多单体接枝聚丙烯对PBT/PP共混体系的形态结构及力学性能影响研究

研究了甲基丙烯酸缩水甘油酯 (GMA)和苯乙烯 (St)多单体熔融接枝聚丙烯 (PP g (GMA co St) )对聚对苯二甲酸丁二酯 (PBT) 聚丙烯 (PP)共混物的形态结构和力学性能的影响 .利用双螺杆挤出机对PBT PP合金进行共混挤出 ,使用DSC、FT IR和SEM、TEM等手段对共混物进行了分析和相形态观察 ,并测试了力学性能 .实验证明 ,熔融共混过程中PP g (GMA co St)的环氧基团可以与PBT的端羧基发生化学反应 ,就地生成了PBT g PP共聚物 ,该共聚物可对PBT PP合金起到良好的增容剂作用 ,使共混物的相区尺寸显著减小 ,共混物的拉伸强度和冲击强度等力学性能同时得到明显改善 ,达到了弹性体系或小分子增容所难以达到的力学性能平衡的效果 .此外 ,TEM的研究还在PBT PP g (GMA co St)共混物中发现了特殊的微相分离结构     

SEP对PP/PS共混物的增容作用

研究了苯乙烯 -乙烯 /丙烯二嵌段共聚物 (SEP)对聚丙烯 /聚苯乙烯 (PP/PS)共混物的形态和力学性能的影响。结果表明 ,SEP在PP/PS共混物中作为增容剂 ,降低了分散相的聚结 ,减小了分散相的平均粒子尺寸 ,大大改变了共混物的形态 ,提高了共混物的力学性能 ,对PP/PS( 2 0 /80 )共混物的增容作用较为显著     

PP/PC共混材料的研究概况

从加工方式对制备简单机械共混PP/PC共混物性能的影响,增容体系中增容剂的种类、增容效果和不同填充物对共混体系的增强效果三方面综述了近年来国内外对PP/PC共混材料的研究概况,指出了其研究方向和发展前景。     

POE-g-PMAH反应性增容PA1010/PP共混物的性能研究

乙烯-辛烯共聚物-g-聚马来酸酐(POE-g-PMAH)作为反应性增容剂,采用熔体共混的方法制备了PA1010/PP共混物,通过扫描电镜(SEM)、力学性能、傅立叶变换红外光谱(FTIR)和示差扫描量热(DSC)测试,研究了POE-g-PMAH对PA1010/PP共混物的增容作用.结果表明,POE-g-PMAH的加入可以减小共混物的相区尺寸,当PA1010/PP/POE-g-PMAH=70/30/15时,分散相尺寸小而均匀;FTIR结果表明接枝在POE上的马来酸酐基团和PA1010在熔融共混期间发生了化学反应;DSC研究结果表明共混体系中PA1010和PP的结晶温度和结晶度随POE-g-PMAH的加入而降低,表明POE-g-PMAH的增容作用对PA1010和PP的结晶有抑制作用.力学性能测试结果表明随着POE-g-PMAH的增加,共混物的冲击强度逐渐增加,当POE-g-PMAH含量增加到15%时,干态冲击强度达到21.13 kJ/m2,是不加增容剂的3.1倍,而拉伸和弯曲强度可以保持较高水平.POE-g-PMAH的增容机理在于其支链中的马来酸酐能与PA1010中的胺基(NH2—)发生化学反应,而主链POE与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

PTW对PA1010/PP共混物的增容作用

为了增加聚酰胺1010/聚丙烯(PA1010/PP)共混物的相容性,提高共混物的力学性能,采用一种新型的反应型增容剂乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PTW)进行增容,通过扫描电镜(SEM)、力学性能、傅里叶变换红外光谱(FTIR)和差示扫描量热(DSC)测试,研究了PTW对PA1010/PP共混物的增容作用.结果表明,随着PTW的加入,共混物的相区尺寸明显变小,当PA1010/PP/PTW质量比为70∶30∶7时,分散相尺寸细小而均匀,表明PTW有较好的增容作用.FTIR结果表明,PTW上的环氧基团和PA1010在熔融共混中发生了化学反应.DSC研究结果表明,PA1010的结晶温度随PTW的加入而降低,说明PTW对PA1010结晶有抑制作用.另外,PTW的加入使PP的结晶温度下降,当PTW质量分数为5%时出现2个结晶峰,即出现异相成核结晶和均相成核结晶,PP均相成核结晶的出现从另一个方面说明,在PA1010基体中分散相PP尺寸非常细小.当PTW质量分数为7%时共混物的力学性能最佳,干态冲击强度达到13.93kJ/m2,是未加增容剂时的2倍,拉伸和弯曲性能基本不变.PTW的增容机理在于其分子链中的甲基丙烯酸缩水甘油酯能与PA1010发生化学反应,而乙烯链段与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

