Regulation of the cis-1,4- and trans-1,4-Polybutadiene Multiblock Copolymers via Chain Shuttling Polymerization Using a Ternary Neodymium Organic Sulfonate Catalyst

Multiblock copolymers of cis-1,4- and trans-1,4-polybutadiene (PBD) have shown exciting and unique elastic properties. But the catalyst that can steadily regulate the content and the distribution of the stereoselective monomers in the PBD copolymer is full of challenge. We reported here a ternary catalyst of Nd(CF3SO3)3·H2O·3TBP/Mg(n-Bu)2/MMAO (TBP: tributyl phosphate; MMAO: modified methylaluminoxane) that can synthesize such copolymer via chain shuttling polymerization in a highly efficient and tunable way. The stereoselectivity of the cis-1,4 and trans-1,4 monomers in the PBD copolymers can be well regulated through the [MMAO]/[Nd] ratio, the [Mg]/[Nd] ratio, and the delayed feeding time of MMAO. The increase of the [MMAO]/[Nd] ratio and the delayed feeding time of MMAO as well as the reduced [Mg]/[Nd] ratio all result in the increase of the trans-1,4 content in the product from 8.4% to 95.3%. The multiblock rather than the diblock structure for the copolymer is validated by NMR, WAXD, and DSC. Finally...

[1]  G. Stoclet,et al.  Isoprene chain shuttling polymerisation between cis and trans regulating catalysts: straightforward access to a new material. , 2017, Chemical communications.

[2]  Bo Liu,et al.  Regioselective Chain Shuttling Polymerization of Isoprene: An Approach To Access New Materials from Single Monomer , 2016 .

[3]  S. Norsic,et al.  Deciphering the Mechanism of Coordinative Chain Transfer Polymerization of Ethylene Using Neodymocene Catalysts and Dialkylmagnesium , 2016 .

[4]  Xuequan Zhang,et al.  Highly trans-1,4-stereoselective coordination chain transfer polymerization of 1,3-butadiene and copolymerization with cyclic esters by a neodymium-based catalyst system , 2015 .

[5]  Xuequan Zhang,et al.  Synthesis of polybutadienes with controllable microstructure by a novel binary Nd(3-NBSO3)3/alkylaluminum catalyst system , 2015, Chinese Journal of Polymer Science.

[6]  G. Stoclet,et al.  Isoprene-styrene chain shuttling copolymerization mediated by a lanthanide half-sandwich complex and a lanthanidocene: straightforward access to a new type of thermoplastic elastomers. , 2014, Angewandte Chemie.

[7]  P. Zinck,et al.  Trans-stereospecific polymerization of butadiene and random copolymerization with styrene using borohydrido neodymium/magnesium dialkyl catalysts , 2013 .

[8]  Liping Zhao,et al.  Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems , 2013 .

[9]  Xuequan Zhang,et al.  Reversible coordinative chain transfer polymerization of isoprene and copolymerization with ε-caprolactone by neodymium-based catalyst , 2012 .

[10]  M. Visseaux,et al.  Combining Polyethylene CCG and Stereoregular Isoprene Polymerization: First Synthesis of Poly(ethylene)-b-(trans-isoprene) by Neodymium Catalyzed Sequenced Copolymerization , 2012 .

[11]  P. Zinck,et al.  Isoprene polymerization using a neodymium phenolate pre-catalyst combined to aluminum based co-catalysts , 2012 .

[12]  Kunyu Zhang,et al.  Chain-shuttling polymerization at two different scandium sites: regio- and stereospecific "one-pot" block copolymerization of styrene, isoprene, and butadiene. , 2011, Angewandte Chemie.

[13]  P. Zinck,et al.  Half‐lanthanocene/dialkylmagnesium‐mediated coordinative chain transfer copolymerization of styrene and hexene , 2011 .

[14]  Liana Annunziata,et al.  Chain Growth Polymerization of Isoprene and Stereoselective Isoprene–Styrene Copolymerization Promoted by an ansa-Bis(indenyl)allyl–Yttrium Complex , 2011 .

[15]  P. Zinck,et al.  Borohydrido rare earth based coordinative chain transfer copolymerization: A convenient tool for tuning the microstructure of isoprene/styrene copolymers , 2011 .

[16]  P. Zinck,et al.  Rare earths/main group metal alkyls catalytic systems for the 1,4‐trans stereoselective coordinative chain transfer polymerization of isoprene , 2010 .

[17]  Fosong Wang,et al.  Preparation of high cis‐1,4 polyisoprene with narrow molecular weight distribution via coordinative chain transfer polymerization , 2010 .

