Parameters affecting the free‐radical melt grafting of maleic anhydride onto linear low‐density polyethylene in an internal mixer

Our main objective of this study was to study the parameters affecting the free‐radical melt grafting of maleic anhydride (MA) onto linear low‐density polyethylene (LLDPE) with dicumyl peroxide (DCP) in an internal mixer. The degree of grafting (DG) was measured with titrometry and Fourier transform infrared spectroscopy. The extent of chain‐branching/crosslinking was evaluated with gel content and melt flow index measurements. The flow behavior and melt viscoelastic properties of the grafted samples were measured by using rheometric mechanical spectrometry. Feeding order, DCP and MA concentration, reaction temperature, rotor speed, and grade of LLDPE were among parameters studied. The results show that the reactant concentration (MA and DCP) played a major role in the determination of the grafting yield and the extent of the chain‐branching/crosslinking as competitive side reactions. The order of feeding also had an appreciable effect on the DG and the side reactions. Increasing the rotor speed increased the grafting yield and reduced side reactions by means of intensification of the mixing of reactants into the polyethylene (PE) melt. Chain‐branching dominated the side reactions for lower molecular weight PE, whereas for higher molecular weight PE, chain‐branching led to crosslinking and gel formation. The results of the melt viscoelastic measurements on the grafted samples provided great insight into the understanding of the role of influential parameters on the extent of side reactions and resulting changes in the molecular structure of the grafted samples. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 141–149, 2006     

Comparison of maleic anhydride grafting onto powder and granular polypropylene in the melt by reactive extrusion

The grafting of powder and granular polypropylene (PP) with maleic anhydride (MA) was investigated in a reactive extrusion process with dicumyl peroxide (DCP) as an initiator. The effects of the MA and DCP contents in the feed on grafting were investigated. Under the experimental conditions applied in this study, the grafted monomer unit content was varied from 0.023 to 0.5%. The MA grafting efficiency of powder PP was higher than that obtained for the granular form of PP. In general, the grafting degree first increased with the MA or DCP content in the feed, then reached a maximum value, and finally decreased because of several possible alternative reactions during the grafting. The grafting of powder PP was more successful because of better initial mixing and less diffusional resistance during the grafting. An increase in the MA content in the feed caused significant reductions in the melt‐flow index of the graft copolymers. The results obtained with Fourier transform infrared, differential scanning calorimetry, and X‐ray powder diffraction analyses indicated that the structure, macrotacticity, crystallinity, crystallization, and thermal behavior of PP changed with grafting and depended on the grafting degree. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3675–3684, 2004     

Melt grafting of maleic anhydride onto polypropylene with assistance of α‐methylstyrene

Melt grafting of maleic anhydride (MA) and α‐methylstyrene (AMS) onto polypropylene (PP) was performed by reactive extrusion. Effects of AMS on the graft degree of MA, crystallization behavior, and thermal properties of the graft copolymer were investigated. Results show that the addition of AMS as a comonomer can efficiently improve the MA graft degree. When the molar ratio of AMS to MA is 0.9:1, the maximum MA graft degree is attained, which increases about 56% compared with that using single monomer of MA. The results of the graft degree of MA obtained by chemical titration (CT) agree well with those obtained by Fourier transform infrared spectroscopy (FTIR). Melt flow rate (MFR) measurements indicate that the addition of AMS effectively reduces the degradation of PP molecules. The wide‐angle X‐ray diffraction (WAXD) results show that in comparison with the PP‐g‐MA sample, the PP‐g‐(MA‐AMS) sample shows no new crystalline form, but has a slight decrease in the average crystalline domain size. According to the results of thermogravimetry (TG) and differential scanning calorimetry (DSC), the graft PP in the presence of AMS exhibits a lower melting point and a higher crystallization temperature and thermal stability in comparison with that without AMS. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of maleic anhydride grafted polypropylene compatibilizer on the morphology and properties of polypropylene/multiwalled carbon nanotube composite

