Block copolymers of isotactic polypropylene and 1,4-polybutadiene

Two block copolymers of isotactic polypropylene and 1,4 polybutadiene were synthesized using techniques involving a transformation from anionic to Ziegler–Natta polymerization mechanisms. The yield of block copolymer was about fifteen percent (weight basis) in both polymerizations, the remainder being unreacted polybutadiene from the first block synthesis. Molecular characterization experiments and model reactions were consistent with a block-like structure for the copolymers; definitive evidence for the proposed molecular structure was obtained through transmission electron microscopy which clearly revealed microphase-separated morphologies characteristic of block copolymers.     

Degradation of pre-aged polymers exposed to simulated recycling: Properties and thermal stability

Accelerated thermal and photo-aging of four homopolymers, low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and high-impact polystyrene (HIPS), was performed and the impact of subsequent reprocessing conditions on their properties studied. Polymer samples oven-aged at 100 °C for varying periods of time or UV irradiated in a Weather-o-meter (WOM) at λ = 340 nm were reprocessed in a Brabender plasticorder at 190 °C/60 rpm for 10 min. Chemical changes and the evolution of rheological and mechanical properties accompanying the gradual degradation of the individual polymers were monitored and evaluated (DSC, FTIR, colorimetric method, MFI, tensile impact strength). LDPE and HIPS were found to be more susceptible to thermo-oxidation than HDPE and PP, whereas HDPE and PP were affected to a greater extent by UV exposure; the crucial role here is being played by the stabilization of the studied resins. In HDPE the scission and crosslinking reactions competed both in thermo-and photo-degradation. In the case of LDPE, scission prevailed over branching during thermo-oxidation, whereas photo-oxidation of the same sample led predominantly to crosslinking. Abrupt deterioration of the LDPE rheological properties after one week of thermal exposure was suppressed by re-stabilization. The scission reaction was also predominant for PP during thermo-oxidation, and it took place even faster during UV exposure. In the case of HIPS a slight photo-degradation of PS matrix is accompanied by simultaneous crosslinking of the polybutadiene component.     

Mechanical and morphological properties of injection-molded rice husk polypropylene composites

In this work, the investigation of the physical, mechanical, and morphological properties of the rice husk flour/polypropylene composites was performed utilizing various filler loadings and coupling agent. Five levels of filler loading (35, 40, 45, 50, and 55 wt%) were designed. In addition, to help the interaction between fiber and polypropylene matrix, struktol coupling agent was added to the composites. All of tensile strength, Young's modulus, flexural strength, flexural modulus, and impact strength properties of the composites were carried out. Moreover, the 50 wt% filler-loaded composites had optimum tensile strength, flexural strength, and flexural modulus, whereas the 35 wt% of filler loading case was the best regarding Young's modulus, flexural strength, flexural modulus, and impact strength. Furthermore, the scanning electron microscope results demonstrate that as filler loading increases, more voids and fiber pullout occur.     

New structures from the thermal rearrangement of polybutadiene revealed by 2D HSQC NMR

The thermal reactions of polybutadiene (PB) at 260 °C in inert atmosphere were followed by ¹H and ¹³C NMR spectroscopy. Within 24 h of heating, the change in the intensities of some peaks and the appearance of new peaks of NMR spectra permits to follow the reactions occurring in polybutadiene. The sample, after heating for 6 h, was then characterized by a two dimensional HSQC NMR spectrum, showing the appearance of CH₃CH moiety, and the migration of double bond in polybutadiene. From these results the new mechanism of intra/intermolecular reactions was proposed.     

The enhanced nucleating ability of carbon nanotube-supported β-nucleating agent in isotactic polypropylene

A kind of β-nucleating agent, calcium pimelate, for polypropylene (PP) was chemically supported onto the surface of multi-wall carbon nanotubes, and the effect of the multi-wall carbon nanotube-supported β-nucleating agent on the mechanical properties and morphology of isotactic polypropylene composites was investigated. The composites of isotactic polypropylene and multi-wall carbon nanotube-supported β-nucleating agent exhibited excellent impact toughness compared with pure isotactic polypropylene and β-nucleated isotactic polypropylene, being more than seven times over that of pure isotactic polypropylene and more than three times over that of β-nucleated isotactic polypropylene. The excellent impact behaviors of the composites were also evidenced by the fracture morphology based on scanning electron microscopy observations. Differential scanning calorimetry and wide-angle X-ray diffraction results verified the enhanced nucleating ability of the multi-wall carbon nanotube-supported β-nucleating agent, which greatly improved the impact toughness without significantly deteriorating the strength and stiffness of the polypropylene composites.     

