CPE增韧硬质聚氯乙烯的结构形态和增韧机理

对氯化聚乙烯（CPE）改性聚氯乙烯（PVC）体系的性能随组成的变化进行了研究。用电子显微镜（TEM、SEM）考察了共混体系的形态结构。结果发现：PVC和CPE相容性较好，共混体系在断裂过程中产生网丝结构。网丝结构与CPE用量密切相关，是脆－韧转变后体系发生塑性变形的结果，是PVC基体韧性突增的主要原因。     

A Study of the Viscoelastic and Rheological Properties of PVC/CPE Blends Modified by Using Polylauryllactam

Abstract

Polylauryllactam was used to improve the impact strength of polyvinylchloride (PVC)/chlorinated polyethylene (CPE) blends without sacrificing their tensile properties. The enhancement of the impact strength increased with the increase of the CPE content in the PVC/CPE blends due to the formation of intermolecular hydrogen bonds among PVC, polylauryllactam and CPE macromolecules. A doubled impact strength of the PVC/CPE blend with 20 weight percent of CPE was obtained after the addition of 1.5 phr polylauryllactam. The PVC/CPE blends with polylauryllactam have a better dimensional stability compared with the PVC/CPE blends without the additive, according to their viscoelastic characteristics. Polylauryllactam shortened the processing time to reach a minimum melt viscosity in the processing of the PVC/CPE blends.     

Compatibilizers for recycling of the plastic mixture wastes. II. The effect of a compatibilizer for binary blends on the properties of ternary blends

In this article, we discuss the effect of a compatibilizer for binary blends on the properties of ternary blends composed of high‐density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) and poly(vinyl chloride) (PVC) virgin polymers with a simulated waste plastics fraction. Chlorinated polyethylene (CPE), ethylene–propylene rubber (EPR), and their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PP/PVC ternary blend. CPE, styrene‐ethylene‐propylene block copolymer (SEP), or their 1/1 (w/w) mixture were tested as compatibilizers for the HDPE/PS/PVC ternary blend. The composition of the ternary blends were fixed at 8/1/1 by weight ratio. The amount of the compatibilizer was 3 phr. Rheological, mechanical, and thermal properties were measured. For the 8/1/1 HDPE/PP/PVC ternary blends, the tensile strength was slightly decreased, but the impact strength was significantly increased by adding EPR, CPE, or their mixture. EPR exhibited the most significant impact modification effect for the ternary blends. In a similar way, for 8/1/1 HDPE/PS/PVC ternary blends, on adding SEP, CPE, or their mixture, the tensile strength was slightly decreased, but the impact strength was noticeably increased. It was found that the SEP worked much better as an impact modifier for the ternary blends than CPE or the SEP/CPE mixture did. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1048–1053, 2000     

Mechanical Properties and Morphology of Recycled. Plastic Wastes by Solution Blending

In this study, bottles of mineral water and yogurt as well as Styrofoam bowls were recycled and identified by infrared spectroscopy as poly(vinyl chloride) (PVC), high-impact polystyrene (HIPS), and polystyrene (PS). Solution blending was employed to make polymer blends from these recycled plastics, including PVC/PS, PVC/HIPS/PS blends, and PVC/HIPS blends with or without a com-patibilizer, styrenelp-chlorostyrene (ST-CMS). Thermal behavior from differential scanning calorimetry was used to examine the compatibility of the blends. For the PVC/PS and PVC/HIPS/PS systems, it is found that although the third component (HIPS) may not be good enough as a compatibilizer, the addition of HIPS to the two-component blend (PVC/PS) may enhance the mechanical properties at the specific composition, especially for the blends at the intermediate concentrations. For PVC/HIPS blends with the ST-CMS copolymer as a compatibilizer, all the mechanical properties of the blends except the elongation at break, in general, increased with increasing the concentration of compatibilizer due to the increase of compatibility. The abnormal fracture strain was attributed to the differences in adhesion when various amounts of ST-CMS was added. The results of mechanical properties of the blends were consistent with the morphology from scanning electron microscopy.     

Chlorinated polyethylene modification of blends derived from waste plastics. Part II: Mechanism of modification

Previous publications have shown that the stress-strain behavior, especially ductility, of some incompatible polymer blends are greatly improved by the addition of slurry produced chlorinated polyethylenes (CPE). This improvement is greatest for blends containing polyethylene and PVC. The most effective CPE's have some residual polyethylene crystallinity and may be described as block-like polymers with ethylene sequences and chlorine containing sequences. It is postulated that CPE addition improves the blend properties by increasing the adhesion between domains in the blend via interactions with the blend components. This hypothesis was explored by thermal analysis, dynamic mechanical testing, adhesion studies, and microscopy. It is concluded that the interaction of CPE with polyethylene derives from compatibility of rather long methylene sequences in CPE with the polyethylene which results in good adhesive bonding. The interaction of CPE with PVC may not be owing to segmental compatibility but simply good mutual adhesion between similar polar materials. There is no interaction or adhesion between CPE and polystyrene as would be expected. CPE addition to blends is accompanied by a decrease in component domain size. The relationship between CPE structure and its effectiveness as a blend modifier is discussed.     

