Poly(ether ketone)–polyisobutylene block copolymers: Synthesis and phase behavior

Telechelic poly(ether ketone)s (PEKs) and polyisobutylenes (PIBs) were combined to form PIB? PEK? PIB triblock copolymers and (PIB? PEK)_n multiblock copolymers via the formation of urea linkages. Monovalent and bivalent amino telechelic PIBs were prepared quantitatively from allyl telechelic PIBs by a newly developed reaction sequence featuring nucleophilic reaction steps. Telechelic PEK? NCO polymers were prepared from the corresponding amino telechelic PEKs via a reaction with diphosgene. The highly reactive PEK? NCO and PIB? NH₂ telechelics formed PEK? PIB block copolymers only quantitatively when appropriately reactive primary amino groups were present on the amino telechelic PIBs. The obtained block copolymers were microphase‐separated and featured mostly lamellar structures, as determined by small‐angle X‐ray scattering (SAXS). Temperature‐dependent SAXS measurements revealed ordered polymers in the melt up to 210 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 188–202, 2005     

Supramolecular poly(ether ketone)–polyisobutylene pseudo‐block copolymers

The association behavior of telechelic hydrogen‐bonded poly(ether ketone) (PEK) and polyisobutylene (PIB) polymers and the formation of a new class of pseudo‐block copolymers is reported. The attachment of complementing hydrogen bonds (thymine/2,6‐diaminotriazine and cytosine/2,6‐diaminotriazine) onto the respective PIB and PEK polymers leads to a dramatic increase in the miscibility between the normally immiscible PEK and PIB polymers. The structure formation in the liquid state was studied by dynamic NMR spectroscopy as well as in the solid state via solid‐state NMR‐spectroscopy, DSC, and TEM methods. The polymers form a nanophase structure with a periodicity of 70 nm with the microphase separation occurring specifically within the donor–acceptor pair with the higher binding constant (thymine/2,6‐diaminotriazine) and not within the weaker bonded cytosine/2,6‐diaminotriazine pair. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 162–172, 2004     

Synthesis and characterization of polymethylphenylsilane–polystyrene block copolymers

Block copolymers of polymethylphenylsilane (PMPS) and polystyrene (PS) have been successfully prepared by the condensation of α,ω-dichloro-polymethylphenylsilane with polystyryl-lithium. These new materials have been characterized by UV spectroscopy, ²⁹Si-NMR, and size exclusion chromatography. These block copolymers show a good emulsifying activity to compatibilize blends of the two homopolymers (PMPS and PS). © 1993 John Wiley & Sons, Inc.     

Functional polymers and sequential copolymers by phase transfer catalysis. XXVIII. Synthesis and characterization of alternating block copolymers and polyformals of polyisobutylene and aromatic polyether sulfone

Alternating—i.e., -(A-B)_n- type—block copolymers of polyisobutylene (PIB) and aromatic polyether sulfone (PSU) have been prepared by phase transfer catalyzed Williamson polyetherification of α,ω-di(phenol)PIB with α,ω-di(chloroallyl)- or -(bromobenzyl)PSU. Block copolymers of the two prepolymers were also synthesized by the phase transfer catalyzed polyetherification of methylene chloride with α,ω-di(phenol)PIB and α,ω-di(phenol)PSU (bisphenol-A-terminated PSU). This method leads to -[(A)_x-(B)_y]_n- block copolymers with formal linkages between segments. At sufficiently high segment lengths, both types of block copolymers exhibit two distinct T_gs, indicating phase separation into rubbery PIB and glassy PSU domains.     

Synthesis,characterization, and Diels–Alder extension of cyclopentadiene telechelic polyisobutylene. III. Silylcyclopentadiene-telechelic polyisobutylene

Telechelic polyisobutylenes with silylcyclopentadiene termini (CpSi-PIB-SiCp) were prepared, starting with α,ω-di(t-chloro)polyisobutylene and followed by dehydrochlorination, hydrosilylation, and cyclopentadienylation. The prepolymer was characterized and found to have a terminal functionality close to 2.0. Thermal chain extension by Diels–Alder addition of the end groups did not occur, most likely because of fluxional isomerization of the silylcyclopentadiene end groups, confirmed by model studies. Chain coupling of CpSi-PIB-SiCp prepolymers with stoichiometric amounts of bismaleimide gave rise to degrees of extension of more than 11.     

