Effect of polymerization catalyst technology on the melt processing stability of polyethylenes,Part 3: Additives blends performance

This article considers the interaction between additives that occur during the stabilization process. The simultaneous effects of the additives and associated interactions on melt processing stability and processing discoloration were of particular interest. Melt stability is an important factor to consider because physical changes in the processed polymer can occur during the compounding and fabrication steps. Furthermore, discoloration is one of the most important problems affecting commercial polymers. Most discoloration manifests itself as yellowing, especially in the case of polyolefins. Although yellowing can often be associated with degradation processes caused by various agents, such as light or heat, this is not always the case; yellowing can also be due to the interaction of additives in the stabilizer packages. Blends of primary antioxidants (AOs), secondary AOs, and hindered amine light stabilizers have been studied with the intention of further improving stabilization performance together with cost reduction of the stabilized polymer. Although synergism between AOs and a stabilizer is fairly common, antagonism was also observed in terms of melt flow protection and in color stability in some of the AOs tested. The effects of a range of thermal and light stabilizers on the melt stability (investigated via multiple pass extrusion) and color stability of three different polyethylenes (PEs) were examined. The PEs varied in terms of the catalyst system used to synthesize the polymers and included a high‐density polyethylene (HDPE) produced by using a chromium‐based Phillips catalyst and two linear low‐density polyethylenes (LLDPEs) produced via chromium‐based metallocene and titanium‐based Ziegler‐Natta catalysts. The apparent lack of influence of polymerization catalyst system on the mode of stabilizer interaction should lead to the reassessment of stabilizer formulation strategies in relation to PE type/catalyst system and associated commercial/economic considerations. J. VINYL ADDIT. TECHNOL., 22:117–127, 2016. © 2014 Society of Plastics Engineers     

Color inhibition of phenolic antioxidants in Ziegler‐Natta polyethylene. I. In‐situ polymer studies

Although the level of transition‐metal catalyst residues in polyethylene (PE) has been drastically reduced over the years, they can still give rise to discoloration, particularly when associated with other additives such as antioxidants. This first of this series of papers screens a variety of candidate color suppressants featuring a range of functional groups, including alcohols, amine/sulfur compounds, and acid‐containing species. These candidate color suppressants were melt‐blended into a Ziegler‐Natta linear low‐density PE in combination with 2,2′‐isobutylidenebis(4,6‐dimethylphenol) (a highly discoloring hindered bisphenol antioxidant) and zinc stearate antacid. Yellowness index measurements made after multiple extruder passes indicated that dipentaerythritol (DPE) and triisopropylamine (TIPA) gave good color inhibition and, in some cases, outperformed established phosphites. The DPE and TIPA were found (via melt flow rate measurement) not to affect melt stability, and hydroperoxide determination revealed that DPE had no peroxide decomposition activity. The latter results indicate that the color‐suppression mechanism of DPE and TIPA is different from that associated with phosphites. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Effects of type of polymerization catalyst system on the degradation of polyethylenes in the melt state. Part 1: Unstabilized polyethylenes (including metallocene types)

Several polyethylene resins namely, high‐density polyethylene (HDPE) (Phillips metal oxide catalyst) and linear low‐density polyethylenes (LLDPE) (formed by using Ziegler‐Natta and metallocene catalyst technologies), were used in order to acquire insight into the effect of different polymerization catalyst systems on the production of degradation products during melt processing. Infrared spectroscopy, color measurement, hydroperoxide determination, and melt flow rate measurement were used to monitor the degradation as a function of the number of passes through a twin‐screw extruder. The metallocene PEs were shown to exhibit superior melt stability relative to Phillips HDPE. The latter showed high levels of hydroperoxide formation. The superior thermo‐oxidative stability of the metallocene PEs was attributed to low levels of metallic catalyst residues, together with low vinyl unsaturation content. In all of the PEs examined, the rate of crosslinking was greater than that of chain scission. IR spectroscopy indicated that crosslinking (most prevalent in the Phillips HDPE) proceeded via the addition of macroradicals to vinyl unsaturation. The Ziegler‐Natta LLDPE showed an intermediate tendency for crosslinking but notable formation of trans‐vinylidene and the most noticeable color development. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Color inhibition of phenolic antioxidants in Ziegler‐Natta polyethylene. II. In‐situ solution studies

