form single phase morphology, have single glass transition temperature (T_g), and show mechanical properties that are not inferior than that of neat PVC. Reactive PVC/PBA and PVC/PEHA blends are incompatible and two discrete phases are observed in each blend. However, those blends exhibit single glass transition owing to low content of the dispersed phase particles, which is probably too low to be detected by dynamic mechanical thermal analysis (DMTA) as a separate T_g value. The reactive PVC/PEHA show exceptional high elongation at break (～90%) owing to energy absorption optimized at this dispersed particle size (0.2–0.8 µm). Copyright © 2005 John Wiley & Sons, Ltd.     

Degradation of polymer mixtures. IV. Blends of poly(vinyl acetate) with poly(vinyl chloride) and other chlorine-containing polymers

The degradation of the binary polymer blends, poly(vinyl acetate)/poly(vinyl chloride), poly(vinyl acetate)/poly(vinylidene chloride) and poly(vinyl acetate)/polychloroprene has been studied by using thermal volatilization analysis, thermogravimetry, evolved gas analysis for hydrogen chloride and acetic acid, and spectroscopic methods. For the first two systems named, strong interaction occurs in the degrading blend, but the polychloroprene blends showed no indication of interaction. In the PVA/PVC and PVA/PVDC blends, hydrogen chloride from the chlorinated polymer causes substantial acceleration in the deacetylation of PVA. Acetic acid from PVA destabilizes PVC but has little effect in the case of PVDC because of the widely differing degradation temperatures of PVA and PVDC. The presence of hydrogen chloride during the degradation of PVA results in the formation of longer conjugated sequences, and the regression in sequence length at high extents of deacetylation found for PVA degraded alone is not observed.     

PPEKK/PEI共混物的相容性及拉伸性能

作为相容体系 ,聚芳醚酮与聚醚酰亚胺 (ＰＥＩ)共混物体系的研究受到了研究者的重视[1～ 4] .由于现在已商品化的聚芳醚酮基本上都是半结晶型聚合物 ,所以有有关无定型聚芳醚酮与聚醚酰亚胺共混物的研究鲜见报道 .含二氮杂萘酮结构聚芳醚酮酮 (ＰＰＥＫＫ)是一种新型耐高温聚合物 ,相比于已经商品化的各种聚芳醚酮 ,ＰＰＥＫＫ除具有优异的综合性能外 ,它最大的特点表现在以下两方面 ,ＰＰＥＫＫ耐热性突出 ,玻璃化转变温度 (Ｔｇ)为 2 4 5℃左右 ,远高于各种商品化的聚芳醚酮 ;ＰＰＥＫＫ为无定型聚合物 ,易溶于多种有机极性溶剂 ,大大的扩…