Mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and a catalyst in catalytic degradation of polyethylene

The possibility of mesoporous acid solid as a carrier for metallocene catalyst in ethylene polymerization and catalyst for polyethylene (PE) catalytic degradation was investigated. Here, HMCM- 41 and AIMCM-41, and mesoporous silicoaluminophosphate molecular sieves (SAPO1 and SAPO2) were synthesized and used as acid solid. Much more gases were produced during catalytic degradation in PE/acid solid mixtures via in situ polymerization than those via physical mixing. The particle size distribution results exhibited that the particle size of SAPO1 in the PE/SAPO1 mixture via in situ polymerization was about 1/14 times of that of the original SAPO1 or SAPO1-supported metallocene catalyst. This work shows a novel technology for chemical recycling of polyolefin.

Effect of copolymerized ethylene unit on the crystallization behavior of poly(propylene-co-ethylene)s

The crystallization behavior of two kinds of commercial poly(propylene-co-ethylene)s (PPE1, PPE2) with similar average molecular weight and molecular weight distribution, isotacticity and copolymerized ethylene unit content and their fractions was investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and polarized optical microscopy (POM) techniques. The results indicate that the PPE1 isothermally crystallized films possess thicker and less cross-hatched lamellar structure than those of the PPE2. As for the fractionated samples, the thin films of low temperature (less than or equal to 90 degreesC) fractions (PPE1-80, PPE2-80) of both PPE1 and PPE2 exhibit similar crystallization behavior, while for the high temperature ( greater than or equal to 95 degreesC) fractions (PPE1-108, PPE2-108), the crystalline morphology has marked differences. Compared with PPE2-108, the PPE1-108 isothermally crystallized thin films possess thicker lamellae and less crosshatched lamellar structure, while for the fibrous crystal number, the former is less than that of the latter. The main reason to create the crystallization behavior differences between the two PPEs and their fractions is due to the effect of molecular chain structure, i.e. the different distribution of copolymerized ethylene unit in polypropylene chains.

Effect of the gamma-form crystal on the thermal fractionation of poly(propylene-co-ethylene)

The effect of the gamma-form crystal on the thermal fractionation of a commercial poly(propylene-co-ethylene) (PPE) has been studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) techniques. Two thermal fractionation techniques, stepwise isothermal crystallization (SIC) and successive self-nucleation and annealing (SSA), have been used to characterize the molecular heterogeneity of the PPE. The results indicate that the SSA technique possesses a stronger fractionation ability than that of the SIC technique. The heating scan of the SSA fractionated sample exhibits 12 endothermic peaks, whereas the scan of the SIC fractionated sample only shows eight melting peaks. The WAXD observations of the fractionated PPE samples prove that the content of the gamma-form crystals formed during the thermal treatment of the SIC technique is much higher than that of the SSA treatment. The former is 57.4%, whereas the later is 12.6%. The effect of they-form crystals on thermal fractionation ability is discussed.

Isothermal crystallization kinetics of iPP during self-nucleation process

In this paper, the isothermal crystallization kinetics of polypropylene (iPP) during self-nucleation was studied by means of differential scanning calorimetry(DSC). The iPP was melted at 438 K and then isothermally crystallized in the range of temperature between 421 and 425 K. The mechanism of nucleation and growth of iPP was discussed. The Avrami equation was applied to analyzing the process of isothermal crystallization of iPP from the melt. The average value of Avrami exponent is n=3.01, suggesting that the primary crystallization maybe corresponds to three-dimensional spherulitic growth. The K-g value obtained from Lauritzen-Hoffman equation is 1.128 X 10(5) K-2, which suggests that crystallization species should be regime I. The decrease of crystallization active energy and chain folding work indicates that the self-nucleation can greatly promote the overall crystallization of iPP.

Crystallization kinetics and morphology of nylon 1212

The isothermal and non-isothermal crystallization processes of nylon 1212 were investigated by polarized optical microscopy. The crystal growth rates of nylon 1212 measured in isothermal conditions at temperatures ranged from 182 to 132 degreesC are well comparable with those measured by non-isothermal procedures (cooling rates ranged from 0.5 to 11 degreesC/min). The kinetic data were examined with the Hoffman-Lauritzen nucleation theory on the basis of the obtained values of the thermodynamic parameters of nylon 1212. The classical regime I --> II and regime II --> III transitions occur at the temperatures of 179 and 159 degreesC, respectively. The crystal growth parameters were calculated with (100) plane assumed to be the growth plane. The regime I --> II --> III transition is accompanied by a morphological transition from elliptical-shaped structure to banded spherulite and then non-banded spherulite. The development of morphology during isothermal and non-isothermal processes shows a good agreement.

