聚丙烯-聚乙烯嵌段共聚物和相应共混物的热分析

用DSC研究了预期为聚丙烯-聚乙烯两嵌段共聚物(PP-PE)和相应共混物(PP+PE)在热学性能上的差异。经用不同分子量的PP和PE及其共混物进行试验后发现,由于PP和PE在结晶时出现过冷的难易不同。在共混物降温热分析曲线上,当降温速率较快时仅出现一个放热峰,而降温速率较慢时出现PP和PE各自的结晶放热峰,从而解释了文献中的不同结果。并发现共混物的PP和PE熔融、结晶温度均较组分相同的嵌段共聚物的相应温度为高;嵌段共聚物中PP和PE的△H_f值均低于均聚物的△H_f值,而PE的值降低尤甚。我们认为这与嵌段间的共价键限制嵌段活动和结晶过程有关,从而确认DSC热分析可以作为识别是否为嵌段共聚物的一种方法. 本工作的结果表明,所研究的PP-PE试样具有嵌段结构。     

Structure and properties of propylene-ethylene block copolymers and the corresponding blends

Structure and properties of presumed polypropylene(PP)-b-polyethylene(PE) block copolymers (PPPE) and the corresponding blends (PP/PE) have been investigated by wide-angle x-ray scattering (WAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), torsional pendulum apparatus, and other techniques measuring mechanical properties. Crystallinity, morphological structure, and mechanical properties of the block copolymers and blends vary with the PP and PE compositions. Compared with PP homopolymers and PP/PE blends, PP and PE segments in PP-PE block copolymers have a reduced crystallinity, especially PE segments. An additional peak at about ?40°C is observed in dynamic relaxation spectra; substantially different morphology is revealed; and mechanical properties are greatly improved for the sequentially copolymerized PP-PE block copolymers, indicating the existence of PP-PE block structure.     

Mutual influence of LDPE and PP in their blends during crystallization

An indication for the mutual influence of LDPE and PP was the change of the morphology parameters of PE and PP at different ratios of the polymers in blends. That influence depends on the blend composition and is different for PE and PP. It is especially interesting in the blend PE75/PP25 where the influence between PE and PP shows dependence also on the sample geometry. Melting parameters, non-isothermal crystallization parameters - crystallization peak temperature T_c, crystallization begin temperature T_onset, half-width w_1/2 of the crystallization peak, degree of crystallinity α and crystallization rate coefficient CRC, as well as the isothermal kinetics parameters showed dependence on the blend composition. It was established that PE is more stable then PP concerning the mutual influence of both polymers on their crystallization. It was established that PE affects the crystal nucleation of PP and causes a decreasing of PP spherulite size.     

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.     

Effect of PEG on the crystallization of PPDO/PEG blends

A new biodegradable polymer system, poly(p-dioxanone) (PPDO)/poly(ethylene glycol) (PEG) blend was prepared by a solvent casting method using chloroform as a co-solvent. The PPDO/PEG blends have different weight ratios of 95/5, 90/10, 80/20 and 70/30. Crystallization of homopolymers and blends were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). When 5% of PEG was blended, the crystallization exothermal peaks (T_c) of PPDO increased sharply and the crystallization exothermal peaks (T_c) of PEG decreased slightly compared with the homopolymers. The crystallization rates of both components increased, and caused greater relative crystallization degree (X_t%). But when the content of PEG was more than 5%, the crystalline behaviors of blends had no more significant changes accordingly. The melting points of each sample varied little over the entire composition range in this study. The nonisothermal crystallization of PPDO homopolymer and blend (PPDO/PEG = 70/30) were also studied by DSC. The crystallization began at a higher temperature when the cooling rates were slower. The nonisothermal crystallization kinetics of blends was analyzed by Ozawa equation. The results showed that the Ozawa equation failed to describe the whole crystallization of the blend, but Mo equation could depict the nonisothermal crystallization perfectly.     

