Alkenylsuccinic anhydrides

Last updated
General structure of alkenyl succinic anhydrides (ASA) without stereochemistry; R and R are alkyl groups. ASA Struktur.svg
General structure of alkenyl succinic anhydrides (ASA) without stereochemistry; R and R are alkyl groups.

Alkenyl succinic anhydrides (ASA) are derivatives of succinic anhydrides. One H of the succinic anhydride ring is replaced with an iso-alkenyl chain (C14 to C22). ASA's are colorless and usually viscous liquids. They are widely used, especially in surface sizing of paper, paperboard, and cardboard, as well as in the hydrophobicization of cellulose fibers. Products treated with it show reduced penetration of aqueous media, such as inks or drinks (like milk or fruit juices). [1]

Contents

In terms of their mode of action, the anhydride is proposed to react with the hydroxyl groups on the cellulose, forming an ester. The alkenyl side-chain modifies the surface properties of the paper product. [2] The application is similar to that for alkyl ketene dimers. In the United States alkenylsuccinic anhydrides are the preferred paper sizing agents, whereas in Europe, alkyl ketene dimers (AKDs) predominate.

History

The reaction of maleic anhydride (MA) with aliphatic monounsaturated n- and iso-alkenes was described as early as 1936 in a patent. The alkenes are obtained from the "cracked distillate", a distillate fraction with a high content of unsaturation formed by cracking of petroleum. [3]

En-Reaktion zu ASA ASA-Syntheseschema.svg
En-Reaktion zu ASA

The patent describes the reaction of the alkenes with excess maleic anhydride at 200 °C in an autoclave. The excess alkene is removed by distillation in vacuo, the resulting alkenyl succinic anhydride hydrolyzed with dilute sodium hydroxide solution and the disodium salt reacted with an acid to achieve an alkenebutanedioic acid. However, under the "many useful applications" described for the products obtained, the use as a size has not yet been mentioned. 30% higher reaction yields were achieved with a pre-cleaned cracked petroleum distillate in an autoclave at 210 °C and it was found that the hydrolysis of the succinic anhydride can already be carried out with steam. [4]

In the early technical applications as lubricants and rust inhibitors, the products dark brown color and black, tar-like polymer residues was unproblematic. However, for later use in cleaners and detergents, clear (meaning polymer-free) and less dark colored alkenyl succinic anhydride (ASA) were needed.

The use of alkenylsuccinic anhydrides to hydrophobize cellulose-based (cotton) textiles [5] (first patented in 1959) and the transfer of this concept to the hydrophobization of paper using iso-octadecenyl succinic anhydrides (C18-ASA) in 1963 [6] [7] required liquid, particle-free colours with a colour as light as possible.

After initial difficulties in using ASA for paper sizing (particularly the rapid hydrolysis to alkenyl succinic acids and the formation of poorly soluble calcium salts in hard water and deposits in the paper machine), process parameters could be adjusted to make alkenyl succinic anhydrides the most important sizing agents in the US.

Preparation

ASAs are prepared in the Alder-ene reaction of alkenes with maleic anhydride at high temperatures (> 200 °C). Thereby, competing reactions occur, such as oxidation, condensation and (alternating co-) polymerization. [8] The undesirable secondary products are formed reduce the yield of ASA and adversely affect color, texture and processability of the final products. Unbranched 1-alkenylsuccinic anhydrides, [9] which can be obtained from 1-alkenes, are solid at room temperature and not suited for engine sizing from aqueous emulsion. [10]

In the SHOP process, even-numbered 1-alkenes (CH2=CH-(CH2)n-CH3, produced by oligomerization of ethylene) are isomerized on magnesium oxide catalysts with displacement of the double bond to a position along the carbon chain. Subsequently, the crude product is separated by distillation into the desired fractions, the fraction preferred for ASA production is the C14 – C22.

