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.     

Nonisothermal crystallization behavior of isotactic polypropylene/ thermoplastic rubber blends

The morphology and crystallization behavior of blends of polypropylene (PP) and an ethylene-based thermoplastic elastomer (TPO) were investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The SEM images showed a two-phase morphology for these blends. As TPO was partially crystalline, two distinct peaks were observed in both heating and cooling scans of DSC. The crystallization temperature of TPO in blends was higher than pure TPO. In contrast, the crystallization temperature of PP in blends was lower than pure PP. The crystallization behavior of blends was modeled by Avrami equation. It was observed that the presence of TPO accelerated the growth rate of crystals of PP in PP/TPO blends.     

The influence of KH-550 on properties of ammonium polyphosphate and polypropylene flame retardant composites

Ammonium polyphosphate (APP)/polypropylene (PP) composites were prepared by melt blending and extrusion in a twin-screw extruder. APP was first modified by a silane coupling agent KH-550 then added to polypropylene. The surface modification of APP by the coupling agent decreased its water solubility and its interface compatibility with the PP matrix. Limiting oxygen index (LOI) and thermogravimetric analysis (TGA) were used to characterize the flame retardant property and the thermal stability of the composites. The addition of APP improved the flame retardancy of PP remarkably. The crystal structures of APP/PP composites were characterized by X-ray diffraction (XRD). The results indicated that β-crystal phase PP may be formed. The structures and morphologies of APP, KH-550/APP and APP/PP composites were characterized by field-emission scanning electron microscope (FESEM). The mechanical property tests showed good mechanical properties of composite materials. Compared with unmodified one, the impact strength, tensile strength and elongation of modified APP/PP were all improved.     

An efficiently halogen-free flame-retardant long-glass-fiber-reinforced polypropylene system

In order to solve the “candlewick effect” caused by glass fibers, which results in the decrease of flame retardancy of flame-retardant long-glass-fiber-reinforced polypropylene (LGFPP) systems, and the deterioration of mechanical properties caused by adding an additional amount of flame retardants compared with flame-retardant non-glass-fiber-reinforced polypropylene systems so as to keep a same flame retardancy, a novel intumescent flame retardant (IFR) system, which is composed of a charring agent (CA), ammonium polyphosphate (APP) and organically-modified montmorillonite (OMMT), was used to flame retard LGFPP. The thermal stability, combustion behavior, char formation, flame retardant mechanism and mechanical properties of the IFR-LGFPP samples were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 test, cone calorimeter test, scanning electronic microscopy, and mechanical property tests. When the content of IFR is 20 wt%, the LOI value of IFR-LGFPP reaches 31.3, and the vertical burning test reaches UL-94 V-0 rating, solving the “candlewick effect” caused by long glass fiber without additional amount of the IFR. All the relevant cone calorimeter parameters also show that IFR-LGFPP has much better flame-retardant behaviors than LGFPP. Furthermore, the mechanical properties of IFR-LGFPP almost remain unchanged in comparison with those of LGFPP containing no IFR. The flame retardant mechanism was also discussed.     

Effects of coating amount and particle concentration on the impact toughness of polypropylene/CaCO3 nanocomposites

The effects of the coating amount of surfactant and the particle concentration on the impact strength of polypropylene (PP)/CaCO₃ nanocomposites were investigated. Nanocomposites prepared with monolayer-coated CaCO₃ nanoparticles had the best mechanical properties, including Young’s modulus, tensile yield stress and impact strength because of the good dispersion of the nanoparticles in the polymer matrix. In addition, the good dispersibility of the monolayer-coated nanoparticles allowed us to study the effects of particle concentration on the impact strength of the nanocomposites. H-PP and E-PP, which were the low and high molecular weight PPs, respectively, were used as polymer matrices. Critical particle concentrations of 10 and 25 wt% corresponding to an abrupt increase in the impact toughness were determined for the E-PP and H-PP nanocomposites, respectively. Good particle dispersion in a polymer matrix is the prerequisite for the calculation of the critical ligament thickness using the critical particle concentration. We propose that the observed critical ligament thickness actually corresponds to the critical thickness at which the plane-strain to plane-stress transition occurs. In addition, the critical ligament thickness of a nanocomposite depends on the properties of the polymer matrix, such as molecular weight, even for a given type of polymer.     

Tensile behaviour of isotactic polypropylene modified by specific nucleation and active fillers

Commercial-grade polypropylene was modified with a specific nucleation agent based on an amide of dicarboxylic acid, which promotes crystallization predominantly in the β-phase. The resulting material was used as a matrix for composites containing 10%, 20%, and 30% (by weight) of different calcium carbonate fillers. These fillers differed in particle size and surface treatment. The β-phase content, morphology and tensile mechanical properties were investigated. A distinct β-nucleation activity was found with surface-treated fillers; nevertheless, to obtain stiff and reasonably ductile composite materials, a matrix containing a critical nucleant concentration (0.03 wt%) was necessary.     

Polyethylene and polypropylene nanocomposites based upon an oligomerically modified clay

Montmorillonite clay was modified with an oligomeric surfactant, which was then melt blended with polyethylene and polypropylene in a Brabender mixer. The morphology was characterized by X-ray diffraction and transmission electron microscopy, while thermal stability was evaluated from thermogravimetric analysis and the fire properties by cone calorimetry. The nanocomposites are best described as mixed immiscible/intercalated/delaminated systems and the reduction in peak heat release rate is about 40% at 5% inorganic clay loading.     

成核剂对聚丙烯熔融行为的影响

成核剂对聚丙烯熔融行为的影响陈彦徐懋（中国科学院化学研究所高分子物理开放实验室北京１０００８０）关键词成核剂，聚丙烯，平衡熔点聚合物的熔融过程受分子量大小、分子量分布、分子链构型（等规度、分子结构单元的键接序列）、不同的结晶晶型、不同的热历史等...     

Orientation mechanisms during biaxial drawing of polymer films

Summary Second drawing of monoaxially drawn PP and PET films perpendicular to the first drawing direction has been investigated. At low draw ratios structural systems having an angle of 45° with regard to the second draw direction are formed. By increasing the draw ratio the structures rotate into the new preferred direction. The results lead to the impression that the structural transformations do not turn out molecule by molecule, but domain by domain.

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Zusammenfassung Die Zweitverstreckung monoaxial verstreckter PP- und PET-Folien senkrecht zur Erstverstreckrichtung wird untersucht. Bei kleinen Verstreckgraden bilden sich Struktursysteme unter 45° zur Zweitverstreckrichtung; bei weiterer Verdehnung drehen sich die Strukturen in die Vorzugsrichtung. Die Ergebnisse vermitteln den Eindruck, daß die Strukturänderung nicht Molekül für Molekül, sondern Bereich für Bereich abläuft.

With 10 figures and 2 tables