Crystallization behavior and morphology of PE-g-LCP copolymers

 This study presents DSC and optical microscopy investigations on copolymers of semiflexible liquid crystalline polymer SBH 112 grafted to functionalized low molecular mass polyethylene (PEox) obtained by melt polycondensation or reactive blending procedures. The crystallization behavior of the PE-g-SBH copolymers has been studied under non-isothermal measurement conditions carried out at different cooling rates. The crystallization temperature (T _cr) of the PE component of the copolymers decreases steadily upon increasing the concentration of the SBH grafts. It was found that the copolymers prepared by reactive blending crystallize at slightly higher T _cr than those prepared by polycondensation and with a higher rate, confirmed by the determination of the crystallization rate coefficients (CRC). The results have been interpreted by the fact that the PE crystallizable segments and SBH grafts of the copolymers obtained by reactive blending are longer than those of the copolymers prepared by polycondensation. The overall nonisothermal crystallization kinetics has been studied by the Harnisch and Muschik equation. The results show that the mechanism of the crystallization of the PE phase changes only when the SBH content overruns ca.50%, due to the decrease of both nucleation and crystal growth rates. The morphology of the copolymers crystallized nonisothermally from melt has been examined by polarization microscopy. Fairly homogeneous morphology with tiny PE spherulites is observed for PE-g-SBH copolymers prepared by polycondensation with SBH as the minor phase. No sign of the dispersed LCP domains can be recognized. On the contrary, the morphology of the copolymers prepared by reactive blending is distinctly biphasic. The allegedly longer PE segments crystallize into tiny spherulites too, but the LC domains formed by the long SBH branches present in this type of copolymers appear clearly in the micrographs at room temperature. It is concluded that the copolymers prepared by reactive blending would be more effective as compatibilizers for PE/SBH blends than those prepared by polycondensation. Received: 9 October 1996 Accepted: 13 January 1997     

WAXS studies on block copolymers of ethylene and propylene

Wide-angle X-ray scattering from presumed block copolymers of polypropylene (PP) and ethylene-propylene copolymer (EPR), i.e., PP-EPR and PP-EPR-PP, synthesized by sequential polymerization with δ-TiCl₃? Et₂AlCl, was examined and compared with WAXS of mechanical blends and chain-transfer mixtures of PP and EPR with comparable compositions. The peak at 2θ = 20° for both the copolymers and the mixtures was attributed to the γ modification of PP in EPR. A strong variation in the ratio of diffraction intensities I₀₄₀/I₁₁₀ of PP in block copolymers and mixtures was explained in terms of crystallite growth in different directions. Analysis of the patterns and calculation of crystallinity, crystallite size, and lattice parameters led to the conclusion that block structure existed in the prepared copolymers.     

Crystallization and melting behaviors of polystyrene-b-poly(ethylene-co-butene) block copolymers

Non-isothermal and isothermal crystallization behaviors of polystyrene-b-poly(ethylene-co-butene) (PSt-b-PEB) block copolymers with different compositions and chain lengths were investigated by differential scanning calorimetry (DSC). The results show that crystallization of PEB block is strongly dependent on the composition. Crystallization temperature (T_c), melting temperature (T_m) and fusion enthalpy (ΔH_f) increase rapidly with PEB volume fraction (V_E) for block copolymers with V_E below 50%, but there is little change when PEB block becomes the major component. Glass transition temperature (T_g) of the PSt block and order-disorder transition temperature (T_ODT) of block copolymers also have a weak effect. The isothermal crystallization kinetics results show that Avrami exponent (n) was strongly dependent on the composition and crystallization temperature. For the block copolymers with V_E below 38.7 vol%, the values of n vary between 0.9 and 1.3, indicating that crystallization is confined. For the PSt-b-PEB block copolymers with V_E higher than 50%, fractionated crystallization behavior is usually observed. A two-step isothermal crystallization procedure is applied to these block copolymers. It is found that breakout crystallization occurs at higher T_c, but confined at lower T_c. Two overlapped melting peaks are observed for the block copolymers with fractionated crystallization behavior after two-step crystallization, and only the higher melting peak corresponding to breakout crystallization can be used to derive equilibrium melting temperature.     

