RAFT乳液聚合法合成线形三嵌段丙烯酸酯共聚物及其在PVC中的应用

摘要 本文采用可逆加成断裂链转移试剂（RAFT）通过乳液聚合法合成了分子量分布指数为1.8的甲基丙烯酸甲酯-g-丙烯酸丁酯-g-甲基丙烯酸甲酯（MMA-g-BA-g-MMA,MBM）三嵌段共聚物并将其与PVC进行共混。利用转矩流变仪测试了共混物的塑化行为;用动态力学谱仪(DMA)测试了共混物的动态力学行为并测试了共混物的力学性能。结果表明,MBM的加入可以有效减小PVC的塑化时间和平衡扭矩;随着MBM含量的升高,共混物储能模量 随MBM含量的增加出现一定程度的减小,力学内耗tanδ峰值先减小后增大,共混物的Tg升高了约5 ℃。当MBM含量在25 wt％时,共混物具有最大的冲击强度,相较于纯PVC提高了3.0倍。MBM可以作为PVC的一种有效的加工助剂和增韧助剂。     

Rheology and Mechanical Properties of PVC/Acrylonitrile–Chlorinated Polyethylene-Styrene/MAP-POSS Nanocomposites

The nanocomposite of the Poly(vinyl chloride)/acrylonitrile-chlorinated- polyethylene-styrene (ACS)/methylacryloylpropyl-contaning polyhedral oligomeric silsesquioxane (MAP-POSS) (PVC/ACS/MAP-POSS) was prepared. Plasticizing behavior, dynamic rheology behavior and mechanical properties of the nanocomposites were investigated. The results showed that the plastic time decreased with increasing MAP-POSS content. The dynamic storage modulus G ′, loss modulus G″ and complex viscosity η* of the nanocomposites all exhibit a monotonic change with increasing frequency, and all have maximum when MAP-POSS content is 4 wt%, at the same frequency. The MAP-POSS can be used as an efficient process aid and impact aid of PVC/ACS blend at appropriate content.     

PROPERTIES OF POLYPROPYLENE/NATURAL RUBBER/RECYCLE RUBBER POWDER BLENDS

Thermoplastic elastomers have been prepared by blending polypropylene (PP), natural rubber (NR), and recycle rubber powder (RRP). The blends were melt-mixed using a Brabender Plasticorder torque rheometer at 190°C and 50 rpm. A fixed 70:30 blend ratio (wt%) of PP and rubber was prepared. The effect of partial replacement of NR with RRP at a fixed rubber content (NR+RRP), 30 wt% on mechanical properties, swelling behavior, torque development, and morphological properties of PP/NR/RRP blends was studied. Results show that the tensile strength, Young's modulus, and swelling resistance increase with increasing RRP content in the PP/NR/RRP blends whereas the stabilization torque and elongation at break exhibit opposite trend.     

PVC/NBR热塑性弹性体加工流变性能研究

采用反应挤出动态硫化法制备了聚氯乙烯／丁腈橡胶(PVC／NBR)热塑性弹性体，用锥板流变仪、毛细管流变仪和转矩流变仪研究了动态硫化的PVC／NBR热塑性弹性体的流交性能和塑化性能。实验结果表明，动态硫化的PVC／NBR热塑性弹性体的熔体属于剪切稀化的假塑性流体，具有良好的返炼性能，综合性能超过国外同类产品。     

Rheological Behavior and Mechanical Properties of Blends of Poly(vinyl chloride) with CP-POSS

In this work, a polyhedral oligomeric silsesquioxane which contains 3-chloropropyl groups (CP-POSS) was synthesized. The rheological behavior of CP-POSS/PVC blends was investigated by torque rheometer and capillary rheometer. Mechanical properties were investigated by electronic material tester. Influences of blending composition, shear rate and shear stress on melt apparent viscosity and non-Newtonian index (n) were discussed. The results show that the plastic time decreases and melt viscosity increases with increasing content of CP-POSS. CP-POSS has a good compatibility with PVC. The blend has the best impact strength when the content of CP-POSS is 7 wt%. The CP-POSS can be used as a processing aid and impact-resistant aid for PVC.     

