Investigation of the gel effect in reactive extrusion processes for free radical polymerization

The gel effect in the reactive extrusion process for free radical polymerization in a closely intermeshing co-rotating twin screw extruder was investigated. First the reaction kinetic model was constructed mainly on the basis of entanglement theory. Next, numerical calculation expressions for the initiator and monomer concentrations, monomer conversion, average molecular weight and apparent viscosity were deduced. Finally, the evolution of the above variables were shown and discussed for the example of butyl methacrylate. The simulated results of the monomer conversion are in good agreement with experimental results.

Computer simulation of reactive extrusion processes for free radical polymerization

The reactive extrusion for polymerization is an integrated polymer processing technology. A new semi-implicit iterative algorithm was proposed to deal with the complicated relationships among the chemical reaction, the macromolecular structure and the chemorheological property. Then the numerical computation expressions of the average molecular weight, the monomer conversion, and the initiator concentration were deduced, and the computer simulation of the reactive extrusion process for free radical polymerization was carried out, on basis of which reactive processing conditions can be optimized.

Study on reactive extrusion processes of block copolymer

The anionic copolymerization process of styrene-buradiene (S/B) block copolymer in a closely intermeshing co-rotating twin screw extruder with butyl-lithium initiator was studied. According to the anionic copolymerization mechanism and the reactive extrusion characteristics, the mathematical models of monomer conversion, average molecular weight and fluid viscosity during the anionic copolymerization of S/B were constructed, and then the reactive extrusion process was simulated by means of the finite volume method and the uncoupled semi-implicit iterative algorithm. Finally, the influence of the feeding mixture composition on conversion was discussed. The simulated results were nearly in agreement with the experimental results.

Numerical simulation of reactive extrusion processes of PA6

To analyze the complicated relationships among the variables during the reactive extrusion process of polyamide 6 (PA6), and then control the chemical reaction and the material structures, the process of continuous polymerization of caprolactam into PA6 in a closely intermeshing co-rotating twin screw extruder was simulated by means of the finite volume method, and the influences of three key processing parameters on the reactive extrusion process were discussed. The simulated results of an example were in good agreement with the experimental results.

Free radical grafting of polyethylene with vinyl monomers by reactive extrusion

The free radical grafting of polyethylene with vinyl monomers by reactive extrusion was studied numerically. Numerical computation expressions of key variables, such as the concentrations of the initiator and polymer, grafting degree, average molecular weight and apparent viscosity, were deduced. The evolutions of the above variables were predicted by means of an uncoupled semi-implicit iterative algorithm. The monomer conversion monotonically increases with decreasing throughput or increasing initial initiator concentration; with increasing barrel temperature, the monomer conversion first increases then decreases. The simulated results are nearly in good agreement with the experimental results.

Self-assembly of diblock copolymer mixtures in confined states: A Monte Carlo study

The self-assembly of diblock copolymer mixtures (A-b-B/A-b-C or A-b-B/B-b-C mixtures) subjected to cylindrical confinement (two-dimensional confinement) was investigated using a Monte Carlo method. In this study, the boundary surfaces were configured to attract blocks A but repel blocks B and C. Relative to the structures of the individual components, the self-assembled structures of mixtures of the diblock copolymers were more complex and interesting. Under cylindrical confinement, with varying cylinder diameters and interaction energies between the boundary surfaces and the blocks, we observed a variety of interesting morphologies. Upon decreasing the cylinder's diameter, the self-assembled structures of the A(15)B(15)/A(15)C(15) mixtures changed from double-helix/cylinder structures (blocks B and C formed double helices, whereas blocks A formed the outer barrel and inner core) to stacked disk/cylinder structures (blocks B and C formed the stacked disk core, blocks A formed the outer cylindrical barrel), whereas the self-assembled structures of the A(15)B(7)/B7C15 mixtures changed from concentric cylindrical barrel structures to screw/cylinder structures (blocks C formed an inside core winding with helical stripes, whereas blocks A and B formed the outer cylindrical barrels) and then finally to the stacked disk/cylinder structures.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.

