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A superabsorbent polymer (SAP) (also called slush powder) is a water-absorbing hydrophilic homopolymers or
copolymers In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are som ...
that can absorb and retain extremely large amounts of a liquid relative to its own
mass Mass is an Intrinsic and extrinsic properties, intrinsic property of a physical body, body. It was traditionally believed to be related to the physical quantity, quantity of matter in a body, until the discovery of the atom and particle physi ...
. Water-absorbing
polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
s, which are classified as
hydrogels A hydrogel is a biphasic material, a mixture of porous and permeable solids and at least 10% of water or other interstitial fluid. The solid phase is a water insoluble three dimensional network of polymers, having absorbed a large amount of ...
when mixed, absorb aqueous solutions through
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
bonding with
water molecules Water () is a polar inorganic compound that is at room temperature a tasteless and odorless liquid, which is nearly colorless apart from an inherent hint of blue. It is by far the most studied chemical compound and is described as the "univer ...
. A SAP's ability to absorb water depends on the ionic concentration of the aqueous
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...
. In deionized and
distilled Distillation, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixt ...
water, a SAP may absorb 300 times its weight (from 30 to 60 times its own volume) and can become up to 99.9% liquid, and when put into a 0.9% saline solution the absorbency drops to approximately 50 times its weight. The presence of valence cations in the solution impedes the polymer's ability to bond with the water molecule. The SAP's total absorbency and
swelling capacity The swelling capacity of a polymer is the amount of a liquid that can be absorbed by it. This test can done by two methods: # Beaker test method # Tea bag A tea bag (or teabag) is a small, porous, sealed bag or Packet (container), packet typ ...
are controlled by the type and degree of cross-linkers used to make the gel. Low-density cross-linked SAPs generally have a higher absorbent capacity and swell to a larger degree. These types of SAPs also have a softer and stickier gel formation. High cross-link density polymers exhibit lower absorbent capacity and swell, and the gel strength is firmer and can maintain particle shape even under modest pressure. Superabsorbent polymers are crosslinked in order to avoid dissolution. There are three main classes of SAPs: 1.   Cross‐linked polyacrylates and polyacrylamides 2.   Cellulose‐ or starch‐acrylonitrile graft copolymers 3.   Cross‐linked maleic anhydride copolymers The largest use of SAPs is found in personal
disposable A disposable (also called disposable product) is a product designed for a single use after which it is recycled or is disposed as solid waste. The term is also sometimes used for products that may last several months (e.g. disposable air filt ...
hygiene Hygiene is a set of practices performed to preserve health. According to the World Health Organization (WHO), "Hygiene refers to conditions and practices that help to maintain health and prevent the spread of diseases." Personal hygiene refer ...
products, such as baby
diaper A diaper (, North American English) or a nappy (British English, Australian English, Hiberno-English) is a type of underwear that allows the wearer to urinate or defecate without using a toilet, by absorbing or containing waste products to p ...
s,
adult diaper An adult diaper (or adult nappy in Australian English, British English, and Hiberno-English) is a diaper made to be worn by a person with a body larger than that of an infant or toddler. Diapers can be necessary for adults with various conditions, ...
s and
sanitary napkin A menstrual pad is an absorbent item worn in the underwear when menstruating, bleeding after giving birth, recovering from gynecologic surgery, experiencing a miscarriage or abortion, or in any other situation where it is necessary to absorb ...
s. SAPs are also used for blocking water penetration in underground power or communications cable, in self-healing concrete, horticultural water retention agents, control of
spill A spill occurs when the contents of something, usually in liquid form, are emptied out onto a surface, person or clothes, often unintentionally. Spill may also refer to: *Oil spill *Chemical spill *Data spill *Leadership spill *Spill (audio), whe ...
and waste aqueous fluid, and artificial snow for motion picture and stage production. The first commercial use was in 1978 for use in feminine napkins in
Japan Japan is an island country in East Asia. Located in the Pacific Ocean off the northeast coast of the Asia, Asian mainland, it is bordered on the west by the Sea of Japan and extends from the Sea of Okhotsk in the north to the East China Sea ...
and disposable bed liners for nursing home patients in the United States. Early applications in the US market were with small regional diaper manufacturers as well as
Kimberly Clark Kimberly-Clark Corporation is an American multinational consumer goods and personal care corporation that produces mostly paper-based consumer products. The company manufactures sanitary paper products and surgical & medical instruments. Kimb ...
.


