HDPE functionalization via high shear stress‐induced initiation and its effects on HDPE/GF composite

The functionalization reaction of high density polyethylene (HDPE) with maleic anhydride (MAH) or with MAH and γ‐methacryloxy‐propyltrimethoxysilane (MAS) performed in melt state through a high shear stress‐induced initiation by increasing the screw rotation speed of twin‐screw extruder and through a compounded initiation by adding some initiator and increasing the screw rotation speed was investigated in this article. The results show that by increasing the screw rotation speed during melt‐extruding process, the scission of HDPE chain bonds can be caused to form macroradicals, the functionalization reaction of HDPE with MAH or with MAH, and MAS can be realized. The percentage of grafting and the melt flow rate of the functionalized products depend on the screw rotation speed and reaction temperature. The crosslinking reaction during melt extrusion can be suppressed by increasing the screw rotation speed and the reaction of HDPE with MAH can also be promoted by adding a second grafting monomer MAS. The high shear stress‐induced reaction products have a higher reactivity with the coupling agents coated on the surface of glass fibers and can obviously increase the mechanical properties of HDPE/GF composite. The SEM experimental results indicate that an oriented crystal transition layer exists between the interface of glass fiber and the matrix, the interfacial bonding strength is the determining factor of the formation of the oriented crystal layer. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

高剪切应力诱导引发马来酸酐官能化三元乙丙橡胶

在熔融挤出过程中,采用提高双螺杆挤出机螺杆转速所产生的高剪切应力诱导引发的方法及添加引发剂与提高螺杆转速的复合引发方法,研究了三元乙丙橡胶(EPDM)与马来酸酐(MAH)的官能化反应.结果表明,双螺杆挤出机的高螺杆转速所产生的高剪切应力作用可诱导EPDM的断链反应,引起官能化产物黏均相对分子质量的明显减小及接枝率与熔体流动速率的明显增大;在适量过氧化物类引发剂存在的条件下,此种高剪切应力作用可抑制EPDM官能化过程中的交联副反应,使产物的凝胶含量明显下降,接枝率及熔体流动速率明显增大;此种官能化反应过程易于控制,可制得接枝率0.80%～1.13%、熔体流动速率0.11～0.28 g/min及凝胶质量分数不大于1.0%的MAH官能化EPDM.     

熔融法制备分散型黏度指数改进剂及其对增黏性能的影响

以具有较低门尼黏度的三元乙丙橡胶(EPDM)为原料,通过添加引发剂与提高双螺杆挤出机螺杆转速的应力诱导复合引发方法,研究EPDM与马来酸酐(MAH)的官能化反应,表征官能化产物胺化反应后作为分散型黏度指数改进剂的性能。结果表明:官能化反应主要是由引发剂引发和应力诱导引发共同作用所完成;所得分散型黏度指数改进剂的增稠能力都随着螺杆转速的增加而增大,当螺杆转速为800 r/min时,黏度指数达218,稠化能力最强为14.47 mm2/s。当胺化物加入量为0.24%时,黏度指数改进剂的黏度指数达223,稠化能力达到最大值14.74 mm2/s。     

应力诱导引发MAH官能化PE-LD及其对铝箔/PET复合薄膜层间剥离强度的影响

采用提高双螺杆挤出机螺杆转速的应力诱导引发方法和添加引发剂与提高螺杆转速的复合引发方法,研究了高剪切应力作用下马来酸酐(MAH)与低密度聚乙烯 (PE-LD)的官能化反应,并且考察了官能化产物PE-LD-g-MAH对铝萡/PET薄膜（Al/PET）热熔胶的T型黏合接头剥离强度的影响。结果表明,高剪切应力作用可直接引起大分子链的断链,形成大分子自由基,引发PE-LD的接枝反应;通过改变螺杆转速可有效抑制交联副反应,制得具有较高接枝率、较好熔体流动速率和较低凝胶含量的官能化产物,当螺杆转速为800 r/min时,产物的接枝率为0.71 %,熔体流动速率为0.87 g/10 min,凝胶含量0.40 %;高剪切应力诱导引发法所得官能化产物可明显提高Al/PET热熔胶T型黏合接头的剥离强度,当反应温度为310 ℃,螺杆转速为600 r/min,三元乙丙橡胶（EPDM）含量为80 %（质量分数,下同）时,可使Al/PET的T型黏合接头的剥离强度达3.87 N/mm。     

