原位固相接枝改性碳酸钙/聚丙烯复合材料的制备

用马来酸酐（MAH）在碳酸钙（CaCO3）表面引入双键,通过原位固相接枝法将聚丙烯蜡（PPW）化学键合在CaCO3表面,制得3种接枝率的CaCO3-MAH-PPW。 将这3种改性CaCO3填充聚丙烯（PP）制备复合材料,研究了PP/CaCO3界面作用对复合材料强度的影响。 结果表明,CaCO3表面经PPW接枝改性后在PP中的分散性提高,与PP相容性变好;随着改性CaCO3表面PPW接枝率的提高,CaCO3与PP之间界面作用逐渐增强。 当PPW接枝率为4.48 mg PPW/g CaCO3时,CaCO3与PP之间的界面作用最强,复合材料拉伸强度下降最小,杨氏模量提升最大,当m(PP)∶m(CaCO3)=100∶50时,杨氏模量达0.86 GPa,是纯PP的1.63倍;而PPW化学接枝率为2.49 mg PPW/g CaCO3时,CaCO3与PP之间的界面作用适中,复合材料缺口冲击强度提升最大,且当m(PP)∶m(CaCO3)=100∶10时,缺口冲击强度达3.91 kJ/m2,是纯PP的1.35倍。     

PP-g-(MAH/St)和PP-g-MAH对聚丙烯/木粉复合材料性能的影响

在转矩流变仪中用熔融接枝法制备马来酸酐(MAH)和苯乙烯(St)接枝聚丙烯（PP）-PP-g-(MAH/St)和PP-g-MAH,将其作为聚丙烯/木粉复合材料的相容剂。 FTIR证实MAH和St单体与PP发生接枝反应。 用SEM和DSC等手段考察两种相容剂对PP/木粉复合材料微观形貌和结晶性能的影响,探索了各种PP/木粉复合材料加工和力学性能不同的内在原因。 SEM显示,PP-g-(MAH/St)改性木粉比PP-g-MAH改性木粉在PP基体中分散性更佳,木粉与PP的界面更加模糊,相容性进一步改善。 DSC结果表明,PP-g-(MAH/St)改性体系可增强木粉对PP的异相成核作用,提高结晶温度和结晶度。 复合材料的加工和力学性能测试结果表明,PP-g-(MAH/St)改性效果明显优于PP-g-MAH。 复合材料的熔体质量流动速率随相容剂用量的增加而逐步下降,PP-g-(MAH/St)改性体系拉伸强度和弯曲强度却逐步上升,并在相容剂用量为4.8 g/100 g PP时达到极值。 此时其拉伸强度达40.62 MPa,分别是未改性体系和PP-g-MAH改性体系的1.29和1.17倍;其弯曲强度达45.72 MPa,分别是未改性体系和PP-g-MAH改性体系的1.23和1.59倍;而无缺口冲击强度却在相容剂用量为3.6 g/100 g PP时达到极值13.35 kJ/m2,分别是未改性体系和PP-g-MAH改性体系的1.62倍和1.42倍。     

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.     

马来酸酐化1,2-聚丁二烯熔融接枝聚丙烯木塑复合材料相容剂的研究

采用熔融接枝法,将马来酸酐化1,2-聚丁二烯(MAPB)在过氧化二异丙苯(DCP)的存在下接枝到聚丙烯(PP)上。使用傅里叶变换红外光谱(FTIR)、热重分析(TG)和差示扫描量热(DSC)法对接枝产物进行表征,将其作为木塑复合材料(WPCs)界面相容剂,以复合材料力学性能为指标对接枝工艺配方进行评价。结果表明:MAPB可以与PP发生接枝反应,并且MAPB的加入能够提高PP的结晶温度和热稳定性。当接枝反应温度为180℃,质量比m(MAPB)∶m(PP)∶m(DCP)=13∶37∶0.2时,所制得的接枝产物对木塑复合材料力学性能提高有最好的效果,以此来确定MAPB-g-PP的工艺配方。     

PP/PP-g-MAH与铝板粘接界面相的XPS研究

用X射线光电子能谱(XPS)研究铝板/聚丙烯层状复合材料的粘接界面相，提出了粘接界面的化学反应机制.研究发现,聚丙烯(PP)中加入马来酸酐接枝聚丙烯(PP-g-MAH)时，铝板面上Al 2p、O 1s谱线明显向高结合能端移动，表明PP-g-MAH与铝板表面发生了化学反应，形成Al－O－C配位键.配位键的形成使界面粘接强度明显提高. PP中不含PP-g-MAH时，铝板面上Al 2p、O 1s谱线处于低结合能端，聚丙烯未与铝板表面形成化学配位作用.     

