Continuous polymerization of lactam–lactone block copolymers in a twin‐screw extruder

Continuous copolymerizations of ?‐caprolactone with ?‐caprolactam and ω‐lauryl lactam were carried out in a modular intermeshing corotating twin‐screw extruder. Sodium hydride (initiator) and N‐acetyl caprolactam (coinitiator) were used to synthesize lactam–lactone copolymers in a twin‐screw extruder. We consider the variables of feeding order and feed rate of comonomers on the reactive extrusion of lactam–lactone copolymers. It was observed that simultaneous feeding of both monomers with initiator and coinitiator in the first hopper produced a mixture of homopolymers. When we fed the lactam into the first hopper and caprolactone sequentially into the second hopper, we obtained the lactam–caprolactone block copolymers. However, when we fed caprolactone first into the first hopper and the lactam into the second hopper, the extruded product was a mixture of poly(?‐caprolactone) and lactam monomer. We synthesized high molecular weight copolymers of poly(caprolactam‐b‐caprolactone) and poly(lauryl lactam‐b‐caprolactone) with different block lengths by sequential feeding of monomers. The block length of the block copolymer could be adjusted by controlling the feed rate of each monomer during reactive extrusion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1429–1437, 2003     

Fundamental foaming mechanisms governing the volume expansion of extruded polypropylene foams

This article describes the fundamental foaming mechanisms that governed the volume expansion behavior of extruded polypropylene (PP) foams. A careful analysis of extended experimental results indicated that the final volume expansion ratio of the extruded PP foams blown with butane was governed by either the loss of the blowing agent or the crystallization of the polymer matrix. A charge coupling device (CCD) camera was installed at the die exit to carefully monitor the shape of the extruded PP foams. The CCD images were analyzed to illustrate both mechanisms, gas loss and crystallization, during foaming at various temperatures, and the maximum expansion ratio was achieved when the governing mechanism was changed from one to the other. In general, the gas loss mode was dominant at high temperatures and the crystallization mode was dominant at low temperatures. When the gas loss mode was dominant, the volume expansion ratio increased with decreasing temperature because of the reduced amount of gas lost. By contrast, when the crystallization mode was dominant, the expansion ratio increased with increasing temperature because of the delayed solidification of the polymer. The processing window variation with the butane concentration, the change in the temperature ranges for the two governing modes, and the sensitivity of melt temperature variations to the volume expansion ratio are discussed in detail on the basis of the obtained experimental results for both branched and linear PP materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2661–2668, 2004     

塑料异型材挤出模中的压力分布

本文对塑料异型材挤出模机头典型流道结构进行了分析，给出了各种类型流道的压力降计算公式，并用一实例说明文中所述方法的正确性。     

Microstructure of high modulus solid state extruded polyethylene: 2. X-ray scattering studies of 12, 24 and 36 extrusion draw ratio

The microstructure of a series of solid state extruded polyethylene fibres was examined by wide- and small-angle X-ray scattering. By measuring absolute intensities using a two dimensional position sensitive detector, accurate values of the small-angle invariant for anisotropic samples were obtained. This measurement coupled with wide-angle X-ray scattering and d.s.c. permitted determination of the density of the noncrystalline component. The use of a two phase model for solid state extruded polyethylene is justified if consideration is given to the effective densities of the crystalline and noncrystalline phases, which change with deformation. The effective density of the crystalline phase decreases by 1% (0.999–0.990 g cm^?3) from the unextruded billet compared to a 36 draw ratio extrudate, while the noncrystalline phase density increases by 6% (0.84–0.89 g cm^?3). These changes lead to an overall decrease in the mean squared electron density fluctuation of 63%. The average axial crystallite length measured by wide-angle X-ray scattering increases with extrusion draw ratio while the SAXS long period decreases and weakens considerably. These observations and the electron microscopy results from the previous paper, (Polymer, 1982, 23, 1069), are fully consistent with the key features of the Peterlin model of fibre microstructure.     

LLDPE／LDPE共混物熔体挤出胀大行为的研究

应用毛细管流变仪，考察了实验条件下线性低密度聚乙烯与低密度聚乙烯共混物（ＬＬＤＰＥ／ＬＤＰＥ）熔体挤出胀大行为及其影响因素。结果表明，挤出胀大比Ｂ与剪切应力近似呈幂律关系，而随口型长径比的增加呈指数衰减，当共混比为５０／５０时，Ｂ产生局部极涉值现象。     