Part I of this series of papers showed that color suppression (in some cases superior to that with established phosphites) of polyethylenes (PEs) containing a highly discoloring hindered phenolic antioxidant, Lowinox 22IB46 [2,2′‐isobutylidenebis(4,6‐dimethylphenol)] (L22IB46), and titanium catalyst residues could be achieved by using a range of relatively low cost multifunctional compounds, among which dipentaerythritol (DPE) and triisopropanolamine (TIPA) performed notably well. It was speculated that the latter compounds in some way blocked the formation of highly chromophoric species, which were thought to be titanium phenolates. The studies conducted in Part II further investigate this effect via a solution‐based model‐compound approach, with decahydronaphthalene and titanium and aluminum isopropoxides as models for the PE and Ti‐ and Al‐based catalyst residues, respectively. This approach enabled the use of second‐derivative UV spectroscopy of refluxing solutions for the detection of chromophoric species. The level of antioxidant consumption was determined by using UV spectroscopy, and L22IB46 – (color suppressant) reaction products were characterized by using infrared spectroscopy. Titanium(IV) was found to play a major role in discoloration (via production of titanium phenolates) and the consumption of L22IB46 relative to that of aluminum, which displayed little color formation activity. This observation shows that L22IB46 oxidation products are not necessarily the major cause of discoloration. The DPE and TIPA also performed well in this solution‐based study, though interesting chain‐length‐related (and possibly solubility‐related) effects were apparent with poly(ethylene glycol). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Optimization of stabilizer formulations for polyolefin processing

An approach to formulation is presented that is based on a statistical experimental design package for use on a personal computer. The total level of phosphite + hindered phenol, and the ratio of phosphite to hindered phenol are used as experimental variables. The approach was tested on extrusions of polypropylene using melt flow retention and yellowness index as observed variables. A quadratic model gave a satisfactory fit to the data for both variables. Contour plots are presented of the performance of the systems for two commercially available hindered phenols and two polypropylene samples. The largest difference between the resins is in the degree of color generation on extrusion. For both hindered phenols, a resin made using “3rd generation” or “high activity” catalyst gave lowest color development on extrusion. There were also small differences in the response of the melt flow of the resins to phosphite level.     

Aspects of stabilization with phosphorous antioxidants in polymers

As plastics are being used in a variety of applications, demands on a greater level of processing stability are increasing. Phosphites are noteworthy as effective processing stabilizer and the performance of phosphite antioxidants can be correlated to the chemical structure of phosphites. Cyclic phosphite esters derived from 2, 2′ methylene bis-2, 4-di-tert-butylphenol and some commercially available phosphites were submitted to comparative studies. Decomposition of cumene hydroperoxide, melt flow of polypropylene and consumption of additives after multiple extrusions were investigated to understand the activity of phosphites as process stabilizers in polypropylene. This study suggests that phosphites play an important role in process stabilization when used in combination with sterically hindered phenols, and that the activity of phosphites may be predicted by their reactivity on hydroperoxide.     

Additive interactions in the stabilization of film grade high-density polyethylene. Part I: Stabilization and influence of zinc stearate during melt processing

The melt stabilization activity of some of the most commercially significant phenolic antioxidants and phosphites (alone and in combination), without and with zinc stearate, was studied in high-density polyethylene (HDPE) produced by Phillips catalyst technology. Multiple pass extrusion experiments were used to degrade the polymer melt progressively. The effect of stabilizers was assessed via melt flow rate (MFR) and yellowness index (YI) measurements conducted as a function of the number of passes. The level of the phenolic antioxidant remaining after each extrusion was determined by high-performance liquid chromatography (HPLC). Phenolic antioxidants and phosphites both improved the melt stability of the polymer in terms of elt viscosity retention; the influence of zinc stearate was found to be almost insignificant. However, phosphites and zinc stearate decreased the discoloration caused by the phenolic antioxidants. A correlation was found between the melt stabilization performance of phosphites and their hydroperoxide decomposition efficiency determind via a model hydroperoxide compound. Steric and electronic effects associated with the phosphorus atom influenced the reactivity towards hydroperoxides. Furthermore, high hydrolytic stability did not automatically result in lower efficiency. Besides phosphite molecular structure, stabilization activity was also influenced by the structure of the primary phenolic antioxidant and the presence of zinc stearate.     

Synthesis and antioxidative properties of novel multifunctional stabilizers

New multifunctional stabilizers containing hindered amino, phosphite, and in some cases also free phenolic moieties have been synthesized starting from tris(diethylamino)phosphine. Some of them proved to be efficient stabilizers for model hydrocarbons and for polypropylene during processing, thermo‐, and photooxidation. Various sterically hindered phenols, amines (HAS), and phosphites have been modified by the reaction with isophorone diisocyanate (IPDI) to get new multifunctional stabilizers for polymers. The synthesized products have been investigated regarding their thermal and antioxidative behavior. The novel urethane stabilizers are, depending during the polymer processing to release the antioxidatively active parent phenols.     

