Polyisobutylene-containing block polymers by sequential monomer addition. II. Polystyrene–polyisobutylene–polystyrene triblock polymers: Synthesis,characterization, and physical properties

New linear and three-arm star thermoplastic elastomers (TPEs) comprising a rubbery polysobutylene (PIB) midblock flanked by glass polystyrene (PSt) blocks have been synthesized by living carbocationic polymerization in the presence of select additives by sequential monomer addition. First, isobutylene (IB) was polymerized by bi- and trifunctional tert-ether (dicumyl- and tricumyl methoxy) initiators in conjunction with TiCl₄ conintiator in CH₃Cl/methylcyclohexane (MeCHx) (40/60 v/v) solvent mixtures at ?80°C. After the living, narrow molecular weight, distribution PIB (M?_w/M?_n = 1.1-1.2) has reached the desired molecular weight, styrene (St) together with an electron pair donor (ED) and a proton trap (di-tert-butylpyridine, DtBP) were added to block PSt from the living chain ends. Uncontrolled initiation by protic impurities that produces PSt contamination is prevented by the use of DtBP. PSt-PIB-PSt blocks obtained in the absence of additives are contaminated by homopolymer and /or diblocks due to inefficient blocking and initiation by protic impurities, and exhibit poor physical properties. In contrast in the presence of the strong ED N,N-dimethylacetamide (DMA) and DtBP the blocking of St from living PIB chain occurs efficiently and block copolymers exhibiting good mechanical properties can be prepared. Virgin TPEs can be repeatedly compression molded without deterioration of physical properties. The products exhibit a low and a high temperature T_g characteristic of phase separated PIB and PSt domains. Transmission electron microscopy of linear triblocks containing ～ 34 wt % PSt also indicates microphase separation and suggests PSt rods dispersed in a PIB matrix.     

Polyisobutylene-containing block polymers by sequential monomer addition. IV. New triblock thermoplastic elastomers comprising high Tg styrenic glassy segments: Synthesis,characterization and physical properties

New linear triblock thermoplastic elastomers (TPEs) comprising a rubbery polyisobutylene (PIB) midblock flanked by two glassy endblocks of various styrenic polymers have been synthesized by living carbocationic polymerization by sequential monomer addition. First isobutylene (IB) was polymerized by a bifunctional tert-ether (dicumyl methyl ether) initiator in conjunction with TiCl₄ coinitiator in CH₃Cl/methylcyclohexane (MeCHx) (40/60 v/v) solvent mixtures at ?80°C. After the living narrow molecular weight distribution PIB midblock ( = 1.1–1.2) has reached the desired molecular weight, the styrenic monomers together with an electron pair donor (ED) and a proton trap (di-tert-butylpyridine, DtBP) were added to start the blocking of the glassy segments from the living ⊕PIB⊕ chain ends. While p-methylstyrene (pMeSt), p-t-butylstyrene (ptBuSt) and indene (In) gave essentially 100% blocking to the corresponding glassy endblocks, the blocking of 2,4,6-trimethylstyrene (TMeSt) and α-methylstyrene (αMeSt) were ineffective. Uncontrolled initiation by protic impurities was prevented by the use of DtBP. In the simultaneous presence of DtBP and the strong ED N,N-dimethylacetamide (DMA), TPEs with good mechanical properties (10–20 MPa tensile strength, 300–600% elongation) were prepared. The products exhibit a low and a high temperature T_g characteristic of phase separated rubbery and glassy domains. The service temperature of these new TPEs exceeds that of PSt–PIB–PSt triblock copolymers due to the higher T_gs (PpMeSt = 108, PptBuSt = 142 and PIn = 220–240°C) of the outer blocks. The T_g of the glassy blocks can be regulated by copolymerizing two styrene derivatives; a triblock copolymer with outer blocks of poly(pt-butylstyrene-co-indene) showed a single glassy transition T_g = +165°C, i.e., in between that of PptBuSt and PIn. Virgin TPEs have been repeatedly compression molded without deterioration of physical properties. The high melt flow index obtained with a TPE containing PptBuSt endblocks suggests superior processability relative to those with PSt end-blocks. The tensile strength retention at 60°C of the former TPE is far superior to that of a PSt–PIB–PSt triblock of similar composition.     

