Melt rheology of poly(lactic acid): Consequences of blending chain architectures

The rheology of blends of linear and branched poly(lactic acid) (PLA) architectures is comprehensively investigated. Measurement of the melt rheological properties of PLA is complicated by degradation effects but the addition of 0.35 wt% tris(nonylphenyl) phosphite (TNPP) provides excellent stabilization over a range of temperatures. Master curves of dynamic viscosity constructed using time‐temperature superposition show significant dispersion for unstabilized samples; this behavior is accompanied by a loss of molecular weight. TNPP stabilized samples show excellent superposition throughout the entire frequency range and minimal loss in molecular weight. For the linear architecture, the Cox‐Merz rule is valid for a large range of shear rates and frequencies. The branched architecture deviates from the Cox‐Merz equality and blends show intermediate behavior. Both the zero shear viscosity and the elasticity (as measured by the recoverable shear compliance) Increase with increasing branched content. The viscosities of both the unstabilized samples and the TNPP stabilized samples roughly obey a log additivity mixing rule. The recoverable shear compliance is monotonic in blend composition and a mixing rule for this property is also presented. For the linear chain, the compliance is independent of temperature but this behavior is apparently lost for the branched and blended materials. Tensile and thermal properties of the blends are also measured and found to be roughly equal within the statistical error of the experiments. The results suggest that excellent control over rheological behavior of PLA is possible through blending chain architectures without compromising mechanical properties.     

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.     

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.     

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     

Structural effect of secondary antioxidants on mechanical properties and stabilization efficiency of polyamide 6/halloysite nanotube composites during heat ageing

Hindered phenol (Irganox 1010) was combined with two kinds of secondary antioxidants [i.e., tris(2,4‐di‐tert‐butylphenyl) phosphite (Irgafos168) and tris(nonylphenyl) phosphite (TNPP)] to form antioxidant mixtures, and their influences on mechanical properties and thermo‐oxidative degradation of polyamide 6 (PA6) and halloysite nanotube (HNT) filled composites were investigated. The results showed that the antioxidant combinations provided an improvement in the oxidative induction time, decomposition temperature (T_d), processability, and tensile properties of PA6. Irganox/TNPP (1:1) was found to exhibit the best thermal oxidative resistance. The study of heat ageing in the air oven at 130 °C showed that the stabilized composites with 5 wt % of HNT could retain 92% of strength without loss of modulus. The physical characteristics of antioxidants such as low volatility and possible interaction with filler in the composites played a crucial role in stabilizing efficiency during heat ageing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45360.     

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.     

Hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) blends

The hydrolytic degradation of poly(l ‐lactic acid)/poly(methyl methacrylate) (PLLA/PMMA) blends was carried out by the immersion of thin films in buffer solutions (pH = 7.24) in a shaking water bath at 60 °C for 38 days. The PLA/PMMA blends (0/100; 30/70; 50/50; 70/30; 100/0) were obtained by melt blending using a Brabender internal mixer and shaped into thin films of about 150 µm in thickness. Considering that PMMA does not undergo hydrolytic degradation, that of PLLA was followed via evolution of PLA molecular weight (recorded by size exclusion chromatography), thermal parameters (differential scanning calorimetry (DSC)) and morphology of the films (scanning transmission electron microscopy). The results reveal a completely different degradation pathway of the blends depending on the polymethacrylate/polyester weight ratio. DSC data suggest that, during hydrolysis at higher PMMA content, the polyester amorphous chains, more sensitive to water, are degraded before being able to crystallize, while at higher PLLA content, the crystallization is favoured leading to a sample more resistant to hydrolysis. In other words, and quite unexpectedly, increasing the content of water‐sensitive PLLA in the PLLA/PMMA blends does not mean de facto faster hydrolytic degradation of the resulting materials. © 2018 Society of Chemical Industry     

Hydrolysis and thermal degradation of poly(L‐lactide) in the presence of talc and modified talc

Talc and talc modified with trimethoxy(octadecyl)silane (O‐talc) were melt compounded with poly (L ‐lactide) (PLA). The crystallization behavior, tensile properties, and impact strength of the PLA composites were examined before and after the incorporation of talc and O‐talc. The molecular weight of PLA in the PLA composites was measured as a function of the hydrolysis time and temperature. The effect of talc and O‐talc on the thermal stability of PLA was examined and quantified by the activation energy of thermal degradation and the integral procedural decomposition temperature value determined from the corresponding thermo‐gravimetric analysis weight loss profiles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

