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Polyurethane synthesis, wherein the urethane groups — NH-(C=O)-O- link the molecular units.

A polyurethane (PUR and PU) is polymer composed of a chain of organic units joined by carbamate (urethane) links. Polyurethane polymers are formed by combining two bi- or higher functional monomers. One contains two or more isocyanate functional groups and the other contains two or more hydroxyl groups. More complicated monomers are also used. The alcohol and the isocyanate groups combine to form a urethane linkage:

ROH + R'NCO → ROC(O)N(H)R' (R and R' are alkyl or aryl groups)

This combining process, sometimes called condensation, typically requires the presence of a catalyst.

Polyurethanes are used in the manufacture of flexible, high-resilience foam seating; rigid foam insulation panels; microcellular foam seals and gaskets; durable elastomeric wheels and tires; automotive suspension bushings; electrical potting compounds; high performance adhesives; surface coatings and surface sealants; synthetic fibers (e.g., Spandex); carpet underlay; and hard-plastic parts (i.e., for electronic instruments). Polyurethane is also used for the manufacture of hoses and skateboard wheels as it combines the best properties of both rubber and plastic.

History[link]

The pioneering on polyurethane polymers was conducted by Otto Bayer and his coworkers in 1937 at the laboratories of I.G. Farben in Leverkusen, Germany.^[1] They recognized that using the polyaddition principle to produce polyurethanes from liquid diisocyanates and liquid polyether or polyester diols seemed to point to special opportunities, especially when compared to already existing plastics that were made by polymerizing olefins, or by polycondensation. The new monomer combination also circumvented existing patents obtained by Wallace Carothers on polyesters.^[2] Initially, work focused on the production of fibres and flexible foams. With development constrained by World War II (when PUs were applied on a limited scale as aircraft coating^[2]), it was not until 1952 that polyisocyanates became commercially available. Commercial production of flexible polyurethane foam began in 1954, based on toluene diisocyanate (TDI) and polyester polyols. These materials were also used to produce rigid foams, gum rubber, and elastomers. Linear fibers were produced from hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO).

The first commercially available polyether polyol, poly(tetramethylene ether) glycol, was introduced by DuPont in 1956 by polymerizing tetrahydrofuran. Less expensive polyalkylene glycols were introduced by BASF and Dow Chemical in 1957. Polyether polyols offered technical and commercial advantages such as low cost, ease of handling, and better hydrolytic stability over polyester polyols and quickly replaced them in the manufacture of polyurethane goods. Other PU pioneers were Union Carbide and Mobay, a U.S. Monsanto/Bayer joint venture.^[2] In 1960 more than 45,000 metric tons of flexible polyurethane foams were produced. As the decade progressed, the availability of chlorofluoroalkane blowing agents, inexpensive polyether polyols, and methylene diphenyl diisocyanate (MDI) heralded the development and use of polyurethane rigid foams as high performance insulation materials. Rigid foams based on polymeric MDI (PMDI) offered better thermal stability and combustion characteristics than those based on TDI. In 1967, urethane modified polyisocyanurate rigid foams were introduced, offering even better thermal stability and flammability resistance compared to low-density insulation products. During the 1960s, automotive interior safety components such as instrument and door panels were produced by back-filling thermoplastic skins with semi-rigid foam.

In 1969, Bayer exhibited an all plastic car in Düsseldorf, Germany. Parts of this car were manufactured using a new process called RIM, Reaction Injection Molding. RIM technology uses high pressure impingement of liquid reactive components followed by the rapid flow of the reaction mixture into a mold cavity. Large parts, such as automotive fascia and body panels, can be molded in this manner. Polyurethane RIM evolved into a number of different products and processes. Using diamine chain extenders and trimerization technology gave poly(urethane urea), poly(urethane isocyanurate), and polyurea RIM. The addition of fillers, such as milled glass, mica, and processed mineral fibres gave rise to reinforced RIM (RRIM), which provided improvements in flexural modulus (stiffness), reduction in coefficient of thermal expansion and thermal stability. This technology allowed production of the first plastic-body automobile in the United States, the Pontiac Fiero, in 1983. Further increases in flexural modulus were obtained by incorporating pre-placed glass mats into the RIM mold cavity, also known broadly as resin injection molding (a process technology that also includes thermosetting polyester resins, epoxide resins, etc.) or more specifically for PUR systems as SRIM, or structural RIM.

Starting in the early 1980s, water-blown microcellular flexible foams were used to mold gaskets for panel and radial seal air filters in the automotive industry. Since then, increasing energy prices and the pressures to eliminate PVC plastisol from automotive applications have greatly increased market share. Costlier raw materials are offset by a significant decrease in part weight and in some cases, the elimination of metal end caps and filter housings. Highly filled polyurethane elastomers, and more recently unfilled polyurethane foams are now used in high temperature oil filter applications.

