Polysuccinimide

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Polysuccinimide
PSI Struktur.svg
Names
IUPAC name
Poly(2,5-dioxopyrrolidine-1,3-diyl)
Identifiers
3D model (JSmol)
  • *C1CC(=O)N(C1=O)*
Properties
(C4H3NO2)n
Molar mass 97.07 g·mole −1
Appearancesolid
* insoluble in water [1]
  • soluble in Dimethylformamid, Dimethylacetamid, Dimethylsulfoxid, [2] N-Methylpyrrolidone, und Mesitylen+Sulfolan [3]
  • 30 to 35 at 20 °C in g·100 ml−1 in Triethylenglycol [4]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Polysuccinimide (PSI), also known as polyanhydroaspartic acid or polyaspartimide, is formed during the thermal polycondensation of aspartic acid and is the simplest polyimide. [5] 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. [5]

Contents

The name is derived from the salt of succinic acid, the structurally related succinate.

Production

The production of polysuccinimide was reported by Hugo Schiff as early as 1897. [6] When dry aspartic acid was heated for about 20 hours at 190 °C to 200 °C, a colorless product was obtained. Above 200 °C, a weak yellowing occurs, the yield was almost quantitative. [7]

polysuccinimide-Polykondensation PSI Polykondensation.svg
polysuccinimide-Polykondensation

In the experiments by Hugo Schiff, oligomers and low-molecular polymers were formed in a solid state reaction by polycondensation upon water elimination. This is generally the case in the absence of strong acids, which suppress the thermal decomposition of free amino end groups and thus chain interruption reactions. The formation of the polyimide polysuccinimide can be followed by the intensive absorption band in the infrared spectrum at 1714 cm−1. Many process variants described in the patent literature yield besides a relatively low degree of polymerization often branched and yellow to brown discolored products. [8]

Recent work has focused on increasing the molar mass and achieving a linear chain structure while avoiding decomposition reactions. With a simple "oven process" in which a mixture or paste of crystalline aspartic acid and concentrated phosphoric acid or polyphosphoric acid in a thin layer is heated to 200 °C for 2 to 4 hours, polysuccinimide is produced with molar masses in the range of 30,000 g/mol and cream white shade. [9] The implementation of the polycondensation in several steps [10] (precondensation, comminution, postcondensation), with other dehydrating substances (for example zeolites, triphenyl phosphite [11] ) or in the presence of solvents [12] (for example propylene carbonate) provides higher molecular weight products with molar masses in the range of 10,000 to 200,000 g/mol. However, the patent literature does not address the polymer morphology, in particular the degree of branching.

A recent patent [13] describes the simple preparation of high molecular weight, virtually colorless and linear, unbranched polysuccinimide. For this purpose, aspartic acid, which is present as crystalline zwitterion and practically water-insoluble, is firstly dissolved with an aqueous, volatile acid (preferably hydrochloric acid) and mixed with phosphoric acid as condensing agent. The resulting homogeneous solution is evaporated at 120 °C and the resulting glassy mass is then polycondensed at 180 °C to 200 °C for at least one hour. The phosphoric acid is washed out and the dried polysuccinimide is converted by mild alkaline hydrolysis into water-soluble polyaspartic acid; the molar mass of which can be determined by gel permeation chromatography. The process provides reproducible polysuccinimide with molar masses above 100,000 g/mol.

Synthetic routes for polysuccinimides based on maleic acid monoammonium salt, [14] maleic anhydride and ammonia [15] or based on the intermediately formed maleic acid monoamide [16] achieved only low molar masses of a few 1,000 g/mol and yielded colored products. The same was the case for "green" process variants in supercritical carbon dioxide and while avoiding mineral acids as catalysts. [7]

PSI via Maleinsaureanhydrid PSI via Maleinsaureanhydrid.svg
PSI via Maleinsäureanhydrid

Due to the lower cost of maleic anhydride and ammonia, starting materials produced from fossil raw materials, no L-aspartic acid (of biogenic origin) is used in the production of the commercial product Baypure® polysuccinimide either.

