我国高熔体强度聚丙烯生产技术进展

综述了国内高熔体强度聚丙烯(HMSPP)的生产技术。射线辐照法所制HMSPP可在常温条件下进行,纯度较高,但无法精确控制HMSPP的结构,生产成本较高;直接聚合法可通过改变外给电子体种类及加入量、聚合工艺条件等得到具有支化结构的HMSPP,其具有良好的拉伸性能和耐热性能,但催化剂及聚合工艺条件的研发周期长;化学交联改性法可减少凝胶含量,降低单体用量,但反应温度较高时,聚丙烯易发生降解;共混改性法制备的共混物中各树脂间的协同效应和化学反应性好,但会影响HMSPP的力学性能;反应挤出法工艺稳定,操作简单,适合工业化连续化生产,但各树脂在掺混时会降低HMSPP的力学性能,且各相间的相容性差。     

Preparation of polypropylene with high melt strength by wet reaction blending of lignin

In this paper, the melt strength of polypropylene is shown to be significantly improved by lignin-cooperative construction of heterophase network structure and the evolution mechanism of lignin on the topology of polypropylene is investigated. Electron paramagnetic resonance (EPR) analysis shows that the free radicals generated by polypropylene irradiation can remain active for 2 weeks; rheological studies show that lignin promotes the formation of heterogeneous network structures in polypropylene, and its melt is characterized by long-chain branching. Phase angle-complex modulus, complex viscosity-complex modulus, Han's, and Cole–Cole curves are used to analyze the liquid–solid transformation, and the results indicate that the enhanced interfacial action is due to the formation of the heterogeneous network structures. The mechanical properties show that the impact strength is increased by 1.8 times due to the synergistic effect of lignin and acrylamide. SEM shows the formation of a fibrous network structure around the lignin, which undergoes interfacial yielding, improving the interfacial interaction between the components.     

Structure and properties of high melt strength polypropylene prepared by combined method of blending and crosslinking

High melt strength polypropylene (HMSPP) was prepared by in situ heat induction reaction, in which pure polypropylene (PP) powders without any additives was used as basic resin, and low density polyethylene (LDPE) and trimethylolpropane triacrylate (TMPTA) were added as blending resin and as crosslinking agent, respectively. Microstructure of the obtained HMSPP (PP/LDPE/TMPTA blends) was characterized by FTIR, Wide‐angle X‐ray diffraction (WAXD), and testing of gel content. The effect of LDPE content on melt strength and melt flow rate of HMSPP were investigated. When the content of LDPE was 40 wt %, the melt strength of the HMSPP was above 16 CN, which was much higher than those of pure PP powder (2.6 CN) and PP/LDPE blends without TMPTA (6.1 CN). Moreover, thermal behavior and mechanical properties of the HMSPP were also investigated. The results showed that the thermal stability and impact strength of HMSPP were greatly improved. In addition, HMSPP possessed good processing performance and good foaming properties. The foams produced by HMSPP showed uniform, closed, and independent cells. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

反应挤出制备高熔体强度PP

采用反应挤出方法制备高熔体强度聚丙烯,通过凝胶渗透色谱仪、差示扫描量热仪、偏光显微镜等研究了改性产品的结构与性能,并进行挤出发泡应用实验。结果表明：采用特殊的过氧化物引发剂和支化促进剂,与聚丙烯基础树脂共混后通过双螺杆挤出机熔融连续反应挤出,可以直接制备具有长链支化结构的聚丙烯,熔体强度提高300％;挤出发泡试样泡孔均匀,发泡倍率达到50倍,具有较好的可发性能。     

