Thermal stability of PVC/chlororubber-20-graft polyblend–styrene–acrylonitrile blends. I

Thermal stability of PVC blends with chlororubber-20-graft polyblend-styrene-acrylonitrile [CR-20gp-SAN (2:1)] was studied by HCI evolution techniques and thermogravimetry under isothermal condition. The thermal stability of PVC/CR-20gp-SAN (2:1) blends has been compared with those of PVC/CR-20 and PVC/KM-365B blends. It has been observed that the thermal stability of modified PVC is less than that of unmodified PVC. The CR-20gp-SAN (2:1) modified PVC blends were found to be more stable than PVC/CR-20 blends but less stable than PVC/KM-365B blends. The rate of degradation in PVC blends were observed to be unaffected by the concentration of the modifiers, but the PVC/KM-365B blends were found to be degrading slower in comparison with PVC/CR-20 and PVC/CR-20gp-SAN (2:1) blends. The rate of degradation for PVC/CR-20 blends at lower concentrations (<10%) of modifiers is almost equal to that of PVC/CR-20-gp-SAN (2:1) blends, but more at higher concentrations of modifiers (>10%). The experimental results have been explained on the basis of the chemical nature of the modifiers and their miscibility with PVC.     

Recycling of PVC/PU waste and reuse in PVC formulations: Structure‐property relationship

The possibility of poly(vinyl chloride) (PVC) plasticization and modification by regenerated PVC/polyurethane (PU) blends (PVC/PU^R), obtained after partial thermochemical destruction of the PU foam‐backed PVC‐sheet (soundproof materials waste), has been studied. The partial thermochemical destruction of the PU foam‐backed PVC‐sheet was carried out using alkanolamine in a one‐screw extruder. The destruction product was a thermoplastic mixture of PVC and regenerated linear PUs, applicable for reuse without any purification and fractionation. The influence of processing conditions on structure‐property relationships for the PVC/PU^R blends was studied using the methods of differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), size exclusion chromatography (SEC), and mechanical testing. It has been established that PVC/PU^R blends can be reused as an effective polymer plasticizer for PVC resin (PVC_r) and as a modifier for plasticized PVC (PVC_p). POLYM. ENG. SCI. 45:801–808, 2005. © 2005 Society of Plastics Engineers     

Effects of silver nanoparticles on thermal properties of DBSA-doped polyaniline/PVC blends

Dodecylbenzenesulfonic acid (DBSA)-doped polyaniline (PAND) has been synthesized by redoping (PANDR) and aqueous polymerization (PANDA) methods. Silver nanoparticles were incorporated into the PANDR/tetrahydrofuran solution (PANDS) and then mixed with poly (vinyl chloride) (PVC) solution to prepare PANDS/PVC nanocomposites. In the present study, effects of silver nanoparticles on thermal properties of PAND/PVC blends have been investigated by employing thermal gravimetric analysis and heat flow microcalorimetry techniques. From these results it has been observed that the thermal stability of blends have increased by increasing the concentration of PAND in blends and nanocomposites. Addition of silver nanoparticles has suppressed the dehydrochlorination process and evolution/degradation of DBSA in PANDS/PVC nanocomposites. Presence of silver nanoparticles in PAND/PVC nanocomposites has reduced the mobility of PANI chains which in turn inhibited the transfer of free radicals formed during degradation of PAND and PVC through inter-chain reactions; hence, degradation process has been slowed down and thermal stability has been improved. Embedment of silver nanoparticles has reduced thermal weight loss corresponding to polymer degradation step and attains lower heat flow level in inert atmosphere for nanocomposites in contrast to those with no nanoparticles, thereby further improving thermal stability of nanocomposites. The heats of oxidation measured for blends and nanocomposites were independent of PAND/PVC blends composition.     

PVC/PU共混超滤膜性能研究

PVC膜对糖类化合物有较强的排斥力,但其亲水性差,而聚氨酯有较强的亲水性,本课题研究聚氯乙烯(PVC)与聚氨酯(PU)的共混膜,探讨相转化法制备PVC/PU共混超滤膜的性能。实验结果表明,当聚合物浓度为16%,PVC/PU以8/2(质量分数)共混时,可制的水通量、截留率较好的多孔膜。     

Compatibility of poly(vinyl chloride) and polyurethane blends

The compatibility and the mechanical properties of the blends of polyurethane (PU) elastomer and poly(vinyl chloride) (PVC) were studied. The results showed partial compatibility between PU and PVC. When the portion of PVC in blends exceeded 75%, the compatibility decreased. On the other hand, increasing the molecular weight of the glycol in PU improved the compatibility. The elongation decreased and the Young's modulus increased as the proportion of the weight of PVC in blends was increased. The tensile strength reached a minimum when PU/PVC was 50/50.     

