Improvements of polypropylene grafted maleic anhydride with ultrasonication, pre-irradiation and co-irradiation methods

This paper presented many improvements of polypropylene (PP) grafted maleic anhydride (MAH), including how to increase graft degree (G) and graft efficiency (G _E ) of MAH onto PP and how to reduce side reactions during grafting. Three grafting methods ultrasonication, pre-irradiation and co-irradiation were employed, and a lot of additives were adopted in our research, such as styrene (St), ethyl benzoate, dibutyl phthalate (DBP), 2,2′-bipyridine, divinylbenzene (DVB), benzoyl peroxide (BPO) and p-hydroquinone. The effects of the different grafting methods and additives were determined by G and G _E values, viscosity, FTIR and DSC. Experimental results showed that the highest G value was obtained in co-irradiation method in the presence of St, and side reactions could be also reduced. The best reflux time for G value measuring, the storage time on G and batch feeding times of MAH on G in pre-irradiation method, and the mechanism of PP grafted MAH were all studied.     

Styrene‐assisted free‐radical graft copolymerization of maleic anhydride onto polypropylene in supercritical carbon dioxide

The free‐radical graft copolymerization of maleic anhydride (MAH) onto polypropylene (PP) with the assistance of styrene (St) in supercritical carbon dioxide (CO₂) was studied. The effects of the St concentration and initiator concentration on the functionality degree of the grafted PP in supercritical CO₂ were investigated. The addition of St drastically increased the MAH functionality degree, which reached a maximum when the molar ratio of MAH and St was 1:1. St, an electron‐donating monomer, could interact with MAH through charge‐transfer complexes to form the St–MAH copolymer (SMA), which could then react with PP macroradicals to produce branches by termination between radicals. There was SMA in the grafting reaction system characterized by Fourier transform infrared and differential scanning calorimetry. Furthermore, the highest MAH functionality degree was obtained when the concentration of 2,2′‐azobisisobutyronitrile (AIBN) was 0.6 wt % based on PP. The effects of the temperature and pressure of supercritical CO₂ on the functionality degree of the grafted PP were analyzed. An increase in the temperature accelerated the decomposition rate constant of AIBN, thereby promoting the grafting reaction. In addition, an increase in the temperature increased the diffusion of monomers and radicals in the disperse reaction system of supercritical CO₂. The highest degree of functionality was found at 80°C. Also, the functionality degree of grafted PP decreased with an increase in the pressure of supercritical CO₂ within the experimental range. The morphologies of pure PP and grafted PP were significantly different under polarizing optical microscopy. The PP spherulites were about 38 μm in size, and the grafted PP spherulites were significantly reduced because of heterogeneous nucleation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 853–860, 2003     

马来酸酐及苯乙烯同时接枝聚丙烯的研究

用过氧化二异丙苯(DCP)作为引发剂，采用双螺杆反应挤出的苯乙烯、马来酸酐2种单体同时接枝聚丙烯．研究了单体总浓度、单体比例、引发剂浓度对PP的接枝率、接枝效率和熔体流动速率的影响。通过实验发现苯乙烯的加入使接枝率和接枝效率比单独的马来酸酐接枝都有很大的提高。     

Melt grafting of maleic anhydride onto polypropylene with 1‐decene as a second monomer

The influence of 1‐decene as the second monomer on the melt‐grafting behavior of maleic anhydride (MAH) onto polypropylene (PP) was studied with differential scanning calorimetry and Fourier transform infrared spectroscopy. We found that the value of the grafting degree increased from 0.68% for pure MAH‐g‐PP to 1.43% for the system with a 1‐decene/MAH molar ratio of 0.3, whereas the maximum value with styrene (St) as the second monomer was 0.98% under an St/MAH molar ratio of 1.0. Compared with the contribution of St/MAH‐g‐PP to the peeling strength between the PP and polyamide (PA) layer for a PP/PA laminated film, the introduction of 1‐decene/MAH‐g‐PP increased the peeling strength from 180 g/15 mm to 250 g/15 mm. 1‐Decene inhibited the chain scission behavior of PP. 1‐Decene reacted with MAH to form a 1‐decene/MAH copolymer or the Alder‐ene reaction product before the two monomers grafted onto PP. The grafting of the reactive product onto PP greatly improved the grafting degree of MAH. What is more, because of the similar chemical structures of 1‐decene and PP, the affinity of 1‐decene with PP was higher than that of St. Compared with St, the introduction of less 1‐decene led to a higher grafting degree and higher peeling strength. Therefore, we concluded that 1‐decene was more effective for improving the grafting degree of MAH onto PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of polypropylene with maleic anhydride: Ultrasonic irradiation effects