PP/PP-g-MAH/PA6共混物结构与可纺性研究

运用DSC、SEM、纺丝成形等手段研究了增容剂聚丙烯接枝马来酸酐 (PP g MAH)对聚丙烯 聚酰胺 6(PP PA6 )共混物结构和性能的影响 .结果表明 ,共混物呈典型海岛型两相结构 ;增容剂PP g MAH与PA6之间的在位反应改善了PP PA6共混体系的相容性 ,使共混物中PA6的热结晶峰消失 ,PP的结晶生长速率和成核速率降低 ,可纺性提高     

动态固化聚丙烯/环氧树脂共混物的研究

将动态硫化技术应用于热塑性树脂 热固性树脂体系 ,制备了动态固化聚丙烯 (PP) 环氧树脂共混物 .研究了动态固化PP 环氧树脂共混物中两组分的相容性、力学性能、热性能和动态力学性能 .实验结果表明 ,马来酸酐接枝的聚丙烯 (PP g MAH)作为PP和环氧树脂体系的增容剂 ,使分散相环氧树脂颗粒变细 ,增加了两组分的界面作用力 ,改善了共混物的力学性能 .与PP相比 ,动态固化PP 环氧树脂共混物具有较高的强度和模量 ,含 5 %环氧树脂的共混物拉伸强度和弯曲模量分别提高了 30 %和 5 0 % ,冲击强度增加了 15 % ,但断裂伸长率却明显降低 .继续增加环氧树脂的含量 ,共混物的拉伸强度和弯曲模量增加缓慢 ,冲击强度无明显变化 ,断裂伸长率进一步降低 .动态力学性能分析 (DMTA)表明动态固化PP 环氧树脂共混物是两相结构 ,具有较高的储能模量 (E′)     

马来酸酐接枝热塑性弹性体在PP/PA6共混物中的作用

研究了马来酸酐接枝热塑性弹性体 (TPEg )作为增容剂对聚丙烯 (PP) 尼龙 6 (PA6 )共混体系的相容性、相态以及物理力学性能的影响 .研究结果表明TPEg的加入大大改善了PP PA6共混体系的相容性 ,且随TPEg含量的增大分散相粒径明显降低 ,共混物的韧性以及延展性大大提高 ,同时拉伸强度及模量仍保持较好的水平 .TPEg增容的PP PA6共混物的非等温结晶行为的研究表明 ,共混物中PP和PA6的结晶行为不同于各自纯的聚合物 ,PA6作为成核剂使PP的结晶温度提高 ;而PA6由于TPEg的加入 ,出现分级结晶现象 ,一级结晶温度略低于纯PA6的结晶温度 ,且随TPEg含量增大结晶受阻 ,二级结晶温度与PP的接近 .由于PP、PA 6以及TPEg之间存在较强的相互作用 ,三元共混物中PP及PA6的玻璃化转变温度分别较其纯聚合物升高 .基于上述结果 ,提出了本共混体系的结构模型     

剪切作用下马来酸酐接枝乙烯-辛烯共聚物和乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物对PA1010/PP共混物的增容作用比较

采用熔体共混的方法制备了两种增容剂增容的聚酰胺1010/聚丙烯(PA1010/PP)共混物,通过扫描电镜(SEM)、力学性能和差示扫描量热(DSC)测试,对动态保压注射成型(动态)和普通注射成型(静态)中增容剂POE-g-MAH(马来酸酐接枝乙烯-辛烯共聚物)和PTW(乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物)对PA1010/PP共混物的增容作用进行了比较研究.研究结果表明,普通注射成型中,PTW增容体系具有更小的分散相粒子,在DSC测试中出现两个结晶峰,即出现异相成核结晶和均相成核结晶,具有更好的拉伸和冲击性能,增容作用更佳.动态保压注射成型中施加剪切可以提高所有共混物的拉伸强度、拉伸模量和缺口冲击强度,PTW和POE-g-MAH两种增容剂增容体系冲击性能相近,但POE-g-MAH增容体系的分散相相区尺寸减小明显、分布均匀性显著增加,材料冲击强度增加幅度更大,表明剪切更有利于POE-g-MAH增容作用的进行.两种增容剂增容作用的不同源于它们化学组成的不同引起的材料形态差别.     

