Anionic living polymerization of macromonomers: Preparation of a particle-like purging reagent and characterization of poly(macromonomer)s

A cross-linked polystyrene particle (Merrifield resin, R-C₆H₅) was reacted with benzoyl chloride in nitrobenzene to produce R-C₆H₄-COC₆H₅ having a benzophenone group, and the R-C₆H₅-COC₆H₅ was reacted with a sodium mirror in THF under 10⁻⁵ mmHg to produce R-C₆H₅-CO⁻C₆H₅Na⁺ containing a benzophenone sodium as a particle-like purging reagent (PPBNa). (4-vinylbenzyl)Polystyrene macromonomers (PSM4: M_n=4.6₂×10³, M_w/M_n=1.0₃ and PSM7: M_n=7.1₀×10³, M_w/M_n=1.0₂) were dried under 10⁻⁶ mmHg for more than 72 h, purified by a special procedure using the PPBNa, and then were living anionically polymerized by sec-BuLi in benzene or n-BuLi in tetrahydrofuran to produce the corresponding poly(PSM)_n star polymers. The resultant star polymers were characterized by gel permeation chromatography equipped with low-angle laser light-scattering (GPC-LALLS), membrane osmometry (OSM), and light-scattering (LS). Anionic living polymerization of the PSM macromonomers was confirmed by the fact that the molecular weight of the poly(PSM)_n increased and by the fact that the initiation efficiency was constant despite an increase in the polymer yields. Some solution properties and specific dimensions characteristic to the poly(PSM)_n star polymers are discussed by comparing the GPC-LALLS, OSM, and LS results for those polymers with the results for linear polystyrenes.     

Half-sandwich samarium (III) diketiminate bromide as a catalyst for methyl methacrylate polymerization

Half-sandwich samarium(III) diketiminate bromide was successfully synthesized and was shown to be active in methyl methacrylate (MMA) polymerization. The effects of temperature, polymerization time and catalyst concentration were studied. Activities of ca. 18 kg of polymethacrylate (PMMA) per mol of samarium per hour were obtained under optimum conditions (0 °C and a MMA/catalyst molar ratio of 100/1), giving a polymer with a molar mass M_n>24,000 g mol⁻¹ and a molar mass distribution (M_w/M_n)<1.4. After 1 h of polymerization, conversions of MMA as high as 96% were observed.     

Polymerization of vinyl ethers using titanium catalysts containing tridentate triamine ligand of the type N[CH2CH(Ph)(Ts)N]2

Titanium complexes having tridentate triamine of the type N[CH₂CH(Ph)(Ts)N]₂²⁻ in combination with methylaluminoxane (MAO) was able to polymerize ethyl vinyl ether in good yields. The polymers obtained in general were having molecular weight in the order of 10⁵ with narrow molecular weight distributions. Polymerization conditions had an impact on the molecular weight and the polydispersity index (PDI). Using chlorobenzene as the solvent the polymer had an M_n of 350?000 and PDI of 1.21, where as under neat conditions the M_n was 255?000 with PDI of 1.21. The type of solvent and the temperature dictated the polymerization rate and the polymer stereo regularity. The molecular weight of the polymer is distinctly governed by the polymerization temperature. Temperature ranging between −50 and ambient (30 °C) resulted in high molecular weight polymers and vice versa at a temperature of 60-70 °C resulted in low molecular weight polymers in moderate yields. The polymers obtained below 30 °C are highly stereo-regular compared to that of the ones produced at and above ambient temperature. The polymerization of iso-butyl vinyl ether (IBVE) was faster than that of linearly substituted n-butyl vinyl ether (BVE) and less bulky ethyl vinyl ether (EVE). The order of isotacticities of the polymers obtained are polyIBVE > polyBVE > polyEVE. The use of borate cocatalyst for activation generated narrow molecular weight polymers with a linear increase in the yield and molecular weight over time suggesting the living nature of the catalyst system.     