Isomerisierung von terminalen Alkenen zu iso-Alkenen Isomerisierung zu iso-Alkenen.svg
Isomerisierung von terminalen Alkenen zu iso-Alkenen

The alkenyl succinic anhydrides are prepared with an excess of isoalkene at temperatures >200 °C under nitrogen atmosphere for more than 3 hours; the excess iso-alkene is distilled off at reduced pressure.

Synthese von ASA mit Maleinsaureanhydrid und iso-Alken ASA-Synthese mit iso-Alken.svg
Synthese von ASA mit Maleinsäureanhydrid und iso-Alken

Extensive patent literature exists with regard to the suppression of side reactions in the production of ASA. The formation of polymer can be reduced by the addition of antioxidants or polymerization inhibitors (for example hydroquinone or phenothiazine). Thereby, a quantitative reaction of the maleic anhydride can be achieved. [11] Later, it was also achieved to improve the color of the obtained solid ASA from dark brown to amber by washing with water. [12] By combining a reducing agent (such as a trialkyl phosphite) with a phenolic antioxidant, a significant lightening and reduction of tar formation is achieved.

However, recent patents show that the problem of discoloration and tar formation in ASA synthesis is still insufficiently resolved. Recent patents include a sterically hindered phenol (BHT as a primary antioxidant), a thioether (as a secondary antioxidant) and N,N'-disalicylidene-1,2-diaminopropane as a metal ion deactivator in a "synergistic blend". [13] The C12-ASA formed from dodecene and MAN after six hours at 220 °C is light yellow in color but still contains significant amounts of black, tarry decomposition products. A dramatic improvement (by 600%) in sizing efficiency is found with alkenyl succinic anhydrides based on symmetrical alkenes, such as the C22 alkene docos-11-en (by alkene metathesis from dodec-1-ene). [14]

Use

Alkenylsuccinic anhydrides - and the alkenylsuccinic acids obtainable therefrom by hydrolysis - possess reactive and surface-active properties. They find use as hardeners for epoxy resins, as corrosion inhibitors in lubricating oils, as reactants in alkyd resins and unsaturated polyester resins, as an additive in motor oil and fuels, as components in plasticizers, as additives in toner resins, as surfactants, as water-binding and moisture-controlling additives, as metal cleaners and as chemical intermediates. By far the most important use of alkenylsuccinic anhydrides by volume is the surface and bulk sizing of paper and cardboard with a global consumption of approximately 47,000 tonnes (in 2005). [15]

Alkenylsuccinic anhydrides as paper sizing agents

Solid alkylketene dimers (AKD) [16] were introduced in the 1950s as hydrophobizing agents for cellulose-based products. They were followed in the 1960s by liquid alkenyl succinic anhydrides. Both compound classes are hydrophobic and therefore virtually insoluble in water - the solubility of the commonly used iso-octadecenylsuccinic anhydride (C18-ASA) is only 5.33x10−5 mgl−1. ASA are less hydrophobic and thus less water repellent than AKD because of their shorter chain length. Their vapor pressure is higher than that of AKD, allowing them to diffuse faster into and through the paper layer. However, they also tend to form deposits on machine covers. AKD are at room temperature aqueous dispersions, while ASA are oil-in-water emulsions. The main difference, however, is the much higher reactivity of the cyclic carboxylic anhydride structure in the ASA compared to the diketene structure in AKD. This is accompanied by the much faster hydrolysis in aqueous, especially alkaline media. [17] Therefore, alkenyl succinic anhydrides can be converted into an emulsion only before the use in the paper machine, while AKD can be delivered and stored as stable emulsions.

ASA emulsions are prepared like AKD dispersions with polycations as protective colloids and retention aids (especially with cationic starch [18] or cationic polyacrylamides (C-PAM) in the ratio ASA to cation of about 2: 1) and with about 1% anionic or nonionic surfactants. An optimal particle size of about 1 μm is obtained with high shear.