Dynamic rheological behavior and mechanical properties of PVC/CPE/MAP–POSS nanocomposites

Poly(vinyl chloride)/chlorinated polyethylene (PVC/CPE)/methylacryloylpropyl‐containing polyhedral oligomeric silsesquioxane (MAP–POSS) nanocomposites are prepared. The plastic behavior and dynamic rheological behavior of PVC/CPE/MAP–POSS are investigated. The influences of composition on dynamic storage modulus G′, loss modulus G″, and complex viscosity η* of PVC/CPE/MAP–POSS melts are discussed. The dynamic mechanical properties, mechanical properties, and morphology are determined. The results show that both plastic time and balance torque of the nanocomposites decrease, but the G′, G″, and η* all increase with increasing MAP–POSS content. The maximum value of the dynamic mechanical loss tan δ decreases and elasticity increases when MAP–POSS is added. The impact strength of the nanocomposites increases with increasing MAP–POSS content and has the best value at 10% content of MAP–POSS, which is 5.38 kJ/m² higher than that of the blend without MAP–POSS. The MAP–POSS can be used as an efficient process aid and impact aid for the PVC/CPE blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of dynamic crosslinking on the morphology,crystallization, and dynamic mechanical properties of PA6,12/EVA blends

This study investigated the effect of dynamic crosslinking of polyamide 6,12 and random copolymers of ethylene and vinyl acetate blends (PA6,12/EVA) on the morphology, crystallinity, and dynamic mechanical properties. The crosslinking agent was dicumyl peroxide (DCP), and the blends were processed in a torque rheometer. The morphology depended on the DCP content, and all blends exhibited the same crystallinity index. However, with increasing crosslinking degree, the interfacial tackiness (E) values increased from 1.8 to 2.7 nm. The lamellar structures of all blends started forming at approximately 160 °C, close to the temperature of pure polyamide. The crosslinked phase enhanced the pseudo‐elastic behavior of the blends and increased their molecular mobility activation energy. Samples with higher crosslinking degree exhibited smaller permanent deformation (0.01%) than those with low crosslinking. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44206.     

Mechanical,morphological, and thermal properties of poly(vinyl chloride)/low‐density polyethylene composites filled with date palm leaf fiber

This article investigates the mechanical, morphological, and thermal properties of poly(vinyl chloride) (PVC) and low‐density polyethylene (LDPE) blends, at three different concentrations: 20, 50, and 80 wt% of LDPE. Besides, composite samples that were prepared from PVC/LDPE blend reinforced with different date palm leaf fiber (DPLF) content, 10, 20, and 30 wt%, were also studied. The sample in which PVC/LDPE (20 wt%/80 wt%) had the greatest tensile strength, elongation at break, and modulus. The good thermal stability of this sample can be seen that T_10% and T_20% occurred at higher temperatures compared to others blends. DPLF slightly improved the tensile strength of the polymer blend matrix at 10 wt% (C10). The modulus of the composites increased significantly with increasing filler content. Ageing conditions at 80°C for 168 h slightly improved the mechanical properties of composites. Scanning electron microscopic micrographs showed that morphological properties of tensile fracture surface are in accordance with the tensile properties of these blends and composites. Thermogravimetric analysis and derivative thermogravimetry show that the thermal degradation of PVC/LDPE (20 wt%/80 wt%) blend and PVC/LDPE/DPLF (10 and 30 wt%) composites took place in two steps: in the first step, the blend was more stable than the composites. In the second step, the composites showed a slightly better stability than the PVC/LDPE (20 wt%/80 wt%) blend. Based on the above investigation, these new green composites (PVC/LDPE/DPLF) can be used in several applications. J. VINYL ADDIT. TECHNOL., 25:E88–E93, 2019. © 2018 Society of Plastics Engineers     

The rheological behavior and dynamic mechanical properties of syndiotactic 1,2‐polybutadiene

The rheological behavior and the dynamic mechanical properties of syndiotactic 1,2‐polybutadiene (sPB) were investigated by a rotational rheometer (MCR‐300) and a dynamic mechanical analyzer (DMA‐242C). Rheological behavior of sPB‐830, a sPB with crystalline degree of 20.1% and syndiotactic content of 65.1%, showed that storage modulus (G′) and loss modulus (G″) decreased, and the zero shear viscosity (η₀) decreased slightly with increasing temperature when measuring temperatures were lower than 160°C. However, G′ and G″ increased at the end region of relaxation curves with increasing temperature and η₀ increased with increasing temperature as the measuring temperatures were higher than 160°C. Furthermore, critical crosslinked reaction temperature was detected at about 160°C for sPB‐830. The crosslinked reaction was not detected when test temperature was lower than 150°C for measuring the dynamic mechanical properties of sample. The relationship between processing temperature and crosslinked reaction was proposed for the sPB‐830 sample. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Rheological and Mechanical Properties of Clay-Thermoplastic Elastomers Derived from PVC and NBR

