基于拉伸流变挤出的马来酸酐接枝聚丙烯性能

使用新型的拉伸流变挤出机制备聚丙烯马来酸酐接枝物(PP-g-MAH)。相比于传统双螺杆挤出,基于拉伸流变挤出的PP-g-MAH具有较稳定的单体接枝率(相对接枝率在6%~7%),受设备参数影响较小,单体残留率较低。拉伸流场对聚丙烯(PP)分子链降解程度较低,分别测定了拉伸流场和剪切流场下,不同转速对PP-g-MAH的接枝率/熔体流动速率(G/M)比值的影响,发现前者的产物的G/M比值随转速增加而增加,表明拉伸流场对PP分子链降解程度较低。在PP-g-MAH相对接枝率均为6%的条件下,利用拉伸流变挤出制备的PP-g-MAH的拉伸强度比双螺杆挤出产物高25%。分别和PP以不同比例共混,前者挤出的PP共混物的冲击强度比双螺杆挤出的高11%~35%。     

聚合物反应挤出加工技术及其应用

介绍了反应性挤出加工的特点,并详细介绍了反应性挤出,在聚合物的降解、合成、接枝、增容等方面的应用     

低挥发高接枝率马来酸酐接枝聚丙烯的制备及其在增强聚丙烯材料中的应用

利用含有双键结构的苯乙烯弹性体苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)和苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS),通过双螺杆挤出机进行反应性熔融挤出制备马来酸酐接枝聚丙烯(PP-g-MAH)。利用傅里叶变换红外光谱仪(FTIR)、熔体质量流动速率仪、水分测定仪和酸碱滴定法测定了PP-g-MAH的物质结构、熔体质量流动速率、挥发分含量和接枝率,通过双螺杆挤出制备了玻璃纤维(GF)/聚丙烯(PP)(30/70)复合材料,对复合材料的力学性能和微观形貌进行了研究。结果表明,添加SBS或SIS有利于PP-g-MAH熔体质量流动速率的提高、挥发分含量的降低和接枝率的提高;GF增强PP材料中GF与PP的相容性变好,其力学性能也有较大幅度的增加。     

PP-g-Si熔融接枝工艺对接枝率的影响

以聚丙烯(PP)为基体,γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)为接枝单体,过氧化二异丙苯为引发剂,通过熔融接枝法制备了硅烷接枝PP(PP-g-Si)大分子相容剂,采用傅里叶变换红外光谱(FTIR)仪对PP-g-Si进行了表征,并从定性及定量分析两方面讨论了KH570在PP上的接枝效果,研究了挤出温度和螺杆转速对PP-g-Si接枝率的影响。结果表明,KH570以侧链的形式成功接枝到PP分子链上;挤出温度和螺杆转速对PP-g-Si接枝率的影响较为复杂,总体上高螺杆转速下PP-g-Si的接枝率较高,当螺杆转速为140 r/min时,挤出温度为170℃的接枝率最高,而其它螺杆转速下,挤出温度为180℃的接枝率最高;PP-g-Si的最优制备工艺条件为挤出温度180℃、螺杆转速120 r/min或挤出温度170℃、螺杆转速140 r/min。     

PP熔融接枝AMPS的研究

以过氧化二异丙苯(DCP)为引发剂,采用反应挤出技术制备了聚丙烯接枝2-丙烯酰胺-2-甲基丙磺酸共聚物(PP-g-AMPS)。研究了引发剂、单体及第二单体丙烯酰胺(AM)用量、以及温度、螺杆转速等工艺条件对接枝共聚反应的影响,用红外光谱对制备的接枝物进行了表征。结果表明:PP熔融接枝AMPS反应的适宜温度范围及螺杆转速分别为190～200℃和25Hz;接枝共聚反应中DCP及AMPS的最佳用量分别为PP的0.3%和4.0%;添加一定量的AM有利于接枝产物接枝率的提高,AM的最佳用量为PP的0.5%;AM的加入在一定程度上抑制了PP的降解。     

聚丙烯接枝改性的研究

在双螺杆挤出机上研制马来酸酐(MAH)接枝的聚丙烯(PP)。主要讨论了聚丙烯(PP)与马来酸酐(MAH)在熔融挤出反应中,引发剂DCP的用量、MAH的用量以及反应温度、物料的停留时间对接枝物的影响。     

马来酸酐熔融接枝聚丙烯及其共混物

用双螺杆挤出机通过反应性挤出制备了马来酸酐熔融接枝的聚丙烯(PP),对均聚PP、嵌段共聚PP、PP/三元乙丙橡胶和PP/聚烯烃热塑性弹性体复合体系与马来酸酐的熔融接枝及其工艺条件进行了探讨.结果表明,采用嵌段共聚PP接枝马来酸酐,在螺杆温度190～210 ℃、过氧化二异丙苯质量分数0.1%、马来酸酐质量分数1.5%及苯乙烯质量分数1.8%时,可获得接枝率3.8%的PP接枝聚合物.用该接枝聚合物与PP、高密度聚乙烯及聚烯烃热塑性弹性体熔融共混制备的黏合性涂覆树脂能够满足化工容器防腐专用料的性能要求.     

