The role of chain scission and chain branching in high density polyethylene during thermo-mechanical degradation

The mechanical and thermo-oxidative degradation of high density polyethylene (HDPE) was measured in a twin-screw extruder using various processing conditions. Two types of HDPE, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturation were analysed. Mild screw profiles, having mainly conveying elements, have short mean residence times then profiles with kneading discs and left hand elements. Carbonyl and traps-vinylene group concentrations increased, whereas vinyl group concentration decreased with number of extrusions. Higher temperature profiles intensified these effects. The thermo-mechanical degradation mechanism begins with chain scission in the longer chains due to their higher probability of entanglements. These macroradicals then react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the levels of extrusion temperature, shear and vinyl end groups content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than does the Ziegler-Natta type. (C) 2004 Elsevier Ltd. All rights reserved.

Investigation of the oxidative degradation mechanisms and melt stabilisation of a new generation metallocene polytehylene

The two main objectives of the research work conducted were firstly, to investigate the processing and rheological characteristics of a new generation metallocene catalysed linear low density polyethylene (m-LLDPE), in order to establish the thermal oxidative degradation mechanism, and secondly, to examine the role of selected commercial stabilisers on the melt stability of the polymers. The unstabilised m-LLDPE polymer was extruded (pass I) using a twin screw extruder, at different temperatures (210-285°C) and screw speeds (50-20rpm) and was subjected to multiple extrusions (passes, 2-5) carried out under the same processing conditions used in the first pass. A traditional Ziegler/Natta catalysed linear low density polyethylene (z-LLDPE) produced by the same manufacturer was also subjected to a similar processing regime in order to compare the processability and the oxidative degradation mechanism (s) of the new m-LLDPE with that of the more traditional z-LLDPE. The effect of some of the main extrusion characteristics of the polymers (m-LLDPE and z-LLDPE) on their melt rheological behaviour was investigated by examining their melt flow performance monitored at two fixed low shear rate values, and their rheological behaviour investigated over the entire shear rates experienced during extrusion using a twin-bore capillary rheometer. Capillary rheometric measurements, which determine the viscous and elastic properties of polymers, have shown that both polymers are shear thinning but the m-LLDPE has a higher viscosity than z-LLDPE and the extent of reduction in viscosity of the former when the extrusion temperature was increased from 210°C to 285°C was much higher than in the case of the z-LLDPE polymer. This was supplied by the findings that the m-LLDPE polymer required higher power consumption under all extrusion conditions examined. It was fUliher revealed that the m-LLDPE undergoes a higher extent of melt fracture, the onset of which occurs under much lower shear rates than the Ziegler-based polymer and this was attributed to its higher shear viscosity and narrower molecular weight distribution (MWD). Melt flow measurements and GPC have shown that after the first extrusion pass, the initial narrower MWD of m-LLDPE is retained (compared to z-LLDPE), but upon further multiple extrusion passes it undergoes much faster broadening of its MWD which shifts to higher Mw polymer fractions, paliicularly at the high screw speeds. The MWD of z-LLDPE polymer on the other hand shifts towards the lower Mw end. All the evidence suggest therefore the m-LLDPE undergoes predominantly cross-linking reactions under all processing conditions whereas z-LLDPE undergoes both cross-linking and chain scission reactions with the latter occurring predominantly under more severe processing conditions (higher temperatures and screw speeds, 285°CI200rpm). The stabilisation of both polymers with synergistic combinations of a hindered phenol (Irganox 1076) and a phosphite (Weston 399) at low concentrations has shown a high extent of melt stabilisation in both polymers (extrusion temperatures 210-285°C and screw speeds 50-200rpm). The best Irganox 1076/Weston 399 system was found to be at an optimum 1:4 w/w ratio, respectively and was found to be most effective in the z-LLDPE polymer. The melt stabilising effectiveness of a Vitamin E/Ultranox 626 system used at a fraction of the total concentration of Irganox 1076/Weston 399 system was found to be higher in both polymers (under all extrusion conditions). It was found that AOs which operate primarily as alkyl (Re) radical scavengers are the most effective in inhibiting the thermal oxidative degradation of m-LLDPE in the melt; this polymer was shown to degrade in the melt primarily via alky radicals resulting in crosslinking. Metallocene polymers stabilised with single antioxidants of Irganox HP 136 (a lactone) and Irganox E201 (vitamin E) produced the highest extent of melt stability and the least discolouration during processing (260°C/1 OOrpm). Furthermore, synergistic combinations of Irganox HP I 36/Ultranox 626 (XP-60) system produced very high levels of melt and colour stability (comparable to the Vitamin E based systems) in the mLLDPE polymer. The addition of Irganox 1076 to an Irganox HP 136/Ultranox 626 system was found not to result in increasing melt stability but gave rise to increasing discolouration of the m-LLDPE polymer. The blending of a hydroxylamine (lrgastab FS042) with a lactone and Vitamin E (in combination with a phosphite) did not increase melt stability but induced severe discolouration of resultant polymer samples.

