Polyisobutylene based thermoplastic elastomers: VI. Poly(α-methylstyrene-b-isobutylene-b-α-methylstyrene) triblock copolymers by coupling of living poly (α-methylstyrene-b-isobutylene) diblock copolymers

Summary Poly(α-methylstyrene-b-isobutylene-b-α-methylstyrene) (PαMeSt-PIB-PαMePSt) triblock copolymers have been prepared via coupling of living diblock copolymers in a one pot procedure. The PαMeSt-PIB diblock copolymers were synthesized by living sequential cationic polymerization in methylcyclohexane (MeChx)/methylchloride (MeCl) solvent mixtures at −80 °C using BCl₃ for αMeSt polymerization and TiCl₄ for IB polymerization as coinitiators. The crossover efficiency, however, was only ∼57 %, due to intermolecular alkylation (indanyl ring formation) after the addition of TiCl₄. By modifying the PαMeSt end with a short segment of p-chloro-α-methylstyrene before IB addition the crossover efficiency was increased to 90 %. Coupling of the living block copolymers with 2,2-bis[4-(1-phenylethenyl)phenyl]propane (BDPEP) was rapid and gave ∼ 90 % efficiency. Received: 13 July 2000/Accepted: 3 August 2000     

Asymmetric polymerization of N-substituted maleimides with organolithium — bisoxazolines complex

Asymmetric anionic polymerizations of achiral N-substituted maleimide (RMI) (N-cyclohexyl (CHMI), N-phenyl (PhMI), N-tert-butyl (TBMI)) by n-butyllithium (n-BuLi) or fluorenyllithium (FlLi) complexes of chiral bisoxazoline derivatives in toluene gave optically active polymers ([α]²⁵ ₄₃₅− 2.9° to − 8.2°). The polymers prerared with initiator of n-BuLi – 2,2′-bis(4,4′-isopropyl-,3-oxazoline) showed negative specific rotations (poly(RMI), [α]²⁵ ₄₃₅− 5.8° to − 8.2°) which were greater than those ([α]²⁵ ₄₃₅− 2.9° to − 5.9°) with other chiral 2,2′-bis(4,4′-alkyl-1,3-oxazoline) (alkyl group = iso-butyl and benzyl). Received: 29 July 1997/Revised: 27 August 1997/Accepted: 1 September 1997     

Radical polymerization of (trimethylsilylethynyl)styrene and thermal properties of polystyrene with ethynyl group

The radical polymerizations of 2-, 3-, and 4-(trimethylsilylethynyl)styrenes (1 a – c) and copolymerizations of 1 a – c (M₁) with styrene (M₂) have been studied. Copolymerization parameters were determined as r₁ = 1.22 and r₂ = 0.54 for 1 a, ₁ = 1.10 and r₂ = 0.90 for 1 b, and r₁ = 1.42 and r₂ = 0.38 for 1 c. The deprotection of the trimethylsilyl groups in poly[(trimethylsilylethynyl)styrene] (2 a – c) and poly[(trimethylsilylethynyl)styrene-co-styrene] (4 a – c) using (C₄H₉)₄NF smoothly proceeded to yield poly(ethynylstyrene) (3 a – c) and poly(ethynylstyrene-co-styrene) (5 a – c), respectively, which underwent curing reactions at elevated temperature to form crosslinking polystyrenes. Received: 31 March 1997/Revised: 2 June 1997/Accepted: 3 June 1997     

Rates for intramolecular excimer formation of poly(α-methylstyrene) measured by using picosecond pulse radiolysis

Summary The rate constants for intramolecular excimer formation, k_DM, of poly(α-methylstyrene) with different molecular weight were determined by using picosecond pulse radiolysis. Values of k_DM for poly(α-methylstyrene) are a little smaller than those for polystyrene with nearly same molecular weight. It appears to be mainly due to steric hindrance by methyl substituent of main chain.     

