Living and highly syndiotactic polymerization of methyl methacrylate and other methacrylates by tert‐butyllithiumtrialkylaluminium in toluene

  title={Living and highly syndiotactic polymerization of methyl methacrylate and other methacrylates by tert‐butyllithiumtrialkylaluminium in toluene},
  author={Tatsuki Kitayama and Tetsunori Shinozaki and T Sakamoto and Masanori Yamamoto and Koichi Hatada},
  journal={Macromolecular Chemistry and Physics},
Highly syndiotactic poly(methyl methacrylate)s (PMMAs) with narrow molecular weight distribution (MWD) were prepared by polymerization of MMA in toluene at low temperatures, initiated with tert-butyllithium (t-C4H9Li) combined with trialkylaluminium compounds such as triethyl-, tributyl-, and trioctylaluminium (mole ratio Al/Li ≥ 3). Polymerization was initiated by the t-C4H9 anion and proceeded in a living manner. Several alkyl methacrylates were also polymerized with t-C4H9Li-(n-C4H9)3Al to… 
Preparation of highly syndiotactic block copolymers of methyl methacrylate and lauryl methacrylate and their characterization
SummaryHighly syndiotactic diblock and triblock copolymers comprising lauryl methacrylate (LMA) and methyl methacrylate (MMA) with narrow molecular weight distributions were prepared by the living
Stereospecific living polymerization and copolymerization of methacrylate and their use for construction of stereoregular chain architecture
Highly isotactic and highly syndiotactic living polymerizations of alkyl methacrylates were carried out in toluene at low temperatures by t-C4H9MgBr and t-C4H9Li-R3A1, respectively. These living
Stereoregular polymerization of polysiobutylene macromonomer having methacryloyl function
SummaryThe polysiobutylene (PIB) macromonomer having methacryloyl function was prepared from a hydroxy-terminated PIB, α-phenyl-ω-(2-hydroxy-1-methylethyl)-poly(1,1-dimethylethylene) and methacryloyl
Syndiotactic-specific polymerization of methyl methacrylate with tert-butyllithium/trialkylaluminum in dichloromethane
By using dichloromethane as a polymerization solvent, syndiotactic-specific polymerization of methyl methacrylate with t-BuLi in the presence of large excess of tributylaluminum at –78 °C proceeded
Stereocomplex formation of isotactic poly(methyl methacrylate) with a wide variety of syndiotactic polymethacrylates
Syndiotactic (st–) polymers of methacrylates with primary and secondary ester groups, prepared by the syndiotactic-specific living polymerization with t-C4H9Li/R3Al, were found to form
Preparation of heterotactic-rich poly(methyl methacrylate) with narrow molecular weight distribution bytert-butyllithium/bis(2,6-di-tert-butylphenoxy)methylaluminum
SummaryPolymerization of methyl methacrylate (MMA) withtert-butyllithium (t-C4H9Li) in toluene in the presence of aluminum alkoxides such as ethoxide,tert-butoxide and 2,6-di-tert-butylphenoxide,
Feature Article: Heterotactic Polymers of Methacrylates and Their Properties
Abstract Heterotactic (ht-) polymer is a kind of stereoregular polymer, which consists of an alternate arrangement of meso (m) and racemo (r) diads. Heterotactic polymerization requires a higher
Syndiotactic-Specific Polymerization of Methacrylates by Tertiary Phosphine-Triethylaluminum
Polymerization of MMA with R3P-R3′Al in toluene at low temperatures was reinvestigated and was found to give highly syndiotactic PMMA. Among the initiators examined Ph3P-Et3Al gave the PMMA with
Highly Isotactic and Living Polymerization of Ethyl Methacrylate with t-C4H9MgBr in Toluene and the Preparation of Block and Random Copolymers with High Stereoregularity
The polymerization of ethyl methacrylate (EMA) with t-C4H9MgBr in toluene at low temperature gave a highly isotactic polymer as in the case of living and highly isotactic polymerization of methyl
Control of Main-Chain Stereostructure of Graft Polymers via Stereospecific Anionic Copolymerization of Syndiotactic Poly(methyl methacrylate) Macromonomer Having Methacryloyl Function with Methacrylate Monomers
Highly syndiotactic PMMA macromonomer having methacryloyl group as a polymerizable function was prepared from the corresponding living PMMA anion formed with t-C4H9Li/(n-C4H9)3Al (1/3) in toluene at


Highly syndiotactic poly(methyl methacrylate) with narrow molecular weight distribution formed by tert-butyllithium-trialkylaluminium in toluene
SummaryPolymerization of MMA with t-C4H9Li in toluene in the presence of trialkylaluminum(alkyl=methyl, ethyl, butyl, isobutyl, and octyl) was examined at various Al/Li ratios. Triethyl-, tributyl
The stereoregularity of poly(methyl methacrylate)s formed in the presence of highly syndiotactic poly(methyl methacrylate)s
Methyl methacrylate (MMA) was radically polymerized in the presence of highly syndiotactic deuterated or undeuterated poly(methyl methacrylate)s. In contrast to observations found in the literature
Living and Highly Isotactic Polymerization of Methyl Methacrylate by t-C4H9MgBr in Toluene
Highly isotactic PMMAs with narrow molecular weight distribution (Mw/Mn<1.2) have been prepared by the polymerization of MMA in toluene at −78°C initiated by t-C4H9MgBr prepared in diethyl ether. The
Preparation of PMMA macromers by o-vinylbenzylmagnesium chloride and their polymerization
SummaryPolymerization of MMA with o-vinylbenzylmagnesium chloride was examined in toluene and in tetrahydrofuran (THF) at various temperatures. The polymer formed in toluene at −78°C was highly
Studies on p- and m-Vinylbenzylmagnesium Chlorides as Initiators and Monomers—Preparations of Macromers and Poly(Grignard reagent)
Abstractp- and m-Vinylbenzylmagnesium chlorides (VBzMgCl) were prepared in diethyl ether from the corresponding chloromethylstyrenes, and used as initiators in the polymerizations of MMA and styrene.
Infrared studies of stereoregular polymerization of methyl methacrylate and methacrylonitrile by organometallic compounds
Infrared spectra of reaction mixtures of methyl methacrylate or methacrylonitrile with an equimolar amount of organometallic compounds were investigated in relation to the stereoregulating ability of
Stereospecific polymerization of alpha-substituted acrylic acid esters polymerization
A large number of methacrylates containing various ester groups have been polymerized and copolymerized with radical and anionic initiators, such as organoalkali metal, magnesium and aluminum
Synthesis and characterization of polyalkylmethacrylate macromonomers
SummaryThe synthesis of polyalkylmethacrylate macromonomers has been performed anionically by direct deactivation of the carbanionic sites with p-vinyl-or p-isopropenylbenzyl bromide. The