Miscibility behavior of di(ethyl-2 hexyl) phthalate in binary and ternary chlorinated polymer blends

The miscibility behavior of ternary blends made by the addition of di(ethyl-2 hexyl) phthalate (DOP) to a mixture of chlorinated polymers was investigated by differential scanning calorimetry. Two chlorinated polymer mixtures were selected: polyvinyl chloride (PVC) with a chlorinated polyethylene containing 48 wt% Cl (CPE48), and PVC with a chlorinated PVC containing 67 wt% Cl (CPVC67). Each binary DOP/chlorinated polymer pair is miscible whereas PVC/CPE48 and PVC/CPVC67 blends are immiscible. DOP/CPE48/PVC and DOP/PVC/CPVC67 ternary blends containing, respectively, more than 55 and 20% DOP exhibit a single glass transition temperature (T_g). The spinodal between the one-T_g zone and the two-T_g zone is symmetrical in the two cases. At high DOP concentrations, a quantitative analysis of the results leads to the conclusion of the presence of a true ternary phase. At low DOP concentrations where two T_gs are observed, the DOP is distributed equally between the two chlorinated polymers forming, in the DOP/CPE48/PVC case for instance, two binary DOP/CPE48 and DOP/PVC phases. The broad immiscibility zone observed in the DOP/CPE48/PVC ternary blend as compared to the DOP/PVC/CPVC67 blend appears to be mainly caused by the high molecular weight of CPE48, as compared with PVC and CPVC67. © 1994 John Wiley & Sons. Inc.     

Thermorheological analysis of PVC blends

The effect of temperature on dynamic viscoelastic measurements of miscible poly (vinyl chloride) (PVC)/ethylene‐vinyl acetate–carbon monoxide terpolymer (EVA‐CO) and immiscible PVC/high‐density polyethylene (HDPE) and PVC/chlorinated polyethylene (CPE) molten blends is discussed. PVC plasticized with di(2 ethyl hexyl) phthalate (PVC/DOP) and CaCO₃ filled HDPE (HDPE/CaCO₃) are also considered for comparison purposes. Thermorheological complexity is analyzed using two time–temperature superposition methods: double logarithmic plots of storage modulus, G′, vs. loss modulus, G″, and loss tangent, tan δ, vs. complex modulus, G*, plots. Both methods reveal that miscible PVC/EVA‐CO and PVC/DOP systems are thermorheologically complex, which is explained by the capacity of PVC to form microdomains or crystallites during mixing and following cooling of the blends. For immiscible PVC/HDPE and PVC/CPE blends the results of log G′ vs. log G″ show temperature independence. However, when tan δ vs. log G* plots are used, the immiscible blends are shown to be thermorheologically complex, indicating that the morphology observed by microscopy and constitued by a PVC phase dispersed in a HDPE or CPE matrix, is reflected by this rheological technique. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 469–477, 2000     

A novel approach to synthesis of functional CPVC and CPE or graft copolymers—in situ chlorinating graft

A new process of graft copolymerization of poly(vinyl chloride) (PVC) and polyethylene (PE) with other monomers was developed. The grafted chlorinated poly(vinyl chloride) (CPVC) and chlorinated polyethylene (CPE) were synthesized by in situ chlorinating graft copolymerization (ISCGC) and were characterized. Convincing evidence for grafting and the structure of graft copolymers was obtained using FT‐IR, ¹H‐NMR, gel permeation chromatography (GPC), and the vulcanized curves. Their mechanical properties were also measured. The results show that the products have different molecular structure from those prepared by other conventional graft processes. Their graft chains are short, being highly branched and chlorinated. The graft copolymers have no crosslinking structure. The unique molecular structure will make the materials equipped with special properties. Copyright © 2007 John Wiley & Sons, Ltd.     

