Comparison of carboxylated and maleated polypropylene as reactive compatibilizers in polypropylene/polyamide‐6,6 blends

Using reactive extrusion, polypropylene is functionalized with maleic anhydride and compared on an equimolar basis to polypropylene that is functionalized with an asymmetric, carboxylic acid containing peroxide. The grafting efficiency for the asymmetric peroxide is double that obtained for the maleic anhydride system. Moreover, the asymmetric peroxide yields a functionalized material with minimal molecular weight degradation and desirable mechanical properties, relative to maleic anhydride‐grafted polypropylene. In compatibilized blends of polypropylene and nylon 6,6, the polypropylene that was functionalized with the asymmetric peroxide is found to be an improved compatibilizer compared to that of maleic anhydride‐grafted polypropylene. The differences in mechanical properties of the two different functionalized polypropylene materials and their respective blends are rationalized on the basis of the grafting efficiency, molecular weight degradation during reactive extrusion, and effect of free functional species on the ability to form graft copolymers in compatibilized blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2398–2407, 2001     

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     

Graft copolymerization of maleic anhydride onto low‐molecular‐weight polyisobutylene through solvothermal method

The free‐radical graft copolymerization of maleic anhydride (MAH) onto highly reactive low molecular weight polyisobutylene was conducted by the use of benzoyl peroxide as an initiator through the solvothermal method. Fourier transform infrared spectra and ¹H‐NMR spectra confirmed that maleic anhydride was successfully grafted onto highly reactive low molecular weight polyisobutylene backbone, and the grafting mechanism also was proposed. The effect of benzoyl peroxide content, MAH concentration, total reactant amount in the reaction vessels, reaction temperature and time, and different kinds and volumes of solvents on MAH's degree of grafting was investigated in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Functionalization of ethylene–propylene–diene monomer rubber with maleic anhydride in the melt state through high‐shear stress‐induced initiation

The functionalization reactions of ethylene–propylene–diene monomer rubber (EPDM) with maleic anhydride (MAH) in melt state through high‐shear‐stress‐induced initiation by an increase in the screw rotation speed of the twin‐screw extruder and through compounded initiation by the addition of some initiator and an increase in the screw rotation speed were investigated. The results show that, with increasing screw rotation speed and reaction temperature, the percentage grafting and melt flow rate of the functionalized products (EPDM‐g‐MAH) were noticeably increased, and the viscosity‐average molecular weight decreased, which implied that the grafting reaction consisted of the chain scission and grafting reaction of the produced macroradicals with MAH. In the presence of a certain peroxide initiator, the crosslinking reaction during melt extrusion was suppressed by an increase in the screw rotation speed. The percentage grafting of EPDM‐g‐MAH amounted to 1.1%, its melt flow rate was between 0.3 and 4.0 g/10 min, and its gel content was less than 1.0%, depending on the screw rotation speed and reaction temperature. Impact testing and scanning electron microscopy showed that the functionalized product prepared through the high shear stress‐induced initiation had a higher blocking activity with the amide terminated of PA66 than that prepared through the peroxide initiation or through the compound initiation, and the impact strength of the PA66/EPDM blends, improved by the high‐shear‐stress‐induced product was noticeably higher than those of the peroxide‐initiated product or the compound‐initiated one. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermoplastic elastomeric composition based on maleic anhydride–grafted ground rubber tire

Ground rubber tire (GRT) powder was maleated in an internal mixer using maleic anhydride and dicumyl peroxide at 160°C. Maleated GRT was characterized by using X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, wettability, and differential scanning calorimetry. The physical properties of the dynamically vulcanized 60 : 40, rubber : plastic composition based on acrylated high‐density polyethylene as the plastic phase and ethylene propylene diene rubber containing maleated GRT as the rubber phase were found to be greater than the corresponding composition containing nonmaleated GRT. The blend was found to be reprocessable, like themoplastic elastomers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 370–378, 2002; DOI 10.1002/app.10348     

线性低密度聚乙烯反应挤出接枝马来酸酐的研究

以过氧化二异丙苯(DCP)为引发剂,在双螺杆挤出机中进行了马来酸酐(MAH)熔融接枝线性低密度聚乙烯(LLDPE)的研究,用红外光谱表征了接枝反应的存在。考察了引发剂用量、单体用量、螺杆转速以及温度对接枝反应的影响,并探讨了苯乙烯(St)作共单体对接枝反应的影响。研究表明:在引发剂含量较低时,用苯乙烯作共单体能够显著提高接枝率。     

Preparation and properties of bitumen modified with the maleic anhydride grafted styrene‐butadiene‐styrene triblock copolymer

