Diacetone acrylamide
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| General | ||||||||||||||||
| Surname | Diacetone acrylamide | |||||||||||||||
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| Molecular formula | C 9 H 15 NO 2 | |||||||||||||||
| Brief description |
white to slightly pale yellow crystal powder or light yellow flakes |
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| properties | ||||||||||||||||
| Molar mass | 169.22 g mol −1 | |||||||||||||||
| Physical state |
firmly |
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| solubility |
very soluble in water, methanol and numerous other organic solvents, such as. B. ethanol , 1-hexanol , acetone , ethyl acetate and benzene , slightly soluble in heptane and petroleum ether |
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| As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . | ||||||||||||||||
Diacetone acrylamide is a functional monomer that, via its ketone group, leads to crosslinking reactions , e.g. B. with hydrazines , and u. a. is used in photopolymers . Because of its comparatively positive toxicological profile, diacetone acrylamide is increasingly used as a comonomer and the like instead of the vinyl monomers commonly used up to now, such as styrene , vinyl pyrrolidone and vinyl caprolactam or acrylates . a. used for radiation- curing printing inks .
Occurrence and representation
The Ritter reaction of acrylonitrile with acetone produces diacetone acrylamide in yields of up to 70%.
The sulfonated intermediate product formed in a strongly exothermic reaction is then hydrolyzed exothermically to give DAAM .
The acetone condensation products diacetone alcohol and mesityl oxide are also suitable as starting materials for the production of DAAM.
The Ritter reaction initially proceeds with the formation of carbocations through the action of strong mineral acids on the diacetone alcohol, which is formed as an intermediate from acetone, whereby a large number of by-products are formed, including tert-butanol , mesityl oxide, diacetone alcohol, mesitylene , phosphoron , isophorone and acrylamide , even with strict temperature control . To optimize the target product yield and selectivity, the partial reactions are separated in time and space, e.g. B. also through the use of microreaction technology . As a result, pure yields of up to 78% can be obtained.
The purity (> 99%) required for high monomer conversions and molar masses in free-radical polymerization can be achieved by gentle short-path distillation and recrystallization.
properties
Diacetone acrylamide is a colorless to light yellow crystalline solid which is obtained by recrystallization , e.g. B. purified from toluene / n-hexane mixture and can be mixed with <100 ppm MEHQ for stabilization . The substance is thermally stable and can be distilled without decomposition under reduced pressure. It polymerizes above its melting point and in solution at room temperature. Diacetone acrylamide is distinguished from other reactive monomers by a weak odor, high hydrophilicity and solubility in many organic solvents, as well as an advantageous toxicological profile.
Applications
As a reactive monomer, diacetone acrylamide forms water-insoluble homopolymers during free-radically initiated polymerisation and water-swellable homopolymers during polymerisation in benzene . With many other monomers, such as B. acrylonitrile, acrylamide or vinyl acetate , copolymers are obtained, which u. a. dissolve in cyclohexanone .
The incorporation of diacetone acrylamide units into the polymer backbone of copolymers gives them hydrophilic properties, such as increased water vapor permeability of polymer films or contact lenses, improved adhesion of adhesives and sealing compounds, higher strength and film-forming tendency in hairsprays, and reinforcement of paper and textile coatings.
The most important applications for diacetone acrylamide as a functional comonomer are in water-based coatings and lacquers, which can be crosslinked at room temperature by reacting with adipic acid dihydrazide,
as well as in photocrosslinkable printing inks and resins.
Individual evidence
- ↑ a b c d e Entry on Diacetone Acrylamide (stabilized with MEHQ) at TCI Europe, accessed on January 2, 2019.
- ↑ a b c d data sheet Diacetone acrylamide from Sigma-Aldrich , accessed on January 2, 2019 ( PDF ).
- ↑ a b Patent US3277056 : N-3-Oxohydrocarbon-substituted acrylamides and polymers thereof. Applied on November 27, 1963 , published October 4, 1966 , applicant: The Lubrizol Corp., inventor: LE Coleman.
- ↑ a b c d L.E. Coleman, JF Bork, DP Wyman, DI Hoke: Synthesis and polymerization of N- [2- (2-methyl-4-oxopentyl)] acrylamides - A new reactive vinyl monomer . In: J. Polym. Sci. Part A: General . tape 3 , no. 4 , 1965, pp. 1601–1608 , doi : 10.1002 / pol . 1965.100030427 .
- ↑ a b Data sheet Diacetone acrylamide from AlfaAesar, accessed on January 2, 2019 ( PDF )(JavaScript required) .
- ↑ Patent US20170009091A1 : Digital printing inks. Filed August 17, 2016 , published January 12, 2017 , applicant: Sun Chemical Corp., inventor: S. Herlihy.
- ↑ a b N.V. Tale, RN Jagtap: Synthesis of diacetone acrylamide monomer and the film properties of its copolymers . In: Iranian Polym. J. Band 19 , no. 10 , 2010, p. 801-810 ( sid.ir ).
- ↑ a b Patent US3649688 : Method for the preparation of N-3-oxohydrocarbon-substituted acrylamides. Applied July 10, 1969 , published March 14, 1972 , applicant: The Lubrizol Corp., inventor: J. Gordon, PR Kaufman, DI Hoke.
- ↑ Patent EP1890801B1 : Step-by-step production of diacetone acrylamide . Registered on April 26, 2006 , published on June 8, 2011 , applicant: DSM Fine Chemicals Austria NFG GmbH & Co KG, inventors: P. Pöchlauer, M. Kotthaus, M. Vorbach, M. Deak, T. Zich, R. Marr.
- ↑ N. Kessel, DR Illsley, JL Keddie: The diacetone acrylamide crosslinking reaction and its influence on the film formation of an acrylic latex . In: J. Coat. Technol. Res. Band 5 , no. 3 , 2008, p. 285-297 , doi : 10.10007 / s11998-008-9096-6 ( surrey.ac.uk [PDF]).
- ↑ X. Zhang, Y. Liu, H. Huang, Y. Li, H. Chen: The diacetone acrylamide crosslinking reaction and its control of core-shell polyacrylate latices at ambient temperature . In: J. Appl. Polym. Sci. tape 123 , no. 3 , 2012, p. 1822-1832 , doi : 10.1002 / app.34660 .
- ↑ Patent US3725231 : Photosensitive diacetone acrylamide resins. Applied on August 20, 1971 , published April 3, 1973 , applicant: The Lubrizol Corp., inventor: RW Jahnke.