Surface photografting of low-density polyethylene films and its relevance to photolamination

Surface modifications of pristine and ozone-pretreated low-density polyethylene (LDPE) films were carried out via UV-induced graft copolymerization with a photoinitiator-containing, epoxy-based commercial monomer (DuPont Somos? 6100 for solid imaging and optical lithography) and also with the photoinitiator-free acrylic acid (AAc). The chemical composition and microstructure of the graft copolymerized surfaces were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). The concentration of surface grafted polymer increased with the UV illumination time and the monomer concentration. For LDPE films graft copolymerized with the epoxy-based monomer, surface chain rearrangement was not observed or was less well pronounced, due to the partial crosslinking of the grafted chains. Simultaneous photografting and photolamination between two LDPE films, or between a LDPE film and a poly(ethylene terephthalate) (PET) film, in the presence of either monomer system, were also investigated. The photolamination rates and strengths depend on the ozone pretreatment time, the UV illumination time, and the UV wavelength, as well as on the nature of the substrate materials. A shear adhesion strength approaching 150 N/cm² could be achieved with either monomer system, provided that the polymer films were pretreated with ozone. The failure mode of the photolaminated surfaces was cohesive in nature in the case of the photoinitiator-containing epoxy monomer, but was either cohesive or adhesional in nature (depending on the substrate assembly) in the case of the photoinitiator-free AAc monomer.     

Bulk surface photografting process and its applications. I. Reactions and kinetics

A bulk surface photografting process which is conducted in the interface between two polymer films was designed and investigated. The bulk surface photografting is a highly efficient process. With this method, the surface of hydrophobic polymers can be made hydrophilic in less than 2 s and a grafted layer 5 μm thick can be obtained in 30 s. The kinetic investigation shows that the bulk surface photografting polymerization involves a four-step reaction process: induction period, surface initiation, successive polymerization, involves a four-step reaction process: induction period, surface initiation, successive polymerization, and solid-phase crosslinking. The photoreduction of benzophenone (BP) takes place in the interlayer between the LDPE films and is a three-stage process: surface photoreduction, secondary photoreduction, and solid-state photoreduction. With regard to the photoreduction of the initiator caused by hydrogen abstraction, the kinetic studies show that the photoreduction rate has a first-order dependence on the BP concentration. The activation energy of the hydrogen abstraction reaction is about 28.5 KJ (6.8 kcal)/mol. With regard to the photografting polymerization reaction, the reaction order of the rate Rp with respect to the monomer is unity and 0.89 with respect to BP. This means that the termination reaction takes place mainly by combination of polymer chain free radicals and semipinacol free radicals from BP. The activation energy of the overall polymerization reaction is around 8.8 kJ (2.1 kcal)/mol. © 1996 John Wiley & Sons, Inc.     

聚合物表面紫外光接枝改性的研究

介绍聚合物表面紫外光接枝改性的研究方法,其中包括液相和气相接枝、接枝反应的引发方式及其机理,溶剂的影响和选择,针对不同改性要求对接枝单体的使用以及连续化操作的发展。此外,还简要介绍了聚合物表面接枝效果的测试方法和接枝后表面形态的观测方法     

Improvement of autohesive and adhesive properties of polyethylene plates by photografting with glycidyl methacrylate

Glycidyl methacrylate (GMA) was photografted with the low‐ and high‐density polyethylene (LDPE and HDPE) plates to provide their surfaces with autohesive and adhesive properties. The chemical composition and wettability of the GMA‐grafted LDPE and HDPE (LDPE‐g‐PGMA and HDPE‐g‐PGMA) plates remained constant above full coverage of the surfaces with grafted PGMA chains. Autohesive strength obtained with 1,4‐dioxane as a good solvent of PGMA increased with an increase in the grafted amount and substrate breaking was observed at the grafted amount of 117 μmol/cm². The grafted amount at substrate breaking was decreased by increasing the temperature and load during heat pressing. Adhesive strength was effectively enhanced by use of multi‐functional amine compounds because of the increase in the reaction between primary or secondary amine groups and epoxy groups appended to the grafted PGMA chains. In addition, the decrease in the amine compound concentration and the increase in the number of amino groups in the amine compounds used led to the decrease in the grafted amounts at substrate breaking. Substrate breaking occurred at lower grafted amounts for the HDPE‐g‐PGMA plates than for the LDPE‐g‐PGMA plates because the location of the photografting was restricted to the outer surface region for the HDPE plate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 493–500, 2007     