A procedure to improve the properties of styrene‐butadiene‐styrene (SBS) copolymer modified bitumen by grafting of maleic anhydride (MAH) onto SBS in the presence of benzoyl peroxide (BPO) as initiator was proposed. The effects of the grafting degree (GD) on the properties of modified bitumen were investigated. FTIR spectroscopy was employed to verify the grafting of MAH onto SBS. The GD of MAH onto SBS was determined by a back titration procedure. To assess the effects of the GD of grafted SBS on properties of modified bitumen, the softening point, penetration, ductility, elastic recovery, penetration index, viscosity, storage stability, and dynamic shear properties were tested. Experimental results indicated that the SBS grafted with maleic anhydride (SBS‐g‐MAH) copolymer was successfully synthesized by solvothermal method, and different GD of the SBS‐g‐MAH was obtained by control the MAH concentration. The GD of the MAH onto SBS has great effect on the rheological properties of the modified bitumen, and the high temperature performance and storage stability of modified bitumen were improved with the GD of the MAH onto SBS increasing. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Reactive extrusion of polypropylene with supercritical carbon dioxide: Free radical grafting of maleic anhydride

A reactive extrusion process for the functionalization of polypropylene with maleic anhydride in the presence of supercritical carbon dioxide was studied. Supercritical carbon dioxide was used in this reactive extrusion system to reduce the viscosity of the polypropylene melt phase by forming a polymer–gas solution in order to promote better mixing of the reactants. Subsequently, the effect of supercritical carbon dioxide on the level of grafting, product homogeneity, and molecular weight was evaluated. Analysis of the products revealed that the use of supercritical carbon dioxide led to improved grafting when high levels of maleic anhydride were used. The experimental results showed no evidence of an improvement in the homogeneity of the product, while melt flow rate measurements showed a reduction in the degradation of polypropylene during the grafting reaction when low levels of maleic anhydride were employed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1116–1122, 2003     

马来酸酐溶液法接枝改性天然橡胶的研究

采用溶液法，选用极性单体马来酸酐(MAH)，在非隔氧条件下，以过氧化苯甲酰(BPO)为引发剂对天然橡胶(NR)进行接枝改性。通过傅立叶红外光谱对接枝物进行定性表征；采用化学滴定法测定了反应产物的接枝率和接枝效率；详细讨论了反应单体和引发剂的用量、反应时间等因素对反应产物接枝率和接枝效率的影响；并应用正交设计法评价了各因素对产物接枝率和接枝效率的影响。     

Polystyrene and polyether polyurethane elastomer blends compatibilized by SMA: Morphology and mechanical properties

Blends of polystyrene (PS) and the polyether polyurethane elastomer (PU‐et) were prepared by melt mixing using poly(styrene‐co‐maleic anhydride) (SMA) containing 7 wt % of maleic anhydride as a compatibilizer. The polyurethane in the blends was crosslinked using dicumyl peroxide or sulfur. The content of maleic anhydride was varied in the blends through the addition of different SMA amounts. The morphology of the blends was analyzed by SEM and a drastic reduction of both the domain size and its distribution was observed with increase of the anhydride content in the blends. The morphology of the PU‐et blends also showed dependence on the crosslinker agent used for the elastomer, and larger domains were obtained for the elastomer phase crosslinked with dicumyl peroxide. The mechanical properties of the blends were evaluated by flexural and impact strength tests. The blend containing 0.5 wt % of maleic anhydride and 20 wt % of PU‐et crosslinked with sulfur showed the highest strength impact, which was three times superior to the PS strength impact, and the blends containing 20 wt % of PU‐et crosslinked with dicumyl peroxide showed the highest deflection at break independent of the anhydride content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 830–837, 2002     

同向双螺杆挤出机螺杆元件对PE-LD-g-MAH熔融接枝过程的影响

通过改变同向双螺杆挤出机主反应区的螺杆元件，研究了螺杆元件对由过氧化二异丙苯引发，低密度聚乙烯（PE-LD）熔融接枝马来酸酐（MAH）的接枝产物和接枝率的影响。红外光谱分析证实有部分MAH已经成功接枝到PBLD分子链上。通过对挤出沿程4个在线取样位置样品的对比分析表明，具有高剪切性能的捏合盘元件的沿程样品的接枝率较大，熔体流动速率较小；具有高拉伸性能的S形元件能够迅速提高接枝率。     

Controlled degradation reactions in EPDM bulk modification with maleic anhydride

Summary Two kinds of EPDM rubber were bulk functionalized with maleic anhydride, using dicumyl peroxide as radical source, in the presence of stabilizers and electron donor in order to minimize degradative oxidation. Different peroxide type initiators were tested aiming to control oxidation without deleteriously affecting grafting efficiency.     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Modification of acrylonitrile–butadiene–styrene terpolymer by grafting with maleic anhydride in the melt. I. Preparation and characterization