Polyisobutylene-Based Thermoplastic Elastomers. I. Synthesis and Characterization of Polystyrene-Polyisobutylene-Polystyrene Triblock Copolymers

Abstract

Polystyrene-polyisobutylene-polystyrene triblock copolymer thermoplastic elastomers have been synthesized by living carbocationic sequential copolymerization using the tert-butyl dicumyl chloride/TiCl₄/methylcyclohexane:methyl chloride (60:40 v:v)/ ?80°C system in the presence of the proton trap 2,6-di-tert-butylpyridine. Structure-property relationships have been examined by varying the M_n of the PIB middle block (39,000 to 156,000) and that of the PSt end-segment (1,000 to 19,000). The tensile strength is controlled by the molecular weight of the PSt segment and independent of the PIB middle block length in the studied range. Phase separation starts when the M_n of the PSt segment reaches ～ 5,000, and it is complete when the M_n reaches ～ 15,000. These triblocks exhibited 23-25 MPa tensile strength, similar to that of styrenic thermoplastic elastomers obtained by anionic polymerization.     

Synthesis of 1-chloro-1-phenylethyl-telechelic polyisobutylene,a new potential macroinitiator by living cationic polymerization

1-Chloro-1-phenylethyl-telechelic polyisobutylene (PIB) was synthesized by living carbocationic polymerization (LCCP). LCCP of isobutylene was induced by a difunctional initiator in conjunction with TiCl₄ as coinitiator in the presence of N,N-dimethylacetamide in CH₂Cl₂/hexane (40:60 v/v) solvent mixture at −78°C. After complete isobutylene conversion a small amount of styrene was added leading to a rapid crossover reaction and thus to the attachment of short outer polystyrene (PSt) blocks to the PIB segment. Quenching the living polymerization of styrene yielded 1-chloro-1-phenylethyl terminal groups. The resulting telechelic polymer (Cl-PSt-PIB-PSt-Cl) is a potential new macroinitiator for atom transfer radical polymerization of a variety of vinyl monomers.     

Investigation of the effect of reaction conditions on the synthesis of multiarm-star polyisobutylene-polystyrene block copolymers

New multi-arm star block copolymers comprising of rubbery polyisobutylene (PIB) midsegment and glassy polystyrene (PS) end blocks have been synthesized by carbocationic polymerization using a new multifunctional initiator, hexaepoxy squalene (HES), with TiCl₄ coinitiator, di-t-butylpyridine (DtBP) as a proton trap and N,N-dimethylacetamide (DMA) as an electron pair donor in methylcyclohexane (MeCHx)/methyl chloride (MeCl) solvent mixtures at −80 °C. It was found that reaction conditions, such as solvent composition, HES/isobutylene (IB) ratio and TiCl₄ concentration, have profound influence on initiator efficiency and functionality. Living conditions were achieved in the presence of DMA in MeCHx/MeCl 60/40 v/v, while in the absence of DMA, the M_n-conversion plot showed a considerable intercept. Depending on the reaction conditions, the PIB midblocks had 3-10 arms. Reaction rates increased with increasing solvent polarity and TiCl₄ concentration. Living narrow molecular weight distribution PIBs (M_w/M_n=1.1-1.2) were reacted with styrene (St) solution containing DtBP and DMA to yield multiarm-star PIB-PS block copolymers. Blocking was evidenced by SEC analysis and copolymers with 8.9-28.6 wt.% PS, M_n∼164,000-609,000 g/mol and M_w/M_n=1.32-1.88 were successfully synthesized.     

Quasiliving Carbocationic Polymerization. XVII. Synthesis Of Poly (Styrene-β-Isobutylene-β-Styrene)

Poly(styrene-b-isobutylene-b-styrene) has been synthesized by sequential carbocationic polymerization under quasiliving conditions at -90°C. The quasiliving synthesis was effected by first continuously and slowly condensing gaseous isobutylene (IB) to a bifunctional initiating system (p-dicumyl chloride/TiCl₄) dissolved in a hexane-methylene chloride (60:40 v/v) mixture. After the quasiliving polyisobutylene (PIB) sequence had reached a desired molecular weight, styrene (St) was continuously and slowly added to produce the polystyrene (PSt) sequence. The products consisted of the target triblock. However, due to initiation by impurities and possibly to chain transfer to both IB and St, it also contained diblocks and small amounts of homopolymers. While the latter could be removed by selective fractionation, the triblocks and diblocks could not be separated. The mechanism of quasiliving polymerization leading to PIB/PSt blocks is discussed.     

