Study on the polymerizations of methyl methacrylate and styrene initiated with chlorotrimethylsilane and CuCl/N,N,N′,N″,N″-pentamethyldiethyltriamine

Methyl methacrylate (MMA) and styrene (St) have been radically polymerized in the presence of chlorotrimethylsilane and CuCl/N,N,N′,N″,N″-pentamethyldiethyltriamine (Me₃SiCl/CuCl/PMDETA). An analysis of the resultant polymers by ¹H NMR discloses terminal silyl group and chlorine atom in all the obtained polymers. Kinetics studies have been carried out by measuring monomer conversions and polymer molecular weights against polymerization time. The results indicate that, for both MMA and St polymerizations, the monomer conversions exhibit a quasi-linear relationship with polymerization time, and the polymer number-average molecular weight (M_n) also increases with monomer conversion. The molecular weights of both PS and PMMA exceed one hundred thousand. Regardless of molecular weight, all the polymers show narrow molecular distributions (M_w/M_n = 1.2-1.5). These polymerization reactions are speculated to follow a mechanism similar to that of atom transfer radical polymerization (ATRP).     

Controlled synthesis and fluorescent properties of poly(9-(4-vinylbenzyl)-9H-carbazole) via nitroxide-mediated living free-radical polymerization

The functional polymer containing carbazole unit, [(poly(9-(4-vinylbenzyl)-9H-carbazole) (PVBK)], was successfully prepared via nitroxide-mediated living free-radical polymerization of 9-(4-vinylbenzyl)-9H-carbazole (VBK). The controlled features of the polymerization were confirmed by the linear increase in the molecular weight with the monomer conversion while keeping the relative narrow molecular weight distribution (M_w/M_n ? 1.51), and successful chain extension with styrene. The resulting polymer absorbed light in the 305-355 nm range and exhibited fluorescent emission at 350 nm. The fluorescent intensity of the polymer was lower than that of monomer and was affected by the properties of the different solvents, which decreased in the following order: DMF > THF > CHCl₃ at the same concentration of carbazole units. The fluorescence intensity of the polymer was apparently influenced by chromophore concentration, and the maximum value was obtained when the carbazole unit concentration was around 8 × 10⁻⁵ mol/L. Moreover, it was shown that the strong fluorescence of PVBK can be quenched by methyl acrylate (MA).     

Ring‐opening metathesis polymerization of functionalized cyclooctene by a ruthenium‐based catalyst in ionic liquid

This paper describes the synthesis of a novel monomer of 5‐substituted cyclooctene with the pendant of imidazolium salt (7) and the ring‐opening metathesis polymerization of the functionalized cyclooctenes ( 4 and 7 ) in CH₂Cl₂ and ionic liquid [bmim][PF₆] by a ruthenium‐based catalyst RuCl₂(PCy₃)(SIMes)(CHPh) (2). The polymerization, which was carried out in ionic liquid, afforded improved control over the molecular weight (M_n) and polydispersity of the resultant products (PDI <1.4). Furthermore, to facilitate the GPC measurement for molecular weight of polymers, the charged polymers (poly‐ 7 ) were hydrolyzed to give uncharged polymers (poly‐ 4 *) by removing the imidazolium pendant from the polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3986–3993, 2007     

Thermal stability and high glass transition temperature of 4-chloromethyl styrene polymers bearing carbazolyl moieties

A new styrene derivative monomer, 4-(N-carbazolyl)methyl styrene (CzMS), was synthesized by reacting 4-chloromethyl styrene with carbazole in the presence of sodium hydride. Then, CzMS was homopolymerized and copolymerized with different monomers such as methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA) and n-butyl acrylate (BA) by free radical polymerization method in N,N-di-methylformamide (DMF) solution at 70 ± 1 °C using azobisisobutyronitrile initiator to give the copolymers I-V in good yields. The structure of all the resulted polymers was characterized and confirmed by FT-IR, ¹H NMR and ¹³C NMR spectroscopic techniques. The average molecular weight and glass transition temperature of polymers were determined using gel permeation chromatograph (GPC) and differential scanning calorimeter (DSC) instruments, respectively. It was found that these polymers with carbazole moieties have high thermal stability and the presence of bulk carbazole groups in polymer side chains leads to an increase in the rigidity and glass transition temperature of polymers.     