[18]  Tobias A Bauer,et al.  An efficient yttrium catalysed version of the "Aufbaureaktion" for the synthesis of terminal functionalised polyethylene. , 2010, Dalton transactions.

[19]  Z. Hou,et al.  Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand. , 2010, Chemical communications.

[20]  P. Roussel,et al.  Reversible coordinative chain transfer polymerization of styrene by rare earth borohydrides, chlorides/dialkylmagnesium systems , 2010 .

[21]  Feng Wang,et al.  Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine , 2009 .

[22]  P. Zinck,et al.  Catalytic Chain Transfer (co-)Polymerization: Unprecedented Polyisoprene CCG and a New Concept to Tune the Composition of a Statistical Copolymer. , 2009, Macromolecular rapid communications.

[23]  Li Wang,et al.  A Novel Linear−Hyperbranched Multiblock Polyethylene Produced from Ethylene Monomer Alone via Chain Walking and Chain Shuttling Polymerization , 2009 .

[24]  S. Mecking,et al.  Catalytic Polymerization of Butadiene in Aqueous Systems with Cationic Nickel(II) Complexes , 2008 .

[25]  Jia Wei,et al.  Living Coordinative Chain-Transfer Polymerization and Copolymerization of Ethene, α-Olefins, and α,ω-Nonconjugated Dienes using Dialkylzinc as “Surrogate” Chain-Growth Sites , 2008 .

[26]  R. Kuhlman,et al.  Investigations of Chain Shuttling Olefin Polymerization Using Deuterium Labeling , 2008 .

[27]  L. Sita,et al.  Highly efficient, living coordinative chain-transfer polymerization of propene with ZnEt2: practical production of ultrahigh to very low molecular weight amorphous atactic polypropenes of extremely narrow polydispersity. , 2008, Journal of the American Chemical Society.

[28]  F. Alfano,et al.  Polypropylene “Chain Shuttling” at Enantiomorphous and Enantiopure Catalytic Species: Direct and Quantitative Evidence from Polymer Microstructure , 2007 .

[29]  P. Hustad,et al.  Catalytic Production of Olefin Block Copolymers via Chain Shuttling Polymerization , 2006, Science.

[30]  Y. Wakatsuki,et al.  Butadiene Polymerization Catalyzed by Lanthanide Metallocene−Alkylaluminum Complexes with Cocatalysts: Metal-Dependent Control of 1,4-Cis/Trans Stereoselectivity and Molecular Weight , 2006 .

[31]  G. Britovsek,et al.  Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: a comparative investigation of highly active catalyst systems across the transition series. , 2005, Journal of the American Chemical Society.

[32]  Tapio Saarinen,et al.  Ethylene–Propylene Copolymerisations: Effect of Metallocene Structure on Termination Reactions and Polymer Microstructure , 2005 .

[33]  A. Tuzi,et al.  Polymerization of Propene and 1,3‐Butadiene with Vanadyl(V) Monoamidinate Precatalysts and MAO or Dialkylaluminum Chloride Cocatalysts , 2004 .

[34]  T. Masuda,et al.  Homogeneous neodymium iso-propoxide/modified methylaluminoxane catalyst for isoprene polymerization , 2003 .

[35]  T. Masuda,et al.  Novel neodymium (III) isopropoxide‐methylaluminoxane catalyst for isoprene polymerization , 2002 .

[36]  S. Kim,et al.  Selective Chain Transfer Reactions in Metallocene Catalyzed Copolymerization of Ethylene with Allylbenzene , 2000 .

[37]  S. Kim,et al.  Copolymerization of ethylene with allylbenzene using rac-ethylenebis(indenyl)zirconium dichloride/methylaluminoxane as a catalyst , 1999 .

[38]  G. Ungar,et al.  Hexagonal columnar phase in 1,4-trans-polybutadiene: morphology, chain extension, and isothermal phase reversal , 1992 .

[39]  M. Thompson,et al.  Ethylene insertion and .beta.-hydrogen elimination for permethylscandocene alkyl complexes. A study of the chain propagation and termination steps in Ziegler-Natta polymerization of ethylene , 1990 .

[40]  D. K. Jenkins.  Butadiene polymerization with a rare earth compound using a magnesium alkyl cocatalyst: 1 , 1985 .

[41]  A. White,et al.  Structure and stereochemistry in 'f-block' complexes of high coordination number. VIII. The [M(unidentate)9] system. Crystal structures of [M(OH2)9] [CF3SO3]3, M = La, Gd, Lu, Y , 1983 .