Synthesis of PP-g-PIP and Properties of PP/PP-g-PIP Binary Blends

The polypropylene-graft-polyisoprene(PP-g-PIP) copolymers with different side chain length were synthesized by the combination of solid phase graft and anionic polymerization. The copolymers were characterized by nuclear magnetic resonance spectrum(~1H-NMR), gel permeation chromatography(GPC) and differential scanning calorimetry(DSC). Five PP/PP-g-PIP blends with PP-g-PIP as a flexibilizer to toughen PP were prepared and characterized by scanning electron microscope(SEM), dynamic mechanical analysis(DMA), DSC, wide-angle X-ray diffraction(WAXD). Their morphologies, glass transition temperatures, crystallinity and mechanical properties were investigated. All the results pointed out that the covalent bonding of PP and PIP increased the compatibility and interfacial adhesion, which led to PIP well dispersed in the system and small size PIP particles in the binary blends. In addition, the toughness of PP was improved while its tensile strength slightly decreased.     

Long term environmental effects on physical properties of vinylester composite pipes

Glass fiber reinforced vinylester pipes (GFRP) have been exposed to outdoor conditions for 60 months. The effect of the outdoor exposure on the glass transition temperature (Tg) and the crosslinking index is discussed. The Tg and the degree of crosslinking has been determined using differential scanning calorimetry (DSC). DSC has become a preferred technique for rapid determination of transition temperatures and crosslinking for pure polymers, however, the use of this technique for composites is quite complex. This complexity arises from the fact that, in addition to the temperature overlap between the Tg and that of the crosslinking range, the amount of glass fibers in the GFRP is not constant. For this reason, a special measuring technique has been developed for the measurement of the amount of crosslinking of GFRP material. In this paper, it is illustrated that the DSC results clearly show the glass transition temperature and the exothermic crosslinking reaction of the vinylester composites. The results show that the glass transition temperature of the vinylester rapidly increases with respect to exposure time up to 12 months and then slightly decreases for longer exposure times. Similar trends were also observed for the change of the degree of crosslinking. The outdoor environment has also affected the weight of the exposed GFRP samples. It is observed that the weight of GFRP has gradually decreased with the exposure time. These physical changes of Tg, crosslinking and weight have impact on the tensile strength of the GFRP. For the initial outdoor exposure up to 24 months there is a 12% increase in strength from 250 MPa to 280 MPa. This increase is attributed to about 12% increase in crosslinking of the GFRP. However, for longer exposure the tensile strength has decreased back to 250 MPa due to slight decrease in crosslinking and small reduction of weight. It is observed that most of the weight loss has taken place at the surface of the GFRP samples.     

Large impact in electrical properties of polypropylene by improving the filler-matrix interface effect in PP/PS blends

Inorganic nanoparticles are widely used to improve space charge behavior, DC breakdown strength and other electrical properties of polymer insulating materials, but the uniform distribution of inorganic nanofillers in matrix is difficult due to their agglomeration and bad compatibility with the polymeric matrix. In this paper, polypropylene (PP)/polystyrene (PS) blends were prepared to suppress space charge accumulation and improve DC breakdown strength. Polypropylene-g-polystyrene (PP-g-PS) graft copolymer was used as compatibilizer to improve the compatibility of PP matrix and PS filler. The evolution of microstructure of PP/PS blends were investigated by scanning electron microscope (SEM), the space charge distributions were measured by a pulsed electro-acoustic (PEA) system, and DC breakdown strength was also tested. The morphologies show that the size of PS particles reduced to 310 nm when the content of PP-g-PS graft copolymer increased to 24 wt%, and the interaction between PP matrix and PS particles enhanced. The presence of PS particles in all PP/PS blends suppressed the space charge accumulation compared to neat PP, but the DC breakdown strength in uncompatibilized blend was lower than neat PP. The increasing of content of PP-g-PS improved the DC breakdown strength with the maximum value of 408.9 kV/mm was obtained. This may attribute to excellent interface structure formed between PP matrix and PS particles.     