Study on controlled/living free-radical polymerization of methyl acrylate in the presence of benzyl 9H-carbazole-9-carbodithioate under thermal condition

The polymerizations of methyl acrylate have been studied under thermal condition using benzyl 9H-carbazole-9-carbodithioate (BCCDT) as control agent. The obtained polymers were characterized by gel permeation chromatography (GPC), ¹H nuclear magnetic resonance (¹H NMR) and MALDI-TOF mass spectra. The results at 60 °C show that the molecular weight of the polymer increases linearly with monomer conversion, the molecular weight distribution is fairly narrow (even inferior to 1.10), and there exists a linear relationship between ln ([M]₀/[M]) and polymerization time. It is worthy of being noticed that the narrow polydispersities are comparable with those from living anionic polymerization. All of the evidences indicate that the polymerization is a good ‘living’ process. When the experiment is carried out at higher temperature, the polymerization rate is markedly faster with controlled polymerization characters except for a relatively broader polydispersity. The good control for free radical polymerization may be correlated with the large conjugation structure of carbazyl of BCCDT.     

Atom transfer radical polymerization of a novel quinoline derivative monomer and fluorescent property

A novel functional monomer incorporating quinoline derivative moiety as the side group, 2-[4-(2,7,7-trimethyl-3-ethoxycarbonyl-5-oxo-1,4,5,6,7,8-hexhydricquinoline)phenoxyl] ethylmethacrylate (HQPEMA), was synthesized and polymerized utilizing atom transfer radical polymerization (ATRP) technique. 2-(4-Chloromethylphenyl)benzoxazole (CMPB) and CuCl/PMDETA were used as the initiator and catalyst, respectively. GPC, ¹H NMR and fluorescent emission spectroscopy were conducted for characterization of polymers. The linear increase of number average molecular weight (M_n) versus conversion and the relatively narrow molecular weight distribution (M_w/M_n) of the obtained polymers confirmed that ATRP of HQPEMA was carried out successfully. In addition, the fluorescence “structural self-quenching effect” was observed in the DMF solution of the monomer HQPEMA, which bearing both electron-donating chromophore group and electron-accepting CC bond. We also found that the fluorescence properties of the newly obtained polymers containing quinoline chromophore depended on both the monomer concentration in solution and the polarity of solvents. The emission of the polymer film showed that the emission peak maxima of the polymer film shifted 50 nm towards high wavelength with respect to the polymer in DMF solution due to the intermolecular or intramolecular interactions of the polymer chains.     

Controlled/living cationic polymerization of styrene with BF3OEt2 as a coinitiator in the presence of water: Improvements and limitations

The controlled/living cationic polymerization of styrene using R-OH/BF₃OEt₂ (R-OH = 1-phenylethanol (1), 2-phenyl-2-propanol (2) and 1-(4-methoxyphenyl)ethanol (3)) at 0 °C in CH₂Cl₂ and in the presence of water was investigated. With 1/BF₃OEt₂, the poor control over molecular weight and molecular weight distribution was ascribed to a competitive protonic initiation induced by water. The molecular weight of the polymers obtained with 2/BF₃OEt₂ and 3/BF₃OEt₂ at low water content ([H₂O] ? 0.11 M) increased in direct proportion to the monomer conversion in agreement with the calculated values, assuming that one initiator molecule generates one polymer chain, but the molecular weight distribution was found relatively broad (M_w/M_n ∼ 1.8). ¹H NMR analyses confirmed that polymerization proceeds via reversible activation of C-OH terminus, but some loss of hydroxyl functionality was revealed. Some trials using high water contents in the recipe ([H₂O] ? 1.6 M) produced only traces of polymer due to catalyst decomposition.     

Real-time mid-IR monitoring of metathesis reactions by fiber optic FTIR spectroscopy

The real-time monitoring of metathesis reactions using a recently developed fiber optic transmission FTIR technique is reported in this paper. The ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene, the ring-closing metathesis (RCM) of 1,7-octadiene and the polymerization of phenylacetylene were investigated. The Schrock carbyne complex, Cl₃(dme)WCCMe₃, was used as the catalyst for these reactions. The phenylacetylene polymerization was also studied with WCl₆ as the catalyst. In the ROMP of 1,5-cyclooctadiene, monomer consumption was followed by monitoring the disappearance of the 1486 cm⁻¹ absorbance, characteristic of the CH₂ deformation vibration (δ_s CH₂) in the monomer. In the RCM of 1,7-octadiene, conversion data was obtained by monitoring the 1832 cm⁻¹ signal, which is an overtone of the wagging absorbance at 910 cm⁻¹ of the CH₂ end group in the monomer. Phenylacetylene polymerization was monitored by the disappearance of the ν -CCH stretch signal at 2110 cm⁻¹. Polymerization was much faster with the Schrock catalyst than with WCl₆, but similar conversions were reached in both reactions. Conversion data obtained by the IR technique agreed well with gravimetric product yields.     