Preparation and characterization of poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones

The two poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones have been prepared via polycondensation reaction of di‐tert‐butyl adipate and di‐tert‐butyl fumarate with 2,2‐bis(p‐chloro dimethylsiloxy‐phenyl)propane to give tert‐butyl chloride as the condensate. The polymerizations were performed under nitrogen at 110°C for 24 h without addition of solvents and catalysts to obtain the poly(silyl ester)s with weight average molecular weights typically ranging from 5000 to 10,000 g/mol. Characterization of the poly(silyl ester)s included ¹H NMR and ¹³C NMR spectroscopies, infrared spectroscopy, ultraviolet spectroscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), gel permeation chromatography, and Ubbelohde viscometer. The glass transition temperatures (T_g) of the obtained polymers were above zero because of the introducing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones. The TGA/DTG results showed that the obtained poly(silyl ester)s were stable up to 180°C and the residual weight percent at 800°C were 18 and 9%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1937–1942, 2006     

Poly(methylphenylphosphazene)–Graft–Poly(methyl Methacrylate) Copolymers Via Atom Transfer Radical Polymerization

Atom transfer radical polymerization (ATRP) was used to graft poly(methyl methacrylate), PMMA, onto poly(methylphenylphosphazene), [(Me)(Ph)PN] _n , PMPP. A two-step process was used to convert a portion of the methyl substituents on [(Me)(Ph)PN] _n to –CH₂C(CH₃)₂OH groups and then to bromoalkyl groups, –CH₂C(CH₃)₂OC(=O)C(CH₃)₂Br, the latter of which served as initiation sites for ATRP of methyl methacrylate (MMA) in the presence of CuCl/bipyridine. Variations in the length of the grafted chains were investigated and the graft copolymers were compared to the parent polymer and blends of similar composition. The new bromoalkyl derivatives of [(Me)(Ph)PN] _n and the PMPP–graft–PMMA copolymers were characterized by elemental analysis, ¹H and ³¹P NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). We dedicate this paper to Professor Harry R. Allcock for consistently maintaining the highest standards in his creative, pioneering work in inorganic rings and polymers.     

Study on Selective Dimerization of α-Methylstyrenes Promoted by Ionic Liquids

The catalytic systems composed of ionic liquids containing BF₄⁻ anion and HBF₄ showed high catalytic activity to produce 4-methyl-2,4-diphenyl-1-pentene (MDP-1) or 1,1,3-trimethyl-3-phenylindan (TPI) under different temperature conditions. Up to 90.8% selectivity to MDP-1 with a 98.7% conversion of α-methylstyrene was obtained at 60 °C in the presence of [HexMIm]BF₄–HBF₄, while exclusive TPI was yielded when the reaction temperature increased to 120 °C. Further studies showed that another ionic liquid, [BMIm]Cl · 2AlCl₃, could act as an excellent catalyst and solvent for the dimerization of α-methylstyrene to produce TPI. The dimerization of α-methylstyrene catalyzed by [HexMIm]BF₄–HBF₄ and [BMIm]Cl · 2AlCl₃ performed the same reaction mechanism and the proton was the active species.     

Exploring the effect of alkyl end group on poly(L-lactide) oligo-esters. Synthesis and characterization

Poly(L-lactide) (PLLA) oligo-esters with α-hydroxyl-ω-alkyl (alkyl = −CH₂−[CH₂−CH₂]_m−CH₃, where m = 1, 2, 4, 5, 6, 7, 8, 9, and 10) end groups were synthesized by ring-opening polymerization of L-lactide (L-LA) catalyzed by tin(II) 2-ethylhexanoate Sn(Oct)₂ in the presence of aliphatic alcohols as initiators (HO−CH₂−[CH₂−CH₂]_m−CH₃, where m = 1, 2, 4, 5, 6, 7, 8, 9, and 10). High yields (~ 62 to 71%) and M _n(NMR) in the range of 2120–2450 Da (PLLA) were obtained. Effects of alkyl end groups on thermal properties of the oligo-esters were analyzed by DSC, TGA and SAXS. Glass transition temperature (T _g) gradually decreases with increase in the percent of−CH₂−[CH₂−CH₂]_m−CH₃ end group, as results alkyl end group provides most flexibility to PLLA. An important effect of alkyl end group on a double cold crystallization (T _c1 and T _c2) was observed, and is directly related with the segregation phase between alkyl end group and PLLA. TGA analysis revealed that PLLA oligo-esters are more thermally stable with docosyl (−C₂₂H₄₅) respect to the butyl (−C₄H₉) end group, probably is due to steric hindrance of the end group (docosyl respect to butyl) toward intermolecular and intramolecular transesterification. SAXS analysis showed that alkyl end group as docosyl restricted the growth of lamellae thickness (D) due to steric hindrance. Characterization of hydroxyl and alkyl end groups in the PLLA oligo-esters was determined by MALDI-TOF, GPC, FT-IR and ¹ H and ¹³ C NMR.     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Effects of phenyl-based pendent groups on helical conformation of poly(<Emphasis Type="Italic">N</Emphasis>-propargylamides)