The effect of maleic anhydride grafted polypropylene (MA‐g‐PP) compatibilizer on the mechanical and electrical properties of a polypropylene‐carbon nanotube composite is presented. Commercially available grades of polypropylene homopolymer (PP) and multiwalled CNT (MCNT) were used to prepare composites (PP/MCNT) by melt compounding. The effects of maleic anhydride graft level and loading on material properties were investigated. The addition of MCNT without compatibilizer enhanced the mechanical properties of PP, whereas addition of both grades of MA‐g‐PP alone had a detrimental effect. When MA‐g‐PP was added as a compatiblizer to the PP/MCNT composite, flexural and tensile moduli increased, indicating that enhanced levels of MCNT dispersion within PP had been achieved. Strength of the nanocomposite decreased with the addition of both grades of MA‐g‐PP, possibly due to the deterioration of the mechanical properties of the polymer in the presence of lower molecular weight MA‐g‐PP. Electrical resistivity improved with both grades of MA‐g‐PP, with higher maleic anhydride graft levels having the most significant effect. Scanning electron microscopy analysis confirmed that the optimum state of dispersion was for the nanocomposite prepared with MA‐g‐PP with highest grafting level. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

The effect of maleic anhydride grafting efficiency on the flexural properties of polyethylene composites

Many authors have reported on the property enhancements possible by compounding high density polyethylene (HDPE) with fillers to produce composites. It is accepted that polyethylene combined with materials such as nanoclay or wood flour will not yield favorable properties unless a compatibilizing material is used to form a link. In this work, compatibilized HDPE was produced by grafting maleic anhydride (MA) to its backbone in a twin screw extruder using a peroxide initiated reactive process. Fourier transform infrared spectroscopy (FTIR) was used to examine the effects of varying peroxide and MA levels on the grafting percentage and it was found that a high percentage could be achieved. The gel content of each HDPE‐g‐MA batch was determined and twin bore rheometry analysis was carried out to examine the effects of crosslinking and MA grafting on the melt viscosity. These HDPE‐g‐MA compatibilizers were subsequently compounded with nanoclay and wood flour to produce composites. The composite materials were tested using a three point bending apparatus to determine the flexural modulus and strength and were shown to have favorable mechanical properties when compared with composites containing no compatibilizer. X‐ray diffraction (XRD) was used to examine the effects of grafted MA content on the intercalation and exfoliation levels of nanoclay composites. The results from XRD scans showed that increased intercalation in polymer nanoclay composites was achieved by increasing the grafted MA content. This was confirmed using a scanning electron microscope, where images produced showed increased levels of dispersion and reductions in nanoclay agglomerates. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

马来酸酐/二乙烯基苯接枝聚乳酸对微晶纤维素/聚乳酸复合材料性能的影响

研究了马来酸酐(MAH)/二乙烯基苯(DVB)接枝聚乳酸(PLA-g-DVB/MAH)对微晶纤维素(MCC)/聚乳酸(PLA)复合材料性能的影响。首先采用熔融接枝法,将DVB作为MAH的共聚单体接枝到PLA分子链上制备PLA-g-DVB/MAH接枝聚合物,然后以PLA-g-DVB/MAH为相容剂,采用注射成型法制备MCC/PLA复合材料。利用FTIR对PLA-g-DVB/MAH进行表征,探究了PLA-g-DVB/MAH对MCC/PLA复合材料流变及力学性能的影响。结果表明,MAH成功接枝到PLA上,并得到接枝聚合物PLA-g-DVB/MAH;添加PLA-g-DVB/MAH后,MCC/PLA复合材料的储能模量、复数黏度、平衡扭矩以及剪切热都有明显升高;PLA-g-DVB/MAH的添加有利于改善MCC和PLA的界面相容性,进而提高了MCC/PLA复合材料的力学性能。     

Parameters affecting the grafting reaction and side reactions involved in the free‐radical melt grafting of maleic anhydride onto high‐density polyethylene