Hyperbranched polymers from divinylbenzene and 1,3-diisopropenylbenzene through anionic self-condensing vinyl polymerization

Hyperbranched polymers were synthesized using anionic self-condensing vinyl polymerization (ASCVP) by forming ‘inimer’ (initiator within a monomer) in situ from divinylbenzene (DVB) and 1,3-diisopropenylbenzene (DIPB) using anionic initiators in THF at −40 °C. The reaction of equimolar amounts of DVB and nBuLi results in the formation of hyperbranched poly(divinylbenzene) through self-condensing vinyl polymerization (SCVP). The hyperbranched polymers were invariably contaminated with small amount of gel (<15%). No gelation was observed when using DIBP with anionic initiators. The presence of monomer-polymer equilibrium in the SCVP of DIPB restricts the growth of hyperbranched poly(DIPB). The inimer synthesized from DIPB at 35 °C undergoes intermolecular self-condensation to different extent depending on the nature of anionic initiator at −40 °C. The molecular weight of the hyperbranched polymers was higher when DPHLi was used as initiator. A small amount of styrene ([styrene]/[Li⁺]=1) was used to promote the chain growth by inducing cross-over reaction with styrene, and subsequent reaction of styryl anion with isopropenyl groups of inimer/hyperbranched oligomer. The hyperbranched polymers were soluble in organic solvents and exhibited broad molecular weight distribution (2<M_w/M_n<17).     

Bulk polymerization of vinyl chloride with half-titanocene/MAO catalyst

Bulk polymerization of vinyl chloride (VC) with Cp^∗Ti(OPh)₃/MAO catalyst was investigated. The bulk polymerization of VC with Cp^∗Ti(OPh)₃/MAO catalyst proceeded to give poly(vinyl chloride) (PVC) with high molecular weight in good yields. The M_n of the polymer increased in direct proportion to polymer yields and the line passed through the origin. The M_w/M_n of the polymer decreased with an increase of polymer yield. The GPC elution curves were unimodal and the whole curves shifted clearly to the higher molecular weight as a function of reaction time. This indicates that the control of molecular weight can be achieved in the polymerization of VC with Cp^∗Ti(OPh)₃/MAO catalyst even in bulk. The structure of PVC obtained from the bulk polymerization of VC with Cp^∗Ti(OPh)₃/MAO catalyst consists of a regular structure. The thermal stability of the polymer obtained with Cp^∗Ti(OPh)/MAO catalyst was higher than that of PVC obtained from radical polymerization and depended on the molecular weight of the polymer. In contrast to that, the initial decomposition temperature of the polymer obtained from a radical polymerization did not depend on the molecular weight. We presumed that the decomposition of the polymer obtained with Cp^∗Ti(OPh)₃/MAO catalyst initiated at the chain end.     

Thermal polymerization of methyl (meth)acrylate via reversible addition-fragmentation chain transfer (RAFT) process

Thermal polymerization of methyl (meth)acrylate (MMA) was carried out using 2-cyanoprop-2-yl-1-dithionaphthalate (CPDN) and cumyl dithionaphthalenoate (CDN) as chain transfer agents. The kinetic study showed the existence of induction period and rate retardation, especially in the CDN mediated systems. The molecular weights of the polymers increased linearly with the monomer conversion, and the molecular weight distributions (M_w/M_ns) of the polymers were relatively narrow up to high conversions. The maximum number-average molecular weights (M_ns) reached to 351?900 g/mol (M_w/M_n = 1.47) and 442?400 g/mol (M_w/M_n = 1.29) in the systems mediated by CPDN and CDN, respectively. Chain-extension reactions were also successfully carried out to obtain higher molecular weight PMMA and PMMA-block-polystyrene (PMMA-b-PSt) copolymer with controlled structure and narrow M_w/M_n. Thermal polymerization of methyl acrylate (MA) in the presence of CPDN, or benzyl (2-phenyl)-1-imidazolecarbodithioate (BPIC) also demonstrated “living”/controlled features with the experimented maximum molecular weight 312?500 g/mol (M_w/M_n = 1.57). The possible initiation mechanism of the thermal polymerization was discussed.     