The benefits of ASA when used in paper sizing include: [15]

The disadvantages of ASA are in particular:

Faster reaction and lower input quantities (and thus material costs in one of the most costly steps in papermaking) speak for the use of ASA, while AKD more sustainable water repellency and better adhesion in material composites with e.g. polyethylene films for water and acid-resistant beverage packaging effect. ASA are desirable, when faster reactions are needed and lower input quantities are used (leading to lower material costs in one of the most costly steps in papermaking). In contrast, AKDs result in more sustainable water repellency and better adhesion in material composites with, for example, polyethylene films for water and acid-resistant beverage packaging.

Paper sizing with alkenyl succinic anhydrides

As with AKD, paper sizing with ASA proceeds in theory in three steps:

  1. the retention or fixation of the ASA emulsion droplets on the wet paper pulp
  2. bursting the emulsion droplets via spreading on the surface and penetration into the pulp
  3. the formation of a hydrophobic paper surface with contact angles >100° by covalent linkage of the ASA molecules with the hydroxyl groups of the cellulose
postulierte ASA-Reaktion mit Cellulose ASA-Reaktion mit Cellulose.svg
postulierte ASA-Reaktion mit Cellulose

Already in the 1990s, Japanese authors published studies that raised considerable doubts about this idealized representation of the hydrophobization of cellulose fiber surfaces. For example, it could be demonstrated that no or only very little ASA is bound to cellulose via covalent ester bonds. [19] This suggests that the ASA-induced hydrophobing is rather based on an adsorptive and associative interaction of the alkenylsuccinic acids (formed by rapid hydrolysis in the aqueous medium) with the constituents of the paper pulp (cellulosic fibers and fillers, such as precipitated calcium carbonate or cationic polymers). Even small amounts and also inhomogeneous distribution are suffice for a high degree of hydrophobicity.

Enormous challenges are posed by the trend towards recycled materials paper as raw material (the so-called secondary fibers), the rapid increase in the volume of cardboard at the expense of printing paper, the growing speeds (> 120 km/h [15] ) and production quantities (maximum daily capacity of a single machine >4,500 tons or >1.5 million tons per year [20] ), the further development of ASA-based sizing agents for cellulose and its formulations. This is especially true given the still very empirical understanding of the basic processes of hydrophobing cellulose fibers.

Polyisobutenylsuccinic anhydride

ASAs are related to the class of polyisobutylenylsuccinic anhydrides, known as PIBSAs. In these compounds, the alkene used is polyisobutylene. Such compounds are commonly used as reactive intermediates in the petroleum additive industry. They are reacted with ethyleneamines to give the corresponding succinimides useful as dispersants in lubricants and fuels. [21] and deposit-control agents [22]

There are two types of polyisobutene used for this purpose, and they are commonly known as conventional and HR (highly reactive) PIB. Conventional PIB is made by polymerizing Raffinate 1 that contains a mixture of C4 butenes with aluminum trichloride as catalyst. In comparison, HR PIB is made by polymerizing isobutene using boron trifluoride as catalyst. The methyl vinylidene content of PIB controls its reactivity toward maleic anhydride. HR PIB has 85% methyl vinylidene, making it more reactive than conventional PIB that only has 10%. Being more reactive, HR PIB requires less forcing conditions for its reaction with maleic anhydride. The PIBSA produced contains less tars and side products as a result. [23]

Literature

Related Research Articles

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or in the terminal position. Terminal alkenes are also known as α-olefins.

<span class="mw-page-title-main">Carboxylic acid</span> Organic compound containing a –C(=O)OH group

In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is R−COOH or R−CO2H, with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.

<span class="mw-page-title-main">Phthalic anhydride</span> Chemical compound

Phthalic anhydride is the organic compound with the formula C6H4(CO)2O. It is the anhydride of phthalic acid. Phthalic anhydride is a principal commercial form of phthalic acid. It was the first anhydride of a dicarboxylic acid to be used commercially. This white solid is an important industrial chemical, especially for the large-scale production of plasticizers for plastics. In 2000, the worldwide production volume was estimated to be about 3 million tonnes per year.

