Synthesis of long-chain branched isotactic-rich polystyrene via cationic polymerization

Cationic polymerization of styrene was conducted with 1-chloro-1-phenylethane (SCl)/AlCl₃/phenyl methyl ether (PME) initiating system in hexane/CH₂Cl₂ (60/40, v/v) at ?80 °C. The kinetics for cationic polymerization of styrene was investigated by in-situ ATR-FTIR spectroscopy. The isotactic-rich polystyrene (iPS) with m dyad of 81%, mm triad of 63% and mmmm pentad of 50% could be synthesized. Small amounts of crystalline regions in iPS formed after flow-induced crystallization and the crystallinity increased with increasing the molecular weight of iPS. Furthermore, the long-chain branched isotactic-rich polystyrene (biPS) with around 12 times higher molecular weight than that of corresponding iPS could be synthesized via cationic polymerization of styrene by introducing a small amount of isoprene (Ip) as a comonomer and branching sites as well. The possible mechanism for long-chain branching formation via intermolecular alkylation reaction by using Ip structural units along polymer chain as branching sites was proposed. The nucleation rate of biPS could be greatly enhanced with increasing the content of branching sites, leading to an obvious increase in crystallinity. The multi-melting temperatures from 140 °C to 237 °C were observed in DSC curves of these PS products. The tensile strength of commercial atactic polystyrene could be improved remarkably from 41.4 MPa to 55.7 MPa by adding 16.7% of biPS.     

Syndiotactic-specific polymerization of methyl methacrylate with <Emphasis Type="Italic">tert</Emphasis>-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 more rapidly than in toluene and gave st-PMMA (rr = 90%) with narrow molar mass distribution. This method allows us to prepare st-PMMA with molar mass up to 350 × 10³ in 48 h.     

Stereospecific propene polymerization with rac-[1,2-bis(η5-(9-fluorenyl))-1-phenylethane]zirconium dichloride/methylalumoxane

Summary Methylalumoxane (MAO)-activated rac-[1,2-bis(η⁵-(9-fluorenyl))-1-phenylethane]zirconium dichloride (1) was used for propene polymerization at 30, 50, and 70°C and constant monomer concentration. The polypropene products are isotactic with stereoregularities depending on the polymerization temperature. The pentad distributions follow “enantiomorphic site statistics”, indicating stereocontrol being conducted by the chiral catalyst site.     

Living ring-opening polymerization of ɛ-caprolactone with combinations of tert-butyllithium and bilky aluminium phenoxides

Summary The polymerization of ɛ-caprolactone (ɛ-CL) with a combination of tert-butyllithium (t-BuLi) and bis(2,6-di-t-butylphenoxy)methylaluminum [MeAl(ODBP)₂] in toluene at 0°C proceeded in a living manner to give polymers with narrow molecular weight distributions (MWD) within a few minutes, while the polymerization with t-BuLi alone gave a polymer with much broader MWD. The yield of the polymer did not reach 100 % at the Al/Li ratio of 5, because the excess MeAl(ODBP)₂ coordinates with ɛ-CL to protect it from the attack by the propagating species. The polymerization with t-BuLi/EtAl(ODBP)₂ gave polymers in quantitative yields regardless of Al/Li ratio, and also narrower MWD even for higher molecular weight polymers. Received: 1 August 2000/Accepted: 11 August 2000     

Synthesis of amphiphilic copolymers by ATRP initiated with a bifunctional initiator containing trichloromethyl groups

Bifunctional polystyrene macroinitiators, having various molecular weights, were prepared by atom transfer radical polymerization (ATRP), initiated with bifunctional initiator 1,3-bis{1-methyl-1[(2,2,2-trichloroethoxy) carbonylamino]ethyl}benzene in conjunction with CuCl catalyst and polyamine ligands. These macroinitiators were subsequently used for ATRP of tert-butyl acrylate (t-BuA), giving BAB triblocks poly[(t-BuA)-b-(Sty)-b-(t-BuA)] as precursors of amphiphilic copolymers. Both the polymerization steps proceeded as controlled processes with linear semi-logarithmic conversion plots and lengths of the blocks following theoretical predictions. Hydrolysis of outer poly(t-BuA) blocks led to triblock copolymers with the central polystyrene block and outer blocks of poly(acrylic acid), the molecular weights of which ranged from ca. 5 × 10³ to almost 1 × 10⁵ Da.     