Polymerization of vinyl chloride with butyllithiums and metallocene catalysts

Polymerizations of vinyl chloride (VC) with butyllithium (BuLi) and metallocene catalysts were investigated. In the polymerization of VC with BuLi, the activity for polymerization decreased in the following order; t‐BuLi > n‐BuLi > s‐BuLi. A polymer controlled structurally in the main chain was found to be synthesized from the polymerization of VC with BuLi. The molecular weights of polymers obtained in bulk polymerization were higher than those of polymers obtained in solution. A linear relationship of the M_n of the polymer and the polymer yields was observed. The M_w/M_n of the polymer did not change significantly during polymerization, although the M_w/M_n was around 2. Thermal stability of the polymer obtained with BuLi was higher than that of polymer obtained with radical initiators, as determined by TGA measurements. In the polymerization of VC with Cp*TiX₃/MAO (X: Cl and OCH₃) catalysts, polymers were obtained with both catalysts, although the rate of polymerization was slow. The Cp*Ti(OCH₃)₃//MAO catalyst in CH₂Cl₂ gave higher‐molecular‐weight polymers in a better yield than in toluene. From elemental analysis and the NMR spectra of the polymers, the Cp*Ti(OCH₃)₃/MAO catalyst gave polymers consisting of repeating regular head‐to‐tail units, in contrast to the Cp*TiCl₃/MAO catalyst, which gave polymers having anomalous units.     

Synthesis of star polymer by means of the living polymerization of [(o-trifluoromethyl)phenyl]acetylene using a MoOCl4-based catalyst and the linking method

A star polymer was synthesized by addition of 1,4-diethynyl-2,5-dimethylbenzene as linking agent (30 °C, 24 h) after living polymerization of [(o-trifluoromethyl)phenyl]acetylene (o-CF₃PA) with MoOCl₄-n-Bu₄Sn-EtOH catalyst (in anisole, 30 °C, 20 min; [Mo]=10 mM, [P^∗]/[Mo]=40%, [o-CF₃PA]₀=200 mM). The M_n values of the living and star polymers were 8.1×10³ and 5.3×10⁴, respectively, according to gel permeation chromatography, while these values determined by multi-angle laser light scattering (MALLS) were 7.8×10³ and 2.5×10⁵. The M_w/M_n and arm number of the star polymer were 1.04 and 29, respectively, according to MALLS. The molecular weight and arm number of star polymer increased with increasing linking agent concentration and polymerization temperature.     

Effect of substituted groups on the living anionic polymerization of 2-vinylcarbazole derivatives

To study the effect of the substituents in the N-position of the carbazole on anionic polymerization, 2-vinylcarbazole derivatives of 9-butyl-2-vinylcarbazole (NBu2VCz), 9-phenyl-2-vinylcarbazole (NPh2VCz), and 9-(pyridin-2-yl)-2-vinylcarbazole (NPy2VCz) were synthesized. The anionic polymerization of NBu2VCz and NPh2VCz using s-BuLi was performed at −78 °C with a 100% yield, but the polymerization of NBu2VCz showed a broader molecular weight distribution (M_w/M_n = 1.23) than NPh2VCz (M_w/M_n = 1.11). The anionic polymerization of NPy2VCz using s-BuLi and DPM-K had a yield below 5%. In particular, the living anionic polymerization of NPh2VCz with s-BuLi/styrene ([s-BuLi/St]₀ = 0.33) shows a narrower M_w/M_n. The block copolymerization of NPh2VCz with styrene, α-methylstyrene (α-MeSt), and 2-vinylpyridine (2VP) was achieved successfully. The resulting block copolymers of PNPh2VCz-b-P2VP with f_PNPh2VCz = 17.7, 34.6, 48.1, 62.4, and 82.9 were synthesized for investigation of living characteristics.     

