Structure and adhesion properties of acrylic acid grafted high‐density polyethylene powders synthesized by a novel photografting method

A novel photografting, nonvapor, and nonliquid phase living graft polymerization was developed to functionalize high‐density polyethylene (HDPE) powder. The structure and adhesion properties of HDPE powder grafted with acrylic acid (AA) were studied by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), water contact angle, peel strength, and graft degree measurements. The result shows that HDPE powder can be grafted with AA via the method with a short reaction time and a high monomer conversion. The graft degree increases with the reaction time. Then, the hydrophilicity of the grafted HDPE powder increases also. The peel strength of HPDE/steel joint improved significantly when acrylic acid grafted HPDE powder was used as hot melt adhesive in place of ungrafted HDPE powder. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal properties and morphology of noncrosslinking linear low‐density polyethylene‐grafted acrylic acid

Noncrosslinking linear low‐density polyethylene‐grafted acrylic acid (LLDPE‐g‐AA) was prepared by melt‐reactive extrusion in our laboratory. The thermal behavior of LLDPE‐g‐AA was investigated by using differential scanning calorimetry (DSC). Compared with neat linear low‐density polyethylene (LLDPE), melting temperature (T_m) of LLDPE‐g‐AA increased a little, the crystallization temperature (T_c) increased about 4°C, and the melting enthalpy (ΔH_m) decreased with an increase in acrylic acid content. Isothermal crystallization kinetics of LLDPE and LLDPE‐g‐AA samples were carried out by using DSC. The overall crystallization rate of LLDPE was smaller than that of grafted samples. It showed that the grafted acrylic acid monomer onto LLDPE acted as a nucleating agent. Crystal morphologies of LLDPE‐g‐AA and LLDPE were examined by using SEM. Spherulite sizes of LLDPE‐g‐AA samples were lower than that of LLDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2626–2630, 2002     

Performance of multilayer films using maleated linear low-density polyethylene blends

Blends of linear low-density polyethylene (LLDPE) and linear low-density polyethylene grafted maleic anhydride (LLDPE-gMA) were prepared by melt mixing and then coextruded as external layers, with a central layer of polyamide (PA) on three-layer coextruded flat films. Blends with contents of 0% to 55 wt% of maleated LLDPE, on the external layers, were analyzed. The T-peel strength and oxygen and water vapor transmission rate of the films were measured. The surfaces of the peeled films were characterized using attenuated total reflection infrared spectroscopy (FTIR-ATR) and scanning electron microscopy (SEM). The observed increase in T-peel strength of the films with 10% and higher levels of maleated LLDPE in the blend suggests good interfacial adhesion between layers. This sharp increase in peel strength appears to be associated, besides interdiffusion, with specific interactions between polymers, as the bond formation between maleic anhydride and the polyamide end groups by in situ block copolymer formation across the interface. No significant modifications in oxygen barrier properties of the films were observed; however, the use of higher contents of LLDPEgMA, even though it increases the adhesion performance, also increases the water vapor transmission rate by a reduction in the degree of crystallinity.     

Surface structure of low density polyethylene films grafted with acrylic acid using corona discharge

Chemical composition, morphology, and crystalline structure of low density polyethylene (LDPE) films surface grafted with acrylic acid (AA) using corona discharge were studied by attenuated total reflection infrared (ATR-IR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) techniques. The grafted film surface is covered with grafted chains. After grafting for 3.0 h in 20% aqueous solution of AA, the depth of the grafted layer is more than 10 nm. A grain structure was observed on the grafted surfaces which was probably caused by the isolated dispersion of active sites generated by corona discharge, and these active sites initiated the graft copolymerization. However, surfaces of grafted films were smoother than that of ungrafted ones. DSC curves of grafted films show a small peak at about 100°C due to vaporization of adsorbed water. The longer the graft copolymerization time, i.e. the higher the graft degree of AA on LDPE, the higher the amount of adsorbed water. The position of each peak in WAXD patterns, crystal axial length, crystal plane distance and crystal grain size remain almost unchanged during the graft copolymerization time of 2.0 h. However, when the graft copolymerization time reaches 3.0 h, twin peaks at about 21.4° and 22.0° are observed, indicating that a different crystal form is formed at longer copolymerization time, i.e. at a higher graft degree.     