低乙烯含量聚丙烯共聚物结晶成核剂研究

利用ＤＳＣ和偏光显微镜等手段研究了部分成核剂对聚丙烯均聚物（ＰＰ）、低乙烯含量聚丙烯共聚物及聚丙烯／聚乙烯（ＰＰ／ＰＥ）共混物结晶行为的影响，结果表明所用成核剂对ＰＰ和改性ＰＰ具有一定的普适性。聚丙烯共聚物中，由于链结构规整性变差，成核剂的作用显得特别突出，而ＰＰ／ＰＥ共混物中，由于成核剂向ＰＥ相迁移而使其对ＰＰ结晶的成核效率降低。     

NUCLEATION MECHANISM OF PEO BLOCK IN DOUBLE-CRYSTALLINE POLY（ETHYLENE-co-BUTENE）-b-POLY（ETHYLENE OXIDE） BLOCK COPOLYMERS

In this paper, we proposed a method to determine the nucleation effect of pre-existing crystals on crystallization of the second block in double crystalline block copolymers, which is usually covered by the suppression effect. The nucleation mechanism of poly（ethylene oxide） （PEO） block from the pre-crystallized polyethylene （PE） block in poly（ethylene-cobutene）-b-poly（ethylene glycol） （EmEOn） diblock copolymers was investigated under variable crystallization environments. The crystallization environment for the PEO block was altered by cooling at different cooling rates or successive selfnucleation （SSN） to the PE block. It was found that the presence of nucleation effect is strongly dependent on composition of the block copolymers. The crystallization temperature （Tc） of PEO block in E174EO90 increases as cooling rate applied to the PE block decreases, indicating that PE block can nucleate the crystallization of PEO block and more perfect PE crystals have stronger nucleation effect. In E182EO41 crystallization of the PEO block is confined, shown by the disappearance of selfnucleation domain, and the PE block has no nucleation effect on the crystallization of PEO block. Double crystallization peaks are observed for the PEO block in E182EO41 and the intensity of the crystallization peak at higher temperature increases as the PE crystals become more perfect. After exclusion of homogeneous nucleation mechanism, the higher temperature crystallization peak of the PEO block in E182EO41 is tentatively ascribed to surface nucleation.     

Ethylene-Coordinative Chain-Transfer Polymerization-Induced Self-Assembly (CCTPISA)

Block copolymers based on ethylene (E) and butadiene (B) were prepared using the ansa-bis(fluorenyl) complex {Me₂Si(C₁₃H₈)₂Nd(BH₄)₂Li(THF)}₂ in combination with (n-Bu)(n-Oct)Mg (BOMAG) as a chain-transfer agent. The diblock copolymers incorporating a soft poly(ethylene-co-butadiene) segment, called ethylene butadiene rubber (EBR), and a hard polyethylene (PE) one were obtained by simply adjusting the different feeds of monomers during the polymerization. The soluble EBR block was formed first by feeding the catalytic system dissolved in toluene at 70 °C with a mixture of ethylene and butadiene (E/B molar ratio 80 : 20). Then the feeding was stopped leading to the consumption of a large part of the residual monomers. The reactor was finally fed with ethylene to form the PE block. By varying the molar mass of the latter, it is shown that the resulting soft-b-hard block copolymers can self-assemble simultaneously to the growth of the PE block in agreement with a polymerization-induced self-assembly (PISA) mechanism. The self-assembly is discussed considering the reaction conditions, the crystallization of the PE block, and the polymerization mechanism involved.     