增塑化学微交联聚氯乙烯中化学交联和物理交联的协同作用

由氯乙烯／ 邻苯二甲酸二烯丙基酯（ＶＣ／ＤＡＰ） 悬浮共聚合成了化学微交联聚氯乙烯（ＰＶＣ） 树脂,并进行增塑加工．共聚得到的化学交联ＰＶＣ 具有溶胶／ 凝胶分配特性,交联密度较低;化学交联ＰＶＣ 的溶胶和凝胶均存在分子链缠结作用,尤其当凝胶含量较高时,物理缠结对凝胶交联密度有较大贡献．化学交联对增塑ＰＶＣ 结晶性的影响较小,因此在增塑化学微交联ＰＶＣ 中同时存在化学交联网络和以分子链物理缠结点和微晶为交联点的物理交联网络,两者协同影响增塑ＰＶＣ 材料的性能．     

固相法氯化聚乙烯对PVC／LLDPE共混体系性能和形态的影响

采用固相法氯化聚乙烯（ＣＰＥ）对聚氯乙烯／线型低密度聚乙烯（ＰＶＣ／ＬＬＤＰＥ）共混体系进行增容改性。扫描电子显微镜、透射电子显微镜、动态力学分析和力学性能测试结果表明，ＣＰＥ对ＰＶＣ／ＬＬＤＰＥ共混体系具有很好的增容作用。     

Kinetics of isothermal thermooxidative degradation of poly(vinyl chloride)/chlorinated polyethylene blends

The thermooxidative degradation of poly(vinyl chloride)/chlorinated polyethylene blends of different compositions was investigated by means of isothermal thermogravimetry in flowing atmosphere of synthetic air at temperatures 240–270 °C. The main degradation processes are dehydrochlorination of PVC and CPE. For calculation of the apparent activation energy and apparent pre-exponential factor two kinetic methods were used: isoconversional method and Prout–Tompkins method. True compensation dependency between Arrhenius parameters, obtained using Prout–Tompkins model, was found. Calculated kinetic parameters of isothermal thermooxidative degradation are close to those from non-isothermal degradation and confirm the assumption of the main degradation process in PVC/CPE blends.     

Properties of radiation‐modified blends of polyethylene with elastomers and liquid crystalline copolyester

The results are given on the effect of γ‐irradiation on properties of blends of high and low‐density polyethylene (HDPE, LDPE) with elastomers ‐ethylene/propylene/diene rubber (EPDM) and chlorinated polyethylene (CPE), and thermotropic liquid crystalline polymer (LCP). The morphological, thermal, mechanical properties (including thermosetting properties) and adhesion properties of blended composites were investigated. A special attention was paid to the applicability of the blends as thermosetting materials (TSM). The LCP used was a copolyester of poly(ethylene terephthalate) with p‐(hydroxybenzoic acid) in the ratio 40 : 60. It was found that addition of LCP essentially influenced the thermomechanical and adhesion properties of PE composites, irradiated up to the absorbed dose 150 kGy, as well as the dimensional stability of thermosetting products, made from polyethylene/elastomer mixtures. The results show that such ternary blends considerably improve the exploitation conditions of irradiated polyethylene and useful thermosetting materials can be obtained.     

Thermooxidative degradation of poly(vinyl chloride) and chlorinated polyethylene with different Ca/Zn carboxylates

The thermooxidative degradation of poly(vinyl chloride) (PVC), chlorinated polyethylene (CPE) and PVC/CPE blend 50/50 was investigated by means of dynamic and isothermal thermogravimetric analysis in the flowing atmosphere of air. To estimate the thermooxidative stability of the samples the characteristics of thermogravimetric (TG) curves were used. Kinetic parameters (the apparent activation energy E and preexponential factor Z) were calculated after isoconversional method for the first stage of dynamic degradation where dehydrochlorination (DHCl) of PVC and/or CPE is the main degradation reaction. Despite the chemical resemblance, the degradation mechanisms of CPE and PVC are different, as a consequence of differences in microregularity of the corresponding polymer chains. The addition of Ca/Zn carboxylates as well as the ratio of Ca and Zn carboxylates have considerably different influence on the investigated polymers. This revised version was published online in August 2006 with corrections to the Cover Date.     

