Polyethylene surface grafting

During the last few years, new developments in polymer photochemistry have made it possible to graft various functional monomers onto surfaces of inert polymers like polyethylene, polypropylene and polyethyleneterephthalate. In the first attempts, initiator and monomer were transferred in vapor phase into a "UV Cure" irradiator containing the polymer sheet to be surface grafted. 

UV light in a second step. In later work reported by Tazuke, Kimura et al. (6-8) successful photograftings on the polymer surface of thin films (polyethylene, polypropylene and polystyrene) were achieved with various monomers. In this work, grafting was induced by UV irradiation through the film which was in contact with a solution containing initiator and monomer. The method is slow and - in addition to surface grafting - large amounts of homopolymer are formed. 

Figure 4. Kinetics of surface grafting of polyethylene (PE) and polypropylene (PP) films with acrylamide (AM) by the vapor phase method measured as light absorption at 600 nm after dipping in an aqueous solution of crystal violet (CV).

Polyester film surface detailed ESC A spectrum, 181/ kinetics of surface grafting, 182 wide-scan ESC A spectra, 179/ Polyethylene... 

Polyethylene film kinetics of surface grafting, 174/ surface grafting, 178/... 

Polyethylene split film ESCA spectra, 183/ kinetics of surface grafting with acrylonitrile, 184/... 

Surface grafting of chemical species to improve the chemical bonding. Can be helped by simultaneous gamma or other irradiation. It is particularly used for polyethylene. 

A similar approach was used in grafting Cjq onto a pregenerated lithiated polyethylene surface [121]. A polyethylene film with terminal diphenylmethyl groups was deprotonated with BuLi to yield an anionic polyethylene surface that was treated with Cg0 and quenched with methanol. The incorporation at the polyethylene surface was determined by XPS, UV/Vis and fluorescence spectroscopy. This reaction also works for polyisopropene, polybutadiene [69], poly(vinylbenzyl chloride) or poly(N-vinylcarbazole) PVK [54] with BuLi or NaH as a base. Charge-transfer interactions in the soluble fullerene-PVK derivative between the positively charged carbazole and Cjq lead to an enhanced photoconductivity compared with PVK [54]. 

Fig. 25a and b. A protein resistant surface based on the steric repulsion argument commonly used in the colloid stability field U0). The interaction between a polyethylene oxide grafted surface and a protein solution is shown, a. suggests an excluded volume or steric repulsion mechanism b. the surface dynamics or polymer chain motion mechanism (from Ref., 33))... 

Keywords Polyethylene Surface modification Characterisation Grafting Radiation... 

Fig. 8 Concept of simultaneous microbe repulsion and biocide release of a specifically designed network. The network is composed of poly(2-hydroxyethylacrylate) crosslinked with polyethyleneimine and surface-grafted with polyethylene glycol. The polyethyleneimine junctions take up silver ions, which then form nanoparticles due to the template character of these nanocontainers. Reproduced and adapted from [90]...

Peroxidases belong to the class of oxidoreductases containing iron (111) and protoporphyrin IX as the prosthetic groups. Peroxidases catalyze the reduction of peroxides and the oxidation of many organic and inorganic compounds. These enzymes are widely used for the removal of phenolic compounds, decolorization of synthetic dyes, deodorization of swine manure, in enzyme immunoassays, for biofuel production and organic and polymer synthesis (Hamid and Rehman, 2009). Peroxidases have also been used for the surface modification of poly-p-phenylene-2,6-benzo-bisthiazole (PBO), polyethylene, and grafting of acrylamide onto kevlar fibers. 

An elegant example of the analysis of colloid surfaces containing covalently attached hydrophilic species has been provided by Brindley et al who studied the surface chemistry of polystyrene colloids with surface grafted polyethylene glycol groups [39]. These colloids were prepared by surfactant-free copolymerization of styrene with PEG using potassium persulphate as an initiator. The XPS analysis of these microparticles is shown in Fig. 11. 

Fig. 3.9 The topography of water-soluble surface-graft 2-(dimethylamino)ethyl methacrylate chains on a polyethylene terephthalate) film imaged by CM-AFM. Reproduced with permission from [23]. Copyright 1997. American Chemical Society...

Wilson, at Bishop College, and Eberhart and Elkowitz at University of Texas (27) have irradiated a silicone substrate in the presence of chloromethylstyrene monomer to produce a reactive graft polymer that can be quarternized with pyridine and reacted with sodium heparin to produce a thromboresistant heparinized product that has a higher blood compatibility than the untreated silicone. The same group has used essentially the same methods to create a heparin grafted polyethylene surface. 

However, in spite of these similarities, the adsorbed amounts and the structure of the adsorbed mucin and collagen layers on the surfaces studied are entirely different. The behavior of these proteins is analyzed here on the hydrophobic polyethylene surface (water contact angle 0 20 95°), on the surface modified polyethy-lenes oxidized polyethylene (0h q 74°) and poly(maleic acid) grafted polyethylene ( Ho0 74°) a d on the hydrophilic mica surface ( H2 0 0°) Acidic pH = 2.75 (for collagen) and slightly alkaline pH = 7.2 (for mucin) were chosen in order to minimize the association of these proteins in solution and to make possible the analysis of their adsorbabilities in comparable conditions. 

The surface density/solution concentration isotherms, not shown in this paper, reflect also the differences in the behavior of mucin and collagen upon their adsorption at solid interfaces. While the collagen isotherms on polyethylene and surface-grafted polyethylene show a plateau of adsorption at solution concentrations higher than 0.05 mg/ml, no plateau values for mucin adsorption are observed on polyethylene and surface oxidized polyethylene. 

Non-cross-linked polymers can be used in this way just as cross-linked polymers can. For example, we have used polyethylene supports with surface grafts to support Pd(0) catalysts [133,134]. In these cases, the polymer-immobilized catalyst is used in exactly the same way as an insoluble polymer-bound catalyst. Such supported catalysts do require that the insoluble polymer be swollen or permeable to substrates or that the catalysts be within a solvent-permeable, thin immobilized graft. While this approach can be useful, it takes no advantage of the polymer s solubility. It is an approach that conceptually is no different than that used with insoluble inorganic supports or with polymers that are by design insoluble by virtue of cross-linking, and is an approach to catalyst immobilization that is not further discussed since this review is focused on polymer-immobilized catalysts that are used under solution-state conditions. 

Low-density polyethylene (LDPE) is commonly used biomaterial which possesses fairly good grafting reactivity compared to other common polymeric materials. A number of plasma modification and plasma polymerization systems have been employed in order to incorporated oxygen-containing functional groups onto polyethylene surfaces for biomaterial applications. i Tiie aim of this work was to introduce acidic sulfur-containing functional groups onto LDPE surfaces by plasma treatment and to assess the potential blood compatibility of the modified materials. 

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