Soft Lens Materials


Introduction

Soft contact lenses have had a massive impact on the global contact lens market since they became widely available in the early 1970s. Since their introduction, the number of soft contact lenses being prescribed around the world has steadily increased, and it is mainly the sale of soft contact lenses that is responsible for an industry that has been estimated to reach US$10 billion globally by 2025. A recent survey has indicated that soft lenses currently make up 87% of all contact lens refits worldwide ( ).

Saturation of the contact lens market with soft lenses has occurred primarily due to two reasons. First, soft lenses provide wearers with what they see as the two most important requirements for successful contact lens wear: good vision and comfort. The major obstacle as far as rigid lenses are concerned is generally accepted as being their lack of comfort and, in particular, their initial discomfort ( ). Second, advances in manufacturing technology have directed the industry towards disposable soft lenses.

Contact lens materials (both soft and rigid) are good examples of biomaterials. A biomaterial may be defined as a natural or synthetic material that is suitable for introduction into living tissues, especially as part of a medical device. The term encompasses a vast array of technologies, including tissue engineering, artificial organs, bioceramics, medical devices and implantable drug delivery systems. Contact lenses are classified as a medical device in most countries.

Very few of us are likely to get through life without having some kind of biomaterial introduced into our bodies. The most common examples include dental fillings, contact lenses, intraocular lenses, heart valves and stents. This list in itself highlights just how diverse biomaterials must be to satisfy their very specific end application; for example, a contact lens material has very different properties compared to a material used for dental fillings.

If a biomaterial is to be successful in its application, it follows that it must also be biocompatible. Biocompatibility refers to the ability of a material to perform with an appropriate host response in a specific application. An ‘appropriate host response’ includes not having toxic or injurious effects on biological systems. Biomaterials manufactured for use as contact lenses must not only satisfy all of these requirements for safe use within the eye but must also additionally have very specific characteristics, such as being transparent (and remain so on the eye), comfortable and relatively cheap to manufacture.

This chapter reviews the building blocks, properties and characteristics of the materials that are used to manufacture soft contact lenses and provides some of the history of development of these materials. Most clinicians are familiar with the United States Adopted Name (USAN) of a particular lens material (e.g. etafilcon A or lotrafilcon A), but any further understanding of the material is often lacking. This chapter aims to give meaning and background to these USAN names to help the reader understand and differentiate between different soft lens materials.

Polymers

All contact lens materials may be classified as polymers. The word ‘polymer’ is derived from ancient Greek, meaning: ‘many parts’. Polymers are solid materials (as opposed to gases or liquids) that are made up of high-molecular-weight chains (i.e. long chains), which in turn are made up from small repeating units. These repeating units are called monomers. Polymers are macromolecules (giant molecules) made from thousands of atoms. The term ‘polymer’ is therefore an umbrella term for materials that include plastics [e.g. polymethyl methacrylate (PMMA), used in the manufacture of ‘hard’ rigid lenses]; fibres (e.g. nylon); elastomers (i.e. rubbers such as silicone rubber); and the materials being discussed in this chapter, hydrogels.

The term ‘hydrogel’ is often used interchangeably with the term ‘soft’ when referring to contact lenses. Soft lenses are so named because they are made from water-swollen, cross-linked, hydrophilic polymers that are flexible and compliant. The term ‘hydrophilic’ is used to show that the networks from which these materials are made are ‘water-loving’.

The widespread use of polymers in many areas of our everyday lives has become a common and accepted phenomenon, so much so that they have been referred to as the ‘steel of the 21st century’. Polymers possess many properties that make them suitable for a wide range of applications, some of which are unique. These properties are in part due to the length of the molecules from which they are made. Additionally, polymers derive their unique characteristics from the ability of certain atoms to join together to form stable covalent bonds.