Five achiral N-propargylamide monomers with various phenyl-based substitutents, [HC ≡ CCH₂NHCOR, R for M1: C₆H₄CH₃; M2: C₆H₄CH₂CH₃; M3: C₆H₄(CH₂)₂CH₃; M4: C₆H₄(CH₂)₃CH₃; M5: C₆H₄C(CH₃)₃], were synthesized and polymerized with a rhodium catalyst, (nbd)Rh⁺B^-(C₆H₅)₄ (nbd = 2,5-norbornadiene). The corresponding five homopolymers were obtained in high yields of 90–95% and with moderate molecular weights (M _n ≥ 10 000). All the polymers possessed high cis contents (≥95%). Poly(1)–poly(3) exhibited UV-vis absorption peaks at approx. 350 nm, which indicates that the three polymers formed helical conformations, while no UV-vis absorption peaks could be observed in poly(4) and poly(5) in the wavelength range of 320–500 nm, demonstrating that these two polymers could not adopt helical structures under the examined conditions. To confirm the helical structures formed in poly(1)–poly(3), a chiral monomer, M6, was utilized to copolymerize with M2, which was used as the representative for M1−M3. M6 was utilized since its polymer could form stable helices under suited conditions. The resulting copolymers exhibited remarkable CD effects, however, the maximum wavelength in the copolymers varied remarkably, mainly depending on the composition of the copolymers. It is concluded that in the formation of ordered helical conformations, the substitutents of varied bulk led to different steric repulsion and varied synergic effects among the neighboring pendent groups.     

Poly(di(ω-alkylphenyl)stannane)s

Poly(di(ω-alkylphenyl)stannane)s, [Sn(C _n H_2n Ph)₂] _m with n = 2–4, and a copolymer of di(3-propylphenyl)stannane and dibutylstannane of weight-average molar masses of 2–8 · 10⁴ g/mol were synthesized by dehydropolymerization of stannanes of the composition H₂SnR₂ using Wilkinson’s catalyst [RhCl(PPh₃)₃]. At least two methylene groups were required as spacers between the phenyl group and the tin atom for polymerization to occur. The polystannanes were characterized by, among other techniques, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, thermal analysis and X-ray diffraction. The polymers featured properties different from those of the corresponding poly(dialkylstannane)s. Specifically, the [Sn(C _n H_2n Ph)₂] _m family displayed glass transitions at remarkably low temperatures, down to ca. −50 °C, and a lower value for a copolymer (−68 °C). Polymers [Sn(C_nH_2nPh)₂]_m with n = 2 and 3 and a copolymer at room temperature were of a gel-like concistence, which enabled facile orientation with shear forces. Finally, the temperature-dependent electrical conductivity was determined for poly(di(3-propylphenyl)stannane), which followed the law of typical semiconductors, with an activation energy for conduction of 0.12 eV.     

The cationic polymerization of α-methylstyrene in liquid sulfur dioxide initiated by the HI/I2 system

The polymerization of α-methylstyrene (αMeSty) initiated by HI/I₂ or HI in the presence of liquid sulfur dioxide has been investigated. The number-average molecular weight increased with the monomer concentration for reactions initiated by the HI/I₂ system. I₂ also participates in the initiation process, increasing the number-average polymer chain at higher monomer concentration. HI alone is also able to initiate the polymerization of αMeSty in the presence of SO₂. With this initiator, transfer reaction can be minimized in systems containing low amount of SO₂. Received: 19 December 1996/Revised: 27 January 1997/Accepted 29 January 1997     

Pervaporation of ethanol/water and benzene/cyclohexane mixtures using novel substituted polyacetylene membranes

Summary In the ethanol/water pervaporation using membranes of Si-containing polymers, poly[1-phenyl-2-(p-trimethylsilyl)phenylacetylene] and poly[1-β-naphthyl-2-(p-trimethylsilyl)phenylacetylene], these polymer membranes permeated ethanol preferentially; α_EtOH/H2O 6.86 and 5.30, respectively, at 10 wt% EtOH content in the feed. Membranes of hydrocarbon-based polymers, poly(diphenylacetylene) and poly(1-β-naphthyl-2-phenylacetylene), which were prepared by desilylation of the two Si-containing polymer membranes, also exhibited ethanol permselectivity in ethanol/water pervaporation; α_EtOH/H2O 5.95 and 3.79, respectively. Further, in benzene/cyclohexane pervaporation, these desilylated membranes, which were insoluble in any organic solvent, showed rather low benzene permselectivity but very large fluxes. The results of the present study are attributed to the presence of many microvoids and, in turn, sparse structures. Received: 6 March 2002/ Accepted: 28 March 2002     