The graft copolymerization of maleic anhydride (MAH) onto acrylonitrile–butadiene–styrene terpolymer (ABS) was carried out with dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as the binary initiators and with styrene as the comonomer in the molten state. IR spectra confirmed that MAH was successfully grafted onto the ABS backbone. A reaction mechanism was proposed: the grafting most likely took place through the addition of MAH radicals to the double bond of the butadiene region of ABS. Influences such as the MAH concentration, the initiators and their concentrations, the reaction temperature, the rotating speed, and the comonomer concentration were studied. The results indicated that using styrene as a comonomer and DCP/BPO as binary initiators was beneficial for the graft copolymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1249–1254, 2003     

Preparation of spherical polymer beads of maleic anhydride–styrene–divinylbenzene and metal sorption of its derivatives

Compounds having acid anhydride moiety have been used for starting materials for many useful derivatives. Spherical crosslinked polymer beads of porous maleic anhydride–styrene–divinylbenzene copolymer are obtained by suspension polymerization. Glycerol is found to be a preferable dispersant to make spherical beads. The beads contained 93% of the anhydride and 7% of the free carboxyls. As one of applications, the beads were hydrolyzed or reacted with anhydrous hydrazine, and the metal sorption behavior of them was examined. The hydrolyzed beads show a similar sorption manner as a conventional cation exchange resin having carboxylic acid groups, but the hydrazide beads sorbed mercury (II) selectively over a wide pH range. This investigation suggests a simple preparative method for the insoluble spherical porous beads of the maleic anhydride copolymer.     

Reactive compatibilization of the poly(butylene terephthalate)–EVA blend by maleic anhydride. II. Correlations among gel contents,grafting yields,and mechanical properties

Correlations among the degree of crosslinking of ethylene vinyl acetate copolymer (EVA), the grafting yield of maleic anhydride (MAH) onto EVA, and the mechanical properties of the blends of poly(butylene terephtalate) (PBT) with EVA‐g‐MAH were investigated. The EVA was functionalized by melt grafting reaction in the presence of MAH and dicumyl peroxide (DCP) using a plasticorder. The grafting yield of MAH was increased by increasing the concentration of MAH and DCP. The flexural strength of PBT–EVA‐g‐MAH blends depends on both the grafting yield of MAH and the degree of crosslinking of EVA, while the crosslinked parts of EVA‐g‐MAH hindered rather than improved the tensile strength regardless of the increase of the grafting yield of MAH. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1305–1310, 2003     

Polyethylenes/PET blend compatibilization with maleic anhydride modified polyethylenes obtained by a UV preirradiation process

The compatibilization of HDPE/LDPE/LLDPE/PET blend during reactive extrusion, using compatibilizing agents, such as modified high, low, and lineal low density polyethylenes with maleic anhydride, was carried out. The agents were prepared in our laboratory by using a UV preirradiation process, containing different grafting and crosslinking degrees. The materials were compared with same maleic anhydride modified polyethylenes prepared by the traditional peroxide method in our laboratory and with a commercial maleic anhydride modified lineal low density polyethylene. The mechanical and thermal properties, as well as their morphology, were evaluated in the compatibilized blends and changes in crystallization phases recorded. The elongation at break and impact strengths increased with compatibilization level and morphology was markedly more homogenous. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 560–567, 2007     

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.     

Modification of a Fischer‐Tropsch wax by grafting with maleic anhydride

The polarity of a hard Fischer‐Tropsch paraffin wax was improved through grafting of maleic anhydride (MA) initiated by dibenzoyl peroxide (DBP), which is reflected by a significant increase in the polar component of the surface free energy. MA and DBP concentrations of 3 wt % each are sufficient for significant modification of the polarity of the wax. FTIR spectra confirm the presence of anhydride groups on the wax chains, while gel permeation chromatograms show the development of a low molecular weight peak, which may be indicative of wax degradation. The grafting of wax by MA decreases the specific enthalpy of melting, as determined through differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 662–668, 2004     

Free radical meleation of soybean oil <Emphasis Type="Italic">via</Emphasis> a single-step process

In this study a new value-added product was developed from soybean oil for use as a chemical feedstock. The investigation and optimization of this work resulted in a fast and simple process to maleate soybean oil. An anhydride functionality was introduced into soybean oil through a free radical-initiated maleation. Two initiators were evaluated, 2,5-bis(tert-butylperoxy)2,5-dimethylhexane peroxide and di-tert-butyl peroxide. The effects of reaction time, initiator concentration, maleic anhydride concentration, and reaction temperature were investigated. The maleated soybean oil was characterized using acid value, iodine value, and FTIR spectroscopy. The acid value was directly related to the initial concentration of maleic anhydride, whereas the concentration and type of initiator had little effect on the acid value. The peroxide-initated functionalization of soybean oil with maleic anhydride in a closed vessel at elevated pressure and temperature was found to proceed by a Diels-Alder mechanism.