Nondegradative melt functionalization of polypropylene with glycidyl methacrylate

The melt grafting of glycidyl methacrylate (GMA) onto powdered isotactic polypropylene (PP) in a Haake Rheocord RC90 mixer was studied. Grafting degrees were determined by nonaqueous back titration of trichloroacetic acid with sodium hydroxide. The extent of degradation and crosslinking of PP during grafting was indicated by the melt-flow rates (MFR) of the grafted samples. The influences of GMA concentration, initiator type and concentration on grafting degree, reaction efficiency, and degradation were evaluated. A novel method was developed to obtain a high grafting degree with little degradation of PP using acrylamide (AM) as the initiating agent. The grafting process occurred before or during the melting of PP (i.e., solid-state grafting), at which temperature crosslinking is preferred over chain scission. Primary free radicals generated from the rapid decomposition of AM have a higher tendency to attack GMA molecules than PP chains. At the same estimated amount of primary radicals, both grafting degree and grafting efficiency increase with decreasing decomposition temperature of the initiator (for the same decomposition half-life) in the order of AM > benzoyl peroxide (BPO) > 2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne (LPO). FunctionalizedPP with the desired grafting degree and little degradation of PP could be obtained by the use of mixed initiators. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1957–1963, 1998     

Graft polymerization of methyl methacrylate onto radiation‐peroxidized ultrahigh molecular weight polyethylene in the presence of metallic salt and acid

Using a radiation peroxide grafting technique, a ultrahigh molecular weight polyethylene (UHMWPE) stored at room temperature for 10 days after irradiation in air was graft copolymerized with methyl methacrylate (MMA) in the presence of metallic salt and acid. The MMA‐grafted UHMWPE samples were analyzed by measuring Fourier transform infrared spectroscopy in attenuated total reflectance (FTIR–ATR) and by electron spectroscopy for chemical analysis (ESCA). The 1,1‐diphenyl‐2‐picrylhydrzyl (DPPH) technique was utilized to evaluate the concentration of peroxide formed in the peroxidized UHMWPE samples by counting the quantity of DPPH consumed from the reaction of peroxide radicals with DPPH. It was shown that the inclusion of an FeSO₄ ·7H₂O and sulfuric acid in MMA grafting solutions was extremely beneficial and led to a most unusual synergistic effect in the radiation‐peroxidized grafting. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 659–666, 1999     

Modification of industrial polypropylene film by grafting of poly(acrylic acid)

Grafting of poly(acrylic acid) onto commercial polypropylene films following irradiation by γ-rays was carried out in order to improve their surface properties. The amount of grafting with the irradiation dose was found not to follow the expected linear dependence as it is normally observed for polypropylene films prepared in laboratory amounts. We therefore analyzed the influence of the industrial manufacture process in terms of orientation of the film and addition of antioxidants by determining the peroxide surface density and the extent of grafting therefrom. The unoriented polypropylene film presented the highest peroxide concentration and was thus the most adapated material for successful grafting. Whereas phenol antioxidants limit the peroxide formation and thus must be removed from the film for grafting, the thickness of the chemical modification and can be controlled by means of phosphites. Atomicforce microscopy and wettability measurements showed that the grafted poly(acrylic acid) was heterogeneously distributed on the surface of the film, explaining the observed low reproducibility of the grafting reaction. However, we observed that the polarity of the surface was increased by the grafting. © 1995 John Wiley & Sons, Inc.     

Free radical grafting of glycidyl methacrylate onto polypropylene in a co-rotating twin screw extruder