Based on the character of a clay that could be separated into many 1-nm thickness monolayers, clay poly(vinylchloride)-nitrile butadiene rubber (PVC/NBR) thermoplastic elastomers (TPEs) were acquired using a Brabender Plasticorder at 150°C and 50 rpm rotor speed. Clay concentrations were progressively increased up to 10 phr of PVC/NBR composites. The rheological behavior of the clay PVC/NBR blends was assessed by dynamic mechanical analysis, as well as Brabender torque rheometry. The results revealed that the complex modulus (E?) and elastic modulus (E′) increased with clay loading, indicating that the actual strength of the blends improved. Tensile properties of the PVC/NBR-clay formulations with different filling amounts were studied. The results showed that the mechanical performance of the rubbery samples improved with clay loadings. The observed trend has been attributed to the reinforcing role played by layered clay due to better dispersion as well as improved interactions.     

Rheology and thermal properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of a poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate) were prepared in a twin-screw extruder. Specimens for thermal properties were investigated by means of an instron capillary rheometer (ICR) and scanning electron microscopy (SEM). The blend viscosity showed a minimum at 10 wt% of LCP and increased with increasing LCP content above 10 wt% of LCP. Above 50% of LCP and at higher shear rate, phase inversion occured and the blend morphology was fibrous and similar to pure LCP. The ultimate fibrillar structure of LCP phase appeared to be closely related to the extrusion temperature. By employing a suitable deformation history, the LCP phase may be elongated and oriented such that a microfibrillar morphology can be retained in the solid state. Thermal properties of the LCP/PEN blends were studied using DSC and a Rheovibron viscoelastomer. These blends were shown to be incompatible in the entire range of the LCP content. For the blends, the T_g and Tm were unchanged. The half time of crystallization for the LCP/PEN blends decreased with increasing LCP content. Therefore, the LCP acted as a nucleating agent for the crystallization of PEN. The dimensional and thermal stability of the blends were increased with increasing LCP content. In studies of dynamic mechanical properties, the storage modulus (E′) was improved with increasing LCP content and synergistic effects were observed at 70 wt% of LCP content. The storage modulus for the LCP/PEN 70/30 blend is twice that of PEN matrix and exceeded pure LCP.     

Effect of the molecular weight on the plasticization properties of poly(hexane succinate) in poly(vinyl chloride) blends

Blends of poly(vinyl chloride) (PVC) and poly(hexane succinate) (PHS) with various molecular weights were analyzed with respect to their mechanical properties, durability, and thermal stability. We found that the molecular weight of PHS played an important role in the plasticizing process, and the single glass-transition temperature (T _g) of the PVC blends measured by dynamic mechanical analysis supported the complete miscibility between PHS and PVC. The plasticizing efficiency of PHS increased as the molecular weight increased; this reflected the gradually increasing elongation at break and the decreased T _g of the PVC blend. Meanwhile, the higher molecular weight of PHS also improved the resistance of migration and thermal stability but decreased the biodegradability of the PVC blends; this was due to the strong intermolecular interactions between PHS and PVC. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47081.     

Preparation of epoxidized cardanol butyl ether as a novel renewable plasticizer and its application for poly(vinyl chloride)

A new type of plasticizer, epoxidized cardanol butyl ether (ECBE), was synthesized via etherification and epoxidation. Successful synthesis was confirmed from Fourier transform infrared, ¹H NMR and ¹³C NMR spectra. The obtained product was evaluated by adding it to poly(vinyl chloride) (PVC) incorporated with dioctyl phthalate (DOP). Mechanical and thermal properties of PVC blends were studied using tensile testing, thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Processability, migration and volatility of plasticizing systems were also investigated. Tensile tests found a maximum increase of 17.8% in elongation at break. DMA results indicated that glass transition temperature shifted to lower temperature with a maximum decrease of 5.76 °C. TGA results revealed that PVC blends with higher content of ECBE had higher thermal stability; initial degradation temperature, 50% weight loss temperature and the first peak degradation temperature increased by 15.3, 14.8 and 4.1 °C, respectively. Processing time was extended from 11.56 to 59.94 min. The plasticizing performance of migration and volatility resistance were higher than those of neat DOP. © 2016 Society of Chemical Industry     

Synergetic association of grafted PLA and functionalized graphene on the properties of the designed nanocomposites