CPE与ACR或MBS协同增韧硬质PVC研究

本文研究了ＰＶＣ／ＣＰＥ／ＡＣＲ或ＭＢＳ共混物的力学性能与增韧剂组成比、加工条件和相形态之间的关系。实验结果表明,适宜组成比和加工条件下,ＣＰＥ与ＡＣＲ或ＭＢＳ对硬质ＰＶＣ有协同增韧作用,共混物形态结构以增韧剂呈精细网－岛相分散为特征。     

CPE对纳米CaCO3增韧PVC复合材料界面和性能的影响

研究了CaCO3/CPE(氯化聚乙烯)/PVC(聚氯乙烯)纳米复合材料的结构和性能,探讨了CPE对纳米CaCO3/PVC复合材料界面作用和力学性能的影响. SEM结果显示,引入CPE可明显改善纳米CaCO3颗粒在PVC基体中的分散性和相容性,提高其界面作用. 引入界面作用参数定量表征纳米CaCO3颗粒与基体之间的界面结合作用,证实随着CPE加入量的增大,基体和颗粒之间的界面作用逐渐增大. 力学性能研究表明,相对于仅用纳米CaCO3增韧PVC,在CPE加入量为PVC的0~8%(w)范围内,用CPE和纳米CaCO3协同增韧可以更好地提高复合材料的冲击强度. 复合材料的冲击强度在CaCO3/CPE/PVC质量比为25/8/100时达到纯PVC的5.6倍,是纳米CaCO3/PVC(25/100)体系的2倍.     

Properties of PVC/CPE/EPDM polyblends

A series of tricomponent blends of poly(vinyl chloride)/chlorinated polyethylene/ethylene propylene diene terpolymer (PVC/CPE/EPDM) were prepared and studied. CPE was used not only to improve the room temperature impact resistance of PVC but also as a polymer compatibilizer; while EPDM was used to enhance the impact resistance of PVC especially in low temperature range. Our data showed that the improvements of PVCs impact strength were significant either at room temperature or at low temperature (-12°C), however, a loss of the yield tensile strength was observed. On the basis of morphology, an impact-toughening mechanism of the tricomponent blend was proposed.     

Application of factorial experimental design to demonstrate the influence of processing conditions on the fusion of poly(vinyl chloride)/chlorinated polyethylene/oxidized polyethylene blends

Poly(vinyl chloride) (PVC)/chlorinated polyethylene (CPE)/oxidized polyethylene (OPE) blends were prepared in a Haake torque rheometer at various temperatures, rotor speeds, and totalized torques. A 2³ factorial experimental design was applied to study the main two-factor interaction, and three-factor interaction effects of temperature, rotor speed, and totalized torque on the heat of fusion of PVC/CPE/OPE blends, which were examined using differential scanning calorimetry. The sequence of the main effects on the heat of fusion of PVC/CPE/OPE blends, in ascending order, is temperature < rotor speed < totalized torque. The sequence of the two-factor interaction effects on the heat of fusion of PVC/CPE/OPE blends, in ascending order, is temperature vs rotor speed < temperature vs totalized torque < rotor speed vs totalized torque. The three-factor interaction effect is not significantly related to the heat of fusion of PVC/CPE/OPE blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2755–2761, 1999     

The experimental results and simulation of temperature dependence of brittle‐ductile transition in PVC/CPE blends and PVC/CPE/nano‐CaCO3 composites

The effect of chlorinated polyethylene (CPE) content and test temperature on the notched Izod impact strength and brittle‐ductile transition behaviors for polyvinylchloride (PVC)/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites is studied. The CPE content and the test temperature regions are from 0–50 phr and 243–363 K, respectively. It is found that the optimum nano‐CaCO₃ content is 15 phr for PVC/CPE/nano‐CaCO₃ ternary composites. For both PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites, the impact strength is improved remarkably when the CPE content or test temperature is higher than the critical value, that is, brittle‐ductile transition content (C_BD) or brittle‐ductile transition temperature (T_BD). The T_BD is closely related to the CPE content, the higher the CPE content, the lower the T_BD. The temperature dependence of impact strength for PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites can be well simulated with a logistic fitting model, and the simulation results can be illustrated with the percolation model proposed by Wu and Jiang. DMA results reveal that both PVC and CPE can affect the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. When the CPE content is enough (20 phr), the CPE is more important than PVC for determining the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. Scanning electron microscopy (SEM) observations reveal that the impact fractured mechanism can change from brittle to ductile with increasing test temperature for these PVC systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Styrene-co-acrylonitrile resin modifications of PVC/CPE blends