Modification of acrylonitrile‐butadiene‐styrene terpolymer by graft copolymerization with maleic anhydride in the melt. II. Properties and phase behavior

The graft copolymerization of maleic anhydride (MAH) onto acrylonitrile‐butadiene‐styrene terpolymer (ABS) using dicumyl peroxide and benzoyl peroxide as the binary initiator and styrene as the comonomer in the molten state was described. The properties and phase morphologies of the modified products (ABS‐g‐MAH) were studied. The results indicate that the melt flow index (MFI) of ABS‐g‐MAH increases with the increase of MAH content, the initiator concentration, and the screw speed, whereas the MFI decreases with the increase of temperature. The impact strength and the percentage elongation of ABS‐g‐MAH both decreased and the tensile strength of ABS‐g‐MAH increased slightly as the grafting degree increased. The phase inversion behavior of the modified product was observed by transmission electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2834–2839, 2004     

机械力引发马来酸酐官能化PE-HD研究

采用机械力引发方法研究了马来酸酐(MAH)熔融接枝高密度聚乙烯(PE-HD)的官能化反应,并考察了接枝产物对PE-HD/PA66及PE-HD/GF材料力学性能的影响。结果表明:通过控制引发剂含量和提高双螺杆挤出机的螺杆转速可抑制PE-HD在接枝过程中的交联副反应,制得具有较高接枝率(Gd=0.75~1.34%),较好熔体流动性(0.3~0.6g/10min)和较低凝胶含量(≤0.9%)的接枝产物;该方法所得产物可使PE-HD/PA66共混材料的缺口冲击强度提高至6.5倍以上,使PE-HD/GF复合材料的拉伸、弯曲和缺口冲击强度显著增大。     

Functionalization of polyolefins with maleic anhydride in melt state through ultrasonic initiation

The functionalization reaction of high-density polyethylene (HDPE), linearly low-density polyethylene (LLDPE), polypropylene (PP) and EPDM rubber with maleic anhydride (MAH) in melt state through ultrasonic initiation was studied. The effect of ultrasonic intensity on the percentage of grafting, viscosity-average molecular weight, melt flow rate and gel content of the functionalized products were investigated by means of chemical titration, Fourier-transform infra-red spectroscopy (FT-IR), intrinsic viscosity and melt flow rate, etc. The molecular structures of the functionalized products prepared via ultrasonic initiation and via peroxide initiation were characterized by ¹H NMR spectroscopy. The results show that the functionalization reaction of HDPE, LLDPE and EPDM with MAH can be realized by ultrasonic initiation. This reaction mainly consists of the chain scission under ultrasonic irradiation, the end chain reaction of the produced macroradicals with MAH, and the terminated reaction of the produced succinyl radicals with the macroradicals or H* radicals through recombination or dismutation. The functionalized product through ultrasonic initiation mainly consists of the products containing an anhydride ring attached to the chain terminus. And the products prepared through peroxide initiation mainly contain an anhydride ring grafted on the side chain.     

Modification of low‐density polyethylene by graft copolymerization with maleic anhydride and blends with polyamide 6

Modification of low‐density polyethylene (LDPE) hyperbranched grafting with a maleic anhydride (MAH) was carried out using corotating twin screw extruder in the presence of benzoyl peroxide. The LDPE/polyamide 6 (PA6) and LDPE‐g‐MAH/PA6 blends were obtained with a corotating twin screw extruder. The melt viscosity of the grafted LDPE was measured by a capillary rheometer. The grafted copolymer was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy The effects of variations in temperature, PA6 loading, and benzoyl peroxide and MAH concentration were investigated. The results show that most MAH monomers were grafted onto the LDPE at a lower MAH concentration. With the proper selection of the reaction parameters, we obtained a grafting degree higher than 4.9%. Mechanical test results indicate that the blends had good interfacial adhesion and good stability of the phase structure during heating, which was reflected in the mechanical properties. Furthermore, the results reveal that the tensile strength of the blends increased continuously with increasing PA6 content. Moreover, the home‐synthesized maleated LDPE could be used for the compatibilization of LDPE/PA 6 blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compatibilizing effect of ethylene–propylene–diene grafted maleic anhydride terpolymer on the blend of polyamide 66 and thermal liquid crystalline polymer