反应挤出制备接枝聚丙烯研究

以过氧化二异丙苯(DCP)为引发剂,利用反应挤出技术将马来酸酐(MAH)接枝到聚丙烯(PP)分子链上。详细考查了接枝产物的结构;MAH/DCP配比及反应挤出条件对接枝率的影响;接枝产物的流变性能。结果表明:在适宜的加工条件下,当PP/MAH/DCP的质量比为100∶3.5∶0.3时,可获得较高的接枝率。并且接枝产物的流变性能与PP一样为假塑性流体。     

反应性单体丙烯酸改性Sb2 O3填充PP的热降解行为

用双螺杆挤出机制备了三氧化二锑／聚丙烯(Sb2O3／PP)和有无引发剂DCP存在下丙稀酸(AA)改性Sb2O3／PP。用TGA方法研究了制备样品的热降解行为。结果表明Sb2O3的加入明显提高了PP的热分解温度和热稳定性。反应性单体丙烯酸改性可改善Sb2O3与PP的界面相互作用和填料的分散性,而对Sb2O3的热降解行为无大的影响。     

反应性挤出制备PP-g-PEGA调温纤维的研究

以过氧化二异丙苯(DCP)为引发剂,通过反应性挤出的方法将相变材料丙烯酸聚乙二醇酯(PE-GA)接枝到聚丙烯(PP)基体上,利用熔融纺丝的方法制备PP-g-PEGA调温纤维。通过红外光谱法和溶剂萃取法表征了PEGA在PP上的接枝情况;通过差示扫描量热仪、纤维强力仪和扫描电镜分别表征了PP-g-PE-GA调温纤维的储热性能、力学性能和外观形态。结果表明:PEGA与PP发生了化学接枝,PP-g-PEGA纤维的接枝率达3.2%;当PEGA的质量分数为8.0%,引发剂DCP质量分数为0.6%时,相变焓达6.93 J/g;PP-g-PEGA调温纤维的断裂强度随着PEGA含量的增加呈先增大后减小的趋势;PP与PEGA相容性良好,纤维的外观光滑均匀。     

功能化聚丙烯研究进展

综述了国内外聚丙烯(PP)功能化的方法,主要包括丙烯与极性单体直接共聚法、中介物功能化法、接枝改性法等,重点讨论了后两种功能化方法。通过化学反应在PP分子结构中引入极性基团是达到PP功能化的根本途径。     

固相力化学法制备PP—g—HMA的微观结构

用FT－IR，X－射线衍射，DSC及偏光显微镜等手段研究固相力化学法制备的PP／N－羟甲基丙烯酰胺（HMA）接枝共聚物（PP－g-HMA)的微观结构，结果表明，应力作用使PP的微晶尺寸变小，HMA在PP上的接枝聚合使其结晶度降低。     

Maleic anhydride grafting of polypropylene: peroxide and solvent effects

Abstract

The grafting of polyolefins with maleic anhydride (MA) has been incorporated into industrial practice to generate copolymers that can act as coupling agents between the non-polar polyolefins and different polar fillers and reinforcements. In the present study, two different peroxides were used to initiate the MA grafting onto polypropylene (PP), namely dicumyl peroxide (DCP) and 1,3-bis (terbutylisopropyl peroxi)benzene (DIBP). The use of DIBP allowed similar grafting yields to DCP to be obtained, but with less chain scission of the polyolefin. Moreover, the utilisation of a coagent, toluene (Tol), leads to a reduction in the chain scission of PP. A monotonous decrease in the melt flow index (MFI) of the polymer was observed with increasing molar ratio of Tol/MA, in the range of ratios considered (0–2·5). In addition, the free radical grafting of MA onto PP remained high and optimum grafting was obtained for a molar ratio Tol/MA of ～0·5. It was observed that the addition of toluene was effective, independent of the reaction process utilised, namely batch mixing or extrusion.     

长链不饱和脂肪酸接枝聚丙烯

系统地研究了长链不饱和脂肪酸 (十一烯酸 )熔融接枝聚丙烯 (PP) ,探讨了加工条件、引发剂类型与浓度、单体浓度等因素对接枝反应的影响 ,并将结果与短链羧酸丙烯酸 (AA)在PP上的接枝进行比较 ,考察链长因素对接枝的影响。结果表明 ,在DCP、BPO的双重引发下 ,十一烯酸在PP上的熔融接枝是成功的。反应条件对接枝率有一定的影响。和短链羧酸丙烯酸在PP上的接枝相比 ,相同接枝条件下十一烯酸的接枝率较低。DSC测试结果表明 ,十一烯酸接枝前后和丙烯酸接枝前后PP的结晶性能有不同的变化趋势。     

A reactive extrusion process for the free radical grafting of silanes onto polypropylene: Effects of processing conditions and properties of water cross‐linked silane‐grafted polypropylene