Surface photografting polymerization of vinyl acetate (VAc), maleic anhydride,and their charge transfer complex. I. VAc(1)

Photografting of vinyl acetate (VAc) onto LDPE films was carried out with lamination technology and simultaneous method, using BP as photoinitiator. Some principal factors affecting the grafting polymerization were investigated in detail. The experimental results showed that oxygen dissolved in monomer solution had great influence on grafting polymerization. Compared with other routine monomers (St, MMA, AN, AA, and AAm), VAc exhibited higher photografting reactivity. It was observed that the reaction temperature affected the graft polymerization markedly. To film samples with a given diameter, there exists optimum thickness of monomer solution. Adding a pertinent amount of water to the photografting polymerization system could accelerate the polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1513–1521, 2000     

Surface photografting polymerization of vinyl acetate (VAc), maleic anhydride (MAH), and their charge transfer complex (CTC). III. VAc(3)

Vinyl acetate (VAc) was grafted onto low‐density polyethylene (LDPE) substrates by UV irradiation with benzophenone (BP) as the photoinitiator. BP preabsorbed film samples and BP precoated film samples were prepared in advance and applied as the substrates onto which VAc was photografted, together with the method in which BP was dissolved in VAc directly. In addition, the efficiency of the polymerizations applying the preirradiation technology was examined. The conversion percent, grafting percent, and grafting efficiency were determined by a gravimetric method. The contact angles of the grafted films against water were also measured. The results show that BP preabsorbing and precoating were favorable to grafting polymerization, especially the BP precoating method, which was due to its simple operation and the ease of controlling the amount of BP. The diffusion of BP and VAc through the substrates proved to be an important factor for grafting polymerization. Through UV irradiation, dormant groups can be introduced onto LDPE film, which may be activated again by UV irradiation or by heating, leading to the formation of free radicals. Grafting polymerization can be initiated during the activation process in the presence of monomer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1426–1433, 2001     

高分子材料表面接枝的方法及应用

介绍了高分子材料表面接枝的方法以及近年来的发展和应用情况。表面接枝方法包括化学接枝、辐射接枝、等离子体接枝、臭氧化接枝和光接枝     

Formation of continuous dense polymer layer at the surface of hollow fiber using a photografting process

The surface modification of a PES hollow fiber by UV photografting has been investigated in order to graft a dense polymer layer. The study focused on a UV photografting process, starting from a monomer solution, enabling the thickness and regularity of the grafted polymer to be followed. 2‐(Acryloyloxy)ethyl trimethylammonium chloride was polymerized on the surface of the PES membrane. Modified membranes were characterized by SEM, FTIR spectroscopy, and liquid and gas permeability. A dense layer of poly(2‐(acryloyloxy)ethyl trimethylammonium chloride) was obtained when a photoinitiator and a photocrosslinker were used. Polymerization of the ammonium material also occurred inside the pores of the membrane. With pretreatment and an increase of the irradiation time, the thickness of the grafted polymer decreased and gas permeability reached measurable levels. However, a CO₂/N₂ selectivity of around 1 was found which suggested the presence of defects in the grafted layer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41514.     

High-performance polymer films. III. Preparation and characterization

A series of polyimide and copolyimide films were prepared by film casting, drying, and thermal imidization from the respective precursor poly(amic acid) (PAA) and copoly(amic acid) solutions derived from two dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and two diamines, 4,4′-oxydianiline (ODA) and a proprietary aromatic diamine (PD) as monomers. Depending on the solution's inherent viscosity value (molecular weight) and the nature of the polymer chains (derived from rigid or flexible monomers), precursor poly(amic acid) and copoly(amic acid) solution concentrations of 8–12% (w/w) were found to be suitable for the preparation of good quality polyimide/copolyimide films. The recovery of film toughness and creasability from the brittleness at the intermediate temperature of the cure cycle depended not only on the molecular weight of the precursor poly(amic acids)/copoly(amic acids) but also on their chain flexibility. The poly(amic acid) derived from both rigid dianhydride and diamine practically gave rise to a brittle film of polyimide even after curing to 360°C. The resulting polyimide and copolyimide films were compared with Du Pont's Kapton H film. The density of the films was in the range 1.39–1.42 g/cm³. The thickness of most of the films was in the range 20–30 μm. The HPF 3 film, based on PMDA–PD, appeared to be highly colored (reddish brown), and the HPF 2 film, based on BTDA–ODA, had the lightest yellow coloring among the films in this investigation, including Kapton H film. HPF 2, HPF 6, and HPF 8 films were more amorphous than the other films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 976–988, 2001     