Preparation and properties of a reactive type nonionic surfactant grafted linear low density polyethylene

A reactive type nonionic surfactant, monostearic acid monomaleic acid glycerol diester (MMGD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene ( LLDPE) with MMGD was carried out by using beta ray irradiation in air in a twin-screw extruder. Evidence of the grafting of MMGD as well as its extent was determined by Fourier-transformed infrared (FT-IR) spectroscopy. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-MMGD was investigated by using differential scanning calorimety ( DSC). Compared with neat LLDPE, the crystallization temperature ( Tc) of LLDPE-g-MMGD increased about 3 degrees C, and the melting enthalpy (Delta H-m) decreased with increase of MMGD content. It showed that the grafted MMGD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-MMGD film. The wettability is expressed by the water contact angle. With an increasing percentage of MMGD, the contact angles of water on film surface of LLDPE- g-MMGD decrease monotonically.

Preparation and properties of a novel nonionic surfactant grafted linear low density polyethylene

A novel nonionic surfactant, glycerol monostearic acid monomaleic acid diester (GMMD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene (LLDPE) with GMMD was carried out by using P-ray irradiation in a twin-screw extruder. Evidence of the grafting of GMMD, as well as its extent, was determined by FT-IR. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-GMMD was investigated by using differential scanning calorimety (DSC). Compared with neat LLDPE, the crystallization temperature (T,) of LLDPE-g-GMMD increased about 3 degrees C, and the melting enthalpy (Delta H-m) decreased with increase of GMMD content. It showed that the arafted GMMD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-GMMD film. Accelerated dripping property of film samples was investigated. The dripping duration of LLDPE-g-GMMD film and commercial anti-fog dripping film at 60 degrees C were 52 days and 17 days, respectively.

Study on crystalline morphology of poly(L-lactide)-poly(ethylene glycol) diblock copolymer

Crystallization behavior, structural development and morphology evolution in a series of diblock copolymers Of poly(L-lactide)-blockpoly(ethylene glycol) (PLLA-b-PEG) were investigated via differential scanning calorimetry, wide-angle X-ray diffraction, polarized optical microscopy and atomic force microscopy. In these copolymers, both blocks are crystallizable and biocompatible. It was interesting that these PLLA-b-PEG diblock copolymers could form spherulites with banded textures, which was undercooling dependent. Single crystals with an abundance of screw dislocations were also observed via AFM. Such results indicated that these ringed spherulites and single crystals were formed during the crystallization of the PLLA blocks.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.

Properties of compatibilized nylon 6/ABS polymer blends

Nylon 6/poly(acrylonitrile-butadiene-styrene)(ABS) blends were prepared in the molten state by a twin-screw extruder. Maleic anhydride-grafted polypropylene (MAP) and solid epoxy resin (bisphenol type-A) were used as compatibilizers for these blends. The effects of compatibilizer addition to the blends were studied via tensile, torque, impact properties and morphology tests. The results showed that the additions of epoxy and MA copolymer to nylon 6/ABS blends enhanced the compatibility between nylon 6 and ABS, and this lead to improvement of mechanical properties of their blends and in a size decrease of the ABS domains.

Helix-sense-selective polymerization of N,N-diphenyl (meth)acrylamide by anionic catalysts

In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diplienyl methacrylamide(DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too. It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

Liquid crystalline phases, microtwinning in crystals and helical chirality transformations in a main-chain chiral liquid crystalline polyester

A main-chain nonracemic chiral liquid crystalline polymer was synthesized from (R)-(-)4'-{w-[2-(p-hydroxy-o-nitrophenyloxy)-1-propyloxy]-1-decyloxyl-4-biphenylcarboxylic acid. This polymer contained 10 methylene units in each chemical repeating unit and was abbreviated PET(R*-10). On the basis of differential scanning calorimetry, wide-angle X-ray diffraction, and polarized light microscopy experiments, chiral smectic C (S-C*) and chiral smectic A (S-A*) phases were identified. Both flat-elongated and helical lamellar crystal morphologies were observed in transmission electron microscopy. Of particular interest was the flat-elongated lamellar crystals were constructed via microtwinning of an orthorhombic cell with dimensions of a = 1.42 nm, b = 1.28 nm, and c = 3.04 nm. On the other hand, the helical lamellar crystals were exclusively left-handed, which was opposite to the right-handed helical crystals grown in PET(R*-9) and PET(R*-11) (having 9 and 11 methylene units, respectively). Note that these three polymers had identical right-handed chiral centers (R*-). Therefore, a single methylene unit difference on the polymer backbones on an atomic length scale substantially changed the chirality of the crystals in the micrometer length scale. Furthermore, aggregates of these helical crystals in PET(R*-10) did not generate banded spherulites in polarized light microscopy. Possible reasons for this change and loss of helical senses (handedness) on different length scales in chirality transferring processes were discussed.