Preparation of shish‐kebab and nanofiber polyethylene with chromium/Santa Barbara amorphous silica‐15 catalysts

Cr/SBA‐15 catalysts were prepared by the grafting of chromium nitrate nonahydrate [Cr(NO₃)₃·9H₂O] complexes onto SBA‐15 mesoporous materials. Shish‐kebab and nanofiber polyethylenes (PEs) were prepared under different temperatures via ethylene extrusion polymerization with the Cr(NO₃)₃·9H₂O catalytic system. The diameter of a single nanofiber was 100–250 nm. Scanning electron microscopy images showed that the polymer obtained from the SBA‐15‐supported catalyst under different polymerization temperatures produced nanofiber and/or shish‐kebab morphologies. X‐ray diffraction and differential scanning calorimetry were used to characterize microstructures of the materials. Polymers obtained with all of the catalysts showed a melting temperature, bulk density, and high load melt index; this indicated the formation of linear high‐density PE. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Organophosphorus antioxidants action mechanisms and new trends

Phosphite and phosphonite esters can act as antioxidants by three basic mechanisms depending on their structure, the nature of the substrate to be stabilized and the reaction conditions. All phosph(on)ites are hydroperoxide-decomposing secondary antioxidants. Their efficiency in hydroperoxide reduction decreases in the order phosphonites > alkylphosphites > arylphosphites > hindered arylphosphites. Five-membered cyclic phosphites are capable of decomposing hydroperoxides catalytically due to the formation of acidic hydrogen phosphates by hydrolysis and peroxidolysis in the course of reaction. Hindered aryl phosphites can act as chain-breaking primary antioxidants being substituted by alkoxyl radicals and releasing hindered aryloxyl radicals which terminate the radical chain oxidation. At ambient temperatures, the chain-breaking antioxidant activity of aryl phosphites is lower than that of hindered phenols, because the rate of their reaction with peroxyl radicals and their stoichiometric inhibition factors are lower than those of phenols. In oxidizing media at medium temperatures, however, hydrolysis of aryl phosph(on)ites takes place giving hydrogen phosph(on)ites and phenols which are effective chain-breaking antioxidants. 2,2,6,6-Tetramethyl- and 1,2,2,6,6-Pentamethylpiperidinyl phosphites and phosphonites (HALS-phosph(on)ites) surpass many common phosphites, phenols and HALS compounds as stabilizers in the thermo- and photo-oxidation of polymers. Their superior efficiency is probably due to an intramolecular synergistic action of the HALS and the phosph(on)ite moieties of their molecules.     

Relationship between bridged groups and antioxidant activity for aliphatic diamine bridged hindered phenol in polyolefins

Four aliphatic diamine bridged hindered phenols were successfully synthesized with aliphatic diamine as the bridged group and 3‐(3,5‐di‐tert‐butyl‐4‐hydroxy‐phenyl)‐propionyl chloride as the material, and their structures were clarified by NMR, Fourier transform infrared spectroscopy, and mass spectrometry. Their performance as antioxidant for polypropylene (PP) and linear low‐density polyethylene (LLDPE) were investigated through the melt flow rate and the oxidation induction time. The thermooxidative stabilities of PP and LLDPE with different aliphatic diamine bridged hindered phenols were assessed by the measurement of the oxidation induction temperature and with long‐term aging testing. The results showed that aliphatic diamine bridged hindered phenols could protect two kinds of polyolefins from thermal oxidative degradation, and the mechanical properties and antioxidant activities of polyolefins stabilized with aliphatic diamine bridged hindered phenols were increased with increasing length of the bridged group for aliphatic diamine bridged hindered phenols at the same concentration of phenolic hydroxyl group. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45095.     

Recycling of off‐grade pet via partial alcoholysis to synthesize functionalized pet oligomer nanocomposites