Free radical grafting of glycidyl methacrylate (GMA) onto molten polypropylene (PP) was studied in a co-rotating twin screw extruder. Grafting yields of GMA obtained under various experimental conditions along the screw length allowed for a good appreciation of the effects of chemical parameters (the presence of styrene and the concentrations of peroxide and monomers) and those of processing parameters (feed rate, screw speed, and specific throughput). Similar to the results obtained in a batch mixer,¹ free radical grafting of GMA carried out in the extruder in the presence or absence of styrene proceeded rapidly, as it was virtually completed half-way down stream of the extruder. Additionally, the presence of styrene as a second monomer increased the GMA grafting yield reatly with reduced PP chain degradation. The ultimate GMA grafting yield increased with increasing concentration of peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene. This similarity between the batch mixer and the extruder is related to the fact that in both cases it is the concentration of the peroxide and its half lifetime that determine the grafting rate and the ultimate grafting yield. On the othe hand, the GMA grafting yield decreased with increasing screw speed or feed rate. For a particular specific throughput (the ratio of throughput to screw speed), an increase in throughput with a concomitant increase in screw speed brought about a decrease in GMA grafting yield. It was concluded that the GMA grafting yield is affected primarily by the residence time in the zone in which free radicals are not depleted. The effects of screw speed, feed rate, and specific throughput manifest mainly through this local residence time distribution. Specific energy is not a good measure of the performance of the extruder with respect to the free radical rafting of GMA onto PP. © 1995 John Wiley & Sons, Inc.     

Concept of nano-reactor for the control of the selectivity of the free radical grafting of maleic anhydride onto polypropylene in the melt

The aim of this work was to apply the concept of nano-reactors to the reactive extrusion process of the free radical grafting of maleic anhydride onto polypropylene (PP), an important process in the polymer industry. Pre-confinement of dicumyl peroxide in the lamellar structures of organically modified montmorillonite allowed slowing down the release of primary radicals and consequently to significantly improve the selectivity of the grafting of maleic anhydride onto PP and decrease the selectivity of PP chain scission. To the authors’ knowledge, this is the first time that a non-chemical method is found to solving the inherent problem facing this complicated process: increasing the grafting degree is always concomitant to increasing PP chain scission.     

Search for nonoxidative,hydrogen-abstracting initiators useful for melt grafting processes

Using organic peroxide initiators in the melt grafting of monomers containing amino groups onto polyethylenes is known to cause serious discoloration of the resulting polymers. To eliminate the discoloration while preserving the controlled degree of grafting, a nonoxidative and hydrogen-abstracting initiator with appropriate thermal stability is needed. In this study, the hydrogen-abstracting capability of three azo initiators with suitable decomposition rates in the melt grafting temperature ranges was evaluated using polyethylene cross-linking and polypropylene degradation experiments (called “hydrogen-abstracting experiments”). Among the three azo initiators tested, only a phenylazo initiator, 2 - phenylazo - 2,4 - dimethyl - 4 - methoxyl - valeronitrile (V-19), demonstrated strong hydrogen-abstracting capability from polymer backbones. These three azo initiators were used in the melt grafting of 2 - (N, N - dimethylamino) ethyl methacrylate (DMAEMA) and 2-(N-t -butylamino) ethyl methacrylate (tBAEMA) onto a linear low-density polyethylene (LLDPE). In agreement with the results obtained from the hydrogen-abstraction experiments, only V-19 led to a considerable amount of grafting of both DMAEMA and tBAEMA onto LLDPE. As expected, polymers grafted with V-19 showed significantly reduced discoloration compared with those grafted with peroxide initiators. Further examination of the grafting results indicated that the initiator efficieny, defined as the number of grafted monomer units per radical generated from initiator decomposition, was higher with the phenylazo initiator than with peroxide initiators. The hydrogen-abstracting capability of the phenyl free radical generated from the decomposition of V-19 was estimated to be higher than peroxide and methyl free radicals produced in the decomposition of peroxide initiatros. © 1993 John Wiley & Sons, Inc.     

Graft polymerization of acrylic acid onto polypropylene monofilament by RF plasma

Plasma‐induced graft polymerization of acrylic acid onto polypropylene monofilament was carried out to introduce carboxyl groups on its surface. The monofilament was treated with oxygen plasma to create hydroperoxide groups and subsequent graft polymerization of acrylic acid on exposed filament was carried out. An increase in the plasma power led to higher graft levels. It was observed that the hydroperoxide build up on PP surface follows linear increase with the increase in the plasma treatment time only up to 180 s beyond which it slowed down significantly. The formation of oxygenated species was ascertained by X‐ray photoelectron spectroscopy, and the peroxide content was measured by the 2′‐diphenylpicrylhydrazyl (DPPH) estimation. The grafting was observed to be considerably influenced by the plasma exposure time, plasma power, reaction temperature, monomer concentration and the storage temperature. A maximum in the degree of grafting was observed at 40% monomer concentration beyond which grafting tended to decrease very fast. The grafting was also found to be maximum at 50°C followed by a sharp decrease, subsequently. The storage of the exposed filament at ?80°C led to the identical grafting all along the 16 days. However, the storage at 25°C showed significant reduction in the degree of grafting. The atomic force microscopy showed that surface morphology is transformed into a nonhomogeneous one after the plasma exposure, but tends to flatten out after the grafting process in the form of globular structures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Grafting of maleic anhydride onto polypropylene by reactive extrusion