The mechanochemical reaction of modificated of polypropylene (PP) with maleic anhydride (MAH) has been studied by ultrasonic irradiation as an energy source at 60°C. Through 2³ factorial experimental design, three variables and their interactions were studied: the percentage of MAH, the percentage of benzoyl peroxide (BPO), and ultrasonic irradiation intensity (Watts). According to the results, an increase of wt % of MAH gave a negative effect in the grafting yield; in addition, this negative effect was observed in the interaction of MAH : BPO at a high range of wt %, this behavior is attributed to the homopolymerization of MAH at the experimental conditions employed. The higher positive effect onto the grafting yield was observed for the variable watts (ultrasonic irradiation intensity), even at low intensity. The better interaction of variables gave a MAH grafting degree of 4.65 wt % (93% yield). In addition, the effect of ultrasonic irradiation on the number-average molar mass (M_n), weight-average molar mass (M_w), and polydispersity index (M_w/M_n) was measured. It was observed that the M_w decreased 13.73% and the M_w/M_n also decreased by 11.98%. The o observed effect was attributed to the degradation mechanism induced by the ultrasound, which consists in the generation of macroradicals and their recombination. The product PP-g-MAH was characterized by infrared spectroscopy, also was used to prepare polypropylene–nylon-6 blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:45–52, 1998     

Synthesis of functional polypropylene via solid‐phase grafting soft vinyl monomer and its mechanism

Solid‐phase grafting of a soft vinyl monomer, butyl methylacrylate (BMA), onto polypropylene (PP) matrixes with 2,2′‐azobisisobutyronitrile (AIBN) as initiator was carried out to enhance the polarity of polymer. Soft vinyl monomer was a novel notion in grafting modification of PP. Effects of swell time, BMA concentration, AIBN concentration, grafting reaction time, and temperature on grafting percentage (G_p) and grafting efficiency (G_e) were examined. The optimal conditions of grafting reaction were obtained: swell time of 60 min, BMA concentration of 6 wt %, AIBN concentration of 0.05 wt %, reaction temperature of 85°C, and reaction time of 2 h. The grafting samples were investigated by such characterization techniques as Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and scanning electron microscope (SEM) analysis. FTIR results indicated that BMA was actually grafted onto PP backbone. TGA results showed that the decomposition temperature increases with addition of BMA into PP backbone. SEM results indicated that the surfaces of PP‐g‐BMA had a markedly bumpy texture, whereas the pure PP surface was very smooth. Water contact angle results showed that the polarity and hydrophilicity of PP were improved effectively. Compared with the traditional monomer MAH, G_p, and G_e, melt flow rate and mechanical property results all indicated that the soft vinyl monomer had a many advantages in the modification of PP. In the end, the mechanism of solid grafting was discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of clay contents on the dynamic mechanical and rheological properties of polypropylene/MAH‐g‐POE/clay composites

A series of polypropylene/maleic anhydride grafted polypropylene octane elastomer (MAH‐g‐POE)/clay (PPMC) nanocomposites were prepared with a novel compatilizer MAH‐g‐POE and different contents of octadecyl amine modified montmorillonite, and the effects of clay contents on the dynamic mechanical and rheological properties of these PPMC composites were investigated. With clay content increasing, the characteristic X‐ray diffraction peak changed from one to two with intensity decreasing, indicating the decreasing concentration of the intercalated clay layers. The gradual decrease of crystallization temperature of PPMC composites with the increase of clay loading should be attributed to the preferred intercalation of MAH‐g‐POE molecules into clay interlayer during blending, which is also reflected by scanning electron microscopy observations. By evaluating the activation energy for the glass transition process of MAH‐g‐POE and polypropylene (PP) in the PPMC composites, it is found that clay intercalation could cause the restriction effect on the glass transition of both MAH‐g‐POE and PP, and this restriction effect appears stronger for PP and attained the highest degree at 5 wt % clay loading. The melt elasticity of PP could be improved apparently by the addition of MAH‐g‐POE, and 5 wt % clay loading is enough for further enhancing the elastic proportion of PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO₂) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO₂ was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44094.     

