Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

Lu, Wei; Huang, Caili; Hong, Kunlun; Kang, Nam-Goo; Mays, Jimmy W.

doi:10.1021/acs.macromol.6b01732

Title: Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

Journal Article · Tue Dec 06 00:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b01732· OSTI ID:1338533

Lu, Wei ^[1]; Huang, Caili ^[2];

^[2];

^[1]; Mays, Jimmy W. ^[1]

Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Living anionic polymerization of acrylates is challenging due to intrinsic side reactions including backbiting reactions of propagating enolate anions and aggregation of active chain ends. In this study, the controlled synthesis of poly(1-adamatyl acrylate) (PAdA) was performed successfully for the first time via living anionic polymerization through investigation of the initiation systems of sec-butyllithium/diphenylethylene/lithium chloride (sec-BuLi/DPE/LiCl), diphenylmethylpotassium/diethylzinc (DPMK/Et₂Zn), and sodium naphthalenide/dipenylethylene/diethylzinc (Na-Naph/DPE/Et2Zn) in tetrahydrofuran at -78 °C using custom glass-blowing and high-vacuum techniques. PAdA synthesized via anionic polymerization using DPMK with a large excess (more than 40-fold to DPMK) of Et₂Zn as the ligand exhibited predicted molecular weights from 4.3 to 71.8 kg/mol and polydispersity indices of around 1.10. In addition, the produced PAdAs exhibit a low level of isotactic content (mm triads of 2.1%). The block copolymers of AdA and methyl methacrylate (MMA) were obtained by sequential anionic polymerization, and the distinct living property of PAdA over other acrylates was demonstrated based on the observation that the resulting PAdA-b-PMMA block copolymers were formed with no residual PAdA homopolymer. The PAdA homopolymers exhibit a very high glass transition temperature (133 °C) and outstanding thermal stability (T_d: 376 °C) as compared to other acrylic polymers such as poly(tert-butyl acrylate) and poly(methyl acrylate). These merits make PAdA a promising candidate for acrylic-based thermoplastic elastomers with high upper service temperature and enhanced mechanical strength.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1338533

Journal Information:: Macromolecules, Vol. 49, Issue 24; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 30 works

Citation information provided by
Web of Science

References (56)

