长支链聚丙烯诱导β晶成核效应

利用乙烯基聚二甲基硅氧烷/苯乙烯接枝型长支链聚丙烯(PP-g-VS/St)在剪切和快速降温过程中可以诱导形成β晶聚丙烯这一优势,研究了PP-g-VS/St在注塑加工过程中作为高分子β晶成核剂对等规聚丙烯(iPP)结晶温度、晶体结构及力学性能的影响。结果表明改性聚丙烯的结晶温度、β晶相对含量和力学性能随着PP-g-VS/St添加量的增加而增加。当PP-g-VS/St的添加量为50%(质量分数)时,改性聚丙烯的结晶温度相对于纯iPP提高约10℃,β晶相对含量达32.8%,冲击强度、弯曲模量和拉伸强度分别相对于纯iPP提高了355.3%、53.8%和15.9%。这些结果为聚丙烯高分子β晶型成核剂的设计提供了新思路。     

纳米ZnO对等规聚丙烯结晶的异相成核作用

采用熔融共混法制备了nano-ZnO/等规聚丙烯(iPP)复合材料,研究了振荡剪切条件下nano-ZnO对iPP结晶的异相成核作用,并与其静态结晶行为作对比。结果表明:静态结晶下,当nano-ZnO质量分数大于5%时,nano-ZnO对iPP结晶有明显的异相成核作用,使iPP结晶温度大幅度提高,相容剂PP接枝马来酸酐(PP-g-MAH)的加入增强了nano-ZnO粒子与iPP基体的界面相互作用,改善了纳米粒子的分散性,促进了iPP基体的异相成核。振荡剪切作用下,降低结晶温度和加入nano-ZnO均能促进iPP成核,当nano-ZnO质量分数大于3%后,异相成核达到饱和,振荡剪切对nano-ZnO/iPP复合材料存在显著的诱导结晶作用;加入PP-g-MAH后,nano-ZnO分散性的改善及其与iPP基体界面相互作用的加强使得nano-ZnO/iPP复合材料的结晶诱导时间明显缩短。     

双单体固相接枝聚丙烯的制备与应用

以马来酸酐(MAH)/苯乙烯(St)双单体固相接枝聚丙烯(PP)制备了PP-g-MAH/St接枝物,采用正交试验确定最佳工艺条件,并通过傅里叶变换红外光谱仪、核磁共振谱仪、差式扫描量热仪和X射线衍射仪对接枝物的结构和性能进行了表征和分析。结果表明,最佳接枝工艺条件为:反应温度120℃,反应时间1 h,n_(St)/n_(MAH)=1.2∶1(摩尔比),m_(MAH)/m_(PP)=0.14,m_(BPO)/m_(PP)=0.02(质量比);接枝前后PP的晶型保持不变,均为α晶,但是PP结晶度降低,结晶温度则有所提高;作为相容剂,PP-g-MAH/St可显著提高PP复合材料的冲击强度。     

PTT/PP共混物的性能研究

通过熔融共混制备了聚对苯二甲酸丙二酯/聚丙烯(PTT/PP=75/25)及其马来酸酐接枝PP(PP-g-MAH)增容共混物,研究了PTT/PP及其增容共混物的结晶性能、力学性能、流变性能和结晶形态。研究结果表明,PTT与PP共混能提高PP、PTT组分的结晶温度;对于增容共混物,随PP-g-MAH用量的增加,PP和PTT的结晶温度基本不变。加入PP使PTT拉伸强度降低,冲击强度提高;PP-g-MAH增容使共混物的拉伸和冲击强度都提高。增容共混物的熔体粘度明显降低,存在明显的剪切变稀现象,但熔体粘度与PP-g-MAH用量无关。在一定用量范围内,随PP-g-MAH用量的增加,PP分散相的尺寸变小。     

双单体接枝聚丙烯的制备及性能研究

研究了以苯乙烯（St）为共聚单体,聚丙烯（PP）熔融接枝丙烯酸（AA）的反应工艺。探讨了AA、共聚单体及引发剂用量等因素对接枝反应的影响。通过FTIR分析证实,AA和St接枝到PP链上形成PP-g-AASt接枝物,并且随着引发剂DCP用量的增大,接枝率呈现先升后降的趋势。通过TGA、WAXD及DSC等方法表征了接枝物的热性能和结晶性能。结果表明,随着接枝产物的接枝率的提高,其分解温度及最大失重率温度先上升,维持一段后再下降。而AA和St主要接枝在PP表面上,未破坏原来的晶型,少量的AA有利于结晶成核,提高结晶度。     