Properties

Polysuccinimide is produced as an odourless, non-hygroscopic, cream-white to brown powder which is soluble in aprotic dipolar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, triethylene glycol or mesitylene/sulfolane mixtures. Polysuccinimide hydrolyses in water only very slowly. In diluted alkaline media (e.g. 1M sodium hydroxide solution), hydrolysis takes place in α- and β-position of the succinimide (2,5-pyrrolidinedione) ring structures and racemization follows at the chiral center of the aspartic acid, yielding the water-soluble sodium salt of the poly(α, β)-DL-aspartic acid. The α form is formed to approx. 30%, the β form to approx. 70% in random arrangement along the polymer chain. [17]

PSI zu Polyasparaginsaure PSI zu Polyasparaginsaure.svg
PSI zu Polyasparaginsäure

In more basic solutions or with longer reaction times, the amide linkages in the polymer chain are attacked upon degradation of the molar mass. The presence of amide bonds makes the polyaspartic acid obtained in the hydrolysis relatively biodegradable (about 70% in wastewater), even of initially highly crosslinked polysuccinimides. [18]

Use

The polysuccinimide [4] developed [19] by Bayer AG and marketed by Lanxess AG under the brand name Baypure® DSP with an average molecular weight of 4,400 g/mol is partially hydrolyzed even at slightly elevated pH values and is thus swellable in highly crosslinked form or water-soluble in linear form. The copoly-(succinimide-aspartic acid) formed by partial hydrolysis and especially polyaspartic acid (trade name Baypure® DS 100) produced by partial hydrolysis is suitable as a long-lasting inhibitor against limescale deposition in water treatment and applications in the oil and mining industries, and as a setting retarder for cement in the construction industry. [19] Patent literature [11] mentions polysuccinimide applications as chelating agents, inhibitors against scale formation, dispersant, humectants, and fertilizer additives.

The opening of the pyrrolidinedione ring structures in polysuccinimide via aminolysis with ammonia water (containgin NH4OH) produces poly-(α, β)-DL-asparagine, with hydrazine poly-(α, β)-DL-aspartylhydrazide (PAHy) and with functional amines, e.g. ethanolamine poly-(α), β)-DL-2-hydroxyethylaspartate (PHEA). [9] PHEA can be used a plasma expander with good biocompatibility and biodegradability, high water solubility at low manufacturing costs and was investigated more intensive as a potential drug carrier) in medical applications. [20] [21]

polysuccinimide Derivatisierung PSI Derivatisierung.svg
polysuccinimide Derivatisierung

Cross-linked poly(α, β)-DL aspartic acid sodium salt, which is the commercially most interesting polysuccinimide derivative, has been extensively tested for its suitability as a biodegradable superabsorbent compared to the non-biodegradable standard cross-linked sodium polyacrylate. [22] [23] The results obtained have not yet led to the use of crosslinked polyaspartic acid in large-volume applications for superabsorbents (e.g. baby diapers).

Related Research Articles

Aspartic acid Amino acid

Aspartic acid (symbol Asp or D; the ionic form is known as aspartate), is an α-amino acid that is used in the biosynthesis of proteins. Like all other amino acids, it contains an amino group and a carboxylic acid. Its α-amino group is in the protonated –NH+
3 form under physiological conditions, while its α-carboxylic acid group is deprotonated −COO− under physiological conditions. Aspartic acid has an acidic side chain (CH2COOH) which reacts with other amino acids, enzymes and proteins in the body. Under physiological conditions (pH 7.4) in proteins the side chain usually occurs as the negatively charged aspartate form, −COO−. It is a non-essential amino acid in humans, meaning the body can synthesize it as needed. It is encoded by the codons GAU and GAC.

Polyethylene Most common thermoplastic polymer

Polyethylene or polythene is the most common plastic in use today. It is a polymer, primarily used for packaging. As of 2017, over 100 million tonnes of polyethylene resins are being produced annually, accounting for 34% of the total plastics market.

Polyethylene glycol Chemical compound

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 weight. The structure of PEG is commonly expressed as H−(O−CH2−CH2)n−OH.

Polyhydroxybutyrate

Polyhydroxybutyrate (PHB) is a polyhydroxyalkanoate (PHA), a polymer belonging to the polyesters class that are of interest as bio-derived and biodegradable plastics. The poly-3-hydroxybutyrate (P3HB) form of PHB is probably the most common type of polyhydroxyalkanoate, but other polymers of this class are produced by a variety of organisms: these include poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO) and their copolymers.