‘Living’ Polymers Szwarc, M. Nature, Vol. 178, Issue 4543 https://doi.org/10.1038/1781168a0	journal	November 1956
A Renaissance in Living Cationic Polymerization Aoshima, Sadahito; Kanaoka, Shokyoku Chemical Reviews, Vol. 109, Issue 11 https://doi.org/10.1021/cr900225g	journal	November 2009
Living ring-opening metathesis polymerization Bielawski, Christopher W.; Grubbs, Robert H. Progress in Polymer Science, Vol. 32, Issue 1, p. 1-29 https://doi.org/10.1016/j.progpolymsci.2006.08.006	journal	January 2007
Controlled/living radical polymerization: Features, developments, and perspectives Braunecker, Wade A.; Matyjaszewski, Krzysztof Progress in Polymer Science, Vol. 32, Issue 1 https://doi.org/10.1016/j.progpolymsci.2006.11.002	journal	January 2007
Recent advance in living anionic polymerization of functionalized styrene derivatives Hirao, Akira; Loykulnant, Surapich; Ishizone, Takashi Progress in Polymer Science, Vol. 27, Issue 8 https://doi.org/10.1016/S0079-6700(02)00016-3	journal	October 2002
Strategic developments in living anionic polymerization of alkyl (meth)acrylates Baskaran, D. Progress in Polymer Science, Vol. 28, Issue 4 https://doi.org/10.1016/S0079-6700(02)00083-7	journal	April 2003
Anionic vinyl polymerization—50 years after Michael Szwarc Baskaran, D.; Muller, A. Progress in Polymer Science, Vol. 32, Issue 2 https://doi.org/10.1016/j.progpolymsci.2007.01.003	journal	February 2007
Anionic polymerization of methacrylates. Novel functional polymers and copolymers Anderson, B. C.; Andrews, G. D.; Arthur, P. Macromolecules, Vol. 14, Issue 5 https://doi.org/10.1021/ma50006a093	journal	September 1981
Anionic polymerization of (meth)acrylic monomers. 4. Effect of lithium salts as ligands on the "living" polymerization of methyl methacrylate using monofunctional initiators Varshney, S. K.; Hautekeer, J. P.; Fayt, R. Macromolecules, Vol. 23, Issue 10 https://doi.org/10.1021/ma00212a004	journal	May 1990
Mechanistic aspects of ‘ligated’ anionic living polymerization (LAP): The case of (meth)acrylic ester monomers: MECHANISTIC ASPECTS OF LAP Wang, Jin-Shan; Jérôme, Robert; Teyssieacute, Philippe Journal of Physical Organic Chemistry, Vol. 8, Issue 4 https://doi.org/10.1002/poc.610080404	journal	April 1995
Controlled polymerization of methyl methacrylate using lithium aluminum alkyls Ballard, D. G. H.; Bowles, R. J.; Haddleton, D. M. Macromolecules, Vol. 25, Issue 22 https://doi.org/10.1021/ma00048a008	journal	October 1992
Preparation of high purity, anionic polymerization grade alkyl methacrylate monomers Allen, R. D.; Long, T. E.; McGrath, J. E. Polymer Bulletin, Vol. 15, Issue 2 https://doi.org/10.1007/BF00263389	journal	January 1986
New initiator system for the living anionic polymerization of tert-alkyl acrylates Fayt, R.; Forte, R.; Jacobs, C. Macromolecules, Vol. 20, Issue 6 https://doi.org/10.1021/ma00172a058	journal	November 1987
Anionic polymerization of (meth)acrylic monomers. 12. Effect of lithium chloride on the stereochemistry of the anionic polymerization of methyl methacrylate in THF and in a 9/1 toluene/THF mixture Wang, Jin Shan; Jerome, Robert; Warin, Roger Macromolecules, Vol. 26, Issue 22 https://doi.org/10.1021/ma00074a021	journal	October 1993
Synthesis and unperturbed dimensions of poly(diphenylmethyl methacrylate) Mays, Jimmy W.; Hadjichristidis, Nikos; Lindner, J. S. Journal of Polymer Science Part B: Polymer Physics, Vol. 28, Issue 11 https://doi.org/10.1002/polb.1990.090281101	journal	October 1990