Many polymers are composed of hydrocarbons [i.e. carbon (C) and hydrogen (H) alone] such as polyethylene and polystyrene. However, even though the basic makeup of many polymers is carbon and hydrogen, other elements can also be present. Oxygen (O), nitrogen (N), chlorine (Cl), fluorine (F) and silicon (Si) are commonly found in the molecular makeup of polymers. Many polymers have carbon backbones (these are considered organic polymers), but some can incorporate silicon or phosphorous backbones (these are considered inorganic polymers).

The atoms making up a polymer and its geometric arrangement give each polymer its chemical distinctiveness and, thus, its particular use and function. Polymers themselves may be completely natural (e.g. cellulose), partly natural (e.g. cellulose acetate) or completely synthetic (e.g. PMMA). Most of the polymers used in the manufacture of soft contact lenses fall into this last category, i.e. they are man-made.

The Structure of Polymers

A polymer chain can be described by specifying the kind of repeating units present and their spatial arrangement. In this way, several broad categories of polymer can be described.

A homopolymer is one in which only one type of monomer is used, i.e. the units are chemically and stereochemically identical, with the exception of the end units. If the chain units are arranged in a linear sequence, the polymer is referred to as a linear homopolymer. This is shown schematically in Fig. 4.1 . Departures from this simple array lead to structures of increasing geometric complexity. A nonlinear or branched structure is shown in Fig. 4.2 .

Fig. 4.1, Linear homopolymer.

Fig. 4.2, Branched homopolymer.

The chemical differences between linear and branched polymers may be quite small; yet, because of the structural differences, the two polymers can have quite markedly different properties. A good example of these differences is found between low-density polyethylene (branched) and high-density polyethylene (linear). Low-density polyethylene is commonly used as a packaging film (e.g. cling film and for carrier bags), whereas high-density polyethylene is used for making pipes and durable plastic bottles because of its higher impact strength.

Nonlinear and network structures can also be prepared from a collection of linear chains by covalently linking together chain units selected from different molecules. Such a system is said to be cross-linked. This is shown schematically in Fig. 4.3 . Here, X represents the chemical species (the cross-linker) that covalently links together the A units from different molecular chains. When a sufficient number of units are intermolecularly cross-linked, an infinite network is formed. A cross-linker is an important ingredient in a soft contact lens monomer mix, which will be discussed later.

Fig. 4.3, Cross-linked system.

A copolymer is one in which more than one type of monomer is used. The properties of a copolymer not only depend on the chemical nature and amounts of the counits but also vary markedly on how the units are distributed along the chain. For linear copolymers, three ‘ideal’ arrangements can be described. The first is an alternating copolymer, which is shown in Fig. 4.4 . In this scenario, each monomer prefers to interact with a fellow monomer rather than itself.

Fig. 4.4, Alternating copolymer.

At the opposite extreme is the ordered or block copolymer, where there is an overwhelming tendency for a unit to be succeeded by another of the same kind. Here, long sequences of one type of unit alternate with long sequences of another kind ( Fig. 4.5 ).

Fig. 4.5, Block copolymer.

The third major classification is the random copolymer. Here, different units are randomly distributed along the chain ( Fig. 4.6 ).

Fig. 4.6, Random copolymer.

Departing from the restrictions of a linear array, branched copolymers, known as ‘graft polymers’, can also be prepared. The backbone of the molecule is composed of one type of unit, and the long side chains, or grafts, are made up of another. More sophisticated types of graft polymers have backbones made up of different repeating units and several distinctly chemically different side groups. This type of polymer is represented schematically in Fig. 4.7 .

Fig. 4.7, Graft copolymer.

One final important classification of polymers is into either amorphous or crystalline polymers (i.e. their macromolecular order) ( Fig. 4.8 ). Crystalline polymers have a geometrically regular structure and are generally stiff, resistant to chemicals, and tough. They have limited use as materials for contact lenses owing mainly to their poor optical qualities (i.e. they tend to be translucent or opaque). A good example of a semicrystalline polymer is polypropylene, which is often used to make casts in the cast-moulded manufacturing process of contact lenses.