Polypropylene/polystyrene/clay blends prepared by an innovative eccentric rotor extruder based on continuous elongational flow: Analysis of morphology,rheology property,and crystallization behavior

The polypropylene (PP)/polystyrene (PS)/montmorillonite (MMT) blends were prepared by an innovative eccentric rotor extruder based on continuous elongational flow. Addition of MMT nanoparticles was found to reduce the PS droplet size and improve the compatibility of PP/PS. The MMT nanoparticles had clear intercalation and/or exfoliation structures and were located mostly at the interface of PP/PS. It was found that the intercalation and exfoliation of MMT was finished under the synergy of interfacial interaction and tensile deformation so that we called the mechanism as “MMT exfoliation mechanism induced by synergy of interface and tensile deformation”. The rheological analysis showed that incorporation of MMT led to an increase in complex viscosity to an optimum level (5 wt%), after which any further increase in MMT concentration decreased the complex viscosity. Moreover, the degree of crystallinity of blends was controlled by the heterogeneous nucleation effect of MMT and the inhibition effect of PS.     

高强超韧高密度聚乙烯/聚丙烯共混物性能与微相分离结构的研究

在常规注射过程中 ,难以获得超高性能的共混体系注射制件 ,已有的研究表明 ,采用高剪切注射 ,可以抬高共混体系的最低临界相容温度曲线 (LCST)的位置 ,增加相容性 .当熔体进入模具后 ,冷却的同时相容性下降 ,开始相分离 ,相分离程度发展到某一程度即可获得高性能的制件 .对于高密度聚乙烯 (HDPE)、聚丙烯 (PP)两组分均为结晶型聚合物的共混体系 ,由于其相形态与结晶形态相互制约、竞争 ,微相分离程度难以控制 ,因此对其液 液相形态与结晶过程的控制是获得共混物最终形态与性能的关键 .采用振动保压注射成型技术不仅对HDPE、PP各自力学性能有明显的自增强作用 ,而且对HDPE/PP共混体系的力学性能也有十分明显的改善 .DSC、WAXD、SEM结果表明共混体系拉伸强度的提高主要取决于试样中串晶数量和大分子链的定向程度 ,而冲击强度则主要取决于两组分微观的相分离程度 .研究结果表明 ,HDPE/PP含量为 92 / 8的试样拉伸强度为 97 1MPa,80 / 2 0试样的缺口冲击强度为 4 5 5kJ/m2 ,较静态试样分别提高 4 3倍和 9 5倍 .采用振动填充注射技术针对某一组分可以获得高强度、高韧性的共混制件 .     

Synthesis of PP-<Emphasis Type="Italic">g</Emphasis>-PIP and properties of PP/PP-<Emphasis Type="Italic">g</Emphasis>-PIP binary blends

The polypropylene-graft-polyisoprene (PP-g-PIP) copolymers with different side chain length were synthesized by the combination of solid phase graft and anionic polymerization. The copolymers were characterized by nuclear magnetic resonance spectrum (¹H-NMR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Five PP/PP-g-PIP blends with PP-g-PIP as a flexibilizer to toughen PP were prepared and characterized by scanning electron microscope (SEM), dynamic mechanical analysis (DMA), DSC, wide-angle X-ray diffraction (WAXD). Their morphologies, glass transition temperatures, crystallinity and mechanical properties were investigated. All the results pointed out that the covalent bonding of PP and PIP increased the compatibility and interfacial adhesion, which led to PIP well dispersed in the system and small size PIP particles in the binary blends. In addition, the toughness of PP was improved while its tensile strength slightly decreased.     

Effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene compatibilizer on the recycled polypropylene and recycled high‐impact polystyrene blends

The recycled polypropylene/recycled high‐impact polystyrene (R‐PP/R‐HIPS) blends were melt extruded by twin‐screw extruder and produced by injection molding machine. The effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene copolymer (SEPS) used as compatibilizer on the mechanical properties, morphology, melt flow index, equilibrium torque, and glass transition temperature (T_g) of the blends were investigated. It was found that the notch impact strength and the elongation at break of the R‐PP/R‐HIPS blends with the addition of 10 wt% SEPS were 6.46 kJ/m² and 31.96%, which were significantly improved by 162.46% and 57.06%, respectively, than that of the uncompatibilized blends. Moreover, the addition of SEPS had a negligible effect on the tensile strength of the R‐PP/R‐HIPS blends. Additionally, the morphology of the blends demonstrated improved distribution and decreased size of the dispersed R‐HIPS phase with increasing the SEPS content. The increase of the melt flow index and the equilibrium torque indicated that the viscosity of the blends increased when the SEPS was incorporated into the R‐PP/R‐HIPS blends. The dynamic mechanical properties test showed that when the content of SEPS was 10 wt%, the difference of T_g decreased from 91.72°C to 81.51°C. The results obtained by differential scanning calorimetry were similar to those measured by dynamic mechanical properties, indicating an improved compatibility of the blends with the addition of SEPS.     