Polyurethane foam (including foam rubber) is often made by adding small amounts of volatile materials, so-called blowing agents, to the reaction mixture. These volatile chemicals yield important performance characteristics, primarily density reduction, cushioning/energy absorption and thermal insulation. In the early 1990s, because of their impact on ozone depletion, the Montreal Protocol led to the greatly reduced use of many chlorine-containing blowing agents, such as trichlorofluoromethane (CFC-11). Other haloalkanes, such as the hydrochlorofluorocarbon 1,1-dichloro-1-fluoroethane (HCFC-141b), were used as interim replacements until their phase out under the Integrated Pollution Prevention and Control (IPPC) directive on greenhouse gases in 1994 and by the Volatile Organic Compounds (VOC) directive of the EU in 1997 (See: Haloalkanes). By the late 1990s, the use of blowing agents such as carbon dioxide, pentane, 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) became more widespread in North America and the EU, although chlorinated blowing agents remained in use in many developing countries.^[3]

Building on existing polyurethane spray coating technology and polyetheramine chemistry, extensive development of two-component polyurea spray elastomers took place in the 1990s. Their fast reactivity and relative insensitivity to moisture make them useful coatings for large surface area projects, such as secondary containment, manhole and tunnel coatings, and tank liners. Excellent adhesion to concrete and steel is obtained with the proper surface treatment and primer. During the same period, new two-component polyurethane and hybrid polyurethane-polyurea elastomer technology was used to enter the marketplace of spray-in-place load bed liners and military marine applications for the U.S. Navy. A one-part polyurethane is specified as high durability deck coatings under MIL-PRF-32171^[4] for the US Navy. This technique for coating creates a durable, abrasion resistant composite with the metal substrate, and eliminates corrosion and brittleness associated with drop-in thermoplastic bed liners.

Chemistry[link]

generalized polyurethane reaction

Polyurethanes are in the class of compounds called reaction polymers, which include epoxies, unsaturated polyesters, and phenolics.^{[5][6][7][8][9]} A urethane linkage is produced by reacting an isocyanate group, -N=C=O with a hydroxyl (alcohol) group, -OH. Polyurethanes are produced by the polyaddition reaction of a polyisocyanate with a polyalcohol (polyol) in the presence of a catalyst and other additives. In this case, a polyisocyanate is a molecule with two or more isocyanate functional groups, R-(N=C=O)_{n ≥ 2} and a polyol is a molecule with two or more hydroxyl functional groups, R'-(OH)_{n ≥ 2}. The reaction product is a polymer containing the urethane linkage, -RNHCOOR'-. Isocyanates will react with any molecule that contains an active hydrogen. Importantly, isocyanates react with water to form a urea linkage and carbon dioxide gas; they also react with polyetheramines to form polyureas. Commercially, polyurethanes are produced by reacting a liquid isocyanate with a liquid blend of polyols, catalyst, and other additives. These two components are referred to as a polyurethane system, or simply a system. The isocyanate is commonly referred to in North America as the 'A-side' or just the 'iso'. The blend of polyols and other additives is commonly referred to as the 'B-side' or as the 'poly'. This mixture might also be called a 'resin' or 'resin blend'. In Europe the meanings for 'A-side' and 'B-side' are reversed. Resin blend additives may include chain extenders, cross linkers, surfactants, flame retardants, blowing agents, pigments, and fillers.

The first essential component of a polyurethane polymer is the isocyanate. Molecules that contain two isocyanate groups are called diisocyanates. These molecules are also referred to as monomers or monomer units, since they themselves are used to produce polymeric isocyanates that contain three or more isocyanate functional groups. Isocyanates can be classed as aromatic, such as diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI); or aliphatic, such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI). An example of a polymeric isocyanate is polymeric diphenylmethane diisocyanate, which is a blend of molecules with two-, three-, and four- or more isocyanate groups, with an average functionality of 2.7. Isocyanates can be further modified by partially reacting them with a polyol to form a prepolymer. A quasi-prepolymer is formed when the stoichiometric ratio of isocyanate to hydroxyl groups is greater than 2:1. A true prepolymer is formed when the stoichiometric ratio is equal to 2:1. Important characteristics of isocyanates are their molecular backbone, % NCO content, functionality, and viscosity.