Highly syndiotactic poly(methyl methacrylate) with narrow molecular weight distribution formed by tert-butyllithium-trialkylaluminium in toluene Kitayama, Tatsuki; Shinozaki, Tetsunori; Masuda, Eiji Polymer Bulletin, Vol. 20, Issue 6 https://doi.org/10.1007/BF00263663	journal	December 1988
Living and highly syndiotactic polymerization of methyl methacrylate and other methacrylates by tert-butyllithiumtrialkylaluminium in toluene Kitayama, Tatsuki; Shinozaki, Tetsunori; Sakamoto, Takashi Die Makromolekulare Chemie, Vol. 15, Issue S19891 https://doi.org/10.1002/macp.1989.020151989116	journal	June 1989
Preparation of Highly Isotactic Poly(methyl methacrylate) of Low Polydispersity Hatada, Koichi; Ute, Koichi; Tanaka, Katsuji Polymer Journal, Vol. 17, Issue 8 https://doi.org/10.1295/polymj.17.977	journal	August 1985
New Ligands for the Living Isotactic Anionic Polymerization of Methyl Methacrylate in Toluene at 0 °C. 1. Ligation of Butyllithium by Lithium Silanolates Zundel, Thomas; Teyssié, Philippe; Jérôme, Robert Macromolecules, Vol. 31, Issue 8 https://doi.org/10.1021/ma9711001	journal	April 1998
Anionic polymerization of alkyl methacrylates in the presence of diethylzinc Ozaki, Hiroyuki; Hirao, Akira; Nakahama, Seiichi Macromolecular Chemistry and Physics, Vol. 196, Issue 7 https://doi.org/10.1002/macp.1995.021960702	journal	July 1995
Controlled Polymerization of Acrylates and Methacrylates ¹ Davis, T. P.; Haddleton, D. M.; Richards, S. N. Journal of Macromolecular Science, Part C: Polymer Reviews, Vol. 34, Issue 2 https://doi.org/10.1080/15321799408009636	journal	May 1994
Anionic polymerization of acrylic monomers. 6. Synthesis, characterization, and modification of poly(methyl methacrylate)-poly(tert-butyl acrylate) di- and triblock copolymers Varshney, Sunil K.; Jacobs, Christian; Hautekeer, Jean Paul Macromolecules, Vol. 24, Issue 18 https://doi.org/10.1021/ma00018a003	journal	September 1991
Anionic Polymerization of Acrylic Monomers. 21. Anionic Sequential Polymerization of 2-Ethylhexyl Acrylate and Methyl Methacrylate Wang, J. -S.; Jerome, R.; Bayard, Ph. Macromolecules, Vol. 27, Issue 18 https://doi.org/10.1021/ma00096a010	journal	August 1994
Polymerization of N,N -Dialkylacrylamides with Anionic Initiators Modified by Diethylzinc Nakahama, S.; Kobayashi, M.; Ishizone, T. Journal of Macromolecular Science, Part A, Vol. 34, Issue 10 https://doi.org/10.1080/10601329708010312	journal	October 1997
Controlled Anionic Polymerization of tert -Butyl Acrylate with Diphenylmethyl Anions in the Presence of Dialkylzinc Ishizone, Takashi; Yoshimura, Ken; Hirao, Akira Macromolecules, Vol. 31, Issue 25 https://doi.org/10.1021/ma9809482	journal	December 1998
Anionic polymerization of primary acrylates as promoted by lithium 2‐(2‐methoxyethoxy) ethoxide Nugay, N.; Nugay, T.; Jérôme, R. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 35, Issue 2 https://doi.org/10.1002/(SICI)1099-0518(19970130)35:2<361::AID-POLA19>3.3.CO;2-X	journal	January 1997
Evaluation of the Spacer Effect on Adamantane-Containing Vinyl Polymer T _g 's Acar, Havva Yagci; Jensen, Jennifer J.; Thigpen, Kevin Macromolecules, Vol. 33, Issue 10 https://doi.org/10.1021/ma991621j	journal	May 2000
Prediction of the Glass Transition Temperature of Multicyclic and Bulky Substituted Acrylate and Methacrylate Polymers Using the Energy, Volume, Mass (EVM) QSPR Model Cypcar, Christopher C.; Camelio, Philippe; Lazzeri, Veronique Macromolecules, Vol. 29, Issue 27 https://doi.org/10.1021/ma961170s	journal	January 1996