低乙烯含量共聚聚丙烯链结构和相结构与应力应变行为的关系

研究了两种典型的低温抗冲共聚聚丙烯(ICPP)的应力应变行为及温度依赖性,其低温应力应变行为揭示ICPP具有优异的低温抗冲性能和综合力学性能的结构本质.从初始弹性模量、屈服应力及断裂伸长随温度变化所显示的变化规律进一步确认了两种ICPP的序列结构特征和相结构特征.断裂伸长变化显示了乙丙橡胶相的增韧作用,屈服应力变化显示了分散相对基质结合紧密程度的影响,弹性模量则与基质的结晶状况和结晶形态有着比较密切的关系,同时也与乙丙橡胶相和聚丙烯基质的玻璃化转变温度密切相关.     

聚丙烯/纳米级金红石型二氧化钛/聚烯烃弹性体复合材料的抗老化性能研究

采用TEM和UV-Vis等测试手段表征了金红石型纳米级TiO2和体相TiO2的性能特征;通过熔融共混法分别制备了PP/纳米级TiO2/POE和PP/体相TiO2/POE复合材料,采用GB/T16422·2-1999所述的塑料实验室光源暴露实验方法,用氙灯气候试验机对纯PP和复合材料进行28天人工加速老化.结果表明,二氧化钛粒子在PP/POE基体中分散性良好,而纳米粒子对PP/POE基体具有增韧作用;改性后的两类复合材料均具有优异的抗老化性能,而PP/(1·0wt%)纳米级TiO2/POE复合材料的抗老化性能更加优异,其加速老化28天后的无缺口冲击强度达到80·45kJ·m-2,比纯PP提高4倍多,而同期加速老化28天后的PP/(1·0wt%)体相TiO2/POE复合材料的无缺口冲击强度只有47·88kJ·m-2;对纯PP老化过程中的羰基指数和冲击性能的变化情况进行了分析,发现二者近似成线性关系,其相关系数r在0·9以上.     

PP-g-MAH对聚丙烯/滑石粉复合材料的性能影响

研究了两种马来酸酐接枝聚丙烯（PP-g-MAH）在不同含量时对聚丙烯（PP）/滑石粉复合材料的力学性能、雾化性能和线性膨胀系数的影响.结果表明,接枝物的加入能提高复合材料的拉伸性能、冲击性能和弯曲性能,但随着含量的增加拉伸强度、冲击强度和弯曲强度及弯曲模量有所降低.在含量相同时,接枝物1对冷凝组份的影响更小.复合材料的线性膨胀系数随接枝物含量的增加先减小后增加.     

Effect of Silane Coupling Agent and Compatibilizer on Properties of Short Rossells Fiber/Poly(propylene) Composites

Rossells fiber reinforced polypropylene composites were prepared by melt mixing. The fiber content was 20 wt%. Octadecyltrimethoxysilane (OTMS) and maleic anhydride grafted polypropylene (MAPP) were used to improve the adhesion between poly(propylene) (PP) and the fiber. The mechanical, rheological, and morphological properties, and heat distortion temperature (HDT) of the composites were investigated. Tensile strength, impact strength, flexural strength and HDT of MAPP modified PP composites increased with an increase in MAPP content. However, no remarkable effect of MAPP content on the Young's modulus of the composites was found. OTMS resulted in small decreases of tensile strength and Young's modulus, and increase in impact strength. Scanning electron micrographs revealed that MAPP enhanced surface adhesion between the fiber surface and PP matrix.     

Cationic polymerization of α-methylstyrene from polydienes. I. Synthesis and characterization of poly(butadiene-g-α-methylstyrene) copolymers

The preparation of poly(butadiene-g-α-methylstyrene) copolymers was investigated with three different alkylaluminum coinitiators. The alkylaluminum compounds in conjunction with polybutadiene which contained a low concentration of labile chlorine atoms initiated the polymerization of α-methylstyrene to produce graft copolymers. Trimethylaluminum gave higher grafting efficiencies than diethylaluminum chloride at comparable monomer conversions. Triethylaluminum produced only very low monomer conversions (<5%), even at long reaction times, and for this reason was not studied extensively. The number of grafts per polybutadiene backbone was determined for a number of copolymers and found to increase slightly as the allylic chlorine concentration in the polybutadiene backbone was increased. In all cases, however, only a low percentage of the available labile chlorine sites along the polybutadiene backbone resulted in grafted α-methylstyrene side chains. The addition of small quantities of water to the polymerization solvent greatly enhanced the grafting rate and ultimate monomer conversion during the synthesis of these poly(butadiene-g-α-methylstyrene) copolymers. The mechanistic role of water during these grafting reactions is unknown at the present time.     