Maleic anhydride grafting onto polypropylene was conducted in a twin‐screw extruder according to an experimental design in which the maleic anhydride and peroxide concentrations were varied. The modified polypropylene was characterized by FTIR spectroscopy, melt‐flow index measurements, size‐exclusion chromatography, differential scanning calorimetry, and nuclear magnetic resonance. The results showed that only the independent variable peroxide concentration influenced the amount of reacted maleic anhydride, whereas the two variables studied influenced the molecular weight of the grafted polypropylene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2706–2717, 2002     

Synthesis and characterisation of PP-g-butyl acrylate copolymers

Butyl acrylate was grafted onto isotactic polypropylene using benzoyl peroxide as an initiator and toluene as a solvent. Effects of various parameters such as monomer and initiator concentration, reaction time and temperature on rates of polymerization, percentage grafting and grafting efficiency were studied. The extent of grafting achieved was 2.85%. The graft copolymers were characterized by IR, thermal, viscometric and contact-angle studies. Improved thermal stability and decreased intrinsic viscosity and critical surface tension were observed for graft copolymers.     

聚丙烯纤维接枝丙烯酸反应条件优化

The optimum conditions of grafting copolymerization reaction of acrylic acid (AA) onto polypropylene (PP) fiber was studied by using benzoyl peroxide (BPO) as initiator. The primary and secondary sequences of the grafting copolymerization reaction conditions was analysed. The results showed that grafting copolymerization reaction was greatly influenced by the temperature, reaction time, concentration of BPO and that of AA in the primary and secondary role as the above sequence. The optimum reaction conditions of gaining higher exchange capacity for the weak acidic cation-exchange fiber are as follows: the grafting temperature 80℃, the reaction time 7h, the concentration of BPO 2% and AA 80%.     

Effect of radical grafting of tetramethylpentadecane and polypropylene on carbon nanotubes' dispersibility in various solvents and polypropylene matrix

Multiwalled carbon nanotubes (MWCNTs) have been functionalized by tetramethylpentadecane (TMP), 1-dodecanethiol (DT) and polypropylene (PP) through radical addition onto MWCNTs' surface using dicumyl peroxide as hydrogen abstractor. Surface functionalized MWCNTs were characterized by Raman, IR spectroscopy, elementary analysis (EA) and thermogravimetric analysis (TGA). We studied the effect of temperature, peroxide concentration and solvent on TMP grafting densities and it was found that this surface treatment lead to a fair solubility in various solvents. TMP-functionalized MWCNTs were also imaged by transmission electronic microscopy showing single long functionalized MWCNTs distinct from the starting pristine bundles. For the first time, PP was then grafted onto MWCNTs through a radical grafting reaction. However, scanning electronic microscopy images of PP-functionalized MWCNTs/PP composites did not show a significant improvement in MWCNTs dispersion within the PP matrix.     

Electron spin resonance studies on graft copolymerization of gaseous styrene onto preirradiated polypropylene. II. Preirradiation under vacuum

Graft copolymerization of gaseous styrene was carried out at 40°C onto polypropylene preirradiated under vacuum. In order to investigate the origin of graft initiation activity, ESR spectra of irradiated polymers were measured and discussed. Although there are about three times as many radicals trapped in the sample irradiated at ?78°C as in the sample irradiated at room temperature, both the samples showed nearly same degree of grafting. This is due to the ineffectiveness of radicals trapped in the amorphous region for grafting. The samples irradiated under vacuum showed more grafting than those irradiated in an oxygen atmosphere. This is compatible with the conclusion in the previous paper that in grafting of polypropylene irradiated in an oxygen atmosphere the carbon radicals produced by hydrogen abstraction by trapped peroxy radicals are the effective active centers.     