History

Until the 1920s, water-absorbing materials were fiber-based products. Choices were
tissue paper Tissue paper, or simply tissue, is a lightweight paper or light crêpe paper. Tissue can be made from recycled pulp (paper), paper pulp on a paper machine. Tissue paper is very versatile, and different kinds are made to best serve these purposes ...
,
cotton Cotton (), first recorded in ancient India, is a soft, fluffy staple fiber that grows in a boll, or protective case, around the seeds of the cotton plants of the genus '' Gossypium'' in the mallow family Malvaceae. The fiber is almost pure ...
,
sponge Sponges or sea sponges are primarily marine invertebrates of the animal phylum Porifera (; meaning 'pore bearer'), a basal clade and a sister taxon of the diploblasts. They are sessile filter feeders that are bound to the seabed, and a ...
, and
fluff pulp Fluff pulp (also called comminution pulp or fluffy pulp) is a type of chemical pulp made from long fibre softwoods. Important parameters for fluff pulp are bulk and water absorbency. History Fluff pulp was first developed for use in disposable san ...
. The water-absorbing capacity of these types of materials is only up to eleven times their weight and most of it is lost under moderate pressure. In the early 1960s, the
United States Department of Agriculture The United States Department of Agriculture (USDA) is an executive department of the United States federal government that aims to meet the needs of commercial farming and livestock food production, promotes agricultural trade and production, ...
(USDA) was conducting work on materials to improve water conservation in
soils Soil, also commonly referred to as earth, is a mixture of organic matter, minerals, gases, water, and organisms that together support the life of plants and soil organisms. Some scientific definitions distinguish dirt from ''soil'' by restri ...
. They developed a resin based on the grafting of
acrylonitrile Acrylonitrile is an organic compound with the formula and the structure . It is a colorless, volatile liquid. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group () linked to a nitrile (). It is an im ...
polymer onto the backbone of
starch Starch or amylum is a polymeric carbohydrate consisting of numerous glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants for energy storage. Worldwide, it is the most common carbohydrate in human diet ...
molecules (i.e. starch-grafting). The hydrolyzed product of the hydrolysis of this starch-
acrylonitrile Acrylonitrile is an organic compound with the formula and the structure . It is a colorless, volatile liquid. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group () linked to a nitrile (). It is an im ...
co-polymer gave water absorption greater than 400 times its weight. Also, the gel did not release liquid water the way that fiber-based absorbents do. The polymer came to be known as “Super Slurper”. The USDA gave the technical know-how to several US companies for further development of the basic technology. A wide range of grafting combinations were attempted including work with
acrylic acid Acrylic acid (IUPAC: prop-2-enoic acid) is an organic compound with the formula CH2=CHCOOH. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. This colorless liquid has ...
,
acrylamide Acrylamide (or acrylic amide) is an organic compound with the chemical formula CH2=CHC(O)NH2. It is a white odorless solid, soluble in water and several organic solvents. From the chemistry perspective, acrylamide is a vinyl-substituted primary ...
and
polyvinyl alcohol Polyvinyl alcohol (PVOH, PVA, or PVAl) is a water- soluble synthetic polymer. It has the idealized formula H2CH(OH)sub>''n''. It is used in papermaking, textile warp sizing, as a thickener and emulsion stabilizer in polyvinyl acetate (PVAc) a ...
(PVA). Today's research has proved the ability of natural materials, e.g.
polysaccharides Polysaccharides (), or polycarbohydrates, are the most abundant carbohydrates found in food. They are long-chain polymeric carbohydrates composed of monosaccharide units bound together by glycosidic linkages. This carbohydrate can react with wat ...
and proteins, to perform super absorbent properties in pure water and saline solution (0.9%wt.) within the same range as synthetic polyacrylates do in current applications.
Soy protein Soy protein is a protein that is isolated from soybean. It is made from soybean meal that has been dehulled and defatted. Dehulled and defatted soybeans are processed into three kinds of high protein commercial products: soy flour, concen ...
/poly(acrylic acid) superabsorbent polymers with good mechanical strength have been prepared.
Polyacrylate An acrylate polymer (also known as acrylic or polyacrylate) is any of a group of polymers prepared from acrylate monomers. These plastics are noted for their transparency, resistance to breakage, and elasticity. Acrylate polymer is commonly used ...
/
polyacrylamide Polyacrylamide (abbreviated as PAM or pAAM) is a polymer with the formula (-CH2CHCONH2-). It has a linear-chain structure. PAM is highly water-absorbent, forming a soft gel when hydrated. In 2008, an estimated 750,000,000 kg were produced, ...
copolymers were originally designed for use in conditions with high electrolyte/mineral content and a need for long term stability including numerous wet/dry cycles. Uses include agricultural and horticultural. With the added strength of the acrylamide monomer, used as medical spill control, wire and cable water blocking.