Toughening of PP/EPDM blend by compatibilization

To improve the mechanical properties of blends of polypropylene (PP) and terpolymer of ethylene–propylene–diene (EPDM), a triblock copolymer, (PP‐g‐MAH)‐co‐[PA‐6,6]‐co‐(EPDM‐g‐MAH), was synthesized by coupling reaction of maleic anhydride (MAH)‐grafted PP (PP‐g‐MAH), EPDM‐g‐MAH, and PA‐6,6. The newly prepared block copolymer brought about a physical interlocking between the blend components, and imparted a compatibilizing effect to the blends. Introducing the block copolymer to the blends up to 5 wt % lead to formation of a β‐form crystal. The wide‐angle X‐ray diffractograms measured in the region of 2θ between 10° and 50° ascertained that incorporating the block copolymer gave a new peak at 2θ = 15.8°. The new peak was assigned to the (300) plane spacings of the β‐hexagonal crystal structure. In addition, the block copolymer notably improved the low‐temperature impact property of the PP/EPDM blends. The optimum usage level of the compatibilizer proved to be 0.5 wt %. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1267–1274, 2000     

Crystallization behavior of PP/PP‐g‐MAH/GFR PA66 blends: Establishment of their continuous‐cooling‐transformation of relative crystallinity diagrams

Polypropylene/polypropylene‐grafted‐maleic anhydride/glass fiber reinforced polyamide 66 (PP/PP‐g‐MAH/GFR PA 66) blends‐composites with and without the addition of polypropylene‐grafted‐maleic anhydride (PP‐g‐MAH) were prepared in a twin screw extruder. The effect of the compatibilizer on the thermal properties and crystallization behavior was determined using differential scanning calorimetry analysis. The hold time was set to be equal to 5 min at 290°C. These conditions are necessary to eliminate the thermomechanical history in the molten state. The crystallization under nonisothermal conditions and the plot of Continuous‐Cooling‐Transformation of relative crystallinity diagrams of both PP and PA 66 components proves that PP is significantly affected by the presence of PP‐g‐MAH. From the results it is found that an abrupt change is observed at 2.5 wt % of PP‐g‐MAH as a compatibilizer and then levels off. In these blends, concurrent crystallization behavior was not observed for GFR PA66. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1620–1626, 2007     

马来酸酐接枝聚丙烯的研究

研究了聚丙烯(PP)与马来酸酐(MAH)的接枝配方;并且探索了接枝反应过程中PP自由基的降解抑制方法。结果表明,以引发剂A为引发剂,以嵌段PP为基础树脂,以MAH为接枝单体,以St为第二单体的PP／A／St/ MAH反应体系使PP自由基降解得到了有效的抑制,可制备接枝为1．5％-4．0％的接枝聚丙烯。     

The effect of graft copolymers of maleic anhydride and epoxy resin on the mechanical properties and morphology of PP/ABS blends

In this work, maleic anhydride‐grafted polypropylene (PP‐g‐MAH) and maleic anhydride‐grafted poly(acrylonitrile‐butadiene‐styrene) (ABS‐g‐MAH) at 2 : 1 mass ratio were added as a compatibilizer in the PP/ABS blends. The compatibilizing effect was evaluated by adding the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ). The reaction in reactive extrusion, morphological structure, and properties of PP and ABS blends were investigated by using infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray spectrum, transmission electron microscope (TEM), dynamic thermomechanical analysis (DMA), differential scanning calorimetry (DSC), and mechanical properties tests. The results showed that the compatibilizing effect was greatly improved because of the addition of the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ) because the link structure of PP‐g‐MAH and ABS‐g‐MAH was formed by the reaction of anhydride group with epoxy group catalyzed by the imidazole. The size of the dispersed phase decreased dramatically, the interfacial adhesion between ABS particles and PP matrix was improved, and the tensile strength and flexural modulus of the PP/ABS blends increased further. The optimizing properties were obtained at 3 phr E51/2E4MZ. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40898.     