Fig. 4.8, Schematic representation of macromolecular order showing an amorphous polymer (left) and a crystalline polymer (right) ( Kastl, Refojo, & Dabezies, 1984 ).

Amorphous polymers, on the other hand, do not have a regular structure. The polymer chains intermingle and are in random positions (imagine a pile of spaghetti on a plate), which often allow for these polymers to be transparent. Depending on their chain mobility, amorphous polymers can be classified as either ‘plastic’ or ‘glassy’ ( ).

Polymerization

The chemical reaction that monomers undergo to form long-chained polymers is known as polymerization. Broadly speaking, monomers can be chemically joined together in two ways: by step growth (condensation) and chain growth (addition) processes. Condensation polymers are produced by the reaction of monomeric units with each other, resulting in the elimination of a small molecule (e.g. water). However, hydrogels are generally formed through chain growth (addition) polymerization.

Before entering into the intricacies of polymerization, it is important to establish that to make a contact lens material, the following three basic ‘ingredients’ are required in the monomer ‘mix’: (1) the monomer(s), (2) a cross-linking agent and (3) an initiator. In some cases, a solvent is also added to the monomer mix. A solvent is used when lenses are manufactured by ‘wet casting’, where the solvent is gradually replaced with saline. If a solvent is not used, the manufacturing process is often referred to as ‘dry casting’ (i.e. the contact lens is cast as a xerogel).

The monomers used in chain polymerization are unsaturated and sometimes referred to as vinyl monomers. Essentially, this means that the monomer has one or more carbon-to-carbon double bonds. During the polymerization process, the monomer concentration decreases steadily with time, resulting in a reaction mixture that contains monomer, high-molar-mass polymer, and a low concentration of growing chains. Chain polymerization is characterized by three distinct stages: initiation, propagation, and termination.

Initiation

A hydrogel monomer mixture usually contains an initiator. This is a chemical whose role is to start the polymerization process. Initiators readily fragment into free radicals (a highly chemically reactive atom, molecule or molecular fragment with a free or unpaired electron) when activated by heat or some other form of radiation (e.g. ultraviolet light).

The type of initiator used depends on the manufacturing method. For example, a thermal initiator is usually required in the manufacture of buttons or rods that eventually form lathed lenses, and a photoinitiator is usually required for spun-cast and cast-moulded lenses.

The fragmentation of the initiator is schematically represented by the following equation, where I represents the initiator molecule and I represents a free radical.


I I Δ 2 I

The free radicals formed are then able to combine with the monomer (M), resulting in a free radical of the monomer (this is why the polymerization of hydrogels is sometimes referred to as free radical polymerization).


I + M I M

Propagation

The monomer radical, which is a transient compound, is now able to combine with another monomer unit, resulting in another new compound


I M + M I M M

By the continuation of this process, the polymer chain is propagated. The resultant chain may consist of thousands of monomer units


I M n + M I M ( n + 1)

Termination

Polymerization does not usually continue until all of the monomer has been used up because the free radicals involved are so reactive that they inevitably find a variety of ways of losing their reactivity. Polymerization can be terminated in two main ways. The first method is recombination. This occurs when two growing molecules containing free radicals meet, share their unpaired electrons and form a stable covalent bond, thereby extinguishing their reactivity. The second method of termination is known as disproportionation. This occurs when two radicals interact via hydrogen abstraction, leading to the formation of two reaction products, one of which is saturated and the other unsaturated.

The conditions under which polymerization takes place become important when one considers that soft contact lenses can be made using three main methods of manufacture: lathing, spin casting and cast moulding; however, cast moulding is by far the most commonly used method. Lenses made by these different methods of manufacture undergo very different polymerization conditions that are likely to have an effect on the resultant material. How a material is processed is likely to affect almost every aspect of a lens, from its clinical performance to its physical and chemical properties ( ).

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