Glass transition temperatures of polymethacrylates with alicyclic side groups Mays, Jimmy W.; Siakali-Kioulafa, Ekaterini; Hadjichristidis, Nikos Macromolecules, Vol. 23, Issue 14 https://doi.org/10.1021/ma00216a022	journal	July 1990
Synthesis of Poly(decahydro-2-naphthyl methacrylate)s with Different Geometric Structures and Effects of Side-Group Dynamics on Polymer Properties Investigated by Thermal and Dynamic Mechanical Analyses and DFT Calculations Ozaki, Anri; Sumita, Koha; Goto, Kunihiro Macromolecules, Vol. 46, Issue 8 https://doi.org/10.1021/ma400254d	journal	April 2013
Anionic Polymerizations of 1-Adamantyl Methacrylate and 3-Methacryloyloxy-1,1′-biadamantane Ishizone, Takashi; Tajima, Hiroyuki; Torimae, Hiroshi Macromolecular Chemistry and Physics, Vol. 203, Issue 16 https://doi.org/10.1002/macp.200290018	journal	December 2002
All-Acrylic Multigraft Copolymers: Effect of Side Chain Molecular Weight and Volume Fraction on Mechanical Behavior Goodwin, Andrew; Wang, Weiyu; Kang, Nam-Goo Industrial & Engineering Chemistry Research, Vol. 54, Issue 39 https://doi.org/10.1021/acs.iecr.5b02560	journal	September 2015
Synthesis and thermal, optical, and mechanical properties of sequence-controlled poly(1-adamantyl acrylate)- block -poly( n -butyl acrylate) containing polar side group Nakano, Yoshinori; Sato, Eriko; Matsumoto, Akikazu Journal of Polymer Science Part A: Polymer Chemistry, Vol. 52, Issue 20 https://doi.org/10.1002/pola.27322	journal	July 2014
Cyclodextrin inclusion complexes: studies of the variation in the size of alicyclic guests Eftink, Maurice R.; Andy, Maria L.; Bystrom, Katarina Journal of the American Chemical Society, Vol. 111, Issue 17 https://doi.org/10.1021/ja00199a041	journal	August 1989
Cucurbit[ 7 ]uril-Based Vesicles Formed by Self-assembly of Supramolecular Amphiphiles Li, Jiaxi; Zhou, Lipeng; Luo, Quan Chinese Journal of Chemistry, Vol. 30, Issue 9 https://doi.org/10.1002/cjoc.201200603	journal	September 2012
Highly Elastic Supramolecular Hydrogels Using Host–Guest Inclusion Complexes with Cyclodextrins Kakuta, Takahiro; Takashima, Yoshinori; Harada, Akira Macromolecules, Vol. 46, Issue 11 https://doi.org/10.1021/ma400695p	journal	May 2013
Polymer Networks Assembled by Host−Guest Inclusion between Adamantyl and β-Cyclodextrin Substituents on Poly(acrylic acid) in Aqueous Solution Li, Li; Guo, Xuhong; Wang, Jie Macromolecules, Vol. 41, Issue 22 https://doi.org/10.1021/ma8020147	journal	October 2008
High temperature resistant tailor-made poly(meth)acrylates bearing adamantyl group via atom transfer radical polymerization Kavitha, A. Amalin; Singha, Nikhil K. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 46, Issue 21 https://doi.org/10.1002/pola.23015	journal	November 2008
Photopolymerization of 1-adamantyl acrylate pohotoinitiated by free radical photoinitiators Wang, Kemin; Cui, Rong; Gu, Juming Journal of Applied Polymer Science, Vol. 123, Issue 1 https://doi.org/10.1002/app.34496	journal	July 2011
Living Anionic Polymerizations of 4-(1-Adamantyl)styrene and 3-(4-Vinylphenyl)-1,1‘-biadamantane Kobayashi, Shingo; Matsuzawa, Takahiro; Matsuoka, Shin-ichi Macromolecules, Vol. 39, Issue 18 https://doi.org/10.1021/ma060977+	journal	August 2006
Experimental techniques in high-vacuum anionic polymerization Uhrig, David; Mays, Jimmy W. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 24 https://doi.org/10.1002/pola.21016	journal	January 2005
Synthesis and characterization of polystyrene-poly(ethylene oxide) graft copolymers Candau, Françoise; Afchar-Taromi, Faramarz; Rempp, Paul Polymer, Vol. 18, Issue 12 https://doi.org/10.1016/0032-3861(77)90289-0	journal	December 1977