Atom Transfer Radical Polymerization of Styrene Using Multifunctional Iniferter Reagents as Initiators

Summary: Two multifunctional iniferters, 1,4-bis-(α-N,N-diethyldithiocarbamyl-isobutyryloxy)-benzene (BDCIB) and 1,3,5-tris-(α-N,N-diethyldithiocarbamyl-isobutyryloxy)-benzene (TDCIB), were successfully synthesized and used as initiators to initiate the polymerization of styrene in the presence of a CuBr/PMDETA complex. The polymerization results demonstrated that the kinetic plots in all cases were first-order to the monomer, the molecular weight of the polymers increased linearly with the monomer conversion; meanwhile, the molecular weight distribution of the polymer was kept to a very low value (M_w/M_n ≤ 1.35). Furthermore, the measured molecular weights were very close to the calculated values, which indicated the high efficiency of the initiator for the polymerization of styrene. The effect of catalyst concentration and initiator concentration was not obvious and the influence of polymerization temperature was apparent, and the polymerization rate increased with the polymerization temperature. The results of chain-extension and ¹H NMR analysis proved that the polymer obtained was capped with diethylthiocarbamoylthiy (DC) group.     

Synthesis characterizations and properties of a new fluoro-maleimide polymer

Novel 4-(4-trifluoromethyl)phenoxy N-phenyl-maleimide (FPMI) was synthesized. The free radical-initiated polymerization of FPMI was carried out in 1,4-dioxane solution using azobisisobutyronitrile as initiator. The monomer was investigated by FTIR, ¹H NMR, ¹³C NMR and elemental analysis, while the polymer was investigated by FTIR, ¹H NMR and ¹³C NMR. The effect of the monomer concentration, initiator concentration and temperature on the rate of polymerization (R_p) was studied. The activation energy of the polymerization was calculated (ΔE = 48.94 kJ/mol). The molecular weight of PFPMI and polydispersity index of the polymer were determined by gel permeation chromatography and were equal to 73,500, 16,700 and 2.27, respectively. The properties of PFPMI, including thermal behavior, thermal stability, the glass transition temperature (T_g = 236 °C), photo-stability, solubility and solution viscosity were studied.     

Synthesis, characterization, and ethylene polymerization behavior of [(RR′-admpzp)2Ti(OPr)2] complexes (RR′-admpzp = 1-dialkylamino-3-(3,5-dimethyl-pyrazol-1-yl)-propan-2-olate)

[(RR′-admpzp)₂Ti(OPrⁱ)₂] complexes (2a-c), synthesized from reaction of Ti(OPrⁱ)₃Cl (0.5 equiv) with 1-dialkylamino-3-(3,5-dimethyl-pyrazol-1-yl)-propan-2-ol compounds in the presence of triethylamine (0.5 equiv), are pseudo-octahedral with each RR′-admpzp ligand κ²-O,N(pyrazolyl) coordinated to the titanium center. In solution, 2a-c adopt isomeric structures that are in dynamic equilibrium. At 23 °C, 2a-c/1000 MAO catalyst systems furnished high molecular weight polymers with narrow molecular weight distributions (M_w/M_n = 2.7-2.8). At 100 °C, 2a-c/MAO catalyst systems exhibited increased polymerization activity and 2c/1000 MAO system furnished high molecular weight polyethylene with a molecular weight distribution (M_w/M_n = 2.1) that is close to that found for single-site catalysts.     