Silane grafting and water cross‐linking of polypropylene (PP) are a recent method to modify its properties, such as melt strength, heat, and chemical resistance. This work aims at grafting silanes onto PP by reactive extrusion. The occurrence of the grafting of silane onto PP was confirmed by Fourier transform infrared (FTIR) and a method based on FTIR was developed to quantify the amount of polymerized silane and that of silane grafted onto PP. The molar mass of the silane‐grafted PP and its melt viscosity were also measured. A multiobjective optimization strategy was used to study the effects of processing conditions on the quality of the silane‐modified PP. It was concluded that to maximize the amount of silane grafted on PP and minimize the amount of polymerized silane and the decrease in PP chain scission, screw speed and barrel temperature should be low and feed rate high. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

改性氯化聚丙烯的性能与应用

氯化聚丙烯(CPP)被广泛用作聚丙烯(PP)塑料上涂层的附着力促进剂。向CPP中引入含氧的极性基团可以大幅度提高其与丙烯酸树脂的相容性,改善涂层对PP底材的附着力。通过红外光谱、紫外-可见光谱、X-射线光电子能谱和X-射线衍射等方法分析了一种新型的基于CPP的附着力促进剂,并与市场上普遍使用的同类产品进行了比较,考察了由此新型附着力促进剂制备的PP底漆、色漆和金属涂料的性能。     

Oxygen plasma treatment of sisal fibers and polypropylene: Effects on mechanical properties of composites

Polypropylene powder and sisal fibers were oxygen plasma treated, and the mechanical properties of their composites were tested. Two main effects were investigated: the incorporation of oxygen polar groups in the polypropylene surface and the surface degradation and chain scission of both polypropylene and sisal fibers. Prior to these treatments, three reactor configurations were tested to investigate the best condition for both effects to occur in PP films. Results showed that polypropylene‐cellulose adhesion forces are about an order of magnitude higher for PP film treatments at 13.56 MHz than at 40 kHz owing to much higher chain scission at lower frequencies, although it probably also occurs at high frequency and high power. Polypropylene powder treated with oxygen plasmas in optimum conditions for polar group incorporation did not result in improvement in any composite mechanical property, probably owing to the polymer melting. Sisal fibers and PP powder treated in conditions of surface degradation did not improve flexural or tensile properties but resulted in higher impact resistance, comparable to the improvement obtained with the addition of compatibilizer.     

Synthesis and characterization of macromolecular surface modifier PP--PEG for polypropylene

A novel macromolecular surface modifier, polypropylene-grafted-poly(ethylene glycol) copolymer (PP-g-PEG), was synthesized by coupling polypropylene containing maleic anhydride with monohydroxyl-terminated poly(ethylene glycol). The effects of the reaction condition on the graft reactions were studied. The copolymers were characterized by IR, ¹H NMR, thermogravimetry (TG) and differential scanning calorimetry (DSC). The results indicated that the graft reactions were hindered by increasing the molecular weight of PP or PEG. The graft copolymer was found to have a higher initial thermal degradation temperature and lower crystallization capacity as compared with pure PP, and the side chain of PEG hindered the PP chain from forming a perfect ? crystal. The thermal stability of PP-g-PEG decreased with the increasing content or molecular weight of PEG. The copolymers were blended with polypropylene to modify the surface hydrophilicity of the products. The results of attenuated total reflectance FTIR spectroscopy (ATR-FTIR) showed that PP-g-PEG could diffuse preferably onto the surface of the blends and be suitable as an effectual macromolecular surface modifier for PP.     

The melt grafting preparation and rheological characterization of long chain branching polypropylene

To study the rheological properties of long chain branching (LCB) polypropylene (PP), long chain branches (LCB) were grafted onto the linear PP by melt grafting reaction in the presence of a novel chain extender, poly(hexamethylendiamine-guanidine hydrochloride) (PHGH). The branching reactions between the functionalized PP and PHGH were confirmed by transient torque curves and FTIR. By differential scanning calorimetry (DSC) and polarized microscope measurements, the presence of long chain branching structures was further confirmed. Also, the viscoelastic properties of the LCB PP and linear PP under shear flow were investigated for distinguishing LCB PP from linear PP. It was found that the elastic response of LCB PP at low frequencies was significantly enhanced in comparison with that of the linear PP, implying a presence of a long relaxation time mode that was not revealed in linear PP. Moreover, the branching levels of LCB PP were quantified using a detailed method, which was in correspondence with the molar amount of PHGH grafted on PP.     

长支链聚丙烯增容聚丙烯共混物的研究

以聚丙烯（PP）为原料,通过熔融接枝法制备长支链聚丙烯（LCBPP）,将LCBPP分别加入到PP／聚苯乙烯（PS）、PP／苯乙烯-丙烯腈嵌段共聚物（SAN）和PP／聚对苯二甲酸乙二醇酯（PET）共混体系里。采用傅里叶变换红外（FTIR）和拉伸流变仪对LCBPP进行表征。采用扫描电子显微镜对共混物的断面进行观察。结果表明,LCBPP对分散相具有一定极性的体系表现出良好的增容效果;在组分比为70/30的PP/SAN 和PP/PET体系中加入５％的LCBPP后,体系分散相尺寸明显细化且分散均匀,但是其增容效果没有枝马来酸酐接聚丙烯（PP-g-MAH）的增容效果明显;LCBPP对于PP/PS体系的相容性有轻微的改善。