The second essential component of a polyurethane polymer is the polyol. Molecules that contain two hydroxyl groups are called diols, those with three hydroxyl groups are called triols, et cetera. In practice, polyols are distinguished from short chain or low-molecular weight glycol chain extenders and cross linkers such as ethylene glycol (EG), 1,4-butanediol (BDO), diethylene glycol (DEG), glycerine, and trimethylolpropane (TMP). Polyols are polymers in their own right. They are formed by base-catalyzed addition of propylene oxide (PO), ethylene oxide (EO) onto a hydroxyl or amine containing initiator, or by polyesterification of a di-acid, such as adipic acid, with glycols, such as ethylene glycol or dipropylene glycol (DPG). Polyols extended with PO or EO are polyether polyols. Polyols formed by polyesterification are polyester polyols. The choice of initiator, extender, and molecular weight of the polyol greatly affect its physical state, and the physical properties of the polyurethane polymer. Important characteristics of polyols are their molecular backbone, initiator, molecular weight, % primary hydroxyl groups, functionality, and viscosity.

PU reaction mechanism catalyzed by a tertiary amine

carbon dioxide gas formed by reacting water and isocyanate

The polymerization reaction is catalyzed by tertiary amines, such as dimethylcyclohexylamine, and organometallic compounds, such as dibutyltin dilaurate or bismuth octanoate. Furthermore, catalysts can be chosen based on whether they favor the urethane (gel) reaction, such as 1,4-diazabicyclo[2.2.2]octane (also called DABCO or TEDA), or the urea (blow) reaction, such as bis-(2-dimethylaminoethyl)ether, or specifically drive the isocyanate trimerization reaction, such as potassium octoate.

One of the most desirable attributes of polyurethanes is their ability to be turned into foam. Blowing agents such as water, certain halocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-134a (1,1,1,2-tetrafluoroethane), and hydrocarbons such as n-pentane, can be incorporated into the poly side or added as an auxiliary stream. Water reacts with the isocyanate to create carbon dioxide gas, which fills and expands cells created during the mixing process. The reaction is a three step process. A water molecule reacts with an isocyanate group to form a carbamic acid. Carbamic acids are unstable, and decompose forming carbon dioxide and an amine. The amine reacts with more isocyanate to give a substituted urea. Water has a very low molecular weight, so even though the weight percent of water may be small, the molar proportion of water may be high and considerable amounts of urea produced. The urea is not very soluble in the reaction mixture and tends to form separate "hard segment" phases consisting mostly of polyurea. The concentration and organization of these polyurea phases can have a significant impact on the properties of the polyurethane foam.^[10] Halocarbons and hydrocarbons are chosen such that they have boiling points at or near room temperature. Since the polymerization reaction is exothermic, these blowing agents volatilize into a gas during the reaction process. They fill and expand the cellular polymer matrix, creating a foam. It is important to know that the blowing gas does not create the cells of a foam. Rather, foam cells are a result of blowing gas diffusing into bubbles that are nucleated or stirred into the system at the time of mixing. In fact, high-density microcellular foams can be formed without the addition of blowing agents by mechanically frothing or nucleating the polyol component prior to use.

Surfactants are used to modify the characteristics of the polymer during the foaming process. They are used to emulsify the liquid components, regulate cell size, and stabilize the cell structure to prevent collapse and surface defects. Rigid foam surfactants are designed to produce very fine cells and a very high closed cell content. Flexible foam surfactants are designed to stabilize the reaction mass while at the same time maximizing open cell content to prevent the foam from shrinking. The need for surfactant can be affected by choice of isocyanate, polyol, component compatibility, system reactivity, process conditions and equipment, tooling, part shape, and shot weight.

Though the properties of the polyurethane are determined mainly by the choice of polyol, the diisocyanate exerts some influence, and must be suited to the application. 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.^[11]

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.

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.

Chemical nomenclature detail[link]

Polyurethane products often are inaccurately called “urethanes”, but must not be confused with urethane proper (ethyl carbamate), because polyurethanes neither contain nor are produced from ethyl carbamate.

Raw materials[link]

For the manufacture of polyurethane polymers, two groups of at least bifunctional substances are needed as reactants; compounds with isocyanate groups, and compounds with active hydrogen atoms. The physical and chemical character, structure, and molecular size of these compounds influence the polymerization reaction, as well as ease of processing and final physical properties of the finished polyurethane. In addition, additive such as catalysts, surfactants, blowing agents, cross linkers, flame retardants, light stabilizers, and fillers are used to control and modify the reaction process and performance characteristics of the polymer.

Isocyanates[link]

Isocyanates with two or more functional groups are required for the formation of polyurethane polymers. Volume wise, aromatic isocyanates account for the vast majority of global diisocyanate production. Aliphatic and cycloaliphatic isocyanates are also important building blocks for polyurethane materials, but in much smaller volumes. There are a number of reasons for this. First, the aromatically linked isocyanate group is much more reactive than the aliphatic one. Second, aromatic isocyanates are more economical to use. Aliphatic isocyanates are used only if special properties are required for the final product. For example, light stable coatings and elastomers can only be obtained with aliphatic isocyanates. Even within the same class of isocyanates, there is a significant difference in reactivity of the functional groups based on steric hindrance. In the case of 2,4-toluene diisocyanate, the isocyanate group in the para position to the methyl group is much more reactive than the isocyanate group in the ortho position.