A study of PP/PET composites: Factorial design,mechanical and thermal properties

Due to the economic importance of polypropylene (PP) and polyethylene terephthalate (PET), and the large amount of composites made with PP matrix and recycled PET as reinforcing material; an investigation was performed regarding the mechanical and thermal behavior of PP composites containing recycled polyethylene terephthalate fibers (rPET). Interfacial adhesion between the two materials was achieved by adding a compatibilizer, maleic anhydride grafted polypropylene, PP-g-MA. Mechanical behavior was assessed by tensile, flexural, impact and fatigue tests, and thermal behavior by HDT (Heat Deflection Temperature). Fractured surfaces and fiber were investigated by scanning electron microscopy. Multiple regression statistical analysis was performed to interpret interaction effects of the variables. Tensile strength, tensile modulus, flexural strength, flexural modulus and HDT increased after rPET fiber incorporation while strain at break, impact strength and fatigue life decreased. Addition of compatibilizer increased tensile strength, flexural strength and flexural modulus, fatigue life and HDT while tensile modulus, strain at break and impact strength decreased. However, at low fiber content, the impact strength increased, probably due to nucleation effects on PP.     

Effect of compatibilisers on mechanical and thermal properties of bentonite filled polypropylene composites

Bentonite filled polypropylene composites were prepared using a Polydrive Thermo Haake, internal mixer at 180 °C and at 50 rpm of rotor speed. Effect of compatibilisers on mechanical, thermal, water absorption and morphological properties of bentonite filled polypropylene composites was investigated. Two types of compatibilisers namely, palm oil fatty acid additive (POFA) and polypropylene grafted-maleic anhydride (PPMAH) have been used in this study. The mixing of the composites improved with the addition of POFA. The impact strength and elongation at break increased with the presence of both compatibilisers whilst, tensile strength and Young's modulus improved only with addition of PPMAH. Morphological investigation using SEM revealed that the improvement in impact strength and elongation at break was due to enhancement of the interfacial adhesion between bentonite and PP. The thermal stability of bentonite filled PP improved with the incorporation of POFA and PPMAH. Less percentage of water absorption has been observed in PP-bentonite system with PPMAH.     

聚丙烯催化合金的相结构研究

聚丙烯 (ＰＰ)由于其价格低廉、性能较好、应用范围广而得到了极为迅速的发展 .然而 ,它的一些缺点也极大地限制了它在一些特殊领域中的应用 .人们为了进一步扩大其应用范围 ,对ＰＰ进行了各种各样的改性 .其中以提高ＰＰ抗冲强度为目的的改性研究进行得最多[1～ 4 ] .这种改性的方法是将ＰＰ和一种以上的其它聚合物以机械共混的方法进行混合 ,使其得到一种宏观上均匀的聚合物共混物 .但是 ,这种混合往往达不到真正均匀的状态 ,因而共混物的抗冲强度提高不显著 .聚合物的性能取决于其内部结构———相态结构和分子结构 ,而相态结构对材料的…     

Grafting polypropylene and treatment of calcium carbonate to improve structure and properties of polypropylene composites

In this paper, calcium carbonate was chemically treated with two kinds of dicarboxylic acids before compounding with polypropylene in the presence of dicumyl peroxide (DCP). It was observed that the mixture of dicarboxylic acids could improve the crystallization and impact strength properties of calcium carbonate/polypropylene composite. With further addition of DCP, more PP-g-MA was produced in the blend, resulting in PP composites with larger β-phase content and improved mechanical properties. In the experiments, the maximum K _β value of 52.0 % was obtained. The elongation at break of composite increased from 252 % for PP composite with untreated calcium carbonate to 444 % for PP composite with chemically treated calcium carbonate.     

Revealing toughening mechanism for alternating multilayered polypropylene/poly(ethylene-co-octene) sheets

Alternating multilayered (16, 32, and 128 layers) polypropylene/poly(ethylene-co-octene) (PP/POE) sheets were prepared via multilayer co-extrusion. Impact (−20°C), tensile, and dynamic rheological tests were carried out on the prepared multilayered samples. The toughening mechanism for the multilayered samples was revealed via investigating their fracture surface morphology and analyzing the work of fracture. The results showed that the impact energy for the notched multilayered samples is mainly absorbed by the continuous thin ductile POE layers due to cavitation, whereas for the unnotched multilayered samples the continuous thin POE and PP layers both contributed significantly to the total work of fracture due to multiple crazing, cracking and distinct plastic deformation in both PP and POE layers, and thus significantly extended crack propagation paths. Hence, the multilayered samples possessed much higher unnotched impact strength than notched impact strength. Moreover, the multilayered samples exhibited slightly increased notched impact strength and obviously increased unnotched impact strength with increasing layer number. Interestingly, the multilayered samples exhibited lower notch sensitivity than the PP sample. In addition to significantly improved low temperature impact toughness, the multilayered samples maintained the strength and stiffness as well as having superior extensibility to that of the PP sample.     