The critical lowest molecular weight for PEG to crystallize in cross-linked networks

Poly(ethylene glycol) (PEG) networks were synthesized by gamma-irradiation. The crystalline behavior of PEG was investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). It was shown that the crystallinity of PEG is dramatically lower in the cross-linked, networks than in pure PEG. When the molecular weight of PEG in the networks decreased to 1000, it could not crystallize at all. Moreover, we also found that the melting temperature of PEG is greatly affected by the presence of a cross-linked network.

Properties of a nanocomposite polymer electrolyte from an amorphous comb-branch polymer and nanoparticles

Three fully amorphous comb-branch polymers based on poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether of different molecular weights as side chains were synthesized. SiO2 nanoparticles of various contents and the salt LiCF3SO3 were added to these comb-branch polymers to obtain nanocomposite polymer electrolytes. The thermal and transport properties of the samples have been characterized. The maximum conductivity of 2.8x10(-4) S cm(-1) is obtained at 28 degreesC. In the system the longer side chain of the comb-branch polymer electrolyte increases in ionic conductivity after the addition of nanoparticles. To account for the role of the ceramic fillers in the nanocomposite polymer electrolyte, a model based on a fully amorphous comb-branch polymer matrix in enhancing transport properties of Li+ ions is proposed.

Brittle-ductile transition of particle toughened polymers: influence of the matrix properties

It was theoretically pointed out that the product of the yield stress and yield strain of matrix polymer that determined the brittle-ductile transition (BDT) of particle toughened polymers. For given particle and test condition, the higher the product of the yield stress and the yield strain of the matrix polymer, the smaller the critical interparticle distance (IDc) of the blends was. This was why the IDc (0.15 mum) of the polypropylene (PP)/rubber blends was smaller than that (0.30 mum) of the nylon 66/rubber blends, and the IDc of the nylon 66/rubber blends was smaller than that (0.60 mum) of the high density polyethylene (HDPE)/rubber blends.

Grafting of maleic anhydride onto linear polyethylene: A Monte Carlo study

Monte Carlo simulation was used to study the graft of maleic anhydride (MAH) onto linear polyethylene (PE-g-MAH) initiated by dicumyl peroxide (DCP). Simulation results revealed that major MAH monomers attached onto PE chains as branched graft at higher MAH content. However, at extremely low MAH content, the fraction of bridged graft was very close to that of branched graft. This conclusion was somewhat different from the conventional viewpoint, namely, the fraction of bridged graft was always much lower than that of branched graft under any condition. Moreover, the results indicated that the grafting degree increased almost linearly to MAH and DCP concentrations. On the other hand, it was found that the amount of grafted MAH dropped sharply with increasing the length of grafted MAH, indicating that MAH monomers were mainly attached onto the PE chain as single MAH groups or very short oligomers. With respect to the crosslink of PE, the results showed that the fraction of PE-(MAH)(n)-PE crosslink structure increased continuously, and hence the fraction of PE-PE crosslink decreased with increasing MAH concentration.

Effect of annealing on the viscoelastic and viscoplastic responses of low-density polyethylene

Two series of tensile tests with constant crosshead speeds (ranging from 5 to 200 mm/min) and tensile relaxation tests (at strains from 0.03 to 0.09) were performed on low-density polyethylene in the subyield region of deformations at room temperature. Mechanical tests were carried out on nonannealed specimens and on samples annealed for 24 h at the temperatures T = 50, 60, 70, 80, and 100 degreesC. Constitutive equations were derived for the time-dependent response of semicrystalline polymers at isothermal deformations with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical crosslinks, and lamellar blocks). The network is thought of as an ensemble of mesoregions linked with each other. The viscoelastic behavior of a polymer is modeled as a thermally induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects sliding of junctions in the network with respect to their reference positions driven by macrostrains. Stress-strain relations involve five material constants that were found by fitting the observations.

The viscoelastic and viscoplastic behavior of low-density polyethylene

Three series of tensile tests with constant cross-head speeds (ranging from 5 to 200 mm/min), tensile relaxation tests (at strains from 0.03 to 0.09) and tensile creep tests (at stresses from 2.0 to 6.0 MPa) are performed on low-density polyethylene at room temperature. Constitutive equations are derived for the time-dependent response of semicrystalline polymers at isothermal deformation with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. The viscoelastic behavior of a polymer is modelled as thermally-induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects mutual displacement of meso-domains driven by macro-strains. Stress-strain relations for uniaxial deformation are developed by using the laws of thermodynamics. The governing equations involve five material constants that are found by fitting the observations. Fair agreement is demonstrated between the experimental data and the results of numerical simulation.