Sizing or size is a substance that is applied to, or incorporated into, other materials—especially papers and textiles—to act as a protective filler or glaze. Sizing is used in papermaking and textile manufacturing to change the absorption and wear characteristics of those materials.

<span class="mw-page-title-main">Cellulose acetate</span> Organic compounds which are acetate esters of cellulose

In biochemistry, cellulose acetate refers to any acetate ester of cellulose, usually cellulose diacetate. It was first prepared in 1865. A bioplastic, cellulose acetate is used as a film base in photography, as a component in some coatings, and as a frame material for eyeglasses; it is also used as a synthetic fiber in the manufacture of cigarette filters and playing cards. In photographic film, cellulose acetate film replaced nitrate film in the 1950s, being far less flammable and cheaper to produce.

<span class="mw-page-title-main">Organic peroxides</span> Organic compounds of the form R–O–O–R’

In organic chemistry, organic peroxides are organic compounds containing the peroxide functional group. If the R′ is hydrogen, the compounds are called hydroperoxides, which are discussed in that article. The O−O bond of peroxides easily breaks, producing free radicals of the form RO•. Thus, organic peroxides are useful as initiators for some types of polymerization, such as the acrylic, unsaturated polyester, and vinyl ester resins used in glass-reinforced plastics. MEKP and benzoyl peroxide are commonly used for this purpose. However, the same property also means that organic peroxides can explosively combust. Organic peroxides, like their inorganic counterparts, are often powerful bleaching agents.

<span class="mw-page-title-main">Straight-chain terminal alkene</span>

Straight-chain terminal alkenes, also called linear alpha olefins (LAO) or normal alpha olefins (NAO), are alkenes (olefins) having a chemical formula CnH2n, distinguished from other alkenes with a similar molecular formula by being terminal alkenes, in which the double bond occurs at the alpha position, and by having a linear (unbranched) hydrocarbon chain.

<span class="mw-page-title-main">Succinic anhydride</span> Chemical compound

Succinic anhydride, is an organic compound with the molecular formula (CH2CO)2O. This colorless solid is the acid anhydride of succinic acid.

<span class="mw-page-title-main">Phenylboronic acid</span> Chemical compound

Phenylboronic acid or benzeneboronic acid, abbreviated as PhB(OH)2 where Ph is the phenyl group C6H5-, is a boronic acid containing a phenyl substituent and two hydroxyl groups attached to boron. Phenylboronic acid is a white powder and is commonly used in organic synthesis. Boronic acids are mild Lewis acids which are generally stable and easy to handle, making them important to organic synthesis.

<span class="mw-page-title-main">Diketene</span> Organic compound with formula (CH2CO)2

Diketene is an organic compound with the molecular formula C4H4O2, and which is sometimes written as (CH2CO)2. It is formed by dimerization of ketene, H2C=C=O. Diketene is a member of the oxetane family. It is used as a reagent in organic chemistry. It is a colorless liquid.

The wet strength of paper and paperboard is a measure of how well the web of fibers holding the paper together can resist a force of rupture when the paper is wet. Wet strength is routinely expressed as the ratio of wet to dry tensile force at break.

Microcrystalline cellulose (MCC) is a term for refined wood pulp and is used as a texturizer, an anti-caking agent, a fat substitute, an emulsifier, an extender, and a bulking agent in food production. The most common form is used in vitamin supplements or tablets. It is also used in plaque assays for counting viruses, as an alternative to carboxymethylcellulose.

In polymer chemistry, cationic polymerization is a type of chain growth polymerization in which a cationic initiator transfers charge to a monomer, which then becomes reactive. This reactive monomer goes on to react similarly with other monomers to form a polymer. The types of monomers necessary for cationic polymerization are limited to alkenes with electron-donating substituents and heterocycles. Similar to anionic polymerization reactions, cationic polymerization reactions are very sensitive to the type of solvent used. Specifically, the ability of a solvent to form free ions will dictate the reactivity of the propagating cationic chain. Cationic polymerization is used in the production of polyisobutylene and poly(N-vinylcarbazole) (PVK).