CO2‐assisted polymer processing: A new alternative for intractable polymers

CO₂‐assisted polymer processing is proposed as an alternative route for intractable and high molecular weight polymers based on the plasticization effects of CO₂ and its direct effect on the melting behavior of semicrystalline polymers. A modified processing system was used to process a variety of polymers in the presence of high‐pressure CO₂. The system includes an extruder that was modified to allow for high pressures created by the injection of CO₂. The new design includes a modified feed section that allows a given mass of polymer to interact with CO₂ before and during the extrusion process. The inherent shear mixing and the presence of CO₂ allow for a specific control over the extrudate morphology. Results suggest that this alternative design provides a new and easy route to melt process high melt viscosity polymers of commercial importance, such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), and syndiotactic polystyrene (s‐PS). The increased processability of these systems in CO₂ is related to the plasticization effect of CO₂ that was quantified through a depression in the glass‐transition temperature according to the Chow model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1501–1511, 2004     

Extension-dominated improved dispersive mixing in single-screw extrusion. Part 2: Comparative analysis with twin-screw extruder

In Part 1 of this work, the possibility of improving single-screw extruders (SSE) better dispersive mixer was explored by harnessing extensional flows provided by the hyperbolic contracting–diverging channels of extensional mixing elements (EME). Addition of the EME to the pin screw generated enhanced breakup for polymer blends and nanocomposite systems without significant penalty in flow rate. In Part 2, experiments are performed on immiscible polymer blends (low-viscosity ratio and high-viscosity ratio) and nanocomposites on both SSE and twin-screw extruder (TSE) with the same rotation speed and throughput. Morphological results show tremendous improvement in dispersive mixing capability of SSE when equipped with EME that are mainly comparable to conventional TSE that is, with kneading blocks as mixing sections, although not as good as TSEs equipped with EMEs. Mechanical results also show enhanced modulus when EME is used in SSE operations.     

Poly (vinyl alcohol)/polylactic acid blend film with enhanced processability,compatibility, and mechanical property fabricated via melt processing

Poly (vinyl alcohol)/polylactic acid (PVA/PLA) blend film, which is environment friendly and has potential applications in food and electronic packaging fields, was fabricated by melt extrusion casting. Fourier transform infrared spectroscopy analysis confirmed the formation of the hydrogen bonding between PLA and PVA, which improved the compatibility of PLA with PVA, making PLA uniformly dispersed in PVA matrix as small spheres, even when PLA content increase to 15 wt%. In this way, the original hydrogen bond network among PVA was disturbed and the chain mobility of PVA was activated, endowing PVA/PLA blends with lower melt viscosity than bot modified PVA and PLA, and the blend films with the increased crystallinity, mechanical property, and water resistance. Compared with PVA film, the crystallinity, tensile strength and Young's modulus of the blend film with 15 wt% PLA, respectively, increased by 15.1%, 9 and 51 MPa, and the water contact angle enlarged from 23° to 60°.     

A study on melt recycling of bio-based polypropylene/thermoplastic starch compound

The compulsion to use bioplastics has increased significantly today. One of the important aspects of plastics is their recyclability. Therefore, the important question of this research is that although bio-based compounds containing starch are sensitive to thermal-mechanical recycling processes, are such products thermally recyclable? To answer the question, polypropylene (PP)/thermoplastic starch (TPS) compound granules were extruded up to five times, and in the other part, single-extruded granules were blended at different ratios with virgin granules by extrusion. In order to characterize these samples, Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, rotational disc rheometry, tensile properties, and appearance evaluation were used. The results showed that it is possible to recycle PP/TPS granules up to four times repetition of the extrusion operation and the fifth repetition also showed slight changes. There was also a blend of single-extruded granules with virgin material up to a 50:50% composition without significant variation.     

Melt extrusion and blow molding parts-per-million POSS interspersed the macromolecular network and simultaneously enhanced thermomechanical and barrier properties of polyolefin films

There has been the expectation that polymers filled with small concentrations of nanosized particles will exhibit superior thermomechanical properties. We demonstrate that dispersing parts-per-million (ppm) polyhedral oligomeric silsesquioxane (POSS) nanochemicals by melt extrusion with polyolefins increased the tensile Young's modulus, yield stress, and toughness of blow molded and extruded films without penalizing extensibility, which is common to polymers reinforced with nano/microparticles. Transmission electron microscopy showed that the key to mechanical reinforcement is the spatial distribution of POSS at ca. single nanocage thus enabling interspersion of the macromolecular network. The thermal stability, water contact angle, and oxygen transmission of the films were also enhanced enabling a single component food package capable to keep food without decay for two weeks. The physical properties are improved when the nanoparticle size <D> is about the size of the virtual tube diameter d_t, that is, <D>/d_t ≈ 1. The enhancement of physical properties by placing the nanoparticle in the free space of the molecular network is a new paradigm in engineering polymer nanocomposites and opens opportunities for recyclable single component packaging films and tunable lightweight engineering and biomimetic materials.