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.     

马来酸酐接枝改性氯化聚氯乙烯的制备及其在PVC中的应用

采用固相法制备马来酸酐接枝氯化聚氯乙烯(CPVC-g-MAH),得到了接枝率达2.91 %的CPVC-g-MAH,并对其进行了性能测试,探讨了聚氯乙烯(PVC)/CPVC-g-MAH共混物的冲击性能和加工性能,与PVC/氯化聚氯乙烯(CPVC)共混物进行对比以观察改性效果。结果表明,CPVC-g-MAH的热性能较CPVC有较大提高;PVC/CPVC-g-MAH共混物的冲击性能比PVC/CPVC共混物有所提高,而平衡转矩有所降低,说明CPVC-g-MAH相比于CPVC对PVC共混物加工性能改善效果更加明显。     

Morphology of polyurethane modified by plasticizing,blending, or reinforcing

The morphology of modified thermoplastic PU has been studied by SEM and DSC. The PU was modified by addition of various amounts of dibutyl phthalate (DBP) plasticizer, vinyl polymers (PVA, PVAc, PVC, VAc–VC copolymer), polysiloxane or fiber reinforcement (glass or cotton) to diolpolyether, followed by mixing and vigorous stirring with dephenylmethane diisocyanate. SEM observations indicated that PU and its modifications have a cellular (foam) structure. A homogeneous matrix was observed in binary blends of PU and DBP in ratios of 20:1 down to 6.6:1; PVA, PVAc, VAc–VC copolymer with a weight ratio of 40:1, PU containing glass fiber (20:1) or cotton fiber (40:1). Blends of PU—with PVA at a weight ratio of 20:1, with PVC in ratios from 20:1 down to 5:1, or with polysiloxane polymer—were heterogeneous and thus not miscible, as evidenced by SEM observations. With the exception of the PU—PSO mixtures, the thermal behavior of the heterogeneous blends did not permit any conclusion regarding miscibility.     

A Reactive Blending Method for Preparation of Polyvinyl Chloride/Thermosetting Polyurethane Blends

An attempt was made to prepare polyvinyl chloride (PVC)/thermosetting polyurethane (PU) blends via direct formation of the thermosetting minor phase from its reactants during blending into PVC. Chemorheological approaches were employed in order to investigate the formation reaction of PU. The results of chemorheological analyses were utilized to adjust appropriate reactive blending temperature. PVC/PU reactive blending process was carried out in a laboratory internal mixer. PVC and PU reactive mixture were fed into the internal mixer using two different feed orders. In the first method, porous particles of PVC and liquid mixture of PU monomers were premixed in a high-speed mixer at ambient temperature. The blending was then followed by processing the prepared paste in the preheated internal mixer. In the second method, PVC was loaded into the internal mixer. Afterward, PU reactive compound was introduced into the PVC after torque equilibrium. For both feed orders, the PU content of blends and rotor speed were among parameters studied. The mechanical properties of PVC/PU blends prepared by reactive blending and pure PVC showed that incorporation of PU elastomer into PVC through the proposed reactive blending technique resulted in an increase in the elongation at break and toughness of the brittle PVC.     

Thermal and mechanical properties of electron beam irradiated poly(vinyl chloride)/polystyrene blends

The effect of electron beam irradiation on the thermal and mechanical properties of poly(vinyl chloride)/polystyrene (PVC/PS) blends and PVC/PS blends containing epoxidized natural rubber (ENR) was studied. The thermogravimetric analysis study showed that the thermal decomposition of the plasticized PVC individual polymer goes through two stages, whereas PS decomposes through one stage. However, the temperature of the maximum rate of reaction (T_max) of PS is much higher than that for PVC and their blends. Meanwhile, the T_max was found to increase with increasing PS ratios in the blend. The thermal stability of PVC/PS blends was greatly increased after electron beam irradiation in comparison with unirradiated blends. Moreover, the addition of ENR to PVC/PS increased the thermal stability. On the other hand, the mechanical properties in terms of tensile strength and elongation at break of PVC/PS blends are lower than pure PVC polymer because of the immiscibility. However, the addition of ENR to the PVC/PS (80/20) blend increased the elongation at break from 114 to 321% associated with a small effect on the tensile properties. These behaviors were supported by structure morphology studies observations, which indicate an improvement in the interfacial adhesion between the phases. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