The parameters affecting the grafting reaction and side reactions in free‐radical melt grafting of maleic anhydride (MA) onto high‐density polyethylene with the aid of 2,5‐dimethyl‐2,5‐di(t‐butyl peroxy)hexane peroxide(DTBPH) have been studied using an internal mixer. MA grafting degree of the maleated samples was measured with titrometry and FTIR spectroscopy methods. The extent of chain‐branching/crosslinking side reactions was evaluated with gel content and MFI determination. The flow behavior and melt viscoelastic properties of the samples were measured using a rheometric mechanical spectrometer. DTBPH and MA concentrations, reaction temperature, rotor speed, the type and concentration of coagents were among the studied parameters. The results show that MA and DTBPH concentration has a major role on the grafting reaction, chain‐branching/crosslinking side reactions and also the grafts microstructure in the final product. The reaction temperature has a complex effect on the maleation reaction. Increasing the rotor speed causes an increase in MA grafting degree of the samples and reduces the competitive side reactions. By using Gaylord additives, gel formation reduces at the expense of a dramatic decrease in the grafting degree. MA grafting degree is increased by the use of comonomers in the reaction and this is accompanied with a decrease in crosslinking side reaction when the vinyl type styrene comonomer is used. The results of processing torque in combination with the measurements of the melt viscoelastic property and gel content of the samples provide a great insight into understanding the gel formation mechanism. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The effect of N,N-dimethylformamide and polymer grafting on the morphology of polyester fibers in fabric substrate

Photo-induced graft polymerization of acrylic acid (AA) and methyl acrylate (MA) in the liquid and vapor phase, respectively, onto N,N-dimethyformamide (DMF)-pretreated poly(ethylene terephthalate) (PET) fibers in fabric substrate was studied. The effect of various synthesis conditions and DMF pretreatment on the graft yields on PET was investigated. The internal morphology and properties of DMF-pretreated and grafted PET fibers in the fabric were characterized using density and birefringence measurements, differential thermal analysis (DTA), Fourier transform infrared spectroscopy (FTIR), dyeing methods, and critical dissolution times. The grafting was promoted by increasing DMF pretreatment temperature and the amount of DMF retention in the PET. Increasing biacetyl and monomer flow time and irradiation time enhanced grafting. DMF pretreatment resulted in increases in total void content, degree of crystallinity, trans-isomer content, chain folding, segmental mobility, and molecular packing of the PET, but caused decreases in its amorphous orientation, intermolecular forces, and individual void size through longitudinal shrinkage, lateral swelling, and removal of oligomers. Subsequent graft copolymerization led to further changes in the internal morphology and properties of the PET. PET grafted with AA had a higher cohesive energy density, lower degree of molecular packing, and larger individual void size, but less total void content, lower segmental mobility, less chain orientation, and a lower degree of crystallinity. PET grafted with MA showed increases in total void content, individual void size, segmental mobility, and molecular packing, but showed decreases in chain orientation and degree of crystallinity. © 1996 John Wiley & Sons, Inc.     

Effect of the maleic anhydride content on the structural,thermal, rheological and film properties of the n-butyl methacrylate–maleic anhydride copolymers

Various copolymers of n-butyl methacrylate (nBMA)-maleic anhydride (MA) were synthesized by free radical solution polymerization using xylene as a solvent, with monomer ratio of (nBMA/MA) 80/20, 65/35 and 50/50 wt%. The nBMA/MA copolymers were analyzed by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), gel permeation chromatography (GPC) differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), rheology, acid value, microhardness and friction resistance. The formation of the nBMA/MA copolymers was proven by FTIR and ¹H NMR. The conversion percentage, glass transition temperature (T_g), thermal stability, hardness and the friction resistance of the nBMA/MA copolymers increased with the MA contents in the copolymers. All copolymers presented a thinning-shear rheological behavior due to the presence of entanglements. All films of the copolymers showed a good chemical resistance to HCl and NaCl solutions, but in the presence of NaOH solutions the films exhibited a blister.     

Ultrasound initiated maleic anhydride grafted onto a novel polypropylene copolymer

The reaction of maleic anhydride (MAH) grafted onto propylene‐based copolymer (DP) without adding any initiator was conducted through ultrasound assisted extrusion in this article. The effects of ultrasound power, die temperature, and MAH content on the grafting degree and efficiency were studied. With increasing ultrasound power, the grafting degree and efficiency of DP‐g‐MAH increase. The presence of ultrasound with higher power and lower die temperature is beneficial to increase the grafting degree and efficiency. The increase of MAH content can increase the grafting degree but reduce the grafting efficiency. Based on the results of melt flow index, dynamical rheological, gel permeation chromatograph (GPC), and Fourier transform infrared spectroscopy (FTIR) tests, the mechanisms of the grafting reaction were proposed. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Maleic anhydride/styrene melt grafting and crosslinking onto ethylene‐octene copolymer