Anionic polymerization: High vacuum techniques Hadjichristidis, Nikos; Iatrou, Hermis; Pispas, Stergios Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 18 https://doi.org/10.1002/1099-0518(20000915)38:18<3211::AID-POLA10>3.0.CO;2-L	journal	January 2000
Mechanisms and kinetics of the anionic polymerization of acrylates, 3. Effect of lithium chloride and lithium tert‐butoxide on the oligomerization of tert‐butyl acrylate Janata, Miroslav; Lochmann, Lubomír; Müller, Axel H. E. Die Makromolekulare Chemie, Vol. 194, Issue 2, p. 625-636 https://doi.org/10.1002/macp.1993.021940222	journal	February 1993
Anionic polymerization of 4-(9-carbazolyl)methylstyrene Cho, Young-Sun; Kim, See-Woo; Ihn, Chi-Sung Polymer, Vol. 42, Issue 18 https://doi.org/10.1016/S0032-3861(01)00259-2	journal	August 2001
Effect of Biphenyl Spacers on the Anionic Polymerization of 2-(4′-Vinylbiphenyl-4-yl)pyridine Kang, Nam-Goo; Changez, Mohammad; Kim, Myung-Jin Macromolecules, Vol. 47, Issue 19 https://doi.org/10.1021/ma500974m	journal	October 2014
Anionic polymerization of methacrylate esters initiated with esters of α-metallocarboxylic acids Lochmann, Lubomír; Rodová, Miroslava; Trekoval, Jiří Journal of Polymer Science: Polymer Chemistry Edition, Vol. 12, Issue 9 https://doi.org/10.1002/pol.1974.170120924	journal	September 1974
Polymerization of Styrene by n-Butyllithium. II. Effect of Lewis Acids and Bases ¹ Welch, F. J. Journal of the American Chemical Society, Vol. 82, Issue 23 https://doi.org/10.1021/ja01508a009	journal	December 1960
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
The SN2-SN1 spectrum. 4. The SN2 (intermediate) mechanism for solvolyses of tert-butyl chloride: a revised Y scale of solvent ionizing power based on solvolyses of 1-adamantyl chloride Bentley, T. William; Carter, Gillian E. Journal of the American Chemical Society, Vol. 104, Issue 21 https://doi.org/10.1021/ja00385a031	journal	October 1982
Morphological transition during the thermal deprotection of poly(isobornyl acrylate)-b-poly(1-ethoxyethyl acrylate) Wouters, Daan; Van Camp, Wim; Dervaux, Bart Soft Matter, Vol. 3, Issue 12 https://doi.org/10.1039/b708494c	journal	January 2007
Synthesis and characterization of poly(1-adamantyl methacrylate): effects of the adamantyl group on radical polymerization kinetics and thermal properties of the polymer Matsumoto, Akikazu; Tanaka, Satoshi; Otsu, Takayuki Macromolecules, Vol. 24, Issue 14 https://doi.org/10.1021/ma00014a008	journal	July 1991
Dependence of the glass transition temperature of poly(methyl methacrylate) on tacticity and molecular weight Thompson, Edward V. Journal of Polymer Science Part A-2: Polymer Physics, Vol. 4, Issue 2 https://doi.org/10.1002/pol.1966.160040204	journal	April 1966
Glass transitions of polymers with compressed fluid diluents: type II and III behavior Condo, P. D.; Paul, D. R.; Johnston, K. P. Macromolecules, Vol. 27, Issue 2 https://doi.org/10.1021/ma00080a008	journal	January 1994
Component relaxation dynamics in a miscible polymer blend: poly(ethylene oxide)/poly(methyl methacrylate) Zawada, Jeffrey A.; Ylitalo, Caroline M.; Fuller, Gerald G. Macromolecules, Vol. 25, Issue 11 https://doi.org/10.1021/ma00037a017	journal	May 1992
Molecular photochemistry. XXXIII. Photochemistry of 1-adamantylacetone Gagosian, Robert B.; Dalton, J. Christopher; Turro, Nicholas J. Journal of the American Chemical Society, Vol. 92, Issue 15 https://doi.org/10.1021/ja00718a057	journal	July 1970