Comparison of the Mechanism and Kinetics of Living Carbocationic Isobutylene and Styrene Polymerizations Based on Real-Time FTIR Monitoring

This paper will compare the mechanism and kinetics of living carbocationic polymerization of isobutylene (IB) and styrene (St), initiated by the 2-chloro-2,4,4-trimethyl-pentane (TMPCl) / TiCl₄) system in 60/40 (v/v) methylcyclohexane / methyl chloride mixed solvent at −80 and −75 °C. The rate of initiation was found to be first order in TiCl₄ in both systems. While initiation is instantaneous in IB polymerization at [TiCl₄]₀ ⩾ [TMPCl]₀, it is slow in St polymerization. Kinetic derivation showed that initiating efficiency is dependent on [M] in this latter system, which was also demonstrated experimentally. The apparent initiation rate constant was determined from initiator consumption rate data and was found to be k_i,app = 1.39 l²/mol²sec. The rate of St consumption measured using a real time fibre-optic mid-FTIR monitoring technique compared well with gravimetric data and was found to be closer to first order in TiCl₄ at [TiCl₄]₀ < [TMPCl]₀. However, the rate followed a close to second order in TiCl₄ at [TiCl₄]₀ ⩾ [TMPCl]₀. The mechanistic model proposed earlier for living carbocationic IB polymerization, which yielded good agreement with experimental data, seems to apply to carbocationic St polymerization as well. This model reconciles the discrepancy between rate constants published for carbocationic IB and St polymerizations, and accounts for shifting TiCl₄ orders. However, independent investigations are necessary to verify the proposed mechanistic model. Optimized conditions led to living carbocationic St polymerization producing high molecular weight PS with 100% initiating efficiency.     

Star and Hyperbranched Polyisobutylenes via Terminally Reactive Polyisobutylene-Polystyrene Block Copolymers

Unique, highly branched polyisobutylenes (PIB) were prepared via quasiliving carbocationic copolymerization of isobutylene and styrene (St) monomers. The junction points were formed by Friedel-Crafts self alkylation of PSt segments by the carbocationic chain ends. First, linear PIB was prepared with reactive chain ends. This was reacted with St monomer to form PIB-b-PSt AB, and PSt-b-PIB-b-PSt ABA type triblock copolymers with reactive carbocationic chain ends. The terminal carbonations react with the phenyl group of the polystyrene end-segments of the block copolymers leading to chain coupling, and thus PIB star polymers in the case of AB and hyperbranched PIB from ABA block copolymers. The resulting branched polymers were characterized and the branch formation was confirmed by gel permeation chromatography (GPC) and proton nuclear magnetic resonance spectroscopy (¹H NMR).     

Living carbocationic copolymerization of isobutylene with styrene

The carbocationic copolymerization of isobutylene (IB) and styrene (St), initiated by 2‐chloro‐2,4,4‐trimethylpentane/TiCl₄ in 60/40 (v/v) methyl chloride/hexane at ?90 °C, was investigated. At a low total concentration (0.5 mol/L), slow initiation and rapid monomer conversion were observed. At a high total comonomer concentration (3 mol/L), living conditions (a linear semilogarithmic rate and M_n–conversion plots) were found, provided that the St concentration was above a critical value ([St]₀ ～ 0.6 mol/L). The breadth of the molecular weight distribution decreased with increasing IB concentration in the feed, reaching M_w/M_n ～ 1.1. St homopolymerization was also living at a high total concentration, yielding polystyrene with M_n = 82,000 g/mol, the highest molecular weight ever achieved in carbocationic St polymerization. An analysis of this system by both the traditional gravimetric–NMR copolymer composition method and FTIR demonstrated penultimate effects. IB enrichment was found in the copolymers at all feed compositions, with very little drift at a high total concentration and above the critical St concentration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1778–1787, 2007     

