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     

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     

Free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid onto molten ethylene‐vinyl acetate copolymer

Distinctive features of free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid (TEDA) onto macromolecules of molten ethylene‐vinyl acetate copolymer (EVA) in the course of reactive extrusion have been investigated along with structure, mechanical characteristics, and high‐elastic properties of molten functionalized products (EVA‐g‐TEDA). It is shown that EVA‐g‐TEDA yield depends on both the peroxide initiator concentration and content of vinyl acetate units in the copolymer molecular structure. At functionalization, acid grafting is accompanied by secondary reactions of macromolecular degradation and crosslinking. With a low‐peroxide initiator concentration (0.1 wt %), degradation prevails; with a higher (0.3 wt %) concentration, crosslinking of macromolecules prevails. It is reported that monomers being grafted attach mostly over secondary carbon atoms in the polymer chain. EVA‐g‐TEDA appears to have a less perfect crystal structure with a lower‐melting temperature and crystallinity as against the starting polymer. The functionalized products display enhanced rigidity and lower deformability in comparison with the initial copolymer. Variations in the swelling ratio and melt strength of EVA‐g‐TEDA depend on the course of competing secondary processes of macromolecular degradation and crosslinking. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

EVA-g-MAH的制备及在聚合物共混相容中的应用

采用溶液接枝法合成得到乙烯-乙酸乙烯酯接枝马来酸酐聚合物（EVA-g-MAH）,利用核磁共振仪和红外光谱仪对产物进行分子链结构分析,结果表明：马来酸酐已成功接枝在EVA主链与酯基相连的叔碳原子上。通过调节马来酸酐（MAH）与EVA中乙酸乙烯酯（VA）单元的投料比,得到了不同接枝率（摩尔分数4.87%~12.3%）的产物。以EVA-g-MAH接枝共聚物为相容剂,通过聚合物加工制备了高密度聚乙烯（HDPE）/聚碳酸酯（PC）/EVA-g-MAH共混物,利用SEM对样品脆断面表面形貌进行对比观察,验证了EVA-g-MAH是HDPE/PC共混聚合物的良好相容剂。最后,研究了EVA-g-MAH对尼龙（PA6）/EVA共混物抗冲击强度的影响,当EVA-g-MAH加入质量分数为6%时对共混合金冲击强度提高最大。     

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。     

基于二元接枝单体制备PE⁃HD相容剂、粘接树脂及其性能研究

以双螺杆挤出机熔融挤出为接枝方法,高密度聚乙烯(PE-HD)作为接枝主链,无味过氧化二异丙苯(BIBP)为引发剂,将马来酸二丁酯(DBM)和马来酸酐(MAH)两个极性单体进行复配接枝到PE-HD上,制备含有二元极性单体的相容剂PE-HD-g-(DBM-co-MAH);再将其与PE-HD、线形低密度聚乙烯(PE-LLD)...     

Functionalization of high density polyethylene with maleic anhydride in the melt state through ultrasonic initiation

Grafting of maleic anhydride (MAH) onto high density polyethylene (HDPE) performed in the melt state through ultrasonic initiation by a laboratory‐scale ultrasonic extrusion reactor was studied in this paper. The effect of sonic intesity on the amount of grafted MAH, viscosity‐average molecular weight and melt flow index of the grafted product was investigated. The results show that the ultrasonic waves can obviously decrease the molecular weight of the grafted product and cause the increase of the amount of grated MAH, implying that the grafting reaction consists of the chain scission and the grafting reaction of the produced macroradicals with MAH. The percentage of grafting of the product amounts to 0.6%; its melt‐flow index is between 0.5 and 2.0 g/10 min, depending upon ultrasonic intensity, MAH content and grafting temperature. Compared with the method of peroxide initiation, in this method the crosslinking reaction can be prevented easily through the allocation of ultrasonic intensity. The mechanical properties of the improved HDPE/GF composite produced by ultrasonic initiatives are higher than in those produced by peroxide initiatives.     

Effects of compatibilizer on the layered silicate/ethylene vinyl acetate nanocomposite

Dispersion behavior of monmorillonite (MMT) is investigated in ethylene vinyl acetate (EVA)/MMT nanocomposite with various vinyl acetate content. Maleic anhydride (MAH) grafted polyethylenes with various MAH contents are used as a compatibilizer to enhance the dispersion of MMT. DMA and XRD studies indicate that an intercalated/exfoliated structure is obtained and vinyl acetate content and the concentration of PEMA play a critical role in EVA/MMT nanocomposite. Higher vinyl acetate content and concentration of grafted maleic anhydride result in better dispersion of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1057–1061, 2004     

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.     

马来酸酐接枝乙烯-丙烯酸丁酯共聚物的研究

以过氧化物为引发剂、马来酸酐（MAH）为单体,采用溶液法对乙烯-丙烯酸丁酯共聚物（EBA）进行接枝改性,并用傅立叶红外光谱技术对接枝物（EBA—g—MAH）进行了表征。系统考察了引发剂种类及用量、反应温度、反应时间、单体用量等因素对接枝率及熔体流动速率的影响。实验结果显示,EBA接枝MAH的优化反应条件是：原料配比为m（EBA）：m（MAH）：m（BPO）=100：2：0．28,反应时间为4h,反应温度为90℃,接枝率可达0．78％。随着反应温度的升高,接枝物的熔体流动速率急剧下降。不同的过氧化物引发剂对接枝反应的影响明显不同,与过氧化二异丙苯（DCP）相比,选择过氧化二苯甲酰（BPO）为引发剂,接枝效果较好,同时所得接枝物的MFR值适中。     

