Polyurethane

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A polyurethane is any polymer consisting of a chain of organic units joined by urethane links. It is widely used in flexible and rigid foams, durable elastomers and high performance adhesives and sealants, fibers, seals, gaskets, condoms, carpet underlay, and hard plastic parts. Polyurethane products are often called "urethanes". They should not be confused with the specific substance urethane, also known as ethyl carbamate. Polyurethanes are not produced from ethyl carbamate, nor do they contain it.

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[edit] Production

The main polyurethane producing reaction is between a diisocyanate (aromatic and aliphatic types are available) and a polyol, typically a polyethylene glycol or polyester polyol, in the presence of catalysts and materials for controlling the cell structure, (surfactants) in the case of foams. Polyurethane can be made in a variety of densities and hardnesses by varying the type of monomer(s) used and adding other substances to modify their characteristics, notably density, or enhance their performance. Other additives can be used to improve the fire performance, stability in difficult chemical environments and other properties of the polyurethane products.

Though the properties of the polyurethane are determined mainly by the choice of polyol, the diisocyanate exerts some influence. The cure rate is influenced by the functional group reactivity and the number of functional isocyanate groups. The mechanical properties are influenced by the functionality and the molecular shape. The choice of diisocyanate also affects the stability of the polyurethane upon exposure to light. Polyurethanes made with aromatic diisocyanates yellow with exposure to light, whereas those made with aliphatic diisocyanates are stable.[1]

Softer, elastic, and more flexible polyurethanes result when linear difunctional polyethylene glycol segments, commonly called polyether polyols, are used to create the urethane links. This strategy is used to make spandex elastomeric fibers and soft rubber parts, as well as foam rubber. More rigid products result if polyfunctional polyols are used, as these create a three-dimensional cross-linked structure which, again, can be in the form of a low-density foam.

An even more rigid foam can be made with the use of specialty trimerization catalysts which create cyclic structures within the foam matrix, giving a harder, more thermally stable structure, designated as polyisocyanurate foams. Such properties are desired in rigid foam products used in the construction sector.

Polyurethane foam (including foam rubber) is usually made by adding small amounts of volatile materials, so-called blowing agents, to the reaction mixture. These can be simple volatile chemicals such as acetone or methylene chloride, or more sophisticated fluorocarbons which yield important performance characteristics, primarily thermal insulation.

Another common route to produce foams is the addition of water to one of the liquid precursors of polyurethane before they are mixed together. This reacts with a portion of the isocyanate, generating carbon dioxide throughout the liquid, creating relatively uniform bubbles which then harden to form a solid foam as polymerization progresses.

The presence of water means that a small proportion of reactions result in urea linkages —NC(=O)N—, rather than urethane linkages, so that the resulting material should technically be called poly(urethane-co-urea).

Careful control of viscoelastic properties — by modifying the catalysts and polyols used —can lead to memory foam, which is much softer at skin temperature than at room temperature.

There are then two main foam variants: one in which most of the foam bubbles (cells) remain closed, and the gas(es) remains trapped, the other being systems which have mostly open cells, resulting after a critical stage in the foam-making process (if cells did not form, or became open too soon, foam would not be created). This is a vitally important process: if the flexible foams have closed cells, their softness is severely compromised, they become pneumatic in feel, rather than soft; so, generally speaking, flexible foams are required to be open-celled.

The opposite is the case with most rigid foams. Here, retention of the cell gas is desired since this gas (especially the fluorocarbons referred to above) gives the foams their key characteristic: high thermal insulation performance.

A third foam variant, called microcellular foam, yields the tough elastomeric materials typically experienced in the coverings of car steering wheels and other interior automotive components.

[edit] Uses

Polyurethane products have many uses. Over three quarters of the global consumption of polyurethane products is in the form of foams, with flexible and rigid types being roughly equal in market size. In both cases, the foam is usually behind other materials: flexible foams are behind upholstery fabrics in commercial and domestic furniture; rigid foams are inside the metal and plastic walls of most refrigerators and freezers, or behind paper, metals and other surface materials in the case of thermal insulation panels in the construction sector. Its use in garments is growing: for example, in lining the cups of brassieres.

The precursors of expanding polyurethane foam are available in many forms, for use in insulation, sound deadening, flotation, packing material, and even cast-in-place upholstery padding. Since they adhere to most surfaces and automatically fill voids, they have become quite popular in these applications.