Amine-terminated aromatic and semi-aromatic hyperbranched polyamides: synthesis and characterization

A facile synthetic approach to aromatic and semiaromatic amine-terminated hyperbranched polyamides via direct polymerization of triamine (B₃) with different diacid chlorides (A₂) was explored. An aromatic triamine, 1,3,5-tris(4′-aminophenylcarbamoyl)benzene (TAPCB), was synthesized and monomers were characterized by elemental analysis, FTIR, ¹H and ¹³C NMR spectroscopy. Finally, the polycondensation reaction of TAPCB with terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), sebacoyl chloride (SC) and adipoyl chloride (AC) resulted in the preparation of four hyperbranched polyamides i.e., HBPA 1, 2, 3 and 4, respectively. FTIR and ¹H NMR analyses confirmed the structures of the ensuing polymers and DB was found between 0.51–0.55. These thermally stable amorphous HBPAs were soluble in polar aprotic solvents at room temperature having glass transition temperatures (T_g) between 138–198 °C. Inherent viscosities (η_inh) and weight average molecular weights (M_w) were in the range of 0.27–0.35 dL/g and 1.3 × 10⁴–2.7 × 10⁴, respectively. Future prospects are envisaged.     

Studies on the radical polymerization of N-vinyl 2-pyrrolidone initiated by diphenyl ditelluride

N-vinyl pyrrolidone (NVP) was polymerized in dioxan at 60 ± 0.1°C for 1 h using diphenyl ditelluride as radical initiator. The system follows ideal kinetics i.e. R _p α [DPDT]^0.5[NVP]. The activation energy and dissociation constant is computed as 46 kJ mol⁻¹ and 1.1 × 10⁻¹¹ s⁻¹, respectively. The polymer was characterized with the help of FTIR, ¹H-NMR, ¹³C-NMR, ESR spectroscopy. The FT-IR spectrum showed bands at 1660–1680 cm⁻¹ due to combination of >C = O and C–N stretching. The gyromagnetic constant ‘g’ has been computed as 2.2203. The main product of this reaction were poly(N-vinylpyrrolidone)s with phenyl tellanyl ends. The presence of tellurium in polymer is confirmed by ICP analysis. The DSC shows the T _g of poly(N-vinylpyrrolidone) is 168°C due to rigid pyrrolidane group. The TGA showed that polymer was stable up to 380°C.The GPC studies showed that the weight average molecular weight decreases with increase of [DPDT].     

Synthesis,Optical Properties,and Photoluminescence of Organometallic Acetylide Polymers of Platinum Functionalized with Si and Ge-Bridged Bis(3,6-Diethynyl-9-butylcarbazole)

A series of light-emitting group 14 element-containing organometallic platinum polyynes of the form trans-[–Pt(PBu₃)₂C≡ CArC≡ C(ER₂)C≡ CArC≡ C–] _n (Ar = 9-butylcarbazole-3,6-diyl, ER₂ = SiMe₂, SiPh₂, GeMe₂, GePh₂) were synthesized and spectroscopically characterized. The solution properties and regiochemical structures of this new structural class of organosilicon- and organogermanium-based metallopolyynes were studied by IR and NMR (¹H, ¹³C, ²⁹Si, and ³¹P) spectroscopies. The optical absorption and photoluminescence spectra of these metallopolymers were examined and compared with their well-defined dinuclear model complexes trans-[Pt(Ph)(PEt₃)₂C≡ CArC≡ C(ER₂)C≡ CArC≡ CPt(Ph)(PEt₃)₂]. The influence of the heavy platinum atom and the group 14 silyl or germyl structural unit possessing different side group substituents on the thermal and phosphorescence properties were investigated in detail. We have also established the goal for studying the evolution of the lowest singlet and triplet excited states with the nature of ER₂ unit in these metallopolymers. The present work indicates that the phosphorescence emission efficiency harnessed through the heavy-atom effect of platinum in the main chain changes significantly with the identity of ER₂ in the general orders GeR₂ > SiR₂ (R = Me, Ph) and EMe₂ > EPh₂ (E = Si, Ge). Dedicated to Professor Ian Manners in recognition of his outstanding contribution to inorganic and organometallic polymers.     