Effect of the compatibilization of linear low‐density polyethylene‐g‐acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low‐density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low‐density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method. For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE‐g‐AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE‐g‐AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE‐g‐AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/LLDPE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE‐g‐AA decreased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1059–1066, 2002; DOI 10.1002/app.10399     

新型引发剂DMDPB在LLDPE熔融接枝MAH中的应用

采用熔融接枝的方法,在双螺杆挤出机中用2,3－二甲基－2,3－二苯基丁烷（DMDPB）和过氧化二异丙苯（DCP）两种不同的引发剂将马来酸酐（MAH）接枝到线形低密度聚乙烯（LLDPE）上。用二甲苯溶解－丙酮抽提（或沉淀）法处理接枝物,用红外光谱证实了在新型引发剂DMDPB的引发下,马来酸酐成功地接上了PE。用化学实验方法定量测定了接枝率的大小和凝胶含量,结果发现DMDPB引发的接枝物无凝胶现象。通过溶体流动速率的测定说明了接枝物加工性能的优劣。并对两种引发剂做进一步的比较。     

Mechanical properties and morphology of polylactide,linear low‐density polyethylene,and their blends

Melt blending of linear low density polyethylene (LLDPE) and polylactide (PLA) was performed in an extrusion mixer with post extrusion blown film attachment with and without compatibilizer‐grafted low density polyethylene maleic anhydride. The blend compositions were optimized for tensile properties as per ASTM D 882‐91. On the basis of this, LLDPE 80 [80 wt % LLDPE and 20 wt % poly(L ‐lactic acid) (PLLA)] and MA‐g‐low‐density polyethylene 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) were found to be an optimum composition. The blends were characterized according to their mechanical, thermal, and morphological behavior. Fourier transform infrared spectroscopy revealed that the presence of compatibilizer enhanced the blend compatibility to some extent. The morphological characteristics of the blends with and without compatibilizer were examined by scanning electron microscopy. The dispersion of PLLA in the LLDPE matrix increased with the addition of compatibilizer. This blend may be used for packaging applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of silicone oil and polymeric modifiers on the mechanical properties of highly filled LLDPE

The effects of coupling agents, silicone oil, and three types of polymeric modifiers on the mechanical properties of linear low density polyethylene (LLDPE) composites highly filled with aluminium hydroxide [Al(OH)₃] were studied. Polymeric modifiers that contain polar groups, such as silane‐grafted polyethylene (Si‐g‐PE) and acrylic‐acid‐grafted ethylene‐vinyl acetate copolymer (AA‐g‐EVA), improve the mechanical properties dramatically, while nonpolar modifiers improve them to some extent. When Al(OH)₃ was treated using a titanate coupling agent, the silicone oil increased the impact strength and elongation at break of the LLDPE/Al(OH)₃ composites. Introduction of a polymeric modifier containing polar groups destroys the beneficial effects of silicone oil on film mechanical properties, while the introduction of a nonpolar elastomeric polymeric modifier retains the high impact strength and elongation at break. SEM analyses provide the indirect evidence of the encapsulation of silicone oil around the filler. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 121–128, 2002     

Linear low‐density polyethylene/(soya powder) blends containing polyethylene‐g‐(maleic anhydride) as a compatibilizer

Blends were made from linear low‐density polyethylene (LLDPE) and various amounts of soya powder. The soya powder content was varied from 5 to 20 wt%. Polyethylene‐g‐(maleic anhydride) (PE‐g‐MA) was used as a compatibilizer. Tensile strength and elongation at break (EB) decreased with increasing soya powder content. However, Young's modulus increased with the incorporation of soya powder. The addition of PE‐g‐MA as a compatibilizer increased the tensile strength, EB, and modulus of the blends. The interfacial adhesion between soya powder and LLDPE was improved by the incorporation of PE‐g‐MA, as demonstrated by scanning electron microscopy. Increasing the content of soya powder reduced the crystallinity of the LLDPE phase. The addition of PE‐g‐MA had no significant effect on melting temperature, but the degree of crystallinity of the LLDPE was increased. The thermal stability of the blends was determined by using thermogravimetric analysis. Thermal stability decreased with increasing soya powder loading. However, the addition of PE‐g‐MA slightly increased the thermal stability of LLDPE/(soya powder) blends. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