Development of polymer films and its application on leather surfaces

Ten different formulations are prepared with a urethane acrylate oligomer in combination with two monofunctional monomers (EHA with low T_g and NVP with a carboamide group) and a difunctional acrylate monomer (TPGDA) in the presence of a plasticizer. Polymer films are prepared with these formulated solutions under UV radiation. Their properties (gel, hardness, tensile characters, etc.) are determined. These solutions are coated on leather substrates and cured under UV radiation. The improvement of quality of leather is manifested through the enhancement of tensile strength and elongation of the coated leather. The coating also imparts high gloss on the leather surface as well as high wear resistance. It also protects the leather from the damage of weathering effect. The best formulation is determined to be the one containing NVP with a carboamide group and a plasticizer. © 1996 John Wiley & Sons, Inc.     

High-Temperature Bulk Copolymerization of Methyl Methacrylate and Acrylonitrile: III. Thermal Polymerization

The thermally initiated copolymerization of methyl methacrylate and acrylonitrile has been studied in the bulk phase. Experiments for estimating reactivity ratios were conducted at 120°C and 140°C. Feed composition constraint approaches were used to design the reactivity ratio experiments. The error in variables model (EVM) method was employed to evaluate the reactivity ratios and analyze the error. The results showed that the reactivity ratios did not vary significantly with temperature up to 140°C for both thermally initiated and experiments with initiator. Full conversion range experiments were also conducted at 140°C. The rate of reaction, copolymer composition, M¯ _n , M¯ _w , and glass transition temperatures of samples were measured.     

In‐situ formation of metal nanoparticle/acrylic polymer hybrid and its application to miniemulsion polymerization

We present in‐situ formation of metal nanoparticle/acrylic polymer hybrid and its application to prepare hybrid latex particles by miniemulsion polymerization. On the surface of a silver nanoparticle/silica nanoparticle/acrylic polymer hybrid layer formed in‐situ on a polyethylene terephthalate (PET) substrate, a copper film is deposited using electroless copper deposition. Silver nanoparticles, which are formed in‐situ via the reduction of silver ion by radical species and subsequent annealing, work as a catalyst for the electroless deposition. Miniemulsion polymerization via the in‐situ formation of nanoparticles affords nanoparticle/acrylic polymer hybrid latex particles and polymer particles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42675.     

PBA/PS核壳聚合物的制备及其与PS共混

采用种子乳液聚合方法制备了丙烯酸丁酯/苯乙烯核壳结构聚合物,研究了不同核壳单体质量比对乳液聚合过程的影响.结果表明,单体的总转化率超过98%;假设乳胶粒为球形生长时,乳胶粒理论粒径与实测值基本一致,说明该聚合体系没有明显的二次成核过程.随着核壳单体质量比的增加,低温区(聚丙烯酸丁酯)的玻璃化转变温度变化不大,而高温区(聚苯乙烯)的玻璃化转变温度呈下降趋势,这说明该核壳结构界面存在明显的过渡层.将该乳液聚合物与聚苯乙烯共混,随着核壳单体质量比的增加,共混物的冲击强度呈先增加后降低的趋势,说明该核壳聚合物对聚苯乙烯的增韧存在最佳条件.     