Polymerization of 1,3-butadiene with VO(P204)2 and VO(P507)2 activated by alkylaluminum

The oxovanadium phosphonates (VO(P₂₀₄)₂ and VO(P₅₀₇)₂) activated by various alkylaluminums (AlR₃, R = Et, i-Bu, n-Oct; HAlR₂, R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P₂₀₄)₂ and VO(P₅₀₇)₂ showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl₃, V(acac)₃). Among the examined catalysts, the VO(P₂₀₄)₂/Al(Oct)₃ system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M_n of 3.76 × 10⁴ g/mol, and M_w/M_n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 °C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 °C (polymer yield > 33%); the M_n value and M_w/M_n ratio were independent of polymerization temperature in the range of 40-70 °C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (>65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.     

RAFT-mediated polymerization and grafting of sodium 4-styrenesulfonate from cellulose initiated via γ-radiation

Ambient temperature (20 °C) reversible addition fragmentation chain transfer (RAFT) polymerization of sodium 4-styrenesulfonate (SS) conducted directly in aqueous media under γ-irradiation at different dose rates (0.09, 0.03 and 0.02 kGy h⁻¹) proceeds in a controlled fashion (typically, M_w/M_n < 1.25) to near quantitative conversions via 4-cyanopentanoic acid dithiobenzoate (CPADB) mediation. By applying CPADB modified cellulose as a macro chain transfer agent, a graft copolymer with SS was prepared in aqueous media under γ-irradiation. RAFT mediated graft polymerizations provided copolymers with higher graft frequencies compared to those obtained by conventional methods. Thermally initiated grafting of SS from a CPADB-functionalized cellulose surface at 70 °C was also studied which resulted in a reduced graft frequency in comparison to γ-initiated ones.     

RAFT polymerization and self-assembly of thermoresponsive poly(N-decylacrylamide-b-N,N-diethylacrylamide) block copolymers bearing a phenanthrene fluorescent α-end group

Phenanthrene α-end-labeled poly(N-decylacrylamide-b-N,N-diethylacrylamide) (PDcA_n-b-PDEA_m) block copolymers consisting in a highly hydrophobic block (n = 11) and a thermoresponsive block with variable length (79 ≤ m ≤ 468) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. A new phenanthrene-labeled chain transfer agent (CTA) was synthesized and used to control the RAFT polymerization of a hydrophobic acrylamide derivative, N-decylacrylamide (DcA). This first block was further used as macroCTA to polymerize N,N-diethylacrylamide (DEA) in order to prepare diblock copolymers with the same hydrophobic block of PDcA (number average molecular weight: M_n = 2720 g mol⁻¹, polydispersity index: M_w/M_n = 1.13) and various PDEA blocks of several lengths (M_n = 10,000-60,000 g mol⁻¹) with a very high blocking efficiency. The resulting copolymers self-assemble in water forming thermoresponsive micelles. The critical micelle concentration (CMC) was determined using Förster resonance energy transfer (FRET) between phenanthrene linked at the end of the PDcA block and anthracene added to the solution at a low concentration (10⁻⁵ M), based on the fact that energy transfer only occurs when phenanthrene and anthracene are located in the core of the micelle. The CMC (∼2 μM) was obtained at the polymer concentration where the anthracene fluorescence intensity starts to increase. The size of the polymer micelles decreases with temperature increase around the lower critical solution temperature of PDEA in water (LCST ∼ 32 °C) owing to the thermoresponsiveness of the PDEA shell.     

Homogeneous neodymium iso-propoxide/modified methylaluminoxane catalyst for isoprene polymerization

The neodymium iso-propoxide [Nd(Oi-Pr)₃] catalyst activated by modified methylaluminoxane (MMAO) is homogeneous and effective in isoprene polymerization in heptane to provide polymers with high molecular weight (M_n∼10⁵), narrow molecular weight distribution (M_w/M_n=1.1-2.0) and mainly cis-1,4 structure (82-93%). The polymer yield increased with increasing [Al]/[Nd] ratio (50-300 mole ratio) and polymerization temperature (0-60 °C), while the molecular weight and cis-1,4 content decreased. On the other hand, the same catalyst resulted in relatively low polymer yield and low molecular weight in toluene. The cyclized polyisoprene was formed in dichloromethane, which is attributable to the cationic active species derived from MMAO alone. When chlorine sources (Et₂AlCl, t-BuCl, Me₃SiCl) were added, the cis-1,4 stereoregularity of polymer improved up to 95% even at a high temperature of 60 °C, though the polymer yield decreased.     

