Morphology and properties of PBT/nylon 6/EVA‐g‐MAH ternary blends prepared by reactive extrusion

Morphology and properties of poly(butylene terephthalate) (PBT)/nylon 6 (PA6)/EVA‐g‐MAH ternary blends were investigated. The blends were prepared in a corotating, intermeshing, twin‐screw extruder. The incorporation of maleic anhyride (MAH) grafted onto ethylene‐vinyl acetate copolymer (EVA) (EVA‐g‐MAH) in the PBT/PA6 binary blends decreased the tensile and flexural strength but increased the impact strength, while the mechanical properties of the PBT/PA6 blends were decreased with increasing PA6 content regardless of the presence or absence of the EVA‐g‐MAH. The morphology studies of the ternary blends showed gross phase separation. The rheological properties of the ternary blends suggested that excessively high reactivity between amine end groups of PA6 and MAH grafted onto EVA makes the compatibility between PBT and PA6 worse, although EVA‐g‐MAH was expected to work as a compatibilizer for PBT/PA6 blends. The degree of reactivity between functional groups in PBT, PA6, and EVA‐g‐MAH was also examined by investigating the effect of blending sequence on the properties of the ternary blends.     

Effect of blending sequence on the microstructure and properties of PBT/EVA‐g‐MAH/organoclay ternary nanocomposites

Ternary nanocomposites based on poly(butylene terephthalate) (PBT), maleic anhydride grafted poly(ethylene‐co‐vinyl acetate) (EVA‐g‐MAH), and organically modified montmorllonite (organoclays) were prepared through four different blending sequences in a Haake rheocord mixer: (1) To blend PBT, EVA‐g‐MAH and organoclays in one step; (2) First to prepare EVA‐g‐MAH/organoclay nanocomposite, then mix it with PBT to get the final nanocomposite; (3) To mix PBT with organoclays first, then the PBT/organoclay nanocomposite with EVA‐g‐MAH. (4) To mix organoclays with the PBT/EVA‐g‐MAH blend. The microstructure of the PBT/EVA‐g‐MAH/organoclay ternary hybrids was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that the blending sequence significantly influences the microstructure of PBT/EVA‐g‐MAH/organoclay ternary hybrids and the dispersion behavior of the organoclays in the polymer matrix. Tensile and impact properties of the hybrids were also studied. The results showed that the mixing sequence (2) gives the best tensile and impact strength due to its fine “sea‐island” morphology of PBT/EVA‐g‐MAH blend and good dispersion of the organoclays in the continuous PBT matrix.     

Grafting maleic anhydride onto EVA and effect on the physical and rheological properties of PETG/EVA-g-MAH blends

Maleic anhydride (MAH) was grafted onto ethylene vinyl acetate copolymer (EVA) in the internal mixer in the presence of dicumyl peroxide (DCP), and a prepared reactive compatibilizer, MAH-g-EVA, was blended with Poly (ethylene glycol-co-cyclohexane-1,4-dimethanol terephthalate) (PETG). The gel content determination and element analysis (EA) was performed to confirm the grafting reaction. It was found that grafting reaction of MAH on to EVA could compete with crosslinking reaction of DCP during the modification process. In addition, the introduction of small amount of MAH showed a great effect on reducing gel content by decreasing crosslink reaction. As MAH content increased, grafted MAH concentration increased, whereas the grafting yield decreased. It was also confirmed that MAH-g-EVA acted as a reactive compatibilizer in the blend with PETG, and enhanced compatibility by reacting with the hydroxyl end groups, OH, of PETG. Addition of EVA in the blend leads a plastic deformation of PETG, and MAH had a great effect on enhancing interfacial adhesion resulting in significant increasing of % strain; however, improved compatibility could not be changed much in low strain tensile strength and Young's modulus. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties of uncompatibilized and compatibilized poly(butylene terephthalate)–LLDPE blends