The synthesis, characterisation and electrical conductivity of poly(styrene-co-acetylene)

A novel metathesis catalyst for the polymerisation of acetylene has been developed. The polyacetylene produced by this new catalyst has been characterised by infra-red and NMR spectroscopy. The conductivity of the pristine material has been studied as a function of temperature, pressure and frequency. The effect on the conductivity of doping the material has also been investigated. The new metathesis catalyst has been incorporated into an anionic-to-metathesis transformation reaction. This novel reaction has been used to prepare samples of poly(styrene-co-acetylene). The copolymer has been characterised using U.V./Visible, NMR, infra-red spectroscopy and the surface morphology looked at using scanning electron microscopy. GPC was also used to give some idea of the molecular weights of the materials prepared. The conductivity of the copolymer has been studied as a function of temperature, pressure and frequency. The effect of doping on the conductivity the material has also been investigated. The conductivity results obtained from both materials have been used to try and gain an insight into the mechanism of the conduction processes occurring within the materials. An attempt has also been made to synthesise polyacetylene oligomers (polyenes) by modifying the Ziegler/Natta type catalysts commonly used to synthesise polyacetylene. The polyenes were characterised using U.V./Visible and infra-red spectroscopy together with GPC and GCMS.

Study into the densification behaviour of polyethylenes for rotational moulding

The melting and densification behaviour of a range of Polyethylenes (PEs) produced from 2 different catalysts, Ziegler-Natta and Metallocene types, were investigated using a novel visual data acquisition and analysis system (TP Picture®), developed by Total Petrochemicals Research Feluy [1]. Differences in the dissolution behaviour of the bubbles were observed and correlations with the material density, densification rate, bubble size / distribution and MFI were determined.

Isospecific polymerization of styrene with modified ziegler-type catalysts

Effects of various kinds of additives as well as aging of the catalyst on the polymerization of styrene catalyzed by TiCl4/MgCl2-AlEt3 system have been studied. Experiments show that in toluene the isotacticity of polystyrene can be up to 83% for aged catalyst, whereas when the catalyst is not aged. non-stereospecific polymer is the main product. When PCl3 is used as an additive, the catalyst system gives high activity and isotacticity. The use of a mixture of AlEt3/H2O (1: 1 mole ratio) as a cocatalyst is also efficient. The catalyst [TiCl4-PCl3/MgCl2-AlEt3/H2O] displays high activity and product isotacticity (94%) with an average molecular weight up to 2 X 10(-6). When Co(acac)(3) is added to to [TiCl4/MgCl2-AlEt3] catalyst after it was aged, the isotacticity can be up to 97%. (C) 2001 Elsevier Science Ltd. All rights reserved.

A profluorescent azaphenalene nitroxide for nitroxide-mediated polymerization

A novel nitroxide-mediated polymerization (NMP) control agent; 1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl (TMAO), was used in the free-radical polymerization of styrene. The conversion of styrene during NMP was studied using FT-Raman spectroscopy and the effectiveness of TMAO as a NMP control agent was assessed by GPC analysis. Fidelity of the TMAO-alkoxyamine end-group on the synthesized polymers was confirmed by GPC, UV-Vis and fluorescence spectroscopic analyses. Comparison to the well known NMP control agent, TEMPO was made. TMAO showed control of molecular weight approaching that of TEMPO. Attempts to improve the properties of TMAO as an NMP control agent by synthesizing an analogue with bulkier substituents around the nitroxide did not generate the target molecule but demonstrated some of the interesting chemistry of the azaphenalene ring system

Living characteristics of the free-radical ring-closing polymerization of diallyldimethylammonium chloride

In this communication we provide the most recent results on RAFT-mediated ring-closing polymerization of diallyldimethylammonium chloride (DADMAC). The polymerization was carried out in aqueous solution employing 2,2′-azobis(2-methylpropionamidine)-dihydrochloride as the free radical initiator and trithiocarbonate RAFT agent (2-{[(dodecylsulfanyl)carbonothioyl sulfanyl]}propanoic acid, DoPAT) as the controlling RAFT agent. The results show that – while the system is not as completely controlled as previously described – it is nevertheless possible to mediate the polymerization of DADMAC and impart some living characteristics onto the system. The initial study on the RAFT-mediated polymerization of DADMAC may have overestimated the degree of livingness within this reaction. However, it is possible – at low conversions – for some living characteristics to be observed, as the evolution of molecular weight with conversion is linear. In addition, polymers with a reasonably narrow polydispersity can be isolated.

Crowded Diphosphinomethane Ligands in Catalysis: [(R2PCH2PR′2-κ2P)-NiR″]+ Cations for Ethylene Polymerization without Activators

The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR′2 is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-η3-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)2]+[B(3,5-(CF3)2C6H3)4]−, while the complex [(dtbpm κ2P)Ni(η3-CH(CH2Ph)Ph]+[B(3,5-(CF3)2C6H3)4]−is obtained from protonation of the Ni(0) olefin complex (dtbpm-κ2P)N(η2-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic η3-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the η3-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R′ on the phosphine ligand has been examined, and a clear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial η3 to η3 haptotropic shift processes of the[(R2PCH2PR′2)Ni] fragment and the η3−η1 change of the coordination mode of the benzyl group required for polymerization in those cations.

Reversible addition fragmentation chain transfer (RAFT) polymerization : mechanism, process and applications

The present article gives an overview of the reversible addition fragmentation chain transfer (RAFT) process. RAFT is one of the most versatile living radical polymerization systems and yields polymers of predictable chain length and narrow molecular weight distribution. RAFT relies on the rapid exchange of thiocarbonyl thio groups between growing polymeric chains. The key strengths of the RAFT process for polymer design are its high tolerance of monomer functionality and reaction conditions, the wide range of well-controlled polymeric architectures achievable, and its (in-principle) non-rate-retarding nature. This article introduces the mechanism of polymerization, the range of polymer molecular weights achievable, the range of monomers in which polymerization is controlled by RAFT, the various polymeric architectures that can be obtained, the type of end-group functionalities available to RAFT-made polymers, and the process of RAFT polymerization.