官能化线性低密度聚乙烯的流变行为及力学性能

利用毛细管流变仪研究了官能化ＬＬＤＰＥ（ＬＬＤＰＥ－ｇ－ＡＡ、ＬＬＤＰＥ－ｇ－ＧＭＡ）的流变行为。结果表明：在高的剪切应力下ＬＬＤＰＥ－ｇ－ＡＡ、ＬＬＤＰＥ－ｇ－ＧＭＡ的表观粘度比纯ＬＬＤＰＥ的小。表明官能化ＬＬＤＰＥ的流动性提高了,其加工性能变好。官能化ＬＬＤＰＥ的表观粘度随接枝单体含量的增加而降低,这说明接枝到ＬＬＤＰＥ分子链土的单体起到了内润滑剂的作用。利用Ｉｎｓｔｒｏｎ１１２１拉力机测试了     

Glycidyl methacrylate–grafted linear low‐density polyethylene fabrication and application for polyester/polyethylene bonding

The grafting of glycidyl methacrylate (GMA) onto linear low‐density polyethylene (LLDPE) was investigated. The grafting was performed by free‐radical grafting in the melt state in a twin‐screw extruder using an organic peroxide as initiator. The effect of initial GMA and peroxide concentration, styrene comonomer addition, as well as initial resin viscosity, on the final content in grafted moieties, unbound homopolymer, and unreacted monomer was assessed. The effect of process parameters such as flow rate, screw rotation speed, and barrel temperature was also investigated. Chemical composition was shown to be the main parameter for controlling grafting level and grafting efficiency. Grafting levels up to 1.8% and efficiency of 90% were reported even though in most conditions, the graft efficiency was severely decreased by the homopolymerization of GMA into polyGMA chains not bound to LLDPE. Finally, the effect of grafting level and the presence of unbound GMA‐based species on the efficiency GMA‐grafted LLDPE as adhesive between polyethylene and polyester were discussed. Good adhesion to poly(ethylene terephthalate) copolymer was found for low viscosity grafted polyethylene resins. A significant improvement in adhesive strength on polyester was observed when the molecular weight of the grafted LLDPE was increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3180–3191, 2004     

Degradation behaviors of linear low‐density polyethylene and poly(L‐lactic acid) blends

In this study, the degradability of linear low‐density polyethylene (LLDPE) and poly(L ‐lactic acid) (PLLA) blend films under controlled composting conditions was investigated according to modified ASTM D 5338 (2003). Differential scanning calorimetry, X‐ray diffraction, and Fourier transform infrared spectroscopy were used to determine the thermal and morphological properties of the plastic films. LLDPE 80 (80 wt % LLDPE and 20 wt % PLLA) degraded faster than grafted low‐density polyethylene–maleic anhydride (M‐g‐L) 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) and pure LLDPE (LLDPE 100). The mechanical properties and weight changes were determined after composting. The tensile strength of LLDPE 100, LLDPE 80, and M‐g‐L 80/4 decreased by 20, 54, and 35%, respectively. The films, as a result of degradation, exhibited a decrease in their mass. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface structure and adhesive properties of biaxially oriented polypropylene film grafted with poly(acrylic amide) using corona discharge

Corona discharge was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene (BOPP) film. The active species formed in air was used to induce graft copolymerization of acrylic amide (AAM) in aqueous solution. The surface structure, hydrophilicity and adhesion of the grafted BOPP film were characterized by the extent of grafting, electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), peel strength and contact angle measurements. Surface graft‐copolymerization of AAM onto BOPP film by corona discharge in air can be carried out with high efficiency. With increasing copolymerization time, the degree of grafting of AAM onto BOPP increases. The degree of grafting achieved a relatively high value of 2.13 wt% for the conditions of 1 min corona discharge and a copolymerization reaction time of 2.5 hr in 20% AAM aqueous solution at 70°C. After corona discharge grafting, the contact angle of water on the BOPP film decreased and the peel strength increased compared with those for ungrafted BOPP film. The hydrophilicity and adhesion of BOPP were improved by surface graft copolymerization with AAM induced by corona discharge.     