Polyglycolide Chemical compound

Polyglycolide or poly(glycolic acid) (PGA), also spelled as polyglycolic acid, is a biodegradable, thermoplastic polymer and the simplest linear, aliphatic polyester. It can be prepared starting from glycolic acid by means of polycondensation or ring-opening polymerization. PGA has been known since 1954 as a tough fiber-forming polymer. Owing to its hydrolytic instability, however, its use has initially been limited. Currently polyglycolide and its copolymers are widely used as a material for the synthesis of absorbable sutures and are being evaluated in the biomedical field.

Polylactic acid Biodegradable polymer

Polylactic acid, also known as poly(lactic acid) or polylactide (PLA), is a thermoplastic polyester with backbone formula (C
3H
4O
2)
n or [–C(CH
3)HC(=O)O–]
n, formally obtained by condensation of lactic acid C(CH
3)(OH)HCOOH with loss of water. It can also be prepared by ring-opening polymerization of lactide [–C(CH
3)HC(=O)O–]
2, the cyclic dimer of the basic repeating unit.

Sodium polyaspartate Chemical compound

Sodium polyaspartate is a sodium salt of polyaspartic acid. It is a biodegradable condensation polymer based on the amino acid aspartic acid.

Sodium polyacrylate Anionic polyelectrolyte polymer

Sodium polyacrylate (ACR), also known as waterlock, is a sodium salt of polyacrylic acid with the chemical formula [−CH2−CH(CO2Na)−]n and has broad applications in consumer products. This super-absorbent polymer (SAP) has the ability to absorb 100 to 1000 times its mass in water. Sodium polyacrylate is an anionic polyelectrolyte with negatively charged carboxylic groups in the main chain. Sodium polyacrylate is a chemical polymer made up of chains of acrylate compounds. It contains sodium, which gives it the ability to absorb large amounts of water. When dissolved in water, it forms a thick and transparent solution due to the ionic interactions of the molecules. Sodium polyacrylate has many favorable mechanical properties. Some of these advantages include good mechanical stability, high heat resistance, and strong hydration. It has been used as an additive for food products including bread, juice, and ice cream.

Polyester Category of polymers, in which the monomers are joined together by ester links.

Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in plants and insects, as well as synthetics such as polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not. Synthetic polyesters are used extensively in clothing.

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.

Biodegradable polymer

Biodegradable polymers are a special class of polymer that breaks down after its intended purpose by bacterial decomposition process to result in natural byproducts such as gases (CO2, N2), water, biomass, and inorganic salts. These polymers are found both naturally and synthetically made, and largely consist of ester, amide, and ether functional groups. Their properties and breakdown mechanism are determined by their exact structure. These polymers are often synthesized by condensation reactions, ring opening polymerization, and metal catalysts. There are vast examples and applications of biodegradable polymers.

<i>N</i>,<i>N</i>-Methylenebisacrylamide Chemical compound

N,N′-Methylenebisacrylamide (MBAm or MBAA) is the organic compound with the formula CH2[NHC(O)CH=CH2]2. A colorlesss solid, this compound is a crosslinking agent in polyacrylamides, e.g., as used for SDS-PAGE.

Polyaspartic acid Chemical compound

Polyaspartic acid (PASA) is a biodegradable, water-soluble polymerized amino acid. It is a biodegradable replacement for water softeners and related applications. PASA can be chemically crosslinked with a wide variety of methods to yield PASA hydrogels. The resulting hydrogels are pH-sensitive such that under acidic conditions, they shrink, while the swelling capacity increases under alkaline conditions.

Polybutylene succinate Biodegradable polymer

Polybutylene succinate (PBS) is a thermoplastic polymer resin of the polyester family. PBS is a biodegradable aliphatic polyester with properties that are comparable to polypropylene.

Poly(ethylene adipate) Chemical compound

Poly(ethylene adipate) or PEA is an aliphatic polyester. It is most commonly synthesized from a polycondensation reaction between ethylene glycol and adipic acid. PEA has been studied as it is biodegradable through a variety of mechanisms and also fairly inexpensive compared to other polymers. Its lower molecular weight compared to many polymers aids in its biodegradability.

