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     

Preparation and properties of dynamically cured PP/MAH‐g‐EVA/epoxy blends

A method concerning with the simultaneous reinforcing and toughening of polypropylene (PP) was reported. Dynamical cure of the epoxy resin with 2‐ethylene‐4‐methane‐imidazole (EMI‐2,4) was successfully applied in the PP/maleic anhydride‐grafted ethylene‐vinyl acetate copolymer (MAH‐g‐EVA), and the obtained blends named as dynamically cured PP/MAH‐g‐EVA/epoxy blends. The stiffness and toughness of the blends are in a good balance, and the smaller size of epoxy particle in the PP/MAH‐g‐EVA/epoxy blends shows that MAH‐g‐EVA was also used as a compatibilizer. The structure of the dynamically cured PP/MAH‐g‐EVA/epoxy blends is the embedding of the epoxy particles by the MAH‐g‐EVA. The cured epoxy particles as organic filler increases the stiffness of the PP/MAH‐g‐EVA blends, and the improvement in the toughness is attributed to the embedded structure. The tensile strength and flexural modulus of the blends increase with increasing the epoxy resin content, and the impact strength reaches a maximum of 258 J/m at the epoxy resin content of 10 wt %. DSC analysis shows that the epoxy particles in the dynamically cured PP/MAH‐g‐EVA/epoxy blends could have contained embedded MAH‐g‐EVA, decreasing the nucleating effect of the epoxy resin. Thermogravimetric results show the addition of epoxy resin could improve the thermal stability of PP, the dynamically cured PP/MAH‐g‐EVA/epoxy stability compared with the pure PP. Wide‐angle x‐ray diffraction analysis shows that the dynamical cure and compatibilization do not disturb the crystalline structure of PP in the blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamically cured polypropylene/epoxy blends

The dynamic vulcanization process, usually used for the preparation of thermoplastic elastomers, was used to prepare polypropylene (PP)/epoxy blends. The blends had crosslinked epoxy resin particles finely dispersed in the PP matrix, and they were called dynamically cured PP/epoxy blends. Maleic anhydride grafted polypropylene (MAH‐g‐PP) was used as a compatibilizer. The effects of the reactive compatibilization and dynamic cure were studied with rheometry, capillary rheometry, and scanning electron microscopy (SEM). The crystallization behavior and mechanical properties of PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends were also investigated. The increase in the torque at equilibrium for the PP/MAH‐g‐PP/epoxy blends indicated the reaction between maleic anhydride groups of MAH‐g‐PP and the epoxy resin. The torque at equilibrium of the dynamically cured PP/epoxy blends increased with increasing epoxy resin content. Capillary rheological measurements also showed that the addition of MAH‐g‐PP or an increasing epoxy resin content increased the viscosity of PP/epoxy blends. SEM micrographs indicated that the PP/epoxy blends compatibilized with PP/MAH‐g‐PP had finer domains and more obscure boundaries than the PP/epoxy blends. A shift of the crystallization peak to a higher temperature for all the PP/epoxy blends indicated that uncured and cured epoxy resin particles in the blends could act as effective nucleating agents. The spherulites of pure PP were larger than those of PP in the PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends, as measured by polarized optical microscopy. The dynamically cured PP/epoxy blends had better mechanical properties than the PP/epoxy and PP/MAH‐g‐PP/epoxy blends. With increasing epoxy resin content, the flexural modulus of all the blends increased significantly, and the impact strength and tensile strength increased slightly, whereas the elongation at break decreased dramatically. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1437–1448, 2004     

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     

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)...     

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。     

Effect of the compatibilizer on the morphology and properties of dynamically cured PP/POE/epoxy blends

Dynamic vulcanization was successfully applied to epoxy resin reinforced polypropylene (PP)/ethylene‐octene copolymer (POE) blends, and the effects of different compatibilizers on the morphology and properties of dynamically cured PP/POE/epoxy blends were studied. The results show that dynamically cured PP/POE/epoxy blends compatibilized with maleic anhydride‐grafted polypropylene (MAH‐g‐PP) have a three‐phase structure consisting of POE and epoxy particles dispersed in the PP continuous phase, and these blends had improved tensile strength and flexural modulus. While using maleic anhydride‐grafted POE (MAH‐g‐POE) as a compatibilizer, the structure of the core‐shell complex phase and the PP continuous phase showed that epoxy particles could be embedded in MAH‐g‐POE in the blends, and gave rise to an increase in impact strength, while retaining a certain strength and modulus. DSC analysis showed that the epoxy particles in the blends compatibilized with MAH‐g‐PP were more efficient nucleating agents for PP than they were in the blends compatibilized with MAH‐g‐POE. WAXD analysis shows that compatibilization do not disturb the crystalline structure of PP in the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

反应性相容剂的制备及其在PP/玻璃纤维复合材料中的应用

以马来酸酐(MAH)为接枝单体、丙烯酸-2-羟乙酯为共聚单体,利用熔融接枝技术对聚丙烯(PP)进行改性;以MAH/丙烯酸-2-羟乙酯熔融接枝改性PP为相容剂,研究相容剂对PP/玻璃纤维复合材料结构和性能的影响。结果表明:与未接枝PP相比,熔融接枝PP分子上接枝了MAH和—OH基团,而且熔融接枝反应对PP的熔点和热稳定性具有明显影响。另外,随着接枝PP含量的增加,PP/玻璃纤维复合材料的力学性能明显改善。当接枝PP含量为15%时,复合材料的拉伸强度提高了32%,冲击强度提高了13%,表明采用熔融共接枝工艺制备的PP具有优良的增容、偶联和分散效果。     