Melt grafting of the multimonomer system of maleic anhydride (MAH)/styrene (St) onto ethylene‐octene copolymer (POE) was performed by a twin‐screw extruder. The effects of St and initiator contents as well as MAH/St on the grafting reaction were investigated. The structure and properties of the grafted POE were characterized by the Fourier transform infrared spectroscopy, melt flow index, dynamic rheological behaviors, and thermogravimetric analysis. It is shown that the addition of St can significantly enhance MAH grafting degree onto POE. MFI values of grafted POE are affected not only by MAH/St copolymer concentration, but also by initiator concentration. These data indicate that the interaction and reaction between MAH and St monomers plays an important role in the grafting reaction. St improves the grafting reactivity of MAH and reacts with MAH before the two monomers graft onto POE. And high grafting degree can be obtained while the gel content is still low. Compared with neat POE, grafted POE shows different dynamic rheological behaviors and high thermal stability. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effects of molecular weight and grafted maleic anhydride of functionalized polylactic acid used in reactive compatibilized binary and ternary blends of polylactic acid and thermoplastic cassava starch

Polylactic acid (PLA) was reactively functionalized with maleic anhydride (MA) and 2,5‐bis(tert‐butylperoxy)?2,5‐dimethylhexane (Luperox 101 or L101) using a twin screw extruder (TSE). The effects of functionality (grafted MA level) and/or number average molecular weight of functionalized PLA (PLA‐g‐MA) as the reactive polymer pairs (binary blends) and reactive compatibilizer (ternary blends) were investigated. Due to the dominant side reaction during melt free radical grafting, polymer degradation or chain scission, PLA‐g‐MA having a higher grafted MA had lower molecular weights and intrinsic viscosity as well as broader molecular weight distribution values. The thermal, physical, mechanical, and morphological properties of binary blends produced by using the TSE and injection molding at a ratio of 70 wt % PLA‐g‐MA and 30 wt % thermoplastic cassava starch (TPCS) were analyzed. The reactive blends having grafted MA more than 0.4 wt % had poor tensile strength and elongation at break. Similar trends in morphology and tensile properties were observed in the reactive ternary blends. The use of PLA‐g‐MA strongly impacted the elongation at break but not the modulus or tensile strength. An increase of PLA‐g‐MA's number average molecular weight ( or M_n) improved the tensile properties of the blends. The reactive ternary blend having 0.1 wt % grafted MA on PLA and PLA‐g‐MA basis and PLA‐g‐MA's M_n of 45 kDa offered the highest elongation at break. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42230.     

Grafting of polyethylenes by reactive extrusion. II. Influence on rheological and thermal properties

In this article, the effects of the grafting degree and the processing conditions employed to prepare LLDPEs-g-DEM and HDPEs-g-DEM via reactive extrusion on their rheological and thermal properties were studied. The rheological properties of the virgin samples of LLDPEs, HDPEs, and their functionalized products were determined using capillary and dynamic rheometry. The thermal behavior of the virgin materials and their grafted products was examined by differential scanning calorimetry (DSC). It was found that the rheological properties are more sensitive than are the molecular structure characteristics to the changes produced by the grafting reactions with DEM, under the employed experimental conditions. There is an increase in the dynamic viscosity at low frequencies, in the storage modulus, and in the shear-thinning behavior when the grafting degree increases. The crossover between G″ and G′ moves to lower frequencies and the relaxation time spectrum functions are broader in the grafted materials. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2549–2567, 1999     

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     

Improvement of the thermal stability of polyhydroxybutyrates by grafting with maleic anhydride by different methods: Differential scanning calorimetry,thermogravimetric analysis,and gel permeation chromatography

The crystallization and thermal degradation behaviors of polyhydroxybutyrate (PHB) grafted with maleic anhydride (MA) by different techniques were analyzed with differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). The results of DSC, TGA, and GPC analyses indicated that the grafting method could affect the crystallization rate, crystallinity, and thermal stability of PHB because of changes in the molecular weight of PHB and the amount of MA grafted during the reaction. The reduction of the molecular weight of PHB that reacted during the processing followed this order of methods: melt grafting > solvent grafting > mechanical grafting. However, the grafting ratio of MA followed this order of methods: melt grafting > mechanical grafting > solvent grafting. All three grafting methods significantly improved the thermal stability, therefore increasing the crystallization rate and melting temperature of the as‐received PHB. A grafting ratio of MA as low as 0.07 wt % could result in a significant improvement in the heat resistance of PHB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