Off‐grade poly(ethylene terephthalate) (PET) of industrial manufacturers was partially depolymerized using excess ethylene glycol in the presence of manganese acetate as a transesterification catalyst to synthesize PET oligomers. Influences of reaction time, Ethylene Glycol (EG)/PET molar ratio, catalyst concentrations, and particle size of off‐grade PET on yield of partial glycolysis reaction were investigated based on Box–Behnken's design of experiment. Thermal analyses of glycolyzed products are examined by differential scanning calorimetry. The optimum samples were also well‐characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR). The optimal conditions to synthesize PET oligomer (melting point of about 180°C) for a 120‐min glycolysis reaction time were EG/PET molar ratio of 2 with no catalyst using granule‐shaped PET. The same results were obtained for a 60‐min glycolysis reaction time, including EG/PET molar ratio of 1 with the weight ratio (catalyst to PET) of 0.5% using average particle size of PET. Then, maleated PET as a compatibilizer for preparing PET nanocomposites was produced via reaction between maleic anhydride/phthalic anhydride composition and optimized PET oligomers based on central composite design of experiment. The combination of reaction time of 106 min and PhA/MA molar ratio of 0.85 gave the best results based on d‐spacing and peak shift of nanocomposite samples. Hence, melt mixing of maleated PET with organoclay produced a good intercalation of layered silicate and good dispersion of clay in maleated PET matrix. Analysis of variance (ANOVA) was studied for both glycolyzed products and functionalized PET oligomers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of the melt flow index and melt flow rate on the thermal degradation kinetics of commercial polyolefins

In this study, several polyolefins, including different grades of polypropylene (PP), high‐density polyethylene, linear low‐density polyethylene, and low‐density polyethylene, were tested by thermogravimetric analysis (TGA), and the relationships of their melt flow index (MFI) and melt flow ratio (MFR) values to the thermogravimetry (TG) curves, differential thermogravimetry (DTG) curves, and activation energy of thermal degradation were investigated. Kinetic evaluations were performed by Friedman and Kissinger analysis methods, and the apparent activation energy values for the overall degradation of different grades of polyethylenes (PEs) and PPs were determined. We found that for the samples with lower MFIs, the thermograms shifted to higher temperatures. Meanwhile, a higher activation energy was needed for their thermal degradation. Also, for samples with higher values of MFR, as a means of molecular weight distribution, a lower activation energy was needed for their thermal degradation, and their TGA thermograms shifted to lower temperatures. The breadth of the DTG curves depended on the MFR in the PEs, although MFR had little effect on the DTG curves in the studied PP grades. Among all of the samples studied, the injection‐molding grades with medium MFIs and low MFRs degraded at higher temperatures and showed better thermal stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Synthesis of high molecular weight aromatic polyesters via integrated alternating ring-opening copolymerization and chain extension methods

Due to their good mechanical properties, high molecular weight polyesters (PEs) are highly desirable for a wide range of applications especially in the packaging industry. However, the synthesis of high molecular weight polymers by energy efficient methods is difficult. In this study, a series of semi-aromatic PEs were synthesized via the alternating ring-opening copolymerization (ROCOP) of phthalic anhydride (PA) and cyclohexene oxide (CHO) using a salen chromium(III) complex as a catalyst and 4-(dimethylamino)pyridine as a cocatalyst. By varying the molar ratios between CHO and PA, PEs of different molecular weights were obtained. Hexamethylene diisocyanate was used as a chain extender that further increased the molecular weights of these PEs. These chain extended aromatic polyesters (PE-Xs) showed significant improvement in the glass transition temperature (T_g) values. Thus, integration of ROCOP with the chain extension method can be used as an effective strategy to prepare high molecular weight PEs with improved thermal stabilities and enhanced mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47200.     

Phosphites in polyolefin process stabilization

The use of stabilizer systems containing phosphites in polyolefins is well-established in the technical and patent literature. In addition to the known effects of improved heat and color stability for polyolfins, we have recently found that phosphite-containing stabilizer systems impart a process stabilizing effect as evidenced by melt flow analysis. By monitoring the poly-olefin melt flow after multiple extrusions with increasing temperature, it was found that the combination of phenolics and phosphites has a marked influence on the control of melt flow of polyolefins and the effect appears to be synergistic in operation.     

Synthesis,characterization, and application of oligomer‐type‐based phosphites

Organic alkyl and aryl phosphites are effective antioxidants and photostabilizers with applications in a wide range of polymers. The primary role of phosphites is to decompose hydroperoxide. However, aryl phosphites are also capable of reacting as antioxidants by affecting the kinetics. In particular, oligomer‐type phosphites have a greater effect on polymer degradation because of their high compatibility, reactivity, and solubility with almost all polymers. Generally, phosphites are sensitive to hydrolysis. In order to overcome this hydrolytic sensitivity in phosphites, a novel hydrolytically stable oligomeric phosphite incorporating a sterically hindered aromatic alcohol (2,4‐di‐tert‐butyl‐6‐methylphenol) that gives hydrolytic stability to the phosphite was synthesized and characterized, and its performance as an antioxidant for polypropylene was investigated. J. VINYL ADDIT. TECHNOL., 22:146–155, 2016. © 2014 Society of Plastics Engineers     

Effect of catalyst residues on the chain structure and properties of a Phillips type polyethylen