Synthesis and characterization of polystyrene–poly(ethylene oxide)–heparin block copolymers

A procedure for the preparation of new block copolymers composed of a hydrophobic block of polystyrene, a hydrophilic spacer-block of poly(ethylene oxide) and a bioactive block of heparin was investigated. Polystyrene with one amino group per chain was synthesized by free radical oligomerization of styrene in dimethylformamide, using 2-aminoethanethiol as a chain transfer agent. This amino group was used in the coupling reaction with amino-telechelic poly(ethylene oxide) to produce an AB type diblock copolymer with one amino group per polystyrene (PSt)–poly(ethylene oxide) (PEO) chain. The amino-semitelechelic oligo-styrene was converted into the isocyanate-semitelechelic oligo-styrene using toluene 2,4-diisocyanate and subsequent coupling with H₂N–PEO–NH₂ afforded AB type block copolymers with terminal amino groups. The coupling of PSt–PEO–NH₂ with heparin was performed in a DMF–H₂O mixture, first by activating the heparin carboxylic groups with EDC at pH 5.1–5.2 and subsequently reacting the activated carboxylic groups with the amino groups of the PSt–PEO–NH₂ at pH 7.5. Depending on the molecular weights of the diblock copolymer used 25–29% w/w heparin was incorporated. These polymers will be further evaluated for their blood-compatibility.     

Synthesis and characterization of polysiloxane–polyamide block and graft copolymers

The synthesis of copolymers constituted of a central polydimethylsiloxane (PDMS) block flanked by two polyamide (PA) sequences is described. α, ω-diacyllactam PDMS, when used as macroinitiator of lactam polymerization, gives rise to the expected triblock copolymer. Likewise, PDMS-g-PA graft copolymers are obtained from acyllactam containing polysiloxanes. NaAlH₂(OCH₂CH₂OMe)₂ turns out to be the best suited activating agent for the polymerization of ?-caprolactam, in the experimental conditions required for the synthesis of polysiloxane–polyamide copolymers. The nucleophilic species formed by reaction of NaAlH₂(OCH₂CH₂OMe)₂ with ?-caprolactam—2-[bis(methoxyethoxy) aluminumoxy]-1-azacycloheptane sodium—is indeed nucleophilic enough to bring about the growth of PA chains and mild enough to stay inert towards PDMS. © 1993 John Wiley & Sons, Inc.     

Synthesis and photophysical characterization of amphiphilic dendritic–linear–dendritic block copolymers

Amphiphilic dendritic–linear–dendritic triblock copolymers based on hydrophilic linear poly(ethylene oxide) (PEO) and hydrophobic dendritic carbosilane were synthesized with a divergent approach at the allyl end groups of diallyl‐terminated PEO. Their micellar characteristics in an aqueous phase were investigated with dynamic light scattering, fluorescence techniques, and transmission electron microscopy. The block copolymer with the dendritic moiety of a third generation could not be dispersed in water. The block copolymers with the first (PEO–D ‐Si‐1G) and second (PEO–D ‐Si‐2G) generations of dendritic carbosilane blocks formed micelles in an aqueous phase. The critical micelle concentrations of PEO–D ‐Si‐1G and PEO–D ‐Si‐2G, determined by a fluorescence technique, were 27 and 16 mg/L, respectively. The mean diameters of the micelles of PEO–D ‐Si‐1G and PEO–D ‐Si‐2G, measured by dynamic light scattering, were 170 and 190 nm, respectively, which suggests that the micelles had a multicore‐type structure. The partition equilibrium constants of pyrene in the micellar solution increased with the increasing size of the dendritic block (e.g., 7.68 × 10⁴ for PEO–D ‐Si‐1G and 9.57 × 10⁴ for PEO–D ‐Si‐2G). The steady‐state fluorescence anisotropy values (r) of 1,6‐diphenyl‐1,3,5‐hexatriene were 0.06 for PEO–D ‐Si‐1G and 0.09 for PEO–D ‐Si‐2G. The r values were lower than those of the linear polymeric amphiphiles, suggesting that the microviscosity of the dendritic micellar core was lower than that of the linear polymeric analogues. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 918–926, 2001     

Synthesis and characterization of polycholesteryl methacrylate–polyhydroxyethyl methyacrylate block copolymers