In this work, blends of poly(butylene terephthalate) (PBT) and linear low‐density polyethylene (LLDPE) were prepared. LLDPE was used as an impact modifier. Since the system was found to be incompatible, compatibilization was sought for by the addition of the following two types of functionalized polyethylene: ethylene vinylacetate copolymer (EVA) and maleic anhydride‐grafted EVA copolymer (EVA‐g‐MAH). The effects of the compatibilizers on the rheological and mechanical properties of the blends have been also quantitatively investigated. The impact strength of the PBT–LLDPE binary blends slightly increased at a lower concentration of LLDPE but increased remarkably above a concentration of 60 wt % of LLDPE. The morphology of the blends showed that the LLDPE particles had dispersed in the PBT matrix below 40 wt % of LLDPE, while, at 60 wt % of LLDPE, a co‐continuous morphology was obtained, which could explain the increase of the impact strength of the blend. Generally, the mechanical strength was decreased by adding LLDPE to PBT. Addition of EVA or EVA‐g‐MAH as a compatibilizer to PBT–LLDPE (70/30) blend considerably improved the impact strength of the blend without significantly sacrificing the tensile and the flexural strength. More improvement in those mechanical properties was observed in the case of the EVA‐g‐MAH system than for the EVA system. A larger viscosity increase was also observed in the case of the EVA‐g‐MAH than EVA. This may be due to interaction of the EVA‐g‐MAH with PBT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 989–997, 1999     

Melt grafting of poly(ethylene‐vinyl acetate) copolymer with maleic anhydride

Poly(ethylene‐vinyl acetate) (EVA) copolymer was melt grafted with maleic anhydride (MAH) in a twin screw extruder in the presence of peroxide. It is confirmed that MAH has been melt grafted on the backbone of EVA by FTIR using the method of hydrolysis. The NMR analysis suggests that the grafting reaction occurs on the tertiary carbon of main chain of EVA other than the methyl moiety of vinyl acetate (VA) group. The incorporation of VA groups onto the matrix shows a competitive effect on the grafting. The existence of VA groups promotes the extent of MAH graft onto EVA; nevertheless, it also weakens the crystallizability of main chain. When the content of peroxide initiator is 0.1 wt % based on the polymer matrix, the grafting degree increases with increasing the concentration of monomer. When the peroxide content is higher than 0.1 wt %, side reactions such as crosslinking or disproportionation will be introduced into this system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 841–846, 2006     

EVA-g-MAH反应挤出研究及其在LDPE/MH体系中的应用

采用同向双螺杆研究了不同熔融指数的复合EVA熔融接枝马来酸酐,考察了引发剂用量、MAH用量对接枝率及熔体流动速率的影响.结果表明,接枝率随着马来酸酐、引发剂用量的增加而增加,熔体流动速率随着引发剂用量的增加而减少.通过制备的接枝物添加到阻燃体系中,考察了接枝率对体系性能的影响.     

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     

过氧化物交联改性PE-HD/EVA防水材料的研究

用过氧化二异丙苯（DCP）交联法改善高密度聚乙烯/乙烯醋酸乙烯共聚物（PE-HD/EVA）防水材料的尺寸稳定性,研究了交联剂用量对PE-HD/EVA片材热稳定性和力学性能的影响。采用傅里叶变换红外光谱仪、差示扫描量热仪、X射线衍射仪、索氏提取交联度测试法等对片材进行了分析,研究了片材力学性能的影响因素。结果表明,随着交联度的增大,片材的软化温度和结晶度逐渐降低,晶体结构基本不变,晶粒尺寸减小, 拉伸强度提高;当DCP用量为1.2 %（质量分数,下同）时,片材的拉伸强度达到了最大值,其断裂伸长率比未交联片材降低了77 %,尺寸稳定性得到明显改善;交联改性对于PE-HD/EVA解决防水材料尺寸稳定性差等问题具有一定的指导意义。     

Tailoring viscoelastic and mechanical properties of the foamed blends of EVA and various ethylene‐styrene interpolymers

Foamed materials (EVA/ESI) have been prepared from blends of ethylene‐vinyl acetate copolymer (EVA) and ethylene‐styrene interpolymers (ESI) in the presence of various amounts of dicumyl peroxide (DCP). Four ESIs of different compositions were employed in this study; their styrene contents ranged from 30 to 73 wt% and their T_g ranged from −2 to 33°C. It has been found that microcellular morphology, degree of crosslinking and expansion ratio were strongly affected by the DCP concentration and the type of ESI employed. A minimum degree of crosslinking was required for making good foams and the same degree of crosslinking could be achieved by employing a smaller amount of DCP for an EVA/ESI blend having a higher styrene content. In contrast to other EVA blends, such as EVA/LDPE, these EVA/ESI blends exhibited no existence of any optimum DCP concentration, and the α glass transition temperatures of the foams varied with the ESI type, covering a wide span from 0°C to 37°C. Therefore, it was possible to tailor the T_g of an EVA/ESI blend by choosing an appropriate type of ESI. Furthermore, by correctly tailoring the T_g, the EVA/ESI foam could be made into a rubbery material with a custom‐designed damping factor. Tensile strength and modulus of the EVA/ESI foams increased generally with an increase in the styrene content, with the exception that ESIs with very low styrene content will confer on the blend a high modulus at small strain and a large elongation at break.     

