High temperature synthesis of vinyl terminated polymers based on dendronized acrylates: A detailed product analysis studyf

Zorn, A. M., Malkoch, M., Carlmark, A., & Barner-Kowollik, C. (2011) High temperature synthesis of vinyl terminated polymers based on dendronized acrylates: A detailed product analysis studyf. Polymer Chemistry, 2(5).

View at publisher


The combination of dendrons and high temperature acrylate polymerization represents a viable route to form dendronized macromonomers. Dendronized acrylates based on 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) were synthesized using dendrimer synthesis and click chemistry (copper catalyzed azide alkyne cycloaddition (CuAAC)). The synthesis was carried out up to the 3rd generation and with a carbon spacer length of 6 or 9 between the acrylic function and the dendron core. These dendronized acrylates were subjected to auto-initiated high temperature acrylate polymerization. The polymerization was performed at 140 °C in a 5 wt% solution of hexyl acetate with a 2,2'-azobis(isobutyronitrile) (AIBN) concentration of 5 x 10-3 g mol-1. The vinyl terminated polymers were in-depth characterized via size exclusion chromatography (SEC) and size exclusion chromatography coupled to electrospray ionization mass spectrometry (SEC-ESI-MS) to assess the generated product spectrum and the efficiency of the process. The achievable number average molecular weight, Mn, was between 1700 and 4400 g mol -1. The degree of polymerization, DPn, decreases with increasing generations of the dendronized acrylates from 6.3 to 3.4. The purity of vinyl terminated oligomers containing a geminal double bond is up to 83%, with the dendronized acrylates of the 1st generation providing the best result. Moderate deprotection of the acetonide groups occurred spontaneously during the macromonomer formation process and reached its maximum at generation 3. © The Royal Society of Chemistry 2011.

Impact and interest:

12 citations in Scopus
Search Google Scholar™
12 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 99289
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :12
Export Date: 5 September 2016
Correspondence Address: Malkoch, M.; Fiber and Polymer Technology, School of Chemical Science and Engineering, Royal Institute of Technology, Teknikringen 56-58, SE-100 44 Stockholm, Sweden; email: malkoch@kth.se
References: Grayson, S.M., Frecher, J.M.J., (2001) Chem. Rev., 101, pp. 3819-3867; Malkoch, M., Malmstr̈m, E., Hult, A., (2002) Macromolecules, 35, pp. 8307-8314; Buhleier, E., Wehner, W., Vögtle, F., (1978) Synthesis, pp. 155-158; Vogtle, F., Gestermann, S., Hesse, R., Schwierz, H., Windisch, B., (2000) Prog. Polym. Sci., 25, pp. 987-1041; Tomalia, D.A., Fréchet, J.M.J., (2002) J. Polym. Sci., Part A: Polym. Chem., 40, pp. 2719-2728; Newkome, G.R., Yao, Z., Baker, G.R., Grupta, Y.K., (1985) J. Org. Chem., 50, pp. 2003-2004; Trollsås, M., Hendrik, J.L., Meccerreyes, D., Dubois, P., Jerome, R., Ihre, H., Hult, A., (1997) Macromolecules, 30, pp. 8508-8511; Knapen, J.W.J., Van Der Made, A.W., De Wilde, J.C., Van Leeuwen, A.W., Wijkens, P., Grove, D.M., Van Koten, G., (1994) Nature, 372, pp. 659-663; Busson, P., Ihre, H., Hult, A., (1998) J. Am. Chem. Soc., 120, pp. 9070-9071; Jansen, J.F.G.A., De Brabander-Van Den Berg, E.M.M., Meijer, E.W., (1994) Science, 266, pp. 1226-1229; Cordova, A., Janda, K.D., (2001) J. Am. Chem. Soc., 123, pp. 8248-8259; Carlmark, A., Hawker, C., Hult, A., Malkoch, M., (2009) Chem. Soc. Rev., 38, pp. 352-362; Schlüter, A.D., Rabe, J.P., (2000) Angew. Chem., Int. Ed., 39, p. 864; Li, W., Wu, D., Schlüter, A.D., Zhang, A., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, pp. 6630-6640; Xu, J., Tao, L., Liu, J., Bulmus, V., Davis, T.P., (2009) Macromolecules, 42, pp. 6893-6901; Hao, X., Malmström, E., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Aust. J. Chem., 58, pp. 483-491; Nyström, A., Hult, A., (2005) J. Polym. Sci., Part A: Polym. Chem., 43, pp. 3852-3867; Carlmark, A., Malmström, E., (2004) Macromolecules, 37, pp. 7491-7496; Malkoch, M., Carlmark, A., Woldegiorgis, A., Hult, A., Malmström, E., (2004) Macromolecules, 37, pp. 322-329; Benhabbour, S.R., Parrott, M.C., Gratton, S.E.A., Adronov, A., (2007) Macromolecules, 40, pp. 5678-5688; Rahm, M., Westlund, R., Eldsäter, C., Malmström, E., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, pp. 6191-6200; Hedrick, J.L., Trollsås, M., Hawker, C.J., Atthoff, B., Claesson, H., Heise, A., Miller, R.D., (1998) Macromolecules, 31, pp. 8691-8705; Nyström, A., Malkoch, M., Furó, I., Nyström, D., Unal, K., Antoni, P., Vamvounis, G., Hult, A., (2006) Macromolecules, 39, pp. 7241-7249; Chiefari, J., Chong, Y.K., Ercole, F., Krstina, J., Jeffery, J., Le, T.P.T., Mayadunne, R.T.A., Thang, S.H., (1998) Macromolecules, 31, p. 5559; Moad, G., Barner-Kowollik, C., The mechanism and kinetics of the RAFT process (2008) Handbook of RAFT Polymerization, , ed. C. Barner-Kowollik, Wiley-VCH, Weinheim; Matyjaszewski, K., Xia, J., (2001) Chem. Rev., 101, p. 2921; Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem. Rev., 301, p. 3661; Dubois, P., Coulembier, O., Raquez, J.-M., (2009) Handbook of Ring-Opening Polymerization, , Wiley-VCH, Weinheim; Albertson, A.-C., Varma, I.K., (2003) Biomacromolecules, 4, pp. 1466-1486; Chiefari, J., Moad, G., Rizzardo, E., Gridnev, A.A., (1998) US Pat., 98/47927; Chiefari, J., Jeffery, J., Mayadunne, R.T.A., Moad, G., Rizzardo, E., Thang, S.H., (1999) Macromolecules, 32, pp. 7700-7704; Nikitin, A.N., Hutchinson, R.A., Buback, M., Hesse, P., (2007) Macromolecules, 40, pp. 8631-8641; Junkers, T., Barner-Kowollik, C., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 7585-7605; Willemse, R.X.E., Van Herk, A.M., Panchenko, E., Junkers, T., Buback, M., (2005) Macromolecules, 38, pp. 5098-5103; Barner-Kowollik, C., Du Prez, F.E., Espeel, P., Hawker, C.J., Junkers, T., Schlaad, H., Van Camp, W., (2011) Angew. Chem., 50, pp. 60-20; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Polymer, 45, pp. 7791-7805; Junkers, T., Bennet, F., Koo, S.P.S., Barner-Kowollik, C., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 3433-3437; Zorn, A.-M., Junkers, T., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, pp. 2028-2035; Barner-Kowollik, C., Inglis, A.J., (2009) Macromol. Chem. Phys., 201, pp. 987-992; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40, p. 2004; Kolb, H.C., Sharpless, K.B., (2003) Drug Discovery Today, 8, pp. 1128-1137; Inglis, A.J., Stenzel, M.H., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, pp. 1792-1798; Inglis, A.J., Sinnwell, S., Stenzel, M.H., Barner-Kowollik, C., (2009) Angew. Chem., 48, pp. 2411-2414; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, pp. 331-334; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2008) Anal. Chem., 80, pp. 6915-6927; Wu, P., Malkoch, M., Hunt, J., Vestberg, R., Kaltgrad, E., Finn, M.G., Fokin, V.V., Hawker, C.J., (2005) Chem. Commun., pp. 5775-5777; Malkoch, M., Schleicher, K., Drockenmuller, E., Hawker, C.J., Russell, T.P., Wu, P., Fokin, V.V., (2005) Macromolecules, 38, p. 3663; Van Hook, J.P., Tobolsky, A.V., (1958) J. Am. Chem. Soc., 80, p. 779; Koo, S.P.S., Junkers, T., Barner-Kowollik, C., (2009) Macromolecules, 42, pp. 62-69; Junkers, T., (2008) Aust. J. Chem., 61, p. 646
Keywords: 2 ,2'-azobis(isobutyronitrile), 3rd generation, A-carbon, Azide-alkyne cycloaddition, Click chemistry, Copper catalyzed, Degree of polymerization, Dendrimer synthesis, Dendrons, Deprotection, Double bonds, Electrospray ionization mass spectrometry, Formation process, Hexyl acetate, High temperature, High-temperature synthesis, Macro-monomers, Macromonomer, Number average molecular weight, Product analysis, Propionic acids, Spacer lengths, Acetylene, Acrylic monomers, Chemical bonds, Electrospray ionization, Fatty acids, Gel permeation chromatography, Mass spectrometry, Methanol, Monomers, Oligomers, Polymerization, Salts, Size exclusion chromatography, Dendrimers
DOI: 10.1039/c0py00411a
ISSN: 17599954
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 05 Oct 2016 01:30

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page