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。     

The effect of epoxy and tetramethyl thiuram disulfide on melt‐grafting of maleic anhydride onto polypropylene by reactive extrusion

In this report, melt grafting of maleic anhydride (MAH) and epoxy resin onto polypropylene (PP) by peroxide‐initiated reactive extrusion has been investigated. As evidenced by Fourier transform infrared spectroscopy, both MAH and epoxy resin were successfully grafted onto PP through the reactions of MAH with PP and epoxy resin with MAH. It was found that tetramethyl thiuram disulfide could promote the grafting of MAH and inhibit the degradation of PP, as revealed by chemical titration and melt flow experiments, through prolonging the lifetime of the macroradical; meanwhile, epoxy resin could reduce the sublimation of MAH and the maximum grafting degree of MAH. Furthermore, the introduction of grafted products was found to enhance the mechanical properties of PP/glass fiber composites, and this influence was very significant at high grafting degrees with a high content of epoxy resin, which could be interpreted in terms of improved compatibility and adhesion at the interface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43422.     

苯乙烯存在下马来酸酐熔融接枝聚丙烯的研究

分别在哈克流变仪（Haake）和双螺杆挤出机（TSE）中,研究了苯乙烯（St）存在下马来酸酐（MAH）熔融接枝聚丙烯（PP）的过程。讨论了过氧化二异丙苯（DCP）用量、St用量、MAH用量、反应时间、反应温度、螺杆转速以及反应器型式对接枝反应的影响．实验发现：随DCP用量的增加,MAH的接枝率先增加后减小,熔体流动速率（MFR）一直增加;保持MAH用量不变增加St用量时,MAH的接枝率在MAH与St的摩尔比为1：1时达到最大,MFR却一直减小;保持St用量不变增加MAH用量,MAH的接枝率先增加后略有减小,MFR却存在极大值;随反应时间的增加,MAH的接枝率与MFR都先增加后减小;温度过高,MAH的接枝率降低,PP热降解较严重;螺杆转速较低时,MAH的接枝率较低,螺杆转速较高时,PP降解增加;在TSE中的MAH接枝率比Haake中的低,但降解比Haake中的小得多。     

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.     

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.     

Morphology,rheological, crystallization behavior,and mechanical properties of poly(L‐lactide)/ethylene‐co‐vinyl acetate blends with different VA contents

Poly(L‐lactide)/ethylene‐co‐vinyl acetate (PLLA/EVA) blends with different contents of Vinyl Acetate (VA) in EVA phase were prepared through melt blending process. Although the composition of the blends was invariant (70/30), different phase morphologies were observed, namely, sea‐island morphologies for the blends with VA contents of 7.5, 18, and 28 wt %, whereas approximate co‐continuous morphology for the blend with VA content of 40 wt % was observed. The interfacial interaction between PLLA and EVA was visualized by Fourier transform infrared and rheological measurements. The nonisothermal and isothermal crystallization behaviors of the blends were investigated by wide angle X‐ray diffraction, Differential scanning calorimetry, and polarization optical microscope. Post‐thermal treatment was applied to improve the crystalline structure of PLLA. The results show that all the samples are mainly in amorphous state during the injection molding process. However, annealing promotes the second crystallization of PLLA matrix, leading to the improvement of the crystalline structure. Especially, the effect of annealing on crystalline structure of PLLA matrix is greatly dependent on the VA content of EVA. As expected, addition of EVA results in the improvement of the ductility and fracture toughness of the blends. The decreased tensile modulus and tensile strength can be enhanced through annealing process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of maleic anhydride on the moisture crosslinking of EVM-GMA grafted with amino silane

Moisture crosslinking would be a good substitution to cure ethylene-vinyl acetate-glycidyl methacrylate rubber (EVM-GMA) due to the characteristics of low cost and environmental friendliness. Our previous study found amino silane grafted onto EVM-GMA with low degree due to the low epoxy group content in rubber matrix. Consequently, the moisture crosslinking density of rubber compound is low. So, it is necessary to find an effective method to improve the moisture crosslinking density of EVM-GMA. In this paper, EVM-GMA grafted with γ-aminopropyltriethoxysilane and maleic anhydride (EVM-GMA-g-APTES/MAH) composites were prepared by melt blending, and then the moisture crosslinking of composites was achieved in a 90°C water bath with the aid of catalyst dibutyltin dilaurate (DBTL). The grafting of MAH onto the EVM-GMA molecular chain and its reaction with amino silane were confirmed by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). Furthermore, the moisture crosslinking density of the samples before and after grafting MAH was compared. The results indicated that the moisture crosslinking density of the grafted MAH was higher than that of the unmodified rubber, thus achieving better overall mechanical properties. Therefore, grafting MAH was a feasible way to improve the moisture crosslinking density of EVM-GMA with the existence of silane.     

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%。     

管道防腐用改性EVA热熔胶的研制

在有机过氧化物的引发下,马来酸酐与熔融的EVA树脂接枝聚合,配合增黏树脂、填料及其它助剂,制备出用于油气管道密封防腐的热熔胶。首先考察了不同VA含量、熔体指数的EVA树脂的粘接强度,试验结果表明VA含量为28、MI值为280的EVA树脂具有最佳的性能,通过对MAH不同加入量对热熔胶性能影响的探讨,发现接枝改性后的热熔胶粘接强度得到了极大的提高,在MAH用量为12份时剥离强度可达17．4kN／m。冷热交变及耐介质实验也表明热熔胶具看优异的耐侯性和耐腐蚀性。