PP/PMMA/PP-g-MAH共混物的结晶和相形态研究

采用偏光显微镜和相差显微镜详细研究PP/PMMA不相容聚合物共混物体系和PP/PMMA/PP-g-PMMA增容共混体系的结晶和相形态.偏光显微照片的研究结果表明,增容剂PP-g-MAH中PP结晶需要克服更多的能垒,导致PP结晶形态变得不完善,球晶尺寸变小.比较PP/PMMA和PP/PMMA/PP-g-MAH的相差显微照片可以看出,由于增容剂的加入,PP与PMMA相之间的界面变得模糊,两相的相容性变好.随着PP-g-MAH中MAH接枝率的增加,PMMA分散相的尺寸减小且变得均匀;当增容剂的接枝率为2.41%,添加的质量分数为4.71%,PP/PMMA共混体系中PMMA分散相的相?尺寸可达最小.PP-g-MAH作为反应型增容剂,一方面与PP在界面区域产生共晶;另一方面,MAH极性基团与PMMA的极性基团间产生的强的化学键合作用,使得界面区域的PP-g-MAH分子采取有利于降低构象熵的构象来起到增容作用.PP/PMMA共混物在130℃等温结晶的结果显示,PMMA相对PP的结晶形态的影响较小,PP结晶呈现典型的均相成核特征.PP/PMMA共混体系中加入PP-g-MAH,PP结晶尺寸减少.与非等温结晶相比,等温结晶的PP/PMMA共混物中PMMA相区尺寸明显偏大.     

INVESTIGATION OF PP-EPR DIBLOCK COPOLYMER AS COMPATIBILIZER FOR PP/EPT BLEND

Blending isotactic polypropylene (PP) with ethylene-propylene terpolymer (EPT) is one of thesimplest and most effective ways for toughening PP. In order to further improve the toughness ofPP/EPT blend and to enhance the stability of the dispersed rubber phase, a diblock copolymer com-posed of PP and ethylene-propylene rubber blocks (PP-EPR) was added into the blend, as it is con-sidered that "forced compatibility" of the two components will be effected through the two chemi-cally bonded blocks, while two-phase structure still remains. Experimental results indicate that PP-EPR is an effective compatibilizer for PP/EPT blend. Itnot only increases the toughness of the blend, but also decreases the loss of tensile strengths usuallyaccompanying the toughening of plastics with an elastomer, which is very well explained by the mor-phological structure changes when an appropriate amount of PP-EPR was added into the blend.     

Effects of reprocessing on polymers—Part III: Photo-oxidation of polyethylene-polypropylene blends

It is shown that blends of low density polyethylene (LDPE) and polypropylene (PP) photo-oxidise more readily than LDPE alone and there was evidence of cross-linking between the two phases. An ethylene-propylene rubber (EPDM) which improved the mechanical performance of LDPE/PP blends caused an increase in the rate of photo-degradation as measured by carbonyl formation and by loss of toughness.     

SPECIAL EFFECT OF ULTRA-FINE RUBBER PARTICLES ON PLASTIC TOUGHENING

According to the present theories of plastic toughening, it is impossible to enhance the toughness, stiffness and/orheat resistance of plastics simultaneously by using rubber. A series of novel nano-rubber particles (UFPR) were introduced,which were prepared through irradiating common rubber lattices and spray drying them. Epoxies toughened with UFPRshowed a much better toughening effect than those with CTBN, and the heat resistance of epoxy was unexpectedly elevated.For polypropylene toughening, UFPR can improve the toughness, stiffness and heat resistance of PP simultaneously. Thesespecial toughening effects overcome the deficiencies in rubber toughening technology and are worth further investigating.     

Structure and properties of sequentially polymerized propylene-b-[ethylene-co-propylene]-b-propylene copolymers

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using δ-TiCl₃-Et₂-AlCl as a catalyst system. The results indicate that the intrinisic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP/EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.     