高熔体强度聚丙烯技术进展

高熔体强度聚丙烯(HMSPP)是聚丙烯改性的研究的重要产品之一。本文综述了高熔体强度聚丙烯的性能特点、制备方法、用途以及国内外研究和开发情况。     

通过反应挤出提高聚丙烯的熔体强度

利用反应挤出技术研究了不同反应物对聚丙烯(PP)熔体强度的影响。考察了不同用量的低密度聚乙烯(LDPE)、乙烯-乙酸乙烯酯共聚物(EVA)、季戊四醇三丙烯酸酯(PETA)、二乙烯基苯(DVB)以及上述物质的混合物在过氧化二异丙苯的引发下对PP熔体强度、熔体流动速率、熔垂的影响。结果表明,LDPE、EVA的加入对产物熔体强度的影响有限,PFTA也只能使其提高1倍左右;而DVB的加入可使产物的熔体强度显著提高,仅加入1％就可使熔体强度提高20倍,熔垂实验也证明了这一点;几种反应物混合使用效果不如单独使用好。     

高熔体强度聚丙烯的研制

用过氧化物引发聚丙烯(PP)交联制备高熔体强度聚丙烯(HMSPP),研究了过氧化物的用量、反应温度、螺杆转速对HMSPP性能的影响。得到的HMSPP比普通PP的熔体强度提高约3倍。用所研制的HMSPP进行发泡实验,制得泡孔结构较均匀且闭孔的发泡制品。     

高熔体强度聚丙烯树脂的结构与性能

采用差示扫描量热法、傅里叶变换红外光谱、毛细管流变、熔体拉伸等方法,从结晶性、黏弹性及物理机械性能等方面对高熔体强度聚丙烯(HMSPP)树脂进行结构表征与性能分析。结果表明:HMSPP树脂具备较高的弯曲模量,同时具备优异的抗熔垂能力和更宽的加工温度;拉伸黏度随拉伸速率的增大而增大,呈现出HMSPP应变硬化这一明显行为,使得熔体在热成型过程中具有均匀变形的自我调节能力,从而克服普通聚丙烯在热成型加工中的严重熔垂问题;含有较长接枝链段的HMSPP树脂在刚性、熔体强度、结晶性能等方面均优于普通聚丙烯。     

高熔体强度聚丙烯的研究应用进展

通用聚丙烯（PP）由于熔体强度低和加工温度范围较窄,因而在挤出发泡、挤出涂布和热成型等条件下难以加工成型,所以限制了通用聚丙烯的应用领域。高熔体强度聚丙烯（HMSPP）具有较高的熔体强度和优异的物理机械性能,因此拓宽了聚丙烯的应用范围。文章综述了国内外高熔体强度聚丙烯的性能特点、制备方法、研究进展和应用现状。     

高熔体强度PP的制备研究

用辐照法制备出了高熔体强度聚丙烯（PP）：对其物理机械性能、熔体强度、熔体拉伸粘度、粘垂等进行了测试，研究了辐照剂量、交联剂种类和浓度，辐照后PP的热处理条件等对制备高熔体强度PP的影响；并在此基础上，还制备出了发泡倍率为15倍以上的发泡PP。     

Structure of blown film from blends of polyethylene and high melt strength polypropylene

The structure of blown film processed from linear low density polyethylene blended with up to 30 wt[percnt] of a high melt strength polypropylene (hmsPP) was examined using primarily atomic force microscopy and wide angle X-ray scattering. The study focused on two polyethylene resins with the same density: a conventional Ziegler-Natta catalyzed linear low density polyethylene (znPE) and a blend of a Ziegler-Natta catalyzed and a metallocene catalyzed linear low density polyethylene (zn/mPE). Parallel characterization was performed on blown film of the hmsPP and blown film of each of the polyethylene resins. In films of the blends, the hmsPP was well-dispersed in the polyethylene matrix as elongated domains. In the domains, the hmsPP crystallized as planar row-nucleated structures with the long axis of the lamellae perpendicular to the extrusion direction. Row-nucleated hmsPP lamellae provided a template for epitaxial crystallization of polyethylene lamellae. The 42° angle of the lattice match imparted a characteristic herringbone texture to the polyethylene. Blending with hmsPP increased the tensile modulus and strength of polyethylene film without significantly affecting the ultimate elongation.     

