Superabsorbent polymer
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A superabsorbent polymer (SAP) (also called slush powder) is a water-absorbing hydrophilic homopolymers or copolymers that can absorb and retain extremely large amounts of a liquid relative to its own mass. Water-absorbing
polymer A polymer (; Greek '' poly-'', "many" + '' -mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
s, which are classified as hydrogels when mixed, absorb aqueous solutions through hydrogen bonding with water molecules. A SAP's ability to absorb water depends on the ionic concentration of the aqueous solution. In deionized and distilled
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
, 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 are controlled by the type and degree of cross-linkers used to make the
gel 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 di ...
. 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. Super‐ Absorbent 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 filte ...
hygiene Hygiene is a series 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 /ˈdaɪpə(r)/ (American and Canadian English) or a nappy (Australian English, British English, and Hiberno-English) is a type of underwear that allows the wearer to urinate or defecate without using a toilet, by absorbing or cont ...
s, adult diapers and sanitary napkins. SAP was discontinued from use in tampons due to 1980s concern over a link with
toxic shock syndrome Toxic shock syndrome (TSS) is a condition caused by bacterial toxins. Symptoms may include fever, rash, skin peeling, and low blood pressure. There may also be symptoms related to the specific underlying infection such as mastitis, osteomyeli ...
. SAP is 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 ( ja, 日本, or , and formally , ''Nihonkoku'') is an island country in East Asia. It is situated in the northwest Pacific Ocean, and is bordered on the west by the Sea of Japan, while extending from the Sea of Okhotsk in the n ...
and disposable bed liners for nursing home patients in the USA. Early applications in the US market were with small regional diaper manufacturers as well as Kimberly Clark.


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 paper pulp on a paper machine. Tissue paper is very versatile, and different kinds of tissue are made to best serve these purposes, w ...
, cotton, sponge, and fluff pulp. The water absorbent capacity of these types of materials is only up to 11 times their weight and most of it is lost under moderate pressure. In the early 1960s, the United States Department of Agriculture (USDA) was conducting work on materials to improve water conservation in soils. 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 although commercial samples can be yellow due to impurities. It has a pungent odor of garlic or onions. In terms of its molecula ...
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 die ...
molecules (i.e. starch-grafting). The hydrolyzed product of the hydrolysis of this starch-acrylonitrile 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 USA companies for further development of the basic technology. A wide range of grafting combinations were attempted including work with
acrylic acid Acrylic acid (IUPAC: propenoic 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 a ...
,
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 primar ...
and
polyvinyl alcohol Poly(vinyl 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) ...
(PVA). Today's research has proved the ability of natural materials, e.g. polysaccharides 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/poly(acrylic acid) superabsorbent polymers with good mechanical strength have been prepared. Polyacrylate/
polyacrylamide Polyacrylamide (abbreviated as PAM) 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, mainly fo ...
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: propenoic 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 a ...
blended with
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and al ...
in the presence of an initiator to form a poly-acrylic acid sodium salt (sometimes referred to as sodium polyacrylate). This polymer is the most common type of SAP made in the world today. According to 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 double bonds). Ethylene ...
maleic anhydride Maleic anhydride is an organic compound with the formula C2H2(CO)2O. 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 pol ...
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 as 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), also known as polyvinyl cyanide and Creslan 61, is a synthetic, semicrystalline organic polymer resin, with the linear formula (C3H3N)n. Though it is thermoplastic, it does not melt under normal conditions. It degrades bef ...
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 Suspension polymerization is a heterogeneous radical polymerization process that uses mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such as water, while the monomers polymerize, forming spheres of polymer. Th ...
or solution polymerization. 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 containing 60-70% water. The logs are shredded or ground and placed in various sorts of driers. Additional cross-linking agent 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 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-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 encountered a dual engine stall descending into
Hong Kong Hong Kong ( (US) or (UK); , ), officially the Hong Kong Special Administrative Region of the People's Republic of China (abbr. Hong Kong SAR or HKSAR), is a List of cities in China, city and Special administrative regions of China, special ...
from Surabaya. The aircraft landed safely with no fatalities. The investigation concluded that superabsorbent polymer (SAP), a component of a fuel monitor installed in a fuelling dispenser at
Juanda International Airport Juanda International Airport (JIA) ( id, Bandar Udara Internasional Juanda) , is an international airport located in Sedati, Sidoarjo. It is now the third busiest airport in Indonesia (after Soekarno-Hatta and Ngurah Rai airport). This airp ...
caused the 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 w ...
entered the fuel supply, this is what caused the SAP particles to enter the fuel lines.


Uses


See also

* Sodium polyacrylate * Potassium polyacrylate


Citations


References

* * * {{cite book , title=Modern Superabsorbent Polymer Technology , editor1=Buchholz, Fredric L , editor2=Graham, Andrew T , isbn=978-0-471-19411-8 , publisher=John Wiley & Sons, year=1997 , edition=1


External links


Nonwovens Containing Immobilized Superabsorbent Polymer Particles
Polymers