radical polymerization; atom transfer radical polymerization (ATRP)
Abstract :
[en] NiBr2(PPh3)2 has been found to be an efficient catalyst for the ATRP of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) initiated by an alkyl halide in the absence of any activator (e.g., Lewis acid) at 85 °C. The molecular weight distribution of the poly(meth)acrylates is narrow (Mw/Mn = 1.1−1.4). However, some side reactions (more likely coupling reactions) are observed at high monomer conversions in the case of n-BuA. An excess of PPh3 has proved to increase the polymerization rate of MMA while preserving the control of the molecular parameters. When the catalyst/initiator molar ratio is too small (e.g., 0.05), the polymerization rate decreases, the polydispersity increases, and the initiation is less efficient. α-Acid and α-hydroxyl end groups have been successfully attached to the chains by using functional initiators, such as 2-bromo-2-methylpropionic acid and 2,2‘,2‘ ‘-tribromoethanol. Reactivity ratios for the MMA/n-BuA comonomer pair have been measured and found to be close to the values observed for a conventional free-radical polymerization. Diethyl meso-2,5-dibromoadipate has been used as a difunctional initiator for the n-BuA polymerization, leading to α,ω-bromo-poly(n-BuA) of narrow molecular weight distribution. Finally, the thermal stability of PMMA is consistent with the lack of termination reactions, while Tg is as high as 125 °C.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Moineau, Georges; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Minet, Michaël; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Senninger, Thierry; Groupement de Recherches de Lacq, France > Service Polymères de Grande Diffusion et Catalyse
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Controlled radical polymerization of (meth)acrylates by ATRP with NiBr2(PPh3)2 as catalyst
Publication date :
12 January 1999
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
scite shows how a scientific paper has been cited by providing the context of the citation, a classification describing whether it supports, mentions, or contrasts the cited claim, and a label indicating in which section the citation was made.
Bibliography
(a) Szwarc, M.; Levy, M.; Milkovich, R. J. Am. Chem. Soc. 1956, 78, 2657.
Ando, T.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 16, 4507.
Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 2249.
No catalyst degradation have been noticed even after 2 days in contact with air.
Sawamoto has recently studied the performance of differents initiators and demonstrated that the dimer of MMA end-capped by Br (dimethyl 2-bromo-2,4,4′-trimethylglutarate) was more efficient than the 2-ethylbromoisobutyrate. See: Ando, T.; Kamigaito, M.; Sawamoto, M. Tetrahedron 1997, 53 (45), 15445.
(a) Van de Kuil, L. A.; Grove, D. M.; Gossage, R. A.; Zwikker, J. W.; Jenneskens, L. W.; Drenth, W.; Van Koten, G. Organometallics 1997, 16, 4985.
(b) Matyjaszewski, K.; Coca, S.; Gaynor, S. G.; Wei, M.; Woodworth, B. E. Macromolecules 1998, 31, 5967.
Mn,calc = ([monomer]0/[initiator]0) x MWmonomer x conversion.
See for example: Gridnev, A. A. Macromolecules 1997, 30, 7651 and references therein.
(a) Wayland, B. B.; Poszmik, G.; Mukerjee, S. L.; Fryd, M. J. Am. Chem. Soc. 1994, 116, 7943.
(b) Wayland, B. B.; Basickes, L.; Mukerjee, S.; Wei, M.; Fryd, M. Macromolecules 1997, 30, 8109.
Wang, J.-S.; Gaynor, S. G.; Matyjaszewski, K. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1995, 36 (1), 465.
(a) Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901.
(b) Gaynor, S.; Matyjaszewski, K. Macromolecules 1997, 30, 4241.
(c) Percec, V.; Kim, H.-J.; Barboui, B. Macromolecules 1997, 30, 6702.
(d) Matyjaszewski, K.; Nakagawa, Y.; Jasieczek, C. B. Macramolecules 1998, 31, 1535.
(a) Hutchinson, R. A.; Aronson, M. T.; Richards, J. R. Macromolecules 1993, 26, 6410.
(b) Lyons, R. A.; Hutovic, J.; Piton, M. C.; Christie, D. I.; Clay, P. A.; Manders, B. G.; Kable, S. H.; Gilbert, R. G. Macromolecules 1996, 29, 1918.
Matyjaszewski et al. recently suggested the use of zerovalent metal as a way to reduce the amount of catalyst. See: Matyjaszewski, K.; Coca, S.; Gaynor, S. G.; Wei, M.; Woodworth, B. E. Macromolecules 1997, 30, 7348.
Fischer, H. J. Am. Chem. Soc. 1986, 108, 3925.
(b) Fischer, H. Macromolecules 1997, 30, 5666.
The synthesis of semi-telechelic polymer by ATRP has already been described. See: (a) Matyjaszewski, K.; Coca, S.; Nakagawa, Y.; Xia, J. Polym. Mater. Sci. Eng. 1997, 76, 147.
(b) Haddleton, D. M.; Waterson, C.; Derrick, P. J.; Jasieczek, C. B.; Shooter, A. J. Chem. Commun. 1997, 683.
(c) Haddleton, D. M.; Heming, A. M.; Kukulj, D.; Duncalf, D. J.; Shooter, A. J. Macromolecules 1998, 31, 2016.
(a) Hawker, C. J.; Hedrick, J. L.; Malmström, E. E.; Trollsås, M.; Mecerreyes, D.; Moineau, G.; Dubois, P.; Jérôme, R. Macromolecules 1998, 31, 213.
(b) Mecerreyes, D.; Moineau, G.; Dubois, P.; Jérôme, R.; Hedrick, J. L.; Hawker, C. J.; Malmström, E. A.; Trollsas, M. Angew. Chem., Int. Ed. Engl. 1998, 37 (9), 1274.
Dube, M.; Sanayei, R. A.; Penlidis, A.; O'Driscoll, K. F.; Reilly, P. M. J. Polym. Sci., Part A: Polym. Chem. 1991, 29, 703.
Tg was measured during the second heating run.
(a) Wunderlich, W.; Benfaremo, N.; Klapper, M.; Müllen, K. Macromol. Rapid Commun. 1996, 17, 433.
(b) Colombani, D.; Steenbock, M.; Klapper, M.; Müllen, K. Macromol. Rapid Commun. 1997, 18, 243.
Hatada, K.; Kitayama, T.; Fujimoto, N.; Nishiura, T. J. M. S. Pure Appl. Chem. 1993, A30, 645.
The temperature was first raised to 130°C for 30 min and then increased to 250°C (heating rate of 10°C/min) and maintained at that temperature for 6 h. All these steps were performed under nitrogen flow.
Similar publications
Sorry the service is unavailable at the moment. Please try again later.
This website uses cookies to improve user experience. Read more
Save & Close
Accept all
Decline all
Show detailsHide details
Cookie declaration
About cookies
Strictly necessary
Performance
Strictly necessary cookies allow core website functionality such as user login and account management. The website cannot be used properly without strictly necessary cookies.
This cookie is used by Cookie-Script.com service to remember visitor cookie consent preferences. It is necessary for Cookie-Script.com cookie banner to work properly.
Performance cookies are used to see how visitors use the website, eg. analytics cookies. Those cookies cannot be used to directly identify a certain visitor.
Used to store the attribution information, the referrer initially used to visit the website
Cookies are small text files that are placed on your computer by websites that you visit. Websites use cookies to help users navigate efficiently and perform certain functions. Cookies that are required for the website to operate properly are allowed to be set without your permission. All other cookies need to be approved before they can be set in the browser.
You can change your consent to cookie usage at any time on our Privacy Policy page.