聚丙烯固相接枝物增容PA6/PS共混体系

采用FTIR和WAXD研究了聚丙烯固相接枝苯乙烯（St)和马来酸酐（MAH）的结构，并研究了它对聚酰胺6／聚苯乙烯（PA6／PS）共混体系力学性能的影响及其非等温结晶动力学，研究结果表明，PP上可固相接枝St,MAH;gPP(PP接枝St和MAH双组分接枝物）增容PA6／PS的非等温结晶动力学与MandelKern理论基本吻合。     

双单体固相接枝制备亲水性PP

研究了以苯乙烯(St)为共聚单体、聚丙烯(PP)固相接枝丙烯酸(AA)的反应工艺。探讨了反应时间、温度、共聚单体用量及引发剂用量等因素对接枝反应的影响。通过FTIR分析证实,AA和St确实接枝到PP链上形成PP-g-(St-AA)接枝物,并采用水接触角方法表征了接枝物的亲水性能。结果表明,当反应温度为120℃、反应时间为90min,PP∶AA∶St∶BPO(过氧化苯甲酰)质量比为100.0∶10.0∶2.0∶0.4时,可获得AA最大接枝率为4.46%。与相同试验条件下,未加入St的PP固相接枝AA体系相比,提高了2.32%,水接触角由81.3°减小到76.4°,亲水性能得到进一步改善。     

苯乙烯/二乙烯苯协助马来酸酐熔融接枝聚丙烯研究

采用液-固溶胀的方法将马来酸酐(MAH)、共单体[苯乙烯(St)、二乙烯苯(DVB)]和引发剂过氧化二异丙苯分散到聚丙烯(PP)颗粒内部,利用流变仪研究了共单体协助MAH熔融接枝PP反应,采用红外光谱、热重分析和水接触角对接枝物的结构及性能进行分析,并对接枝反应机理加以探讨。结果表明,在最优反应条件下,添加St时接枝物的MAH接枝率和凝胶率分别为2.25%、1.56%;添加DVB时接枝物的MAH接枝率和凝胶率分别为3.06%、46.31%,并且接枝物的热稳定性和极性均有不同程度提高;接枝机理分析认为,在接枝反应时共单体首先接枝到PP链上,有效抑制了PP的降解,并与MAH主要以共聚形式接枝到PP主链上;DVB在分子结构上比St多了一个碳碳双键,一方面显著提高MAH接枝率,另一方面明显增大接枝PP大分子自由基间双基偶合终止的机会。     

乙烯基硅烷/苯乙烯接枝聚丙烯的结晶和力学性能

研究了乙烯基硅烷（VS）和苯乙烯（St）双单体接枝聚丙烯（PP-g-VS/St）的结晶性能和力学性能。结果表明,长支链的引入使PP-g-VS/St的结晶峰值温度和熔融峰值温度相对于线形等规聚丙烯（iPP）分别提高了10、2 ℃,且球晶得到了细化; PP-g-VS/St在10 ℃/min的降温速率下结晶产生的晶型为α晶型与少量γ晶型的混合物;在注塑条件下结晶产生的晶型为α晶型与β晶型的混合物; 利用莫志深法研究PP-g-VS/St的非等温结晶动力学过程发现,在结晶的早期和后期,长支链对PP-g-VS/St的结晶分别起到了加速成核和阻碍生长两种相反的作用;相对于iPP,PP-g-VS/St的拉伸强度、弯曲模量和冲击强度分别提高了29 %、40 %和453 %。     

PP-g-GMA的制备及其改性PP/PA6合金性能

采用双螺杆熔融接枝的方法,在引发剂过氧化二异丙苯(DCP)作用下,将甲基丙烯酸缩水甘油酯(GMA)和共单体苯乙烯(St)接枝到聚丙烯(PP)上。通过傅立叶变换红外光谱仪确定了接枝物的生成,采用酸碱滴定法测定了接枝率。探讨了GMA,St,DCP不同用量对PP接枝物的接枝率和熔体流动速率的影响,并将接枝产物PP–g–(St–co–GMA)加入PP/尼龙6(PA6)的合金中,通过注塑成型样条,测定其力学性能,并观察微观结构。结果表明,St的加入能够提高接枝率,抑制副反应的发生。在PP/PA6合金中加入接枝物PP–g–(St–co–GMA),其拉伸强度可提高46.45%,弯曲强度可提高32.47%,但对冲击强度影响不大。     

The effect of polypropylene/polyamide 66 blending modification on melt strength and rheologic behaviors of polypropylene