无甲醛聚合物胶粘剂的合成与应用研究

将尿素与两种活性化合物在一定条件下进行共缩聚反应,合成了尿素-化合物L-化合物R共缩聚(ULR)初期树脂。通过胶合板制造实验、力学性能测试以及甲醛释放量测试,初步探讨了ULR树脂作为胶粘剂应用于胶合板制造的可能性。结果表明:一定反应条件下,反应时间对ULR树脂的粘度影响不大;面粉添加量对ULR树脂胶接胶合板的胶合强度影响较大;当反应时间为120min、面粉添加量为15%时,ULR树脂胶接胶合板的胶合强度能够满足国家标准(≥0．7MPa),甲醛释放量接近0。因此,ULR树脂作为胶粘剂应用于胶合板制造是可行的。     

钢铁表面导电聚苯胺膜的制备

对Q195冷轧钢进行氟铁酸盐转化膜预处理,然后通过原位聚合反应在其表面成功制备墨绿色导电聚苯胺膜.采用扫描电镜和红外光谱分别对聚苯胺膜层的表面形貌的结构进行了表征,并通过极化曲线、中性盐雾试验对其耐腐蚀性进行了研究.结果表明,聚苯胺膜处于中间氧化态,导电聚苯胺膜使钢铁的腐蚀电位正移了49 mV,使钢铁的耐蚀性能明显提高...     

Synthesis, characterization and application of well-defined environmentally responsive polymer brushes on the surface of colloid particles

Well-defined poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) brushes with high density were synthesized on the surface of polystyrene latex by atom transfer radical polymerization (ATRP) using acetone/water as the solvent and CuCl/CuCl₂/bpy as the catalyst. It was found that the polydispersity of PDMAEMA brushes decreased with the increasing external CuCl₂ concentration. The polymer brushes showed their lower critical solution temperature (LCST) at 31 and 33 °C under pH values of 10.0 and 8.0, respectively. Dynamic light scattering studies demonstrate that PDMAEMA brushes were pH- and salt-responsive. PDMAEMA domains were used as the nanoreactors to generate gold nanoparticles on the surface of colloid particles. TEM results indicate that monodispersed gold nanoparticles were obtained. These gold composite nanoparticles displayed effective catalytic activity in the reduction of 4-nitrophenol by NaBH₄.     

Modification of high‐performance polymer composite through high‐energy radiation and low‐pressure plasma for aerospace and space applications

In this investigation, attempts are made to modify a high‐performance polymer such as polybenzimidazole (PBI) (service temperature ranges from ?260°C to +400°C) through high‐energy radiation and low‐pressure plasma to prepare composite with the same polymer. The PBI composites are prepared using an ultrahigh temperature resistant epoxy adhesive to join the two polymer sheets. The service temperature of this adhesive ranges from ?260°C to +370°C, and in addition, this adhesive has excellent resistance to most acids, alkalis, solvents, corrosive agents, radiation, and fire, making it extremely useful for aerospace and space applications. Prior to preparing the composite, the surface of the PBI is ultrasonically cleaned by acetone followed by its modification through high‐energy radiation for 6 h in the pool of a SLOWPOKE‐2 (safe low power critical experiment) nuclear reactor, which produces a mixed field of thermal and epithermal neutrons, energetic electrons, and protons, and γ‐rays, with a dose rate of 37 kGy/h and low‐pressure plasma through 13.56 MHz RF glow discharge for 120 s at 100 W of power using nitrogen as process gas, to essentially increase the surface energy of the polymer, leading to substantial improvement of its adhesion characteristics. Prior to joining, the polymer surfaces are characterized by estimating surface energy and electron spectroscopy for chemical analysis (ESCA). To determine the joint strength, tensile lap shear tests are performed according to ASTM D 5868–95 standard. Another set of experiments is carried out by exposing the low‐pressure plasma‐modified polymer joint under the SLOWPOKE‐2 nuclear for 6 h. Considerable increase in the joint strength is observed, when the polymer surface is modified by either high‐energy radiation or low‐pressure plasma. There is further significant increase in joint strength, when the polymer surface is first modified by low‐pressure plasma followed by exposing the joint under high‐energy radiation. To simulate with spatial conditions, the joints are exposed to cryogenic (?196°C) and high temperatures (+300°C) for 100 h. Then, tensile lap shear tests are carried out to determine the effects of these environments on the joint strength. It is observed that when these polymeric joints are exposed to these climatic conditions, the joints could retain their strength of about 95% of that of joints tested under ambient conditions. Finally, to understand the behavior of ultrahigh temperature resistant epoxy adhesive bonding of PBI, the fractured surfaces of the joints are examined by scanning electron microscope. It is observed that there is considerable interfacial failure in the case of unmodified polymer‐to‐polymer joint whereas surface‐modified polymer essentially fails cohesively within the adhesive. Therefore, this high‐performance polymer composite could be highly useful for structural applications in space and aerospace. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1959–1967, 2006     