Investigation on lipase-catalyzed solution polymerization of cyclic carbonate

In this study, 26-membered macrocyclic carbonate, cyclobis(decamethylene carbonate) [(DMC)₂] was attempted to undergo ring-opening polymerization by lipase catalysis in toluene. Novozym-435 exhibited even higher catalytic activity towards (DMC)₂ polymerization compared with SnOCt₂ while high molecular weight (M_n) of 5.4 × 10⁴ and yield of 99% was still achieved at ultra-low enzyme/substrate (E/S) weight ratio of 1/200. ¹H NMR spectra demonstrated the existence of terminal hydroxyl group. Solid phase polymerization in the absence of toluene unexpectedly took place at the temperature lower than (DMC)₂’s melting point of 110 °C. Compared with solvent-free case, the addition of toluene solvent resulted in marked increase in reaction rate. As to the polymerization during 48 h with the E/S weight ratio of 1/100, a region existed at around toluene/carbonate (vol/wt, ml/g) ratio of 1∼2 where the polymerizations gave optimal results in terms of both higher molecular weight and monomer conversion. It was found that much higher molecular weight polymers may be obtained by decreasing enzyme concentrations. Plots of ln{[M]₀:[M]_t} versus reaction time were in linear agreement, indicating no chain termination, and monomer consumption follows a first-order rate law. The Novozym-435 catalyzed polymerization of (DMC)₂ in toluene presented pseudo-living characteristic. Compared with 6-membered trimethylene carbonate, much lower reaction activity of large-sized (DMC)₂ is observed, which is opposite to the result concerning the enzymatic polymerization of lactones with different ring-size.     

Bis(pyrrolide-imine) Ti complexes with MAO: A new family of high performance catalysts for olefin polymerization

This contribution reports on the syntheses, structures and olefin polymerization behavior of Ti complexes having a pair of chelating pyrrolide-imine [N⁻,N] ligands. X-ray analyses as well as ¹H NMR studies demonstrate that bis(pyrrolide-imine) Ti complexes (named PI Catalysts) contain approximately octahedrally coordinated metal centers with mutually trans-pyrrolide-Ns, cis-imine-Ns and cis-Cls. DFT studies suggest that PI Catalysts, when activated, provide a metal alkyl in the cis position to a vacant coordination site for monomer binding. These theoretical studies also show that the active species derived from PI Catalysts normally possess higher electrophilicity and a sterically more open nature compared with those produced using bis(phenoxy-imine) Ti complexes (Ti-FI Catalysts) which are known as high performance olefin polymerization catalysts. These structural as well as electronic features suggest that PI Catalysts have high potential for the polymerization of olefinic monomers.Unlike high performance Ti-FI Catalysts, PI Catalysts do not require the presence of steric bulk in close proximity to the anionic donor. PI Catalysts combined with MAO display high ethylene polymerization activities (max. 33,200 kg-polymer/mol-cat/h, 25 °C, atmospheric pressure) comparable to those obtained with early group 4 metallocene catalysts (e.g., Cp₂TiCl₂ 16,700 kg-polymer/mol-cat/h) under identical conditions. As expected, PI Catalysts exhibit higher incorporation capability for propylene and 1-hexene relative to FI Catalysts though the incorporation levels are lower than those for Cp₂TiCl₂. To our surprise, PI Catalysts/MAO show remarkably high norbornene (NB) incorporation, superior to that seen with the [Me₂Si(Me₄Cp)N-tBu]TiCl₂ (CGC) catalyst system, and they readily form ethylene-NB copolymers with high NB contents. The highly electrophilic and sterically open nature is probably responsible for the high NB affinity. Additionally, PI Catalysts/MAO possess characteristics of living ethylene polymerization (though under limited conditions) and afford high molecular weight PEs with very narrow molecular weight distributions (M_n 225,000, M_w/M_n 1.15, 10-s polymerization, 25 °C). Moreover, these catalysts can copolymerize ethylene and NB in a highly controlled living manner to afford monodisperse alternating copolymers with very high molecular weights (M_n > 500,000, M_w/M_n < 1.2) at room temperature. This unique living nature allows the preparation of a number of ethylene- and NB-based block copolymers, including PE-b-poly(ethylene-co-NB) and poly(ethylene-co-NB)_a-b-poly(ethylene-co-NB)_b, in which each segment contains a different NB content. These are probably the first examples of the syntheses of block copolymers from ethylene and NB. Consequently, the discovery and application of PI Catalysts has exercised a significant influence on olefin polymerization catalysis and polymer synthesis.     

