Additive interactions in the stabilization of film grade high-density polyethylene. Part II: Stabilization during long-term service

In the second part of this study, the performance of phenol/phosphite/zinc stearate packages and the contribution of each additive to the long-term thermal stabilization and photostabilization were evaluated in high-density polyethylene produced by using Phillips catalyst technology. Infrared spectroscopy, ultraviolet spectroscopy, and yellowness index measurements were used to establish the performance of the different additive packages. The HPLC analysis of dichloromethane extracts of the polymer was carried out after melt processing in order to determine the amount of phenolic antioxidant remaining in the samples. The long-term thermal stabilization was dependent only upon the phenolic antioxidant concentration, whereas both phenolic antioxidants and phosphites contributed directly to photostabilization. Zinc stearate did not show any significant influence on the stabilization under either thermooxidative or photooxidative conditions.     

Performance and antioxidant activity of phenol/phosphite antioxidants in synergistic blends in the thermal and photooxidation of high‐density polyethylene (HDPE) film: Influence of zinc stearate

The influence of zinc stearate (ZnSt) on the thermal and photochemical stabilities of phenolic antioxidant/phosphite combinations has been determined in HDPE by using FTIR analysis. The results show that while under thermal aging the effects are generally antagonistic, under photooxidation the effects are synergistic. The interactions appear to be dominated by the role of complex formation between the phosphites and ZnSt. Such interactions would remove the hydroperoxide effectiveness of the phosphite in thermal oxidation, while under light they could cause stabilization. Derivative UV and FTIR analysis on pre‐melt blends of the additives in solution shows evidence for strong complexation for the phosphite antioxidants. Other acid scavengers such as hydrotalcite and calcium stearate also appear to influence the behavior of phenolic antioxidants in thermal oxidation. The antagonistic effect of zinc stearate was also confirmed following a single pass in an extruder, where for all formulations there was a greater reduction in MFI associated with crosslinking.     

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     

Comparative evaluation of the efficiency of a series of commercial antioxidants studied by kinetic modeling in a liquid phase and during the melt processing of different polyethylenes

An antioxidant response in condensed polymeric environments is often ambiguous and may vary strongly depending on the nature of the polymer and the conditions of polymer storage, processing, and use. The impact of polymeric environments during melt processing on the intrinsic efficiency of a set of commercial antioxidants was studied. The antioxidative activity of primary antioxidants Lowinox CPL, Lowinox 22IB46, Naugard 445, hydroxylamine Genox EP, and secondary phosphite Weston TNPP were determined by using two versions of the model reaction of cumene initiated (2,2′‐azobisisobutyronitrile, AIBN, and cumyl hydroperoxide, ROOH) oxidation. The melt stabilizing efficiency of the antioxidants was also studied during multipass extrusion testing in HDPE (Phillipstype), metallocene LLDPE, and (Ziegler‐Natta) LLDPE. The kinetic measurements showed that each of the three functional hydroxyl groups of Lowinox CPL is consumed in the model reaction (version 1) with the same high inhibition rate constant (k₇), whereas the two functional groups of Lowinox 22IB46 have different activity stipulated by hydrogen bonding between the hydroxyls. All the primary stabilizers involved afforded transformation products with additional antioxidative activity. For phenolic Lowinox CPL and amine Naugard 445, these products exhibited lower inhibition rate constants than that of the main functionality, but for Lowinox 22IB46, the discrepancy was not observed. Genox EP revealed three inhibition centers with different rate constants which, however, have low values of the inhibition coefficients (f). This effect is presumably due to the versatility of the inhibition pathways for the antioxidant and its intermediates, including the path of active interception of cumylalkyl (R^?) radicals. The secondary stabilizer Weston TNPP, tested by means of the second version of the model system, along with the expected decomposition of hydroperoxide appeared to be an effective radical scavenger. Kinetic parameters of the antioxidizing activity of the stabilizers – inhibition rate constants, coefficients of the oxidation chain termination, and total antioxidative activity {A = ∑[k_7(i) (fn[InH])_(i)]} — were determined for each functional group and for the whole antioxidant molecule. The phenolic stabilizers manifested powerful antioxidative activity. Their strongest functional groups have very high inhibition rate constant values: (log k₇) = 5.4 ± 0.15 (Lowinox 22IB46) and 5.2 ± 0.1 M^?1s^?1 (Lowinox CPL). In terms of the total inhibiting activity in the liquid system the antioxidants can be ordered as: Lowinox CPL > Lowinox 22IB46 > Naugard 445 > Genox EP > Weston TNPP. The effect of stabilizers during multipass extrusion experiments was assessed via melt flow rate and yellowness index measurements conducted as a function of the number of passes. Phenolic antioxidants and Genox EP significantly improved the melt stability of the polyethylenes in terms of melt viscosity retention and in partial compliance with the data from kinetic modeling measurements. According to the melt stabilizing efficiency data, the antioxidants can be arranged as: Lowinox 22IB46 > Lowinox CPL > Genox EP > Naugard 445 > Weston TNPP. The Lowinox 22IB46 with relatively lower molecular weight exhibited the best results among the primary stabilizers because of the unrestricted molecular dynamics in the viscous‐flow state of the polymer. Yellowness index measurements made after multiple extruder passes indicated that Weston TNPP effectively decreased the color development caused by the phenolic antioxidants. Genox EP displayed high efficiency as an antioxidant and melt‐processing stabilizer and additionally provided good color protection. Generally, we received a good correlation between the activity of the antioxidants in the model system and their melt stabilization performance in HDPE, metallocene LLDPE, and LLDPE. The model reaction of cumene‐initiated oxidation has demonstrated excellent applicability as an effective tool for preliminary quantitative assessment of antioxidant radical‐scavenging efficiency. J. VINYL ADDIT. TECHNOL., 2010. © 2009 Society of Plastics Engineers     