Lewis acid-assisted anionic polymerization of methyl cyclobutene-1-carboxylate

A cyclobutene monomer, methyl cyclobutene-1-carboxylate (MHCB), has been polymerized by anionic addition polymerization. Although MHCB may be regarded as a member of α,β-disubstituted acrylate derivatives which are reluctant to undergo anionic addition polymerization, anionic polymerization of MHCB with tert-butyllithium (t-BuLi) in combination with bis(2,6-di-tert-butylphenoxy)ethylaluminum [EtAl(ODBP)₂] in toluene at −78 °C gives a polymer consisting of 1,2-linked cyclobutane ring in the main chain with narrow molecular weight distribution. Copolymerization of MHCB and methyl methacrylate with t-BuLi/EtAl(ODBP)₂ proceeds in a monomer-selective and living manner to form a block-like copolymer. Poly(MHCB) undergoes unique thermal reaction through ring opening of the cyclobutane units to form CC bonds between successive monomer units.     

Monodisperse, micrometer-sized low molar mass polystyrene particles by two-stage dispersion polymerization

Free-radical dispersion polymerization of styrene was carried out in ethanol and in ethanol-water mixtures in the absence and presence of carbon tetrabromide (CBr₄) as a chain transfer agent. When CBr₄ was present at the onset of the reaction, particles with a broad size distribution were obtained. If, however, the addition of CBr₄ was delayed ca 1 h, so that the particle nucleation step was complete, then 1-2 wt% chain transfer agent, dissolved in monomer plus solvent, could be added to the reaction without a deleterious affect on particle formation. The particle size and size distribution was essentially identical to that obtained in the absence of CBr₄. When more CBr₄ was added, other problems arose. These problems appeared to be due to solubility of low molar mass polymer in the reaction medium. They could be overcome by running the reaction in ethanol-water mixtures (e.g. 5 wt% water) to decrease the solubility of oligo-styrene at 70 °C, the reaction temperature. In this way, monodisperse particles could be prepared in the presence of 3 wt% CBr₄ based upon total styrene, consisting of polymers with M_n=7060, M_w/M_n=2.4.     

Effect of nitrobenzene on initiator-fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′-azobisisobutyrate

The polymerization of divinylbenzene (DVB) with dimethyl 2,2′-azobisisobutyrate (MAIB) was conducted at 70 and 80 °C in benzene in the presence of nitrobenzene (NB) as a retarder. When the concentrations of DVB, MAIB, and NB were 0.45, 0.50, and 0.50 mol/l, respectively, the polymerization proceeded without any gelation to yield soluble polymers. The polymer yield (up to 65%) and the molecular weight (M_n=1.5-4.2×l0⁴ at 70 °C and 1.3-3.9×l0⁴ at 80 °C) increased with time. The polymer formed in the polymerization at 80 °C for 4 h consisted of the DVB units with (4 mol%) and without double bond (41 mol%), methoxycarbonylpropyl group as MAIB-fragment (48 mol%), and NB unit (7 mol%). Incorporation of such a large number of the initiator-fragments as terminal groups in a polymer molecule indicates that the polymer is of a hyperbranched structure. The polymer showed an upper critical solution temperature (40 °C on cooling) in an acetone-water [14:1 (v/v)] mixture. The results of MALLS and viscometric measurements and TEM observation supported that the polymers formed in the present polymerization have a hyperbranched structure. The polymerization system at 70 °C involved an ESR-observable nitroxide radical formed by the addition of polymer radical to the nitro group of NB. The polymerization was kinetically investigated in dioxane. The initial polymerization rate (R_p) at 70 °C was expressed by R_p=k[MAIB]^0.5[DVB]^0.9[NB]^−0.4. The kinetic results were explained on the basis of the reversible addition of polymer radical to NB and the termination between the polymer radical and the nitroxide radical. The overall activation energy of the polymerization was 27.8 kcal/mol.     