<span class="mw-page-title-main">Paper chemicals</span> Chemicals used in paper manufacturing

Paper chemicals designate a group of chemicals that are used for paper manufacturing, or modify the properties of paper. These chemicals can be used to alter the paper in many ways, including changing its color and brightness, or by increasing its strength and resistance to water. The chemicals can be defined on basis of their usage in the process.

<span class="mw-page-title-main">Alkylation unit</span>

An alkylation unit (alky) is one of the conversion processes used in petroleum refineries. It is used to convert isobutane and low-molecular-weight alkenes (primarily a mixture of propene and butene) into alkylate, a high octane gasoline component. The process occurs in the presence of an acid such as sulfuric acid (H2SO4) or hydrofluoric acid (HF) as catalyst. Depending on the acid used, the unit is called a sulfuric acid alkylation unit (SAAU) or hydrofluoric acid alkylation unit (HFAU). In short, the alky produces a high-quality gasoline blending stock by combining two shorter hydrocarbon molecules into one longer chain gasoline-range molecule by mixing isobutane with a light olefin such as propylene or butylene from the refinery's fluid catalytic cracking unit (FCCU) in the presence of an acid catalyst.

The surface chemistry of paper is responsible for many important paper properties, such as gloss, waterproofing, and printability. Many components are used in the paper-making process that affect the surface.

<span class="mw-page-title-main">Alkyl ketene dimer</span> Class of chemical compounds

Alkyl ketene dimers (AKDs) are a family of organic compounds based on the 4-membered ring system of oxetan-2-one, which is also the central structural element of propiolactone and diketene. Attached to the oxetane ring of technically relevant alkyl ketene dimers there is a C12 – C16 alkyl group in the 3-position and a C13 – C17 alkylidene group in the 4-position.

Vinylene carbonate (VC) or 1,3-dioxol-2-one, is the simplest unsaturated cyclic carbonic acid ester. Vinylene carbonate can also be thought of as the cyclic carbonate of the hypothetical (Z)-ethene-1,2-diol. The activated double bond in this five-membered oxygen-containing heterocycle makes the molecule a reactive monomer for homopolymerization and copolymerization and a dienophile in Diels-Alder reactions. Below room temperature vinylene carbonate is a colorless stable solid.

Polysuccinimide (PSI), also known as polyanhydroaspartic acid or polyaspartimide, is formed during the thermal polycondensation of aspartic acid and is the simplest polyimide. Polysuccinimide is insoluble in water, but soluble in some aprotic dipolar solvents. Its reactive nature makes polysuccinimide a versatile starting material for functional polymers made from renewable resources.