EPDM与马来酸酐的反应挤出接枝

用同向双螺杆挤出机,对三元乙丙共聚物（EPDM）进行熔融接枝马来酸酐（MAH）,考察了单体、引发剂（DCP）用量和加工条件对接枝率的影响。结果表明,在EPDM接枝MAH的反应中,随着DCP用量的增加,接枝率增大,随着MAH用量的增加,接枝率趋于一个平衡值,较佳的实验配方为EPDM：MAH：DCP=100：1：0.03。     

Influence of high density polyethylene‐g‐maleic anhydride on compatibility and properties of poly(butylene terephthalate)/high density polyethylene blends

Poly(butylene terephthalate)/high density polyethylene (PBT/HDPE) blends and PBT/HDPE‐grafted maleic anhydride (PBT/HDPE‐g‐MAH) blends were prepared by the reactive extrusion approach, and the effect of blend compositions on the morphologies and properties of PBT/HDPE blends and PBT/HDPE‐g‐MAH blends was studied in detail. The results showed that flexural strength, tensile strength, and notched impact strength of PBT/HDPE blends decreased with the addition of HDPE, and flexural strength and tensile strength of PBT/HDPE‐g‐MAH blends decreased, while the notched impact strength of PBT/HDPE‐g‐MAH increased with the addition of HDPE‐g‐MAH. Compared with PBT/HDPE blends, the dimension of the dispersed phase particles in PBT/HDPE‐g‐MAH blends was decreased and the interfacial adhesion was increased. On the other hand, the effects of HDPE and HDPE‐g‐MAH contents on the crystalline and the rheological properties of the blends were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6081–6087, 2006     

Toughening effects of ethylene–vinyl acetate copolymers with different vinyl acetate content and viscosity on nylon 1010 blends

Nylon 1010 blends with ethylene–vinyl acetate copolymer (EVA) and maleated ethylene–vinyl acetate (EVA‐g‐MAH) were prepared through melt blending. The vinyl acetate (VA) content and viscosity of EVA significantly affected the notched impact strength of nylon/EVA/EVA‐g‐MAH (80/15/5) blends. The nylon/EVA/EVA‐g‐MAH blends with high notched impact strength (over 60 kJ/m²) were obtained when the VA content in EVA ranged from 28 to 60 wt%. The effect of VA content on the notched impact strength of blends was related to the glass transition temperature for EVA with high VA content and crystallinity for EVA with low VA content. For nylon blends with EVA with the same VA content, low viscosity of EVA led to high notched impact strength. Fracture morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends showed that blends with ductile fracture behavior usually had large matrix plastic deformation, which was the main energy dissipation mechanism. A relationship between the notched impact strength and the morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends was well correlated by the interparticle distance model. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

反应挤出法制备马来酸酐接枝POE

采用双螺杆挤出机反应挤出制备马来酸酐接枝乙烯-1-辛烯共聚物(POE-g-MAH)。通过红外光谱分析(FTIR)、化学滴定等方法,揭示MAH过氧化二异丙苯(DCP)及供电子体(EDS)对接枝物的接枝率(GD)、凝胶率、熔体指数(MI)的影响规律。MAH和DCP的加入使MI降低,GD增大;过量的MAH使激发态的MAH猝灭,导致能引发接枝反应的激发态MAH和大分子自由基的数量减少,从而使MI上升及GD下降。在高剪切、短停留时间的挤出机中,EDS会使接枝物的性能恶化。与传统的EPDM-g-MAH增韧尼龙相比,PA/POE-g-MAH复合材料的强度保持相当,而韧性明显提高。     