Synergistic compatibilization and reinforcement of HDPE/wood flour composites

Multi‐monomer grafted copolymers, high‐density polyethylene‐grafted‐maleic anhydride‐styrene (HDPE‐g‐(MAH‐St)) and polyethylene wax‐grafted‐ maleic anhydride ((PE wax)‐g‐MAH), were synthesized and applied to prepare high‐performance high‐density polyethylene (HDPE)/wood flour (WF) composites. Interfacial synergistic compatibilization was studied via the coordinated blending of high‐density polyethylene‐grafted‐maleic anhydride (MPE‐St) and polyethylene wax‐grafted‐ maleic anhydride (MPW) in the high‐density polyethylene (HDPE)/wood flour (WF) composites. Scanning electron microscopy (SEM) morphology and three‐dimensional WF sketch presented that strong interactive interface between HDPE and WF, formed by MPE‐St with high graft degree of maleic anhydride (MAH) together with the permeating effect of MPW with a low molecular weight. Experimental results demonstrated that HDPE/WF composites compatibilized by MPE‐St/MPW compounds showed significant improvement in mechanical properties, rheological properties, and water resistance than those compatibilized by MPE, MPE‐St or MPW separately and the uncompatibilized composites. The mass ratio of MPE‐St/MPW for optimizing the HDPE/WF composites was 5:1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42958.     

Interfacial adhesion and water resistance of stainless steel–polyolefin improved by functionalized silane

The adhesion strength and water resistance of stainless steel and adhesive resin composites determine the long‐term performance of wires and cables; however, adhesion at stainless steel interfaces is difficult. Herein, we prepared ethylene acrylic acid/linear low‐density polyethylene (EAA/LLDPE) blends with good mechanical and adhesive properties. Silane was anchored to the surface of stainless steel. The effects of silane functionalization on the adhesion surface were investigated by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The reaction mechanism between the stainless steel, silane, and EAA/LLDPE revealed adhesion was optimized when a 3:7 volume ratio of 3‐methacryloxypropyltrimethoxysilane (MEMO): 3‐aminopropyltrimethoxysilane (A‐1110) was used to modify the stainless steel substrate. SEM images of EAA/LLDPE film peel surfaces found the silane‐treated stainless steel substrates produced rough surfaces with a uniform void indicating the silane treatment enhanced the stainless steel and EAA/LLDPE film interaction. The stainless steel and EAA/LLDPE film adhesion and water resistance improved and the peel strength after water resistance testing at 68°C for 168 h increased from 3.18 N/cm to 9.37 N/cm compared to untreated stainless steel. Silane‐modified stainless steel and EAA/LLDPE blend film composite materials demonstrate potential for application in wires and cables used in environmental corrosion‐resistant applications. POLYM. ENG. SCI., 59:1866–1873, 2019. © 2019 Society of Plastics Engineers     

Comparative ozonization of LDPE and HDPE and grafting of some monomers to elaborate new ion exchange membranes

A comparative study of the ozonization of low density polyethylene (LDPE) and high density polyethylene (HDPE) was carried out. A grafting study of acrylic acid (AA), N,N‐dimethylamino‐2‐ethylmethacrylate (MADAME) and vinyl phosphonic acid (VPA) on LDPE and HDPE was performed in mass and solution. The ozonized polyethylene and the grafting polymers were characterized by IR spectroscopy and elementary analysis. Ion exchange membranes were prepared from grafted copolymers and characterized by the exchange capacity and electrical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4423–4429, 2006     

The study of melt grafting mechanism of acrylic acid and butyl acrylate onto low density polyethylene and its application as internal plasticizer