Novel nickel(II) and copper(II) complexes with phenoxy-imidazole ligands: Syntheses, crystal structures and norbornene addition polymerization

The novel nickel(II) (1) and copper(II) (2) complexes bearing 2′-(4′,6′-di-tert-butylhydroxy-phenyl)-1,4,5-triphenyl imidazole ligand have been synthesized and characterized. The molecular structure analyses of complexes 1 and 2 indicated that Ni(II) centre in 1 adopts a distorted tetrahedral coordination geometry with a dihedral angle of 85.2° between Ni(1)O(1)N(1) plane and Ni(1)O(1A)N(1A) plane, while the Cu(II) centre in 2 represents a distorted square planar coordination geometry with a cis-N₂O₂ arrangement of the donor atoms, the dihedral angle being 32° between Cu(1)O(1)N(1) plane and Cu(1)O(1A)N(1A) plane. After activation with methylaluminoxane (MAO), both Ni(II) and Cu(II) complexes can be used as catalysts for the addition polymerization of norbornene (NB). The polynorbornenes (PNBs) are produced with very high polymerization activity (10⁸ g PNB mol⁻¹ Ni h⁻¹) for Ni(II) complex and moderate catalytic activity (10⁵ g PNB mol⁻¹ Cu h⁻¹) for Cu(II) complex, respectively. The high molecular weight polynorbornenes (10⁶) are obtained for complexes 1 and 2. Moreover, the distinct effects of polymerization temperature and Al/M ratio on catalytic activities and molecular weights of polymers are discussed.     

Synthesis of tertiary-butyl acrylate polymers and preparation of diblock copolymers using atom transfer radical polymerization

The synthesis of tert-butyl acrylate by atom transfer radical polymerization (ATRP) is reported. This polymer was prepared using FeCl₂ · 4H₂O(PPh₃)₂ catalyst system in conjunction with methyl 2-bromopropionate as initiator, in bulk and in solution using acetone as a solvent. The addition of solvent was necessary in order to decrease the polymerization rate and to afford low polydispersity polymers. The number-average molecular weights of the resulting polymers increased in direct proportion to the monomer conversion, and the polydispersities (M_w/M_n) were as low as 1.2. In addition, the preparation of an AB diblock copolymer of poly (n-butyl methacrylate)-block-poly (tert-butyl acrylate) by ATRP is reported. The resulting polymers and copolymers were characterized by means of size exclusion chromatography and ¹H-NMR Spectroscopy.     

Polymerization of [o-(trimethylgermyl)phenyl] acetylene and polymer characterization

[o-(Trimethylgermyl)phenyl]acetylene was polymerized in the presence of WCl₆, W(CO)₆-hv, etc., to give polymers whose weight-average molecular weights reached ca. 7.0 X 10⁵ at the highest. When the MoOCl₄-n-Bu₄Sn-EtOH (1 : 1 : 1) catalyst was used, the polydispersity ratio of the polymer obtained was 1.08, and the number-average molecular weight increased in direct proportion to monomer conversion; these indicate that this polymerization is a living polymerization. The polymer had the structure ? [CH?C(C₆H₄-o-GeMe₃)]_n ? and was a dark purple solid (λ_max = 551 nm, ε_max = 6100 M^-1 cm^-1 in THF) soluble in organic solvents such as toluene and chloroform. The onset temperature of weight loss of the polymer in TGA in air was ca. 230°C, and the glass transition temperature was above 180°C. The Po₂ of the present polymer is 105 barrers—larger than the value of natural rubber and fairly close to that of poly(dimethylsiloxane). © 1993 John Wiley & Sons, Inc.     

The WCl6-e-Al-CH2Cl2 catalyzed polypentenamer formation via ring-opening metathesis polymerization (ROMP)

The synthesis of polypentenamer by an electrochemically generated metathesis polymerization catalyst from methylene chloride solution of WCl₆ was investigated. The active species formed by electroreduction of this salt under controlled potential of +900 mV at a platinum cathode with an aluminum anode were found to catalyze the ring-opening metathesis polymerization (ROMP) of cyclopentene, monocyclic olefin of relatively low strain, in high yield (89%) and at short period (32 min) under mild conditions. The effect of reaction parameters, e.g., olefin/catalyst ratio, reaction time, electrolysis time, catalyst aging, on the polymerization yield have been studied. The resulting polymer has been characterized by ¹H and ¹³C NMR, IR and gel permeation chromatography (GPC) techniques. Analysis of the polypentenamer microstructure by means of ¹³C NMR spectroscopy indicates that the polymer contains a mainly trans stereoconfiguration of the double bonds (σ_c = 0.31) and a slightly blocky distribution (r_tr_c > 1) of cis and trans double bond dyads (r_tr_c = 1.44). However, this electrochemical system is reluctant to facilitate the competing vinyl type addition polymerization reactions.     