Etude de l'influence de silanes sur l'interface fibres de verre/matrice polypropylene

Several types of coupling agents containing silane groups have been introduced during the extrusion process of polypropylene reinforced by glass fibres. The influence of these additives on mechanical properties, especially tensile and impact strength, is studied in addition to the correlated observation of the rupture areas in tension by scanning electron microscopy. The results are interpreted in terms of more or less adhesion of the fibres in the matrix, as a result of the possible reactions of polymerization, crosslinking or grafting which can occur according to the nature of the addictive.     

含铵根离子等规聚丙烯离聚体的合成及性能研究

合成了一系列高分子量、窄分子量分布且高等规度,含有不同―NR_3~+X~-离子基团含量的聚丙烯离聚体(iPP-NR_3~+X~-).以PP/IUD共聚物作为反应中间体,与三乙胺或N-甲基咪唑氨化得到聚丙烯离聚体.通过离子交换反应制备不同反离子的N-甲基咪唑聚丙烯离聚体,包括双三氟甲基磺酰亚胺根离子(Tf_2N~-)、四氟硼酸根离子(BF_4~-)和六氟磷酸根离子(PF_6~-).热重分析结果发现N-甲基咪唑聚丙烯离聚体的热稳定性明显优于三乙胺聚丙烯离聚体,表明不含β-H的N-甲基咪唑聚丙烯离聚体具有较高的热稳定性.同时,聚丙烯离聚体的表面亲水性得到明显改善.并且,聚丙烯离聚体的断裂伸长率也得到显著提高,最高达到900%.比较不同反离子聚丙烯离聚体的屈服强度和断裂强度发现I~-聚丙烯离聚体具有最优的力学性能.     

Polymerization of Butadiene Using Ziegler-Natta Catalysts—Recent Developments

The products of Ziegler-Natta catalyzed reactions, including high density polyethylene, polypropylene, and other thermoplastics and elastomers, have become familiar to all. While an enormous volume of experimental work was completed during the 1950s and 1960s, it has only been during the 1970s that the multiplicity of mechanistic schemes developed have been subjected to scrutiny. The majority of these have been concerned with polymerization of ethylene and α-olefins and because they have been adequately reviewed recently, are discussed only briefly here. A similarly large volume of empirical experimental work has enabled commercial production of polybutadiene using stereoregular catalysts. However, the mechanisms involved are of recent development, largely due to the additional configurational complexity of products, the multicompound nature of the catalyst complex, and the susceptibility of the system to contamination. Advances which have been made during the last decade are highlighted, with particular emphasis on those modifications to catalyst or to polymer structure which are of practical importance. In Australia, all production of stereoregular (high cis) polybutadiene is achieved using an aluminum alkyl halide-cobalt salt based catalyst. The fundamental technology of this process is discussed with emphasis upon process control. In particular, the control of molecular weight, processing behavior, and reduction in cross-linked material are included in more recent developments. In a broader context, technological changes which have been stimulated by such diverse influences as the increased awareness of industrial hygiene, fluctuations in feedstock availability and cost, and the general acceptance of radial ply tires are discussed. Experimental activities currently in progress in Australia, together with challenges still remaining, are examined.     

Influence of electron beam irradiation on the impact properties of polystyrene/EPDM rubber blends

The influence of electron beam (EB) irradiation on the impact properties of compatibilized polystyrene/ethylene-propylene-diene-monomer (PS/EPDM) blends was studied. The change in impact value upon irradiation proved to be strongly dependent on the type of compatibilizer used. Using a polystyrene/polybutadiene (SB) diblock copolymer as a compatibilizer, a twofold increase in Izod value could be achieved upon irradiation. Irradiation of a blend using a polystyrene/ethylene-propylene (SEP) copolymer as a compatibilizer resulted in a decrease in impact strength. These observations can be related to a radiation induced increase in interfacial adhesion in case of the SB copolymer, which does not occur for the SEP copolymer. Due to the abundance of double bonds in the SB copolymer, this copolymer reacts very fast upon irradiation and may co-crosslink with, or graft onto the EPDM phase. For the SEP copolymer crosslinking occurs only at much higher doses and is (partly) overruled by chain scission and consequently the adhesion between matrix and dispersed phase will hardly change. This view is supported by analytical methods as FT-IR and NMR as well as from T_g measurements.     

Viscoelastic relaxation mechanisms of conventional polypropylene toughened by a plastomer

Plastomers are new alternatives that provide a higher impact strength in polypropylene synthesized by conventional methods. This study presents an analysis of the structure and thermal characterization of two sets of polypropylene/plastomer blends. The difference between the two polypropylene samples is their molecular weight. With the structural knowledge obtained, a comprehensive analysis of the different relaxation processes has been performed. Neither component is miscible. The area under the loss tangent curves provides preliminary information about how the toughness is enhanced with this type of impact modifier. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1878–1888, 2003