Common linear polypropylene (PP) was modified by blending with polyamide 66 (PA66) under the act of compatibilizer in a twin-screw extruder in an attempt to improve the melt strength (MS) of PP. The MS of pure PP and modified PPs were measured by MS testing unit at three temperature of 190, 210, and 230 °C, and the MS improvement of PP was verified. The MS of the modified PPs increased with increasing the content of PA66. The steady- and dynamic-shear rheological behaviors of pure PP and modified PPs were investigated using a capillary rheometer and a parallel-plate rotating rheometer. The steady-shear rheological analysis results revealed that modified PPs had higher melt shear viscosity, stronger non-Newtonian behaviors, and higher zero shear-rate viscosity. The dynamic-shear rheological analysis showed modified PPs had higher melt complex modulus and smaller phase angle, which indicated that the melt viscosity and melt elasticity of PP were also enhanced. The modified PPs was characterized by DSC. DSC results revealed that the PA66 phase and PP phase of the modified PPs were in state of crystallization. The enhancement of MS, melt viscosity, and melt elasticity of modified PPs could be due to undisaggregated PA66 crystallization phase within the melt of PP blends.     

Preparation and foamability of high melt strength polypropylene based on grafting vinyl polydimethylsiloxane and styrene

A novel strategy was developed by melt grafting reaction in the presence of macromonomer vinyl polydimethylsiloxane (VS) and comonomer styrene (St) for preparing high melt strength polypropylene (HMSPP), and the rheological behavior, melt strength, and foaming ability of HMSPP were investigated. The results showed that VS and St were successfully grafted onto isotactic polypropylene (iPP), and the melt strength of HMSPP increased by more than 12 times compared to that of the virgin iPP. Moreover, HMSPP exhibited excellent foaming ability with smaller cell size, higher cell density, and higher expansion ratio compared to the virgin iPP when supercritical carbon dioxide was used as the blowing agent. POLYM. ENG. SCI., 55:251–259, 2015. © 2014 Society of Plastics Engineers     

马来酸酐及苯乙烯同时接枝聚丙烯的研究

用过氧化二异丙苯(DCP)作为引发剂，采用双螺杆反应挤出的苯乙烯、马来酸酐2种单体同时接枝聚丙烯．研究了单体总浓度、单体比例、引发剂浓度对PP的接枝率、接枝效率和熔体流动速率的影响。通过实验发现苯乙烯的加入使接枝率和接枝效率比单独的马来酸酐接枝都有很大的提高。     

山梨醇类成核剂对改性聚丙烯发泡性能的影响

以过氧化苯甲酰（BPO）为引发剂,经熔融挤出过程将苯乙烯（St）接枝到等规聚丙烯（iPP）上,同时加入山梨醇类成核剂［1,3:2,4二（对甲基卞叉）山梨醇,MDBS］,制备可发泡的iPP,并考查MDBS在其发泡过程中所起的作用。结果发现,St接枝到iPP上,降低了iPP的熔体流动速率,即提高了其熔体强度;在发泡过程中,MDBS起固定泡孔和泡孔成核的作用,使iPP泡沫具有规则完整的泡孔结构,且泡孔密度从纯iPP的1.1×10^7个/cm3增加到1.2×10^8个/cm3,适宜发泡温度范围拓宽至150~160 ℃。     

Melt rheology of polypropylene reinforced with polyaniline‐coated short glass fibers

This research deals with the melt rheology of isotactic polypropylene (iPP) reinforced with short glass fibers (SGF) coated with electrically conductive polyaniline (PAn). Composites containing 10, 20, and 30 wt % PAn‐SGF were studied. Moreover, a composite of 30 wt % PAn‐SGF was also prepared with a blend of iPP and PP‐grafted‐maleic anhydride (iPP/PP‐gMA). The composites showed linear viscoelastic regime at small strain amplitudes. The onset of nonlinearity decreased as the concentration of filler increased. The time‐temperature superposition principle applied to all composites. The filler increased the shear moduli (G′, G″) and the complex viscosity η*. Steady‐state shear experiments showed yield stress for the composites with 20 and 30 wt % PAn‐SGF. Strikingly, the 10 wt % composite showed higher steady state viscosity than the 20 wt %. Rheo‐optics showed that shear induced disorder of microfibers at a concentration of 10 wt %. However, at 20 wt % concentration shear aligned the microfibers along the flow axis, this would explain the anomalous steady state viscosity values. The viscosity exhibited a shear thinning behavior at high shear rates for all composites. Creep experiments showed that the filler induced greater strain recovery in the composites and that the amount of strain recovery increased as the PAn‐SGF concentration increased. However, the enhancement of strain recovery (as well as shear viscosity) was more significant when using the iPP/PP‐gMA blend, suggesting greater adhesion between this matrix and the filler PAn‐SGF. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Shear amplification and re-crystallization of isotactic polypropylene from an oriented melt in presence of oriented clay platelets

