Melt free‐radical grafting of hindered phenol antioxidant onto polyethylene

A monomeric antioxidant (3) was prepared by reacting 3,5‐di‐tert‐butyl‐4‐hydroxybenzyl alcohol (1) with N‐[4‐(chlorocarbonyl) phenyl] maleimide (2). This reactive antioxidant was grafted onto polyethylene (PE) by melt processing with free‐radical initiators in a mini‐max molder. The IR spectra of the grafted PE showed that the monomeric antioxidant was introduced onto the PE. IR spectroscopic methods and titration were used for the quantitative determination of the extent of grafting of the monomeric antioxidant. Also, the extent of crosslinking was indicated by the gel content. Grafting occurred in the following order: dicumyl peroxide (DCP) > benzoyl peroxide > 2,2′‐azobisisobutyronitrile. The influences of the DCP concentration and monomeric antioxidant on the extent of grafting were studied. The effects of the reaction time and temperature were also determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2968–2973, 2000     

Effects of phenolic antioxidants on ultrahigh molecular weight polyethylene/decalin solution

The degradation of ultrahigh molecular weight polyethylene (UHMW‐PE) during its dissolution into decalin is discussed. The stabilization of the solution by three phenolic antioxidants, octadecyl β‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate (1076), tetrakis[methylene‐β‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate]methane (1010), and 1,1,3‐tris(2‐methyl‐4‐hydroxy‐5‐tert‐butylphenyl)butane (CA), and an auxiliary antioxidant, dilaurylthiodipropionate (DLTP) is also discussed. Among the three phenolic antioxidants, 1076 had the greatest effect. The auxiliary antioxidant was effective in stabilizing the solution when combined with one of the three phenolic antioxidants. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2877–2881, 2000     

Polyolefin elastomer grafted unsaturated hindered phenol esters: synthesis and antioxidant behavior

Monomeric antioxidants are synthesized from esterification of 3,5-di-tert-butyl-4-hydroxybenzoic acid and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with unsaturated fatty alcohols. The antioxidant activity is evaluated both in blending and radical grafting processes. The effect of chain length and phenolic group is investigated on efficiency of antioxidants. It is demonstrated that the esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid exhibit significantly longer induction time. The results of radical grafting reaction shows synthesized antioxidants can be successfully grafted onto polymer chains and the phenolic moiety is functional after extraction process, while pure and commercially stabilized samples are degraded instantaneously. Also, different initiator systems are utilized to enhance the extent of grafting. Among MEK, DCP, and DHBP peroxides, DHBP can be more effective in increasing the antioxidant grafted onto polymer. In addition, possibility of rising in graft content is investigated in presence of redox initiator. Using this approach, polymer-bound antioxidant with prolonged thermal stability can be achieved.     

Synthesis and performance of phenolic polybutadiene‐bound stabilizers

An antioxidant derivative, 6‐sulfanylhexyl 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propanoate, was synthesized and examined. With a radical initiator, the addition of this compound to pending vinyls of OH‐telechelic, low molecular weight liquid polybutadiene (LBH) was performed to various degrees of conversion to form polymeric antioxidants (PAOs) in which the phenolic moiety was separated from the main chain by a spacer [? CH₂CH₂? S? (CH₂)₆? O? CO? ]. Pure, unstabilized LBH was mixed in several ratios with PAOs, Irganox 1520, and Irganox 1076, and the oxidation stabilities of these mixtures, determined by thermogravimetric analysis and differential scanning calorimetry, were compared. Probably because of their good compatibility with LBH, PAOs exhibited equal or better effectiveness than commercial antioxidants of the Irganox type. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 885–889, 2003     

Functionalization of high‐density polyethylene in the molten state by glycidyl methacrylate grafting