The two most important commercial, aromatic isocyanates are toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). TDI consists of a mixture of the 2,4- and 2,6-diisocyanatotoluene isomers. The most important product is TDI-80 (TD-80), consisting of 80% of the 2,4-isomer and 20% of the 2,6-isomer. This blend is used extensively in the manufacture of polyurethane flexible slabstock and molded foam.^[12] TDI, and especially crude TDI and TDI/MDI blends can be used in rigid foam applications, but have been supplanted by polymeric MDI. TDI-polyether and TDI-polyester prepolymers are used in high performance coating and elastomer applications. Prepolymers are available that have been vacuum stripped of TDI monomer, which greatly reduces their toxicity. Diphenylmethane diisocyanate (MDI) has three isomers, 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI, and is also polymerized to provide oligomers of functionality three and higher.

Only the 4,4'-MDI monomer is sold commercially as a single isomer^{[citation needed]}. It is provided either as a frozen solid or flake, or in molten form, and is used to manufacture high performance prepolymers^{[citation needed]}. Monomer blends, consisting of approximately 50% of the 4,4'-isomer and 50% of the 2,4'-isomer, are liquid at room temperature and are used to manufacture prepolymers for polyurea spray elastomer applications^{[citation needed]}. 4,4'-MDI blends containing MDI uretonimine, carbodiimide, and allophonate moieties are also liquid at room temperature, and are used in the manufacture of integral skin and microcellular foams. 4,4'-MDI-glycol prepolymers offer increased mechanical properties in the same applications, but are prone to freezing at temperatures below 20 °C. Polymeric MDI (PMDI) is used in rigid pour-in-place, spray foam, and molded foam applications. Polymeric MDI that contains a very high portion of high-functionality oligomers is used to manufacture polyurethane and polyisocyanurate rigid insulation boardstock. Modified PMDI, which contains high levels of MDI monomer, is used in the production of polyurethane flexible molded and microcellular foams. The relative percentage of the 4,4'- and 2,4'- isomers is adjusted to change the reactivity and storage stability of the isocyanate blend, as well as the firmness and other physical properties of the finished goods. Other aromatic isocyanate include p-phenylene diisocyanate (PPDI), naphthalene diisocyanate (NDI), and o-tolidine diisocyanate (TODI).

The most important aliphatic and cycloaliphatic isocyanates are 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), and 4,4'-diisocyanato dicyclohexylmethane (H₁₂MDI or hydrogenated MDI). They are used to produce light stable, non-yellowing polyurethane coatings and elastomers. Because of their volatility and toxicity, aliphatic isocyanate monomers are converted into prepolymers, biurets, dimers, and trimers for commercial use. HDI adducts are used extensively for weather and abrasion resistant coatings and lacquers. IPDI is used in the manufacture of coatings, elastomeric adhesives and sealants. H₁₂MDI prepolymers are used to produce high performance coatings and elastomers with optical clarity and hydrolysis resistance. Other aliphatic isocyanates include cyclohexane diisocyanate (CHDI), tetramethylxylene diisocyanate (TMXDI), and 1,3-bis(isocyanatomethyl)cyclohexane (H₆XDI).

Polyols[link]

Polyols are higher molecular weight materials manufactured from an initiator and monomeric building blocks. They are most easily classified as polyether polyols, which are made by the reaction of epoxides (oxiranes) with an active hydrogen containing starter compounds, or polyester polyols, which are made by the polycondensation of multifunctional carboxylic acids and hydroxyl compounds. They can be further classified according to their end use as flexible or rigid polyols, depending on the functionality of the initiator and their molecular weight. Taking into account functionality, flexible polyols have molecular weights from 2,000 to 10,000 (OH# from 18 to 56). Rigid polyols have molecular weights from 250 to 700 (OH# from 300 to 700). Polyols with molecular weights from 700 to 2,000 (OH# 60 to 280) are used to add stiffness or flexibility to base systems, as well as increase solubility of low molecular weight glycols in high molecular weight polyols.