Copolymer chemistry

Superabsorbent polymers are now commonly made from the polymerization of
acrylic acid Acrylic acid (IUPAC: prop-2-enoic acid) is an organic compound with the formula CH2=CHCOOH. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. This colorless liquid has ...
blended with
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
in the presence of an initiator to form a poly-acrylic acid sodium salt (sometimes referred to as
sodium polyacrylate Sodium polyacrylate (ACR, ASAP, or PAAS), also known as waterlock, is a sodium salt of polyacrylic acid with the chemical formula CH2−CH(CO2Na)− and has broad applications in consumer products. This Superabsorbent polymer, super-absorb ...
). This polymer is the most common type of SAP made in the world today. According to the U.S. Food & Drug Administration, sodium polyacrylate is listed in Food Additive Status List, and there are strict limitations. Other materials are also used to make a superabsorbent polymer, such as polyacrylamide copolymer,
ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon bond, carbon–carbon doub ...
maleic anhydride Maleic anhydride is an organic compound with the formula . It is the acid anhydride of maleic acid. It is a colorless or white solid with an acrid odor. It is produced industrially on a large scale for applications in coatings and polymers. Str ...
copolymer, cross-linked
carboxymethylcellulose Carboxymethyl cellulose (CMC) or cellulose gum is a cellulose derivative with carboxymethyl groups (-CH2-COOH) bound to some of the hydroxyl groups of the glucopyranose monomers that make up the cellulose backbone. It is often used in its sodiu ...
, polyvinyl alcohol copolymers, cross-linked
polyethylene oxide Polyethylene glycol (PEG; ) is a polyether compound derived from petroleum with many applications, from industrial manufacturing to medicine. PEG is also known as polyethylene oxide (PEO) or polyoxyethylene (POE), depending on its molecular we ...
, and starch grafted copolymer of
polyacrylonitrile Polyacrylonitrile (PAN) is a synthetic, semicrystalline organic polymer resin, with the linear formula (CH2CHCN)n. Almost all PAN resins are copolymers with acrylonitrile as the main monomer. PAN is used to produce large variety of products in ...
to name a few. The latter is one of the oldest SAP forms created. Today superabsorbent polymers are made using one of three primary methods: gel polymerization,
suspension polymerization In polymer chemistry, suspension polymerization is a heterogeneous radical polymerization process that uses Agitator (device), mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such as water, while the monomers p ...
or
solution polymerization Solution polymerization is a method of industrial polymerization. In this procedure, a monomer is dissolved in a non-reactive solvent that contains a catalyst or initiator. The reaction results in a polymer which is also soluble in the chosen sol ...
. Each of the processes have their respective advantages but all yield a consistent quality of product.