Coagulation of polymer–Cu2+ complexes in polymer films and its application for producing semiconducting CuI surface layers

In poly(vinyl alcohol) and polyacrylamide films containing the corresponding polymer–Cu²⁺ complexes, the reason why the films may gain surface electrical semiconductivity as high as 10^?3 Ω^?1 when treated with acetone solution of iodine was investigated. Optical and scanning electron microscope observations indicated that the coagulated polymer–Cu²⁺ complexes favor the appearance of the high conductivity and that the state of coagulation depends on the anions of the copper salts used as well as two parameters, F₁ ≡ [Cu²⁺]/[MU] and F₂ ≡ [OH^?]/[Cu²⁺], where [MU] is the molar concentration of monomeric units of the polymer and [OH^?] is that of hydroxide ions added. The effectiveness of the anions in causing coagulation decreases in the order of SO₄^2? > Cl^? > NO₃^? ≈ Br^?. The whitish substance that appears on the film surface after the iodine treatment gives x-ray Debye–Scherrer rings characteristic of γ-CuI. The γ-CuI surface layer adheres to the film rather firmly, at least in polyacrylamide, and is responsible for the conductivity. By controlling the state of coagulation of the complexes and hence the formation of the γ-CuI surface layer, we have produced films with anisotropic surface electrical semiconductivity, i.e., σ_∥ ≈ 10^?4 Ω^?1 and σ_∥/σ_⊥ = 1 ? 10³. Optical and ESR spectra are also obtained to understand the mechanism of γ-CuI formation and to clarify the optical properties of the films.     

Synthesis and characterization of a polymer/multiwalled carbon nanotube composite and its application in the hydration of ethylene oxide

Multiwalled carbon nanotubes (MWNTs) were incorporated into the crosslinking network of a styrene–divinylbenzene copolymer (PS–DVB) via suspension polymerization. The prepared crosslinking PS–DVB with MWNTs was first treated with chloromethyl methyl ether to introduce chloromethyl groups through Friedel–Craft reaction; then, the chloromethylation product was reacted with trimethyl amine to obtain the target polymer/carbon nanotube composite: PS–DVB/MWNT ion‐exchange resin. The obtained composite was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy, and X‐ray photoelectron spectroscopy. The results show the successful incorporation of MWNTs into the polymer network. The physical and chemical properties of the PS–DVB/MWNT ion‐exchange resin were nearly the same as those of the controlled sample. With its excellent antiswelling properties, the catalytic behavior of the polymer composite was examined in the hydration of ethylene oxide. Also, it demonstrated excellent stability as a catalyst without a decline in conversion and selectivity in a long‐time run. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of phosphor coated with a polymer by emulsion polymerization and its application in low‐density polyethylene

The long‐afterglow phosphor SrAl₂O₄ : Eu²⁺, Dy³⁺ is liable to hydrolyze in water with deterioration of its luminescent properties. In this study, in situ emulsion polymerization was first used to prepare phosphor coated with poly(methyl methacrylate‐co‐butyl acrylate) [P(MMA‐co‐BA)] to improve water resistance. Fourier transform infrared spectra suggested that the polymer attached to the phosphor by chemical bonding. Observation by scanning electron microscopy (SEM) showed that a polymer layer formed on the surface of the phosphor. The resistance to water of the phosphor coated with the polymer layer was much better than that of the uncoated phosphor because the transparent polymer layer could suppress its hydrolysis process. Low‐density polyethylene (LDPE) plastics, doped with long‐afterglow phosphors, were manufactured with an extrusion technique. Through coating with P(MMA‐co‐BA), the compatibility of phosphor with the LDPE matrix was improved, as determined by SEM. The luminous LDPE plastics blended with the phosphor coated with polymer showed long and strong phosphorescence with little loss of persistence phosphorescence compared to the uncoated phosphor. The LDPE plastics still retained their mechanical properties through doping with 3% (mass fraction) of the phosphors. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008