超支化聚乙烯亚胺接枝二氧化硅的制备及在聚丙烯改性中的应用

首先利用3-缩水甘油氧基丙基三甲氧基硅烷(简称GPS)作为偶联剂,对纳米SiO2进行表面改性,获得表面含有环氧基的SiO2纳米粒子(SiO2-GPS).利用这些环氧基与超支化聚乙烯亚胺(HPEI)分子中的氨基进行反应,得到SiO2接枝超支化聚乙烯亚胺的纳米粒子(SiO2-GPS-g-HPEI).然后利用SiO2-GPS-g-HPEI与聚丙烯(PP)和PP接枝的马来酸酐(PP-g-MAH)共混、模压,制备PP/SiO2-GPS-g-HPEI/PP-g-MAH复合材料.红外光谱测试和热失重分析(TGA)测试结果表明,SiO2纳米粒子表面依次接枝了GPS和HPEI;扫描电子显微镜(SEM)的测试结果显示,SiO2-GPS-g-HPEI在聚丙烯基体中分散良好,其材料的冲击断裂为韧性断裂;复合材料共混时,扭矩的增加证明了共混物中分散相(SiO2-GPS-g-HPEI)与基体(PP/PP-g-MAH)界面之间存在一定的相互作用.少量SiO2-GPS-g-HPEI加入PP/PP-g-MAH中,冲击强度可增加96.3%,拉伸强度也有较大的提高.     

双单体原位接枝插层法制备聚丙烯纳米复合材料的研究Ⅰ.制备、表征及力学性能的研究

用有机插层剂处理蒙脱土原土 ,制得有机蒙脱土 (O MMT) .采用双单体 (马来酸酐和苯乙烯 )原位接枝插层法 ,制备了聚丙烯 蒙脱土纳米复合材料母料 .将母料与聚丙烯基体在双螺杆上共混挤出 ,制得聚丙烯 蒙脱土纳米复合材料 (PP Montmorillonetenanocomposites,PMNC) .这是制备聚合物纳米复合材料的一种新方法 .通过X 射线衍射测试 (XRD)表明 ,有机蒙脱土片层 0 0 1面间距从原土的 1 4 9nm扩大到 2 96nm ,复合材料中蒙脱土片层 0 0 1面间距由有机蒙脱土的 2 96nm扩大到 4 0nm .力学性能测试表明 ,复合材料的力学性能明显优于PP基体 ,在提高材料拉伸强度的同时 ,缺口冲击强度也得到很大的提高 .用扫描电镜 (SEM)对材料的冲击断面形貌进行了研究 ,并从理论上分析了断裂机理 .随着蒙脱土含量的增加 ,冲击断裂形式逐渐从脆性断裂变成韧性断裂     

大分子相容剂改性Mg(OH)2/PP阻燃材料的性能

用双螺杆挤出机熔融挤出法制备了相容剂改性氢氧化镁/聚丙烯[Mg(OH)2/PP]阻燃材料。研究了马来酸酐接枝聚丙烯(PP-g-MA),马来酸酐接枝(乙烯/辛烯)共聚物(POE-g-MA)和马来酸酐接枝聚醋酸乙烯酯(EVA-g-MA)3种大分子相容剂对阻燃材料的熔体流动性、结晶行为、力学性能和断口形态的影响。结果表明:相容剂PP-g-MA和POE-g-MA的加入使阻燃材料的熔体流动速率降低,PP结晶温度提高,EVA-g-MA的加入使阻燃材料熔体流动速率数提高;Mg(OH)2对PP结晶存在异相成核作用,Mg(OH)2的加入使PP的冲击强度、拉伸强度和断裂伸长率降低,杨氏模量提高;相容剂改性后Mg(OH)2/PP阻燃材料的拉伸强度提高,其中以PP-g-MA最为明显,而POE-g-MA则提高了阻燃材料的冲击强度。     

马来酸酐接枝聚丙烯的改性方法及其应用

马来酸酐(MAH)是聚丙烯改性中最常用的极性单体,在连续反应中酸酐基呈现很高的活性,反应产物热稳定性良好,可被应用于合金,塑料等材料的生产。随着各种技术的广泛应用,马来酸酐接枝聚丙烯改性方法得到了快速的发展。各种马来酸酐接枝聚丙烯的改性方法有:溶液接枝法、熔融接枝法、固相接枝法和辐射接枝法。文章阐述了马来酸酐接枝聚丙烯改性方法的研究现状及其产物在不同领域的应用。     