Gel polymerization

A mixture of acrylic acid, water, cross-linking agents and UV initiator chemicals are blended and placed either on a moving belt or in large tubs. The liquid mixture then goes into a "reactor" which is a long chamber with a series of strong UV lights. The UV radiation drives the polymerization and cross-linking reactions. The resulting "logs" are sticky
gels A gel is a semi-solid that can have properties ranging from soft and weak to hard and tough. Gels are defined as a substantially dilute cross-linked system, which exhibits no flow when in the steady state, although the liquid phase may still ...
containing 60 to 70% water. The logs are shredded or ground and placed in various types of driers. Additional cross-linking agents may be sprayed on the particles' surface; this "surface cross-linking" increases the product's ability to swell under pressure—a property measured as Absorbency Under Load (AUL) or Absorbency Against Pressure (AAP). The dried polymer particles are then screened for proper particle size distribution and packaging. The gel polymerization (GP) method is currently the most popular method for making the sodium polyacrylate superabsorbent polymers now used in baby diapers and other disposable hygienic articles.


Solution polymerization

Solution polymers offer the absorbency of a granular polymer supplied in solution form. Solutions can be diluted with water prior to application, and can coat or saturate most substrates. After drying at a specific temperature for a specific time, the result is a coated substrate with superabsorbency. For example, this chemistry can be applied directly onto wires and cables, though it is especially optimized for use on components such as rolled goods or sheeted substrates. Solution-based polymerization is commonly used today for SAP manufacture of co-polymers, particularly those with the toxic acrylamide monomer. This process is efficient and generally has a lower capital cost base. The solution process uses a water-based monomer solution to produce a mass of reactant polymerized gel. The polymerization's own
exothermic reaction In thermochemistry, an exothermic reaction is a "reaction for which the overall standard enthalpy change Δ''H''⚬ is negative." Exothermic reactions usually release heat. The term is often confused with exergonic reaction, which IUPAC define ...
energy is used to drive much of the process, helping reduce manufacturing cost. The reactant polymer gel is then chopped, dried and ground to its final granule size. Any treatments to enhance performance characteristics of the SAP are usually accomplished after the final granule size is created.


Suspension polymerization

The suspension process is practiced by only a few companies because it requires a higher degree of production control and product engineering during the polymerization step. This process suspends the water-based reactant in a
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
-based solvent. The net result is that the suspension polymerization creates the primary polymer particle in the reactor rather than mechanically in post-reaction stages. Performance enhancements can also be made during, or just after, the reaction stage.


Aviation

On 13 April 2010, Cathay Pacific flight 780 from
Surabaya Surabaya is the capital city of East Java Provinces of Indonesia, province and the List of Indonesian cities by population, second-largest city in Indonesia, after Jakarta. Located on the northeastern corner of Java island, on the Madura Strai ...
to Hong Kong encountered a dual engine stall whilst descending into
Hong Kong International Airport Hong Kong International Airport is an international airport on the island of Chek Lap Kok in western Hong Kong. The airport is also referred to as Chek Lap Kok International Airport or Chek Lap Kok Airport, to distinguish it from its predec ...
, the aircraft landed safely with no fatalities. The investigation concluded that superabsorbent polymer (SAP) spheres, a component of a
fuel filter A fuel filter is a filter used to screen out foreign particles or liquids from the fuel. Most internal combustion engine An internal combustion engine (ICE or IC engine) is a heat engine in which the combustion of a fuel occurs with an o ...
monitor installed in a fueling dispenser at
Juanda International Airport Juanda International Airport is an international airport, international joint-use airport located in Sedati, Sedati District, Sidoarjo Regency, Sidoarjo, Indonesia. It is now the List of the busiest airports in Indonesia, third busiest airport ...
caused the main metering valves in the fuel metering unit to seize. It was discovered that
salt water Saline water (more commonly known as salt water) is water that contains a high concentration of dissolved salts (mainly sodium chloride). On the United States Geological Survey (USGS) salinity scale, saline water is saltier than brackish wate ...
had contaminated the fuel supply at Juanda International Airport, which led to damage of the filter monitors and release of SAP spheres into the aircraft's fuel, eventually entering the main fuel supply lines.


Uses


See also

*
Sodium polyacrylate Sodium polyacrylate (ACR, ASAP, or PAAS), also known as waterlock, is a sodium salt of polyacrylic acid with the chemical formula CH2−CH(CO2Na)− and has broad applications in consumer products. This Superabsorbent polymer, super-absorb ...
* Potassium polyacrylate


Citations


References

* * * {{Authority control Polymers History of hygiene