Polyamide 66–thermal liquid crystalline polymer (PA66/TLCP) composites containing 10 wt% TLCP was compatibilized by ethylene–propylene–diene‐grafted maleic anhydride terpolymer (MAH‐g‐EPDM). The blending was performed on a twin‐screw extrusion, followed by an injection molding. The rheological, dynamic mechanical analysis (DMA), thermal, mechanical properties, as well as the morphology and FTIR spectra, of the blends were investigated and discussed. Rheological, DMA, and FTIR spectra results showed that MAH‐g‐EPDM is an effective compatibilizer for PA66/TLCP blends. The mechanical test indicated that the tensile strength, tensile elongation, and the bending strength of the blends were improved with the increase of the content of MAH‐g‐EPDM, which implied that the blends probably have a great frictional shear force, resulting from strong adhesion at the interface between the matrix and the dispersion phase; while the bending modulus was weakened with the increase of MAH‐g‐EPDM content, which is attributed to the development of the crystalline phase of PA66 hampered by adding MAH‐g‐EPDM. POLYM. COMPOS., 27:608–613, 2006. © 2006 Society of Plastics Engineers     

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.     

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     

复合引发GMA熔融接枝POE及其增韧PBT的研究

采用双螺杆加工过程中的机械力引发同时添加引发剂的双重引发方法,研究了引发剂的用量、螺杆转速和接枝反应温度对甲基丙烯酸缩水甘油酯（GMA）接枝乙烯-辛烯共聚弹性体（POE）产物的接枝率、熔融指数的影响。对于单纯采用引发剂引发方法和引发剂与机械力双重引发方法所得接枝产物增韧聚对苯二甲酸丁二醇酯（PBT）的效果也进行了比较。后者在接枝物含量为30％时,可使PBT／POE—g—GMA共混材料的缺口冲击强度达到原未改性材料的22倍左右。     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

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。     

马来酸酐接枝PS相容剂的研究

研究了马来酸酐(MAH)在螺杆挤出机中与聚苯乙烯的接枝反应，确定了挤出接枝反应的最佳工艺条件，初步探索了温度、螺杆转速、引发剂浓度以及MAH浓度对接枝反应的影响。     

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     

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。     

Effect of EPDM‐g‐MAH on the morphology and properties of PA6/EPDM/HDPE ternary blends

The formation of core‐shell morphology within the dispersed phase was studied for composite droplet polymer‐blend systems comprising a polyamide‐6 matrix, ethylene‐propylene‐diene terpolymer (EPDM) shell and high density polyethylene (HDPE) core. In this article, the effect of EPDM with different molecular weights on the morphology and properties of the blends were studied. To improve the compatibility of the ternary blends, EPDM was modified by grafting with maleic anhydride (EPDM‐g‐MAH). It was found that core‐shell morphology with EPDM‐g‐MAH as shell and HDPE as core and separated dispersion morphology of EPDM‐g‐MAH and HDPE phase were obtained separately in PA6 matrix with different molecular weights of EPDM‐g‐MAH in the blends. DSC measurement indicated that there may be some co‐crystals in the blends due to the formation of core‐shell structure. Mechanical tests showed that PA6/EPDM‐g‐MAH/HDPE ternary blends with the core‐shell morphology exhibited a remarkable rise in the elongation at break. With more perfect core‐shell composite droplets and co‐crystals, the impact strength of the ternary blends could be greatly increased to 51.38 kJ m^?2, almost 10 times higher than that of pure PA6 (5.50 kJ m^?2). POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

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