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     

铝塑复合板用热熔胶的制备及性能研究

以过氧化二异丙苯(DCP)为引发剂、马来酸酐(MAH)为接枝改性单体和聚乙烯(PE)为主要原料,采用熔融挤出法制备了铝塑复合板用PE-g-MAH(聚乙烯接枝马来酸酐)基HMA(热熔胶),并着重探讨了DCP和MAH含量对PE-g-MAH的接枝效率和粘接性能等影响。结果表明:在试验范围内,PE-g-MAH的接枝效率(y)与DCP含量(x1)或MAH含量(x2)之间的关系符合y=28.03x1+1.49或y=0.73x2+10.65的线性关系;当w(DCP)=0.44%、w(MAH)=2%时,PE-g-MAH基HMA的粘接性能相对最好,其剪切强度(6.10 MPa)高于杜邦HMA(4.26 MPa),并且其接枝效率为12.91%。     

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     

Dynamic mechanical properties of polypropylene‐g‐maleic anhydride and ethylene–propylene–diene terpolymer blends: Effect of blend preparation methods

In this work, we attempted two different ways of processing to improve interfacial adhesion of polypropylene (PP) and ethylene–propylene–diene terpolymer (EPDM) by introducing maleic anhydride (MAH); In one way, the in situ grafting and dynamic vulcanization (ISGV) were performed simultaneously from PP and EPDM with MAH in the presence of dicumyl peroxide (DCP) in an intensive mixer. In another way, PP was first grafted with MAH and then the PP‐g‐MAH was blended with EPDM in the intensive mixer in the presence of DCP by the dynamic vulcanization (DV). It was found that the glass transition temperatures (T_gs) of both PP and EPDM phases were shifted to higher temperature as the EPDM content increased for the blends prepared by both IGSV and DV methods, mainly due to the crosslinking of EPDM. The higher T_gs and larger storage moduli were observed for the blends prepared by the ISGV method than those prepared by the DV method, while the morphology showed that the size reduction of dispersed particles in latter blends was larger than that of the former blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2777–2784, 2000     

乙烯—醋酸乙烯酯共聚物的化学接枝改性

综述了乙烯－醋酸乙烯酯共聚物的化学接枝方法,重点探讨了乙烯－醋酸乙烯酯与马来酸酐的接枝原因,并对接枝物的表征及应用加以论述。     

Influence of the degree of grafting on the morphology and mechanical properties of blends of poly(butylene terephthalate) and glycidyl methacrylate grafted poly(ethylene‐co‐propylene) (EPR)

Poly(ethylene‐co‐propylene) (EPR) was functionalized to varying degrees with glycidyl methacrylate (GMA) by melt grafting processes. The EPR‐graft‐GMA elastomers were used to toughen poly(butylene terephthalate) (PBT). Results showed that the grafting degree strongly influenced the morphology and mechanical properties of PBT/EPR‐graft‐GMA blends. Compatibilization reactions between the carboxyl and/or hydroxyl of PBT and epoxy groups of EPR‐graft‐GMA induced smaller dispersed phase sizes and uniform dispersed phase distributions. However, higher degrees of grafting (>1.3) and dispersed phase contents (>10 wt%) led to higher viscosities and severe crosslinking reactions in PBT/EPR‐graft‐GMA blends, resulting in larger dispersed domains of PBT blends. Consistent with the change in morphology, the impact strength of the PBT blends increased with the increase in EPR‐graft‐GMA degrees of grafting for the same dispersion phase content when the degree of grafting was below 1.8. However, PBT/EPR‐graft‐GMA1.8 displayed much lower impact strength in the ductile region than a comparable PBT/EPR‐graft‐GMA1.3 blend (1.3 indicates degree of grafting). Morphology and mechanical results showed that EPR‐graft‐GMA 1.3 was more suitable in improving the toughness of PBT. SEM results showed that the shear yielding properties of the PBT matrix and cavitation of rubber particles were major toughening mechanisms. Copyright © 2006 Society of Chemical Industry     

乙烯-醋酸乙烯共聚物的硅烷交联及无卤阻燃研究

采用过氧化物为引发剂,用熔融法制备了硅烷交联EVA和无卤阻燃硅烷交联EVA.用红外方法(IR)和差示扫描量热法(DSC)对EVA的硅烷接枝反应进行了表征.研究了过氧化物含量对体系凝胶含量,相对接枝率和力学性能的影响,同时还研究了交联对体系阻燃性能的影响.DSC实验表明,硅烷A171比硅烷A151更容易接枝到EVA上.随DCP含量增加,体系的凝胶含量,相对接枝率,拉伸强度增加,而断裂仲长率降低.氧指数结果表明,交联以后可以适当提高氧指数值,改善阻燃性能.