Styrene‐assisted grafting of maleic anhydride onto polypropylene by reactive processing

The grafting of maleic anhydride (MA) onto polypropylene (PP) was performed in the presence of the electron‐donating monomer styrene (ST) according to a central composite experimental design, in which the initial MA and ST concentrations were varied. The grafting of MA onto PP in the absence of ST was also performed. All reactions were carried out in the molten state in a Haake rheometer. The amount of reacted MA and the extent of degradation in PP were determined by means of Fourier transform infrared spectroscopy and melt flow index (MFI) measurements, respectively. The results showed that the presence of ST in the reactive processing caused a reduction in MFI and an increase in the level of reacted MA when the initial MA concentration equaled the initial ST concentration. An increase in the initial MA concentration presented distinct behavior that depended on the ST content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

马来酸酐熔融接枝全同聚1-丁烯

采用马来酸酐(MAH)熔融接枝全同聚1-丁烯,研究了MAH及第二单体苯乙烯(St)、复配引发剂、温度对接枝率的影响,用傅里叶变换红外光谱法表征接枝产物。结果表明:2种单体和复配引发剂用量对接枝率有较大影响,加入St提高了接枝率,引发剂过氧化二异丙苯与过氧化二苯甲酰质量比为3:1时接枝率最高,接枝率随着温度的升高而增大。     

Styrene‐assisted melt‐free radical grafting of glycidyl methacrylate onto isotactic poly(1‐butene)

The melt‐free radical grafting of glycidyl methacrylate (GMA) onto powered isotactic poly(1‐butene) (iPB‐1) using styrene (St) as a comonomer in a Haake mixer was studied. The effects of temperature, initial GMA, and peroxide concentration, as well as the addition of St comonomer, on the final grafting degree, grafting efficiency, and the melt flow rate of grafted polymer were studied. It was shown that the addition of St as a comonomer could significantly enhance the grafting degree of GMA on iPB‐1 and reduce the extent of degradation of iPB‐1 to some degree. It has been found that the grafting degree of dual‐monomer melt‐grafted iPB‐1 was about twice that of single‐monomer‐grafted iPB‐1 for the same monomer and peroxide concentrations. The grafting of GMA onto iPB‐1 remarkably accelerated the crystal form II → I transformation of iPB‐1. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

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     

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.     

马来酸酐固相接枝ABS树脂

采用固相接枝法制备了马来酸酐(MAH)接枝丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)(ABS-g- MAH),研究了反应温度、反应时间及单体和引发剂用量对接枝率的影响。确定最佳接枝条件为:反应温度70℃,反应时间5～6 h,引发剂质量分数8％,单体质量分数10％,此时可得到接枝率为1．4％的ABS-g-MAH。对ABS的组分分离证明,接枝发生在ABS的丁二烯部分。     

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     

Bulk grafting of poly(styrene‐alt‐maleic anhydride) onto preirradiated polyolefin membranes in supercritical carbon dioxide

To take advantage of the property of supercritical carbon dioxide as both a solvent and swelling agent, the bulk grafting of poly(styrene‐alt‐maleic anhydride) [P(MAH‐alt‐St)] onto preirradiated polyolefin membranes was performed by a combination of γ‐ray‐preirradiation‐induced graft copolymerization and supercritical fluid‐swollen polymerization. The trapped radicals on the polyolefin backbones were uniformly distributed by γ‐ray irradiation under a nitrogen atmosphere. Subsequently, these polymeric trapped radicals initiated the alternating copolymerization of styrene (St) and maleic anhydride (MAH) infused into the swollen polymer matrix with the aid of supercritical CO₂. It was important that the graft copolymers were relatively pure without any contaminants, including homopolymers, monomers, and initiators. The experimental results show that the degree of grafting could be easily controlled. In addition, St/MAH could synergistically promote the bulk grafting process and strongly effect on the alternating trend; this was confirmed by element analysis and differential scanning calorimetry. Soxhlet extraction, X‐ray diffraction, and Fourier transform infrared spectroscopy indicated that the P(MAH‐alt‐St) was covalently bonded to the polymeric backbones. Scanning electron microscopy showed that the alternating graft chains were uniformly dispersed throughout the 5‐mm thickness of the polymer membranes on the nanometer scale. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

马来酸酐溶液法接枝聚丙烯的探讨

采用溶液法制备了马来酸酐接枝聚丙烯。采用单因素及正交实验方法研究了单体、引发剂用量、反应温度、反应时间、溶剂用量及引发剂加入工艺等因素对产物接枝率的影响。结果表明,各因素对聚丙烯接枝率都有一定的影响,马来酸酐及二甲苯的用量对聚丙烯接枝率影响最大,当马来酸酐、二甲苯与聚丙烯之间比例为0.1/2/1时,聚丙烯的接枝率最大,接枝率可达4.36%。     

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     

Melt grafting of maleic anhydride onto elastomeric ethylene‐octene copolymer by reactive extrusion

Melt grafting of maleic anhydride onto elastomeric ethylene‐octene copolymer was carried out in a twin‐screw extruder, in the presence of dicumyl peroxide as an initiator. Dimethyl formamide was used as an inhibitor to reduce crosslinking and as a solvent for peroxide initiator. The aim of the work is to produce the copolymer with reactive functionality without the expense of elastomeric characteristics. Particular consideration was, therefore, given to the effects of initiator and monomer concentrations, and of screw speed on the degree of grafting, percentage of conversion, amount of crosslinked products, and on the stress‐strain behaviors of the grafted products. The degree of grafting was found to be dependent mainly on the initiator and monomer concentrations. Increasing the initiator concentration increased the degree of grafting, and at the same time, increased the amount of gel (crosslinking). An increase in gel content of the grafted products resulted in a change of tensile behaviors from uniform deformation followed by strain‐hardening at high strains to low extensibility and fracture at low strains.     

