聚丙烯接枝改性及其挤出发泡研究

以有机过氧化物为引发剂,以双螺杆挤出机为反应器,将线型不饱和聚酯(ULP)接枝到聚丙烯(PP)分子链上。通过FTIR、DSC及凝胶含量测试,对MPP的结构和性能进行了研究,表明PP发生了接枝反应;泷变性能和熔体流动速率(MFR)测定表明,接枝反应有效地改善了PP流变性能,用双螺杆挤出机对未接枝和接枝的PP进行了发泡研究,SEM分析表明接枝PP具有更好的发泡效果。     

胍盐低聚物及其在聚丙烯中的热稳定性分析

将自制的胍盐低聚物(PHMG)分别以熔融共混和键合反应的方式引入到聚丙烯(PP)基体中.用透射电子显微镜(TEM)观察了两种不同引入方式下 PHMG 在 PP 基体中的分布,并用热重分析法(TGA)研究了它们的热分解特性.研究表明:PHMG 与 PP 的熔融共混由于两者之间极性相差较大,PHMG 倾向于以团簇的形式分布在 PP 基体中,分布不均匀,其共混物倾向于按PHMG、PP 各自的规律降解;但 PHMG 与 PP 进行键合后,PHMG 则均匀分布在 PP 基体中,PHMG 倾向于与 PP 同时降解.     

聚丙烯多相体系中β晶的研究进展

综述了近年来聚丙烯(PP)基多相体系,如PP/弹性体(橡胶)、PP/聚乙烯(PE)、PP/对苯二甲酸乙二脂(PET)、PP/聚酰胺(PA)等共混体系和PP/CaCO3、PP/滑石粉、PP/蒙脱土(MMT)以及PP与其它无机物的复合体系中聚丙烯β晶的研究进展,阐述了在这些聚丙烯基共混和复合体系中影响聚丙烯β晶生成的因素、聚丙烯β晶的生成机理以及聚丙烯β晶对多相体系结构和性能的影响,并对富含β晶的聚丙烯(PP)基多相体系的研究和应用的发展趋势进行了展望。     

等规聚丙烯离聚体增容聚丙烯/尼龙11共混体系研究

以碘代等规聚丙烯为大分子反应中间体,通过季胺化亲核取代反应和点击化学反应,制备了N-甲基咪唑聚丙烯离聚体(IA)和邻巯基苯胺盐酸盐聚丙烯离聚体(IB),并将其作为等规聚丙烯/生物基尼龙11 (i PP/PA11)共混体系的增容剂.通过动态力学分析(DMA)、扫描电镜(SEM)和力学性能测试,对i PP/PA11/聚丙烯离聚体三元共混体系的相形态与性能进行了系统研究. DMA测试结果显示,2种聚丙烯离聚体使i PP/PA11共混体系的玻璃化转变温度Tg相互靠近;SEM结果显示,离聚体的加入使分散相粒子尺寸显著减小,两相界面作用力增加;力学性能测试表明,i PP/PA11/IA、i PP/PA11/IB三元共混体系的拉伸强度和冲击强度保持较好的水平.以上研究结果表明,IA和IB均可以显著改善i PP/PA11共混体系的相容性.     

甲基丙烯酸缩水甘油酯/苯乙烯固相接枝聚丙烯

以苯乙烯(St)为共单体，过氧化苯甲酰(BPO)为引发剂，采用固相接枝反应将甲基丙烯酸缩水甘油酯(GMA)接枝到聚丙烯(PP)大分子链上。研究了反应时间、单体用量、引发剂用量等因素对接枝率的影响。采用凝胶渗透色谱(GPE)测定了PP和接枝物PP-g-(GMA-St)的分子量和分子量分布。结果 表明固相接枝PP反应条件为[GMA／[St]=2，反应3．5h，加入GMA 10份，BPO 5份。St的加入有助于GMA与PP的接枝，同时在一定程度上抑制了PP的降解。     

聚丙烯表面光氧化的XPS研究

利用X射线光电子能谱(XPS)研究了光氧老化的聚丙烯(PP)表面的化学结构和组成变化。结果表明:(1)在受光氧老化的PP表面上形成了C-O、C=O及O-C=O官能团;(2)低分子抗氧剂在PP表面发生富集;(3)表面Ols/Cls强度比率可以较好地与冲击强度保留率相关联。     