发泡用高熔体强度聚丙烯的研究

以过氧化苯甲酰(BPO)为引发剂,在同向双螺杆挤出机上对聚丙烯(PP)进行硅烷交联,制备了高熔体强度聚丙烯(HMSPP),然后制得高发泡倍率的PP制品.实验对改性PP的熔体强度、力学性能、热性能和发泡性能进行了表征.结果表明:自制HMSPP的熔体强度是纯PP的5.01倍,力学性能和耐热性与纯PP相比均有较大提高,可用于成型高发泡倍率制品.     

Trimethylolpropane trimethacrylate functionalized polypropylene/polyhexene-1 blend with enhanced melt strength

ABSTRACT

This study was aimed at investigating the variations in the melt strength of polypropylene as a result of blending with another polymer having long side branches in the presence of multi-functional agent and radical initiator. The formation of long chain branches was confirmed by strain hardening behavior in extensional viscometry and grafting efficiency data obtained from FTIR spectroscopy. strain hardening behavior, rheological parameters and grafting efficiency kept their ever-increasing trends by increasing the concentration of Trimethylol-propane-trimethacrylate (TMPTMA) until 3 phr, and the inefficiency of TMPTMA in branching reactions at concentrations higher than 3 phr is rooted in homo-polymerization of TMPTMA.     

Preparation and characterization of high melt strength polypropylene with long chain branched structure by the reactive extrusion process

The reactive extrusion of maleic anhydride grafted polypropylene (PP‐g‐MAH) with ethylenediamine (EDA) as coupling agent is carried out in a corotating twin‐screw extruder to produce long chain branched polypropylene (LCBPP). Part of PP‐g‐MAH is replaced by maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH) or linear low‐density polyethylene (LLDPE‐g‐MAH) to obtain hybrid long chain branched (LCB) polyolefins. Compared with the PP‐g‐MAH, PE‐g‐MAH, and their blends, the LCB polyolefins exhibit excellent dynamic shear and transient extensional rheological characteristics such as increased dynamic modulus, higher low‐frequency complex viscosity, broader relaxation spectra, significantly enhanced melt strength and strain‐hardening behaviors. The LCB polyolefins also have higher tensile strength, tensile modulus, impact strength and lower elongation at break than their blends. Furthermore, supercritical carbon dioxide (scCO₂) is constructively introduced in the reactive extrusion process. In the presence of scCO₂, the motor current of the twin extruder is decreased and LCB polyolefins with lower melt flow rate (MFR), higher complex viscosity and increased tensile strength and modulus can be obtained. This indicates that the application of scCO₂ can reduce the viscosity of melt in extruder, enhance the diffusion of reactive species, and then facilitate the long chain branching reaction between anhydride group and primary amine group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Molecular structure of high melt strength polypropylene and its application to polymer design

We report a numerical technique to investigate the branching process of linear Ziegler-Natta polypropylenes. Using an iterative procedure, linear chains are created based on the molecular weight distribution (MWD) of linear Ziegler-Natta polypropylenes as determined by GPC. By varying one parameter, MWDs of polymers with various levels of branching are simulated, and the simulated MWDs agree very well with experimental GPC data of branched polymers. From the simulation, the average branching parameters as well as the branching distributions of the polymers can be obtained. The branching information is related to the moments of the MWD, and a criterion of the onset of gelation is proposed. The melt flow rate (MFR) is correlated with the weight-average molecular weight. These relationships make it possible to design a polymer having a prescribed MFR.     