We report the synthesis and characterization of a series of novel diblock copolymers, poly(cholesteryl methacrylate‐b‐2‐hydroxyethyl methacrylate) (PCMA‐b‐PHEMA). Monomers, cholesteryl methacrylate (CMA) and 2‐(trimethylsiloxy)ethyl methacrylate (HEMA‐TMS), were prepared from methyacryloyl chloride and 2‐hydroxyethyl methacrylate, respectively. Homopolymers of CMA, PCMA, with well‐defined molecular weights and polydispersity indices (PDI), were prepared by reversible addition fragmentation and chain transfer (RAFT) method. Precursor diblock copolymers, PCMA‐b‐P(HEMA‐TMS), were synthesized using PCMA as macromolecular chain transfer agent and monomer, HEMA‐TMS. Product diblock copolymers, PCMA‐b‐PHEMA, were prepared by deprotecting trimethylsilyl units in the precursor diblock copolymers using acid catalysts. Detailed molecular characterization of the precursor diblock copolymers, PCMA‐b‐P(HEMA‐TMS), and the product diblock copolymers, PCMA‐b‐PHEMA, confirmed the composition and structure of these polymers. This versatile synthetic strategy can be used to prepare new amphiphilic block copolymers with cholesterol in one block and hydrogen‐bonding moieties in the second block. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6801–6809, 2008     

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.     

Synthesis of end‐functionalized AB copolymers. II. Synthesis and characterization of carboxyl‐terminated poly(ethylene glycol)–poly(amino acid) block copolymers

AB block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(amino acid) with a carboxyl group at the end of PEG were synthesized with α‐carboxylic sodium‐ω‐amino‐PEG as a macroinitiator for the ring‐opening polymerization of N‐carboxy anhydride. Characterizations by ¹H NMR, IR, and gel permeation chromatography were carried out to confirm that the diblock copolymers were formed. In aqueous media this copolymer formed self‐associated polymer micelles that have a carboxyl group on the surface. The carboxyl groups located at the outer shell of the polymeric micelle were expected to combine with ligands to target specific cell populations. The diameter of the polymer micelles was in the range of 30–80 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3527–3536, 2004     

Synthesis,characterization, and diels–alder extension of cyclopentadiene telechelic polyisobutylene. IV. α,ω-Di(3-cyclopentadienylpropyldimethylsilyl)polyisobutylene

The synthesis and chain extension of polyisobutylene having nonfluxional terminal cyclopentadiene groups is described. The fluxional behavior of silylcyclopentadiene end groups was previously found to prevent Diels–Alder dimerization of the end groups. The incorporation of a propyl moiety between the silicon atom and the cyclopentadiene ring was found to prevent this fluxional isomerization. Polyisobutylene was synthesized having 3-cyclopentadienylpropyldimethylsilyl end groups with a functionality near 2.0. While thermal extension at 80°C resulted in threefold molecular weight increase, coupling with bisdienophiles yielded greater than tenfold molecular weight increases. The retro-Diels–Alder reaction of coupled end groups prevents the attainment of high-molecular-weight polymers at equilibrium.     

Radical block polymerization of vinyl chloride. II. Synthesis and characterization of vinyl chloride block copolymers

Peroxidized polypropylene has been used as a heterofunctional initiator for a two-step emulsion polymerization of a vinyl monomer (M₁) and vinyl chloride with the production of vinyl chloride block copolymers. Styrene, methyl-, and n-butyl methacrylate and methyl-, ethyl-, n-butyl-, and 2-ethyl-hexyl acrylate have been used as M₁ and polymerized at 30–40°C. In the second step vinyl chloride was polymerized at 50°C. The range of chemical composition of the block copolymers depends on the rate of the first-step polymerization of M₁ and the duration of the second step; e.g., with 2-ethyl-hexyl acrylate block copolymers could be obtained with a vinyl chloride content of 25–90%. The block copolymers have been submitted to precipitation fractionation and GPC analysis. Noteworthy is the absence of any significant amount of homopolymers, as well as poly(M₁)n as PVC. The absence of homo-PVC was interpreted by an intra- and intermolecular tertiary hydrogen atom transfer from polypropylene residue to growing PVC sequences. The presence of saturated end groups on the PVC chains is responsible for the improved thermal stability of these block polymers, as well as their low rate of dehydrochlorination (180°C). Molecular aggregation in solution has been shown by molecular weight determination in benzene and tetrahydrofuran.     

Polyamide 6‐polycaprolactone multiblock copolymers: Synthesis,characterization, and degradation

This work describes the synthesis and characterization of polyamide 6 (PA 6)‐polycaprolactone (PCL) multiblock copolymers. Low molar mass, fully amine end‐capped PA 6 was prepared by the addition of a diamine monomer during ε‐caprolactam polymerization. A low molar mass PCL was selected to be incorporated as the biodegradable block and was fully end‐capped with toluene 2,4‐diisocyanate. End group analysis and molecular weight characterizations were performed for both end‐functionalized polymers by SEC, NMR and titration analysis. Incorporation of PCL into PA 6 was mainly achieved by solution mixing of the two end‐functional blocks and, was continued after the removal of the solvent with solid state polymerization (SSP) by gradual heating until about 40 °C below the melting temperature of the PA 6. Molecular weights started to grow immediately during solution mixing and only increased marginally during the SSP treatment. FTIR and SEC studies confirmed the reaction between the two components. DSC data, in combination with the enhanced molar mass during solution mixing pointed to a blocky microstructure, for which distinct melting and crystallization temperatures were observed for the PCL and the PA 6 blocks. Hydrolytic and enzymatic degradation studies were performed at 25 °C where the degree of degradation was followed by weight loss analysis, SEM and SEC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