Effects of polymerization catalyst technology on the melt processing stability of polyethylenes. part 2. single stabilizer performance

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 an HDPE produced by using a chromium‐based Phillips catalyst and two LLDPEs produced via chromium‐based metallocene and titanium‐based Ziegler‐Natta catalysts. The additive types included a range of phenolics of different functionality, phosphites, hindered piperidines, an hydroxylamine, and Vitamin E. The results obtained for the three PEs confirmed that primary antioxidants (AOs) such as highly hindered and less, hindered phenols or hydroxylamines promoted good melt stability but in some cases tended toward yellowing. The secondary AOs such as the phosphites or thioethers behaved in the opposite way; color suppression was good, but melt stabilization was poor. It was also shown that for different types of phenols (all with similar molar activity), reducing steric hindrance to the phenolic OH enhanced the tendency to form chromophoric groups and hence color led to better efficiency than high hindrance. Those phenol with higher molar activity (mol OH/kg AO) showed the best processing performance. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Effect of metal stearate antacid on the melt stabilization performance of phenolic/phosphite antioxidants in metallocene LLDPE. Part 1: Melt processing stability

The influence of metal stearates on the melt stabilization performance of combinations of phenolic and phosphite antioxidants in a metallocene LLDPE (mLLDPE) has been investigated. This study focused on the effect of both the origin of the stearine blend (i.e., vegetable or animal) used in the formation of the metal stearates and the type of metal stearate (i.e., calcium and zinc stearate). A multiple extrusion experiment was carried out and melt stabilization performance was monitored by melt flow rate (MFR) measurements. The level of consumption of antioxidants was evaluated by HPLC analysis of solvent extracts. Although antagonism was observed with all formulations containing metal stearates, a noticeably greater detrimental effect was apparent with metal stearates based on the vegetable derived stearine blend. Furthermore, it was apparent that the vegetable zinc stearate had a greater detrimental effect than the calcium stearate equivalent. The presence of impurities such as peroxides and metal oxides in the metal stearates investigated was believed to account for the antagonism observed. J. Vinyl Addit. Technol. 10:137–143, 2004. © 2004 Society of Plastics Engineers.     

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.     