The synergetic association of poly(lactic acid) grafted with maleic anhydride (MA-g-PLA) containing 0.44 wt% of maleic anhydride and epoxy-functionalized graphene (GFe) on the properties of the designed nanocomposites was studied. Rheological, mechanical and barrier properties of PLA nanocomposites were studied using different content of epoxy-functionalized graphene and MA-g-PLA compatibilizer. The PLA/MA-g-PLA/GFe nanocomposites prepared by melt blending, containing 5 wt% of MA-g-PLA, yield a maximum in storage modulus G′ and a rheological plateau at low frequencies, with a content of epoxy-functionalized graphene comprised between 4 and 7 wt%. This phenomenon was ascribed to a pseudo-solid behavior resulting from the high degree of epoxy-functionalized graphene exfoliation due to strong interfacial interactions with PLA and epoxy-functionalized graphene. The better mechanical and barrier performances were obtained with PLA/GFe containing 10 wt% of epoxy-functionalized graphene and 5 wt% of MA-g-PLA compatibilizer. The variation of the percentage of compatibilizer showed that 5 wt% of maleated PLA was sufficient to improve the thermal, rheological, mechanical and barrier properties of the PLA nanocomposite containing 7 wt% of epoxy-functionalized graphene.     

Miscibility and rheological properties of poly(vinyl chloride)/styrene–acrylonitrile blends prepared by melt extrusion

Styrene–acrylonitrile (SAN) with acrylonitrile (AN) concentrations of 11.6–26 wt % and α‐methylstyrene acrylonitrile (αMSAN) with a wide range of AN concentrations are miscible with poly(vinyl chloride) (PVC) through solution blending. Here we examine the rheological properties and miscibility of PVC/SAN and PVC/αMSAN blends prepared by melt extrusion for commercial applications. We have investigated the rheological properties of the blends with a rheometer and a melt indexer. The PVC/SAN and PVC/αMSAN blends have a low melting torque, a long degradation time, and a high melt index, and this means that they have better processability than pure PVC. The miscibility of the blends has been characterized with differential scanning calorimetry, dynamic mechanical thermal analysis, and advanced rheometrics expansion system analysis. The miscibility of the blends has also been characterized with scanning electron microscopy. The SAN series with AN concentrations of 24–31 wt % is immiscible with PVC by melt extrusion, whereas αMSAN with 31 wt % AN is miscible with PVC, even when they are blended by melt extrusion, because of the strong interaction between PVC and αMSAN. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of nano‐organomontmorillonite on the viscoelasticity of the poly(trimethylene terephthalate)/glass fiber/organomontmorillonite hybrid nanocomposites materials

The influences of organically modified montmorillonite (OMMT) on the viscoelasticity of poly(trimethylene terephthalate)/glass fiber/OMMT (PTT/GF/OMMT) hybrid nanocomposite materials at liquid, elastic and glassy states, respectively, were investigated by using the rotational rheometer and dynamic mechanical analyzer (DMA). The viscoelasticity results suggest that OMMT has many important influences on the structure, modulus and toughness of the hybrid nanocomposite materials. At melton state, the shear‐thinning phenomena of the hybrid composite melts become remarkable with increasing OMMT content. At low frequency, the shear storage modulus (G′) and shear loss modulus (G″) of the melts increase with increasing OMMT content. The melt's elastic response increases by OMMT, and OMMT improves the creep resistance of the melts; in addition, the stress relaxation of the hybrid composite melts become slow with increasing OMMT content, and the stress leavings becomes much higher with increasing OMMT content. At glassy state, the storage modulus of the hybrid nanocomposites increases with increasing OMMT content, while the materials' loss modulus increases first and then decreases with increasing OMMT content; therefore, OMMT nanosheets have reinforcement effect on the composites, and it also has definite toughening effect on the hybrid composite when the OMMT content is no >2 wt%. At rubbery state, the hybrid composites show lower decreasing storage modulus but have lower cold‐crystallization ability than that of pure PTT and PTT/GF composite. POLYM. COMPOS., 35:795–805, 2014. © 2013 Society of Plastics Engineers     

Synthesis of a novel polyester plasticizer based on glyceryl monooleate and its application in poly(vinyl chloride)