聚环氧乙烷/聚乙基■唑啉共混体系结晶行为及相容性的研究

用偏光显微镜（ＰＬＭ）、ＤＳＣ、ＩＲ和ＷＡＸＤ等测试方法对聚环氧乙烷（ＰＥＯ）／聚乙基唑啉（ＰＥＯｘ）共混体系结晶行为及相容性进行了研究．结果表明，ＰＥＯ含量在３０％以上的共混体系中，几乎完全被球晶充满，非晶态ＰＥＯｘ作为微区分散在大球晶之间或之中；含量为２０％的共混体系照片上呈树枝状晶；含量低于１０％时则看不到结晶出现，体系形成单一的非晶相．对任何组成的共混物，均只出现单一的玻璃化转变温度（Ｔｇ），而且符合Ｆｏｘ方程揭示的规律；随ＰＥＯｘ组分含量的增加，共混体系的结晶度减小，熔点下降，并利用平衡熔点方程计算出ＰＥＯ与ＰＥＯｘ的相互作用能密度．非晶ＰＥＯ与ＰＥＯｘ热力学相容，其相容性是由于这两种分子间存在着特殊相互作用．ＰＥＯｘ的加入不会改变ＰＥＯ的晶胞参数．     

Mechanical properties and characteristic of surface treated bamboo fiber reinforced PP/PS blends

Bamboo fiber (BF) as organic filler is characterized by mechanical properties analysis and morphology examination for polypropylene (PP) and polystyrene (PS) matrix blends. Effects of different filler content on tensile strength, flexural properties, and impact strength are proposed. It is observed from scanning electron microscopy (SEM) studies that addition of BF is beneficial in increasing mechanical strength via increasing the interface dispersed phase. The optimum tensile properties and impact properties of BF content were at 40 wt% for PP/PS/BF composite on melt mixing conditions. The results showed a significant improvement in mechanical properties of PP/PS/BF ternary blend composite. Comparing with untreated BF, content of carbon and nitrogen of treated BF decreased to 66.57 and 2.31%, oxygen content increased to 21.07%, and silicon content increased from 0 to 10.04%. The element ratio of O/C, N/C, and Si/C changed to 31.65, 3.47, and 15.08, respectively.     

The mechanical and thermal behaviors of glass bead filled polypropylene

Notch Izod impact strength of poly(propylene) (PP)/glass bead blends was studied as a function of temperature. The results indicated that the toughness for various blends could undergo a brittle‐ductile transition (BDT) with increasing temperature. The BDT temperature (T_BD) decreased with increasing glass bead content. Introducing the interparticle distance (ID) concept into the study, it was found that the critical interparticle distance (ID_c) reduced with increasing test temperature correspondingly. The static tensile tests showed that the Young's modulus of the blends decreased slightly first and thereafter increased with increasing glass bead content. However, the yield stress decreased considerably with the increase in glass bead content. Dynamic mechanical analysis (DMA) measurements revealed that the heat‐deflection temperature of the PP could be much improved by the incorporation of glass beads. Moreover, the glass transition temperature (T_g) increased obviously with increasing glass beads content. Differential scanning calorimetry (DSC) results implied that the addition of glass beads could change the crystallinity as well as the melting temperature of the PP slightly. Thermogravimetric analysis (TGA) measurements implied that the decomposition temperature of the blend could be much improved by the incorporation of glass beads. Copyright © 2004 John Wiley & Sons, Ltd.     

聚乙烯/聚己内酯-聚乙二醇共聚物共混物组分相容性及其光水双降解的研究

用动态力学振簧仪、DSC、FT IR、光辐照、浸水降解法研究了马来酸酐化线型低密度聚乙烯 (MPE) /聚己内酯 聚乙二醇共聚物 (PCE)共混物的组分相容性、晶区的熔化和结晶行为以及降解特性 .结果表明 ,马来酸酐化是发生在LLDPE短支链的甲基末端上并通过马来酸酐与PCE的羟基形成氢键相互作用 ,使两组分存在部分相容性 ,PCE的主转变与MPE支链的 β转变发生内移现象 .在共混物中加入乙烯 丙烯酸共聚物(EAA)可以起增容作用 ,同时使MPE和PCE组分的熔点和熔化热进一步下降 .对不同含量PCE的MPE/PCE/EAA共混物的降解特性的研究表明 ,PCE的加入使体系发生光、水降解 ,且随PCE含量的增加降解速度加快 .光 水联合作用的降解速度比单一光或水降解更快 .     