Living carbocationic polymerization of isobutyl vinyl ether and the synthesis of poly[isobutylene-b-(isobutyl vinyl ether)]

The MeCH(O-i-Bu)Cl/TiCl₄/MeCONMe₂ initiating system was found to induce the rapid living carbocationic polymerization (LC^⊕Pzn) of isobutyl vinyl ether (IBuVE) at ?100°C. Degradation by dealcoholation which usually accompanies the polymerization of alkyl vinyl ethers by strong Lewis acids is “frozen out” at this low temperature and poly(isobutyl vinyl ether)s (PIBuVEs) with theoretical molecular weights up to ca. 40,000 g/mol (calculated from the initiator/monomer input) and narrow molecular weight distributions (M?_w/M?_n ≤ 1.2) are readily obtained. According to ¹³C-NMR spectroscopy, PIBuVEs prepared by living polymerization at ?100°C are not stereoregular. The MeCH(O-i-Bu)Cl/TiCl₄ combination induces the rapid LC^⊕Pzn of IBuVE even in the absence of N,N-dimethylacetamide (DMA). The addition of the common ion salt, n-Bu₄NCl to the latter system retards the polymerization and meaningful kinetic information can be obtained. The kinetic findings have been explained in terms of TiCl₄. IBuVE and TiCl₄ · IBuVE and TiCl₄ · PIBuVE complexes. The HCl (formal initiator)/TiCl₄/DMA combination is the first initiating system that can be regarded to induce the LC^⊕Pzn of both isobutylene (IB) and IBuVE. Polyisobutylene (PIB)–PIBuVE diblocks were prepared by sequential monomer addition in “one pot” by the 2-chloro-2,4,4-trimethylpentane (TMP-Cl)/TiCl₄/DMA initiating system. Crossover efficiencies are, however, below 35% because the PIB^⊕ + IBuVE → PIB-b-PIBuVE^⊕ crossover is slow. © 1993 John Wiley & Sons, Inc.     

The role of pyridine derivatives in living carbocationic polymerization: Lewis base or nucleophile?

The living cationic polymerization of isobutylene induced by the 2-chloro-2,4,4-trimethylpentane/TiCl₄/hexane:methyl chloride (60:40, v:v)/-80°C system was studied in the presence of pyridine derivatives. Protic initiation, substantial in the absence of these additives, was virtually eliminated in their presence, and polyisobutylenes with controlled molecular weight and narrow molecular weight distribution were obtained. With some additives, however, proton elimination occurs, resulting in the exclusive formation of the exo olefin. The rate of elimination is independent of monomer concentration, i.e., it occurs during and after the polymerization. Results suggest that the proton elimination is due to the presence of an uncomplexed base, especially when complex formation with TiCl₄ is hindered by steric compression, but its approach of the polymer cation is not fully blocked.     

Novel Epoxide Initiators for the Carbocationic Polymerization of Isobutylene

Summary: We recently reported the synthesis of polyisobutylene (PIB) via direct initiation by epoxycyclohexyl isobutyl polyhedral oligomeric silsesquioxane (POSS®) (Figure 1 ) in conjunction with titanium tetrachloride (TiCl₄). This system successfully initiated the living carbocationic polymerization of isobutylene (IB) in hexane/methyl chloride (Hx/MeCl -60/40, v/v) at T = −80 °C, yielding an asymmetric telechelic PIB with one POSS® cage head group and one tert-Cl end group. 1 This paper will discuss IB polymerizations initiated by 1,2-epoxycyclohexane and bis[3,4-(epoxycyclohexyl)ethyl]-tetramethyl-disiloxane, in conjunction with TiCl₄.     