Highly isotactic poly(vinyl alcohol). III: Heterogeneous cationic polymerization of tert-butyl vinyl ether

We studied the polymerization of tert-butyl vinyl ether (tBVE) and benzyl vinyl ether with heterogeneous catalysts, that is, modified Ziegler type (Vandenberg type) catalysts and metal sulfate-sulfuric acid complexes.Vandenberg type catalysts gave high molecular weight and highly isotactic poly(tBVE)s with relatively narrow molecular weight distribution at high temperature, and then the resultant poly(tBVE)s were converted into the stereoregular poly(vinyl alcohol)s (PVAs). With titanium based Vandenberg type catalyst, a relative high isotactic PVA, which has 52% triad isotacticity, was obtained from the poly(tBVE) polymerized at 30 °C. It was found from NMR study that the content of the triad tacticity of PVAs derived from poly(tBVE) catalyzed by titanium based catalysts agreed with the value calculated from the chain-end control model (Bovey's model). This fact suggests that the steric structure of the adding monomer in this system is determined by same mechanism to homogeneous BF₃ complexes catalysts system. On contrast to that, the metal sulfate-sulfuric acid complexes show significantly low activity to tBVE polymerization.     

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.     

Control of main chain structure and possibility of molecular weight control of polymer on polymerization of vinyl chloride with tert-butyllithium

The controlled polymerization of vinyl chloride (VC) with tert-butyllithium (tert-BuLi) was investigated. The polymerization of VC with tert-BuLi at −30 °C proceeded to give a high molecular weight polymer in good yield. In the polymerization of VC −30 to 0 °C under nearly bulk, the relationship between the M_n of polymers and polymer yields gave a straight line passed through the origin, but the M_w/M_n of PVC was not narrow. When CH₂Cl₂ was used as polymerization solvent, the M_n of PVC increased with the polymer yield, and the M_w/M_n of 1.25 was obtained. Structure analysis of the resulting polymers indicates that the main chain structure could be regulated in the polymerization of VC with tert-BuLi. Accordingly, a control of molecular weight of polymer and main chain structure is possible in the polymerization of VC with tert-BuLi.     

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.     

Diffusivity of small molecules in polymers: Carboxylic acids in polystyrene

Gravimetry was used to study the diffusion of a homologous series of linear carboxylic acids (C_n, with n = 2, 6–16) in amorphous polystyrene at temperatures from 35 °C to 165 °C, that is, both below and above the polymer glass transition temperature of 100 °C. All the mass uptake results are well described by a simple Fickian model (for t < t_1/2) and were used to calculate the corresponding diffusion coefficients using the thin-film approximation. Acetic acid exhibits a peculiar diffusion rate: its diffusion coefficients in polystyrene do not follow the same trend of all the remaining acids, being smaller than those of hexanoic acid at the same temperatures. Polystyrene swells at a higher rate in hexanoic and octanoic acids than in acetic acid, at the same temperature. This peculiarity is confirmed using NMR spectroscopy for acetic and hexanoic acids. For all the carboxylic acids considered, the temperature dependence of the diffusion coefficients is non-Arrhenius in character. For each liquid penetrant, its log(D) increases linearly with the decrease in liquid viscosity associated with an increase in temperature. Plots of log(n²D) versus n suggest that higher-n carboxylic acids diffuse through a reptation-like mechanism at higher temperatures.     

Synthesis and characterization of hetero-bimetallic aryloxides and application in the polymerization of lactides

The reactions of 2,2′-ethylidene-bis(4,6-di-tert-butylphenol) (EDBPH₂) with sodium/potassium and (ⁿBu)₂ Mg in tetrahydrofuran (THF), give [(EDBP)₂ Mg][(Na)₂(THF)₅]·THF (1) and [(EDBP)₂ Mg][(K)₂(THF)₅]·THF (2) in high yield. Experimental results show that sodium/potassium complexes 1 and 2 are efficient catalysts for the ring-opening polymerization of lactides. Furthermore, complexes 1 and 2 have slight isotactic selectivity for the ring-opening polymerization of rac-lactide.     

Stereospecific anionic polymerization of styrene initiated by R2Mg/ROMt ‘ate’ complexes

Various ‘ate’ complexes formed by reaction of alkali metal (Li, Na, K) derivatives and alkyl metals (Mg, Al, Zn) were used as initiator for the styrene anionic polymerization in hydrocarbon media and their influence on polystyrene microstructure has been investigated. A strong dependence of the polymer tacticity on both the nature of the alkali metal and of the associated metal alkyl used is observed. Binary systems like potassium derivatives/dialkylmagnesium yield isotactic-rich polystyrene. Eighty-five percent isotactic polystyrene (mm triad) is obtained in methylcyclohexane at −40 °C with the potassium tert-butoxide/n,s-dibutylmagnesium system. The characteristics of solubility of the stereoregular polystyrenes are in agreement with isotactic polystyrene chains containing some stereostructural defects and suggest that one single type of isospecific propagating centres is operating during the polymerization. When lithium or sodium derivatives are used in association to dialkylmagnesium instead of a potassium derivative, a strong decrease of the isotacticity is observed. The influence, on the extent of stereoregulation, of other parameters of these initiating systems as well as that of the solvent has also been investigated. The stereoregulation mechanisms involved in these styrene anionic polymerizations may be related to styrene insertion into carbon-metal bonds of the ‘ate’ complexes with a covalent character.     