Electron spin resonance studies on graft copolymerization of gaseous styrene onto preirradiated polypropylene. III. Preirradiation under vacuum followed by exposure to oxygen at −78°C

Grafting of styrene vapor was carried out onto polypropylene γ-irradiated under vacuum followed by exposure to oxygen at ?78°C. A comparison with the results on polypropylene irradiated in an oxygen atmosphere leads to an interesting result. Two samples were irradiated at room temperature under vacuum and in an oxygen atmosphere, respectively, the former being followed by exposure to oxygen. Although irradiation was carried out at room temperature for either sample and nearly the same amounts of the peroxy radicals are trapped, the former showed more grafting than the latter. The origin of this difference was investigated by means of electron spin resonance. Significant differences were observed in ESR spectra as well as in isothermal decays of the trapped peroxy radicals. In the former sample, the trapped peroxy radicals had a higher mobility, and consequently a significant hydrogen abstraction by the peroxy radicals was observed during storage at 40°C. This result supports the conclusion of the previous paper that the radicals effective in the grafting reaction of polypropylene preirradiated in an oxygen atmosphere are the carbon radicals which are produced by hydrogen abstraction by the peroxy radicals.     

Preparation of grafted copolymers via oxidized polypropylene

A new and novel class of oxidized polypropylene containing bound peroxide functionalities can be used as polymerization initiators to produce polypropylene‐grafted copolymers. Upon heat treatment, the peroxide functionalities in the oxidized polypropylene act as a source of free radicals, reacting with the unsaturated double bonds of the monomer and initiating polymerization. The grafting reaction is carried out in the solid state in a reactor. The advantage of grafting via this new class of oxidized polypropylene is the elimination of expensive and environmentally unfriendly organic peroxides. A number of monomers have been grafted using oxidized polypropylene, including vinyl acetate, vinyl pyrrolidinone, methacrylic anhydride, and maleic anhydride. Oxidized polypropylene‐grafted copolymers are effective compatibilizers for PP/ETP blends and good coupling agents in glass‐ reinforced formulations. Preparation, characterization, and mechanical properties of terpolymers prepared from sequential grafting of oxidized polypropylene are also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

塑料涂料用马来酸酐接枝氯化聚丙烯的合成与性能

以甲苯为溶剂、过氧化苯甲酰(BPO)为引发剂、马来酸酐(MAH)为接枝单体,对氯化聚丙烯(CPP)进行接枝改性.考察了引发剂和接枝单体用量、反应温度、反应时间以及原料的含氯量对接枝率的影响,并对改性产物进行了傅立叶红外光谱表征.结果表明,氯化聚丙烯成功地接枝上马来酸酐,反应条件和原料的含氯量会影响接枝率,优化的工艺条件为:m(BPO)/m(CPP)=0.04,m(MAH)/m(CPP)=1.1,反应温度为100 ℃,反应时间为3 h.涂料性能测试结果说明,改性产物在部分酮酯类溶剂中的溶解性能优良,对多种塑料材料有良好的附着性能,而附着力的大小受到接枝率的直接影响.     

Peroxide‐catalyzed swell grafting of maleic anhydride onto polypropylene

A new grafting method was developed to incorporate maleic anhydride directly onto solid‐state polypropylene powders. Maleic anhydride grafts altered the nonpolar characteristics of polypropylene so that much better mixing was achieved in blends and composites of polypropylene with many other polymers and fillers. Maleic anhydride was grafted onto polypropylene by the peroxide‐catalyzed swell grafting method, with a maximum extent of grafting of 4.60%. Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, tensile testing, and impact testing were used to characterize the isotactic polypropylene (iPP), maleic anhydride grafted polypropylene (MAH‐g‐iPP), and (isotactic polypropylene)/(calcium carbonate) composites (iPP/CaCO₃). The crystallinity and heat of fusion of the MAH‐g‐iPP decreased as the extent of grafting increased. The mechanical properties of the CaCO₃ filled polypropylene were improved by adding MAH‐g‐iPP as a compatibilizing agent. The dispersion of the fillers in the polymer matrix and the adhesion between the CaCO₃ particles and the polymer matrix were improved by adding the compatibilizer.     