:This study concerns the melt‐free radical grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE). We studied the effect of two initiators (tert‐butyl cumyl peroxide and di‐tert‐butyl peroxide) onto HDPE. Crosslinking of polymer was observed in the presence of 0.3 wt % tert‐butyl cumyl peroxide but not with 0.3 wt % di‐tert‐butyl peroxide. The grafting was carried out in a Brabender batch mixer at 190 °C. The grafting yield of GMA onto HDPE (determined by infrared spectrometry) is weak (<1 wt % for an initial concentration in monomer of 6 wt %). Moreover, it was noted that the degree of grafting did not vary with the concentration and the nature of peroxide used. To increase the grafting yield of GMA, we added to the HDPE/peroxide/GMA system an electron‐donating monomer, such as styrene. Adding this comonomer multiplied the rate of grafted GMA 3‐ or 4‐fold, resulting in a ratio [styrene]_i/[GMA]_i = 1 mol/mol with [GMA]_i = 6 wt %. So, the copolymerization is favored compared with the homopolymerization. This kind of copolymer presenting reactive functions is very attractive in the field of compatibilizing immiscible polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 581–590, 2001     

Grafted stock synthesis of ABS at the ultimate high ratio of polybutadiene to poly(styrene‐co‐acrylonitrile)

This study describes the emulsion grafting of styrene and acrylonitrile onto 60–70% polybutadiene (PB), in the presence or absence of tert‐dodecanetiol as a chain transfer reagent with a radical initiator, and the properties of the obtained grafted stock. There was no significant difference in terms of effect of the initiation mode on the grafting efficiency resulting from the high grafting reactivity of PB. However, the grafted stock with 70% PB prepared in the presence of tert‐dodecanetiol and the adequate selection of an initiation system gave a homogeneous dispersion of the PB particles into poly(styrene‐co‐acrylonitrile) (SAN) matrix. The initiation system involves tert‐butyl peroxylaurate, tert‐butyl peroxyacetate, and tert‐butyl peroxyisopropylcarbonate coupled with ferrous sulfate. The efficient coverage of the SAN grafted layer around 70% PB particles was observed by TEM to eventually give excellent impact resistance, high surface gloss, and good thermal resistance. The absence of tert‐dodecanetiol resulted in a toughness reduction of ABS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3462–3470, 2001     

Novel stabilization system for polypropylene via the Ziegler–Natta catalyzed polymerization in the presence of aluminum aryloxide

The aluminum aryloxide was prepared via the reaction of phenolic antioxidant, 3‐(3,5‐di‐t‐butyl‐4‐hydroxyphenyl)‐N‐octadecylpropionamide, with triethyl aluminum. Propylene polymerization using supported Ziegler–Natta catalyst systems was carried out in the presence of the antioxidant or its aluminum aryloxide. Although the antioxidant gave rise to decrease in catalyst yield and change in hydrogen response, the aluminum aryloxide had no influence on the catalytic polymerization behavior, and thus the obtained polymer characteristics such as molecular weight, polydispersity, and meso pentad as a stereoregularity were comparable to that polymerized without the antioxidant and the aluminum aryloxide. Polypropylene obtained in the presence of the aluminum aryloxide was well stabilized for oxidation and its stability was over 1000 h at 100°C (estimated to be over 30 years at room temperature). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1350–1358, 2006     

Synthesis and antioxidant activities in polyolefin of dendritic antioxidants with hindered phenolic groups and tertiary amine

Two novel primary antioxidants with dendritic structure and hindered phenolic groups were synthesized using 3‐(3,5‐diter‐butyl‐4‐hydroxyphenyl) propionic acid as raw material and dendritic poly(amidoamine) (PAMAM) as linker in chloroform. The antioxidant activities of the dendritic antioxidants were evaluated in polyolefin by melt flow index (MFI), yellowness index (Y.I.), and oxidation induction time (OIT). The dendritic antioxidants had excellent processing property and oxidation resistance behavior in polyolefin. At the same weighed amount of antioxidant, the MFI and Y.I. values of mulitiple‐extruded polyethylene (PE) stabilized with the dendritic antioxidants were smaller than those of the commercial antioxidants, as well as the OIT values of polyethylene (PE) stabilized with the dendritic antioxidants were larger. Applying to polypropylene, the antioxidant ability of the second‐generation dendritic antioxidant (G2.0 dendritic antioxidant) with larger molecular weight was superior to the commercial antioxidants and that of the first‐generation dendritic antioxidant (G1.0 dendritic antioxidant) was equal to the commercial antioxidants. The dendritic antioxidants can prevent polyolefin from breaking of macromolecular chain in processing and had stabilizing effect in polyolefin in service life by donating H‐atoms and electron to free radicals. The dendritic antioxidants combined with Irgafos 168 had improvement of antioxidant activities of the dendritic antioxidants in polyolefin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation,structural characterization,and antioxidative behavior in natural rubber of antioxidant GM functionalized nanosilica