A METHOD TO QUANTIFY CRAZING DEFORMATION BY TENSILE TESTS FOR POLYSTYRENE/POLYOLEFIN ELASTOMER IMMISCIBLE BLENDS

A method to quantify crazing deformations by tensile tests for polystyrene （PS） and polyolefin elastomer （POE） blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume （△V） against longitudinal variation （△I） showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.     

Two kinds of nanoscale dynamic heterogeneity in single‐phase polymer blends and their common origin

Differential scanning calorimetry (DSC) and laser‐interferometric creep rate spectroscopy (CRS) were used for kinetic and discrete analysis of segmental motion within (and close to) glass transition range in polystyrene ‐ poly(α‐methyl styrene) (PS/PMS) and polystyrene ‐ poly(vinyl methyl ether) (PS/PVME) miscible blends. Two kinds of segmental dynamics heterogeneity were found. Separate ‘unfreezing’ of PS and PMS segmental motions was observed that manifested itself in two T_gs and simultaneous large drop in the Tg s, as well as glass transition activation energy, motional event scale and cooperativity degree values, down to the β‐relaxation parameters. The wide activation energy dispersion within a single broad glass transition in PS/PVME blends was found, and this relaxation region was subdivided, by CRS, into several predicted kinds of segmental motion. Both results are treated in the framework of the concept of common segmental nature of α‐ and β‐relaxations in flexible chain polymers.     

Mechanical and thermal properties of epoxidized soybean oil plasticized polybutylene succinate blends

Epoxidized soybean oil (ESO) was blended as a novel plasticizer with polybutylene succinate (PBS) in a twin‐screw extruder. The effects of ESO on the mechanical and thermal properties of the PBS/ESO blends were investigated by means of tensile test, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electronic microscope. ESO improved elongation at break for PBS, which increased and then decreased with the increase in ESO. Elongation at break reached a maximum of 15 times than that for pure PBS when the ESO loading was 5 wt%. The tensile strength and modulus for the blends were lower than those for pure PBS. Compared with pure PBS, the blends exhibited lower glass transition temperature, crystallization temperature, and melting temperature. The storage modulus and tan δ peaks for the blends were lower compared with that for pure PBS. ESO had very limited compatibility with PBS, and phase separation was observed when more ESO was added. Copyright © 2011 John Wiley & Sons, Ltd.     

新型sPS/PA6/SsPS-H塑料合金的性能和形态结构

研究新型sPS PA6 SsPS H塑料合金的力学性能和微观形态结构 .间规聚苯乙烯 (sPS)的磺化产物磺化间规聚苯乙烯 (SsPS H)的加入明显地改善了sPS PA6(聚酰胺 6)二组分合金的力学性能 ,在sPS PA6 SsPS H重量组成为 80 2 0 5时 ,三组分合金的冲击强度最大 ,为 1 5 6kJ m2 ,约为纯sPS冲击强度的 3倍 DMA和SEM结果表明 ,SsPS H对sPS和PA6共混有良好的增容作用 ,它起到了降低合金的微相尺寸和加强相间界面粘结的作用 .此外 ,FTIR结果还表明SsPS H和PA6之间存在特殊相互作用 ,其作用方式是通过SsPS H的磺酸基将其质子转移给PA6酰胺基的氮     

Thermal and structural studies of polypropylene blended with esterified industrial waste lignin

Microwave-assisted chemical modification of lignin was achieved through esterification using maleic anhydride. Modified lignin (ML) was blended in different proportions up to 25 mass% with polypropylene (PP) using Brabender electronic Plasticorder at 190 °C. The structural and thermal properties of blends were investigated by thermogravometric analysis (TG), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM). TG analysis showed increased thermal stability of blends due to antioxidant property of ML, which opposed oxidative degradation of PP. DSC analysis indicted slight depression in a glass transition temperature and melting temperature of blends due to partial miscible blend behavior between PP and ML. All blends showed higher crystallization temperatures and continuously reducing percentage crystallinity with increasing ML proportion in the blends. WAXD analysis indicated that PP crystallized in β polymeric form in addition to α-form in the presence of ML. However, proportion of β-form did not show linear relation with increase in ML proportion, thus ML acts as β nucleating agent in the PP matrix. SEM analysis showed good dispersion/miscibility in PP matrix indicating modification in lignin is useful.     