聚丙烯/石墨导电纳米复合材料的制备与性能

用溶液插层及其与熔体混合相结合的母料熔体混合 (MMM)方法制备了聚丙烯 (PP) 马来酸酐接枝聚丙烯 (gPP) 膨胀石墨 (EG) (gPP EG =3 2wt)导电纳米复合材料 ,其室温逾渗阀值 (c)分别为 6wt%和 8wt % ,明显低于直接熔体混合制得复合材料和PP EG对照材料的c=11wt%和 12wt% .增加gPP含量 (Cg)能提高复合材料的电导率 (σ) ,例如对于MMM法制备的复合材料 ,固定PP gPP =1 1wt时 ,c 降为 7wt% ;保持EG含量 =9wt%时 ,σ在Cg>30wt %后跃升 7个数量级以上 .通过TEM、SEM和OM观察 ,从制备方法、EG和gPP含量影响复合材料形态和微结构的角度 ,分析说明了出现上述差异和现象的原因 .     

Effect of functionalization on non-isothermal crystallization behavior of polypropylene

The non-isothermal crystallization kinetics of three functionalized polypropylenes (PPs; polypropylenes-g-acrylic acid [PP-g-AA], polypropylenes-g-glycidyl methacrylate [PP-g-GMA], polypropylenes-g-maleic anhydride [PP-g-MAH]) at different cooling rates were investigated by differential scanning calorimetry, using the Jeziorny method, Ozawa method, and Mo method. The result showed that Mo method can adequately describe the non-isothermal crystallization kinetics of pure PP and functionalized PPs, and at a given relative crystallinity, the crystallization rate obtained using Mo method followed an order of PP-g-AA > PP-g-GMA > PP > PP-g-MAH. The crystallization activation energy for these samples was calculated using Kissinger's method, which indicated that the introduction of monomers had a confinement effect on the motion of PP chains.     

等规聚丙烯β晶型向α晶型的相转变行为研究进展

等规聚丙烯(iPP)是典型的多晶型半结晶性聚合物,其常见晶型有单斜(α),三方(β),三斜(γ)以及四方或双四方(e),其中稳定性最好的α晶型和处于亚稳态的β晶型工业和经济价值较大,因此二者之间的相转变行为得到了人们的广泛关注.本文综述了近年来β→α-iPP生长相转变的研究进展.在高临界温度(141°C)和低临界温度(100°C)区间内,β-iPP生长速率高于α-iPP,而温度高于141°C,或低于100°C,由于α-iPP在动力学上占优势,β-iPP会发生向α-iPP的生长转变.但由于α-iPP是热力学上最稳定的晶型,β-iPP熔融重结晶过程也会发生β→α-iPP相转变.此外,拉伸形变过程中也会发生β→α-iPP相转变,广泛用于制备聚丙烯气体交换膜、过滤膜或锂电池隔膜等.目前对变形过程中的β→α-iPP相转变机理还存在争议,本文也对2种主要的机理进行了介绍,并对聚丙烯晶型转变行为的研究方向进行了展望.     

Modeling Study on Effects of Liquid Propylene in Horizontally Stirred Gas-Phase Reactors for Polypropylene

Modeling study was carried out for JPP-HORIZONE, which has horizontally stirred gas reactors in which the heat of polymerization is removed by vaporization of liquid propylene (LPP). The effects of LPP were estimated by the model which has a couple of continuous stirred bed reactors different in propylene form, gas of liquid, combined with a less stereospecific catalyst as a probe. LPP affects isotacticity further than catalyst efficiency in the developed model. Observed isotacticity was lower than that estimated by the model without LPP, which can be explained only by the presence of LPP.     