To restrain the migration and extractability of the antioxidants and improve the dispersion of nanosilica in natural rubber (NR), antioxidant 2‐tert‐butyl‐6‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐4‐methyphenyl acrylate (GM) functionalized nanosilica was prepared using antioxidant coupling agent (KH590‐GM) as functional modifier, which was first synthesized through thiol‐ene reaction between the mercapto group of γ‐mercaptopropyl trimethoxysilane (KH590) and the CC double bonds of antioxidant GM. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance confirmed the structure of KH590‐GM and GM functionalized nanosilica. Thermogravimetry analysis indicated that the grafting rate of GM functionalized nanosilica reached 13.4%, and the antioxidant had good thermal stability. Scanning electron microscope and mechanical properties measurement showed GM functionalized nanosilica was dispersed uniformly in NR vulcanizates, and helpful for the increase of the tensile strength and tensile stress of NR vulcanizates. Based on the study of the antioxidative behavior and extraction resistance of the NR vulcanizates, it was found that in contrast to NR vulcanizates with GM, the ageing coefficient and oxidation induction time of that with GM functionalized nanosilica increased to 0.66 and 39 min from 0.58 and 30 min, respectively. Furthermore, the NR vulcanizates with GM functionalized nanosilica also exhibited excellent extraction resistance. POLYM. COMPOS., 38:1241–1247, 2017. © 2015 Society of Plastics Engineers     

Grafting of polyacrylonitrile onto guar gum under microwave irradiation

Using microwave (MW) irradiation grafting of polyacrylonitrile (PAN) onto guar gum in water was done without using any radical initiator or catalyst within a very short reaction time. The extent of grafting could be adjusted by controlling the reaction conditions and maximum percentage grafting (%G) of about 188% was obtained under optimum conditions in 1.66 min. The average molecular weight of the grafted PAN chains and water‐retention power of the alkali hydrolyzed MW‐grafted gums were also determined and compared with those of the conventionally synthesized (cs) graft copolymer. A representative MW‐grafted copolymer, guar‐g‐polyacrylonitrile was characterized by IR, NMR, XRD, TGA, and elemental analysis. A plausible mechanism for the grafting under MW was proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1569–1575, 2004     

Controlled synthesis of low‐molecular‐weight polyethylene waxes by titanium–biphenolate–ethylaluminum sesquichloride based catalyst systems

Soluble complexes of titanium(IV) bearing sterically hindered biphenols, such as biphenol, 1,1′‐methylene di‐2‐naphthol, 2,2′‐methylene bis(4‐chlorophenol), 2,2′‐methylene bis(6‐tert‐butyl‐4‐ethyl phenol), and 2,2′ ethylidene bis(4,6‐di‐tert‐butyl phenol), were prepared and characterized. These catalyst precursors, formulated as [Ti(O∧O)X₂], were active in the polymerization of ethylene at high temperatures in combination with ethylaluminum sesquichloride as a cocatalyst. The ultra‐low‐molecular‐weight polyethylenes (PEs) were linear and crystalline and displayed narrow polydispersities. The catalytic polymerization leading to PE waxes in this reaction exhibited unique properties that have potential applications in surface coatings and adhesive formulations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1531–1539, 2007     

Preparation and evaluation of some novel organo‐phosphorus compounds as antioxidants and antifatigue agents in rubber

Six organo‐phosphorus compounds were synthesized and incorporated in NR and SBR mixes. The rheometric characteristics of the green rubber mixes were determined using the oscillating disc rheometer. The prepared compounds were evaluated as antioxidants and antifatigue agents in NR and SBR vulcanizates. It was found that the prepared compounds are good antioxidant and antifatigue agents and their efficiency was better than that obtained by 4‐methyl‐2,6‐di‐tert‐butyl phenol, which is used in the rubber industry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2984–2992, 2002; DOI 10.1002/app.2327     