Synthesis and properties of thermally cross-linkable main-chain azobenzene polymers containing diacetylene moieties

A series of main chain azobenzene polymers containing diacetylene moieties with different lengths of the spacer {-[CC-CH₂-O-C₆H₄-OCO-(CH₂)_m-O-C₆H₄-NN-C₆H₄-O-(CH₂)_m-OCO-C₆H₄-O-CH₂-CC]_n-, where m = 3, 6, 11} were synthesized by oxidative coupling polymerization. These polymers had molecular weights of 17,600-68,600 and polydispersity indices of 1.2-1.8 as determined by gel permeation chromatography using polystyrene as a standard. Their structures and properties were characterized and evaluated with NMR, FT-IR, X-ray diffraction (XRD), thermogravimetry (TG), differential scanning calorimetry (DSC) and nonlinear optical (NLO) analyses. All the polymers could be cross-linked at the elevated temperatures due to the polymerization reactions of the diacetylene groups in the polymer backbone, and the cross-linked polymers showed dramatically modified properties, such as thermal stability and solvent resistance. The third-order nonlinear susceptibilities of the cross-linked polymers were evaluated by means of the Z-scan technique and calculated to be 3.60 × 10⁻⁹, 2.73 × 10⁻⁹, 2.28 × 10⁻⁹ esu, respectively, whereas the un-cross-linked polymers showed no obvious NLO property.     

Synthesis and characterization of polyoctenamer with WCl6?e−?Al?CH2Cl2 catalyst system via ring‐opening metathesis polymerization

A typical low‐strain monomer, cyclooctene, was polymerized via ring‐opening metathesis polymerization with electrochemically produced active species. The structural properties of the polyoctenamer were determined by NMR, gel‐permeation chromatography and differential scanning calorimetry. Analysis of the polyoctenamer microstructure by ¹H and ¹³C NMR spectroscopy indicates that the polymer contains a highly cis stereoconfiguration of the double bonds (σ_c = 0.75). The resulting polymer is of low molecular weight and has a reasonably broad molecular weight distribution (M_w = 18 000, PDI = 1.9). The glass transition temperature and melting point of the polyoctenamer are ?11.3 °C and 36.5 °C respectively. Copyright © 2005 John Wiley & Sons, Ltd.     

Neodymium alk(aryl)oxides-dialkylmagnesium systems for butadiene polymerization and copolymerization with styrene and glycidyl methacrylate

The application of well-defined neodymium alkoxides/aryloxides in combination with dialkylmagnesium reagents for 1,3-butadiene (BD) polymerization and copolymerization with styrene (St) and glycidyl methacrylate (GMA) has been investigated. The trinuclear complex Nd₃(Ot-Bu)₉(THF)₂ (1) provided a low-activity system for BD polymerization, even at high temperature, but with a high trans-1,4 stereospecificity (trans-1,4≈95%). Aryloxide complexes Nd(O-2,6-t-Bu₂-4-Me-Ph)₃(THF) (2) and Nd(O-2,6-t-Bu₂-4-Me-Ph)₃ (3) were found to give more active systems. The polymerization displayed a controlled character, i.e. a precise control of the molecular weight and a low polydispersity (M_w/M_n<1.30) for high catalyst concentration, keeping the same level of stereocontrol over the polymerization course. The statistical copolymerization of BD and styrene with those systems was successful. High-molecular weight copolymers (M_n up to 50?000 g mol⁻¹) with noticeable styrene content (3-15 mol%) were synthesized. Determination of the microstructure by ¹³C-NMR showed exclusively trans-1,4-BD-St sequences. The livingness of BD polymerization encouraged attempts of diblock copolymerization with GMA. In this case, low-molecular weight polymers with variable polydispersities were obtained (M_n<20?000 g mol⁻¹; M_w/M_n=1.4-5.0). The composition of the copolymers was analyzed by ¹H- and ¹³C-NMR and IR spectroscopies. SEC analyses confirmed the true nature of the diblock copolymer. The influence of the alkylating agent on those (co)-polymerizations was briefly studied. Finally, the mechanism of polymerization is also discussed.