Styrene‐assisted melt free radical grafting of glycidyl methacrylate onto an ethylene and propylene rubber

This article deals with the efficiency of using styrene (St) as a comonomer to promote the melt free radical grafting of glycidyl methacrylate (GMA) onto an ethylene and propylene rubber (EPR) in a batch mixer and a corotating self‐wiping twin screw extruder. The addition of St to an EPR/GMA/peroxide system increases not only GMA's grafting yield but also its grafting rate. The time required for the EPR/GMA/peroxide system without St to reach a given amount of grafted GMA is at least 10 times that needed for the same system in the presence of an equimolar amount of St. For example, about 60 min are required for the EPR/GMA/dicumyl peroxide (composition: 100/3.0/0.3 by weight) to reach 1.5 phr (parts per hundred resin) GMA (i.e., 1.5 g grafted GMA per 100 g EPR). The same amount of grafted GMA is reached in < 3 min when 3.0 phr St is charged to the system. This significant reduction of reaction time is crucial for a successful free radical grafting of GMA on EPR in a corotating twin screw extruder, because the residence time in such a machine is typically on the order of 0.5–5 min. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 125–133, 1999     

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。     

马来酸酐接枝聚丙烯的方法及其发展

介绍了马来酸酐(MAH)接枝聚丙烯(PP)的方法,主要有熔融接枝、溶液接枝、固相接枝、悬浮接枝等。指出了每种接枝方法的优缺点及研究进展。提出了工业放大、接枝机理的研究以及接枝过程中应考虑经济环保等是接枝技术的发展方向。     

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     

Solid‐state grafting of succinic anhydride onto poly(vinyl alcohol)

The graft reaction of succinic anhydride onto poly(vinyl alcohol) (PVA) was catalyzed by p‐toluenesulfonic acid monohydrate in solid state. The infrared spectra and ¹H‐NMR spectra confirmed that succinic anhydride was successfully grafted onto PVA backbone. The influences of reaction temperature, reaction time, the amount of succinic anhydride, and the amount of catalyst on the graft reaction were studied. Uncrosslinked PVA graft copolymer with grafting degree up to about 6.5% could be obtained under low reaction temperature, short reaction time, and low amount of catalyst, whereas crosslinked PVA with high gel content could be obtained under high reaction temperature, long reaction time, and high amount of catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 848–852, 2007     

线型低密度聚乙烯固相接枝马来酸酐研究

利用固相接枝技术,在自由基引发剂存在下,用2种不同熔体流动速率(MFR)的线型低密度聚乙烯(LLDPE)制备了马来酸酐接枝物(LLDPE-g-MA),研究了工艺条件对产物接枝率(DG)和凝胶含量(DC)的影响,结果表明,在相同工艺条件下,反应6 h后,接枝率都保持在2%以上,但低MFR的LLDPE原料,在接枝反应过程中容易发生交联,产品的凝胶含量接近60%,而用高MFR的LLDPE原料得到的产品凝胶含量低于2%。同时用IR、DSC和X衍射表征了产物的结构,结果表明,MA接枝主要发生在PE的非晶区,对PE的结晶结构没有很大影响。     

马来酸酐熔融接枝二元乙丙橡胶的研究

在转矩流变仪中,以过氧化二异丙苯(DCP)为引发剂,采用多单体熔融接枝技术,研究了二元乙丙橡胶(EPM)熔融接枝马来酸酐(MAH),考察了MAH含量、DCP用量、反应温度、反应时间、转子转速以及第二单体苯乙烯(St)的用量对接枝反应的影响,并用红外光谱(FTIR)对接枝产物进行了表征.研究结果表明:对于EPM-g-MAH体系,MAH和DCP最佳用量分别为3.0 phr和0.22 phr,最佳反应温度为170℃,反应时间8 min,转子转速60 r/min,此时接枝率最高达到0.46％;加入第二单体St后,当n(St) /n(MAH)为1/1时,EPM-g-(MAH-co-St)的接枝率为0.64％,接枝率明显提高.     

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.     

New insight into the action of supercritical carbon dioxide for grafting of maleic anhydride onto isotactic polypropylene by reactive extrusion

The reactive extrusion process of isotactic polypropylene (iPP) grafting maleic anhydride (PP-g-MAH) initiated by dicumyl peroxide (DCP) in the presence of supercritical carbon dioxide (scCO₂) is investigated. Because of its moderate supercritical conditions and well swollen performance in iPP melts, scCO₂ is selected to be imported into the extruder system to reduce process temperature and melt viscosity as well as strengthen the mass transport. It has been found that the process temperature of reactive sections of co-rotating twin screw extruder can be successfully reduced from conventional 190 to 160 °C when assisted with the addition of scCO₂. Consequently, effective suppression of main chain degradation is observed, which leads to the products with relative higher molecular weight and narrower molecular weight distribution. The experimental results also indicate a significant increase in both the grafting degree of resultant PP-g-MAH and the grafting efficiency of MAH under certain operation conditions. Especially, the grafting efficiency is close to 90% when low concentration of both MAH and DCP are employed. A potential mechanism has been proposed to explain the effects of scCO₂ in the reactive extrusion. In comparison with traditional molten grafting process, the work presents a novel approach to increase the grafting efficiency of MAH and control the molecular weight of resultant PP-g-MAH simultaneously.