Acrylic acid-based ionomers

This versatile technique is generally used where a ply of polyethylene or copolymer thereof is required in a structure. Other polymers may be used in specialized areas but the handling can become more difficult. The process is widely used within the Packaging Industry for the coating of paper, board, foils, cellulose film and thermoplastic films. The most common coating resin used is low-density polyethylene, but this now extends to copolymers such as Ethylene-vinyl acetate, ethylene-acrylic acid, polypropylene, high density polyethylene and ionomers (e.g. Surlyn). The acrylic acid-based materials and ionomers are used in areas in which enhanced adhesive strength is required, such as resistance to difficult environments. 

Ionomer resins consisting of ethylene—methacrylic acid copolymers partially neutralized with sodium or zinc were commercially introduced in 1964 by Du Pont under the Sudyn trademark (1). More recently, a similar line of products, sold as Hi-Mdan resins, has been commercialized by Mitsui—Du Pont in Japan. lolon ionomeric resins, based on ethylene—acrylic acid, are produced by Exxon in Belgium. Ionomers containing about 1 mol % of carboxylate groups are offered by BP in Europe as Novex resins. Low molecular weight, waxy Aclyn ionomers are produced and sold by AHiedSignal. 

In nonrigid ionomers, such as elastomers in which the Tg is situated below ambient temperature, even greater changes can be produced in tensile properties by increase of ion content. As one example, it has been found that in K-salts of a block copolymer, based on butyl acrylate and sulfonated polystyrene, both the tensile strength and the toughness show a dramatic increase as the ion content is raised to about 6 mol% [10]. Also, in Zn-salts of a butyl acrylate/acrylic acid polymer, the tensile strength as a function of the acrylic acid content was observed to rise from a low value of about 3 MPa for the acid copolymer to a maximum value of about 15 MPa for the ionomer having acrylic acid content of 5 wt% [II]. Other examples of the influence of ion content on mechanical properties of ionomers are cited in a recent review article [7],... 

A variety of ionomers have been described in the research literature, including copolymers of a) styrene with acrylic acid, b) ethyl acrylate with methacrylic acid, and (c) ethylene with methacrylic acid. A relatively recent development has been that of fluorinated sulfonate ionomers known as Nafions, a trade name of the Du Pont company. These ionomers have the general structure illustrated (10.1) and are used commercially as membranes. These ionomers are made by copolymerisation of the hydrocarbon or fluorocarbon monomers with minor amounts of the appropriate acid or ester. Copolymerisation is followed by either neutralisation or hydrolysis with a base, a process that may be carried out either in solution or in the melt. 

Polyelectrolytes are polymers having a multiplicity of ionizable groups. In solution, they dissociate into polyions (or macroions) and small ions of the opposite charge, known as counterions. The polyelectrolytes of interest in this book are those where the polyion is an anion and the counterions are cations. Some typical anionic polyelectrolytes are depicted in Figure 4.1. Of principal interest are the homopolymers of acrylic acid and its copolymers with e.g. itaconic and maleic adds. These are used in the zinc polycarboxylate cement of Smith (1968) and the glass-ionomer cement of Wilson Kent (1971). More recently, Wilson Ellis (1989) and Ellis Wilson (1990) have described cements based on polyphosphonic adds. 

Here we report the synthesis of inorganic tin II and tin IV ionomers based on a copolymer of ethylene and acrylic acid. 

Despite tlte broad scope of the held and the unusual property combinations obtainable, commercial exploitation has been confined mainly to the original family based on ethylene copolymers. Within certain industries, such as llexihle packaging, the word ionomer is understood to mean a copolymer of ethylene with methacrylic or acrylic acid, partly neutralized with sodium or zinc. 

Within the scope of the original definition, a very wide variety of ionomers can be obtained by the introduction of acidic groups at molar concentrations below 10% into the important addition polymer families., followed by partial neutralization with metal cations or amines. Extensive studies have been reported, and useful reviews of the polymers have appeared (3—8). Despite the broad scope of the field and the unusual property combinations obtainable, commercial exploitation has been confined mainly to the original family based on ethylene copolymers. The reasons for this situation have been discussed (9). Within certain industries, such as flexible packaging, the word ionomer is understood to mean a copolymer of ethylene with methacrylic or acrylic acid, partly neutralized with sodium or zinc. 

Composite resins consist of blends of large monomer molecules, filled with unre-active reinforcing filler. As such, they are hydrophobic, which means that they are unable to bond to the hydrophilic prepared tooth surface [1]. Glass-ionomer cements, by contrast, consist of aqueous solutions of polymeric acid, typically poly(acrylic add) and powdered reactive glass. These two components react together in an acid-base reaction, and thus cause the cement to set. These materials are hydrophilic, and therefore capable of wetting the prepared tooth surface and forming tme adhesive bonds. 

Glass-ionomer cements, which harden not by polymerization, but by the acid-base reaction between an aqueous polyelectrolyte (poly(acrylic acid) or related co-polymers) and a basic fluoro-aluminosilicate (FAS) glass. These materials are not as tough as resin composites, but they chemieally adhere to tooth tissue and are capable of releasing fluoride ions. 

The grafting functionalization of a poly(vinylidene fluoride) powder by y-irradiation was achieved by Valenza et aL The amoimt of grafted meth-acrylic acid onto poly(vinylidene fluoride) (PVDF) powder was 19.7 w%. The grafted polymer was then blended at different ratios with an ionomer based on ethylene-methacrylic acid copolymer, partially neutralized (Surlyn 9970). Nongrafted PVDF and this ionomer are highly immiscible. The functionalization of the PVDF with methacrylic acid allows to compatibilize both... 

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