Melt grafting of acrylic acid (AA) and butyl acrylate (BA) (equal molar ratios) onto low‐density polyethylene (LDPE) was carried out in Haake internal mixter by free radical grafting copolymerization. The graft degree of AA and BA in the grafted LDPE (LDPE‐g‐(AA+BA)) was determined by FTIR. The influences of initiator on the graft degree of AA and BA, melt flow rate (MFR), and gel content were investigated, and the optimum conditions were obtained. The successive self‐nucleation/annealing (SSA) thermal fraction method was used to characterize the molecular structure and polydispersity of LDPE‐g‐(AA+BA) with various graft degrees. The effects of thermal fraction parameters on fraction of LDPE‐g‐(AA+BA) were investigated. On the basis of the results of SSA, the grafting reaction mechanism of AA and BA onto LDPE was proposed, i.e., grafting reaction preferentially occurred on the tertiary carbons of LDPE. The grafted LDPE possessed suitable reactivity and rheological property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of matrix composition on the properties of cellulosic fibers–polyethylene composites

The solution/precipitation method was used for the preparation of polyethylene (PE)/cellulosic fibers composites. Blends of modified linear low density PE [linear low density PE‐grafted maleic anhydride (LLDPE‐g‐MAH)] with low density PE (LDPE) were used as matrices for the aforementioned composites. Blends of LDPE with a copolymer of LDPE and acrylic acid (AA)/n‐butyl acrylate (n‐BA) [(AA/n‐BA)–LDPE] were also studied for the same purpose. The reinforcing effect of cellulosic fibers in terms of tensile strength is more enhanced when mixtures of the modified polar polymer with pure PE were used as matrices, as compared with that corresponding to matrices consisting of modified PE alone. Regarding the Izod impact strength, composites of LLDPE‐g‐MAH presented the best performance with an improvement of 135% in comparison with specimens consisting of LDPE matrix, whereas composites of (AA/n‐BA)‐LDPE matrix showed a modest improvement of their impact resistance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of different compatibilizers on the rheological,thermomechanical, and morphological properties of HDPE/LLDPE blend‐based nanocomposites

The influence of two different compatibilizers and their combination (maleic anhydride grafted high density polyethylene, HDPE‐g‐MA; maleic anhydride grafted linear low density polyethylene, LLDPE‐g‐MA; and 50/50 wt % mixture of these compatibilizers) on the rheological, thermomechanical, and morphological properties of HDPE/LLDPE/organoclay blend‐based nanocomposites was evaluated. Nanocomposites were obtained by melt‐intercalation in a torque rheometer in two steps. Masterbatches (compatibilizer/nanoclay 2:1) were obtained and subsequently diluted in the HDPE/LLDPE matrix producing nanocomposites with 2.5 wt % of nanoclay. Wide angle X‐ray diffraction (WAXD), steady‐state rheological properties, and transmission electron microscopy (TEM) were used to determine the influence of different compatibilizer systems on intercalation and/or exfoliation process which occurs preferentially in the amorphous phase, and thermomechanical properties. The LLDPE‐g‐MA with a high melt index (and consequently low viscosity and crystallinity) was an effective compatibilizer for this system. Furthermore, the compatibilized nanocomposites with LLDPE‐g‐MA or mixture of HDPE‐g‐MA and LLDPE‐g‐MA exhibited better nanoclay's dispersion and distribution with stronger interactions between the matrix and the nanoclay. These results indicated that the addition of maleic anhydride grafted polyethylene facilitates both, the exfoliation and/or intercalation of the clays and its adhesion to HDPE/LLDPE blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1726–1735, 2013     

LLDPE熔融接枝MAH功能化研究

以双螺杆挤出机为反应器 ,在自由基引发剂过氧化二异丙苯 (DCP)存在下 ,加入添加剂 ,采用熔融法对线型低密度聚乙烯 (LLDPE)进行马来酸酐 (MAH)接枝 ,对产物的接枝率 (Gx)、凝胶含量 (gel)以及溶体流动速率(MFR)的影响因素进行了系统的研究 ,并测试了接枝共聚物与铝片的粘接强度