Polyether polyols come in a wide variety of grades based on their end use, but are all constructed in a similar manner. Polyols for flexible applications use low functionality initiators such as dipropylene glycol (f=2), glycerine (f=3) or a sorbitol/water solution (f=2.75).^[13] Polyols for rigid applications use high functionality initiators such sucrose (f=8), sorbitol (f=6), toluenediamine (f=4), and Mannich bases (f=4). Propylene oxide is then added to the initiators until the desired molecular weight is achieved. Polyols extended with propylene oxide are terminated with secondary hydroxyl groups. In order to change the compatibility, rheological properties, and reactivity of a polyol, ethylene oxide is used as a co-reactant to create random or mixed block heteropolymers. Polyols capped with ethylene oxide contain a high percentage of primary hydroxyl groups, which are more reactive than secondary hydroxyl groups. Because of their high viscosity (470 OH# sucrose polyol, 33 Pa·s at 25 °C), carbohydrate initiated polyols often use glycerine or diethylene glycol as a co-initiate in order to lower the viscosity to ease handling and processing (490 OH# sucrose-glycerine polyol, 5.5 Pa·s at 25 °C). Graft polyols (also called filled polyols or polymer polyols) contain finely dispersed styrene-acrylonitrile, acrylonitrile, or polyurea (PHD) polymer solids chemically grafted to a high molecular weight polyether backbone. They are used to increase the load-bearing properties of low-density high-resiliency (HR) foam, as well as add toughness to microcellular foams and cast elastomers. PHD polyols are also used to modify the combustion properties of HR flexible foam. Solids content ranges from 14% to 50%, with 22% and 43% being typical. Initiators such as ethylenediamine and triethanolamine are used to make low molecular weight rigid foam polyols that have built-in catalytic activity due to the presence of nitrogen atoms in the backbone. They are used to increase system reactivity and physical property build, and to reduce the friability of rigid foam molded parts. A special class of polyether polyols, poly(tetramethylene ether) glycols are made by polymerizing tetrahydrofuran. They are used in high performance coating and elastomer applications.

Polyester polyols fall into two distinct categories according to composition and application. Conventional polyester polyols are based on virgin raw materials and are manufactured by the direct polyesterification of high-purity diacids and glycols, such as adipic acid and 1,4-butanediol. They are distinguished by the choice of monomers, molecular weight, and degree of branching. While costly and difficult to handle because of their high viscosity, they offer physical properties not obtainable with polyether polyols, including superior solvent, abrasion, and cut resistance. Other polyester polyols are based on reclaimed raw materials. They are manufactured by transesterification (glycolysis) of recycled poly(ethyleneterephthalate) (PET) or dimethylterephthalate (DMT) distillation bottoms with glycols such as diethylene glycol. These low molecular weight, aromatic polyester polyols are used in the manufacture of rigid foam, and bring low cost and excellent flammability characteristics to polyisocyanurate (PIR) boardstock and polyurethane spray foam insulation.

Many polyols are polydispersive materials, being blends of two or more polyols each of specific molecular weights, to give intermediate molecular weight materials. It is not unusual to find blends of polyether and polyester polyols, to give specific compromises in properties.

Specialty polyols include polycarbonate polyols, polycaprolactone polyols, polybutadiene polyols, and polysulfide polyols. The materials are used in elastomer, sealant, and adhesive applications that require superior weatherability, and resistance to chemical and environmental attack. Natural oil polyols derived from castor oil and other vegetable oils are used to make elastomers, flexible bunstock, and flexible molded foam. Copolymerizing chlorotrifluoroethylene or tetrafluoroethylene with vinyl ethers containing hydroxyalkyl vinyl ether produces fluorinated (FEVE) polyols. Two component fluorinated polyurethane prepared by reacting FEVE fluorinated polyols with polyisocyanate have been applied for make ambient cure paint/coating. Since fluorinated polyurethanes contain high percentage of fluorine-carbon bond which is the strongest bond among all chemical bonds. Fluorinated polyurethanes have excellent resistance to UV, acids, alkali, salts, chemicals, solvents, weathering, corrosion, fungi and microbial attack. These have become the first choice for high performance coating/paints.

Chain extenders and cross linkers[link]