Poly(silyl ester)s: A new route of synthesis via the condensation of Di‐tert‐butyl ester of dicarboxylic acid with dichlorosilane

Poly(silyl ester)s were synthesized by a new route via the condensation of di‐tert‐butyl ester of dicarboxylic acid with dichlorosilane by the elimination of tert‐butyl chloride as a driving force. Three new poly(silyl ester)s with molecular weights typically ranging from 2000 to 5000 amu were produced by the condensation of di‐tert‐butyl adipate with 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl trisiloxane and di‐tert‐butyl fumarate with 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl trisiloxane or 1,3‐dichlorotetramethyl disiloxane. Each polymer was characterized with infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. This new approach showed several advantages. First, it did not require a catalyst or solvent. Second, the tert‐butyl chloride byproduct was volatile and was easily eliminated. Third, there was no reaction between the growing poly(silyl ester)s and the condensation byproduct, tert‐butyl chloride. Fourth, the monomers could be readily purified. Finally, the polymerization could be performed at relatively low temperatures and in a short time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1378–1384, 2006     

Synthesis of (3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl) propionate derivatives and their thermal antioxidation behavior for POM

Polyoxymethylene (POM) has been widely utilized in industry due to its light weight properties in engineering plastics. At present, POM applications are expanding into the car industry, especially in fuel tanks. Hindered alkyl phenol derivatives have been used as antioxidants for POM; however, these compounds are easily extracted by solvents. Two antioxidants with new structures (N,N′‐triethylenedioxy‐bis(3‐tert‐butyl‐4‐hydroxy‐5‐methylhydrocinnamamide) and N,N′,N′‐tris[(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyl‐3‐oxapentyl]melamine) were synthesized and characterized, and their performance as antioxidants for POM was investigated in the present study. The results revealed that N,N′‐triethylenedioxy‐bis(3‐tert‐butyl‐4‐hydroxy‐5‐methylhydrocinnamamide) has good heat aging resistance compared to existing antioxidants for POM, and N,N′,N′‐tris[(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyl‐3‐oxa‐pentyl]melamine has good extraction resistance against solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of antiaging agents on the outdoor natural weathering of bamboo powder/polypropylene foamed composites

The effect of outdoor natural weathering on the properties of injection molded 33 wt% bamboo powder (BP)/polypropylene (PP) foamed composites with and without the antioxidant and hindered amine light stabilizers (HALS) were investigated. The composites containing the antiaging agents had higher color stability, slightly greater retentions of flexural modulus, tensile and notched impact strengths, higher creep resistance, and better rheological stability than the reference composite. The antiaging agents of pentaerythritol tetrakis(3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propionate) and poly‐(n‐hydroxyethyl‐2,2,6,6‐tetramethyl‐4‐hydroxy‐piperidyl succinate) had more beneficial effect than n‐octadecyl‐β‐(4‐hydroxy‐3,5‐di‐tert‐butyl‐phenyl)‐propionate and bis(2,2,6,6‐tetramethyl‐4‐piperidinyl)sebacate. After 12 months of exposure, △E^* decreased from 22.8 of the reference composite to 9.9 of the composite with the antiaging agents. Rheological behavior results indicated that the storage modulus, complex viscosity, and non‐Newtonian fluid index of composites containing the antiaging agents were slightly increased. Natural weathering caused less decreases in the storage and loss moduli, crossover modulus, relaxation time, and average molecular weight for composites containing the antiaging agents than those for the reference composite. Environmental scanning electron microscopy (ESEM) observation confirmed the improved surface durability for composites containing the antiaging agents. J. VINYL ADDIT. TECHNOL., 22:311–319, 2016. © 2014 Society of Plastics Engineers     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Alternating copolymerization and terpolymerization of vinyl‐substituted phenolic antioxidants with propene and carbon monoxide by a palladium(II)‐based catalyst: polyketones containing intramolecular stabilizers