Living carbocationic polymerization. LXII. Living polymerization of styrene,p-methylstyrene and p-chlorostyrene induced by the common ion effect

The effect of common anion producing salt, tetrabutylammonium chloride (n-Bu₄NCl), on the livingness and kinetics of styrene (St), p-chlorostyrene (pClSt), and p-methylstyrene (pMeSt) polymerization initiated by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl₄ system has been investigated. Uncontrolled (conventional) carbocationic polymerization of St and p MeSt can be converted to living polymerization by the use of n-Bu₄NCl. Under similar conditions the polymerization of p ClSt is living even in the absence of n-Bu₄NCl, although the molecular weight distribution (MWD) of the polymer becomes narrower in the presence of this salt. The apparent rates of polymerizations decrease in the presence of n-Bu₄NCl in proportion with the concentration of the salt. The rate of living polymerization of p ClSt is noticeably lower than that of St, while that of p MeSt is higher. The apparent rate constants, k_p^A, of these polymerizations have been determined, and the effects of the electron donating p Me- and electron withdrawing p Cl-substituents relative to the rate of St polymerization have been analyzed. [For part LXI, see J. Si and J. P. Kennedy, Polym. Bull., 33 , 651 (1994)]. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3341–3347, 1997     

Atom Transfer Radical Polymerization of Styrene with 5‐Chloromethyl‐2‐hydroxy‐benzaldehyde as Initiator

Abstract

Atom transfer radical polymerization (ATRP) of styrene (St) proceeded using 5‐chloromethyl‐2‐hydroxy‐benzaldehyde as initiator, CuCl as catalyst, and N,N,N′,N′,N′‐pentamethyldiethyltriamine (PMDETA) as ligand. The results show that the polymerization is a first order reaction with respect to monomer concentration. The polymerization displayed living character as evidenced by a liner increase of monomer weight with conversation and a relatively narrow distribution (M _n/M _w ranges from 1.25 to 1.50). The end structure of PSt was analyzed by ¹H‐NMR, and PSt initiated MMA to form block copolymer (PSt‐b‐PMMA), which also proved that the polymerization could be controlled. The effects of reaction temperature and monomer to initiator mole ratio on the polymerization displayed living character were discussed.     

Cationic polymerization of 1,3-pentadiene and 2-methylpropene: Direct initiation is a general mechanism with AlCl3 in polar medium

Following previous results showing that direct initiation was operating in the cationic polymerization of 1,3-pentadiene in the presence of AlCl₃ in non-polar medium, it is shown on the same system that direct initiation also occurs in polar medium. In the case of 2-methylpropene the use of a proton trap (DtBP) allowed to show that at −30 °C, direct initiation mechanism was operating either in 64/36 or in 36/64 (v/v) CH₂Cl₂/pentane mixtures. These results show that direct initiation is a general mechanism with AlCl₃. SEC studies showed that for 2-methylpropene transfer can be minimized.     

Open mechanistic problems of quasiliving carbocationic polymerization of olefins mediated by nucleophilic additives

This study is a comprehensive overview of the open problems and the existing views on the mechanism of quasiliving carbocationic polymerizations (QLCP) of olefins mediated by nucleophilic additives. The fundamental and general aspects of ideal living and quasiliving polymerizations involving other mechanisms, such as free radical, group transfer, ring-opening metathesis, ring-opening cationic and anionic processes, have been also analyzed and summarized. Quasiliving carbocationic polymerization of olefins in the presence of nucleophiles, which form complexes with the Lewis acid coinitiators, occur By reversible termination. Four different mechanisms have been discussed in this study: (1) reactivity leveling by nucleophiles (“electron donors”); (2) propagation by species with decreased ionicity (“stretched polarized bonds”) mediated by Lewis acid-nucleophile complexes (LA-Nu); (3) propagation by classical ion pair and free ion species; (4) proton scavenging by nucleophiles and 2,6-di-teri-butylpyridine proton trap. It is shown that mechanisms No. 1, 3 and 4 cannot explain all the existing findings, and although the experimental results can be interpreted with mechanism No. 2, the existence of “stretched polarized bonds” can be questionable. It is also concluded that compared to nonliving carbocationic polymerization, kinetic analysis indicates that the propagating species cannot be the same in quasiliving carbocationic polymerizations and in chain transfer dominated classical carbocationic polymerizations with ion pairs and free ions.     

