Polyurethane
Polyurethane (/ˌpɒliˈjʊərəˌθeɪn, -jʊəˈrɛθeɪn/;[1] often abbreviated PUR and PU) refers to a class of polymers composed of organic units joined by carbamate (urethane) links. In contrast to other common polymers such as polyethylene and polystyrene, polyurethane is produced from a wide range of starting materials. This chemical variety produces polyurethanes with different chemical structures leading to many different applications. These include rigid and flexible foams, and coatings, adhesives, electrical potting compounds, and fibers such as spandex and polyurethane laminate (PUL). Foams are the largest application accounting for 67% of all polyurethane produced in 2016.[2]
A polyurethane is typically produced by reacting a polymeric isocyanate with a polyol.[3] Since a polyurethane contains two types of monomers, which polymerize one after the other, they are classed as alternating copolymers. Both the isocyanates and polyols used to make a polyurethane contain two or more functional groups per molecule.
Global production in 2019 was 25 million metric tonnes,[4] accounting for about 6% of all polymers produced in that year.
History
In 1969, Bayer exhibited an all-plastic car in
Starting in the early 1980s, water-blown microcellular flexible foams were used to mold gaskets for automotive panels and air-filter seals, replacing PVC polymers. Polyurethane foams are used in many automotive applications including seating, head and arm rests, and headliners.
Polyurethane foam (including foam rubber) is sometimes made using small amounts of
Chemistry
Polyurethanes are produced by reacting di
The most common application of polyurethane is as solid foams, which requires the presence of a gas, or blowing agent, during the polymerization step. This is commonly achieved by adding small amounts of water, which reacts with isocyanates to form CO2 gas and an amine, via an unstable carbamic acid group. The amine produced can also react with isocyanates to form urea groups, and as such the polymer will contain both these and urethane linkers. 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 foam.[16]
The type of foam produced can be controlled by regulating the amount of blowing agent and also by the addition of various
The properties of a polyurethane are greatly influenced by the types of isocyanates and polyols used to make it. Long, flexible segments, contributed by the polyol, give soft,
Raw materials
The main ingredients to make a polyurethane are di- and tri-
Isocyanates
Isocyanates used to make polyurethane have two or more isocyanate groups on each molecule. The most commonly used isocyanates are the
TDI and MDI are generally less expensive and more reactive than other isocyanates. Industrial grade TDI and MDI are mixtures of isomers and MDI often contains polymeric materials. They are used to make flexible foam (for example slabstock foam for mattresses or molded foams for car seats),[17] rigid foam (for example insulating foam in refrigerators) elastomers (shoe soles, for example), and so on. The isocyanates may be modified by partially reacting them with polyols or introducing some other materials to reduce volatility (and hence toxicity) of the isocyanates, decrease their freezing points to make handling easier or to improve the properties of the final polymers.
Aliphatic and cycloaliphatic isocyanates are used in smaller quantities, most often in coatings and other applications where color and transparency are important since polyurethanes made with aromatic isocyanates tend to darken on exposure to light.[page needed][18] 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). Other more specialized isocyanates include Tetramethylxylylene diisocyanate (TMXDI).
Polyols
Polyols for flexible applications use low functionality initiators such as
Graft polyols (also called filled polyols or polymer polyols) contain finely dispersed
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. Polyester polyols are usually more expensive and more viscous than polyether polyols, but they make polyurethanes with better solvent, abrasion, and cut resistance. Other polyester polyols are based on reclaimed raw materials. They are manufactured by transesterification (
Specialty polyols include
Co-polymerizing chlorotrifluoroethylene or tetrafluoroethylene with vinyl ethers containing hydroxyalkyl vinyl ether produces fluorinated (FEVE) polyols. Two-component fluorinated polyurethanes prepared by reacting FEVE fluorinated polyols with polyisocyanate have been used to make ambient cure paints and coatings. Since fluorinated polyurethanes contain a high percentage of fluorine–carbon bonds, which are the strongest bonds among all chemical bonds, fluorinated polyurethanes exhibit resistance to UV, acids, alkali, salts, chemicals, solvents, weathering, corrosion, fungi and microbial attack. These have been used for high performance coatings and paints.[21]
Bio-derived materials
Interest in
Chain extenders and cross linkers
Chain extenders (f = 2) and cross linkers (f ≥ 3) 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 nonpolar, 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.[12][27][28][29][30] The choice of chain extender also determines flexural, heat, and chemical resistance properties. The most important chain extenders are
Molecule | Mol.