Reactive grafting of glycidyl methacrylate onto polypropylene

This work explored the melt‐phase grafting of glycidyl methacrylate (GMA) onto polypropylene on a closely intermeshing corotating twin‐screw extruder (16‐mm screws, 40 : 1 length/diameter ratio). The modification of the base polypropylene to produce GMA‐grafted polypropylene was achieved via peroxide‐induced hydrogen abstraction from the polypropylene followed by the grafting of the GMA monomer or by the grafting of styrene followed by copolymerization with the GMA. In this study, both the position and order of the reactant addition were investigated as a route to improving graft yields and reducing side reactions (degradation). For the peroxide–GMA system, adding GMA to the melt before the peroxide resulted in significant improvements in the graft levels because of the improved dispersion of GMA in the melt. The addition of a comonomer (styrene) was explored as a second route to improving the graft yield. Although the addition of the comonomer led to a considerable rise in the level of grafted GMA, altering the order of the reactant addition was not found to contribute to an increase in the grafted GMA levels. However, variable levels of grafted styrene were achieved, and this may play an important role in the development of grafted polymers to suit specific needs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structurally bound stabilizers: Melt grafting of UV stabilizers onto polypropylene,polyethylene, and polystyrene

Monomeric ultraviolet stabilizers, 2-hydroxy-4-methacryloyloxy benzophenone and 2-hydroxy-4-acryloyloxy benzophenone were synthesized by a modified process. These reactive UV stabilizers were grafted onto the backbone of polypropylene (PP), low-density polyethylene (LDPE), and polystyrene (PS) by melt processing in the mixer of Brabender Plasticorder. An infrared spectroscopic method was standardized for the quantitative determination of the extent grafting of these additives on the polymer backbone. Grafting of both the additives occurred in the order PS > LDPE > PP. Methacryloxy derivative of benzophenone was found to be more reactive towards the polymers studied than the acryloxy derivative.     

Graft copolymerization of methacrylic acid onto isotactic polypropylene by radiochemical methods

Graft copolymerization of methacrylic acid onto isotactic polypropylene has been studied in water–methanol medium using γ-rays as the source of initiation. Graft copolymerization has been conducted by (1) mutual irradiation, (2) preirradiation, and (3) double irradiation methods. All of the reaction parameters that seem to influence grafting have been studied, and the optimum conditions leading to maximum percentage of grafting have been evaluated. A plausible mechanism for radiation-induced grafting of methacrylic acid onto polypropylene has been suggested, and the results have been explained on the basis of the proposed mechanism. A comparative study of graft copolymerization by different radiation methods has been made, and it was observed that the preirradiation method affords the best results. Evidence of grafting has been obtained from differential scanning calorimetric analysis and the dyeing behavior of the grafted material. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 143–152, 1998     

Influence of grafting formulations and extrusion conditions on properties of silane‐grafted polypropylenes

The melt grafting of unsaturated silanes onto powdered polypropylene (PP) in a Haake TW100 twin‐screw extruder and curing in hot water were studied. The influence of grafting formulations and extrusion conditions on the melt flow rates of grafted PP and the gel percentages of crosslinked PP was investigated. The gel percentages of methacryloylpropyltrimethoxysilane (VMMS)‐grafted PP were markedly higher than those of vinyltriethoxysilane (VTES)‐ and vinyltrimethoxysilane (VTMS)‐grafted PP, while significantly less degradation of PP during grafting was observed for VMMS‐grafted PP. When benzoyl peroxide (BPO) was used as an initiator, no degradation of PP during grafting was observed, and the melt flow rates of grafted PP decreased with increasing BPO concentration. In contrast, use of dicumyl peroxide (DCP) as an initiator resulted in severe degradation of PP, and the melt flow rates of grafted PP increased gradually with increasing DCP concentration. BPO resulted in higher gel percentages than those of DCP at a fixed initiator concentration. Introduction of styrene into the grafting system greatly improved the gel percentage of crosslinked PP and reduced the degradation of PP during grafting. The optimum molar ratio of styrene to monomer is at about 1.5:1. Relatively low processing temperatures and high screw speeds are favorable. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1233–1238, 2000