熔融-拉伸法制备亲水聚丙烯/聚乙烯醇缩丁醛中空纤维膜

以聚丙烯(PP)为基材,聚乙烯醇缩丁醛(PVB)为亲水改性剂,聚丙烯接枝马来酸酐(PP-g-MAH)为增容剂,通过熔融-拉伸法(MS-S)制备亲水PP/PVB中空纤维膜.采用差示扫描量热(DSC)和水接触角(WCA)测试考察了PVB添加量对PP/PVB共混物结晶行为及亲水性的影响;采用广角X射线衍射(WAXD)和小角X射线散射(SAXS)研究了PP/PVB中空纤维热处理后片晶微观结构;采用场发射扫描电镜(FESEM)观察了PP/PVB中空纤维膜内表面孔结构的变化,测试了PP/PVB中空纤维膜的孔隙率及纯水通量.研究结果表明,随着PVB含量的增加,PP/PVB共混物的WCA从103°降低到76°,表明PP/PVB共混物亲水性得到明显改善.同时,PVB可以起到异相成核作用,但由于MAH与PVB发生键合作用,过量添加PVB会阻碍PP分子链段运动,导致晶体结构不完善,这与WAXD和SAXS分析结果相同.PP/PVB2.5(PVB质量分数为2.5%)中空纤维膜热处理后结晶度、片晶取向度、厚度及Shish-kebab结构完善度均高于纯PP样品.对应膜孔隙率为66%,纯水通量达到320 L/(m2·h),比纯PP膜提高了76.8%.     

透明聚丙烯制备工艺技术研发进展

透明聚丙烯(PP)以其优异的光学和力学性吸引了越来越多研究者的重视。本文综述了透明PP制备工艺技术的研究发展状况,重点介绍了提高PP透明性的几种途径,阐述了成核剂增透、无规共聚、茂金属催化、共混改性等研究方法和研究进展。目前,透明聚丙烯制备工艺技术以齐格勒-纳塔催化剂无轨共聚PP和添加成核剂为主,茂金属催化PP为最理想的透明材料。同时展望了透明聚丙烯制备工艺技术发展的某些可能趋势。     

有机小分子对聚丙烯光氧老化的传染作用

以聚丙烯(PP)为研究对象, 选择代表典型小分子降解产物结构的酸、 酯、 醛、 酮和醇类共18种模型小分子, 研究有机小分子对PP光氧老化的传染作用. 研究发现, 所有的小分子都能不同程度地加速PP的光氧老化. 其中, 酸类、 醛类和酮类小分子的加速作用较强, 酯类和醇类小分子的加速作用较弱. 进一步研究了丙酮和乙酸对PP光氧老化的作用机理. 结果表明, 丙酮易光解产生甲基自由基, 通过引发PP氧化的方式加速其老化进程; 乙酸不具备引发能力, 通过催化氢过氧化物分解的方式促进PP中氧化产物的产生和积累.     

协效阻燃聚丙烯的阻燃性能

本文研究了以聚磷酸铵(APP)为主阻燃剂,次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MCA)为辅阻燃剂的协效阻燃体系对聚丙烯(PP)阻燃性能的影响。 采用垂直燃烧测试、极限氧指数(LOI)测试、热重分析、锥形量热仪测试、扫描电子显微镜分析等技术手段对所制备的阻燃样品进行了阻燃性能分析。 结果表明:单独添加任一质量分数30%阻燃剂,均不能使PP获得良好的阻燃性能;当阻燃剂总质量分数保持在30%,m(APP)：m(AHP)：m(MCA)=4：1：1时获得理想阻燃效果,此时阻燃PP的LOI为33%,垂直燃烧测试达到V-0级,热释放速率峰值(PHRR)从765.7 kW/m²降为122.7 kW/m²。     

Phase morphology, crystallisation behaviour and mechanical properties of isotactic polypropylene/high density polyethylene blends

The phase morphology, crystallisation behaviour and mechanical properties of isotactic polypropylene (iPP)/high density polyethylene (HDPE) blends were investigated. It was found that the properties are intimately related to each other. The morphology of the blends showed a two phase structure in which the minor phase was dispersed as domains in the major continuous matrix phase. The domain size of the dispersed phase increased with increasing concentration of that phase due to coalescence. It was also found that the domain size of the dispersed phase depends on the viscosity difference between the two phases. For a given HDPE/iPP blend, where HDPE is the matrix and iPP is the dispersed phase, the iPP domains were smaller than HDPE domains of the corresponding iPP/HDPE blend where iPP is the matrix and HDPE is the dispersed phase. A co-continuous morphology was observed at 50/50 PP/HDPE composition. Crystallinity studies revealed that blending has not much effect on the crystalline melting point of polypropylene and high density polyethylene. The crystallisation enthalpy and heat of fusion values of HDPE and PP in the blend were decreased as the amount of the other component increased. The variation in percent crystallinity of HDPE and PP in the blend was found to depend on the morphology of the blend. All the mechanical properties except Young's modulus and hardness showed negative deviation from the additivity line. This is due to the incompatibility of these blends.     