[edit] Varnish

Polyurethane materials are commonly formulated as paints and varnishes for finishing coats to protect or seal wood. This use results in a hard, abrasion-resistant, and durable coating that is popular for hardwood floors, but considered by some to be difficult or unsuitable for finishing furniture or other detailed pieces. Relative to oil or shellac varnishes, polyurethane varnish forms a harder film which tends to de-laminate if subjected to heat or shock, fracturing the film and leaving white patches. This tendency increases when it is applied over softer woods like pine. This is also in part due to polyurethane's lesser penetration into the wood. Various priming techniques are employed to overcome this problem, including the use of certain oil varnishes, specified "dewaxed" shellac, clear penetrating epoxy, or "oil-modified" polyurethane designed for the purpose. Polyurethane varnish may also lack the "hand-rubbed" lustre of drying oils such as linseed or tung oil; in contrast, however, it is capable of a much faster and higher "build" of film, accomplishing in two coats what may require multiple applications of oil. Polyurethane may also be applied over a straight oil finish, but because of the relatively slow curing time of oils, the presence of volatile byproducts of curing, and the need for extended exposure of the oil to oxygen, care must be taken that the oils are sufficiently cured to accept the polyurethane.

Unlike drying oils and alkyds which cure, after evaporation of the solvent, upon reaction with oxygen from the air, polyurethane coatings cure after evaporation of the solvent by a variety of reactions of chemicals within the original mix, or by reaction with moisture from the air. Certain products are "hybrids" and combine different aspects of their parent components. "Oil-modified" polyurethanes, whether water-borne or solvent-borne, are currently the most widely used wood floor finishes.

Exterior use of polyurethane varnish may be problematic due to its susceptibility to deterioration through ultra-violet light exposure. It must be noted, however, that all clear or transluscent varnishes, and indeed all film-polymer coatings (i.e.paint, stain, epoxy, synthetic plastic, etc.) are susceptible to this damage in varying degrees. Pigments in paints and stains protect against UV damage, while UV-absorbers are added to polyurethane and other varnishes (in particular "spar" varnish) to work against UV damage. Polyurethanes are typically the most resistant to water exposure, high humidity, temperature extremes, and fungus or mildew, which also adversely affect varnish and paint performance.

[edit] Computer mouse pads

Polyurethane is used on the bottom of some mouse pads.

[edit] Glue

Polyurethane is used as an adhesive, especially as a woodworking glue. Its main advantage over more traditional wood glues is its water resistance. It was introduced in the general North American market in the 1990s as Gorilla Glue and Excel, but has been used much longer in Europe. As an adhesive, polyurethane is also used to glue windshields into automobiles.

[edit] Wheels

Polyurethane is also used in making solid tires. Modern roller blading and skateboarding became economical only with the introduction of tough, abrasion-resistant polyurethane parts. Other constructions have been developed for pneumatic tires, and microcellular foam variants are widely used in tires on wheelchairs, bicycles and other such uses. These latter foam types are also widely encountered in car steering wheels and other interior and exterior automotive parts, including bumpers and fenders.

[edit] Furniture

Polyurethane is also used in furniture manufacture for casting soft edges around table tops and panel that are stylish, very durable and prevent injury. These are used in school tables, hospital and bank furniture as well as shop counters and displays.

Much of the foam used in chairs, couchs and mattresses is polyurethane foam. This type of foam is made by mixing polyols, diisocyanates, catalysts, blowing agents and other additives and allowing the resulting foam to rise freely. This can be done in a batch process where relatively small blocks of foam are made in an open-topped mold, or continuously where the components are poured onto an inclined moving belt. The foam is then cut to the desired shape and size for use in making furniture.

Safety concerns about the flammability of polyurethane foam, particularly in upholstered furniture, sometimes requires the addition of flame retardants to this foam.

[edit] Automobile seats

Flexible and semi-flexible polyurethane foams are used extensively for interior components of automobiles, in seats, headrests, armrests, roof liners and instrument panels.

Polyurethanes are used to make automobile seats in a remarkable manner. The seat manufacturer has a mold for each seat model. The mold is a closeable "clamshell" sort of structure that will allow quick casting of the seat cushion, so-called molded flexible foam, which is then upholstered after removal from the mold.

It is possible to combine these two steps, so-called in-situ, foam-in-fabric or direct moulding. In this case, the inner surfaces of the mold have hundreds of small holes that all connect to a vacuum manifold. This creates a constant air flow from the core of the mold to the manifold. The assembly operator first places a complete, fully-assembled seat cover in the mold and adjusts it so that the vacuum in the manifold pulls the seat cover snugly against the mold surface. In some operations, this effect is improved by adding a thin pliable plastic film as a backing to the fabric to help the vacuum work more effectively. When the seat cover is in place, the operator then places the metal frame of the seat into the mold and closes the mold. At this point the mold contains what could be visualized as a "hollow seat", a seat fabric held in the correct position by the vacuum manifold and containing a hollow space with the metal frame in place.