In this study, we first prepared isotactic Polypropylene (iPP)/organoclay nanocomposite specimens via twin-screw extruder and by adding compatibilizer (maleic anhybride grafted PP). Then PP and the composites were subjected to dynamic packing injection molding, in which the melt was firstly injected into the mold then forced to move repeatedly in a chamber by two pistons that moved reversibly with the same frequency as the solidification progressively occurred from the mold wall to the molding core part. The dispersion and orientation of layered organoclay in the nanocomposite were estimated by transmission electron microscopy (TEM) and 2d-wide angle X-ray scattering (2d-WAXS). A much higher degree of orientation of PP was found in the composites compared with the pure PP. This was explained by so called shear amplification in that a great enhancement of local stress occurred in the small interparticles region of two adjacent layered tactoids with different velocities. Furthermore, re-crystallization of isotactic polypropylene (iPP) by melting the dynamic packing injection molded samples has been investigated by polarizing light microscopy (PLM). A highly oriented threadlike crystallites was observed for the first time when crystallization occurs by melting the dynamic packing injection molded samples at 180 °C. However, spherulitic morphology is always obtained once PP crystallizes from an isotropic melt by melting the samples at 200 °C. The shear amplification mechanism and the formation mechanism of oriented threadlike crystallites have been discussed in detail.     

Study of multi‐monomer melt‐grafting onto polypropylene in an extruder

Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry     

Rheology and thermal behavior of long branching polypropylene prepared by reactive extrusion

Long‐chain branching polypropylene (LCB‐PP) was achieved by reactive extrusion in the presence of bifunctional monomer [1,6‐hexanediol diarylate (HDDA)] and peroxide of dicumyl peroxide (DCP). Influences of HDDA and DCP concentrations on the branching efficiency were comparatively evaluated. Fourier transformed infrared spectroscopy (FTIR) results indicated that the grafting reaction took place, and HDDA has been grafted on PP skeleton. In comparison with initial PP, some modified samples showed lower melt flow index because of a large number of LCB in their skeleton. Several rheology plots were used to investigate the rheological properties of the initial PP and modified PPs, and the rheological characteristics confirmed the LCB in modified PPs skeleton. DSC results showed that the crystallization temperatures of modified PPs were higher than those of initial PP and degraded PP, suggesting that the modified PPs had long‐chain branched structure. The contrastive investigation in the rheology of modified PPs suggested that proper concentrations of HDDA and DCP were more beneficial to producing LCB during reactive extrusion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

季铵盐类阳离子单体接枝聚丙烯及其性能研究

以甲基丙烯酞氧乙基三甲基氯化铵 ( DMC)、苯乙烯(St),聚丙烯(PP)为原料,采用多单体熔融接枝的方法,制备了含季铰盐基团的功能化的聚丙烯。考察了几种反应因素对接枝反应的影响,测试了接枝物的力学性能,利用示差扫描量热仪、偏光显微镜研究了接枝产物的结晶性能。结果表明:引发剂过氧化二异丙苯(DCP)用量为0.6份时,DMC与St的物质的量之比为1:1时,DM《的接枝效果最佳,与纯PP相比,其拉伸强度、冲击强度基本不变,晶核密度大幅增加,总结晶速率加快,半结晶时间((tm)缩短,结晶温度(Tc)提高。     

Rheological properties of metallocene isotactic polypropylenes

Rheological properties of metallocene‐catalyzed isotactic polypropylenes (MET‐PP) were evaluated in comparison with those of Ziegler–Natta‐catalyzed isotactic polypropylenes (ZN‐PP) and MET‐PP was generally characterized in a rheological aspect. Based on the characterization, various flow processibilities and their effect on the higher order structure and product properties of the processed article were estimated. The capillary flow properties at various temperatures, elongational flow properties, and dynamic viscoelasticities of MET‐PPs and ZN‐PPs with various melt flow indexes (MFIs) were measured. Furthermore, as an example of application of rheological analysis, the selection of proper raw resin and processing conditions in the sheet‐extrusion of MET‐PP was studied. MET‐PP shows the following rheological features due mainly to the narrow molecular weight distribution in comparison with ZN‐PP with equivalent MFI to that of MET‐PP: while the viscosities at low shear rates are lower, those at high shear rates are higher. Although there is little difference in the loss modulus G″ (viscosity), the storage modulus G′ (elasticity) is very (about one decade) lower. The die swell is much smaller. The entrance pressure loss and end correction coefficient are lower. The critical shear rate at which a melt fracture begins to occur is lower. The melt tension, elongational viscosity, and melt flow index ratio are lower. The flow activation energy is slightly lower. The zero‐shear viscosity obeys the 3.4th‐power law independent of catalyst. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2157–2170, 2002