Chain extenders (f=2) and cross linkers (f=3 or greater) are low molecular weight hydroxyl and amine terminated compounds that play an important role in the polymer morphology of polyurethane fibers, elastomers, adhesives, and certain integral skin and microcellular foams. The elastomeric properties of these materials are derived from the phase separation of the hard and soft copolymer segments of the polymer, such that the urethane hard segment domains serve as cross-links between the amorphous polyether (or polyester) soft segment domains. This phase separation occurs because the mainly non-polar, low melting soft segments are incompatible with the polar, high melting hard segments. The soft segments, which are formed from high molecular weight polyols, are mobile and are normally present in coiled formation, while the hard segments, which are formed from the isocyanate and chain extenders, are stiff and immobile. Because the hard segments are covalently coupled to the soft segments, they inhibit plastic flow of the polymer chains, thus creating elastomeric resiliency. Upon mechanical deformation, a portion of the soft segments are stressed by uncoiling, and the hard segments become aligned in the stress direction. This reorientation of the hard segments and consequent powerful hydrogen bonding contributes to high tensile strength, elongation, and tear resistance values.^{[7][14][15][16][17]} The choice of chain extender also determines flexural, heat, and chemical resistance properties. The most important chain extenders are ethylene glycol, 1,4-butanediol (1,4-BDO or BDO), 1,6-hexanediol, cyclohexane dimethanol and hydroquinone bis(2-hydroxyethyl) ether (HQEE). All of these glycols form polyurethanes that phase separate well and form well defined hard segment domains, and are melt processable. They are all suitable for thermoplastic polyurethanes with the exception of ethylene glycol, since its derived bis-phenyl urethane undergoes unfavorable degradation at high hard segment levels.^[5] Diethanolamine and triethanolamine are used in flex molded foams to build firmness and add catalytic activity. Diethyltoluenediamine is used extensively in RIM, and in polyurethane and polyurea elastomer formulations.

Catalysts[link]

Polyurethane catalysts can be classified into two broad categories, amine compounds and organometallic complexes. They can be further classified as to their specificity, balance, and relative power or efficiency. Traditional amine catalysts have been tertiary amines such as triethylenediamine (TEDA, also known as 1,4-diazabicyclo[2.2.2]octane or DABCO, an Air Products's trade mark), dimethylcyclohexylamine (DMCHA), and dimethylethanolamine (DMEA). Tertiary amine catalysts are selected based on whether they drive the urethane (polyol+isocyanate, or gel) reaction, the urea (water+isocyanate, or blow) reaction, or the isocyanate trimerization reaction (e.g., using potassium acetate, to form isocyanurate ring structure). Since most tertiary amine catalysts will drive all three reactions to some extent, they are also selected based on how much they favor one reaction over another. For example, tetramethylbutanediamine (TMBDA) preferentially drives the gel reaction over the blow reaction. On the other hand, both pentamethyldipropylenetriamine and N-(3-dimethylaminopropyl)-N,N-diisopropanolamine balance the blow and gel reactions, although the former is more potent than the later on a weight basis. 1,3,5-(tris(3-dimethylamino)propyl)-hexahydro-s-triazine is a trimerization catalyst that also strongly drives the blow reaction. Molecular structure gives some clue to the strength and selectivity of the catalyst. Blow catalysts generally have an ether linkage two carbons away from a tertiary nitrogen. Examples include bis-(2-dimethylaminoethyl)ether (also known as A-99, formerly a Union Carbide product), and N-ethylmorpholine. Strong gel catalysts contain alkyl-substituted nitrogens, such as triethylamine (TEA), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and pentamethyldiethylenetriamine (PMDETA). Weaker gel catalysts contain ring-substituted nitrogens, such as benzyldimethylamine (BDMA). Trimerization catalysts contain the triazine structure, or are quaternary ammonium salts. Two trends have emerged since the late 1980s. The requirement to fill large, complex tooling with increasing production rates has led to the use of blocked catalysts to delay front end reactivity while maintaining back end cure. In the United States, acid- and quaternary ammonium salt-blocked TEDA and bis-(2-dimethylaminoethyl)ether are common blocked catalysts used in molded flexible foam and microcellular integral skin foam applications. Increasing aesthetic and environmental awareness has led to the use of non-fugitive catalysts for vehicle interior and furnishing applications in order to reduce odor, fogging, and the staining of vinyl coverings. Catalysts that contain a hydroxyl group or an active amino hydrogen, such as N,N,N'-trimethyl-N'-hydroxyethyl-bis(aminoethyl)ether and N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine that react into the polymer matrix can replace traditional catalysts in these applications.^[19][20]

Organometallic compounds based on mercury, lead, tin (dibutyltin dilaurate), bismuth (bismuth octanoate), and zinc are used as polyurethane catalysts. Mercury carboxylates, such as phenylmercuric neodeconate, are particularly effective catalysts for polyurethane elastomer, coating and sealant applications, since they are very highly selective towards the polyol+isocyanate reaction. Mercury catalysts can be used at low levels to give systems a long pot life while still giving excellent back-end cure. Lead catalysts are used in highly reactive rigid spray foam insulation applications, since they maintain their potency in low temperature and high humidity conditions. Due to their toxicity and the necessity to dispose of mercury and lead catalysts and catalyzed material as hazardous waste in the United States, formulators have been searching for suitable replacements. Since the 1990s, bismuth and zinc carboxylates have been used as alternatives but have shortcomings of their own. In elastomer applications, long pot life systems do not build green strength as fast as mercury catalyzed systems. In spray foam applications, bismuth and zinc do not drive the front end fast enough in cold weather conditions and must be otherwise augmented to replace lead. Alkyl tin carboxylates, oxides and mercaptides oxides are used in all types of polyurethane applications. For example, dibutyltin dilaurate is a standard catalyst for polyurethane adhesives and sealants, dioctyltin mercaptide is used in microcellular elastomer applications, and dibutyltin oxide is used in polyurethane paint and coating applications. Tin mercaptides are used in formulations that contain water, as tin carboxylates are susceptible to degradation from hydrolysis.^[21][22]