Effects of electron-beam irradation on some structural properties of granulated polymer blends

The aim of this article was to show the effects of the electron radiation dose and presence of a compatibiliser on the peak melting temperature (T_pm) of the crystalline phase, crystallinity (X_c), and melt flow rate (MFR) of granulated blends of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET) as well as of blends of LDPE, HDPE, and PP. The purpose of applying the high-energy electron radiation with doses up to 300 kGy and of adding a compatibiliser was to enhance mechanical properties of the studied blends and, at the same time, to investigate the possibility of using this technique in the processes of recycling polymeric materials. As the compatibilisers, the styrene–ethylene/butylene–styrene elastomer grafted with maleic anhydride (SEBS-g-MA) and trimethylol propane trimethacrylate (TMPTA) were utilised; they were added at the amounts of 5, 10, and 15 wt% and 1, 2, and 3 wt%, respectively. The enhancement of mechanical properties was accompanied by the following effects, discussed in this article: (i) a decrease in the peak melting temperature upon the electron radiation for the crystalline phase of LDPE, HDPE, and PP that constituted the studied granulated blends and (ii) changes in MFR upon both the electron radiation and the addition of compatibilisers.     

聚丙烯/聚乙烯共混物的辐射凝胶生成动力学研究

本文研究辐照PP/HDPE共混物的溶胶生成分数s与辐照剂量R的关系,结果表明适用于某些纯聚合物辐射交联规律的Charlesby-Pinner关系式和陈-刘-唐关系式皆不适用于PP/HDPE共混体系。张万喜等人曾研究过许多纯聚合物的辐射交联,提出裂解度正比于R~β的假定,β是与高分子结构相关的参数,这个假定可与大多数聚合物的辐射交联实验数据符合。同样的假定被应用于本文的共混体系,不同的是根据共混物结构特点对R~β项进行了必要的修正,即共混物的R~β=∑f_iR~(βI),其中f_i,β_i分别为共混物第i组分的重量分数及β值。用修正后的R~β处理辐照PP/HDPE共混物的实验数据,R(s+√s)～R~β,有很好的线性关系。     

动态硫化EPDM／PP共混体系中PP相的结晶度及晶体结构的研究

研究了动态硫化ＥＰＤＭ／ＰＰ共混物中ＰＰ相的结晶度及晶体结构,同时讨论了制备工艺条件以共混物中ＰＰ相的结晶度和晶体结构的影响。结果表明：在动态硫化ＥＰＤＭ／ＰＰ共混物中,硫化的ＥＰＤＭ的分子键没有穿入ＰＰ的晶区,ＰＰ的结晶度随ＥＰＤＭ含量的增加而下降。提高共混温度,加入软化剂或碳黑均使共混物中ＰＰ的结晶度降低,共混时间１５ｍｉｎ时,共混物中ＰＰ相的结晶度最低,但ＰＰ的晶格不受制备工艺条件的影响。     

原位聚合聚乙烯/蒙脱土纳米复合材料的结晶行为

用DSC研究了HDPE与MMT负载的催化剂熔融共混和原位聚合得到的两种纳米复合材料的熔融、 结晶行为和等温结晶动力学.  结果表明, HDPE与熔融共混样品的结晶度、 平衡熔点、 球晶生长速率和结晶能力大体相同; 原位聚合得到的HDPE/MMT纳米复合材料的结晶度和平衡熔点高于纯HDPE; 在相同过冷度条件下熔融结晶速率和结晶能力低于纯HDPE, 而在相同结晶温度Tc下, 熔融结晶速率和结晶能力则高于纯HDPE.  纯HDPE的晶体生长侧向单位面积表面自由能最小, 其次是熔融共混样品, 原位聚合样品最大, 且随ＭＭＴ含量的增加逐渐升高.     

Reversible Melting of Semi-Crystalline Polymers 2. Annealing Near to the Melting Point

Annealing experiments have been carried out at a few degrees below the melting point of different polyethylenes (LDPE, LLDPE, HDPE), of polypropylene (PP) and of Nylon-6. The heat capacities decrease during the annealing, within a 2-4 min time scale, to a lower value which corresponds to the extrapolated heat capacity values obtained for the cooling cycle when the polymer is cooled from the melt. Heat capacities in the heating cycle following the cooling cycle of PP, Nylon-6 and HDPE have the same value as during the cooling section. This is not the case for LDPE and LLDPE. Exothermic total heat flow in the cooling section following the annealing indicates that the crystallisation takes place during the cooling rather than during the annealing period. The total melting enthalpy measured before and after the annealing cycle is the same. The reversing heat flow shows an excellent fit to the change of the crystallinity measured by small angle scattering of synchrotron radiation during a heating cycle at temperatures below the melting peak. A coupled thermodynamic interaction of the crystalline and the amorphous phases is concluded from this study. This kind of interaction is possible at the lateral end of polymeric chains incorporated into the crystalline phase. This is an indication of the portion of tie molecules in the system, i.e. the portion of fringed micelle type of crystalline morphology with respect to that of folded chain lamellae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Raman,X-ray diffraction and differential scanning calorimetry studies of the melt-induced changes in uncompatibilized and compatibilized blends of high-density polyethylene and nylon 12