A large number of high‐density polyethylene (HDPE) powder samples produced by Phillips technology were taken from an industrial polymerization reactor and their catalyst residue content was determined by X‐ray fluorescence spectroscopy. The chemical structure of the powder was characterized by diffuse reflectance infrared spectroscopy (DRIFT), while the functional group content of samples processed in the presence and absence of a phenolic antioxidant was determined by Fourier transform infrared spectroscopy (FTIR). The melt flow index (MFI) of all processed samples was measured. Oxygen induction time (OIT) measurements were carried out to characterize the oxidative stability of 15 selected stabilized samples. The results indicate that the distribution of both the amount of chromium‐based catalyst residues and their composition are very heterogeneous in the produced polymer. With increasing catalyst residue content, the concentration of double bonds increases in the samples extruded with or without stabilizer. Viscosity was not influenced by catalyst residues, while discoloration increased slightly with increasing catalyst residue content. The stability of the processed polymer also depends on the concentration of double bonds and on other factors. Since other components of the catalyst, including the SiO₂ support, also take part in the reactions occurring during processing, chromium content is not the sole, and perhaps not even the decisive, factor determining the properties and especially the stability of HDPE produced by a Phillips catalyst.     

Synthesis,characterization, and application of a hydrolytically stable liquid phosphite

Organic alkyl and aryl phosphites are effective antioxidants and photostabilizers with applications in a wide range of polymers. The primary role of phosphites is to decompose hydroperoxide. However, aryl phosphites are also capable of reacting as antioxidants by negatively affecting the kinetics. In particular, liquid phosphites have a greater effect on polymer degradation because of their high compatibility, reactivity, and solubility with almost all polymers, but they are sensitive to hydrolysis. In order to overcome this hydrolytic sensitivity in liquid phosphites, a novel hydrolytically stable liquid phosphite incorporating a sterically hindered aromatic alcohol (2,4‐di‐tert‐butyl‐6‐methylphenol) that gives hydrolytic stability to the phosphite was synthesized and characterized, and its performance as an antioxidant for polypropylene was investigated. J. VINYL ADDIT. TECHNOL., 22:163–168, 2016. © 2014 Society of Plastics Engineers     

Design of Ionic Phosphites for Catalytic Hydrocyanation Reaction of 3‐Pentenenitrile in Ionic Liquids†

The synthesis and characterization of a novel class of ionic phosphites bearing either a single cationic group obtained by quaternization of aminophosphites or three cationic groups prepared by reaction of phosphorus trichloride with imidazolium phenols are reported. The catalytic hydrocyanation reaction of 3‐pentenenitrile (3PN) into adiponitrile has been performed in the presence of Ni(0) with ionic phosphite ligands, and a Lewis acid in biphasic ionic liquid/organic solvent system. The screening of several original cationic phosphites was performed and the experimental conditions were optimized for the tri‐cationic phosphite tris‐4‐[(2,3‐dimethylimidazol‐1‐yl)methyl]phenyl phosphite tris[bis(trifluoromethylsulfonyl)amide]. It is possible to obtain performance similar to molecular systems and the catalyst and the Lewis acid were immobilized in the ionic phase.     

Synthesis and characterization of polyhydroxylated polybutadiene binding 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) with isophorone diisocyanate

A macromolecular hindered phenol antioxidant, polyhydroxylated polybutadiene containing thioether binding 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (PHPBT‐b‐TPH), was synthesized via a two‐step nucleophilic addition reaction using isophorone diisocyanate (IPDI) as linkage. First, the ? OH groups of PHPBT reacted with secondary ? NCO groups of IPDI to form the adduct PHPBT‐NCO, then the PHPBT‐b‐TPH was obtained by one phenolic ? OH of 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (TPH) reacting with the PHPBT‐NCO. The PHPBT‐b‐TPH was characterized by Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H‐NMR), ¹³C‐NMR, and thermogravimetric analysis, and its antioxidant activity in natural rubber was studied by an accelerated aging test. Influences of reaction conditions on the two nucleophilic reactions between ? OH group and ? NCO group were investigated. In addition, catalytic mechanism for the reaction between PHPBT‐NCO and TPH was discussed. The results showed that the adduct PHPBT‐NCO could be obtained by using dibutyltin dilaurate (DBTDL) as catalyst, and the suitable temperature and DBTDL amount were 35°C and 3 wt %, respectively. However, triethylamine (TEA) was more efficient than DBTDL to catalyze the reaction between PHPBT‐NCO and TPH because of steric hindrance effect. In addition, it was found that the thermal stability and antioxidant activity of PHPBT‐b‐TPH were higher than those of the low molecular weight antioxidant TPH. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40942.