助剂复配对聚乙醇酸性能的影响

通过熔融共混方法,采用环氧类扩链剂对聚乙醇酸(PGA)进行反应挤出改性,同时添加亚磷酸酯类抗氧剂来降低熔融加工过程中的热降解。研究了扩链剂与抗氧剂联用对PGA熔体质量流动速率、热稳定性、熔体流变性能以及抗水解性能的影响。结果表明,扩链剂与抗氧剂复配,PGA改性料的熔体质量流动速率由原料的44.2 g/10min下降至11.2 g/10min;起始分解温度T_-5%(质量剩余95%的温度点)提高22.1℃;熔体黏度提高6倍以上;在提高了熔体强度的同时,改性料热稳定性明显改善,同时抗水解稳定性也有一定程度提高。     

Effect of Chain-Extenders on the Properties and Hydrolytic Degradation Behavior of the Poly(lactide)/Poly(butylene adipate-co-terephthalate) Blends

Biodegradable poly(lactide)/poly(butylene adipate-co-terephthalate) (PLA/PBAT) blends were prepared by reactive blending in the presence of chain-extenders. Two chain-extenders with multi-epoxy groups were studied. The effect of chain-extenders on the morphology, mechanical properties, thermal behavior, and hydrolytic degradation of the blends was investigated. The compatibility between the PLA and PBAT was significantly improved by in situ formation of PLA-co-PBAT copolymers in the presence of the chain-extenders, results in an enhanced ductility of the blends, e.g., the elongation at break was increased to 500% without any decrease in the tensile strength. The differential scanning calorimeter (DSC) results reveal that cold crystallization of PLA was enhanced due to heterogeneous nucleation effect of the in situ compatibilized PBAT domains. As known before, PLA is sensitive to hydrolysis and in the presence of PBAT and the chain-extenders, the hydrolytic degradation of the blend was evident. A three-stage hydrolysis mechanism for the system is proposed based on a study of weight loss and molecular weight reduction of the samples and the pH variation of the degradation medium.     

Hydrolytic and thermal degradation of polyethylene glycol compatibilized poly(lactic acid)-nanocrystalline cellulose bionanocomposites

This study investigates the effect of nanocrystalline cellulose (NCC) and polyethylene glycol (PEG) on the hydrolytic degradation behavior of poly(lactic acid) (PLA) bio-nanocomposites compared with that of neat PLA, under specific environmental condition, namely at 37°C in a pH 7.4 phosphate buffer medium for a time period up to 60 days. The water absorption, mass loss, molecular weight, and the morphologies of nanocomposites before and after degradation were explored. Thermogravimetric analysis (TGA) was used to study the thermal decomposition of the PLA/NCC/PEG nanocomposites before and after degradation. The results showed that the presence of hydrophilic NCC and PEG significantly accelerated the hydrolytic degradation of PLA, which was related to the rapid dissolution of PEG causing easy access of water molecules to the composites and initiating fast hydrolytic chain scission of PLA. The thermal degradation temperatures of the nanocomposites slightly decreased due to the poor thermal stability of NCC in comparison with that of the neat PLA. After degradation, the thermal stability of the separated PLA from nanocomposites significantly decreased because the molecular decreased during the hydrolytic process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46933.     

Crystallization behavior and morphology of polylactide and PLA/clay nanocomposites in the presence of chain extenders