Cited By (10)

All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties Lu, Wei; Wang, Yangyang; Wang, Weiyu Polymer Chemistry, Vol. 8, Issue 37 https://doi.org/10.1039/c7py01225j	journal	January 2017
Solution properties, unperturbed dimensions, and chain flexibility of poly(1-adamantyl acrylate) Lu, Wei; Yin, Panchao; Osa, Masashi Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 20 https://doi.org/10.1002/polb.24408	journal	August 2017
Novel Features of 9‐Methylene‐9H‐thioxanthene (MTAE) in Living Anionic Polymerization Chang, Shuang; Han, Li; Ma, Hongwei Macromolecular Chemistry and Physics, Vol. 220, Issue 15 https://doi.org/10.1002/macp.201900052	journal	July 2019
Poly(polyhedral)s: synthesis and study of a new class of polyurethanes composed of homocubanes: Poly(polyhedral)s Hwang, Chiwon; Sultane, Prakash R.; Kang, Dong-Hee Polymer International, Vol. 67, Issue 12 https://doi.org/10.1002/pi.5691	journal	September 2018
A controlled synthesis method of alkyl methacrylate block copolymers via living anionic polymerization at ambient temperature Li, Zheng; Chen, Jianding; Zou, Guijin RSC Advances, Vol. 9, Issue 28 https://doi.org/10.1039/c9ra01577a	journal	January 2019
From design to applications of stimuli-responsive hydrogel strain sensors Zhang, Dong; Ren, Baiping; Zhang, Yanxian Journal of Materials Chemistry B, Vol. 8, Issue 16 https://doi.org/10.1039/c9tb02692d	journal	January 2020
Phosphorus‐Containing Block Copolymers from the Sequential Living Anionic Copolymerization of a Phosphaalkene with Methyl Methacrylate Chen, Leixing; Rawe, Benjamin W.; Adachi, Kaoru Chemistry – A European Journal, Vol. 24, Issue 68 https://doi.org/10.1002/chem.201803582	journal	November 2018
Synthesis of transparent block copolymers consisting of poly(diisopropyl fumarate) and poly(2-ethylhexyl acrylate) segments by reversible addition-fragmentation chain transfer polymerization using trithiocarbonates as the chain transfer agents Takada, Kohei; Matsumoto, Akikazu Journal of Polymer Science Part A: Polymer Chemistry, Vol. 56, Issue 22 https://doi.org/10.1002/pola.29240	journal	October 2018
Synthesis of chain end acyl-functionalized polymers by living anionic polymerization: versatile precursors for H-shaped polymers Takahata, Kazuki; Uchida, Satoshi; Goseki, Raita Polymer Chemistry, Vol. 10, Issue 29 https://doi.org/10.1039/c9py00642g	journal	January 2019
Stereoelectronically Directed Photodegradation of Poly(adamantyl Vinyl Ketone) Sultane, Prakash R.; Bielawski, Christopher W. Macromolecular Rapid Communications, Vol. 40, Issue 19 https://doi.org/10.1002/marc.201900302	journal	July 2019

Similar Records

All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties

Journal Article · Fri Aug 25 00:00:00 EDT 2017 · Polymer Chemistry · OSTI ID:1338533

Lu, Wei; Wang, Yangyang; Wang, Weiyu; +6 more

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

Journal Article · Fri Dec 23 00:00:00 EST 2016 · Macromolecules · OSTI ID:1338533

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun; +2 more

All-acrylic superelastomers: facile synthesis and exceptional mechanical behavior

Journal Article · Tue Oct 17 00:00:00 EDT 2017 · Polymer Chemistry · OSTI ID:1338533

Lu, Wei; Goodwin, Andrew; Wang, Yangyang; +9 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

Citation Formats

References (56)

Cited By (10)

Similar Records

Related Subjects