Investigating effect of ferric stearate on stabilization efficiency of a phenolic antioxidant during thermal oxidation of polyethylene

This study aimed to achieve a formulation for an additive to produce oxo-biodegradable films that accelerates oxidative degradation of the films after preservation of properties over a span of desired service life. Thermal oxidation behavior of high-density polyethylene (HDPE) films (approximately 250 μm thick) containing various weight ratios of a commercially used phenolic antioxidant (Irganox 1010) to ferric stearate as pro-oxidant has been studied in both melt and solid states. Thermo-oxidative stability in melt state was studied using differential scanning calorimetry. The rate of thermal oxidation in solid state was investigated via oven aging experiments at 90 °C followed by measuring changes in tensile properties, gel content, carbonyl index and density. Comparing thermo-oxidative stability of the HDPE samples containing a combination of Irganox 1010 and ferric stearate with the samples containing Irganox 1010 alone confirmed that ferric stearate reduces the stabilization efficiency of the phenolic antioxidant in the polymer either in melt or in solid state. It was also shown that the efficiency of the phenolic antioxidant in thermo-oxidative stabilization of the polymer in both melt and solid states could be changed by altering weight ratio of Irganox 1010/ferric stearate. On the basis of the obtained results, it was concluded that weight ratio of 0.1/0.1 wt% of the antioxidant to the pro-oxidant is suitable for attaining desired stability during melt processing as well as retaining properties during a reasonable service life when is used as a film and a favorable rate of thermal oxidation after the service life.     

Effect of different additives and their mixtures on thermal stability of polyethylene synthesized using iron and titanocene hybrid catalysts

Traditionally, additives are introduced into a polymer matrix via extrusion process which consumes a high amount of energy. In this study, the use of different additives including antioxidants for the in‐reactor stabilization of polyethylene has been investigated in order to provide an energy saving system. Particular attention was dedicated to the efficiency of antioxidant influencing the catalysts activity and properties of polymers. The effect of the addition of Irganox 1330 and Irgafos 168 antioxidants and zinc stearate on the activities of metallocene, post‐metallocene, and their supported hybrid were studied. In addition, the effect of different additives on the thermal characteristics of the synthesized polymers and oxidative induction time (OIT) was evaluated. Our polymerization results exhibited that the factors such as chemical structure of antioxidant and its steric hindrance, type of catalysts, and their hybrid could affect the catalyst performance and OIT contents. The use of antioxidants mixture and hybrid of catalysts is a way that can increase oxidation resistance of polymers considerably. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45482.     

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     

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     

Effect of titanium compounds on thermooxidative properties of stabilized polypropylene

The effect of titanium compounds on thermooxidation stability of stabilized polypropylene was studied. It was found that the presence of titanium compounds shortens the induction period of PP oxidation. This phenomenon is brought about by the thermal reactions of titanium compounds with antioxidants which take place during polymer processing. The first step is the reaction of Ti? Cl with OH groups of phenolic antioxidant, which gives rise to a colored titanate and HCl. Hydrogen chloride functions as a Friedel-Crafts catalyst for degradation and dealkylation of phenolic antioxidants. The products of degradation have a very low stabilization efficiency. Hydrogen chloride acceptors suppress antioxidant degradation and increase the polymer stability even in the presence of small amounts of titanium compounds.     

Effect of metal stearate antacid on the melt stabilization performance of phenolic/phosphite antioxidants in metallocene LLDPE. Part 2: Discoloration

The first part of this series of papers indicated that the melt stabilization performance of phenol/phosphite/metal stearate combinations in metallocene LLDPE (mLLDPE) was influenced by the purity of the fatty acid salt. In this second part, it is shown that the quality of the metal stearate has a direct influence on the discoloration of the aforementioned formulations in the melt state. On the basis of the peroxide and oxide impurity levels in the metal stearates (Part 1), it is suggested that discoloration is directly related to the formation of oxidative transformation products of the phenolic antioxidant. Furthermore, it was observed that the calcium stearates discolored upon aging in air at processing temperatures, while zinc stearates did not. Such discoloration is believed to be partly due to the combination of high levels of conjugated systems consisting of unsaturation and carbonyl groups formed during aging. J. Vinyl Addit. Technol. 10:144–148, 2004. © 2004 Society of Plastics Engineers.     

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.     