Surfactants[link]

Surfactants are used to modify the characteristics of both foam and non-foam polyurethane polymers. They take the form of polydimethylsiloxane-polyoxyalkylene block copolymers, silicone oils, nonylphenol ethoxylates, and other organic compounds. In foams, they are used to emulsify the liquid components, regulate cell size, and stabilize the cell structure to prevent collapse and sub-surface voids. In non-foam applications they are used as air release and anti-foaming agents, as wetting agents, and are used to eliminate surface defects such as pin holes, orange peel, and sink marks.

Production[link]

The main polyurethane producing reaction is between a diisocyanate (aromatic and aliphatic types are available) and a polyol, typically a polypropylene glycol or polyester polyol, in the presence of catalysts and materials for controlling the cell structure^{[disambiguation needed ]}, (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.

Health and safety[link]

Fully reacted polyurethane polymer is chemically inert.^[23] No exposure limits have been established by OSHA (Occupational Safety and Health Administration) or ACGIH (American Conference of Governmental Industrial Hygienists). It is not regulated by OSHA for carcinogenicity. Polyurethane polymer is a combustible solid and can be ignited if exposed to an open flame.^[24] Decomposition from fire can produce mainly carbon monoxide, and trace nitrogen oxides and hydrogen cyanide. Firefighters should wear self-contained breathing apparatus in enclosed areas.

Liquid resin blends and isocyanates may contain hazardous or regulated components. They should be handled in accordance with manufacturer recommendations found on product labels, and in MSDS (Material Safety Data Sheet) and product technical literature. Isocyanates are known skin and respiratory sensitizers, and proper engineering controls should be in place to prevent exposure to isocyanate liquid and vapor. Proper hygiene controls and personal protective equipment (PPE), such as gloves, respirators, and protective clothing and eye wear should be used.

In the United States, additional health and safety information can be found through organizations such as the Polyurethane Manufacturers Association (PMA) and the Center for the Polyurethanes Industry (CPI), as well as from polyurethane system and raw material manufacturers. In Europe, health and safety information is available from ISOPA,^[25] the European Diisocyanate and Polyol Producers Association. Regulatory information can be found in the Code of Federal Regulations Title 21 (Food and Drugs) and Title 40 (Protection of the Environment).

Reducing waste[link]

Students at Yale University have discovered a fungus that could eat polyurethane.^[26]

Manufacturing[link]

The methods of manufacturing polyurethane finished goods range from small, hand pour piece-part operations to large, high-volume bunstock and boardstock production lines. Regardless of the end-product, the manufacturing principle is the same: to meter the liquid isocyanate and resin blend at a specified stoichiometric ratio, mix them together until a homogeneous blend is obtained, dispense the reacting liquid into a mold or on to a surface, wait until it cures, then demold the finished part.

Dispensing equipment[link]

Although the capital outlay can be high, it is desirable to use a meter-mix or dispense unit for even low-volume production operations that require a steady output of finished parts. Dispense equipment consists of material holding (day) tanks, metering pumps, a mix head, and a control unit. Often, a conditioning or heater-chiller unit is added to control material temperature in order to improve mix efficiency, cure rate, and to reduce process variability. Choice of dispense equipment components depends on shot size, throughput, material characteristics such as viscosity and filler content, and process control. Material day tanks may be single to hundreds of gallons in size, and may be supplied directly from drums, IBCs (intermediate bulk containers, such as totes), or bulk storage tanks. They may incorporate level sensors, conditioning jackets, and mixers. Pumps can be sized to meter in single grams per second up to hundreds of pounds per minute. They can be rotary, gear, or piston pumps, or can be specially hardened lance pumps to meter liquids containing highly abrasive fillers such as wollastonite, chopped or hammer milled glass fibres.

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  A high pressure polyurethane dispense unit, showing control panel, high pressure pump, integral day tanks, and hydraulic drive unit.

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  A high pressure mix head, showing simple controls. Front view.

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  A high pressure mix head, showing material supply and hydraulic actuator lines. Rear view.