SYNERGISTIC MODIFICATION OF EPDM AND CROSSLINKING AGENT IN IMMISCIBLE BLENDS OF POLYVINYL CHLORIDE WITH LOW DENSITY POLYETHYLENE

The synergism of ethylene-propylene-diene monomer copolymer （EPDM） and dicumyl peroxide （DCP, a crosslinking agent） in low density polyethylene （LDPE）/poly（vinyl chloride） （PVC） blends was investigated. When EDPM and DCP are added to the blends simultaneously, the tensile properties could be improved significantly, especially for the blends with LDPE matrix. For example, incorporation of 10/1 （mass ratio） EPDM/DCP improves the tensile strength of the LDPE/PVC （mass ratio 80/20） blend from 7.9 MPa to 8.5 MPa and the elongation at break from 25% to 503%. Results from selective extraction, phase-contrast microscopy and thermal analysis reveal that the improvement in the tensile properties of the blends with LDPE matrix is principally due to the formation of a fine crosslinking network of the LDPE and EPDM phase. The outstanding modification effect of EPDM is explained by its dual functions： molecular entanglement with LDPE and the enhanced efficiency of DCP in the blends.     

Remarkably improved toughness and thermal stability of poly (vinyl chloride) (PVC)/poly (α-methylstyrene-acrylonitrile) (α-MSAN) blend with the assistance of two impact modifiers

The key drawback of impact modifier-toughened polymer is that the improved toughness is accompanied by loss in stiffness. Surprisingly, poly (vinyl chloride) (PVC)/poly (α-methylstyrene-acrylonitrile) (α-MSAN) blend was toughened without loss in stiffness by simply combining two impact modifiers-chlorinated polyethylene (CPE) and acrylic resin (ACR). The prepared blend's impact strength was 3.0 times higher than PVC/α-MSAN/CPE blend and 18.6 times higher than pure PVC/α-MSAN blend. An impressive thermal stabilizing effect was also achieved when CPE and ACR were combined. The improved toughness could be attributed to the overlap of the stress field between different impact modifiers, which help to form the continuum percolation of stress volume under impact loading.     

A conductive elastomer based on EPDM and polyaniline: II. Effect of the crosslinking method

Electrically conductive heterogeneous binary polymer blends based on ethylene-propylene-diene-monomer (EPDM) and polyaniline (PAni) were prepared in a Haake Rheocord 90 rheometer, coupled with an internal mixer (counter rotating cam rotors) using different amounts of PAni doped with dodecylbenzenosulfonic acid (DBSA). Blends were crosslinked using two methods: (i) phenolic resin (SP-1045) as crosslinking agent and (ii) electron beam irradiation. The last method avoids the interference of the acid dopant in the crosslinking process and produces blends with higher conductivity.     

Miscible blends of amorphous polymers

Thirty-five polymethacrylate/chlorinated polymer blends were investigated by differential scanning calorimetry. Poly(ethyl), poly(n-propyl), poly(n-butyl), and poly(n-amyl methacrylate)s were found to be miscible with poly(vinyl chloride) (PVC), chlorinated PVC, and Saran, but immiscible with a chlorinated polyethylene containing 48% chlorine. Poly(methyl) (PMMA), poly(n-hexyl) (PHMA), and poly(n-lauryl methacrylate)s were found to be immiscible with the same chlorinated polymers, except the PMMA/PVC, PMMA/Saran, and PHMA/Saran blends, which were miscible. A high chlorine content of the chlorinated polymer and an optimum CH₂/COO ratio of the polymethacrylate are required to obtain miscibility. However, poly(methyl), poly(ethyl), poly(n-butyl), and poly(n-octadecyl acrylate)s were found to be immiscible with the same chlorinated polymers, except with Saran, indicating a much greater miscibility of the polymethacrylates with the chlorinated polymers as compared with the polyacrylates.     

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.     

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.     

纳米级CaCO_3粒子与弹性体CPE微粒同时增韧PVC的研究

研究了平均粒径为 30nm的超细级纳米CaCO3 与氯化聚乙烯 (CPE)对聚氯乙烯 (PVC)共混体系二元协同增韧效应及机制 .结果表明 ,当共混体系中有一定量的CPE时 ,纳米CaCO3 的加入可以明显地提高共混物的韧性 ,而不降低共混物的强度和刚性 .纳米CaCO3 在PVC基体中达到了纳米级的分散 .当纳米CaCO3 的用量为 8份 (质量 )时 ,PVC CPE 纳米CaCO3 共混物的冲击断面产生了大量的有规则的网丝状结构 ,共混物的缺口冲击强度达到 81 1kJ m2 ,比不加纳米CaCO3 的共混体系高 7 3倍 .CPE的加入对共混体系的加工流动性能无影响 ,纳米CaCO3 的加入使共混体系的加工流动性能变差     