Morphology and nonisothermal crystallization of in situ microfibrillar poly(ethylene terephthalate)/polypropylene blend fabricated through slit‐extrusion,hot‐stretch quenching

This study describes the morphology and nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) in situ micro‐fiber‐reinforced blends (MRB) obtained via slit‐extrusion, hot‐stretching quenching. For comparison purposes, neat PP and PET/PP common blends are also included. Morphological observation indicated that the well‐defined microfibers are in situ generated by the slit‐extrusion, hot‐stretching quenching process. Neat iPP and PET/iPP common blends showed the normal spherulite morphology, whereas the PET/iPP microfibrillar blend had typical transcrystallites at 1 wt % PET concentration. The nonisothermal crystallization kinetics of three samples were investigated with differential scanning calorimetry (DSC). Applying the theories proposed by Jeziorny, Ozawa, and Liu to analyze the crystallization kinetics of neat PP and PET/PP common and microfibrillar blends, agreement was found between our experimental results and Liu's prediction. The increases of crystallization temperature and crystallization rate during the nonisothermal crystallization process indicated that PET in situ microfibers have significant nucleation ability for the crystallization of a PP matrix phase. The crystallization peaks in the DSC curves of the three materials examined widened and shifted to lower temperature when the cooling rate was increased. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 374–385, 2004     

iPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为

 用DSC、¹³C-NMR、SEM和WAXD等方法研究了IPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为。实验结果表明,EPDM与PE组分的相容性优于与PP组分的相容性,多数EPDM分子链段能够分布在PE组分中;EPDM含量为15％时,共混物相容性最好,SEM照片呈现晶体微区的互连或网络状结构;随EPDM含量增加,总结晶度X_c减小,其中PE组分结晶度X_cE有较大幅度地降低,PP组分结晶度X_cp基本没有变化,这可以根据EPDM和PE、PP之间相容性的差异以及PE、PP两组分在冷却过程中不同的结晶行为来解释。     

Monte Carlo simulation study of the effect of chain tacticity on demixing of polyethylene/polypropylene blends

The molecular origin of the demixing behavior for 50: 50 (wt/wt) polyethylene/polypropylene (PE/PP) with different tacticity of PP at the melts (473 K) was investigated by Monte Carlo simulation of coarse-grained polymer model. Isotactic (iPP), atactic (aPP) and syndiotactic (sPP) polypropylenes were used for blending with PE. Coarse-graining polymer chains were represented by 50 beads, corresponding to C₁₀₀H₂₀₂ and C₁₅₀H₃₀₂ for PE and PP, respectively. The simulation was performed on a high coordination lattice incorporating short-range intramolecular interactions from the Rotational Isomeric State (RIS) model and long-range intermolecular interactions Lennard-Jones (LJ) potential function of ethane and propane units. Chain dimensions, the characteristic ratio (C _n ) and self-diffusion coefficient (D) of PE in the blends are sensitive to the stereochemistry of PP chains. Compared with neat PE melts, PE dimension was relatively unchanged in PE/iPP and PE/aPP blends but slightly decreased in PE/sPP blends. PP dimension was increased in PE/iPP and PE/aPP mixture but decreased in PE/sPP blend in comparison with neat PP melts. In addition, diffusion of PE and PP chains in PE/PP mixture was decreased and increased, respectively, compared to the pure melts. Interchain pair correlation functions were used to detect the immiscibility of the blends. The tendency of demixing of PE/aPP and PE/iPP blends were weaker than that of PE/sPP blend.     

Crystallization of tethered polyethylene in confined geometries

Ordered poly(ethylene)‐poly(vinylcyclohexane) (PE‐PVCH) block copolymers are employed to study the crystallization of tethered PE in confined geometries. The high T_g of the PVCH component of these materials forces PE chains to crystallize in well‐defined geometries dictated by the mesophase structure of the block copolymer. Effects of chain tethering on crystallization are examined through comparison of singly‐tethered PE chains in PE‐PVCH (EV) diblocks and doubly‐tethered PE in PVCH‐PE‐PVCH (VEV) triblocks. Crystallinity is independent of the block copolymer mesophase structure in both the EV and VEV systems, although crystallinity in VEV depends on the molecular weight of the PE block of the copolymer. Melting temperature data indicate that spatial confinement reduces crystallite size in EV and VEV, and that the double tethering of PE chains in VEV reduces crystallite size further through topological constraints. Crystal nucleation and growth depend strongly on the type of microstructure in both EV and VEV block copolymers. Differences in the overall rate of crystallization are correlated with the dimensional continuity of the PE microdomains. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37:2053–2068, 1999     