马来酸酐固相接枝聚丙烯纤维

了提高非极性聚丙烯纤维(PP)的相容性,采用固相法以马来酸酐(MAH)对聚丙烯纤维进行接枝改性,研究了反应条件对接枝率的影响。结果表明,马来酸酐成功接枝到聚丙烯上,当反应温度为80℃,PP用量为0.5 g,MAH用量为0.2 g,BPO用量为0.05 g,回流时间为2.5 h时,最大接枝率可达到7.51%;BPO的用量、MAH单体的用量以及反应温度对PP纤维的接枝率影响较大。而测定PP纤维接枝率时回流时间对其接枝率的影响不大;接枝聚丙烯纤维的分解温度明显高于纯聚丙烯纤维。     

Effects of polypropylene-g-(maleic anhydride/styrene) compatibilizer on mechanical and rheological properties of polypropylene/clay nanocomposites

To enhance the dispersibility of clay in polypropylene (PP) matrix, PP-g-(maleic anhydride/styrene) (MA/ST) was prepared as a compatibilizer by graft copolymerization of maleic anhydride (MA) and styrene (ST) with PP. The addition of ST was known to be effective in improving the graft degree. PP/clay nanocomposites with the compatibilizer were prepared by melt intercalation. The X-ray diffraction (XRD) peaks of (0 0 1) plane of the organo-modified montmorillonite (O-MMT) were shifted to lower angles by an addition of PP-g-(MA/ST), indicating the intercalation capability of PP-g-(MA/ST) in the silicate layers. Transmission electron microscopy (TEM) photographs showed that the O-MMT in the presence of PP-g-(MA/ST) was intercalated and partly exfoliated during melt mixing. The addition of O-MMT and PP-g-(MA/ST) improved the thermal stability, tensile and rheological properties of the nanocomposites.     

Approaches on the acrylonitrile-butadiene-styrene functionalization through maleic anhydride and dicumyl peroxide

Acrylonitrile-butadiene-styrene (ABS) functionalization is industrially important since it can wide the ABS application range. However, grafting of functional groups must be effective. This work aimed evaluating the effectiveness of ABS functionalization in an internal mixer, using maleic anhydride (MA) and dicumyl peroxide (DCP) as initiator, at 2.5% and 5.0%; and 0.3% and 0.5% contents respectively. Torque rheometry, melt flow rate (MFR), titration, Fourier transform infrared spectroscopy (FTIR), contact angle, thermogravimetry (TG), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to collect the main parameters of produced compounds. For ABS with 5% MA and 0.5% DCP, an efficiency of 62% was reached with the degree of grafting 3.1% MA. FTIR spectra confirmed new band in ABS chain in 1780 cm⁻¹ due to the carbonyl group. Reduction in contact angle and thermal stability were verified, whereas MFR and torque rheometry suggested that viscosity decrease is most due to the molecular weight reduction. In general, MA grafted ABS presented proper functionalization with great potential for applications as reactive compatibilizer.     

The study of melt grafting mechanism of acrylic acid and butyl acrylate onto low density polyethylene and its application as internal plasticizer

Melt grafting of acrylic acid (AA) and butyl acrylate (BA) (equal molar ratios) onto low‐density polyethylene (LDPE) was carried out in Haake internal mixter by free radical grafting copolymerization. The graft degree of AA and BA in the grafted LDPE (LDPE‐g‐(AA+BA)) was determined by FTIR. The influences of initiator on the graft degree of AA and BA, melt flow rate (MFR), and gel content were investigated, and the optimum conditions were obtained. The successive self‐nucleation/annealing (SSA) thermal fraction method was used to characterize the molecular structure and polydispersity of LDPE‐g‐(AA+BA) with various graft degrees. The effects of thermal fraction parameters on fraction of LDPE‐g‐(AA+BA) were investigated. On the basis of the results of SSA, the grafting reaction mechanism of AA and BA onto LDPE was proposed, i.e., grafting reaction preferentially occurred on the tertiary carbons of LDPE. The grafted LDPE possessed suitable reactivity and rheological property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008