References

  1. ↑ Auhorn, Werner J. (2012). "Paper and Board, 3. Chemical Additives". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.o18_o11. ISBN   978-3-527-30673-2.
  2. ↑ Gess, Jerome M.; Rende, Dominic S. (2005). "Alkenyl succinic anhydride (ASA)". TAPPI Journal. 4 (9): 25–30.
  3. ↑ US 2055456,E. Eichwald,"Process and product relating to olefin derivatives",published 1936-09-22, assigned to Shell Development Co.
  4. ↑ US 2230005,F.R. Moser,"Process for the production of valuable products from cracked petroleum distillates",published 1941-01-28, assigned to Shell Development Co.
  5. ↑ US 2903382,R.J. Berls,"Treatment of fabric with alkenylsuccinic acids and anhydrides to impart water repellency",published 1959-09-08, assigned to Armour and Co.
  6. ↑ US 3102064,O.B. Wurzburg, E.D. Mazzarella,"Novel paper sizing process",published 1963-08-27, assigned to National Starch and Chemical Corp.
  7. ↑ US 3821069,O.B. Wurzburg,"Process of sizing paper with a reaction product of maleic anhydride and an internal olefin",published 1974-06-28, assigned to National Starch and Chemical Corp.
  8. ↑ Ramaswamy, R; Achary, P. Sasidharan; Shine, K. G (1987). "Some aspects on the synthesis and characterization of dodecenyl succinic anhydride (DDSA)—a curing agent for epoxy resins". Journal of Applied Polymer Science. 33 (1): 49–65. doi:10.1002/app.1987.070330105.
  9. ↑ Sellars, P.B.; Lue, L.; Burns, I.S.; Work, D.N. (2016), "Freezing properties of alkenyl succinic anhydrides derived from linear isomerized olefins" (PDF), Ind. Eng. Chem. Res. , vol. 55, no. 8, pp. 2287–2292, doi:10.1021/acs.iecr.5b04769
  10. ↑ US 5104486,W.A. Sweeney,"Alkenyl succinic anhydride compositions",published 1992-04-14, assigned to Chevron Research Co.
  11. ↑ US 3412111,P.G. Irwin, C.M. Selwitz,"Process for reacting an olefin with maleic anhydride to obtain an alkenyl succinic anhydride",published 1968-11-19, assigned to Gulf Research & Development Co.
  12. ↑ US 4158664,C.M. Selwitz, H.I. Thayer,"Process for improving color of certain alkenyl succinic ahydrides",published 1979-06-19, assigned to Gulf Research & Development Co.
  13. ↑ US 8350058,D. Leinweber, T. Rau,"Method for producing alkenyl succinic anhydrides",published 2013-01-08, assigned to Clariant Produkte (Deutschcountry) GmbH
  14. ↑ US 7455751,W.J. Ward, K. Andruszkiewicz, R.T. Gray, T.P. McGinnis, R.W. Novak,"Use of alkenyl succinic anhydride compounds derived from symmetrical olefins in internal sizing for paper production",published 2008-11-25, assigned to Nalco Co.
  15. 1 2 3 S. Porkert, Physico-chemical processes during reactive paper sizing with alkenyl succinic anhydride (ASA), Dissertation, Technische Universität Dresden, 2016, http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-219620
  16. ↑ US 2627477,W.F. Downey,"Higher alkyl ketene dimer emulsion",published 1953-02-03, assigned to Hercules Powder Co.
  17. ↑ Lindfors, J.; Salmi, J.; Laine, J.; Stenius, P. (2007), "AKD and ASA model surfaces: Preparation and characterization", BioResources, vol. 2, pp. 652–670
  18. ↑ US 5606773,R.W. Novak,"Emulsification of alkenyl succinic anhydride sizing agents",published 1986-08-19, assigned to Nalco Chemical Co.
  19. ↑ Martorana, E.; Belle, J.; Kleemann, S. (2008), "ASA optimization – Control of particle size, stability and hydrolysis", Professional Papermaking, vol. 5, no. 2, pp. 34–42
  20. ↑ "PM 2- die größte Papiermaschine der Welt" (PDF), Voith Paper (in German), vol. 31, pp. 16–19, 2010
  21. ↑ "Polyisobutylene Succinimides in Engine Oil". Lubrizol. Archived from the original on 2017-02-15. Retrieved 2017-02-14.
  22. ↑ Reid, Jacqueline; Barker, Jim (2013). "Understanding Polyisobutylene Succinimides (PIBSI) and Internal Diesel Injector Deposits". SAE Technical Paper Series. SAE Technical Paper Series. Vol. 1. doi:10.4271/2013-01-2682.
  23. ↑ Mach, H.; Rath, P. (1999). "Highly reactive polyisobutene as a component of a new generation of lubricant and fuel additives". Lubrication Science. 11 (2): 175–85. doi:10.1002/ls.3010110205. S2CID   98517564.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.