The crystallinity of non-molten and pre-molten uncompatibilized and compatibilized polymer blends of high density polyethylene (HDPE)/Nylon 12 have been investigated by using FT-Raman spectroscopy, differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD). The FT-Raman, DSC, and WAXD measurements have revealed that the crystallinity of HDPE of both uncompatibilized and compatibilized blends increases upon melting except for the compatibilized blend with the Nylon 12 content of 80 wt%. The degree of the increase is significantly larger for the uncompatibilized blends than the compatibilized blends. The FT-Raman data suggests that the crystallinity of the compatibilized blend with the Nylon 12 content of 80 wt% decreases slightly after melting. It is very likely that the compatibilized polymer blends are well oriented during the melting and molding process by an extruder because of the existence of maleic anhydride (MAH)-grafted copolymer as a compatibilizer. In contrast, it seems that the uncompatibilized polymer blends are not so much oriented and have more amorphous phase in the Nylon 12 rich region before melting. Thus, the melting process induces a recrystallization process.     

Evaluation of the SEBS copolymer in the compatibility of PP/ABS blends through mechanical,thermal, thermomechanical properties,and morphology

Polypropylene (PP) blends with acrylonitrile-butadiene-styrene (ABS) were prepared using the styrene-ethylene-butylene-styrene copolymer (SEBS) as a compatibilizing agent. The blends were prepared in a co-rotational twin-screw extruder and injection molded. Torque rheometry, Izod impact strength, tensile strength, heat deflection temperature (HDT), differential scanning calorimetry, thermogravimetry, and scanning electron microscopy properties were investigated. The results showed that there was an increase in the torque of PA6/ABS blends with SEBS addition. The PP/ABS/SEBS (60/25/15%) blend showed significant improvement in impact strength, elongation at break, thermal stability, and HDT compared with neat PP. The elastic modulus and tensile strength have not been significantly reduced. The degree of crystallinity and the crystalline melting temperature increased, indicating a nucleating effect of ABS. The PP/ABS blends compatibilized with 12.5% and 15% SEBS presented morphology with well-distributed fine ABS particles with good interfacial adhesion. As a result, thermal stability has been improved over pure PP and the mechanical properties have been increased, especially impact strength. In general, the addition of the SEBS copolymer as the PP/ABS blend compatibilizer has the advantage of refining the blend's morphology, increasing its toughness and thermal stability, without jeopardizing other PP properties.     

侧链液晶离聚物对PA1010/PP共混体系的增容作用

将聚酰胺（PA1010）、聚丙烯（PP）和热致型侧链液晶离聚物（SLCI）进行熔融共混，采用FTIR，SEM，DSC，WAXD研究测定了共混物中的相互作用，用形态结构，热行为和结晶行为，系统地研究了SLCI对PA101／PP共混物的增容作用。结果表明，SLCI有效地改善了PA1010／PP共混物的形态结构，增强了PA1010与PP链间的相互作用，使PA1010／PP熔点升高，结晶度提高。     

Solid-state relaxations in linear low-density (1-octene comonomer), low-density,and high-density polyethylene blends

Extensive thermal and relaxational behavior in the blends of linear low-density polyethylene (LLDPE) (1-octene comonomer) with low-density polyethylene (LDPE) and high-density polyethylene (HDPE) have been investigated to elucidate miscibility and molecular relaxations in the crystalline and amorphous phases by using a differential scanning calorimeter (DSC) and a dynamic mechanical thermal analyzer (DMTA). In the LLDPE/LDPE blends, two distinct endotherms during melting and crystallization by DSC were observed supporting the belief that LLDPE and LDPE exclude one another during crystallization. However, the dynamic mechanical β and γ relaxations of the blends indicate that the two constituents are miscible in the amorphous phase, while LLDPE dominates α relaxation. In the LLDPE/HDPE system, there was a single composition-dependent peak during melting and crystallization, and the heat of fusion varied linearly with composition supporting the incorporation of HDPE into the LLDPE crystals. The dynamic mechanical α, β, and γ relaxations of the blends display an intermediate behavior that indicates miscibility in both the crystalline and amorphous phases. In the LDPE/HDPE blend, the melting or crystallization peaks of LDPE were strongly influenced by HDPE. The behavior of the α relaxation was dominated by HDPE, while those of β and γ relaxations were intermediate of the constituents, which were similar to those of the LLDPE/HDPE blends. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1633–1642, 1997