非对称型受阻酚类抗氧剂的研究新进展

非对称型受阻酚类抗氧剂以其特殊的结构显著提高了聚合物的抗氧化效率,新型非对称型受阻酚的探索与开发代表了当今世界聚合物抗氧化领域的一大发展趋势。简述了非对称型受阻酚类抗氧剂的结构特性及抗氧化机理,重点介绍了几种典型的半受阻酚类抗氧剂的合成及应用,指出了非对称型受阻酚类抗氧剂的研究方向。     

Effect of additive interactions on the thermo‐oxidative stabilization of a film grade metallocene LLDPE

The simultaneous effects of a range of additives and associated interactions on melt processing stability, processing discoloration, and long‐term stability of a blown film‐grade metallocene LLDPE (mLLDPE) were investigated by using a two‐level factorial experimental design. The additives investigated were a phenolic antioxidant, a phosphite processing stabilizer, a calcium stearate antacid, a synthetic silica antiblocking agent, and an erucamide slip additive. A multiple extrusion experiment was carried out to assess processing stability. Melt stabilization performance was monitored by melt flow rate (MFR) measurements, and color development was determined using yellowness index (YI) measurements. Long‐term thermal stability was assessed by monitoring the rate of formation of the non‐volatile carbonyl oxidation products using FTIR. Results were quite consistent with the literature. Therefore, the two‐level factorial experimental design proved to be a very useful tool for screening the simultaneous effects of each additive and the possible interactions between additives present in the stabilizer system investigated. J. Vinyl Addit. Technol. 10:149–156, 2004. © 2004 Society of Plastics Engineers.     

The preparation and performance of “Cage” diphosphites as secondary antioxidants in the stabilization of polyolefins

“Cage” diphosphites, a new family of phosphorus antioxidants, are discussed in regard to their preparation, properties, and effectiveness in polyolefins, particularly, with phenolic stabilizers, in respect to their ability to control melt flow and color during processing. These trivalent phosphorus compounds have two different types of phosphite functionalities in their structure. One phosphorus is part of an eight membered (1,3,2-dioxaphosphocine) ring system while the other is part of a tricyclic cage of carbon and oxygen atoms. This structures can contribute to improved hydrolytic stability over rather similar aryloxy-alkoxy phosphites and show competitive stabilization effectiveness in the processing of polyolefins. The possible modes of formation and of hydrolysis are discussed.     

Improvement of melt stability and degradation efficiency of poly (lactic acid) by using phosphite

Concurrent improvement of melt processing stability and degradation efficiency of poly(lactic acid) (PLA) is still a challenge for the industry. This article presents the use of phosphites: tris(nonylphenyl) phosphite (TNPP) and tris (2,4-di-tert-butylphenyl) phosphite (TDBP), to control the thermal stabilization, mechanical performance, and hydrolytic degradation ability of the compressed PLA films. The hydrolysis process is followed as a function of time at 45, 60, and 75°C. During melt extrusion, both phosphites function as a processing aid, besides acting as a chain extender stabilizing the PLA molecular weight. The phosphite structure plays a crucial role over crystallinity and water absorption, in controlling the hydrolytic degradation of PLA. The application of TNPP significantly catalyzes the hydrolysis of PLA, which is the initial step of the biodegradation process. The optimum amount of TNPP for best hydrolytic degradation efficiency and thermal stabilization of PLA is 0.5 wt%. The excessive TNPP loadings cause a drastic drop in PLA molecular weight and, as a consequence, a reduction of flexural strength. The reactions between PLA and phosphite molecules are discussed.     

Contribution to the study of mechanism of stabilizing action of esters of phosphorous acid

The rate of the reaction of a series of phosphites with cyclohexene hydroperoxide and cyclohexene peroxy radicals was studied. The results of the measurements were compared with the stabilization efficiency of the same compounds in isotactic and in atactic polypropylene at 160°C and 120°C respectively and during the course of atmospheric ageing. It was found the reverse relation between the stabilization efficiency and the reaction constants of the reaction of phosphites with hydroperoxides. The main stabilization reaction of the phosphorous stabilizers seems to be the reaction of phosphites or of their decomposition products with radicals. The possibility of splitting off of free phenol from phosphites as a result of the reaction of the esters with hydroperoxide groups was checked.     

Investigations of stabilizing additives. IV. PEPQ as a primary radical scavenger

Studies of PEPQ in a model antioxidant activity system have demonstrated that this material behaves not only as a hydroperoxide decomposer but as a primary radical scavenger. The temperature dependence of the antioxidant activity also indicates the PEPQ is more effective at higher temperatures than at ambient conditions. The relationship between the model antioxidant activity system and melt stability measurements in polypropylene is in good agreement and implies that PEPQ is an effective melt stabilizer even in the absence of conventional phenolic stabilizers such as BHT.