Crystallization kinetics of maleic anhydride‐modified iPP studied by POM

Melt nucleation and crystallization behavior of homo‐isotatic polypropylene (homo‐iPP), maleic anhydride (MAH)‐grafted‐iPP, and MAH‐modified iPP, produced from iPP and a small amount of MAH‐grafted‐iPP, was investigated by polarizing optical microscopy (POM), at T_c = 121–135^oC. Nucleation processes at a given T_c were faster for modified PP as compared to neat iPP. The induction time for nucleation increased nonlinearly with increasing T_c and decreased for modified PP, probably as a result of promoted heterogeneous nucleation due to the presence of carbonyl groups of MAH‐grafted‐PP. The average spherulite sizes were decreased by modification, and the growth rate was enhanced in maleated PP and modified PP. The induction time approach was applied to the results obtained by POM to compare the tendency for heterogeneous nucleation of neat and MAH‐modified PP. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3107–3118, 2000     

Dynamically cured polypropylene/Novolac blends compatibilized with maleic anhydride‐g‐polypropylene

In this article, the dynamic vulcanization process was applied to polypropylene (PP)/Novolac blends compatibilized with maleic anhydride‐grafted PP (MAH‐g‐PP). The influences of dynamic cure, content of MAH‐g‐PP, Novolac, and curing agent on mechanical properties of the PP/Novolac blends were investigated. The results showed that the dynamically cured PP/MAH‐g‐PP/Novolac blend had the best mechanical properties among all PP/Novolac blends. The dynamic cure of Novolac improved the modulus and stiffness of the PP/Novolac blends. The addition of MAH‐g‐PP into dynamically cured PP/Novolac blend further enhanced the mechanical properties. With increasing Novolac content, tensile strength, flexural modulus, and flexural strength increased significantly, while the elongation at break dramatically deceased. Those blends with hexamethylenetetramine (HMTA) as a curing agent had good mechanical properties at HMTA content of 10 wt %. Scanning electron microscopy (SEM) analysis showed that dynamically cured PP/MAH‐g‐PP/Novolac blends had finer domains than the PP/MAH‐g‐PP/Novolac blends. Thermogravimetric analysis (TGA) results indicated that the incorporation of Novolac into PP could improve the thermal stability of PP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of solid‐phase graft copolymer of polypropylene with styrene and maleic anhydride

Polypropylene (PP) was modified by solid‐phase graft copolymerization with maleic anhydride (MAH) and styrene (St), using benzoyl peroxide as the initiator and xylene as the interfacial agent. Effects of various factors such as monomer concentration, monomer ratio, initiator concentration on grafting percentage, and acid value were investigated. The graft copolymer was characterized by Fourier transform infrared, pyrolysis gas chromatography—mass spectroscopy, and dynamic mechanical analysis, and the intrinsic viscosity of the extractive from the reaction product was investigated. The results showed that the grafting percentage and acid value of the graft copolymer of PP with two monomers (MAH and St) were considerably higher than those of the graft copolymer of PP with MAH alone. The graft segments were shown to be the copolymer of St and MAH with a substantial molecular weight. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2482–2487, 2000     

Crystallization and dynamic mechanical properties of polypropylene/polystyrene blends modified with maleic anhydride and styrene

Polypropylene (PP)/polystyrene (PS) blends modified with reactive monomers, such as maleic anhydride (MAH) and styrene (St), and in situ formed PP/PS blends were prepared by melting extrusion. The crystallization and melting behavior and the dynamic mechanical properties of the PP/PS blends, including the structure of the grafted copolymer, were investigated with differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared. The results indicated that the addition of MAH hardly influenced the crystallization temperature of PP in the blends, but the addition of MAH and St increased the crystallization temperature of PP in its blends. The blends showed no remarkable variety for the melting temperature, but the shapes of the melting peaks were influenced by the addition of the reactive monomers. In addition, a significant increase in the storage and loss moduli of all the modified PP/PS blends was observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2038–2045, 2005     

Synthesis and reaction kinetics model of suspension phase grafting polypropylene with dual monomers

The grafting polymerization of maleic anhydride (MAH) and styrene (St) onto PP was carried out in suspension phase. Infrared (IR) spectra and ¹H-NMR spectra confirmed that MAH and St were successfully grafted onto the PP backbone. The influences, such as monomers concentration, reaction temperature, initiator concentration and reaction time, on the grafting polymerization rate were also studied, and then the polymerization model was obtained to describe the polymerization regularities. The results showed that the model was adequate to reflect the courses, and diffusion and equilibrium adsorption played an important role in suspension polymerization.     