AxBAx‐Type Block–Graft Polymers with Soft Methacrylate Middle Segments and Hard Styrene Outer Grafts: Synthesis,Morphology, and Mechanical Properties

Novel copolymers with controlled architectures can function as new building blocks for well‐defined nanostructures on the basis of microphase separation, unlike conventional ABA triblock copolymers. A series of well‐defined A_xBA_x‐type block–graft copolymers consisting of soft middle segments (dodecyl methacrylate (DMA)) and hard outer graft chains (styrene (St)) were synthesized by ruthenium‐catalyzed living radical block and graft polymerization. NMR spectroscopy and size‐exclusion chromatography combined with multiangle laser light scattering confirmed the well‐defined structure of the A_xBA_x block–graft copolymers with backbones and graft chains of controlled lengths. Transmission electron microscopy and transmission electron microtomography revealed a series of morphologies for the copolymers. Morphological changes were observed from PSt “honeycomb” cylinders to lamellae and poly(DMA) cylinders with increasing PSt‐graft content, whereby the phase diagram was shifted significantly to lower volume fractions of the larger‐number component (St) relative to those of the corresponding ABA triblock copolymers. More specifically, poly(DMA) cylinders were observed even before the St content reached 50 wt %. The A_xBA_x and ABA copolymers with 17–30 wt % of St exhibited characteristics of a thermoplastic elastomer with tensile strengths of 1–6 MPa and elongations at break of 70–300 %. These mechanical properties can be related well to the microphase structures of the A_xBA_x and ABA copolymers.     

Synthesis and characterization of novel dendritic (arborescent,hyperbranched) polyisobutylene–polystyrene block copolymers

The synthesis of novel arborescent (arb; randomly branched, “tree‐like,” and often called “hyperbranched”) block copolymers comprised of rubbery polyisobutylene (PIB) and glassy polystyrene (PSt) blocks (arb‐PIB‐b‐PSt) is described. The syntheses were accomplished by the use of arb‐PIB macroinitiators (prepared by the use of 4‐(2‐methoxyisopropyl) styrene inimer) in conjunction with titanium tetrachloride (TiCl₄). The effect of reaction conditions on blocking of St from arb‐PIB was investigated. Purified block copolymers were characterized by ¹H NMR spectroscopy and Size Exclusion Chromatography (SEC). arb‐PIB‐b‐PSt with 11.7–33.8 wt % PSt and M_n = 468,800–652,900 g/mol displayed thermoplastic elastomeric properties with 3.6–8.7 MPa tensile strength and 950–1830% elongation. Samples with 26.8–33.8 wt % PSt were further characterized by Atomic Force Microscopy (AFM), which showed phase‐separated mixed spherical/cylindrical/lamellar PSt phases irregularly distributed within the continuous PIB phase. Dynamic Mechanical Thermal Analysis (DMTA) and solvent swelling of arb‐PIB‐b‐PSt revealed unique characteristics, in comparison with a semicommercial PSt‐b‐PIB‐b‐PSt block copolymer. The number of aromatic branching points of the arb‐PIB macroinitiator, determined by selective destruction of the linking sites, agreed well with that calculated from equilibrium swelling data of arb‐PIB‐b‐PSt. This method for the quantitative determination of branching sites might be generally applicable for arborescent polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1811–1826, 2005     

Novel substituted epoxide initiators for the carbocationic polymerization of isobutylene

This article presents the first detailed account of the discovery that substituted epoxides can initiate the carbocationic polymerization of isobutylene. α‐Methylstyrene epoxide (MSE), 2,4,4‐trimethyl‐pentyl‐epoxide‐1,2 (TMPO‐1), 2,4,4‐trimethyl‐pentyl‐epoxide‐2,3 (TMPO‐2), and hexaepoxi squalene (HES) initiated isobutylene polymerization in conjunction with TiCl₄. MSE, TMPO‐2, and HES initiated living polymerizations. A competitive reaction mechanism is proposed for the initiation and propagation. According to the proposed mechanism, initiator efficiency is defined by the competition between the S_N1 and S_N2 reaction paths. A controlled initiation with external epoxides such as MSE should yield a primary hydroxyl head group and a tert‐chloride end‐group. The presence of tert‐chloride end‐groups was verified by NMR spectroscopy, whereas the presence of primary hydroxyl groups was implied by model experiments. Multiple initiation by HES was verified by diphenyl ethylene end‐capping and NMR analysis; the resulting star polymer had an average of 5.2 arms per molecule. A detailed investigation of the reaction mechanism and the characterization of the polymers are in progress. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 444–452, 2000