mass |
Density (g/cm3) |
Melting pt (°C) |
Boiling pt (°C) |
---|---|---|---|---|
Hydroxyl compounds – difunctional molecules | ||||
Ethylene glycol | 62.1 | 1.110 | −13.4 | 197.4 |
Diethylene glycol | 106.1 | 1.111 | −8.7 | 245.5 |
Triethylene glycol | 150.2 | 1.120 | −7.2 | 287.8 |
Tetraethylene glycol |
194.2 | 1.123 | −9.4 | 325.6 |
Propylene glycol | 76.1 | 1.032 | Supercools | 187.4 |
Dipropylene glycol | 134.2 | 1.022 | Supercools | 232.2 |
Tripropylene glycol | 192.3 | 1.110 | Supercools | 265.1 |
1,3-Propanediol | 76.1 | 1.060 | −28 | 210 |
1,3-Butanediol | 92.1 | 1.005 | — | 207.5 |
1,4-Butanediol | 92.1 | 1.017 | 20.1 | 235 |
Neopentyl glycol | 104.2 | — | 130 | 206 |
1,6-Hexanediol | 118.2 | 1.017 | 43 | 250 |
1,4-Cyclohexanedimethanol |
— | — | — | — |
HQEE | — | — | — | — |
Ethanolamine | 61.1 | 1.018 | 10.3 | 170 |
Diethanolamine | 105.1 | 1.097 | 28 | 271 |
Methyldiethanolamine | 119.1 | 1.043 | −21 | 242 |
Phenyldiethanolamine | 181.2 | — | 58 | 228 |
Hydroxyl compounds – trifunctional molecules | ||||
Glycerol | 92.1 | 1.261 | 18.0 | 290 |
Trimethylolpropane | — | — | — | — |
1,2,6-Hexanetriol | — | — | — | — |
Triethanolamine | 149.2 | 1.124 | 21 | — |
Hydroxyl compounds – tetrafunctional molecules | ||||
Pentaerythritol | 136.2 | — | 260.5 | — |
N,N,N′,N′-Tetrakis (2-hydroxypropyl) ethylenediamine |
— | — | — | — |
Amine compounds – difunctional molecules | ||||
Diethyltoluenediamine |
178.3 | 1.022 | — | 308 |
Dimethylthiotoluenediamine | 214.0 | 1.208 | — | — |
Catalysts
Polyurethane
Factors affecting catalyst selection include balancing three reactions: urethane (polyol+isocyanate, or gel) formation, the urea (water+isocyanate, or "blow") formation, or the isocyanate trimerization reaction (e.g., using potassium acetate, to form
Surfactants
Production
Polyurethanes are produced by mixing two or more liquid streams. The polyol stream contains catalysts, surfactants,
. Polyurethane can be made in a variety of densities and hardnesses by varying the isocyanate, polyol or additives.Health and safety
Fully reacted polyurethane polymer is chemically inert.[37] No exposure limits have been established in the U.S. by OSHA (Occupational Safety and Health Administration) or ACGIH (American Conference of Governmental Industrial Hygienists). It is not regulated by OSHA for carcinogenicity.