The effect of clay and chain extender on the nonisothermal, isothermal crystallization kinetics, and morphology of polylactide (PLA) was investigated in this study. PLA and PLA‐based nanocomposites containing 2 wt% organoclay were prepared via melt compounding. Three commercially available chain extenders were used: polycarbodiimide (PCDI), tris(nonylphenyl) phosphite (TNPP), and Joncryl ADR4368F. The nanoclay particles were found to act as nucleating agents. Chain extender incorporation, however, had diverse effects on both crystallization rate and degree of crystallinity. Nonisothermal DSC results revealed that the addition of PCDI increased the cold‐crystallization temperature (T_c) from 106 to 114°C, reduced the degree of crystallinity from 6.3 to 5.3%, and resulted in the formation of bimodal melting peaks in PLA. On the other hand, the reduction of chain ends in the presence of TNPP resulted in a significant increase of the crystallization rate and degree of crystallinity from 6.3 to 15.2%. In the case of Joncryl, its incorporation led to the formation of a long‐chain branching structure, which disrupted the chain packing. Therefore, the degree of crystallinity (from 6.3 to 1.6%) and the rate of crystallization decreased, while T_c was increased from 106 to 122°C in the presence of Joncryl. POLYM. ENG. SCI., 2013. © 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     

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.     

Antioxidation and mechanism of phosphites including the free phenolic hydroxyl group in polypropylene

Inhibiting the degradation of polypropylene (PP) in melt processing and usage is an important issue in the plastic industry. It is becoming more and more urgent to increase the antioxidation of phosphites alone while maintaining the water resistance. In this study, one phosphite antioxidant, named bis‐2,2′‐methyl‐4,6‐di‐tert‐butylphenyl phosphite (BM46TBPP), which contains a water‐resistant inner ring and a free phenolic hydroxyl group together, was synthesized. Then, antioxidation in PP was characterized with multiple extrusions and oxidation induction times (OITs). Finally, the hydrogen‐donating ability of this antioxidant was tested with 2,2‐diphenyl‐1‐picrylhydrazyl radical colorimetry to explain the antioxidation mechanism. The results show that the phosphite BM46TBPP displays better antioxidation than tris(2,4‐di‐tert‐butylphenyl) phosphite (Irgafos 168) in melt processing and OIT testing. Furthermore, the priority of this antioxidant was more obvious when it was used in the presence of oxygen, so the antioxidant even made the PP stabilized by it alone show a longer OIT value than the PP stabilized by the complex system including Irgafos 168 and 2,4‐di‐tert‐butylphenol because there was a free phenolic hydroxyl group in the BM46TBPP antioxidant molecule and the hydroxyl group made the antioxidant show intermolecular synergistic antioxidation through hydrogen donation to radicals. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44696.     

Kinetics of hydrolysis and thermal degradation of polyester melts

Polyester melts exhibit two discrete degradation rates depending on the moisture content in the solid state. The initial fast rate is very sensitive to the moisture content while the later slow rate is not sensitive to the moisture content. The former is attributed to hydrolysis and the latter is attributed to thermo-oxidative degradation. A combined kinetic equation which represents both hydrolysis and thermo-oxidative degration of the polyester melt is proposed. The model equation agrees well with the experimental data. A method to determine hydrolytic and thermal degradation rate constants, moisture content, molecular weight for polyesters by means of a melt viscometry is discussed.     

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.     

Poly (ethylene oxide) (PEO) influence on mechanical,thermal, and degradation properties of PLA/PBSeT blends

Poly (lactic acid) (PLA) is an important biodegradable plastic with unique properties. However, its widespread application is hindered by its low miscibility and suboptimal degradation properties. To overcome these limitations, we investigated the mechanical, thermal, and degradation properties of PLA and poly (butylene sebacate-co-terephthalate) (PBSeT) blends in the presence of poly (ethylene oxide) (PEO). Specifically, this study aimed to identify the effects of PEO as a compatibilizer and hydrolysis accelerator in PLA/PBSeT blends. PLA (80%) and PBSeT (20%) were melt blended with various PEO contents (2–10 phr), and their mechanical, thermal, and hydrolytic properties were analyzed. All PEO-treated blends exhibited a higher elongation at break than that of the control sample, and the tensile strength was slightly reduced. In the PEO 10% sample, the elongation at break increased to 800% of that of the control sample. Differential scanning chromatography (DSC) analysis confirmed that when PEO was added to the PLA/PBSeT blends, the two glass transition temperatures (T_g) narrowed, resulting in improved miscibility of PLA and PBSeT. In addition, the hydrolytic degradation of the PLA/PBSeT/PEO blend accelerated as the PEO content increased. It was confirmed that PEO can act as a compatibilizer and hydrolysis-accelerating agent for PLA/PBSeT blends.     

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.