Poly(ethylene succinate) Chemical compound

Poly(ethylene succinate) (PES) is an aliphatic synthetic polyester with a melting point from 103–106 °C. It is synthesized from dicarboxylic acids; either by ring-opening polymerization of succinic anhydride with ethylene oxide or by polycondensation of succinic acid and ethylene glycol. Thermophilic Bacillus sp. TT96 is found in soil and can degrade PES. Mesophilic PES degrading microorganisms were found in the Bacillus and Paenibacillus species; strain KT102; a relative of Bacillus pumilus was the most capable of degrading PES film. The fungal species NKCM1003 a type of Aspergillus clavatus also degrades PES film. The solubility of lithium salts (e.g. lithium perchlorate, LiClO4) in PES made it a good alternative to poly(ethylene oxide) (PEO) during early development of solid polymer electrolytes for lithium ion batteries.

11-Aminoundecanoic acid is an organic compound with the formula H2N(CH2)10CO2H. This white solid is classified as an amine and a fatty acid. 11-Aminoundecanoic acid is a precursor to Nylon-11.

Polyorthoesters are polymers with the general structure –[–R–O–C(R1, OR2)–O–R3–]n– whereas the residue R2 can also be part of a heterocyclic ring with the residue R. Polyorthoesters are formed by transesterification of orthoesters with diols or by polyaddition between a diol and a diketene acetal, such as 3,9-diethylidene-2,4,8,10-tetraoxaspiro[5.5]undecane.

Trisodium dicarboxymethyl alaninate Chemical compound

Trisodium N-(1-carboxylatoethyl)iminodiacetate, methylglycinediacetic acid trisodium salt (MGDA-Na3) or trisodium α-DL-alanine diacetate (α-ADA), is the trisodium anion of N-(1-carboxyethyl)iminodiacetic acid and a tetradentate complexing agent. It forms stable 1:1 chelate complexes with cations having a charge number of at least +2, e.g. the "hard water forming" cations Ca2+ or Mg2+. α-ADA is distinguished from the isomeric β-alaninediacetic acid by better biodegradability and therefore improved environmental compatibility.

β-Butyrolactone Chemical compound

β-Butyrolactone is the intramolecular carboxylic acid ester (lactone) of the optically active 3-hydroxybutanoic acid. It is produced during chemical synthesis as a racemate. β-Butyrolactone is suitable as a monomer for the production of the biodegradable polyhydroxyalkanoate poly(3-hydroxybutyrate) (PHB). Polymerisation of racemic (RS)-β-butyrolactone provides (RS)-polyhydroxybutyric acid, which, however, is inferior in essential properties to the (R)-poly-3-hydroxybutyrate originating from natural sources.