Macromorphology of polypropylene homopolymer tacticity mixtures

The macromorphology of isotactic/atactic (iPP/aPP) and isotactic/syndiotactic (iPP/sPP) polypropylene mixtures is examined by optical microscopy. The spherulitic macrostructure of equimolecular weight [weight‐average molecular weight (M_w) = 200k] iPP/aPP blends is volume‐filling to very high aPP concentrations when the crystallization temperature is 130 °C. Similar spherulitic macrostructures (spherulite size and volume‐filling nature) are observed for iPP homopolymer and a 50/50 iPP/aPP blend at low crystallization temperatures (115–135 °C). At higher crystallization temperatures (140–145 °C), a equimolecular weight (M_w = 200k) 50/50 iPP/aPP blend exhibits nodular texture that blurs the spherulitic boundaries. Double temperature jump experiments show that the nodular texture is due to melt phase separation that develops prior to crystallization. The upper critical solution temperature (UCST) of a 50/50 iPP/aPP blend (M_w = 200k) lies below 155 °C, and the blend is miscible at conventional melt processing temperatures. The UCST behavior is controlled by the blend molecular weight and aPP microstructure. aPP microstructures containing increased isospecific sequencing (although still noncrystalline) exhibit a reduced tendency for phase separation in 50/50 mixtures (M_w = 200k) and the absence of nodular texture at low undercoolings (140–145 °C). Equimolecular weight (M_w = 200k) 50/50 iPP/sPP mixtures exhibit phase‐separated texture at all crystallization temperatures. The size scale of the phase‐separated texture decreases with decreasing crystallization temperature because of a competition between crystallization and phase separation from a melt initially well mixed from the initial solution blending process. Extended melt annealing experiments show that the 50/50 iPP/sPP mixture (M_w = 200k) is immiscible in the melt at conventional melt processing temperatures. The iPP/sPP pair shows a much stronger tendency for phase separation than the iPP/aPP polymer pair. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1947–1964, 2000     

Crystallization of oriented smectic polypropylene I. Thermally induced crystallization

The crystallization induced by thermal treatments of smectic polypropylene fibres has been studied. Analysis was carried out detecting the density and X-ray diffractograms. Density and diffraction data disagree on two important aspects: the critical temperature necessary to activate the crystallization process, and the effects of annealing time on the growth process. The first point seems to suggest that the observed densification at the lower temperatures is related to phenomena differing from a crystallization process, while the observed effects of the annealing time can be explained by assuming that the anisotropy of the fibre structure induces anisotropy in the phase transition and growth process. On the other hand, density and diffraction data agree in indicating that the rate and degree of crystallization increase on increasing the crystallization temperature.     

Single-Ionic Conductivityin Poly(Sodium 2-Methacryloyl 3-[Ω-Methoxyl Oligo(Oxyethylene)]Propylsulfonate)

Abstract

Sodium 2-methacryloyl 3-[ω-methoxyl oligo(oxyethylene)] propylsulfonate was synthesized, from which homopolymer-based polyelectrolyte was prepared. The polyelectrolytes thus obtained show single Na⁺ionic conductivity at ambient temperature, neither adding plasticizer nor hybridizing small molecular salt. The conductivity depends considerably on the length of oligo(oxyethylene) side-chain. Optimally, the highest conductivity of 6.0 × 10^?6 S/cm at 25°C is obtained when the number of (CH₂CH₂O) repeating units equals 16. Results indicate that the conductivity data follow WLF and VTF equations. The WLF parameters are found to be comparable with “universal” values, and analysis of the configuration entropy model suggests that the conduction of Na⁺ ions is carried out by an association mechanism.     

Surface Modification of Polypropylene by Ethylene Plasma and Its Induced β-Form in Polypropylene

This study aims to investigate the chemical structure and morphology of plasmapolymers produced by deposition of ethylene on the surface of polypropylene. The deposition films(sediments) of ethylene plasma on the surface of polypropylene are nonuniform, and the characterization results indicate the existence of hydroxyl groups and aldehyde(or ketone) groups in the sediments. The sediment of ethylene plasma on the polypropylene surface could induce the growth of β-form crystals in the surface layer of polypropylene.     

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。     

The influence of thermoelastomers on the crystallization behavior of isotactic polypropylene under shear

The crystallization behaviors of isotactic polypropylene (iPP) and its blends with thermoelastomers have been investigated with in situ X‐ray scattering and optic microscopy. At quiescent condition, the crystallization kinetics of iPP is not affected by the presence of elastomers; while determined by the viscosity, the differences are observed on sheared samples. With a fixed shear strain, the crystallization rate increases with increasing the shear rate. The fraction of oriented lamellar crystals in blends is higher than that in pure iPP sample, while the percentage of β phase is reduced by the presence of the elastomers. On the basis of experimental results, no direct correlation among the fraction of oriented lamellae, the percentage of β phase, and growth rate can be deduced. The evolution of the fraction of oriented lamellae supports that shear field promotes nucleation rather than growth process. Shear flow induces the formation of nuclei not only with preferring orientation but also with random orientation. The total density of nuclei, which determines the crystallization kinetics, does not control the ratio between nuclei with and without preferring orientation, which determines the fraction of oriented lamellae. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1188–1198, 2006