提高嵌段共聚PP冲击强度的措施探讨

介绍了生产嵌段共聚聚丙烯(PP)的工艺和改善冲击强度的机理,分析了影响嵌段共聚PP冲击强度的主要因素：二聚物的含量、结构及其特性粘数;提出了3条提高嵌段共聚PP冲击强度的措施：提高嵌段共聚PP的键合乙烯量、降低气相比以及控制二聚物特性粘数在适当的范围。     

Influence of polyfunctional monomer on melt strength and rheology of long‐chain branched polypropylene by reactive extrusion

Long chain branching (LCB) were added to linear polypropylene (PP) using reactive extrusion in the presence of selected polyfunctional monomers (PFMs) and a peroxide of dibenzoyl peroxide (BPO). Fourier Transformed Infrared spectra (FTIR) directly confirmed the grafting reaction occurred during the reactive extrusion process. Various rheological plots including viscosity curve, storage modulus, Cole‐Cole plot, and Van‐Gurp plots, confirmed that the LCB structure were introduced into modified PPs skeleton after modification. In comparison with linear PP, the branched samples exhibited higher melt strength, lower melt flow index, and the enhancement of crystallization temperature. The LCB level in modified PPs and their melt strength were affected by the type of PFM used and could be controlled by the PFM properties and structure. PFMs with lower boiling points, such as 1, 4‐butanediol diacrylate (BDDA), could not produce LCB structure in modified PP skeleton. The shorter molecular chain bifunctional monomers, such as 1,6‐hexanediol diacrylate (HDDA), favored the branching reaction if their boiling points were above the highest extrusion temperature. And some polar groups, such as hydroxyl, in the molecule of PFM were harmful to the branching reaction, which might be attributed to the harm of the polarity of groups to the dispersion of PFM in PP matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polydimethylsiloxane assisted supercritical CO2 foaming behavior of high melt strength polypropylene grafted with styrene

Foamable high melt strength polypropylene (HMSPP) was prepared by grafting styrene (St) onto polypropylene (PP) and simultaneously introducing polydimethylsiloxane (PDMS) through?a?one-step?melt extrusion process. The effect of PDMS viscosity on the foaming behavior of HMSPP was systematically investigated using supercritical CO₂ as the foaming agent. The results show that the addition of PDMS has little effect on the grafting reaction of St and HMSPP exhibits enhanced elastic response and obvious strain hardening effect. Though the CO₂ solubility of HMSPP with PDMS (PDMS-HMSPP) is lower than that of HMSPP without PDMS, especially for PDMS with low viscosity, the PDMS-HMSPP foams exhibit narrow cell size distribution and high cell density. The fracture morphology of PDMS-HMSPP shows that PDMS with low viscosity disperses more easily and uniformly in HMSPP matrix, leading to form small domains during the extrusion process. These small domains act as bubble nucleation sites and thus may be responsible for the improved foaming performance of HMSPP.     

Tailoring toughness of injection molded bar of polypropylene random copolymer through processing melt temperature

In this study, a facile route to realize the superior toughness of injection molded polypropylene random copolymer (PPR) is reported. The toughness of PPR is increased about twofold when the processing melt temperature increases from 180 to 250 °C. Systematic and detailed structural characterizations have been carried out to establish the structure–property relationships by using polarized light microscopy, scanning electron microscopy, infrared microscopy and dynamic mechanical analysis. It is found that increasing the melt temperature is beneficial for the coalescence of rubbery domains and enhanced molecular mobility which are mainly responsible for the improvement in toughness. Other factors, such as molecular orientation, crystallinity and so on, seem to have little effect. The vital role of enhanced molecular mobility in improving toughness is further demonstrated by the annealing of injection molded samples at elevated temperature, i.e. 110 °C. Copyright © 2011 Society of Chemical Industry     

低成本制造高强度聚酯纤维研究进展

利用低生产成本的熔融纺丝技术制造高强度PET纤维,通过近年来的许多探索工作,尤其是目前正在日本所开展的以熔体结构控制为核心,结合分子质量控制和拉伸、热处理技术的研究以及数学模型的建立等工作结果表明,这个目标是有希望实现的。