Ultrasonic induced grafting of maleic anhydride onto polypropylene in melt state

This paper presented a model study on maleic anhydride (MAH) grafted polypropylene (PP) performed in melt state through ultrasonic initiation without any chemical initiator and solvent. The structures of PP-g-MAH were characterized by FTIR and ¹³C NMR and the mechanism were discussed. The graft degree (G) was determined by titration using a solution of organic base tetra-butyl ammonium hydroxide (TBAOH) in ethanol, and the effects of ultrasonic intensity, MAH concentration and styrene (St) on G and graft efficiency (G _E ) of MAH were investigated. Results showed that MAH was successfully grafted onto the PP chain and the optimum conditions for grafting were at an ultrasonic intensity of 300 W with a MAH concentration of 25 wt.%, and the maximum G of MAH of 3.34 wt.% was obtained when the molar ratio of St to MAH was 1:1. DSC and XRD were also employed to determine the thermodynamic performance and crystalline structures of the products.     

C5石油树脂熔融接枝马来酸酐的研究

采用熔融法制备C5石油树脂接枝马来酸酐（C5-g-MAH）,研究了过氧化二异丙苯（DCP）、马来酸酐（MAH）用量和第三组分（助交联剂）品种对C5-g-MAH接枝率的影响。研究结果表明,DCP用量为0.2份,MAH用量为4份时接枝率最大,为1.28%;第三组分品种对C5-g-MAH接枝率的影响从大到小依次为：腰果壳油、三烯丙基异三聚氰酸酯（TAIC）、1,2-聚丁二烯（1,2-PBd）,均比空白样有所提高。此外,傅立叶红外光谱（FT-IR）分析证实发生了MAH熔融接枝C5石油树脂的接枝反应。     

马来酸酐苯乙烯双单体接枝聚丙烯的研究

研究了聚丙烯（ＰＰ）采用熔融法接枝马来酸酐（ＭＡＨ）聚乙烯（Ｓｔ）双单体。实验表明,马来酸酐接枝率随其加入量增加而提高;添加两种单体时,马来酸酐添加量保持不变,马来酸酐接枝率随苯乙烯添加量增加而提高。经转矩流变,红外,热失重和差示扫描量热分析表明：马来酸酐,苯乙烯均与聚丙烯发生接枝反应,且有交联网络出现,因此推断出苯乙烯和马来酸酐预先发生交替共聚,共聚物与聚丙烯反应生成最终接枝物。接枝物应用于ＰＰ     

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     

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.     

PP熔融接枝MAH的研究

以PP（EPS30R）为基体树脂,过氧化二异丙苯DCP为引发剂,在反应体系中加入少量的DMF（N,N-二甲基甲酰胺）,在双螺杆挤出机中于175℃-190℃进行了PP熔融接枝MAH的反应。用红外光谱表征了接枝反应的存在,并考察了引发剂用量、N,N-二甲基甲酰胺（DMF）的用量、单体用量对接枝反应的影响。研究表明：DMF能抑制PP的降解,并且确定了较佳的原料配比为m（PP）：in（MAH）：m（DMF）：In（DCP）：100：3：0．6：0．4,其接枝率可达2．95％。     

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。     

Enhancement of graft yield and control of degradation during polypropylene maleation in the presence of polyfunctional monomer

Free‐radical initiated grafting of maleic anhydride (MAH)/polyfunctional acrylate (PFA) multimonomer system onto polypropylene (PP) via reactive extrusion was studied. The effects of PFA and initiator concentration on the grafting reaction were investigated. It was shown that PFA as a comonomer could greatly enhance MAH grafting degree, which increased monotonically as the molar ratio of PFA to MAH increased. The rheology test demonstrated that the viscosity of grafted PP was also promoted as more PFA was used. The formation of branched structure during the grafting process was proved by oscillatory shear rheological analysis. The mechanism of grafting in the presence of PFA was discussed, suggesting PFA had higher reactivity with PP macroradicals than MAH and therefore forming stabilized macroradicals, thus resulting in depression of β‐scission and favoring the formation of branched structure. Higher initiator concentration gave higher MAH grafting degree but more severe degradation. The mechanical properties of the grafted PP were comparable with those of unmodified PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

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 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.     

POE/PP的接枝改性及在制备超韧尼龙中的应用研究

研究了在含有适量聚丙烯的聚烯烃弹性体乙烯-1-辛烯共聚物(POE)熔融接枝马来酸酐(MAH)反应中,引发剂、接枝单体用量、及阻交联剂品种对接枝率的影响及其微观机理。结果表明:控制体系引发剂的含量是获取高接枝率的关键,当DCP的加入量为0.25%,MAH的含量为1.2%时,体系的接枝率达1%左右,从熔体流动速率来看体系未出现明显交联。同时探讨了接枝物在超韧尼龙合金制备中的应用效果。