Copolymerization of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate by rare earth calixarene complexes

Rare earth (Nd, Y, La) p-tert-butylcalix[n]arene (n=4, 6, and 8) complexes alone have been developed to catalyze random and block copolymerizations of trimethylene carbonate (TMC) and 2,2-dimethyltrimethylene carbonate (DTC). The random or block structure and thermal behavior of the copolymers have been characterized by SEC, NMR, DSC, XRD and PLM. Random copolymer with M_w of 14,100 and M_w/M_n of 1.36 was prepared by neodymium p-tert-butylcalix[6]arene complex under the conditions: [TMC+DTC]₀/[Nd]=400, 80 °C, 8 h. The reactivity ratios of TMC and DTC are measured to be r_TMC=4.68 and r_DTC=0.163, respectively. Random copolymerization could be well designed by the feeding ratio to prepare copolymers with controlled T_m and T_g. Only 8% TMC units in the polymer chain destroyed the crystallization of PDTC showing no T_m of the copolymer in the DSC analysis.     

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 °C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M_w/M_n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M_n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with. The current catalyst system is highly active (yield > 80%, 35 min), providing polybutadiene with 1,2, cis-1,4 and trans-1,4 units about 44.0%, 51.0% and 5.0%, respectively.     

Co γ-irradiation-initiated RAFT polymerization of VAc at room temperature

In this work, the reversible addition-fragmentation chain transfer (RAFT) polymerization of vinyl acetate (VAc) was successfully performed at room temperature using ⁶⁰Co γ-irradiation as the initiation source. Under the dose rate of 10 Gy/min irradiation, the polymerization proceeded smoothly and converted approximately 90% of the monomer within 7 h. The molecular weight distribution (M_w/M_n) remained narrow (M_w/M_n < 1.35) up to 90% conversion. Compared to AIBN-initiated RAFT polymerization at 60 °C, ⁶⁰Co γ-irradiation-initiated RAFT polymerization is a technique that can better control the molecular weight, especially at high conversion. The ¹H NMR spectra and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry confirmed that most of the chain ends of poly(VAc) (PVAc) from γ-irradiated RAFT polymerization were living and can be reactivated for chain-extension reactions. The microstructures of PVAc from ⁶⁰Co γ-irradiated RAFT polymerization (almost head-to-tail addition) and AIBN-initiated RAFT polymerization (5% tail-to-tail addition) were different, as revealed by the ¹³C NMR spectra. For the first time, ⁶⁰Co γ-irradiation was used as an initiation source for RAFT polymerization of VAc at room temperature.     

Living radical polymerization of styrene mediated by a piperidinyl-N-oxyl radical having very bulky substituents

A new cyclic nitroxide 1 and the corresponding alkoxyamines 9 and 10 were synthesized and the polymerization of styrene (St) initiated with 10 was investigated. The NO-C bond of 9 is very weak, cleaving at room temperature. On the other hand, alkoxyamine 10 is stable at room temperature and the A_act and E_act for the NO-C bond homolysis were determined to be 1.4 × 10¹⁵ s⁻¹ and 124.5 kJ mol⁻¹, respectively. When the polymerization of St was carried out at 70 °C, the resultant poly(St) showed narrow polydispersities below 1.25. In the polymerization at 90 °C, the resulting poly(St) showed narrow polydispersity until 60% conversion, but M_w/M_n was rapidly increased above 60% conversion. On the other hand, the polymerization at 120 °C gave poly(St) with broad polydispersities. The unusual polymerization behavior was discussed on the basis of the SEC and ESR results.