The pumps can drive low-pressure (10 to 30 bar, ~1 to 3 MPa) or high-pressure (125 to 250 bar, ~12.5 to 25.0 MPa) dispense systems. Mix heads can be simple static mix tubes, rotary element mixers, low-pressure dynamic mixers, or high-pressure hydraulically actuated direct impingement mixers. Control units may have basic on/off – dispense/stop switches, and analogue pressure and temperature gages, or may be computer controlled with flow meters to electronically calibrate mix ratio, digital temperature and level sensors, and a full suite of statistical process control software. Add-ons to dispense equipment include nucleation or gas injection units, and third or fourth stream capability for adding pigments or metering in supplemental additive packages.

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  A low pressure mix head with calibration chamber installed, showing material supply and air actuator lines.

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  Low pressure mix head components, including mix chambers, conical mixers, and mounting plates.

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  5-gallon (20-liter) material day tanks for supplying a low pressure dispense unit.

Tooling[link]

Distinct from pour-in-place, bun and boardstock, and coating applications, the production of piece parts requires some type of tooling to contain and form the reacting liquid. The choice of mold-making material is dependent on the expected number of uses to end-of-life (EOL), molding pressure, flexibility, and heat transfer characteristics. RTV silicone is used for tooling that has an EOL in the thousands of parts. It is typically used for molding rigid foam parts, where the ability to stretch and peel the mold around undercuts is needed. The heat transfer characteristic of RTV silicone tooling is poor. High-performance, flexible polyurethane elastomers are also used in this way.

Epoxy, metal-filled epoxy, and metal-coated epoxy is used for tooling that has an EOL in the tens-of-thousands of parts. It is typically used for molding flexible foam cushions and seating, integral skin and microcellular foam padding, and shallow-draft RIM bezels and fascia.

The heat transfer characteristic of epoxy tooling is fair; the heat transfer characteristic of metal-filled and metal-coated epoxy is good. Copper tubing can be incorporated into the body of the tool, allowing hot water to circulate and heat the mold surface. Aluminum is used for tooling that has an EOL in the hundreds-of-thousands of parts. It is typically used for molding microcellular foam gasketing and cast elastomer parts, and is milled or extruded into shape. Mirror-finish stainless steel is used for tooling that imparts a glossy appearance to the finished part. The heat transfer characteristic of metal tooling is excellent. Finally, molded or milled polypropylene is used to create low-volume tooling for molded gasket applications. Instead of many expensive metal molds, low-cost plastic tooling can be formed from a single metal master, which also allows greater design flexibility. The heat transfer characteristic of polypropylene tooling is poor, which must be taken into consideration during the formulation process.

Applications[link]

In 2007, the global consumption of polyurethane raw materials was above 12 million metric tons, the average annual growth rate is about 5%.^[27]

Testing[link]

Effects of visible light[link]

Polyurethanes, especially those made using aromatic isocyanates, contain chromophores which interact with light. This is of particular interest in the area of polyurethane coatings, where light stability is a critical factor and is the main reason that aliphatic isocyanates are used in making polyurethane coatings. When PU foam, which is made using aromatic isocyanates, is exposed to visible light it discolors, turning from off-white to yellow to reddish brown. It has been generally accepted that apart from yellowing, visible light has little effect on foam properties.^[28][29] This is especially the case if the yellowing happens on the outer portions of a large foam, as the deterioration of properties in the outer portion has little effect on the overall bulk properties of the foam itself.

It has been reported that exposure to visible light can affect the variability of some physical property test results.^[30] Increasing exposure time and/or light intensity during the storage of foam samples under ambient laboratory conditions increased the amount of permanent set induced in some compression set tests (the samples did not fully return to their original size and/or shape). Variability resulted from uncontrolled light exposure of cut samples prior to being compressed. Other foam properties were not substantively affected. It was recommended that specimen preparation and testing be done rapidly to minimize variation in results or if specimens are prepared but not tested for a week or more, that the samples should be protected from light exposure.

Higher-energy UV radiation promotes chemical reactions in foam, some of which are detrimental to the foam structure.^[31]

See also[link]

• Thermoplastic polyurethanes
• Passive fire protection
• Penetrant (mechanical, electrical, or structural)

References[link]

External links[link]

Wikimedia Commons has media related to: Polyurethane foam

• Center for the Polyurethanes Industry: information for EH&S issues related to polyurethanes developments
• Polyurethanes Information Portal: Industry information website describing the applications and benefits of polyurethane
• Polyurethane synthesis, Polymer Science Learning Center, University of Southern Mississippi
• Polyurethane Foam Association: Industry information, educational materials and resources related to flexible polyurethane foam
• European PU insulation industry association: (Formerly BING) European voice for the National trade associations representing the polyurethane insulation industry.