The effects of styrene-co-acrylonitrile resin (AS) on the mechanical properties, morphology, and plasticizing and rheological behaviors of poly(vinyl chloride)/chlorinated polyethylene(PVC/CPE) blends are studied. The results show that the impact strength and the tensile strength are all increased and the plasticizing and rheological behaviors are also improved when a certain amount of AS is added into PVC/CPE blends, which are different in characteristics and regularity from plastics toughened with elastomers. It is blends of brittle—ductile transition regions (i.e., PVC/CPE = 100/10, 100/15) that can obviously be toughened by AS. The analysis of the morphological structure shows that AS promotes the formation of a CPE network that embeds the primary particles of PVC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1455–1460, 1997     

固相法氯化聚乙烯与聚氯乙烯共混物的形态与性能

研究了聚氯乙烯(PVC)与固相法氯化聚乙烯(CPE)共混物的应力-应变行为和冲击强度对CPE用量和氯含量的依赖关系,考察了共混物形态与性能的关系。动态力学性能和透射电子显微镜的研究结果表明,PVC/CPE为部分相容体系,两相间存在着一定的相互作用,当CPE氯含量为36％～42％,用量为7～15份时,CPE在PVC/CPE共混物中形成比较完整的网络结构、共混物具有更好的抗冲击性能。Brabender流变仪研究表明,CPE能促进PVC的塑化,共混物的加工性优于纯PVC。     

Properties and morphology of poly(vinyl chloride) blends with solid‐state‐chlorinated polyethylene

Correlations of the stress‐strain behavior and impact strength of poly(vinyl chloride) (PVC) blends with different amounts and chlorine contents of solid‐state‐chlorinated polyethylene (CPE) were studied. The relationships between the morphology and properties of the PVC/CPE blends also were investigated. The results of dynamic mechanical analysis and transmission electron microscopy showed that PVC/CPE blends are partially compatible systems and that a certain interaction exists between the two phases. When the amount of CPE (chlorine content, 36–42%) was 7–15 phr (parts by weight per hundred parts of resin), an essentially perfect CPE network was formed, and the blends showed better impact resistance. A Brabender Plasticorder study revealed that CPE can promote the plasticity of PVC and improve its processability. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

DSC investigation on the thermal degradation of PVC in blends

The thermal degradation of poly(vinyl chloride) (PVC) has been studied by differential scanning calorimetry (DSC). Due to crosslinking, the glass transition temperature (Tg) of PVC raises during the degradation. The thermal degradation of PVC has also been studied for heterogeneous 1:1 (w/w) blends of PVC with polystyrene (PC), poly(styrene-co-acrylonitrile) (SAN), high-impact PS (poly(styrene-g-butadiene)) (HIPS) and poly(SAN-g-butadiene) (ABS). Tg of the PVC phase raises slower during degradation in the PVC/PS-blend, whereas in the other blends the crosslinking is accelerated, due to a negative influence of the double bonds and/or the nitrile groups on the thermal stability of PVC. Since most methods use the determination of eliminated HCl to study the degradation of PVC, the DSC method is very useful in investigations on PVC-containing polymer blends, if there might be a reaction of HCl with one of the blend components.     

Studies of rigid poly(vinyl chloride) (PVC) compounds. IV. Fusion characteristics and morphology analyses

Poly(vinyl chloride) (PVC), PVC/chlorinated polyethylene (CPE), PVC/oxidized polyethylene (OPE), and PVC/CPE/OPE compounds were prepared in a Haake torque rheometer at various temperatures, rotor speeds, and totalized torques (TTQ). The fusion characteristics of these PVC compounds (fusion time, fusion torque, and fusion temperature) were studied. Longer fusion time results in higher fusion temperature. Higher fusion temperature results in lower fusion torque. The fusion time of PVC/OPE compounds is the longest among these PVC blends. However, the fusion time of PVC/CPE/OPE compounds is the shortest among these PVC blends. The fusion time of the PVC/CPE/OPE compound is significantly different from those of PVC, PVC/OPE, and PVC/CPE compounds at the medium starting temperature and the medium rotor speed. Scanning electron microscopy (SEM) analyses successfully revealed the surface morphological changes of the fusion of PVC, PVC/OPE, PVC/CPE, and PVC/CPE/OPE compounds. The lubrication mechanisms of these PVC compounds have also been postulated. © 1995 John Wiley & Sons, Inc.     