The copolymerization and terpolymerization reactions of the vinyl‐substituted phenolic stabilizers, 6‐tert‐butyl‐2‐(1,1‐dimethylhept‐6‐enyl)‐4‐methylphenol, o‐allylphenol, 4‐methylstyrene‐2,6‐di‐tert‐butylphenol and 2,6‐di‐tert‐butyl‐4‐allylphenol, with propene and carbon monoxide, by using the solvent‐stabilized palladium(II ) phosphine complex [Pd(dppp)(NCCH₃)₂](BF₄)₂ (dppp, 1,3‐bis(diphenylphosphino)propane) as a catalyst precursor and methanol as a co‐catalyst, is described. The influence of functional α‐olefins/CO units, distributed statistically along the propene/carbon monoxide (P/CO) copolymer backbone, on the molecular weight, glass transition temperature (T_g), elastic behavior and stability of the high‐molecular‐weight P/CO copolymer has been investigated. Loss of both elasticity and transparency were observed upon incorporating o‐allylphenol as a termonomer. The terpolymers, which contain phenolic stabilizers, were shown to be more stable when compared to the stabilizer‐free polyketones. In contrast to the propene/carbon monoxide copolymer, no degradation was observed for the 2,6‐di‐tert‐butyl‐4‐allylphenol/P/CO terpolymer; instead, the molar masses increased. Copyright © 2004 Society of Chemical Industry     

Melt grafting of 10‐undecenoic acid onto linear low density polyethylene

The melt grafting of 10‐undecenoic acid (UA) onto a linear low‐density polyethylene (LLDPE) was studied. The grafting reaction was performed in a thermoplastic mixer and 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy) hexane was used as initiator. The concentration of UA and peroxide ranged from 1 to 4% (w/w) and 0.025 to 0.1% (w/w), respectively. Evidence of the grafting of UA as well as its extent was determined by FTIR. Experimental results showed that the amount of UA grafted increases with both the UA and initiator concentrations. However, the greatest efficiency of grafting was found at the lowest concentration of UA investigated. The grafting efficiency ranged from 8 to 40%. The dynamic linear viscoelastic properties of the original polymer and the grafted materials were evaluated at different frequencies at 160°C using a dynamic rotational rheometer. The modification process affected the melt elasticity and viscosity of the LLDPE. When the original polymer was modified only with peroxide both properties increased with respect to those of the original material. However, when UA was grafted onto LLDPE, the resulting polymers displayed values of elastic moduli and viscosity lower than those of the polymer modified with peroxide. Moreover, when a concentration of 4% of UA was used, the values of those properties were even lower than those corresponding to the original LLDPE. These observations combined with the data obtained from the GPC results suggest that scission reactions may be favored by the presence on UA. In contrast with previous observations, the thermal properties measured by DSC were only slightly altered. The fusion temperature of the modified polymers was slightly lower than that corresponding to the original polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2303–2311, 2004     

Synthesis and aging properties of reactive antioxidant NAPM in natural rubber vulcanizates

The rubber antioxidant N‐(4‐anilinophenyl) methacrylamide (NAPM) was synthesized by a two‐step reaction using thionyl chloride (SOCl₂) with methacrylic acid (MAA) and consequently 4‐aminodiphenylamine (ADPA) as precursors. NAPM was characterized by IR, ¹H NMR and elemental analysis. Thermal stability, aging property of NAPM and mechanical properties of natural rubber (NR) vulcanizates containing NAPM were investigated and compared with two other commercial antioxidants N‐isopropyl‐N′‐phenyl‐p‐phenylene diamide (4010NA) and N‐(1, 3‐dimethyl butyl)—N′‐phenyl‐p‐phenylene diamide (4020). It was found that NAPM was an effective antioxidant with a better thermal stability and higher antiaging resistance than unreactive antioxidants 4010NA and 4020. And unsaturation level of NR vulcanizates containing NAPM was lower than that of 4010NA and 4020. Moreover, an antiaging resistant mechanism of a surface reaction between NAPM and cis‐1, 4‐polyisoprene in NR was proposed to explain the better properties of NAPM based on the IR and SEM analyses. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and reactivity of antioxidants based on vernolic acid and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid

The reactivity of sterically hindered phenols toward free radicals of the hydrocarbon cumene was studied. New compounds, i. e. methyl cis-13(12)-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}-12(13)-hydroxyoleate and cis-13(12)-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}-12(13)-hydroxyoleic acid were synthesized starting from vernolic acid and its methyl ester, respectively, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid. Both new compounds possess antioxidant activities similar to those of commercially available antioxidants.