A DSC investigation on the stabilizer distribution in PVC blends

The distribution of a liquid organotin stabilizer between the phases of heterogeneous poly(vinyl chloride) (PVC) blends has been studied by differential scanning calorimetry (DSC). This method can be used even at low stabilizer concentrations. At concentrations > 1 wt.-% the stabilizer can be detected in both phases of a PVC/SAN (poly(vinyl chloride)/poly(styrene-co-acrylonitrile)) blend. At lower concentrations no stabilizer could be found in the SAN phase. Determination of the induction period of thermal degradation at 180°C under nitrogen atmosphere showed no loss of thermal stability for blends containing the stabilizer partly in the SAN phase. Kinetic measurements with the DSC indicate a migration of the stabilizer out of the SAN phase, PVC/PMA (poly(vinyl chloride)/poly(methyl acrylate)) blends showed no solubility of the stabilizer in the soft PMA phase.     

Compatibility and thermal stability studies on PVC/chlororubber-20-graft polyblend-styrene–vinyl acetate–acrylonitrile blends. II

Compatibility and Thermal stability studies have been performed on PVC blends with chlororubber-20-graft polyblend-styrene–vinyl acetate–acrylonitrile (1:1:1) [CR-20gp-SVAAN (1:1:1)]. The grafting of styrene, vinyl acetate, and acrylonitrile onto chlororubber-20 backbone chain generates some amount of heterogeneity in the system. The compatibility behavior of PVC/CR-20gp-SVAAN (1:1:1) blends has been reflected in the ultrasonic velocity and absolute viscosity vs. composition plots of the blend. These blends have been found to be thermally miore stable than PVC/chlororubber-20 blends, but less stable than PVC/KM-365B blends. The rate of degradation is equal to that of the PVC/chlororubber-20 blends. The results have been discussed on the basis of compatibility, stabilizing, and destabilizing behavior of various component polymers with PVC matrix.     

Thermal stability of blends of poly(vinyl chloride) with polyester elastomer

The thermal stability of poly(vinyl chloride) (PVC) under air atmosphere was improved by blending with PETE (polyester elastomer). Its enhanced stability could be explained by a reaction between the ester component of PETE and HCl from dehydrochlorination of PVC, which was identified by IR- and ¹H-NMR spectroscopy. The best result of thermal stability was shown at a composition of 100 parts of PVC with 4 parts of PETE. By surveys of glass transition temperatures, it was found that all PVC/PETE blends were ununiformly distributed. During processing, the fusion time and torque at fusion decreased as the quantity of PETE increased. The mechanical properties of the blends were also changed; as the quantity of PETE increased, tensile strength of the blends decreased, while impact strength increased.     

己二酸锌钙皂纳米氧化铈/氧化镧对PVC/ASA的热稳定作用

合成了己二酸锌钙皂,并将纳米氧化铈和氧化镧分别作为共稳定剂制备了新型复合热稳定剂。采用刚果红法、热失重分析仪、动态力学分析仪等考查了复合热稳定剂对聚氯乙烯/丙烯酸酯苯乙烯丙烯腈接枝共聚物（PVC/ASA）共混材料的热稳定效果及动态力学性能。结果表明,稀土化合物作为共稳定剂可以提高己二酸锌钙皂对PVC/ASA共混材料的热稳定效果,氧化镧与己二酸锌钙皂的协同效果优于纳米氧化铈,而纳米氧化铈的加入可以提高材料的热变形温度。     

Influence of third component on mechanical properties and thermal stability of polypropylene/(regenerated polyurethane) blends

The possibility of polypropylene (PP) modification by regenerated polyurethane (PU), obtained after partial thermochemical decomposition of waste PU, has been studied. The degradation product was a thermoplastic mixture, applicable for reuse without any purification and fractionation. It was proved that regenerated PU could be reused as an effective polymeric plasticizer for PP and that the addition of regenerated PU did not decrease the thermal stability of PP. In order to improve further the elongation at break of PP modified by regenerated PU, a third component was added to the PP/(regenerated PU) blend. The influence of the third component on the mechanical properties and thermal stability of the blends was evaluated by using a universal testing machine (UTM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The data showed that the elongations of PP/(regenerated PU) blends with styrene‐ethylene‐butylene‐styrene polymer (SEBS) were obviously better than those of the PP/(regenerated PU) blend without the third component and with PP‐g‐MA or SEBS‐g‐MA (MA = maleic anhydride). In addition, the thermal stability of PP/(regenerated PU) blends with a third component was almost same as that of the PP/(regenerated PU) blend without a third component. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

3D打印用聚氯乙烯多相复合体系的开发

采用高分子类增塑剂乙烯-乙酸乙烯酯共聚物(EVM)替代聚氯乙烯(PVC)传统增塑剂,制备出具有双连续相结构的PVC/EVM/聚乳酸(PLA)共混物.通过热分析、流变学测试及微观形貌观察等研究了共混物结构与性能间的关系.结果表明,随着填料蒙脱土(OMMT)或碳纳米管的加入,PVC/EVM/PLA共混物的热分解温度和体系燃...     