A study on PVC/LLDPE blends with solid-state-chlorinated polyethylene as compatibilizer

Chlorinated polyethylene (CPE) prepared by solid-state chlorination was used as compatibilizer for poly(vinyl chloride) (PVC)/linear low-density polyethylene (LLDPE) blends. Effects of CPE molecular structure on stress-strain behaviors, dynamic mechanical properties, and morphologies of PVC/LLDPE blends were studied by using SEM, TEM, DMA, and testing mechanical properties. The results showed that the compatibility of PVC/LLDPE blends was improved with the addition of CPE. Also, adhesion strength between the two phases and mechanical properties of the blends were increased. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2535–2541, 1997     

Toughening modification of poly(vinyl chloride)/ α‐methylstyrene‐acrylonitrile‐butadiene‐styrene copolymer blends via adding chlorinated polyethylene

In this study, poly (vinyl chloride) (PVC)/α‐methylstyrene‐acrylonitrile‐butadiene‐styrene copolymer (AMS‐ABS) (70/30)/chlorinated polyethylene (CPE) ternary blends was prepared. With the addition of CPE, it did not exert a negative influence in both the glass transition temperature and heat distortion temperature. Thermogravimetric analysis showed that addition of CPE did not play a negative role in the thermal stability. With regard to mechanical properties, high toughness was observed combined with the decrease in tensile strength and flexural strength. With the addition of 15 phr CPE, the impact strength increased by about 21.0 times and 8.5 times in comparison with pure PVC and PVC/AMS‐ABS (70/30) blends, respectively. The morphology correlated well with the impact strength. It was also suggested from the morphology that shear yielding was the major toughening mechanisms for the ternary blends. And there existed a change in the fibril structures that are observed in scanning electron microphotographs. Our present study shows that combination of AMS‐ABS and CPE improves the toughness without sacrificing the heat resistance, and the value of notched impact strength can be enhanced to the same level of super‐tough nylon. POLYM. ENG. SCI., 54:378–385, 2014. © 2013 Society of Plastics Engineers     

Effect of poly(vinyl chloride)/chlorinated polyethylene blend composition on thermal stability

Blends of poly(vinyl chloride) (PVC) with different ratios of chlorinated polyethylene (CPE) were degradated by the thermogravimetric method under dynamic conditions (50–600°C) in an inert atmosphere. The effect of the miscibility and composition of the PVC/CPE blends on the thermal stability were investigated. DSC curves of the blends show neither a shift of the PVC glass transition temperature nor a shift of the CPE melting temperature, which means that these blends are heterogeneous. The characteristics of the TG curves were determined, some of which (T_1%,T_5%, Δm₁) can be used as indicators of the thermal stability of the blend. The apparent activation energy of PVC dehydrochlorination in the blends was also calculated. Comparison of the experimental TG curves and TG curves predicted by the additivity rule indicates the existence of the components' interaction in the PVC/CPE blends. The addition of CPE improves the thermal stability of PVC for all the investigated blends in the temperature range where α_calc is greater than α_exp. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 166–172, 2000     

Translucent blends of chlorinated polyethylene with poly(vinyl chloride)

Some experimental chlorinated polyethylene (CPE) resins that produced translucent blends with PVC were used to study the effects of CPE chlorine content and chlorine distribution on the morphology, optical clarity, and toughness of blends with PVC. The CPE resins were characterized in terms of the glass transition temperature, residual crystallinity, density, and refractive index. Increasing residual crystallinity and increasing chlorine content both increased the refractive index closer to that of PVC. A linear relationship was observed between the fourth power of the refractive index and the CPE glass transition temperature. With a phase-separated blend morphology in all cases, improved transparency was achieved in this system by reducing the refractive index difference between CPE and PVC. Both haze and transparency showed the predicted linear dependence on the square of the refractive index difference. To a first approximation, modifications of the experimental CPE resins that improved optical transparency of the blends also tended to reduce the toughness enhancement.     

弹性体在车用仪表板表皮材料中的应用

利用DSC和SEM等方法研究了弹性体在汽车仪表板表皮材料用PVC/ABS软质合金中的作用。结果表明,在PVC/ABS共混体系中加入弹性体CPE、NBR后,有助于提高共混体系的相容性,从而使得PVC/ABS共混体系的机械强度和加工性能也发生变化。