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。     

A NOVEL SECOND-ORDER TRANSITION IN ORGANIC HYBRIDS CONSISTING OF POLYMERS AND SMALL MOLECULES

A novel transition appeared above thc glass transition temperature of chlorinated polyethylene (CPE) for binaryblends of CPE and additives such as organic small molecules or oligomers. This transition was assigned to the dissociation ofintermolecular hydrogen bonds between the polymer ard additive within the edditive rich phase. Of particular interest is thata novel pyramid crystal was observed in the annealed CPE/hindered phenol blends. Another intriguing observation is thatthese polymer/small molecule blends organized by intermolecular hydrogen bonding have several potential properties, suchas shape-memorization, self-restoration, self-adhesiveness and super damping.     

热可逆共价交联氯化聚乙烯的制备和性能

以双环戊二烯二羧酸钾 [DCPD(COOK) 2 ]为交联剂 ,通过共混反应法制得了共价交联的氯化聚乙烯(CPE)热塑性弹性体 (TPE) ,研究了共混反应条件 (温度、时间及交联剂用量等 )对TPE物性的影响 .反应溶解性和IR测定数据证明 ,DCPD(COOK) 2 与CPE分子链上的活性氯反应形成共价酯键而交联 ;物性测定数据表明 ,交联CPE的主要力学性能接近CPE常规硫化胶 ,不同的是该交联聚合物具备可塑性 ,经反复加工三次后 ,其力学性能还略有提高     

强紫外光作用下PVC/增韧剂体系结构与性能的演变

通过UV, FTIR, DSC及力学性能和色差的测试分析, 实时追踪了在紫外光老化过程中, 聚氯乙烯/氯化聚乙烯(PVC/CPE), 聚氯乙烯/丙烯酸酯类共聚物(PVC/ACR)及聚氯乙烯/丙烯腈-丁二烯苯乙烯共聚物(PVC/ABS)体系的微观结构和宏观性能的演变过程. 结果表明, 在光老化过程中, ACR和CPE对PVC脱HCl生成共轭双键反应、氧化降解反应、交联反应及玻璃化转变温度(T_g)的变化等均有抑制作用, 而ABS则对这些反应起促进作用. 在宏观上表现为ACR和CPE的加入能提高体系的色泽稳定性, 体系的力学性能保持率较高. 而ABS的作用相反.     

Crosslinking of chlorine‐containing polymers by dicyclopentadiene dicarboxylic salts

Alkali‐ and alkali‐earth‐metal salts of dicyclopentadiene dicarboxylic acid (DCPDCA) were prepared and employed as crosslinkers for chlorine‐containing polymers such as polychloromethylstyrene (PCMS), chlorinated polypropylene (CPP), polyepichlorohydrin (PECH), and poly(vinyl chloride) (PVC). Thermally reversible covalent crosslinks (i.e.,  DCPD bridges) between polymer chains were generated through esterification between the chlorine–carbon bonds of the polymer and the carboxylic salt groups of the crosslinker. The crosslinking reactivity decreased in the following sequence: K > Na > LiDCPDCA > alkali‐earth‐metal salts of DCPDCA. In addition, PCMS and CPP had higher gelation rates than PECH and PVC. Good flowability at about 195 °C and solubility in maleimide‐containing dichlorobenzene on heating indicated that the crosslinked PCMS and CPP exhibited thermally reversible crosslinking because of dimer/monomer (cyclopentadiene) conversion of  DCPD moieties via reversible Diels–Alder cycloaddition. Samples of PECH and PVC crosslinked by the alkali salts of DCPDCA were insoluble even when heated in maleimide‐containing dichlorobenzene. However, these crosslinked polymers could be dissolved partially after the same treatment when the crosslinker was an alkali‐earth‐metal salt of DCPDCA. Thermal degradation such as dehydrochlorination of the PECH and PVC might have been responsible for uncontrolled crosslinking because these two polymers are known to be thermally unstable. The unreacted COOK, COONa, or COOLi of the crosslinkers might have initiated base‐induced dehydrochlorination when PECH and PVC were heated at high temperatures. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 818–825, 2000