Migration Study of Polypropylene (PP) Oil Blends in Food Simulants

Migration study in aqueous and olive oil food simulants was carried out on PP and its blend with oil mixture. It was found that after 10 days at 44 °C PP with oil content up to 0.83% had overall migration into olive oil less than 10 mg/dm². However, under high temperature migration test (at 110–138 C for 4 hours), the overall migration into olive oil was large for both the virgin PP and all its blends. The overall migration in water, 10% ethanol, and 3% acetic acid was smaller than those in olive oil under both migration test conditions. DSC and density measurement showed that addition of oil in PP led to smaller spherulite size and increased degree of crystallinity in the pure PP part. Small decrease in tensile strength in the oil blends was also observed but there was no significant change in tensile strength after migration test.     

聚(碳酸丁二醇酯-co-三环癸烷二甲醇碳酸酯)的制备与性能

采用熔融酯交换和缩聚两步法,合成了以1,4-丁二醇、4,8-三环[5.2.1.0(2,6)]癸烷二甲醇和碳酸二苯酯为原料的聚(碳酸丁二醇酯-co-三环癸烷二甲醇碳酸酯)(PBTCx, x为进料中TCD占二元醇总量的百分比)。用1H NMR和13C NMR对PBTCs的微观结构和组成进行了表征。采用GPC、 DSC、 XRD、 TG对PBTCs的分子量、玻璃化转变温度(Tg)、热稳定性等进行了研究。结果表明,PBTCs的Mw为10500~124800 g?mol-1, Mn为6300~73000 g?mol-1, PDI为1.59~1.73; PBTCs呈无定形态、Tg为-3.43 ℃~70.90 ℃, PBTCs表现出比PBC更高的热稳定性。薄膜拉伸试验结果表明,PBTC30(拉伸强度为33.54 MPa,断裂伸长率为275.69%)和PBTC40(拉伸强度为32.13 MPa,断裂伸长率为294.63%)具有较高的强度和韧性,在薄膜材料中具有一定的应用潜力。     

Morphologies, crystallinity and dynamic mechanical characterizations of polypropylene/polystyrene blends compatibilized with PP-g-PS copolymer: Effect of the side chain length

PP-g-PS copolymers were synthesized with the same polypropylene (PP) backbones and various side chain lengths of PS sequences via reactive comonomer p-allyltoluene (p-AT) by Ziegler–Natta copolymerization and the subsequent living anionic graft-polymerization. ¹H NMR characterized that the PP-g-PS copolymer had grafted 3.15 side chains per 1000 carbons in the PP backbones and the length of PS sequences varied in the range of 25.8–309.9 units. PP/PS blends with the PP-g-PS copolymer as compatibilizer (wt. 75/25/5) were prepared and characterized by SEM, WAXD and DMA to investigate the morphologies, crystallinity and glass transition temperatures of the PP/PS blends. All the results pointed out that the average side chain length (GL) of the graft copolymer (GL is from 25.8 to 309.9) made great effects of the PP/PS blends, such as the PS dispersed phase, the crystallinity of the PP component and the two glass transition temperatures of the blends, which showed the same trend with the increase of the GL. Overall, only with a suitable average side chain length, the PP-g-PS copolymer could achieve optimal compatibilizing efficiency of the PP/PS blends.     

Transmission electron microscopy study of phase morphology in polypropylene/ethylene-octene copolymer blends

Blends of polypropylene (PP) and ethylene-octene copolymers (EOC) were investigated by transmission electron microscopy (TEM) and by differential scanning calorimetry (DSC). The EOC contained 28, 37, 40 or 52 wt% of octene. Only the 50/50 PP/EOC ratio was used for all blends. None of the blends was fully miscible, there was always two-phase morphology. TEM observation followed by image analysis by ImageJ software revealed that the largest particles were in blend containing EOC-28 and the smallest were in blend with EOC-52. The coarsening rate at 200 °C was evaluated by TEM. The glass transition temperature (T_g) shift indicated partial miscibility. Partial miscibility was then confirmed by direct observation of bright PP lamellae in EOC dark phase.