Probing Liquid-Liquid Phase Separation of a Polyethylene Blend with Thermal Analysis

Summary: A series of polyethylene (PE) blends consisting of a high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with a butene-chain branch density of 77/1000 carbon was prepared at different concentrations. The LLDPE only crystallized below 50 °C, therefore, above 80 °C and below the melting temperature of HDPE, only HDPE crystallized in the PE blends. A specifically designed multi-step experimental procedure based on thermal analysis technique was utilized to monitor the liquid–liquid phase separation (LLPS) of this set of PE blends. The main step was first to quench the system from the homogeneous temperatures and isothermally anneal them at a prescribed temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from LLPS, and then cool the system at constant rate to record the non-isothermal crystallization. The crystallization peak temperature (T_p) was used to character the crystallization rate. Because LLPS results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the LLPS for the system indicated by increased T_p. The result showed that the LLPS boundary of the blend measured by this method was close to that obtained by phase contrast optical microscopy method. Therefore, we considered that the thermal analysis technique based on the non-isothermal crystallization could be effective to investigate the LLPS of PE blends.     

Thermal monitoring of morphology in triblock terpolymers with crystallizable blocks

The bulk morphology of poly(1,4‐butadiene)–block–polystyrene–block–poly (ethylene oxide) (PB‐b‐PS‐b‐PEO) and polyethylene–block–polystyrene–block–poly (ethylene oxide) (PE‐b‐PS‐b‐PEO) triblock terpolymers is analyzed under a thermal protocol. This allows the investigation of the morphology during the occurrence of thermal transitions, such as crystallization and melting, which is a neat way of studying the competition between microphase separation and crystallization for the morphology formation. Only one of the studied systems presented a morphological transition upon melting of the PEO and the PE blocks, attributed to the crystallization of the PE block in finite interconnected domains. All the other systems presented no morphological transitions during the thermal scan. The results prove that the crystallization only disrupt the microphases generated in the molten state under very specific circumstances for these block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3197–3206, 2007     

Crystallization properties and thermal stability of polypropylene composites filled with wollastonite

The influence of wollastonite (CaSiO₃) content on the crystallization properties and thermal stability of polypropylene (PP) composites was investigated. The results showed that the crystallization temperature, crystallization end temperature and crystallization temperature interval, as well as the degree of crystallinity of the composites, were higher than those of the unfilled PP resin, while the crystallization onset temperature was little changed from that of the unfilled PP resin. The increase of degree of crystallinity for the composites could be attributed to the heterogeneous nucleation of the CaSiO₃ in the PP matrix. The thermal stability increased with increasing filler weight fraction (ϕ_f); the thermal decomposition rate decreased nonlinearly with increasingϕ_f. Finally, the dispersion of the filler particles in the matrix was observed, and the mechanisms of thermal stability and crystallizing behavior were discussed.     

Non-isothermal crystallization and crystalline structure Of PP/POE blends

Polypropylene (PP) /ethylene-octene copolymer (POE) blends with different content of POE were prepared by mixing chamber of a Haake torque rheometer. The crystallization behaviors and crystal structure of PP/POE blends were systematically investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarized optical microscopy (POM). The results showed that PP spherulites became defective and the crystallization behavior was influenced intensely with the introduction of POE. At the low content of POE, the addition of POE decreases the apparent incubation period (Δt _i) and the apparent total crystallization period (Δt _c) of PP in blends due to the heterogeneous nucleation of POE, and small amount of β-form PP crystals form because of the existence of POE. However, at high content of POE, the addition of POE decreases the mobility of PP segments due to their strong intermolecular interaction and chain entanglements, resulting in retarding the crystallization of PP, decreasing in the amount of β-form PP crystals, and increasing in Δt _i and Δt _c of PP in blends.