Polyurethanes are combustible.[38] Decomposition from fire can produce significant amounts of carbon monoxide and hydrogen cyanide, in addition to nitrogen oxides, isocyanates, and other toxic products.[39] Because of the flammability of the material, it has to be treated with flame retardants (at least in case of furniture), almost all of which are considered harmful.[40][41] California later issued Technical Bulletin 117 2013 which allowed most polyurethane foam to pass flammability tests without the use of flame retardants. Green Science Policy Institute states: "Although the new standard can be met without flame retardants, it does NOT ban their use. Consumers who wish to reduce household exposure to flame retardants can look for a TB117-2013 tag on furniture, and verify with retailers that products do not contain flame retardants."[42]
Liquid resin blends and isocyanates may contain hazardous or regulated components. Isocyanates are known skin and respiratory sensitizers. Additionally, amines, glycols, and phosphate present in spray polyurethane foams present risks.[43]
Exposure to chemicals that may be emitted during or after application of
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. Regulatory information can be found in the Code of Federal Regulations Title 21 (Food and Drugs) and Title 40 (Protection of the Environment). In Europe, health and safety information is available from ISOPA,[45] the European Diisocyanate and Polyol Producers Association.
Manufacturing
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
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
-
A high-pressure polyurethane dispense unit, showing control panel, high-pressure pump, integral day tanks, and hydraulic drive unit
-
A high-pressure mix head, showing simple controls (front view)
-
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 and dispense/stop switches, and analogue pressure and temperature gauges, 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.
-
A low-pressure mix head with calibration chamber installed, showing material supply and air actuator lines
-
Low-pressure mix head components, including mix chambers, conical mixers, and mounting plates
-
5-gallon (20-liter) material day tanks for supplying a low-pressure dispense unit
Tooling
Distinct from pour-in-place, bun and boardstock, and coating applications, the production of piece parts requires 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
In 2007, the global consumption of polyurethane raw materials was above 12 million metric tons, and the average annual growth rate was about 5%.[46] Revenues generated with PUR on the global market are expected to rise to approximately US$75 billion by 2022.[47] As they are such an important class of materials, research is constantly taking place and papers published.[48]
Degradation and environmental fate
Effects of visible light
Polyurethanes, especially those made using
It has been reported that exposure to visible light can affect the variability of some physical property test results.[51]
Higher-energy UV radiation promotes chemical reactions in foam, some of which are detrimental to the foam structure.[52]
Hydrolysis and biodegradation
Polyurethanes may degrade due to hydrolysis. This is a common problem with shoes left in a closet, and reacting with moisture in the air.[53]
Microbial degradation of polyurethane is believed to be due to the action of esterase, urethanase, hydrolase and protease enzymes.[54] The process is slow as most microbes have difficulty moving beyond the surface of the polymer. Susceptibility to fungi is higher due to their release of extracellular enzymes, which are better able to permeate the polymer matrix. Two species of the Ecuadorian fungus Pestalotiopsis are capable of biodegrading polyurethane in aerobic and anaerobic conditions such as found at the bottom of landfills.[55][56] Degradation of polyurethane items at museums has been reported.[57] Polyester-type polyurethanes are more easily biodegraded by fungus than polyether-type.[58]
See also
- Botanol, a material with higher plant-based content
- Passive fire protection
- Penetrant (mechanical, electrical, or structural)
- Polyaspartic
- Polyurethane dispersion
- Thermoplastic polyurethanes
- Thermoset polymer matrix
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External links
- Center for the Polyurethanes Industry: information for EH&S issues related to polyurethanes developments
- Polyurethane synthesis, Polymer Science Learning Center, University of Southern Mississippi
- Polyurethane Foam Association: Industry information, educational materials and resources related to flexible polyurethane foam
- PU Europe: European PU insulation industry association (formerly BING): European voice for the national trade associations representing the polyurethane insulation industry
- ISOPA: European Diisocyanate & Polyol Producers Association: ISOPA represents the manufacturers in Europe of aromatic diisocyanates and polyols