The next step is to inject the polyurethane chemical mixture into the mold cavity. This is a two-part mixture that is metered exactly through a mixing head. Then the mold is held at a preset reaction temperature until the chemical mixture has foamed, filled the mold, and formed a stable soft foam. The time required is about two to three minutes, depending on the size of the seat and the precise formulation and operating conditions. Then the mold is usually opened slightly for a minute or two for an additional cure time, before the fully upholstered seat is removed. The operator then trims any excess seat cover fabric and puts the finished seat onto a conveyor.

[edit] Houses, sculptures, and decorations

The walls and ceiling (not just the insulation) of the futuristic Xanadu House were built out of polyurethane foam. Domed ceilings and other odd shapes are easier to make with foam than with wood. Foam was used to build oddly-shaped buildings, statues, and decorations in the Seuss Landing section of the Islands of Adventure theme park. Speciaty rigid foam manufactures sell foam that replace wood in carved sign and 3D topography industries .

[edit] Watercraft

Some surfboards are made with a solid polyurethane core.

The hull of the Boston Whaler motor boat is polyurethane foam sandwiched in a fiberglass skin. The foam provides strength, buoyancy, and sound deadening.

[edit] Construction sealants and firestopping

Head-of-Wall Firestop Joint: the presence of penetrants demonstrates the need to have both operational and fire-tested compatibility between the joint sealant and mechanical/electrical through-penetrations. In other words, it is easier to insist on the use of joint firestops that can also be used for penetration seals, as otherwise penetrants may be run by mechanical and electrical subtrades that unintentionally void the fire-resistance rating of the wall, which jeopardises the entire fire safety plan in place for a building.
Head-of-Wall Firestop Joint: the presence of penetrants demonstrates the need to have both operational and fire-tested compatibility between the joint sealant and mechanical/electrical through-penetrations. In other words, it is easier to insist on the use of joint firestops that can also be used for penetration seals, as otherwise penetrants may be run by mechanical and electrical subtrades that unintentionally void the fire-resistance rating of the wall, which jeopardises the entire fire safety plan in place for a building.
Head-of-Wall Firestop Joint penetrated by both electrical and mechanical services, demonstrating the need for operational and fire-tested compatibility between the joint firestop system and penetrants, be they electrical, mechanical or structural.
Head-of-Wall Firestop Joint penetrated by both electrical and mechanical services, demonstrating the need for operational and fire-tested compatibility between the joint firestop system and penetrants, be they electrical, mechanical or structural.

Polyurethane sealants are available in 1, 2 and even 3 part systems, either in cartridge, bucket or drum format. The major (though not exclusive) supplier of construction urethanes in the U.S. is Tremco, of Cleveland, Ohio. A version of their Polyurethane sealant is also sold for firestopping applications. Obviously, the sealant by itself provides no serious hindrance to fire, as its hydrocarbon bonds readily support combustion. However, when backed by inorganic insulation, such as rockwool or ceramic fibres, it can act as an effective seal to thwart smoke and hose-stream passage, particularly in inorganic joints. It is, however, advisable to avoid direct contact with metallic penetrants and through-penetrating cables, as the heat carried by the penetrants may jeopardise the sealant. This, however, requires a lot of vigilance. In concrete to concrete, or concrete to masonry joints, however, that are free of mechanical or electrical penetrants, it works well and dependably. As with all passive fire protection products and systems, the key to code compliance is demonstrable bounding.

[edit] Tennis Grips

Polyurethane has been used to make several Tennis Overgrips such as Yonex Supergrap, Wilson Pro Overgrip and many other grips. These grips are highly stretchable to ensure the grip wraps neatly around the racquet's handle.

[edit] Electronic Components

Often electronic components are protected from environmental influence and mechanical shock by enclosing them in polyurethane. Typically polyurethanes are selected for the excellent abrasion resistances, good electrical properties, excellent adhesion, impact strength,and low temperature flexibility. The disadvantage of polyurethanes is the limited upper service temperature (typically 250 F). In production the electronic manufacture would purchase a two part urethane (resin and catalyst) that would be mixed and poured onto the circuit assembly (see Resin casting). In most cases, the final circuit board assembly would be unrepairable after the urethane has cured. Because of its physical properties and low cost, polyurethane encapsulation (potting) is a popular option in the automotive manufacturing sector for automotive circuits and sensors.

[edit] See also

[edit] References

  1. ^ Randall, David; Lee, Steve (2002). The Polyurethanes Book. New York: Wiley. ISBN 0-470-85041-8. 

[edit] External links