Study of dynamically cured PP/MAH‐g‐PP/talc/epoxy composites

In the present study, an epoxy resin was dynamically cured in a polypropylene (PP)/maleic anhydride–grafted PP (MAH‐g‐PP)/talc matrix to prepare dynamically cured PP/MAH‐g‐PP/talc/epoxy composites. An increase in the torque at equilibrium showed that epoxy resin in the PP/MAH‐g‐PP/talc composites had been cured by 2‐ethylene‐4‐methane‐imidazole. Scanning electron microscopy analysis showed that MAH‐g‐PP and an epoxy resin had effectively increased the interaction adhesion between PP and the talc in the PP/talc composites. Dynamic curing of the epoxy resin further increased the interaction adhesion. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had higher crystallization peaks than did the PP/talc composites. Thermogravimetric analysis showed that the addition of MAH‐g‐PP and the epoxy resin into the PP/talc composites caused an obvious improvement in the thermal stability. The dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best thermal stability of all the PP/talc composites. The PP/MAH‐g‐PP/talc/epoxy composites had better mechanical properties than did the PP/MAH‐g‐PP/talc composites, and the dynamically cured PP/MAH‐g‐PP/talc/epoxy composites had the best mechanical properties of all the PP/talc composites, which can be attributed to the better interaction adhesion between the PP and the talc. The suitable content of epoxy resin in the composites was about 5 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Functionalization of polyolefins with maleic anhydride in melt state through ultrasonic initiation

The functionalization reaction of high-density polyethylene (HDPE), linearly low-density polyethylene (LLDPE), polypropylene (PP) and EPDM rubber with maleic anhydride (MAH) in melt state through ultrasonic initiation was studied. The effect of ultrasonic intensity on the percentage of grafting, viscosity-average molecular weight, melt flow rate and gel content of the functionalized products were investigated by means of chemical titration, Fourier-transform infra-red spectroscopy (FT-IR), intrinsic viscosity and melt flow rate, etc. The molecular structures of the functionalized products prepared via ultrasonic initiation and via peroxide initiation were characterized by ¹H NMR spectroscopy. The results show that the functionalization reaction of HDPE, LLDPE and EPDM with MAH can be realized by ultrasonic initiation. This reaction mainly consists of the chain scission under ultrasonic irradiation, the end chain reaction of the produced macroradicals with MAH, and the terminated reaction of the produced succinyl radicals with the macroradicals or H* radicals through recombination or dismutation. The functionalized product through ultrasonic initiation mainly consists of the products containing an anhydride ring attached to the chain terminus. And the products prepared through peroxide initiation mainly contain an anhydride ring grafted on the side chain.     

PP–PP‐g‐MAH–Org‐MMT nanocomposites. I. Intercalation behavior and microstructure

The melt‐direct intercalation method was employed to prepare poly(propylene) (PP)–maleic anhydride grafted poly(propylene) (PP‐g‐MAH)–organic‐montmorillonite (Org‐MMT) nanocomposites. X‐ray diffractometry (XRD) was used to investigate the intercalation effect, crystallite size, and crystal cell parameter in these composites. Two kinds of maleated PP, with graft efficiencies of 0.6 and 0.9 wt %, and two sorts of manufacturing processes were used to prepare nanocomposites and then to investigate their effects on intercalation behavior. The results showed that the intercalation effect was enhanced by increasing the content of PP‐g‐MAH, using maleated PP with higher graft efficiency, and adopting the mold process. The crystallite size of nanocomposites perpendicular to the crystalline plane, such as (040), (130), (111), and (041), reached the minimum value when the content of PP‐g‐MAH was 20 wt %. This result indicated that the crystallite size of PP in nanocomposites decreased by proper addition of PP‐g‐MAH. Maximum values in tensile strength (40.2 MPa) and impact strength (24.3 J/m) were achieved when the content of PP‐g‐MAH was 10 and 20%, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3225–3231, 2003