Synthesis of a novel structural triblock copolymer of poly(gamma-benzyl-L-glutamic acid)-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone)

A novel structural triblock copolymer of poly(gamma-benzyl-L-glutamic acid)-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PBLG-PEO-PCL) was synthesized by a new approach in the following three steps: (1) sequential anionic ring opening polymerization (ROP) of ethylene oxide and epsilon-caprolactone with an acetonitrile/potassium naphthalene initiator system to obtain a diblock copolymer CN-PEO-PCL with a cyano end-group; (2) conversion of the CN end-group into NH2 end-group by hydrogenation to obtain NH2-PEO-PCL; (3) ROP of gamma-benzyl-L-glutamate-N-carboxyanhydrides (Bz-L-GluNCA) with NH2-PEO-PCL as macroinitiator to obtain the target triblock copolymer. The structures from CN-PEO precursor to the triblock copolymers were confirmed by FT-IR and H-1 NMR spectroscopy, and their molecular weights were measured by gel permeation chromatography. The monomer of Bz-L-GluNCA can react almost quantitatively with the amino end-groups of NH2-PEO-PCL macroinitiator by ROP.

Synthesis of four-armed poly(epsilon-caprolactone)-block-poly(ethylene oxide) by diethylzinc catalyst

Biodegradable, amphiphilic, four-armed poly(epsilon-caprolactone)-block-poly(ethylene oxide) (PCL-b-PEO) copolymers were synthesized by ring-opening polymerization of ethylene oxide in the presence of four-armed poly(epsilon-caprolactone) (PCL) with terminal OH groups with diethylzinc (ZnEt2) as a catalyst. The chemical structure of PCL-b-PEO copolymer was confirmed by H-1 NMR and C-13 NMR. The hydroxyl end groups of the four-armed PC L were successfully substituted by PEO blocks in the copolymer. The monomodal profile of molecular weight distribution by gel permeation chromatography provided further evidence for the four-armed architecture of the copolymer. Physicochemical properties of the four-armed block copolymers differed from their starting four-armed PCL precursor. The melting points were between those of PCL precursor and linear poly(ethylene glycol). The length of the outer PEO blocks exhibited an obvious effect on the crystallizability of the block copolymer. The degree of swelling of the four-armed block copolymer increased with PEO length and PEO content.

Studies of instrumental spreading in gel permeation chromatography by coupling with a two-angle laser light scattering detector

The instrumental spreading of a high temperature gel permeation chromatograph (GPC) was evaluated by coupling with a two-angle laser light scattering (TALLS) detector, using narrow polystyrene, polyethylene, and syndiotactic polypropylene samples. The determined spreading factor increased with increasing molecular weight of polymers, and no maximum for spreading 174 tor was observed in the studied retention volume, while the spreading factors for single low molecular weight alkanes are independent of their molecular weight. Neglecting of the spreading effect for GPC would not introduce much error in molecular weight calculation when high quality high performance columns were used, especially when equipped with a laser light scattering detector. The scaling relationship between radius of gyration and molecular weight of polymer, determined by GPC with a TALLS detector, was independent of the instrumental spreading.

Preparation of fully cross-linked CNBR/PP-g-GMA and CNBR/PP/PP-g-GMA thermoplastic elastomers and their morphology, structure and properties

Binary CNBR/PP-g-GMA and ternary CNBR/PP/PP-g-GMA thermoplastic elastomers were prepared by reactive blending carboxy nitrile rubber (CNBR) powder with nanometer dimension and polypropylene functionalized with glycidyl methacrylate (PP-g-GMA). Morphology observation by using an atomic force microscope (AFM) and TEM revealed that the size of CNBR dispersed phase in CNBR/PP-g-GMA binary blends was much smaller than that of the corresponding CNBR/PP binary blends. Thermal behavior of CNBR/PP-g-GMA and CNBR/PP blends was studied by DSC. Comparing with the plain PP-g-GMA, T, of PP-g-GMA in CNBR/PP-g-GMA blends increased about 10degreesC. Both thermodynamic and kinetic effects would influence the crystallization behavior of PP-g-GMA in CNBR/PP-g-GMA blends. At a fixed content of CNBR, the apparent viscosity of the blending system increased with increasing the content of PP-g-GMA. FTIR spectrum verified that the improvement of miscibility of CNBR and PP-g-GMA was originated from the reaction between carboxy end groups of CNBR and epoxy groups of GMA grafted onto PP molecular chains. Comparing with CNBR/PP blends, the tensile strength, stress at 100% strain, and elongation at break of CNBR/PP-g-GMA blends were greatly improved.