Butadiene–styrene copolymerization initiated by n-BuLi/THF/t-AmOK

In this article, the anionic copolymerization of butadiene and styrene initiated by n-BuLi/THF/t-AmOK in cyclohexane at 50°C has been studied in detail. The various ratios of the modifier (THF and t-AmOK) to the initiator (n-BuLi) influence the copolymerization rate and composition of copolymers. It has been shown that this polymerization system is a complex one in which there exist multiple active species. By adjusting the ratio of K to Li and the ratio of THF to Li, copolymers with compositions almost identical to the ratio of initial monomers at different stages of conversion have been obtained. The propagating regularity of various active species has been discussed qualitatively.     

Monomer-selective living copolymerization of butyl acrylate and methyl methacrylate with a difunctional initiator—a facile synthesis of ABA-type triblock copolymer

A difunctional initiator was synthesized through the addition reaction of tert-butyllithium (t-BuLi) to 1,3-diisopropenylbenzene (DIB) in the presence of triethylamine (Et₃N). Under optimized conditions, that is dropwise addition of a mixture of DIB and Et₃N to a stirred toluene solution of t-BuLi at 50 °C at a molar ratio of DIB/Et₃N/t-BuLi=1/2/2, the difunctional initiator was formed without oligomeriazation of DIB. Copolymerization of butyl acrylate (n-BuA) and methyl methacrylate (MMA) with the difunctional initiator in the presence of bis(2,6-di-tert-butylphenoxy)ethylaluminum [EtAl(ODBP)₂] in toluene at low temperature proceeded in a monomer-selective manner; n-BuA is polymerized first, followed by MMA polymerization, to form an ABA-type triblock copolymer [PMMA-block-poly(n-BuA)-block-PMMA], which exhibits microphase separation.     

Preparation of polyacrylonitrile nanoparticles via dispersion polymerization of acrylonitrile using a poly(N-vinyl pyrrolidone)-cobalt complex in an aqueous system

Monodisperse spherical polyacrylonitrile (PAN) nanoparticles were successfully prepared for the first time by dispersion polymerization of acrylonitrile (AN) in water using well-defined poly(N-vinyl pyrrolidone) (PVP) that was end-capped by a cobalt(II) acetylacetonate (Co(acac)₂) complex (PVP-Co(acac)₂) as both a macroinitiator and a colloidal stabilizer. The well-defined PVP-Co(acac)₂ (M_n = 14,000 g/mol, PDI = 1.25) was synthesized by the bulk cobalt-mediated radical polymerization of N-vinyl pyrrolidone at 20 °C using 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) as an initiator and Co(acac)₂ as a regulating agent. The PVP macroradicals generated at 30 °C by the homolytic cleavage of the C–Co bonds in PVP-Co(acac)₂ initiated the dispersion polymerization of AN, as well as successfully stabilized the growing PAN particles. The average diameters of PAN nanoparticles synthesized with 20, 30, 40, and 50 wt% of PVP-Co(acac)₂ at 30 °C for 24 h were 263.5, 163.1, 157.3, and 143.5 nm, respectively. The PAN nanoparticles had a slightly crumpled spherical appearance, and the degree of crystallinity of the PAN nanoparticles prepared using 30 wt% of PVP-Co(acac)₂ was 31.2%. The mol% of VP units in the PAN nanoparticles was about 6 mol%, and the PVP chains were present on the surface of the PAN nanoparticles as a stabilizing layer. The PVP hairy chains could successfully stabilize very small Ag nanoparticles on the surface of the PAN nanoparticles.     

Synthesis of disubstituted amine-functionalized diene-based polymers

Diene-based polymers with two amine groups within each repeat unit were successfully synthesized by bulk and solution free radical polymerization techniques. All polymers have exclusive 1,4-microstructure. The number average molecular weights of the materials obtained were in the range of 30–52 × 10³ g/mol using 2,2′-azobisisobutyronitrile (AIBN), t-butyl peracetate (t-BPA), or t-butyl hydroperoxide (t-BHP) as the initiators. The highest molecular weight achieved was 72 × 10³ g/mol when t-butyl peroxide (t-BPO) was used as the initiator. Quantitative quaternization was achieved yielding hydrophilic water soluble polymers. Prior to quaternization, the polymers are hydrophobic and dissolve in most organic solvents.     