References

  1. ↑ E. Jalalvandi, A. Shavandi (2018), "Polysuccinimide and its derivatives: Degradable and water soluble polymers (review)", Eur. Polym. J., vol. 109, pp. 43–54, doi:10.1016/j.eurpolymj.2018.08.056, S2CID   106107591
  2. ↑ T. Klein, R.-J. Moritz, R. Graupner (2016), Ullmann's Polymers and Plastics, Products and Processes, Volume 1, Part 2: Organic Polymers, Polyaspartates and Polysuccinimide, Weinheim: Wiley-VCH, pp. 742–743, ISBN   978-3-527-33823-8 {{citation}}: CS1 maint: multiple names: authors list (link)
  3. ↑ M. Tomida, T. Nakato, M. Kuramochi, M. Shibata, S. Matsunami, T. Kakuchi (1996), "Novel method of synthesizig poly(succinimide) and its copolymeric derivatives by acid-catalysed polycondensation of L-aspartic acid", Polymer , vol. 37, no. 16, pp. 4435–4437, doi:10.1016/0032-3861(96)00267-4 {{citation}}: CS1 maint: multiple names: authors list (link)
  4. 1 2 Baypure® General Product Information (PDF) Lanxess AG
  5. 1 2 Adelnia, Hossein; Tran, Huong D.N.; Little, Peter J.; Blakey, Idriss; Ta, Hang T. (2021-06-14). "Poly(aspartic acid) in Biomedical Applications: From Polymerization, Modification, Properties, Degradation, and Biocompatibility to Applications". ACS Biomaterials Science & Engineering. 7 (6): 2083–2105. doi:10.1021/acsbiomaterials.1c00150. hdl:10072/404497. PMID   33797239. S2CID   232761877.
  6. ↑ Hugo Schiff (1897-09-01), "Ueber Polyaspartsäuren", Berichte der Deutschen Chemischen Gesellschaft (in German), vol. 30, no. 3, pp. 2449–2459, doi:10.1002/cber.18970300316
  7. 1 2 Kenneth Doll, Randal Shogren, Ronald Holser, J. Willett, Graham Swift (2005-12-01), "Polymerization of L-Aspartic Acid to Polysuccinimide and Copoly(Succinimide-Aspartate) in Supercritical Carbon Dioxide", Letters in Organic Chemistry, vol. 2, no. 8, pp. 687–689, doi:10.2174/157017805774717553 {{citation}}: CS1 maint: multiple names: authors list (link)
  8. ↑ Thomas Klein, Ralf-Johann Moritz, René Graupner (2008), "Polyaspartates and Polysuccinimide", Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, doi:10.1002/14356007.l21_l01, ISBN   978-3-527-30673-2 {{citation}}: CS1 maint: multiple names: authors list (link)
  9. 1 2 Paolo Neri, Guido Antoni, Franco Benvenuti, Francesco Cocola, Guido Gazzei (1973-08-01), "Synthesis of α, β-poly [(2-hydroxyethyl)-DL-aspartamide], a new plasma expander", Journal of Medicinal Chemistry, vol. 16, no. 8, pp. 893–897, doi:10.1021/jm00266a006, PMID   4745831 {{citation}}: CS1 maint: multiple names: authors list (link)
  10. ↑ US 5142062,J. Knebel, K. Lehmann,"Method for increasing the molecular weight in the manufacture of polysuccinimide",issued 1992-08-25, assigned to Röhm GmbH
  11. 1 2 EU 0791616,M. Uenaka et al.,"Process for producing polysuccinimide and use of said compound",issued 1997-8-27, assigned to Mitsubishi Chemical Corp.
  12. ↑ US 5756595,G.Y. Mazo et al.,"Catalytically polymerizing aspartic acid",issued 1998-05-26, assigned to Donlar Corp.
  13. ↑ US 7053170,C.S. Sikes,"Preparation of high molecular weight polysuccinimides",issued 2006-05-30, assigned to Aquero Co.
  14. ↑ EU 0612784,T. Groth et al.,"Process for preparing polysuccinimide and polyaspartic acid",issued 1994-08-31, assigned to Bayer AG
  15. ↑ US 5296578,L.P. Koskan, A.R.Y. Meah,"Production of polysuccinimide and polyaspartic acid acid from maleic anhydride and ammonia",issued 1994-03-22, assigned to Donlar Corp.
  16. ↑ US 5393868,M. B. Freeman et al.,"Production of polysuccinimide by thermal polymerization of maleamic acid",issued 1995-02-28, assigned to Rohm and Haas Co.
  17. ↑ K.C. Low et al.: 6. Commercial Poly(aspartic acid) and Its Uses. In: J.E. Glass: Hydrophilic Polymers, Advances in Chemistry. 248, 1996, ISBN   978-0-8412-3133-7, S. 99–111, doi:10.1021/ba-1996-0248.ch006.
  18. ↑ G. Swift: Degradable Polymers. 2nd ed. Springer Netherlands, 2002, S. 379–412, doi : 10.1007/978-94-017-1217-0_11.
  19. 1 2 T. Klein: Baypure®, An innovate product family for household and technical applications. 5th Green Chemistry Conference 2003, Barcelona.
  20. ↑ K. Seo, D. Kim: Design and synthesis of endosomolytic conjugated polyaspartamide for cytosolic drug delivery. In: E. Jabbari, A. Khademhosseini (Hrsg.): Biologically-responsive hybrid biomaterials: a reference for material scientists and bioengineers. World Scientific Publishing Co., Singapur 2010, ISBN   978-981-4295-67-3, S. 191–212, doi : 10.1142/9789814295680_0009.
  21. ↑ Eberhard W. Neuse, Axel G. Perlwitz, Siegfried Schmitt (1991-11-01), "Water-soluble polyamides as potential drug carriers. III. Relative main-chain stabilities of side chain-functionalized aspartamide polymers on aqueous-phase dialysis", Die Angewandte Makromolekulare Chemie, vol. 192, no. 1, pp. 35–50, doi:10.1002/apmc.1991.051920103 {{citation}}: CS1 maint: multiple names: authors list (link)
  22. ↑ US 5859179,Y. Chou,"Forming superabsorbent polymer",issued 1999-01-19, assigned to Solutia Inc.
  23. ↑ US 6072024,Y. Irizato et al.,"Production process of cross-linked polyaspartic acid",issued 2000-06-06, assigned to Mitsui Chemicals
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