The use of bio‐based polymeric plasticizers could expand the application range of plasticized poly(vinyl chloride) (PVC) materials. In this study, a novel bio‐based polyester plasticizer, poly(glutaric acid‐glyceryl monooleate) (PGAGMO), was synthesized from glutaric acid and glyceryl monooleate via a direct esterification and polycondensation route. The polyester plasticizer was characterized by gel permeation chromatography, ¹H‐nuclear magnetic resonance, and Fourier‐transform infrared spectroscopy. The plasticizing effect of PGAGMO on PVC was investigated. The melting behavior, thermal properties, and mechanical properties of PVC blends were studied. The results showed that the PGAGMO could improve the thermal stability and reduce the glass transition temperature of PVC blends; when phthalates were substituted by PGAGMO in PVC blends, the thermal degradation temperature of PVC blends increased from 251.1°C to 262.7°C, the glass transaction temperature decreased from 49.1°C to 40.2°C, the plasticized PVC blends demonstrated good compatibility, and the decrement of the torque and the melt viscosity of PVC blends were conducive to processing. All results demonstrated that the PGAGMO could partially substitute for phthalates as a potential plasticizer of PVC. J. VINYL ADDIT. TECHNOL., 22:514–519, 2016. © 2015 Society of Plastics Engineers     

Hollow Fiber Ultrafiltration Membranes from Poly(Vinyl Chloride): Preparation,Morphologies, and Properties

Hollow fiber poly(vinyl chloride) membranes were prepared by using the dry/wet spinning method. Cross-section, internal, and external surfaces of the hollow fibers structure were studied by SEM. The pore size and pore size distribution of the hollow fibers were measured by a PMI capillary flow porometer. UF experiments of pure water and aqueous solution of PVP K-90 were carried out. The effect of the PVC concentration on the hollow fibers mechanical properties was also investigated. It was found that the PVC fibers cross-sectional structure was affected by the polymer concentration in the dope solution. In particular, reduction of macrovoids size was observed when increasing PVC concentration from 15 to 19 wt%. The pore size distribution of the PVC hollow fibers was controlled by adjusting the PVC concentration. Indeed, an increase of PVC concentration up to 19 wt% leads to fibers with sharp pore size distribution (the 99% of pores is about 0.15 µm).The pure water permeation flux decreased from 162 to 128 (l/m² · h · bar), while the solute separation performance increased from 82 to 97.5%, when increasing the PVC concentration. The elongation at break, the tensile strength, and the Young's modulus of the PVC hollow fibers were improved with PVC concentration in dope solution.     

Gas permeation of polymer blends. I. PVC/ethylene–vinyl acetate copolymer (EVA)

The transport behavior of O₂ and N₂ were studied for series of physical blends of PVC with EVA having different vinyl acetate (VAc) contents in the EVA (45 and 65 wt-%) and using different milling temperatures (160° and 185°C). The polymer blends were further characterized by dynamic mechanical measurements, density measurements, and x-ray diffraction. At higher VAc content in EVA and with higher milling temperature, the rate of permeation (P) and the rate of diffusion (D) decrease, and the activation energy of D (from Arrhenius plots) increases. Furthermore, the experimental density values of PVC/EVA-45 blends agree well with calculated values, assuming volume additivity of the two components, while those of PVC/EVA-65 blends are higher than the calculated densities. These results are interpreted as due to denser packing of polymer molecules and increased PVC-EVA interaction at higher VAc content and with higher milling temperature, indicating better compatibility between the blend components. The x-ray diffraction data give no evidence of crystallinity. Sharp increases in P and D values at about 7.5% EVA (by weight) are found for PVC/EVA-45 blends (in agreement with our previous work) but not for PVC/EVA-65 blends. This is interpreted as due to a phase inversion at increasing EVA content in the former blends but not in the latter blends. The dynamic mechanical measurements show that the PVC/EVA-65 blends milled at 160°C behave largely as semicompatible systems with maximum interaction between the two polymers at compositions of about 50/50 by weight.     

PUR-T／PVC热塑性弹性体的制备及工艺探究

以热塑性聚氨酯弹性体(PUR–T)、聚氯乙烯(PVC)为主要原材料,通过熔融共混挤出制备PUR–T／PVC共混热塑性弹性体。讨论了PUR–T／PVC共混比、增塑剂用量、挤出共混温度、螺杆转速对共混弹性体性能的影响,利用万能试验机、扫描电子显微镜、转矩流变仪、旋转流变仪等研究了弹性体的加工性能及结构。结果表明,当PUR–T／PVC共混比为70／30,增塑剂邻苯二甲酸二辛酯用量为20份,挤出温度为160℃,螺杆转速为330 r／min时,弹性体材料的综合性能最佳;共混弹性体的表观黏度小于纯PUR–T,PVC含量在20%～50%时,PVC易形成网络结构。