Anionic polymerization of p-(2,2′-diphenylethyl)styrene and applications to graft copolymers

Well-controlled anionic polymerization of an initiator-functionalized monomer, p-(2,2′-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n-BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES-b-PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.     

Low-temperature sintering of porous silicon carbide ceramic support with SDBS as sintering aid

The sintering temperature of porous silicon carbide ceramic support (PSCS) is typically higher than 1500 °C. In this paper, sodium dodecyl benzene sulfonate (SDBS) was used as a sintering additive to fabricate PSCS with high gas permeance and high bending strength at a sintering temperature less than 1200 °C. The PSCS was prepared by the dry pressing method followed by in-situ reaction. The effects of SDBS loading on the porosity, bending strength, gas permeation performance, and microstructure of the PSCS were investigated. The results showed that without SDBS, the required sintering temperature was as high as 1550 °C and resulted in a bending strength of 6.5 MPa but the sintering temperature decreased to 1150 °C with 8% SDBS and the bending strength increased to 16 MPa. The main reason was that SDBS decomposed into Na₂O which reacted with SiO₂ and ZrO₂ to form strong bonding connections. The prepared PSCS with SDBS also showed good gas permeance of 900 m³/(m² h kPa), higher than the 750 m³/(m²·h·kPa) without SDBS. This work describes the effective use of SDBS as a ceramic additive to reduce sintering temperature, while achieving high gas permeation and bending strength. The use of the low cost and commercially available SDBS produces an excellent ceramic filter with much lower energy consumption, and could also be implemented in other ceramic systems.     

Propene polymerization with MgCl2-supported TiCl4/dioctylphthalate catalyst. II. Effects of polymerization conditions on the microstructure of isotactic polymer

Propene was polymerized over the MgCl₂-supported TiCl₄/dioctylphthalate catalyst in heptane. Polymer products obtained under different polymerization conditions were separated into isotactic and atactic polypropenes by the extraction of boiling n-heptane. The effects of polymerization time, cocatalyst type, cocatalyst/catalyst ratio, polymerization temperature, and external base/cocatalyst ratio on the isotactic triad of the isotactic portion of polypropene were investigated 2,2,6,6-Tetramethyl piperidine (TMPIP), dimethoxy diphenyl silane (DMDPS), and t-butylmethyl ether (TBME) were employed as the external Lewis base. High concentrations of the first two bases caused a decrease in isotactic triads in the isotactic polymer, while TBME showed no significant effects. The difference can be attributed to the different roles these external bases play in polymerization. © 1995 John Wiley & Sons, Inc.     

2,2,6,6‐Tetramethylpiperidine‐1‐oxyl‐mediated living mini‐emulsion polymerization of styrene under ambient pressure in a semi‐batch process: effect of ascorbic acid

2,2,6,6‐Tetramethylpiperidine‐1‐oxyl (TEMPO)‐mediated living mini‐emulsion polymerization of styrene with feeding of an ascorbic acid aqueous solution throughout the polymerization was performed at 90 °C under ambient pressure. The concentrations of sodium dodecylbenzenesulfonate (SDBS) and ascorbic acid were varied to study the shell polymerization mechanism of latex particles and evolution of growing chains. Interactions between SDBS and ascorbic acid and incompatibility between ascorbic acid and styrene were evident from UV‐visible analyses. High hydrophilicity of ascorbic acid in the aqueous phase was proved using a gravimetric method. Accordingly, the formation of a surface barrier on particles was proposed because of the interactions between SDBS and ascorbic acid. For higher SDBS concentration, the surface barrier on the particles was denser. Therefore, the polymerization rate decreased with increasing SDBS concentration. However, the polymerization rate increased with increasing ascorbic acid concentration. This was due to a higher consumption rate of TEMPO by ascorbic acid. Free TEMPO tended to reside in surface zones of the particles because of the surface activity between the aqueous and oil phases. The surface zones were thus the main loci where TEMPO was consumed by ascorbic acid. The estimated number‐average molecular weight (M_n) of growing chains increased in a linear fashion with conversion. This indicated that the growing chains were produced via living mini‐emulsion polymerization. For these growing chains, the estimated M_n and final polydispersity increased with increasing SDBS concentration. This was caused by a decrease in TEMPO concentration in the surface zones of particles with increasing SDBS concentration. The ‘livingness’ of polystyrene was identified by conducting bulk polymerization of chain extension. Based on the results obtained, a shell polymerization mechanism of latex particles was proposed, and living mini‐emulsion polymerization was limited to the surface zones of particles. Copyright © 2010 Society of Chemical Industry