New fluorinated thermoplastic elastomers. II. Synthesis and characterization of perfectly alternating fluorinated polyimide–fluorinated polyhybridsiloxane block copolymers via polyhydrosilylation

The synthesis of perfectly alternating fluorinated polyimide–fluorinated polyhybridsiloxane block copolymers (FPI‐FPHSX) was achieved through polyhydrosilylation of α,ω‐diallylfluorinated polyimides (AT‐FPI) and α,ω‐dihydrosilane fluorinated–polyhybridsiloxanes (HT‐FPHSX). A series of three FPI‐FPHSX containing 15, 38, and 56 wt % of polyimide was synthesized and characterized by tuning the number‐average molecular weight either of the hard polyimide segments or of the soft polyhybridsiloxane segments. The influence of the soft and hard segment lengths on the behavior of the thermoplastic elastomer material was studied (hardness, surface tension, thermal stability). The FPI‐FPHSX block copolymers thermomechanical properties are also reported. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 200–207, 2004     

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     

Poly(vinyl chloride)–poly(ethylene oxide) block copolymers: Synthesis and characterization

Poly(vinyl chloride)-poly(ethylene oxide) block copolymers have been synthesized in solution and emulsion. The polymers were made by first synthesizing macroazonitriles through the reaction of 4,4′-azobis-4-cyanovleryl chloride with hydroxy-terminated poly(ethylene oxide) of varying molecular weights. These macroazonitriles had molecular weights in the range of 3000–88,000 and degrees of polymerization from 5 to 24. Thermal decomposition of the azolinkages in the presence of vinyl chloride monomer yielded block copolymers containing form 2 to 20 wt % poly(ethylene oxide). The structures of the block copolymers were characterized by spectrometric, elemental and molecular weight analyses. The possibility of some graft polymerization occurring via free-radical extraction of a methylene hydrogen from the poly(ethylene oxide) was considered. Polymerization of vinyl chloride with an azonitrile initiator in the presence of a poly(ethylene oxide) yielded predominately homopolymer with some grafted poly(vinyl chloride).     

Styrene–isoprene block copolymers. I. Synthesis and solution properties

Copolymers with a different degree of distribution of styrene and isoprene blocks are prepared by anionic polymerization. The products are characterized by means of ¹H-NMR spectroscopy, GPC, viscometry, and light scattering. The results show that the copolymers are homogeneous in molecular weight and chain composition. In the investigated selective solvents, cyclohexane and base lubricating oil, and equilibrium exists between micelle aggregates and individual polymer coils. The influence of the copolymer structure on the micellization is more pronounced in cyclohexane.     

Synthesis of 4-vinylbiphenyl–isoprene block copolymers and their characterization by gel-permeation chromatography

4-Vinylbiphenyl–isoprene ABA block copolymers were prepared by initiating 4-vinylbiphenyl with n-butyllithium in benzene, adding isoprene, and coupling the resulting AB anion with phosgene. Preliminary coupling experiments with a polyisoprene anion have shown that virtually quantitative coupling could be achieved provided the phosgene was added extremely slowly. The block copolymers could be quantitatively analyzed by gel-permeation chromatography from a knowledge of the ratio of the refractive index increments of the two homopolymers and the overall composition.     

Synthesis and properties of polyetheretherketone–polydimethylsiloxane block copolymers

Polyetheretherketone-polydimethylsiloxane (PEEK–PDMS) block copolymers were synthesized from the condensation of dimethylamino terminated PDMS and hydroxy terminated PEEK oligomers in 1-chloronapthalene. Yields for block copolymers synthesised from low molecular weight PDMS oligomers were good but yields were significantly reduced when higher molecular weight PDMS oligomers were used. This was related to the limited solubility of higher molecular weight PDMS in the reaction solvent. Differential scanning calorimetry (DSC) studies indicated that phase separation of the block copolymers occurred at very short segment length (M?_n < 4000). A depression in the crystallinity of both the PEEK and PDMS phases in the block copolymer was observed. Thermogravimetric analysis (TGA) studies indicated that the PEEK–PDMS block copolymers displayed insufficient thermo-oxidative stability to be melt-processed successfully in PEEK based blends.