Silicate and zirconium phosphate modified Nafion/PTFE composite membranes for high temperature PEMFC

The PEMFC performance of MEAs prepared from Nafion-212 (thickness 50 μm, Du Pont Co), porous poly(tetrafluoro ethylene) (PTFE, thickness 15 ~ 18 μm) film reinforced Nafion (NF, thickness 20 ± 2 μm), silicate hybridized NF (NF-Si, thickness 21 ± 2 μm), and zirconium phosphate hybridized NF (NF-Zr, thickness 21 ± 2 μm) membranes were investigated at 110 °C/ 51.7% RH, 120 °C/ 38.2% RH, and 130 °C/ 28.6% RH. We show PEMFC performances of these MEAs decrease in the sequence of: NF-Zr> NF-Si> NF> Nafion-212. The NF, NF-Si, and NF-Zr membranes have lower membrane thickness and lower Nafion content and require less water for proton transport than Nafion-212 at temperatures above 110 °C, and thus have higher conductivity and better PEMFC performance than Nafion-212. Incorporating silicate and zirconium phosphate into NF membranes enhances water retention of membranes at temperatures above 110 °C and improves PEMFC performances. Besides enhancing water retention, incorporating zirconium phosphate into membranes also provides more routes for proton transport via H⁺ exchange between H₃ ⁺O and HPO₄-Zr- and between H₂ ⁺PO₄-Zr- and HPO₄-Zr-. Thus NF-Zr has a higher conductivity and better PEMFC performance than NF and NF-Si.     

Preparation of MCM-41 Supported Heterogenized Chiral Salen Mn (III) Complex and the Catalytic Activity in the Asymmetric Epoxidation

A chiral Manganese (III) salen complex was immobilized on the walls of MCM-41 (mobile crystalline material) through the multi-grafting method. The immobilized complex was characterized by XRD, FTIR, UV-Vis, ICP and Nitrogen sorption, and was applied to the asymmetric epoxidation of unfuctionalized alkenes including 1,2-dihydronaphthalene, α-methylstyrene, cis-β-methylstyrene, styrene using NaClO and m-chloroperbenzoic acid (m-CPBA) as oxidants respectively. The immobilized complex showed good activity and enantioselectivity in the epoxidation of 1,2-dihydronaphthalene by using NaClO as oxidant. It could also be run for 4 times in the epoxidation of α-methylstyrene without obvious loss of activity or enantiomeric excess.     

Synthesis of polyarylene homopolymers and copolymers via nickel(0)-catalyzed homocoupling of arylenebismesylates derived from bisphenols

A general and inexpensive procedure for the synthesis of poly(arylene)-type homopolymers and copolymers containing alternating oligophenylene and a functional group (X) (e.g. X = −O−, −CO−, −SO₂−, −C(CH₃)₂−, −CH₂−CH(Et)−, etc) is described. The synthetic method is based on the Ni(0)-catalyzed homocoupling of aryl bismesylates (MsOAr−X−ArOMs) derived from bisphenols. Symmetric X groups lead to regioregular crystalline and insoluble polymers whereas bulky, asymmetric X groups or the incorporation of comonomers yield regioirregular polymers and, respectively, copolymers with decreased crystallinity and increased solubility. This new synthetic method can be applied to the preparation of polymers with controlled rigidity which are amorphous, crystalline or liquid crystalline. Received: 22 January 1997/Accepted: 24 February 1997     

Polymerization of 4-n-alkylstyrenes with typical Ziegler-Natta and metallocene catalysts

Polymerization of 4-n-alkylstyrenes (alkyl side group; methyl, ethyl, propyl and buthyl) was carried out with the η-C₅(CH₃)₅TiCl₃-methylaluminoxane (MAO) and TiCl₃-triethylaluminum (TEA) catalyst systems. When the η-C₅(CH₃)₅TiCl₃-MAO catalyst was used, the stereoregularity of resulting polymers markedly depended on the length of substituted alkyl groups, i.e., the catalyst gave highly syndiotactic poly(4-methylstyrene), but produced atactic polymers for the monomers with ethyl, propyl and buthyl substituents. On the other hand, all the poly(4-n-alkylstyrene)s obtained with the TiCl₃-TEA catalyst were highly isotactic. As a result, a large difference was observed in the thermal properties of polymers obtained between the two catalyst systems. Received: 6 September 1996/Accepted: 16 October 1996