Mechanical properties of recycled PVC blends with styrenic polymers

The aim of this study is to improve the performance of blends made from recycled polyvinyl chloride (PVC), coming from credit card waste, so that these blends can be used for those applications that must fulfil some requirements with regard to mechanical properties and stability with temperature alterations. With this aim in mind, two polymers of styrenic origin have been combined: styrene acrylonitrile (SAN) and acrylonitrile butadiene styrene (ABS). These polymers are characterized by a satisfactory balance of mechanical properties and thermal stability. PVC blends with both virgin and recycled styrenic polymers have been studied throughout the entire range of compositions. The prior degradation of the recycled materials has been studied by means of Fourier transformed infrared spectroscopy (FTIR).The behavior of the observed T_g values has been analyzed using differential scanning calorimetry (DSC), and the existence of partial miscibility between the different components has been studied. The mechanical properties have been determined using tensile and Charpy impact tests. The thermal stability of the PVC blends with temperature changes has been determined using the Vicat softening temperature (VST). Finally, the fracture surface of the various blends has been analyzed using scanning electron microscopy (SEM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2464–2471, 2006     

EPDM-g-MAN增韧聚氯乙烯的研究

用悬浮法合成三元乙丙橡胶（EPDM）与甲基丙烯酸甲酯（MMA）及丙烯腈（AN）接枝共聚物（EPDM-g-MAN）,用其增韧聚氯乙烯（PVC）树脂。研究了PVC/EPDM-g-MAN共混物的抗冲击性能、增韧机理、相结构以及热稳定性,并与PVC/氯化聚乙烯(CPE)共混物的抗冲击性能进行了对比。结果表明：EPDM-g-MAN比CPE具有更好的增韧效率。SEM分析表明,随着EPDM-g-MAN用量的增加,共混物的增韧机理由裂纹支化终止转变为剪切屈服兼有空穴化。TEM分析表明,EPDM以分散相均匀分散于PVC连续相中,两相界面模糊,具有良好的相容性,且随着EPDM含量的增加,共混物的相结构由“海-岛”结构转变为近连续相结构。EPDM-g-MAN的加入提高了PVC的热稳定性。     

Thermal degradation of ternary blends of poly(ε‐caprolactone)/poly(vinyl acetate)/poly(vinyl chloride)

The thermal degradation of ternary blends of poly(ε‐caprolactone) (PCL), poly(vinyl acetate) (PVAC), and poly(vinyl chloride) (PVC) was studied using a thermogravimetry analyzer under dynamic heating in flowing nitrogen atmosphere. PCL degraded in a single stage, whereas the PVAC and PVC degraded in two stages during which acid is released in the first stage followed by backbone breakage in the second stage. The addition of PVC to either PCL or PVAC affected the thermal stability of the blend, whereas the addition of PVAC to PCL did not alter the thermal stability of the blend. In ternary blends, the addition of PVC affected the degradation of PVAC but did not influence the degradation of PCL in the range investigated. The increased addition of PCL to the binary blends of PVC/PVAC decreased the extent of thermal instability of PVAC because of the addition of PVC. The addition of even 10% PVAC to the PCL/PVC blend removed the thermal instability of PCL resulting from the addition of PVC and can be attributed to the ease of chlorine or hydrogen chloride capture of PVAC over PCL. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1378–1383, 2004     

聚氯乙烯/木质素共混物的热稳定性

采用热重分析法研究了聚氯乙烯（PVC）/木质素共混物的热稳定性。结果表明,共混物的热稳定性取决于2个相反效应的叠加效果：一是木质素分子中的受阻酚类结构单元具有捕捉热降解中形成的自由基的功能,因此可以改善共混物的热稳定性;二是木质素在150~250 ℃的温度区间内会发生轻微的脱水现象,水分对PVC的自催化脱氯化氢过程具有促进作用,因此会降低PVC的热稳定性。在热分解初期,后者起主要作用,共混物的早期热稳定性有所降低;但当木质素在更高温度下完成脱水后,前者变成主要作用,共混物的中期热稳定性有明显提升。