BRITTLE-DUCTILE TRANSITION OF PP/EPDM/ELASTOMERIC NANO-PARTICLE TERNARY BLENDS

The brittle-ductile transition is a very important phenomenon for polymer toughening. Polypropylene （PP） is often toughened by using rubbers, e.g., ethylene-propylene diene monomer （EPDM） has often been used as a modifier. In this article, the toughening of PP by using a new kind of rubber, known as elastomeric nano-particle （ENP）, and the brittleductile transition of PP/EPDM/ENP was studied. Compared to PP/EPDM binary blends, the brittle-ductile transition of PP/EPDM/ENP ternary blends occurred at lower EPDM contents. SEM experiment was carried out to investigate the etched and impact-fractured surfaces. ENP alone had no effect on the impact strength of PP, however, with the same EPDM content, PP/EPDM/ENP ternary blends had smaller particle size, better dispersion and smaller interparticle distance in contrary to PP/EPDM binary blends, which promoted the brittle-ductile transition to occur earlier.     

Peroxide dynamic crosslinking in impact modification of polypropylene with polybutadiene

Polypropylene was blended with polybutadiene in an internal mixer in order to improve its toughness. The rubber content ranged from 10 to 20 wt. % and dicumyl peroxide (DCP) was added to provide required radicals for dynamic crosslinking of polybutadiene, and for in-situ compatibilization of the phases. This was done using two sequences of mixing. In addition, zinc dimethacrylate was utilized as a co-agent to control chain scission of PP, enhance the interfacial reactions and increase compatibility of the components. In obtaining the optimum blend, the Taguchi orthogonal experimental design was applied and results of Izod impact strength test were concordantly related to crystallinity of the polypropylene, morphology of the blends and reactions that may occur. The impact strength was increased about four times at best in comparison to the neat polypropylene, showing versatility of this way of toughening which may be improved further.     

Toughening polypropylene with nanoscale rubber particles

A new kind of powdered rubber, ultra-fine full-vulcanized powdered rubber (UFPR), was invented and used for toughening polypropylene. The UFPR dispersed well in the PP matrix on a nanoscale. Both toughness and stiffness of PP can be improved by toughening with UFPR. DSC data showed that UFPR has some nucleation effect on PP. When PP was toughened with UFPR and EPDM together, the impact strength showed a synergistic toughening effect.     

High‐efficiency impact modifier prepared by coagulation emulsion polymerization through internal voiding toughening mechanism

This paper was an application of our previous study on particle coagulation mechanism (Colloid Polym Sci 291: 2385‐2398, 2013), and the effect of coagulation particle of acrylic impact modifiers (ACR) on polymer blend properties was investigated. The compatibility was relevant with the properties of shell phase rather than the structure of core phase. The rubber content was found to be the main influencing factor for toughening when rubber content less than 5%. However, when it reached to 7%, the dispersion of rubber became the primary parameter to dominate the toughness. The highest impact strength of poly(vinyl chloride) (PVC) toughened by coagulation particles was 1656 J/m, nearly 56 times than pure PVC, whereas only 45 times was reached when toughening by traditional ACR prepared by seeded emulsion polymerization; moreover, the brittle–ductile transition happened in advanced of 2 phr at ACR content. Scanning electron microscopy results showed that the shear yielding of the matrix and rubber cavitation were the major toughening mechanisms. Furthermore, the high performance of blend responsible for coagulation particles was discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

低乙烯含量共聚聚丙烯链结构和相结构与应力应变行为的关系

研究了两种典型的低温抗冲共聚聚丙烯(ICPP)的应力应变行为及温度依赖性,其低温应力应变行为揭示ICPP具有优异的低温抗冲性能和综合力学性能的结构本质.从初始弹性模量、屈服应力及断裂伸长随温度变化所显示的变化规律进一步确认了两种ICPP的序列结构特征和相结构特征.断裂伸长变化显示了乙丙橡胶相的增韧作用,屈服应力变化显示了分散相对基质结合紧密程度的影响,弹性模量则与基质的结晶状况和结晶形态有着比较密切的关系,同时也与乙丙橡胶相和聚丙烯基质的玻璃化转变温度密切相关.     

乙丙嵌段共聚物的X-射线衍射研究

用大角X-射线衍射(WAXD)方法对按嵌段聚合程序合成的聚丙烯(PP)和乙丙共聚物(EPR)的嵌段共聚物PP-EPR和PP-EPR-PP,以及相应的混合物进行对比研究.乙丙共聚物及其共混物均发现在2θ=20°处存在由EPR中PP链段引起的γ-晶型衍射峰.通过诠释X-射线衍射图,计算结晶度,微晶尺寸和晶格参数等表明,用δ-TiCl_3-Et_2AlCl催化剂获得了嵌段共聚物结构.